compost, herbicide compositions, herbicide mixture and method of controlling the growth of unwanted

专利摘要:
COMPOUND, COMPOSITION AND HERBICIDAL MIXTURE AND METHOD OF CONTROLLING UNWANTED VEGETATION GROWTH. Described are compounds of Formula 1, including all stereoisomers, N-oxides and salts thereof: wherein R1, R4, R5, R6, Q1, Q2, Y1 and Y2 are as defined in the specification; and T is J1-A- and also as defined in the descriptive report. Also described are compositions containing the compounds of Formula 1 and methods of controlling unwanted vegetation, which comprise contacting unwanted vegetation or its environment with an effective amount of a compound or composition according to the present invention.
公开号:BR112017017945B1
申请号:R112017017945-8
申请日:2016-03-29
公开日:2021-06-08
发明作者:Andrew Duncan Satterfield；James Francis Bereznak；Andrew Edmund Taggi
申请人:Fmc Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to certain substituted cyclic amides, their N-oxides, salts and compositions, as well as methods of their use for the control of unwanted vegetation. BACKGROUND OF THE INVENTION
[002] The control of unwanted vegetation is extremely important to achieve high production efficiency. Achieving selective control of weed growth, especially in useful crops such as rice, soybeans, sugar beets, corn, potatoes, wheat, barley, tomatoes, and plantation crops, among others, is highly desirable. Uncontrolled weed growth on these useful plants can significantly reduce productivity, resulting in increased costs for the consumer. Controlling unwanted vegetation in non-producing areas is also important. Many products are commercially available for these purposes, but there remains a need for new compounds that are more effective, less expensive, less toxic, environmentally safer, or have different sites of action. BRIEF DESCRIPTION OF THE INVENTION
em que: - Q1 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído por um a quatro substituintes independentemente selecionados a partir de R7; ou um anel heteroaromático com cinco a seis membros, ou um sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S) e os membros de anel de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, em que cada anel ou sistema de anéis opcionalmente substituído por até quatro substituintes independentemente selecionados a partir de R7 sobre membros de anéis de átomos de carbono e selecionados a partir de R9 sobre membros de anéis de átomos de nitrogênio; - Q2 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído por até cinco substituintes independentemente selecionados a partir de R10; ou um anel heteroaromático com cinco a seis membros ou um sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S) e os membros de anel de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, em que cada anel ou sistema de anéis é opcionalmente substituído por até cinco substituintes independentemente selecionados a partir de R10 sobre membros de anéis de átomos de carbono e selecionados a partir de R11 sobre membros de anéis de átomos de nitrogênio; - T é J1-A-, em que a ligação livre que se projeta para a direita ao lado de A indica o ponto de conexão de J1-A- a Q1; ou - T é R17ON=CR17a-, (R18)2C=NO-, (R19)2NN=CR17a-, (R18)2C=NNR20a-, R20N=CR17a-, (R18)2C=N-, R17ON=CR17aC(R23b)2- ou (R18)2C=NOC(R24a)2-, em que a ligação livre que se projeta para a direita indica o ponto de conexão a Q1; - A é uma cadeia saturada, parcialmente insaturada ou totalmente insaturada que contém de um a três átomos selecionados a partir de até três átomos de carbono, até 1 O, até 1 S e até 2 N, em que a cadeia é opcionalmente substituída por até dois substituintes independentemente selecionados a partir de R15 sobre átomos de carbono e R16 sobre átomos de nitrogênio; - Y1 e Y2 são, independentemente entre si, O, S ou NR12; - J1 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído por até cinco substituintes independentemente selecionados a partir de R7’; ou um anel heterocíclico com quatro a seis membros ou sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S) e os membros de anéis de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, cada anel ou sistema de anéis é opcionalmente substituído por até cinco substituintes independentemente selecionados a partir de R7’ sobre membros de anéis de átomos de carbono e selecionados a partir de R9’ sobre membros de anéis de átomos de nitrogênio; ou cicloalquilalcóxi C4-C10, cicloalquilalquila C4-C10, alquenilóxi C2-C8, haloalquenilóxi C2-C8, alcoxialcóxi C2C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, alquilsulfonila C1-C8, haloalquilsulfonila C1-C8, alquinila C2-C8, haloalquinila C2C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, haloaloxialcóxi C3-C8, haloalcóxi- haloalquila C2-C8, haloalquila C1-C8, halocicloalquila C3-C8, alquilcarbonilóxi C2C8 ou haloalquilcarbonilóxi C2-C8; - J2 é -CR2R3- ou -CR2R3-CR2aR3a-, em que a porção -CR2R3 é conectada a N; - R1 é H, hidróxi, amino, ciano, formila, alquilcarbonilalquila C3-C8, -CPh=N-O(alquila C1-C4), -C(alquila C1-C4)=N-O(alquila C1-C4), - C(O)NH2, alquila C1-C6, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, cianoalquila C2-C6, cicloalquila C3-C6, cicloalquilalquila C4-C8, alcoxialquila C2C8, alcoxialcoxialquila C3-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10, fenilcarbonila ou G1; - R2 e R3 são, independentemente entre si, H, halogênio, hidróxi, alquila C1-C4, haloalquila C1-C4 ou alcóxi C1-C4; ou - R2 e R3 são tomados em conjunto com o átomo de carbono ao qual são ligados para formar um anel cicloalquila C3-C7; - R2a e R3a são, independentemente entre si, H, halogênio ou alquila C1-C4; ou - R2a e R3a são tomados em conjunto com o átomo de carbono ao qual são ligados para formar um anel cicloalquila C3-C7; - R4 e R5 são, independentemente entre si, H, halogênio, hidroxila, alcóxi C1-C4 ou alquila C1-C4; - R6 é H, hidróxi, amino, alquila C1-C6, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2-C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R7 é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C4, cianoalquila C1-C4, cianoalcóxi C1-C4, haloalquila C1-C4, alquenila C2-C4, haloalquenila C2-C4, alquinila C2-C4, haloalquinila C2-C4, nitroalquila C1-C4, nitroalquenila C2-C4, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, haloalcoxialquila C2-C4, cicloalquila C3-C4, halocicloalquila C3-C4, ciclopropilmetila, 1-metilciclopropila, 2-metilciclopropila, alcóxi C1-C4, haloalcóxi C1-C4, alquenilóxi C2-C4, haloalquenilóxi C2-C4, alquinilóxi C3-C4, haloalquinilóxi C3-C4, cicloalcóxi C3-C4, alquiltio C1-C4, haloalquiltio C1-C4, alquilsulfinila C1-C4, haloalquilsulfinila C1-C4, alquilsulfonila C1-C4, haloalquilsulfonila C1-C4, hidróxi, - CHO, alquilcarbonila C2-C4, alquilcarbonilóxi C2-C4, alquilsulfonilóxi C1-C4, haloalquilsulfonilóxi C1-C4, amino, alquilamino C1-C4, dialquilamino C2-C4, formilamino, alquilcarbonilamino C2-C4, -SF5, -SCN, trialquilsilila C3-C4, trimetilsililmetila ou trimetilsililmetóxi; ou - dois R7 adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3C7; - cada R10 é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C8, haloalquila C1-C8, nitroalquila C1-C8, alquenila C2-C8, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, cianoalquila C1-C4, cianoalcóxi C1C4, haloalquenila C2-C8, nitroalquenila C2-C8, alquinila C2-C8, haloalquinila C2-C8, cicloalquilalquila C4-C10, halocicloalquilalquila C4-C10, alquilcicloalquilalquila C5C12, cicloalquilalquenila C5-C12, cicloalquilalquinila C5-C12, cicloalquila C3-C8, halocicloalquila C3-C8, alquilcicloalquila C4-C10, cicloalquilcicloalquila C6-C12, cicloalquenila C3-C8, halocicloalquenila C3-C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, cicloalcoxialquila C4-C10, alcoxialcoxialquila C3-C10, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilaminoalquila C2-C8, haloalquilaminoalquila C2-C8, cicloalquilaminoalquila C4-C10, dialquilaminoalquila C3-C10, -CHO, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, -C(=O)OH, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, -C(=O)NH2, alquilaminocarbonila C2-C8, cicloalquilaminocarbonila C4-C10, dialquilaminocarbonila C3-C10, hidróxi, alcóxi C1-C8, haloalcóxi C1-C8, alcoxialcóxi C2-C8, alquenilóxi C2-C8, haloalquenilóxi C2C8, alquinilóxi C3-C8, haloalquinilóxi C3-C8, cicloalcóxi C3-C8, halocicloalcóxi C3C8, cicloalquilalcóxi C4-C10, alquilcarbonilalcóxi C3-C10, alquilcarbonilóxi C2-C8, haloalquilcarbonilóxi C2-C8, cicloalquilcarbonilóxi C4-C10, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, alquilsulfonila C1-C8, haloalquilsulfonila C1-C8, cicloalquilsulfonila C3-C8, amino, alquilamino C1-C8, haloalquilamino C1-C6, cicloalquilamino C3-C8, dialquilamino C2-C8, halodialquilamino C2-C8, formilamino, alquilcarbonilamino C2-C8, haloalquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, haloalquilsulfonilamino C1-C6, -SF5, -SCN, trialquilsilila C3-C12, trialquilsililalquila C4-C12, trialquilsililalcóxi C4-C12 ou G2; ou - dois R10 adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3C7; - cada R7’ é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C8, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, cianoalquila C1C4, cianoalcóxi C1-C4, haloalquila C1-C8, nitroalquila C1-C8, alquenila C2-C8, haloalquenila C2-C8, nitroalquenila C2-C8, alquinila C2-C8, haloalquinila C2-C8, cicloalquilalquila C4-C10, halocicloalquilalquila C4-C10, alquilcicloalquilalquila C5C12, cicloalquilalquenila C5-C12, cicloalquilalquinila C5-C12, cicloalquila C3-C8, halocicloalquila C3-C8, alquilcicloalquila C4-C10, cicloalquilcicloalquila C6-C12, cicloalquenila C3-C8, halocicloalquenila C3-C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, cicloalcoxialquila C4-C10, alcoxialcoxialquila C3-C10, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilaminoalquila C2-C8, haloalquilaminoalquila C2-C8, cicloalquilaminoalquila C4-C10, dialquilaminoalquila C3-C10, -CHO, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, -C(=O)OH, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, -C(=O)NH2, alquilaminocarbonila C2-C8, cicloalquilaminocarbonila C4-C10, dialquilaminocarbonila C3-C10, hidróxi, alcóxi C1-C8, haloalcóxi C1-C8, alcoxialcóxi C2-C8, alquenilóxi C2-C8, haloalquenilóxi C2C8, alquinilóxi C3-C8, haloalquinilóxi C3-C8, cicloalcóxi C3-C8, halocicloalcóxi C3C8, cicloalquilalcóxi C4-C10, alquilcarbonilalcóxi C3-C10, alquilcarbonilóxi C2-C8, haloalquilcarbonilóxi C2-C8, cicloalquilcarbonilóxi C4-C10, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, alquilsulfonila C1-C8, haloalquilsulfonila C1-C8, cicloalquilsulfonila C3-C8, amino, alquilamino C1-C8, haloalquilamino C1-C6, cicloalquilamino C3-C8, dialquilamino C2-C8, halodialquilamino C2-C8, formilamino, alquilcarbonilamino C2-C8, haloalquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, haloalquilsulfonilamino C1-C6, -SF5, -SCN, trialquilsilila C3-C12, trialquilsililalquila C4-C12 ou trialquilsililalcóxi C4-C12; ou - dois R7’ adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3C7; - cada R8 é, independentemente, H, ciano, alquilcarbonila C2 C3 ou haloalquilcarbonila C2-C3; - cada R9, R9’ e R11 é independentemente ciano, alquila C1 C3, alquenila C2-C3, alquinila C2-C3, cicloalquila C3-C6, alcoxialquila C2-C3, alcóxi C1-C3, alquilcarbonila C2-C3, alcoxicarbonila C2-C3, alquilaminoalquila C2-C3 ou dialquilaminoalquila C3-C4; - cada R12 é independentemente H, ciano, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, -(C=O)CH3 ou -(C=O)CF3; - cada G1 é independentemente fenila, fenilmetila (ou seja, benzila), piridinilmetila, fenilcarbonila (ou seja, benzoíla), fenóxi, feniletinila, fenilsulfonila, fenilcarbonilalquila ou um anel heteroaromático com cinco ou seis membros, cada qual opcionalmente substituído sobre membros de anéis com até cinco substituintes independentemente selecionados a partir de R13; - cada G2 é independentemente fenila, fenilmetila (ou seja, benzila), piridinilmetila, fenilcarbonila (ou seja, benzoíla), fenilcarbonilalquila, fenóxi, feniletinila, fenilsulfonila ou um anel heteroaromático com cinco ou seis membros, cada qual opcionalmente substituído sobre membros de anéis por até cinco substituintes independentemente selecionados a partir de R14; - cada R13 e R14 é independentemente halogênio, ciano, hidróxi, amino, nitro, -CHO, -C(=O)OH, -C(=O)NH2, -SO2NH2, alquila C1-C6, haloalquila C1-C6, alquenila C2-C6, alquinila C2-C6, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, alcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, alquilaminocarbonila C2-C8, dialquilaminocarbonila C3-C10, alcóxi C1-C6, haloalcóxi C1-C6, alquilcarbonilóxi C2-C8, alquiltio C1-C6, haloalquiltio C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, alquilaminossulfonila C1C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10, alquilamino C1-C6, dialquilamino C2-C8, alquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, fenila, piridinila ou tienila; - cada R15 é independentemente halogênio, ciano, hidróxi, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R16 é independentemente H, ciano, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R17 é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R17a é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, trialquilsilila C3-C10 ou G1; - cada R18 é independentemente H, hidróxi, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R19 é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R20 é independentemente H, hidróxi, amino, alquila C1 C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R20a é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alcóxi C1-C6, C3-C8, trialquilsilila C3-C10 ou G1; - cada R23b é independentemente H, halogênio, ciano, hidróxi, alquila C1-C4, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R24a é independentemente H, alquila C1-C4, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada u e v é independentemente 0, 1 ou 2 em cada caso de S(=O)u(=NR8)v, desde que a soma de u e v seja 0, 1 ou 2; desde que, quando: a. J1 é um anel fenila não substituído e A é diferente de -CH2-, -O-, -CEC-, -C(=O)- ou -SO2-; ou b. J1 é um anel piridinila não substituído e A é diferente de - CH2-; c. J1 é cicloalquilalquila C4-C10 e A é diferente de alquila; ou d. J1-A- encontra-se na posição para de Q1, A é diferente de O e J1 é diferente de 2-furanilmetila.[003] The present invention relates to compounds of Formula 1 (including all their stereoisomers), their N-oxides and salts, agricultural compositions containing them and their use as herbicides: wherein: - Q1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by one to four substituents independently selected from R7; or a five to six membered heteroaromatic ring, or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four independently selected heteroatoms a from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the carbon ring members. sulfur are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7 on carbon atom ring members and selected to from R9 on ring members of nitrogen atoms; - Q2 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R10; or a five to six membered heteroaromatic ring or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from of up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur ring members are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R10 on carbon atom ring members and selected to from R11 on ring members of nitrogen atoms; - T is J1-A-, where the free link protruding to the right beside A indicates the connection point of J1-A- to Q1; or - T is R17ON=CR17a-, (R18)2C=NO-, (R19)2NN=CR17a-, (R18)2C=NNR20a-, R20N=CR17a-, (R18)2C=N-, R17ON=CR17aC( R23b)2- or (R18)2C=NOC(R24a)2-, where the free link projecting to the right indicates the connection point to Q1; - A is a saturated, partially unsaturated or fully unsaturated chain containing one to three atoms selected from up to three carbon atoms, up to 1 O, up to 1 S and up to 2 N, where the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms; - Y1 and Y2 are, independently of each other, O, S or NR12; - J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R7'; or a four to six membered heterocyclic ring or eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from S(=O)u(=NR8)v, each ring or ring system is optionally substituted by up to five substituents independently selected from R7' on carbon atom ring members and selected from R9' on ring members of nitrogen atoms; or C4-C10 cycloalkylalkoxy, C4-C10 cycloalkylalkyl, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2C8 alkoxyalkoxy, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C8 alkylsulfonyloxy, C1-C8 alkylsulfonyloxy C1-C8, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 haloalkylsulfonyl, C2-C8 alkynyl, C2C8 haloalkynyl, C2-C8 alkoxyalkyl, C2-haloalkoxyalkyl C8, C3-C8 haloaloxyalkoxy, C2-C8 haloalkoxy haloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, C2C8 alkylcarbonyloxy or C2-C8 haloalkylcarbonyloxy; - J2 is -CR2R3- or -CR2R3-CR2aR3a-, wherein the -CR2R3 portion is N-connected; - R1 is H, hydroxy, amino, cyano, formyl, alkylcarbonyl C3-C8 alkyl, -CPh=NO(C1-C4 alkyl), -C(C1-C4 alkyl)=NO(C1-C4 alkyl), - C(O )NH2, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C6 cyanoalkyl, C3-C6 cycloalkyl, C4-C8 cycloalkylalkyl, C2C8 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C8 haloalkoxyalkyl , C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2-8 alkylaminocarbonyl C3-C10, C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, haloalkylsulfonyl C1-C6, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C2-C8 dialkylaminosulfonyl, C3-C10 trialkylsilyl, phenyl carbonyl or G1; - R2 and R3 are, independently of one another, H, halogen, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; or - R2 and R3 are taken together with the carbon atom to which they are attached to form a C3-C7 cycloalkyl ring; - R2a and R3a are, independently of one another, H, halogen or C1-C4 alkyl; or - R2a and R3a are taken together with the carbon atom to which they are attached to form a C3-C7 cycloalkyl ring; - R4 and R5 are, independently of one another, H, halogen, hydroxyl, C1-C4 alkoxy or C1-C4 alkyl; - R6 is H, hydroxy, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl C2-C8, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, alkoxy C1-C6, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, alkylaminosulfonyl C1-C6, C2-C8 dialkylaminosulfonyl, C3-C10 or G1 trialkylsilyl; - each R7 is independently halogen, hydroxyl, cyano, nitro, C1-C4 alkyl, C1-C4 cyanoalkyl, C1-C4 cyanoalkoxy, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2 haloalkynyl -C4, C1-C4 nitroalkyl, C2-C4 nitroalkenyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C4 haloalkoxyalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, cyclopropylmethyl, 1-methylcyclopropyl, 2-methylcyclopropyl, C1 alkoxy -C4, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy, C3-C4 cycloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, haloalkylsulfinyl -C4, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, hydroxy, -CHO, C2-C4 alkylcarbonyl, C2-C4 alkylcarbonyloxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, amino, C1-C4 alkylamino, C2-C4 dialkylamino, formylamino, C2-C4 alkylcarbonylamino, -SF5, -SCN, C3-C4 trialkylsilyl, trimethylsilylmethyl or trimethylsilylmethoxy; or - two adjacent R7 are taken together with the carbon atoms to which they are attached to form a C3C7 cycloalkyl ring; - each R10 is independently halogen, hydroxyl, cyano, nitro, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 nitroalkyl, C2-C8 alkenyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkyl, C1-C4 cyanoalkyl, C1C4 cyanoalkoxy , C2-C8 haloalkenyl, C2-C8 nitroalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C5C12 alkylcycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, C5-C12 cycloalkylalkyny C3-C8, C4-C10 alkylcycloalkyl, C6-C12 cycloalkylcycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkyl, C3-C8 alkylthioalkyl C2-C8, C2-C8 alkylsulfonylalkyl, C2-C8 alkylaminoalkyl, C2-C8 haloalkylaminoalkyl, C4-C10 cycloalkylaminoalkyl, C3-C10 dialkylaminoalkyl, -CHO, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, -C( =O)OH, the C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C8 alkoxy, C1-C8 haloalkoxy, C2-C8 alkoxy, C2-C8 alkenyloxy, C2C8 haloalkenyloxy, C3-C8 alkynyloxy, C3-C8 haloalkynyloxy, C3-C8 cycloalkoxy, C3C8 haloalkoxy, C4-C10 cycloalkylalkoxy C4-C10 alkyloxycarbonyloxy , C2-C8 haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl , C1-C8 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, amino, C1-C8 alkylamino, C1-C6 haloalkylamino, C3-C8 cycloalkylamino, C2-C8 dialkylamino, C2-C8 halodialkylamino, formylamino, C2-C8 alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-C6 alkylsulfonylamino, C1-C6 haloalkylsulfonylamino, -SF5, -SCN, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl, C4-C12 or G2 trialkylsilylalkoxy; or - two adjacent R10 are taken together with the carbon atoms to which they are attached to form a C3C7 cycloalkyl ring; - each R7' is independently halogen, hydroxyl, cyano, nitro, C1-C8 alkyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C1C4 cyanoalkyl, C1-C4 cyanoalkoxy, C1-C8 haloalkyl, C1-C8 nitroalkyl, C2-alkenyl C8, C2-C8 haloalkenyl, C2-C8 nitroalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C5C12 alkylcycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, C5-C12 cycloalkylalkynyl C3-C8 halocycloalkyl, C4-C10 alkylcycloalkyl, C6-C12 cycloalkylcycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkyl, C2-alkylthio, alkoxy C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylaminoalkyl, C2-C8 haloalkylaminoalkyl, C4-C10 cycloalkylaminoalkyl, C3-C10 dialkylaminoalkyl, -CHO, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl (=O)OH, the C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C8 alkoxy, C1-C8 haloalkoxy, C2-C8 alkoxy, C2-C8 alkenyloxy, C2C8 haloalkenyloxy, C3-C8 alkynyloxy, C3-C8 haloalkynyloxy, C3-C8 cycloalkoxy, C3C8 haloalkoxy, C4-C10 cycloalkylalkoxy C4-C10 alkyloxycarbonyloxy , C2-C8 haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl , C1-C8 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, amino, C1-C8 alkylamino, C1-C6 haloalkylamino, C3-C8 cycloalkylamino, C2-C8 dialkylamino, C2-C8 halodialkylamino, formylamino, C2-C8 alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-C6 alkylsulfonylamino, C1-C6 haloalkylsulfonylamino, -SF5, -SCN, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl or C4-C12 trialkylsilylalkoxy; or - two adjacent R7' are taken together with the carbon atoms to which they are attached to form a C3C7 cycloalkyl ring; - each R8 is independently H, cyano, C2C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl; - each R9, R9' and R11 is independently cyano, C1 C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl , C2-C3 alkylaminoalkyl or C3-C4 dialkylaminoalkyl; - each R12 is independently H, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -(C=O)CH3 or -(C=O)CF3; - each G1 is independently phenyl, phenylmethyl (i.e., benzyl), pyridinylmethyl, phenylcarbonyl (i.e., benzoyl), phenoxy, phenylethynyl, phenylsulfonyl, phenylcarbonylalkyl, or a five- or six-membered heteroaromatic ring, each optionally substituted on ring members with up to five substituents independently selected from R13; - each G2 is independently phenyl, phenylmethyl (i.e., benzyl), pyridinylmethyl, phenylcarbonyl (i.e., benzoyl), phenylcarbonylalkyl, phenoxy, phenylethynyl, phenylsulfonyl, or a five- or six-membered heteroaromatic ring, each optionally substituted on ring members by up to five substituents independently selected from R14; - each R13 and R14 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=O)OH, -C(=O)NH2, -SO2NH2, C1-C6 alkyl, C1-C6 haloalkyl, alkenyl C2-C6, C2-C6 alkynyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C2-C8 alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1-C6 alkoxy, haloalkoxy C1-C6, C2-C8 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1C6 alkylaminosulfonyl, C1-C3 dialkylaminosulfonyl, C2-C8 alkylsilyl C10, C1-C6 alkylamino, C2-C8 dialkylamino, C2-C8 alkylcarbonylamino, C1-C6 alkylsulfonylamino, phenyl, pyridinyl or thienyl; - each R15 is independently halogen, cyano, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R16 is independently H, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R17 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl, C3-dialkylamino C4-C10 cycloalkylaminocarbonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C3-C8 dialkylaminosulfonyl, C1-C8 alkylsulfonyl G1; - each R17a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C3-C10 or G1 trialkylsilyl; - each R18 is independently H, hydroxy, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkylthioalkyl C2-C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl-dialkylaminocarbonyl C10, C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-haloalkylsulfonyl C6, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C2-C8 dialkylaminosulfonyl, C3-C10 or G1 trialkylsilyl; - each R19 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl, C3-dialkylamino C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C1-C6 alkylaminosulfonyl, dialkylaminosulfonyl C3-C10 or G1 trialkylsilyl; - each R20 is independently H, hydroxy, amino, C1C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2-C8 alkylcarbonylamino -C10, C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C1-C6 alkylaminosulfonyl -C8, C3-C10 or G1 trialkylsilyl; - each R20a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C6, C3-C8 alkoxy, C3-C10 or G1 trialkylsilyl; - each R23b is independently H, halogen, cyano, hydroxy, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2 alkylcarbonyl -C4, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R24a is independently H, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-alkoxycarbonyl C4 or C3-C6 cycloalkyl; - each u and v is independently 0, 1 or 2 in each case of S(=O)u(=NR8)v, provided that the sum of u and v is 0, 1 or 2; provided, when: a. J1 is an unsubstituted phenyl ring and A is other than -CH2-, -O-, -CEC-, -C(=O)- or -SO2-; or b. J1 is an unsubstituted pyridinyl ring and A is other than -CH2-; ç. J1 is C4-C10 cycloalkylalkyl and A is different from alkyl; or d. J1-A- is in the para position of Q1, A is different from O and J1 is different from 2-furanylmethyl.
More specifically, the present invention relates to a compound of Formula 1 (including all stereoisomers), one of its N-oxides or salts. The present invention also relates to a herbicidal composition comprising a compound according to the present invention (i.e. a herbicide effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. . The present invention further relates to a method of controlling the growth of unwanted vegetation which comprises contacting the vegetation or its environment with an herbicidal effective amount of a compound according to the present invention (e.g., in the form of a composition described in the present).
[005] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, its N-oxides and salts; and (b) at least one additional active ingredient selected from (b1) to (b16); and salts of compounds of (b1) to (b16) as described below. DETAILED DESCRIPTION OF THE INVENTION
[006] As used herein, the expressions "comprises", "which comprises", "includes", "which includes", "possesses", "which has", "contains", "which contains", "characterized by ” or any of its variations are intended to cover non-exclusive inclusion, subject to any expressly stated limitations. A composition, mixture, process, method, article or apparatus that comprises a list of elements, for example, is not necessarily limited only to those elements, but may include other elements not expressly listed or inherent in that composition, mixture, process, method, article or apparatus.
[007] Transition expression “consisting of” excludes any unspecified element, step or ingredient. If it is in the claim, it would close the claim to the inclusion of materials other than those indicated, except for normally associated impurities. When the expression “consisting of” is included in a clause of the body of a claim and not immediately after the preamble, it limits only the element described in that clause; other elements are not excluded from the claim as a whole.
[008] The transition expression "consisting essentially of" is used to define a composition, method or apparatus that includes materials, steps, features, components or elements, in addition to those literally described, provided that these materials, steps, features, components or additional elements do not materially affect the basic and innovative feature(s) of the present invention. The expression "which essentially consists of" occupies an intermediate space between "which comprises" and "which consists of".
[009] When applicants have defined an invention or one of its parts with an open expression such as "which comprises", it should be readily understood that (unless otherwise indicated) the description shall be interpreted as also describing that invention using the expressions "consisting essentially of" or "consisting of".
[0010] In addition, unless expressly stated to the contrary, “or” indicates either inclusive and not or exclusive. A condition A or B, for example, is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present) and both , A and B, are true (or present).
[0011] In addition, the indefinite articles "a" and "an" before an element or component according to the present invention are intended to be non-restrictive with respect to the number of cases (i.e., occurrences) of the element or component. “A” or “an” should therefore be read as including one or at least one and the singular word form of the element or component also includes the plural, unless the number is obviously intended to be singular.
[0012] As indicated herein, the term "sapling", used alone or in a combination of words, indicates a young plant that develops from the embryo of a seed.
[0013] As indicated herein, the expression "broad leaf", used alone or in expressions such as "broad leaf grass", indicates dicotyledon, a term used to describe a group of angiosperms characterized by embryos that have two cotyledons.
[0014] In the above descriptions, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight or branched chain alkyl such as methyl, ethyl, n-propyl, i-propyl or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl and the different isomers of butenyl, pentenyl and hexenyl. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
[0015] "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" indicates substitution of alkoxy over alkyl. Examples of "alkoxyalkyl" include CH3OCH2-, CH3OCH2CH2-, CH3CH2OCH2-, CH3CH2CH2CH2OCH2-, and CH3CH2OCH2CH2-. "Alkoxyalkoxyalkyl" indicates substitution of alkoxy over the alkoxy portion of the alkoxyalkyl portion. Examples of "alkoxyalkoxyalkyl" include CH3OCH2OCH2-, CH3CH2O(CH3)CHOCH2-, and (CH3O)2CHOCH2-. “Alkoxy-alkoxy” indicates alkoxy over alkoxy substitution. "Alkenyloxy" indicates straight or branched chain alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CH=CH2O-, (CH3)2C=CH=CH2O-, (CH3)CH=CH=CH2O-, (CH3)CH=C(CH3)CH2O-, and CH2=CH=CH2CH2O -. "Alkynyloxy" includes straight chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC CCH2O-, CH3C CCH2O- and CH3C CCH2CH2O-. "Alkylthio" includes straight or branched chain alkylthio moieties such as methylthio, ethylthio and the different isomers propylthio, butylthio, pentylthio and hexylthio. "Alkylsulfinyl" includes the two enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)- and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2- and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. Examples of "alkylsulfonylamino" include CH3S(O)2NH-, CH3CH2S(O)2NH-, CH3CH2CH2S(O)2NH-, (CH3)2CHS(O)2NH- and the different butylsulfonylamino, pentylsulfonylamino and hexylsulfonylamino isomers. Examples of "alkylsulfonyloxy" include CH3S(O)2O-, CH3CH2S(O)2O-, CH3CH2CH2S(O)2O-, (CH3)2CHS(O)2O- and the different butylsulfonyloxy, pentylsulfonyloxy and hexylsulfonyloxy isomers. "Alkylthioalkyl" indicates alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2-, CH3SCH2CH2-, CH3CH2SCH2-, CH3CH2CH2CH2SCH2-, and CH3CH2SCH2CH2-. "Cyanoalkyl" indicates an alkyl group substituted by a cyano group. Examples of "cyanoalkyl" include NCCH2-, NCCH2CH2- and CH3CH(CN)CH2-. “Cyanoalkoxy” indicates an alkoxy group substituted by a cyano group. Examples of "cyanoalkoxy" include NCCH2O-, NCCH2CH2O- and CH3CH(CN)CH2O-. "Alkylsulfinylalkyl" indicates substitution of alkylsulfinyl over alkyl. Examples of "alkylsulfinylalkyl" include CH3S(=O)CH2-, CH3S(=O)CH2CH2-, CH3CH2S(=O)CH2-, and CH3CH2S(=O)CH2CH2-. "Alkylsulfonylalkyl" indicates substitution of alkylsulfonyl over alkyl. Examples of "alkylsulfonylalkyl" include CH3S(=O)2CH2-, CH3S(=O)2CH2CH2-, CH3CH2S(=O)2CH2-, and CH3CH2S(=O)2CH2CH2-. "Alkylamino", "dialkylamino" and the like are defined analogously to the above examples. Examples of "alkylaminoalkyl" include CH3NHCH2-, (CH3)2CHNHCH2- and CH3NHCH(CH3)-. Examples of "alkylaminocarbonyl" include CH3NHC(O)-, (CH3)2CHNHC(O)- and CH3CH2NHC(O)-. Examples of "dialkylaminoalkyl" include (CH3)2NCH2-, (CH3)2NC(CH3)H- and (CH3)(CH3)NCH2-. Examples of "alkylaminocarbonyl" include CH3NC(O)- and CH3CH2NC(O)-. Examples of "dialkylaminocarbonyl" include (CH3)2NC(O)-. Examples of "dialkylaminosulfonyl" include (CH3)2NS(O)2-.
[0016] "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" indicates alkyl substitution over a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" indicates cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl and other cycloalkyl moieties attached to straight chain or branched alkyl groups. The term "cycloalkoxy" indicates cycloalkyl bonded through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. "Cycloalkoxyalkyl" indicates cycloalkoxy substitution on an alkyl moiety. Examples of "cycloalkoxyalkyl" include cyclopropoxymethyl, cyclopentoxyethyl and other cycloalkoxy moieties attached to straight chain or branched alkyl groups. "Cycloalkylalkoxy" indicates cycloalkylalkyl bonded through an oxygen atom attached to the alkyl chain. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy and other cycloalkyl moieties attached to straight-chain or branched alkoxy groups. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl, as well as groups with more than one double bond, such as 1,3 and 1,4-cyclohexadienyl.
The term "halogen", alone or in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine or iodine. Furthermore, when used in compound words such as "haloalkyl" or when used in descriptions such as "alkyl substituted by halogen", said alkyl may be fully or partially replaced by halogen atoms which may be identical or different. Examples of "haloalkyl" or "halogen substituted alkyl" include F3C-, ClCH2-, CF3CH2- and CF3CCl2-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", "haloalkenyl", "haloalkynyl" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S- and ClCH2CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S(O)-, CCl3S(O)- , CF3CH2S(O)- and CF3CF2S(O)-. Examples of "haloalkylsulfonyl" include CF3S(O)2-, CCl3S(O)2-, CF3CH2S(O)2-, and CF3CF2S(O)2-. Examples of "haloalkenyl" include (Cl)2C=CH=CH2- and CF3CH2CH=CH=CH2-. Examples of "haloalkynyl" include HC^CCHCl-, CF3CEC-, CCI3CEC- and FCH2CECCH2-. Examples of "haloalkoxyalkoxy" include CF3OCH2O-, ClCH2CH2OCH2CH2O- and Cl3CCH2OCH2O-, as well as branched alkyl derivatives.
[0018] "Alkylcarbonyl" indicates straight chain or branched alkyl moieties attached to a C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)- and (CH3)2CHC(=O)-. Examples of "alkylcarbonylalkoxy" include CH3C(=O)CH2O-, CH3CH2CH2C(=O)CH2O- and (CH3)2CHC(=O)CH2O-. Examples of "alkoxycarbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)- and the different butoxy or pentoxycarbonyl isomers. "Alkylcarbonyloxy" indicates an alkylcarbonyl moiety attached through an oxygen atom attached to the carbonyl. Examples of "alkylcarbonyloxy" include CH3C(=O)O-, CH3CH2CH2C(=O)O-, and (CH3)2CHC(=O)O -.
The total number of carbon atoms in a substituent group is indicated by the suffix "Ci-Cj" where i and j are numbers from 1 to 12. C1-C4 alkylsulfonyl, for example, designates methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl designates CH3OCH2-; C3 alkoxyalkyl designates, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted by an alkoxy group containing in total four carbon atoms, examples of which include CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.
[0020] When a compound is replaced by a substituent that contains a subscript indicating that the amount of said substituents may exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents (for example, ( R10)n, where n is 1, 2, 3, 4 or 5). Furthermore, when the subscript indicates a range, such as (R)i-j, the number of substituents can be selected from integers i to j, inclusive. When a group contains a substituent which may be hydrogen, such as R1 or R6, when that substituent is taken as hydrogen, it is recognized that it is equivalent to said group which is not substituted. When a variable group is shown to be optionally attached to a position, such as (R10)n, where n can be 0, hydrogen can be in the position even if it is not indicated in the variable group definition. When it is said that one or more positions on a group are “unsubstituted”, the hydrogen atoms are bonded to absorb any free valences.
[0021] The expression "fully saturated", with respect to a ring of atoms, indicates that all bonds between the atoms in the ring are simple. The expression "totally unsaturated" with respect to a ring indicates that the bonds between the ring atoms are single or double bonds according to the valence bond theory and, furthermore, the bonds between the ring atoms include as many double bonds as possible, without the double bonds being cumulative (ie without C=C=C, N=C=C etc.). The term "partially unsaturated" with respect to a ring indicates a ring comprising at least one ring member connected to an adjacent ring member via a double bond, which conceptually potentially accommodates an amount of double bonds not accumulated by means of adjacent ring members (ie, in their corresponding fully unsaturated form) greater than the amount of double bonds present (ie, in their partially unsaturated form). When a completely unsaturated ring satisfies Hückel's law, it can also be described as aromatic.
[0022] Unless otherwise indicated, a "ring" or "ring system" as a component of Formula 1 (such as the Q1 substituent) is carbocyclic or heterocyclic. The term “ring system” indicates two or more fused rings. The terms "bicyclic ring system" and "fused bicyclic ring system" denote a ring system consisting of two fused rings, where each ring may be saturated, partially unsaturated, or fully unsaturated, unless otherwise noted. The term "fused heterobicyclic ring system" indicates a fused bicyclic ring system in which at least one ring atom is not carbon. A "bridged bicyclic ring system" is formed by attaching a segment of one or more atoms to non-adjacent ring members of a ring. The term "ring member" indicates an atom or other moiety (such as C=(O), C(=S), S(O) or S(O)2) that forms the backbone of a ring or ring system. rings.
[0023] The expressions "carbocyclic ring" or "carbocyclic ring system" indicate a ring or ring system in which the atoms that form the main ring chain are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Hückel's law, said ring is also called an “aromatic ring”. "Saturated carbocyclic" indicates a ring that contains a main chain consisting of carbon atoms linked together by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
[0024] The expressions "heterocyclic ring", "heterocycle" or "heterocyclic ring system" indicate a ring or ring system in which at least one atom that forms the main ring chain is not carbon, such as nitrogen, oxygen or sulfur. Typically, a heterocyclic ring contains no more than four nitrogens, no more than two oxygens, and no more than two sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel's law, said ring is also called "heteroaromatic ring". The term "heteroaromatic bicyclic ring system" indicates a heterocyclic ring system in which at least one of the ring systems is aromatic. Unless otherwise indicated, heterocyclic rings and heterocyclic ring systems may be linked via any available carbon or nitrogen by replacing hydrogen on said carbon or nitrogen.
[0025] "Aromatic" indicates that each of the ring atoms lies essentially in the same plane and has a p-orbital perpendicular to the ring plane and in which (4n + 2) π electrons, where n is a positive integer , are associated with the ring to comply with Hückel's law. The term "heteroaromatic ring system" indicates a heterocyclic or carbocyclic ring system in which at least one ring in the ring system is aromatic.
[0026] The term "optionally substituted" with respect to heterocyclic rings designates groups that are unsubstituted or that have at least one non-hydrogen substituent that does not eliminate the biological activity of the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term “optionally substituted” is used interchangeably with the term “substituted or unsubstituted” or with the term “(un)substituted”. Unless otherwise indicated, an optionally substituted group can have a substituent at each substitutable position of the group and each substitution is independent of the other.
[0027] As indicated above, Q1, J1 and Q2 may be (among others) phenyl optionally substituted by one or more substituents selected from a group of substituents as defined in the Brief Description of the Invention. An example of phenyl optionally substituted by one to five substituents is the ring illustrated as U-1 in Illustration 1, where Rv is R7 or R7' as defined in the Brief Description of the Invention for Q1 or J1 and r is an integer (from 0 to 4); or Rv is R10 as defined in the Brief Description of the Invention for Q2, and r is an integer (0 to 5).
[0028] As indicated above, Q1, J1 and Q2 may be (among others) a fully unsaturated five- or six-membered heterocyclic ring, optionally substituted by one or more substituents selected from a group of substituents as defined in the Short Description of Invention. Examples of a fully unsaturated five- or six-membered heterocyclic ring optionally substituted by one or more substituents include rings U-2 to U-61 illustrated in Appendix 1, where Rv is any substituent defined in the Brief Description of the Invention for Q1, J1 and Q2 and r is an integer from 0 to 4, limited by the number of positions available in each U-group. Like U-29, U-30, U-36, U-37, U-38, U-39, U- 40, U-41, U-42 and U-43 have only one position available, for these U groups, r is limited to the integers 0 or 1, is r = 0 indicates that the U group is not substituted and a hydrogen is present in the position indicated by (Rv)r.
[0029] As indicated above, Q1, J1 and Q2 may be (among others) an eight to ten membered heteroaromatic bicyclic ring system, optionally substituted by one or more substituents selected from a group of substituents as defined in the Short Description of the Invention (i.e., R7, R7' and R10). Examples of an eight to ten membered heteroaromatic bicyclic ring optionally substituted by one or more substituents include rings U-62 to U-100 shown in Illustration 2, where Rv is any substituent defined in the Brief Description of the Invention for Q1, J1 or Q2 and r is typically an integer from 0 to 4 or 5. ILLUSTRATION 2
[0030] Some examples of a four to six membered saturated heterocyclic ring optionally substituted by one or more substituents include, but are not limited to, the rings U-101 to U-104 shown in Illustration 3, where Rv is any substituent defined in Brief Description of the Invention for Q1 or Q2 and r is typically an integer from 0 to 4 or 5.
[0031] Although Rv groups are shown in structures U-1 to U-104, it is observed that they do not need to be present, as they are optional substituents. Note that when Rv is H when bonded to an atom, it is the same way when said atom is not replaced. Nitrogen atoms that need replacement to fill their valence are replaced by H or Rv. Note that when the point of attachment between (Rv)r and the U group is shown as floating, (Rv)r can be attached to any available carbon atom or nitrogen atom of the U group. point of attachment on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 via any available carbon or nitrogen of the U group, by substitution of a hydrogen atom. Preferably, for greater herbicidal activity, the U group is attached to the rest of Formula 1 via an available carbon or nitrogen on a fully unsaturated U group ring. Note that some U groups can only be replaced by less than four groups Rv (eg U-2 to U-5, U-7 to U-48 and U-52 to U-61).
[0032] A wide variety of synthetic methods are known in the art to enable the preparation of aromatic and non-aromatic heterocyclic rings and ring systems; for extensive analysis, see the eight-volume set Comprehensive Heterocyclic Chemistry, AR Katritzky and CW Rees, Editors-in-Chief, Pergamon Press, Oxford, 1984, and the twelve-volume set of Comprehensive Heterocyclic Chemistry II, AR Katritzky, CW Rees, and EFV Scriven, Editors-in-Chief, Pergamon Press, Oxford, 1996.
The compounds according to the present invention may exist in the form of one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers with identical constitution but different arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation around isolated bonds, where the rotation barrier is high enough to allow isolation of isomeric substances. Those skilled in the art will appreciate that a stereoisomer may be more active and/or may exhibit beneficial effects when enriched with respect to the other stereoisomer(s) or when separated from the other stereoisomer(s) . Furthermore, those skilled in the art know how to selectively separate, enrich and/or prepare the aforementioned stereoisomers. The compounds according to the present invention can be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. Particularly, when each of R4 and R5 is H, the substituents C(O)N(Q2)(R6) and Q1 typically are found mostly in the thermodynamically preferred trans configuration on the pyrrolidinone ring.
[0034] The C(O)N(Q2)(R6) portion (attached to the carbon at the 3-position of the pyrrolidinone ring, where Y1 and Y2 are both oxygen, J2 is -CR2R3 and both, R2 and R3 are H ) and Q1 (attached to carbon at the 4-position of the pyrrolidinone ring), for example, are generally found in the trans configuration. These two carbon atoms (ie, at positions 3 and 4, each of which has the central ring of Formula 1) have a chiral center. The two pairs of enantiomers with the highest incidence are illustrated in Formula 1' and in Formula 1”, where chiral centers are identified (ie, as 3R, 4S or as 3S, 4R). Those skilled in the art will understand that, in some embodiments of the present invention, the R or S designation is determined with respect to other substituents around the same carbon and therefore a compound in accordance with the present invention may also be assigned the 3S designation, 4S. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel W. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
[0035] The molecular illustrations shown herein follow standard illustration and stereochemical conventions. To indicate stereoconfiguration, bonds arising from the plane of the drawing and facing the viewer are indicated by solid wedges, where the wide end of the wedge is fixed to the atom that rises from the plane of the drawing facing the viewer. Bonds that run below the drawing and away from the viewer are indicated by dashed wedges, where the narrow end of the wedge is attached to the atom farthest from the viewer. Lines with constant width indicate links in the opposite or neutral direction relative to links shown with solid or dashed wedges; constant-width lines also illustrate bonds in molecules or parts of molecules where no specific stereoconfiguration is intended to be specified.
[0036] The present invention comprises racemic mixtures, such as equal amounts of the enantiomers of Formulas 1' and 1". In addition, the present invention includes compounds that are enriched compared to the racemic mixture in one enantiomer of Formula 1. Also included are the essentially pure enantiomers of compounds of Formula 1, such as Formula 1' and Formula 1".
[0037] When enantiomerically enriched (ie, enantioenriched), one enantiomer is present in greater amounts than the other and the extent of enrichment can be defined by an expression of enantiomeric excess ("ee"), which is defined as (2x- 1^100%, where x is the molar fraction of the dominant enantiomer in the mixture (20% ee, for example, corresponds to a 60:40 ratio of enantiomers) The compounds according to the present invention can be prepared in a manner enantiomerically enriched (ie, enantiomerically enriched), using a corresponding enantiomerically enriched intermediate throughout the synthesis. In these cases, the enantiomeric excess is not measured in the final product, but it is assumed to be "enantiomerically enriched" based on chemical transformations equivalents, known in the literature.
[0038] Preferably, the compositions according to the present invention have an enantiomeric excess of at least 50%; more preferably, at least 75% enantiomeric excess; even more preferably, at least 90% enantiomeric excess and, more preferably, at least 94% enantiomeric excess of the more active isomer. Particularly noteworthy enantiomerically pure realizations of the most active isomer.
The compounds of Formula 1 may comprise additional chiral centers. Substituents and other molecular components such as R2 and R3, for example, can contain chiral centers. The present invention comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers.
[0040] The compounds according to the present invention may exist in the form of one or more conformational isomers due to restricted rotation around the amide bond (e.g., C(O)N(Q2)(R6)) in the Formula 1. The present invention comprises mixtures of conformation isomers. Furthermore, the present invention includes compounds that are enriched in one conformer over others.
The compounds of Formula 1 typically exist in more than one form and Formula 1 therefore includes all crystalline and non-crystalline forms of the compounds they represent. Non-crystalline forms include embodiments that are solid such as waxes and gums, as well as embodiments that are liquid, such as solutions and melts. Crystalline forms include embodiments that represent essentially a single crystal type and embodiments that represent a mixture of polymorphs (i.e., different crystal types). The term "polymorph" designates a specific crystalline form of a chemical compound that can crystallize into different crystalline forms, such forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs may have the same chemical composition, they may also differ in composition due to the presence or absence of cocrystallized water or other molecules, which may be weakly or tightly bound in the lattice. Polymorphs can differ in chemical, physical and biological properties such as crystal shape, density, hardness, coloration, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate and bioavailability. Those skilled in the art will appreciate that a polymorph of a compound of Formula 1 may exhibit beneficial effects (such as suitability for preparing useful formulations and improved biological performance) over another polymorph or a mixture of polymorphs of the same compound of Formula 1. The preparation and isolation of a specific polymorph of a compound of Formula 1 can be accomplished by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism, see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.
[0042] Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, as nitrogen requires an isolated pair available for oxidation to the oxide; those skilled in the art will recognize nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods of preparing N-oxides of heterocycles and tertiary amines are very well known to those skilled in the art, including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, hydroperoxides of alkyl such as t-butyl hydroperoxide, sodium perborate and dioxiranes such as dimethyldioxirane. These methods of preparing N-oxides have been extensively described and analyzed in the literature; see, for example: T.L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp. 748-750, S.V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, p. 18-20, A.J. Boulton and A. McKillop, Eds., Pergamon Press; M.R. Grimmett and B.R.T. Keene in Advances in Heterocyclic Chemistry, vol. 43, p. 149-161, A.R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, p. 285-291, A.R. Katritzky and A.J. Boulton, Eds., Academic Press; and G.W.H. Cheeseman and E.S.G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, p. 390-392, A.R. Katritzky and A.J. Boulton, Eds., Academic Press.
[0043] Those skilled in the art recognize that, as in the environment and under physiological conditions, the salts of chemical compounds are in equilibrium with their corresponding non-salt forms, the salts share the biological utility of the non-salt forms. In this way, a wide variety of salts of compounds of Formula 1 are useful for the control of unwanted vegetation (ie they are suitable for agricultural use). The salts of the compounds of Formula 1 include acid addition salts with organic or inorganic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric acids , 4-toluenesulfonic or valeric. When a compound of Formula 1 contains an acidic moiety such as carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, their N-oxides and salts suitable for agricultural use.
[0044] Embodiments of the present invention as detailed in the Brief Description of the Invention include (wherein Formula 1 used in the following embodiments includes N-oxides and salts thereof): Embodiment 1. Compound of Formula 1, wherein, when Q1 is a five- or six-membered heteroaromatic ring or an eight- to ten-membered bicyclic heteroaromatic ring system, each ring or ring system is optionally substituted by up to four substituents selected from R7 on carbon atom ring members and selected from of R9 on ring members of nitrogen atoms. Embodiment 2. The compound according to Embodiment 1, wherein Q1 is not substituted by R7 or R9. Embodiment 3. A compound of Formula 1, wherein Q1 is a phenyl ring or naphthalenyl ring system and each ring or ring system is optionally substituted by one to four substituents independently selected from R7. Embodiment 4. The compound according to Embodiment 3, wherein Q1 is a phenyl ring optionally substituted by one to two substituents independently selected from R7. Embodiment 5. A compound according to Embodiment 4, wherein Q1 is a phenyl ring substituted by a substituent selected from R7. Embodiment 6. A compound according to Embodiment 4, wherein Q1 is a phenyl ring unsubstituted by R7. Embodiment 7. A compound of Formula 1 or according to any of Embodiments 1 to 6, wherein, when Q2 is a five- or six-membered heteroaromatic ring or an eight- to ten-membered heteroaromatic bicyclic ring system, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R10 on carbon atom ring members and selected from R11 on nitrogen atom ring members. Embodiment 8. A compound of Formula 1 or according to any of embodiments 1 to 6, wherein Q2 is a phenyl ring optionally substituted by one to five substituents independently selected from R10. Embodiment 9. A compound according to Embodiment 8, wherein Q2 is a phenyl ring optionally substituted by one to three substituents independently selected from R10. Embodiment 10. The compound according to Embodiment 9, wherein Q2 is a phenyl ring optionally substituted by one to two substituents independently selected from R10. Embodiment 11. A compound of Formula 1 or according to any of embodiments 1 to 10, wherein Q2 is a phenyl ring that contains at least one substituent selected from R10 in ortho position (and optionally other substituents). Embodiment 12. A compound of Formula 1 or according to any of Embodiments 1 to 9, wherein, when Q2 is a phenyl ring substituted by at least two substituents selected from R10, at least one substituent is in the ortho position and at least one substituent is in the para position of the phenyl ring. Embodiment 13. A compound of Formula 1 or according to any one of Embodiments 1 to 9, wherein Q2 is a phenyl ring substituted by three substituents selected from R10 and the three substituents are in ortho, meta and para positions of the ring phenyl. Embodiment 14. A compound of Formula 1 or according to any of Embodiments 1 to 13, wherein T is J1-A-. Embodiment 15. A compound according to Embodiment 14, wherein A is a saturated, partially unsaturated or fully unsaturated chain containing from one to three atoms selected from up to three carbon atoms, up to 1 O, up to 1 S and up to 2N, wherein the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms. Embodiment 16. The compound according to Embodiment 15, wherein A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, -S- , -SO- or -SO2-. Embodiment 17. The compound according to Embodiment 16, wherein A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH- or -O-. Embodiment 18. The compound according to Embodiment 17, wherein A is -CH2O- or -O-. Embodiment 19. A compound of Formula 1 or according to any of Embodiments 1 to 18, wherein J 1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from of R7'; or a four to six membered heterocyclic ring or eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from S(=O)u(=NR8), each ring or ring system is optionally substituted by up to five substituents independently selected from R7' on ring members of carbon atoms and selected from R9 ' on ring members of nitrogen atoms; or C4-C10 cycloalkylalkoxy, C4-C10 cycloalkylalkyl, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2C8 alkoxyalkoxy, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C8 alkylsulfonyloxy, C1-C8 alkylsulfonyloxy C1-C8, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 haloalkylsulfonyl, C2-C8 alkynyl, C2C8 haloalkynyl, C2-C8 alkoxyalkyl, C2-haloalkoxyalkyl C8, C3-C8 haloalkoxyalkoxy, C1-C8 haloalkyl, C3-C8 halocycloalkyl, C2-C8 alkylcarbonyloxy or C2-C8 haloalkylcarbonyloxy. Embodiment 20. The compound according to Embodiment 19, wherein J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7'. Embodiment 21. The compound according to Embodiment 20, wherein J1 is a phenyl ring optionally substituted by up to three substituents independently selected from R7'. Embodiment 22. The compound according to Embodiment 21, wherein J1 is a phenyl ring optionally substituted by a substituent independently selected from R7'. Embodiment 23. The compound according to Embodiment 22, wherein J1 is a phenyl ring unsubstituted by R7'. Embodiment 24. The compound according to Embodiment 19, wherein J1 is a four to six membered heterocyclic ring or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected a from carbon atoms and from one to four heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted by up to five independently selected substituents from R7' on carbon atom ring members and selected from R9' on nitrogen atom ring members. Embodiment 25. The compound according to Embodiment 24, wherein J1 is a four to six membered heterocyclic ring containing ring members selected from carbon atoms and one to three heteroatoms independently selected from up to 2 carbon atoms. O, up to 2 S and up to 3 N, wherein up to two carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from of S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted by up to three substituents independently selected from R7' on ring members of carbon atoms and selected from R9' on ring members of nitrogen atoms. Embodiment 26. The compound according to Embodiment 25, wherein J1 is a five- or six-membered heteroaromatic ring optionally substituted by a substituent selected from R7' on carbon atom ring members. Embodiment 27. The compound according to Embodiment 26, wherein J1 is an unsubstituted pyridine ring. Embodiment 28. The compound according to Embodiment 19, wherein J1 is C4-C10 cycloalkylalkoxy, C4-C10 cycloalkylalkyl, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2-C8 alkoxyalkoxy, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 haloalkylsulfonyl C2-C8 alkynyl, C2-C8 haloalkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C3-C8 haloalkoxyalkoxy, C2-C8 haloalkoxy-C2-C8 haloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, C2-C8 alkylcarbonyloxy or C2-C8 haloalkyloxy C8. Embodiment 29. A compound of Formula 1 or according to any of Embodiments 1 to 13, wherein T is R17ON=CR17a-, (R18)2C=NO-, (R19)2NN=CR17a-, (R18)2C=NNR20a- , R20N=CR17a-, (R18)2C=N-, R23ON=CR17aC(R23b)2- or (R18)2C=NOC(R24a)2-, where the free bond that projects to the right indicates the point of connection to Q1. Embodiment 30. The compound according to Embodiment 29, wherein each R17 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, or C1-C6 haloalkyl. Embodiment 31. The compound according to Embodiment 29, wherein each R17a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, or C1-C6 haloalkyl. Embodiment 32. The compound according to Embodiment 29, wherein each R18 is independently H, hydroxy, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl or C1-C6 haloalkyl. Embodiment 33. The compound according to Embodiment 29, wherein each R19 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, or C1-C6 haloalkyl. Embodiment 34. The compound according to Embodiment 29, wherein each R20 is independently H, hydroxy, amino, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl or C1-C6 haloalkyl. Embodiment 35. The compound according to Embodiment 29, wherein each R20a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl or C1-C6 haloalkyl. Embodiment 36. The compound according to Embodiment 29, wherein each R23b is independently H, halogen, cyano, hydroxy, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl or C1-C4 haloalkyl. Embodiment 37. The compound according to Embodiment 29, wherein each R24a is independently H, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl or C1-C4 haloalkyl. Embodiment 38. A compound of Formula 1 or according to any of Embodiments 1 to 37, wherein J2 is -CR2R3-. Embodiment 39. A compound of Formula 1 or according to any of Embodiments 1 to 37, wherein J2 is -CR2R3-CR2aR3a-. Embodiment 40. A compound of Formula 1 or according to any one of Embodiments 1 to 39, wherein R1 is H, hydroxy, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2 cyanoalkyl -C6, C3-C6 cycloalkyl or C4-C8 cycloalkylalkyl. Embodiment 41. The compound according to Embodiment 40, wherein R1 is H, C1-C6 alkyl or C1-C6 haloalkyl. Embodiment 42. The compound according to Embodiment 41, wherein R1 is H, Me, Et or CHF2. Embodiment 43. A compound according to Embodiment 42, wherein R 1 is H, Me or Et. Embodiment 44. Compound according to Embodiment 43, wherein R 1 is H. Embodiment 45. Compound according to Embodiment 43, wherein R 1 is Me. Embodiment 46. Compound of Formula 1 or according to any of Embodiments 1 to 45, where R2 is H or CH3. Embodiment 47. A compound according to Embodiment 46, wherein R2 is H. Embodiment 48. A compound of Formula 1 or according to any one of Embodiments 1 to 47, wherein R3 is H or CH3. Embodiment 49. A compound according to Embodiment 43, wherein R3 is H. Embodiment 50. A compound of Formula 1 or according to any one of Embodiments 1 to 49, wherein R2a is H or CH3. Embodiment 51. A compound according to Embodiment 50, wherein R2a is H. Embodiment 52. A compound of Formula 1 or according to any one of Embodiments 1 to 51, wherein R3a is H or CH3. Embodiment 53. A compound according to Embodiment 52, wherein R3a is H. Embodiment 54. A compound of Formula 1 or according to any one of Embodiments 1 to 53, wherein R4 is H or CH3. Embodiment 55. A compound according to Embodiment 54, wherein R4 is H. Embodiment 56. A compound of Formula 1 or according to any one of Embodiments 1 to 55, wherein R5 is H or CH3. Embodiment 57. A compound according to Embodiment 56, wherein R5 is H. Embodiment 58. A compound of Formula 1 or according to any one of Embodiments 1 to 57, wherein R6 is H or CH3. Embodiment 59. A compound according to Embodiment 58, wherein R6 is H. Embodiment 60. A compound of Formula 1 or according to any of Embodiments 1 to 59, wherein each R7 is independently halogen, cyano, nitro, C1-alkyl C4, C1-C4 cyanoalkyl, C1-C4 cyanoalkoxy, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 nitroalkyl, C2-C4 nitroalkenyl, C2-alkoxyalkyl C4, C2C4 haloalkoxyalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, cyclopropylmethyl, methylcyclopropyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C3 haloalkoxy C3-C4, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, hydroxy, formyl, C2-C4 alkylcarbonyl, C2-C4 alkylcarbonyloxy, C1 alkylsulfonyloxy -C4, C1-C4 haloalkylsulfonyloxy, amino, C1-C4 alkylamino, C2-C4 dialkylamino, formylamino, alkylcarbon C2-C4 ylamino, -SF5, -SCN, C3-C4 trialkylsilyl, trimethylsilylmethyl or trimethylsilylmethoxy. Embodiment 61. The compound according to Embodiment 60, wherein each R7 is independently halogen, cyano, C1-C2 alkyl, C1-C3 haloalkyl, or C1-C3 alkylsulfonyl. Embodiment 62. The compound according to Embodiment 61, wherein each R7 is independently halogen or C1-C2 haloalkyl. Embodiment 63. The compound according to Embodiment 62, wherein each R7 is independently halogen or CF3. Embodiment 64. The compound according to Embodiment 63, wherein each R7 is independently F or CF3. Embodiment 65. A compound of Formula 1 or any of Embodiments 1 to 64, wherein each R10 is independently halogen, cyano, nitro, C1-C2 alkyl, C1-C3 haloalkyl, or C1-C3 alkylsulfonyl. Embodiment 66. The compound according to Embodiment 65, wherein each R10 is independently halogen or C1-C2 haloalkyl. Embodiment 67. The compound according to Embodiment 66, wherein each R10 is independently halogen or CF3. Embodiment 68. The compound according to Embodiment 67, wherein each R10 is independently F or CF3. Embodiment 69. The compound according to Embodiment 68, wherein each R10 is independently F. Embodiment 70. A compound of Formula 1 or any of Embodiments 1 to 69, wherein each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl. Embodiment 71. The compound according to Embodiment 70, wherein each R7' is independently halogen. Embodiment 72. A compound of Formula 1 or according to any one of embodiments 1 to 71, wherein Y1 is O. Embodiment 73. A compound of Formula 1 or according to any one of embodiments 1 to 72, wherein Y2 is O. Embodiment 74 A compound of Formula 1 or any one of embodiments 1 to 73, wherein Y1 and Y2 are both O. Embodiment 75. A compound of Formula 1 or any one of embodiments 1 to 74, wherein each R9, R9' and R11 is independently C1-C3 alkyl or C3-C6 cycloalkyl. Embodiment 76. A compound of Formula 1 wherein T is attached to the 2 or 3 position of Q1. Embodiment 77. A compound of Formula 1 wherein T is attached to the 3-position of Q1. Embodiment 78. Compound of Formula 1, where T is R17ON=CR17a- , (R18)2C=NO- or (R19)2NN=CR17a-, where the free bond projecting to the right indicates the point of attachment to Q1. Embodiment 79. Composite according to Embodiment 77, where T is R17ON=CR17a- or (R19)2NN=CR17a- and the free link projecting to the right indicates the connection point to Q1. Embodiment 80. A compound of Formula 1, wherein J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R7'; or a four to six membered heterocyclic ring or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from of up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur ring members are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted by up to five substituents independently selected from R7' on carbon atom ring members and selected from R9' on ring members of nitrogen atoms. Embodiment 81. A compound of Formula 1, wherein J1 is C4-C10 cycloalkylalkoxy, C4-C10 cycloalkylalkyl, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2-C8 alkoxyalkoxy, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl C8, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 haloalkylsulfonyl, C2-alkynyl C8, C2-C8 haloalkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C3-C8 haloalkoxyalkoxy, C2-C8 haloalkoxy-C2-C8 haloalkyl, C1-C8 haloalkyl, C3-C8 halocycloalkyl, C2-C8 alkylcarbonyloxy or C2-C8 haloalkylcarbonyloxy. Embodiment 82. The compound according to Embodiment 80, wherein J1 is C4-C10 cycloalkylalkoxy, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2-C8 alkoxyalkoxy, C2-C8 alkylsulfonylalkyl, C1-C8 alkylsulfonyloxy, C1C8 haloalkylsulfonyloxy, C1C8 alkylthio -C8, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl, C1-C8 haloalkylsulfonyl, C3-C8 haloalkoxyalkoxy, C2-C8 alkylcarbonyloxy or C2-C8 haloalkylcarbonyloxy. Embodiment 83. The compound of Embodiment 81, wherein J1 is C4-C10 cycloalkylalkyl, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkynyl, C2-C8 haloalkynyl, C2C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C1-C8 haloalkyl or C3-C8 halocycloalkyl. Embodiment 84. The compound according to Embodiment 83, wherein J1 is C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkoxyalkyl or C2-C8 haloalkoxyalkyl. Embodiment 85. A compound of Formula 1 or according to Embodiment 15, wherein A is a saturated, partially unsaturated or fully unsaturated chain containing two to three atoms selected from up to three carbon atoms, up to 1 O, up to 1 S and up to 2N, wherein the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms. Embodiment 86. A compound according to Embodiment 85, wherein A is a saturated, partially unsaturated, or fully unsaturated chain containing two to three atoms selected from up to three carbon atoms, up to 1 O and up to 1 N, wherein the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms. Embodiment 87. A compound according to Embodiment 86, wherein A is a chain containing two to three atoms selected from up to two carbon atoms, up to 1 O and up to 1 N, wherein the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms. Embodiment 88. A compound of Formula 1, wherein A is -CH2-, -CH2O-, -OCH2-, -CH2NH-, -CH2CH2-, -CH=CH-, -CEC-, -NH-, -O-, -S-, -SO- or -SO2-. Embodiment 89. A compound of Formula 1 wherein A is -CH 2 -, -CH 2 O-, -OCH 2 -, -O-SO or -SO 2 -. Embodiment 90. A compound of Formula 1 wherein A is -CH2O-, -OCH2-, -CH2CH2-, -CH=CH- or -CeC-. Embodiment 91. A compound of Formula 1 or any of Embodiments 16 to 19 or 88 to 90, wherein the free bond projecting to the right indicates the point of connection from A to Q1 and the free bond projecting to the left indicates the connection point from A to J1. Embodiment 92. A compound of Formula I, wherein, when J2 is -CR2R3- and J1 is a phenyl ring optionally substituted by up to five substituents independently selected from R7', R7' is other than halogen, hydroxyl, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C2C6 alkenyl, C2-C6 alkynyl, CHO, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, - C(=O)OH, C2-C8 alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5 cycloalkylalkoxycarbonyl -C12, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C8 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1 alkylsulfinyl -C6, C1-C6 haloalkylsulfinyl, C1-C6 alkylamino, C2-C8 dialkylamino, C2-C8 alkylcarbonylamino, C1-C6 alkylsulfonylamino or C3-C10 trialkylsilyl. Embodiment 93. A compound of Formula I, wherein, when J2 is -CR2R3-CR2aR3a- and J1 is a pyridyl ring (i.e., a six-membered heterocyclic ring optionally substituted by up to five substituents independently selected from R7' on members of rings of carbon atoms), R7' is different from halogen, hydroxyl, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, CHO, C2-C8 alkylcarbonyl, C2 haloalkylcarbonyl -C8, -C(=O)OH, C2-C8 alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C6 alkoxy , C1-C6 haloalkoxy, C2-C8 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylamino, C2C8 dialkylamino, C2-C8 alkylcarbonylamino, C1-C6 alkylsulfonylaminoalkylsilyl or C3-C10. Embodiment 94. A compound of Formula 1, wherein, when Q1 is a five- or six-membered heteroaromatic ring or an eight- to ten-membered heteroaromatic bicyclic ring system, wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7 over carbon atom ring members and selected from R9 over nitrogen atom ring members. Embodiment 95. A compound of Formula 1, wherein Q1 is a phenyl ring optionally substituted by one to four substituents independently selected from R7; or a five to six membered heteroaromatic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to four substituents independently selected from R7 over carbon atom ring members and selected from R9 over nitrogen atom ring members. Embodiment 96. A compound of Formula 1 or according to Embodiment 95, wherein Q1 is a phenyl ring optionally substituted by up to four substituents independently selected from R7. Embodiment 97. A compound of Formula 1, wherein Q2 is a phenyl ring optionally substituted by up to five substituents independently selected from R10; or a five to six membered heteroaromatic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to five substituents independently selected from R10 over carbon atom ring members and selected from R11 over nitrogen atom ring members. Embodiment 98. A compound of Formula 1 or according to Embodiment 97, wherein Q2 is a phenyl ring optionally substituted by up to four substituents independently selected from R10. Embodiment 99. A compound of Formula 1, wherein J1 is a phenyl ring optionally substituted by up to five substituents independently selected from R7'; or a four to six membered heterocyclic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to five substituents independently selected from R7' over carbon atom ring members and selected from R9' over nitrogen atom ring members. Embodiment 100. A compound of Formula 1 or according to Embodiment 99, wherein J1 is a phenyl ring optionally substituted by up to four substituents independently selected from R7'; or a six-membered heteroaromatic ring containing ring members selected from carbon atoms and one to three heteroatoms independently selected from 3 N atoms, optionally substituted by up to four substituents independently selected from R7' on members of carbon atom rings and selected from R9' on nitrogen atom ring members. Embodiment 101. A compound of Formula 1 wherein R7 is independently halogen, CH3, CH2CH3 or CF3. Embodiment 102. A compound of Formula 1 wherein R10 is independently halogen, CH3, CH2CH3 or CF3. Embodiment 103. A compound of Formula 1 wherein each R10 is independently cyano or CH3. Embodiment 104. Compound of Formula 1 wherein each R16 is H. Embodiment 105. Compound of Formula 1 wherein each R16 is different from H.
[0045] Embodiments of the present invention, including Embodiments 1 to 105 above as well as any other embodiments described herein, may be combined in any way and descriptions of variables in the embodiments refer not only to the compounds of Formula 1, but also to starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of the present invention, including Embodiments 1 to 105 above as well as any other embodiments described herein and any combinations thereof, pertain to compositions. and methods according to the present invention.
[0046] Combinations of Embodiments 1 to 105 are illustrated by: Embodiment A. Compound of Formula 1 wherein: - Q1 is a phenyl ring substituted by up to two substituents selected from R7; - Q2 is a phenyl ring substituted by one to three substituents selected from R10; and -A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, -S-, -SO- or -SO2-. Embodiment B. A compound according to Embodiment A, wherein: - J1 is a phenyl ring optionally substituted by a substituent independently selected from R7'; -J2 is -CR2R3-; - Y1 and Y2 are both O; - R1 is H, Me or Et; - R4 is H; - R5 is H; - R6 is H; - each R7 is independently halogen or CF3; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - each R10 is independently halogen or CF3. Embodiment C. Compound according to Embodiment A, wherein: - J1 is a five- or six-membered heteroaromatic ring optionally substituted by a substituent selected from R7' on ring members of carbon atoms; -J2 is -CR2R3-; - Y1 and Y2 are both O; - R1 is H, Me or Et; - R4 is H; - R5 is H; - R6 is H; - each R7 is independently halogen or CF3; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - each R10 is independently halogen or CF3. Embodiment D. A compound according to Embodiment B, wherein: - Q1 is a phenyl ring unsubstituted by R7; - Q2 is a phenyl ring substituted by at least two substituents selected from R10, at least one substituent is in the ortho position and at least one substituent is in the para position of the phenyl ring; - A is -CH 2 -, -CH 2 O-, -CH 2 NH-, -CH=CH-, -C C-, -NH- or O; - J1 is a phenyl ring unsubstituted by R7'; - R2 is H; and - R3 is H. Embodiment E. Compound according to Embodiment D, wherein A is -CH2O- or -O-. Embodiment F. A compound according to Embodiment C, wherein: - Q1 is a phenyl ring unsubstituted by R7; - Q2 is a phenyl ring substituted by at least two substituents selected from R10, at least one substituent is in the ortho position and at least one substituent is in the para position of the phenyl ring; -A is CH2, -CH2O-, -CH2NH-, -CH=CH-, -CC-, -NH- or O; - J1 is a five- or six-membered heteroaromatic ring optionally substituted by up to one substituent selected from R7' on ring members of carbon atoms; - R2 is H; and - R3 is H. Embodiment G. A compound according to Embodiment F, wherein: - J1 is an unsubstituted pyridine ring; - Q2 is a phenyl ring substituted by three substituents selected from R10 and the three substituents are in ortho, meta and para positions (of the phenyl ring); and -A is -CH2O- or -O-. Embodiment H. A compound of Formula 1 wherein: - Q1 is a phenyl ring optionally substituted by one to four substituents independently selected from R7; or a five to six membered heteroaromatic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to four substituents independently selected from R7 over carbon atom ring members and selected from R9 over nitrogen atom ring members; - Q2 is a phenyl ring optionally substituted by up to five substituents independently selected from R10; or a five to six membered heteroaromatic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to five substituents independently selected from R10 over carbon atom ring members and selected from R11 over nitrogen atom ring members; - J1 is a phenyl ring optionally substituted by up to five substituents independently selected from R7'; or a four to six membered heteroaromatic ring containing ring members selected from carbon atoms and one to four heteroatoms independently selected from 2 O atoms, up to 2 S and up to 4 N, optionally substituted by up to five substituents independently selected from R7' over carbon atom ring members and selected from R9' over nitrogen atom ring members; - R1 is H, hydroxy, amino, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C6 cyanoalkyl, C3-C6 cycloalkyl or C4-C8 cycloalkylalkyl; and - A is a saturated, partially unsaturated or fully unsaturated chain containing from two to three atoms selected from up to three carbon atoms, up to 1 O, up to 1 S and up to 1 N, wherein the chain is optionally substituted by up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms. Embodiment I. A compound of Formula 1 or according to Embodiment H, wherein: - Q1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by one to four substituents independently selected from of R7; - Q2 is a phenyl ring optionally substituted by one to five substituents selected from R10; and - J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7. Embodiment J. Compound according to Embodiment I, wherein: - A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, - S-, -SO- or -SO2-; - each R7 is independently halogen, cyano, C1 C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R10 is independently halogen, cyano, nitro, C1-C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - Y1 and Y2 are both O. Embodiment K. A compound of Formula 1 or according to Embodiment H, wherein: - Q1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by one to four substituents independently selected from R7; - Q2 is a phenyl ring substituted by one to five substituents independently selected from R10; and - J1 is a four to six membered heterocyclic ring containing ring members selected from carbon atoms and from one to three heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 3 N, in that up to two carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from S(=O)u(=NR8) v, wherein each ring or ring system is optionally substituted by up to three substituents independently selected from R7' on carbon atom ring members and selected from R9' on nitrogen atom ring members. Embodiment L. Compound according to Embodiment K, wherein: - A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, - S-, -SO- or -SO2-; - each R7 is independently halogen, cyano, C1 C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R10 is independently halogen, cyano, nitro, C1-C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - Y1 and Y2 are both O. Embodiment M. A compound of Formula 1 or according to Embodiment H, wherein: - Q1 is a five or six membered heteroaromatic ring or an eight to ten membered heteroaromatic bicyclic ring system , wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7 on carbon atom ring members and selected from R9 on nitrogen atom ring members; - Q2 is a phenyl ring optionally substituted by one to five substituents independently selected from R10; and - J1 is a four to six membered heterocyclic ring containing ring members selected from carbon atoms and from one to three heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 3 N, in that up to two carbon ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring members are independently selected from S(=O)u(=NR8) v, wherein each ring or ring system is optionally substituted by up to three substituents independently selected from R7' on carbon atom ring members and selected from R9' on nitrogen atom ring members. Embodiment N. A compound according to Embodiment M, wherein: - A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, - S-, -SO- or -SO2-; - each R7 is independently halogen, cyano, C1 C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R10 is independently halogen, cyano, nitro, C1-C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - Y1 and Y2 are both O. Embodiment O. A compound of Formula 1 or according to Embodiment H, wherein: - Q1 is a five or six membered heteroaromatic ring or an eight to ten membered heteroaromatic bicyclic ring system , wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7 on carbon atom ring members and selected from R9 on nitrogen atom ring members; - Q2 is a phenyl ring substituted by one to five substituents selected from R10; and - J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted by up to four substituents independently selected from R7'. Embodiment P. Compound according to Embodiment O, wherein: - A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -C=C-, -NH-, -O-, - S-, -SO- or -SO2-; - each R7 is independently halogen, cyano, C1 C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R10 is independently halogen, cyano, nitro, C1-C2 alkyl, C1-C3 haloalkyl or C1-C3 alkylsulfonyl; - each R7' is independently halogen, cyano, nitro, C1-C8 alkyl or C1-C8 haloalkyl; and - Y1 and Y2 are both O.
[0047] Specific embodiments include compounds of Formula 1 selected from the group consisting of: - N-(2,4-difluorophenyl)-2-oxo-4-[3-(phenoxymethyl)phenyl]-3-pyrrolidinecarboxamide; and - 2-oxo-4-[3-(2-pyridinyloxy)phenyl]-N-(2,3,4-trifluorophenyl)-3-pyrrolidinecarboxamide.
[0048] The present invention also relates to a method of controlling unwanted vegetation which comprises applying to the vegetation locus herbicide-effective amounts of the compounds according to the present invention (e.g., in the form of composition described herein) . Those involving the compounds of embodiments described above are noteworthy as embodiments relating to the methods of use. The compounds according to the present invention are particularly useful for selective control of herbs in crops such as wheat, barley, corn, soybean, sunflower, cotton, canola and rice, as well as specialized crops such as sugar cane, citrus, fruits and chestnuts. -
[0049] Also worthy of note as embodiments are the herbicidal compositions according to the present invention comprising the compounds of embodiments described above.
[0050] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, its N-oxides and salts; and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS), (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diversors, (b7) protoporphyrinogene oxidase (PPO) inhibitors, (b8) glutamine synthetase inhibitors ( GS), (b9) very long fatty acid elongase inhibitors (VLCFA), (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors , (b13) solenesyltransferase (HST) homogenotisate (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides, including mitotic switches, organic arsenic, assulam, bromobutide, cinmethylin, cumiluron, dazomet, difenzoquat, dinandron, etobenzanhydron flurenol, phosamine, phosamine-ammonium, hydantocidin, metam, met ildimron, oleic acid, oxaziclomephone, pelargonic acid and pyributicarb; and (b16) herbicide safety agents; and salts of compounds (b1) to (b16).
[0051] "Photosystem II inhibitors" (b1) are chemical compounds that bind to protein D-1 at the QB binding site and therefore block the transport of electrons from QA to QB in the thylakoid membranes of chloroplasts. Electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cell destruction. The QB binding site has three different binding sites: the A binding site binds triazines such as atrazine, triazinenes such as hexazinone and uracils such as bromacyl, the B binding site binds phenylureas such as diuron and the link C link benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenylpyridazines such as pyridate. Examples of photosystem II inhibitors include ametrin, amicarbazone, atrazine, bentazon, bromacil, bromophenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumiluron, cyanazine, daimuron, desmedipham, desmethuron, dimethuron, dimefuron , hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, metabenzothiazuron, methobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, promethon, promethrin, propanyl, propazine, sitomethron, sito, pyridafobutl , terbacil, terbumeton, terbuthylazine, terbutryn and triethazine.
[0052] "AHAS Inhibitors" (b2) are chemical compounds that inhibit the acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS) and therefore kill plants by inhibiting the production of aliphatic chain amino acids branches such as valine, leucine and isoleucine, which are necessary for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bemsulfuron,bensulfuron-methyl, bispyribac-sodium, chloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, chinosulfuron, cyclosulfamuron, diclosulam, etametsulfuron-assuron-methyl, ethoxylamsulfuron, ethoxylsulfuron flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foransulfuron, halosulfuron-methyl, imazametabenzo-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl, (2 iodosulfuron-sodium), N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-di) -hydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5- sulfonamide), metossulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, propisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl) )amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone , thifensulfuron-methyl, triaphamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide) , triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl and tritosulfuron.
[0053] "ACCase Inhibitors" (b3) are chemical compounds that inhibit the enzyme acetyl-CoA carboxylase, which is responsible for the catalysis of an early stage of lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes and without them new cells cannot be produced. Inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production lead to loss of cell membrane integrity, especially in regions of active growth such as meristems. The growth of shoots and rhizomes eventually stops and the shoots of meristems and rhizomes begin to die. Examples of ACCase inhibitors include aloxidim, butroxydim, clethodim, clodinafop, cyclooxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxidim, propaquizafop, quizalofop, sethoxydim, tepraloxydim and tralkoxydim such as fenoxaprop-resolved forms , fluazifop-P, haloxyfop-P, quizalofop-P and ester forms such as clodinafop-propargyl, cy-halofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.
[0054] Auxin is a plant hormone that regulates growth in many plant tissues. “Auxin mimics” (b4) are chemical compounds that mimic the plant growth hormone auxin in order to cause uncontrolled and disorganized growth, causing plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid), its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin ethyl, chloramben, claciphos, climeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid ), halauxifen methyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2, 3,6-TBA, triclopyr and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.
[0055] "EPSP synthase inhibitors" (b5) are chemical compounds that inhibit the enzyme 5-enolpyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP-inhibiting herbicides are easily absorbed by plant foliage and translocated in the phloem to growing points. Glyphosate is a relatively non-selective post-emergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively called sulfosate).
[0056] "Photosystem I electron diversions" (b6) are chemical compounds that accept Photosystem I electrons and, after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and easily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys the integrity of the cell membrane, causing “leakage” of cells and organelles, causing rapid wilting and leaf dissection, and eventually plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.
[0057] "PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, which quickly results in the formation of highly reactive compounds in plants that disrupt cell membranes, causing leakage of cell fluids. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzofendizone, bifenox, butaphenacyl, carfentrazone, carfentrazone-ethyl, clomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl hungersafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazole, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, tidiazimin, trifludimoxazin (dihydro-1,5-dimethyl-6-thioxo-3-[2.2] ,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine- 2,4(1H,3H)-dione) and thiaphenacyl (N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl) )-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate methyl).
[0058] "GS Inhibitors" (b8) are chemical compounds that inhibit the activity of the enzyme glutamine synthetase, which plants use to convert ammonia into glutamine. Consequently, ammonia builds up and glutamine levels are reduced. Plant damage is likely to occur due to the combined effects of ammonia toxicity and deficiency of amino acids necessary for other metabolic processes. GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P (2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.
[0059] "VLCFA elongase inhibitors" (b9) are herbicides that have a wide variety of chemical structures, which inhibit elongase. Elongase is one of the enzymes located in or near chloroplasts that are involved in the biosynthesis of VLCFAs. In plants, very long chain fatty acids are the main components of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrol, dimethachlor, dimethenamid, difenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5 ,5-dimethylisoxazole), fentrazamide, flufenacet, indanophan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone and tenylchlor, including resolved forms such as S-metolachlor, chloroacetamides and oxyacetamides.
[0060] "Auxin transport inhibitors" (b10) are chemical substances that inhibit the transport of auxin in plants, for example, through binding with an auxin protein and carrier. Examples of auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).
[0061] "PDS inhibitors" (b11) are chemical compounds that inhibit the carotenoid biosynthesis process in the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurzon and picolinafen.
[0062] "HPPD inhibitors" (b12) are chemical substances that inhibit the biosynthesis of the synthesis of 4-hydroxyphenylpyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct -3-en-2-one), phenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3 -cyclohexanedione), isoxachlortol, isoxaflutol, mesotrione, pyrasulfotol, pyrazolinate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyrlate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl carbonate] -4-(methylfulsonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl), topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl )carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H ,4H)-dione, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H )-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(m ethylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.
[0063] "HST inhibitors" (b13) impair the ability of plants to convert homogenotisate to 2-methyl-6-solanyl-1,4-benzoquinone in order to disrupt carotenoid biosynthesis. Examples of HST inhibitors include haloxidine, pyrichlor, cyclopyrimorate, 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl (4-morpholinecarboxylate), 3-(2-chloro-3,6-difluorophenyl) 4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[ 2,3-b]pyrazin-6(5H)-one and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.
em que Rd1 é H, Cl ou CF3; Rd2 é H, Cl ou Br; Rd3 é H ou Cl; Rd4 é H, Cl ou CF3; Rd5 é CH3, CH2CH3 ou CH2CHF2; Rd6 é OH ou -OC(=O)-i-Pr; Re1 é H, F, Cl, CH3 ou CH2CH3; Re2 é H ou CF3; Re3 é H, CH3 ou CH2CH3; Re4 é H, F ou Br; Re5 é Cl, CH3, CF3, OCF3 ou CH2CH3; Re6 é H, CH3, CH2CHF2 ou C CH; Re7 é OH, -OC(=O)Et, -OC(=O)-i-Pr ou -OC(=O)-1-Bu; e Ae8 é N ou CH.[0064] HST inhibitors also include compounds of Formulas A and B: where Rd1 is H, Cl or CF3; Rd2 is H, Cl or Br; Rd3 is H or Cl; Rd4 is H, Cl or CF3; Rd5 is CH3, CH2CH3 or CH2CHF2; Rd6 is OH or -OC(=O)-i-Pr; Re1 is H, F, Cl, CH3 or CH2CH3; Re2 is H or CF3; Re3 is H, CH3 or CH2CH3; Re4 is H, F or Br; Re5 is Cl, CH3, CF3, OCF3 or CH2CH3; Re6 is H, CH3, CH2CHF2 or CCH; Re7 is OH, -OC(=O)Et, -OC(=O)-i-Pr or -OC(=O)-1-Bu; and Ae8 is N or CH.
[0065] "Inhibitors of cellulose biosynthesis" (b14) inhibit cellulose biosynthesis in certain plants. They are most effective when applied before emergence or just after emergence on young or fast-growing plants. Examples of inhibitors of cellulose biosynthesis include chlorthiamide, dichlobenil, flupoxam, indaziflam (N2-[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6- (1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
[0066] "Other herbicides" (b15) include herbicides that act through a number of different modes of action, such as mitotic switches (eg, flamprop-M-methyl and flamprop-M-isopropyl), organic arsenic (by example, DSMA and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors, and cell wall biosynthesis inhibitors. Other herbicides include herbicides that have unknown modes of action or do not fall into a specific category listed in (b1) to (b14) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, assulam, amitrol, bromobutide, cinmethylin, clomazone, cumiluron, daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, phosamine, phosamine-ammonium, dazomet, dimron, ipfencarbazone (1-(2,4-diphenyl) -N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldimron, oleic acid, ozacyclomefon, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole .
[0067] “Herbicide safety agents” (b16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of the herbicide in certain crops. These compounds protect crops from damage by herbicides, but typically do not prevent the herbicide from controlling unwanted vegetation. Examples of herbicide safety agents include, but are not limited to, benoxacor, cloquintocet-mexil, cumiluron, ciometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietolate, dimepiperate, fenchlorazol-ethyl, fenchlorim, flurazol, fluxphenim, isadiphenyl, and , mefempyr-diethyl, mefenate, methoxyphenone, naphthalic anhydride, oxabetrinyl, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2- (dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2 ,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.
[0068] The compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations, as described in Schemes 1 to 18, can be used to prepare the compounds of Formula 1. Definitions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q 1 , Q 2 , J 1 . J2, T, Y1 and Y2 in the compounds of Formulas 1 to 19 below are as defined above in the Brief Description of the Invention, unless otherwise indicated.
base/reagente de acoplamento desidratante[0069] As shown in Scheme 1, the compounds of Formula 1a (ie, Formula 1 where T is -A-J1, R1, R4 and R5 are H and Y1 and Y2 are O) can be prepared by reaction of Formula 2 acids with Formula 3 amines in the presence of a dehydrating coupling reagent such as phenylphosphonic anhydride, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide, N,N'-carbonyldi -imidazole, 2-chloro-1,3-dimethylimidazolium chloride or 2-chloro-1-methylpyridinium iodide. Polymer-supported reagents, such as polymer-supported cyclohexylcarbodiimide, are also suitable. These reactions are typically conducted at temperatures ranging from 0 to 60 °C in solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate in the presence of base such as triethylamine, N,N-diisopropylamine or 1, 8-diazabicyclo[5.4.0]undec-7-ene. See Organic Process Research & Development 2009, 13, 900-906 for coupling conditions employing propylphosphonic anhydride. The method of Scheme 1, which uses propylphosphonic anhydride, is illustrated by Step F of Synthesis Example 2. SCHEME 1 base/dehydrating coupling reagent
R' is lower alkyl hidrólise R’ é alquila inferior[0070] As shown in Scheme 2, compounds of Formula 2 can be prepared by hydrolysis of esters of Formula 4 by methods well known to those skilled in the art. The hydrolysis is conducted with aqueous base or aqueous acid, typically in the presence of co-solvent. Suitable bases for the reaction include, but are not limited to, hydroxides such as carbonates and sodium and potassium hydroxide, such as sodium and potassium carbonate. Suitable acids for the reaction include, but are not limited to, inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, in addition to organic acids such as acetic acid and trifluoroacetic acid. A wide variety of co-solvents are suitable for the reaction, including but not limited to methanol, ethanol and tetrahydrofuran. The reaction is conducted at temperatures ranging from -20 °C to the boiling point of the solvent, typically 0 to 100 °C. The method of Scheme 2 is illustrated by Step E of Synthesis Example 2. R' is lower alkyl hydrolysis R' is lower alkyl
5b em que X é CN. 4a em que J2 é CR2R3 4b em que J2 é -CR2R3-CR2aR3a- e R2a e R3a são ambos Hs.[0071] As shown in Scheme 3, a compound of Formula 4a or 4b can be obtained by reducing a compound of Formula 5a and 5b, respectively, and subsequent in situ cyclization of the resulting intermediate amine. A wide variety of methods of reducing the aliphatic nitrile or nitro group in compounds of Formula 5a or 5b are known in the literature. Methods well known to those skilled in the art include catalytic hydrogenation in the presence of palladium on carbon or Raney nickel, metallic iron or zinc in an acidic medium (see, for example, Berichte der Deutschen Chemischen Gesellschaft 1904, 37, 3520-3525) and aluminum hydride and lithium. Reduction of the aliphatic nitro group can also be achieved with samarium(II) iodide in the presence of a proton source such as methanol (see, for example, Tetrahedron Letters 1991, 32 (14), 1699-1702). Alternatively, sodium borohydride can be used in the presence of a nickel catalyst such as nickel(II) acetate or nickel(II) chloride (see, for example, Tetrahedron Letters 1985, 26(52), 64136416). The method of Scheme 3, using sodium borohydride in the presence of nickel(II) chloride, is illustrated by Step D of Synthesis Example 1. SCHEME 3 5b where X is CN. 4a where J2 is CR2R3 4b where J2 is -CR2R3-CR2aR3a- and R2a and R3a are both Hs.
As shown in Scheme 4, a compound of Formula 5a or 5b can be prepared by reacting diesters of Formula 6 with nitroalkanes of Formula 7a or nitriles of Formula 7b, typically in the presence of base. Suitable bases for the reaction include alkali metal lower alkoxides, such as sodium methoxide in methanol or sodium ethoxide in ethanol. Compounds of Formula 6 can be readily prepared by methods known to those skilled in the art, such as by Knoevenagel condensation of aldehydes and malonates (see, for example, G. Jones, Organic Reactions, Volume 15, John Wiley & Sons , 1967).
5c wherein X is NO2 and 5d wherein X is CN. 8a em que X é NO2 e 8b em que X é CN. R’ é alquila inferior 5c em que X é NO2 e 5d em que X é CN.[0073] Compounds of Formulas 5c or 5d (i.e., Formulas 5a or 5b, where R2 and R3 are H) can be prepared by reacting compounds of Formulas 8a or 8b with malonates of Formula 9 in the presence of base as per shown in Scheme 5. Suitable bases for this reaction include, but are not limited to, alkali metal lower alkoxides such as sodium methoxide in methanol or sodium ethoxide in ethanol, or bases such as lithium bis(trimethylsilyl)amide, bis(trimethylsilyl) sodium amide and lithium diisopropylamide in solvents such as tetrahydrofuran. Typically, the reaction is conducted in the range of -78 °C to 23 °C. See Synthesis 2005, 2239-2245 for conditions to effect this transformation. Conditions for carrying out this transformation in refluxing water in the absence of catalyst were reported in Synthetic Communications 2013, 43, 744-748. SCHEME 5 5c wherein X is NO2 and 5d wherein X is CN. 8a where X is NO2 and 8b where X is CN. R' is lower alkyl 5c where X is NO2 and 5d where X is CN.
R’ é alquila inferior ou CH3CN base 8a em que X é NO2 e 8b em que X é CN.Compounds of Formula 6 can be readily prepared by Knoevenagel condensation of aldehydes of Formula 14 and malonates 9 as shown in Scheme 6. Also as shown in Scheme 6, compounds of Formulas 8a and 8b can be prepared by Knoevenagel condensation medium of Formula 14 aldehydes and nitromethane. R' is lower alkyl or CH3CN base 8a where X is NO2 and 8b where X is CN.
A has a terminal -OH, -SH or -NH. A possui terminal -OH, -SH ou -NH.[0075] As shown in Scheme 7, Formula 14 aldehydes can be prepared by reacting Formula 20 aldehydes with corresponding Formula 21 electrophiles in the presence of base with or without metal catalyst. In Formula 21, G indicates a residual group, i.e., nucleofugal. Depending on the selection of J1, suitable electrophiles for the reaction may include aryl or alkyl halides such as chlorides, bromides and iodides, alkylsulfonates, acid anhydrides such as tert-butoxycarbonyl anhydride and acetic anhydride, and haloalkylsilanes such as chlorotrimethylsilane. Suitable bases for the reaction include inorganic bases such as alkali or alkaline earth metal hydroxides, alkoxides, carbonates and phosphates (eg lithium, sodium, potassium and cesium), as well as organic bases such as triethylamine, N,N-di- isopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene. Suitable catalysts include palladium, nickel, rhodium or copper, with or without binders such as phosphines or N-heterocyclic carbenes. A wide variety of solvents are suitable for the reaction, including, for example but not limited to, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, acetonitrile, C2-C6 alcohols and acetone as well. as mixtures of these solvents. This reaction is carried out at temperatures ranging from -20 to 200 °C and typically from 0 to 50 °C. As an example when A is -CH2OH, see Organic and Biomolecular Chemistry 2013, 11, 3046-3056. Formula 20 aldehydes are either commercially available or easily prepared from commercially available material to those skilled in the art. SCHEME 7 The terminal has -OH, -SH or -NH. A has the -OH, -SH or -NH terminus.
[0076] When A comprises 1-3 atoms of C, a compound of Formula 14 can be elaborated by those skilled in the art using standard transition metal cross-coupling methods. For representative palladium catalyzed Heck coupling procedure, see: Bioorg. Chem. 2010, 38, 139-143. For example palladium-catalyzed aryl halide trialkylbismuth procedure, see: Synlett 2010, 19, 2936-2940. For Suzuki-type reactions catalyzed by palladium, see: J. Med. Chem. 2000, 43, 3076 and J. Med. Chem. 2012, 43, 1831-1843.
X chiral catalyst, base 8a wherein X is NO2 and R'«lower alkyl 8b wherein X is CN. catalisador quiral, base R’ é alquila inferior 8a em que X é NO2 e 8b em que X é CN. 5a’ em que X é NO2 e 5b’ em que X é CN.[0077] Compounds of Formulas 5a' and 5a" can be prepared stereoselectively by reacting nitroalkenes of Formula 8a with malonates of Formula 9 in the presence of chiral catalyst and optionally in the presence of appropriate base as shown in the Scheme 7A. Suitable catalysts include, but are not limited to, Ni(II) with neighboring diamine linkers such as bis[(R,R)-N,N'-dibenzylcyclohexane-1,2-diamino]dibromide Ni(II), bis [(S,S)-N,N'-dibenzylcyclohexane-1,2-diamino]dibromide of Ni(II) or nickel(II) bromide with 1,1'-bi(tetrahydroisoquinoline) type diamines chirals. Suitable organic bases for this reaction include, but are not limited to, piperidine, morpholine, triethylamine, 4-methylmorpholine or N,N-diisopropylethylamine. This transformation can be carried out neat or in solvents such as tetrahydrofuran, toluene or dichloromethane. Typically, the reaction is conducted in the range of -78 °C to 80 °C, using 0 to 1 equivalent of catalyst and optionally 0 to 1 equivalent of base. Conditions for carrying out this transformation were reported in J. Am. Chem. Soc. 2005, 9958-9959 or Eur. J. Org. Chem. 2011, 5441-5446 for conditions. Formula 8a nitroalkenes can be readily prepared from aldehydes and nitromethane by methods known to those skilled in the art. SCHEME 7A X chiral catalyst, base 8a wherein X is NO2 and R' lower alkyl 8b wherein X is CN. chiral catalyst, base R' is lower alkyl 8a where X is NO2 and 8b where X is CN. 5a' where X is NO2 and 5b' where X is CN.
Iba wherein J2 is -CR2aCR2b-; Ibb wherein J2 is -CR2CR3CR2aCR3a- ciclização redutiva transferência catalítica hidrogenação R’ é alquila inferior 10a em que X é NO2 e 10b em que X é CN. 1aa em que J2 é -CR2CR3-; 1ab em que J2 é -CR2CR3CR2aCR3a-; 1ba em que J2 é -CR2aCR2b; 1bb em que J2 é -CR2CR3CR2aCR3a-.[0078] As shown in Scheme 8, compounds of Formulas 1aa and 1ab may also be prepared by reductive cyclization of compounds of Formulas 10a and 10b analogous to the method of Scheme 3. As also shown in Scheme 8, compounds of Formulas 1ba and 1bb (ie, Formula 1 where R1 is OH, R4 and R5 are H and Y1 and Y2 are O) can be prepared from compounds of Formula 10b by catalytic transfer hydrogenation with ammonium formate in the presence of palladium on carbon and subsequent in situ cyclization of the hydroxylamine intermediate. See J. Med. Chem. 1993, 36, 1041-1047 for catalytic transfer cyclization/hydrogenation conditions to produce N-hydroxypyrrolidinones. Iba wherein J2 is -CR2aCR2b-; Ibb wherein J2 is -CR2CR3CR2aCR3a- reductive cyclization catalytic transfer hydrogenation R' is lower alkyl 10a where X is NO2 and 10b where X is CN. 1aa where J2 is -CR2CR3-; 1ab where J2 is -CR2CR3CR2aCR3a-; 1ba where J2 is -CR2aCR2b; 1bb where J2 is -CR2CR3CR2aCR3a-.
ESQUEMA 9 7a em que X é NO2; 7b em que X é CN. 10a em que X é NO2; 10b em que X é CN.[0079] As shown in Scheme 9, compounds of Formulas 10a and 10b can be prepared by reacting compounds of Formula 11 with a compound of Formula 7a or a compound of Formula 7b in solvent, in the presence of a base analogous to the method described in Scheme 4. SCHEME 97a where X is NO2; 7b where X is CN. 10a where X is NO2; 10b where X is CN.
R’ é alquila inferior[0080] As shown in Scheme 10, compounds of Formula 10aa (i.e., Formula 10 where R2a and R3a are H), analogous to the method of Scheme 5, can be prepared by reacting Formula 8 nitroalkenes with malonates from Formula 12. R' is lower alkyl
R’ é alquila inferior[0081] As shown in Scheme 11, compounds of Formula 11 can be prepared by reacting malonic amide of Formula 12 with aldehydes of Formula 14 by methods known to those skilled in the art. Also as shown in Scheme 11, Formula 12 malonic amides can be readily prepared from Formula 13 lower alkyl malonyl chlorides, such as methyl malonyl chloride and Formula 3 amines, by methods known to those skilled in the art. SCHEME 11 R' is lower alkyl
fonte de halogênio R4 é Cl, Br, I R5 é Cl, Br, I[0082] As shown in Scheme 12, mixtures of compounds of Formula 1c (i.e., Formula 1 where R1 and R5 are H, R4 is halogen and Y1 and Y2 are O) and of Formula 1d (i.e., Formula 1 in wherein R1 and R4 are H, R5 is halogen and Y1 and Y2 are O) can be prepared by reacting compounds of Formula 1a with a halogen source in solvent, in the presence or absence of initiator. Separation of the regioisomers produced in this reaction can be achieved by standard methods such as chromatography or fractional crystallization. Suitable halogen sources for this reaction include bromine, chlorine, N-chlorosuccinimide, N-bromosuccinimide and N-iodosuccinimide. Suitable initiators for this reaction include 2,2'-azobisisobutyronitrile (AIBN) and benzoyl peroxide. Typically, the reaction is conducted in solvents such as dichloromethane in the range of 0 °C to the boiling point of the solvent. SCHEME 12 halogen source R4 is Cl, Br, I R5 is Cl, Br, I
reagente de aminação[0083] As shown in Scheme 13, compounds of Formula 1e (ie, Formula 1 where R1 is NH2, R4 and R5 are H and Y1 and Y2 are O) can be prepared by reacting compounds of Formula 1a with an amination reagent such as O-(diphenylphosphinyl)hydroxylamine and hydroxylamino-O-sulfonic acid. For procedures, conditions and reagents, see Bioorg. & Med. Chem. Letter 2009, 19, 5924-5926 and J. of Org. Chem. 2002, 67, 6236-6239. SCHEME 13 amination reagent
[0084] As shown in Scheme 14, compounds of Formula 1f (ie, Formula 1 where R4, R5 and R6 are H and Y1 and Y2 are O) can be produced by reacting compounds of Formula 15 with isocyanates ( that is, Formula 16 where Y2 is O) or isothiocyanates (i.e. Formula 16 where Y2 is S) in the presence of base. Examples of the base that can be used for the present process include those listed for the method in Scheme 4. The reaction temperature can be selected from the range of -78°C to the boiling point of the inert solvent used. Typically, the reaction is conducted at temperatures ranging from -78 °C to 100 °C in solvents such as toluene.
[0085] As shown in Scheme 15, compounds of Formula 15 can be prepared by reacting compounds of Formula 17 with corresponding electrophiles of Formula 18 in the presence of base. In Formula 18, G indicates a residual group, i.e., nucleofugal. Depending on the selection of R 1 , suitable electrophiles for the reaction may include alkyl halides such as chlorides, bromides and iodides, alkylsulfonates, acid anhydrides such as tert-butoxycarbonyl anhydride and acetic anhydride and haloalkylsilanes such as chlorotrimethylsilane. Suitable bases for the reaction include inorganic bases such as alkali or alkaline earth metal hydroxides, alkoxides carbonates and phosphates (eg lithium, sodium, potassium and cesium) as well as organic bases such as triethylamine, N,N-diisopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene. A wide variety of solvents are suitable for the reaction, including, for example but not limited to, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, acetonitrile, C2-C6 alcohols and acetone as well. as mixtures of these solvents. This reaction is carried out at temperatures ranging from -20 to 200 °C and typically from 0 to 50 °C. SCHEME 15
[0086] As shown in Scheme 16, compounds of Formula 17 can be prepared by decarboxylation of acids of Formula 2 by methods well known to those skilled in the art. Decarboxylation is conducted by heating compounds of Formula 2 in solvent, typically in the presence of acid. Suitable acids for the reaction include, but are not limited to, p-toluenesulfonic acid. A wide variety of co-solvents are suitable for the reaction, including, but not limited to, toluene, isopropanol acetate, and isobutyl methyl ketone. The reaction is conducted at temperatures ranging from -20 °C to the boiling point of the solvent, typically 0 to 150 °C. SCHEME 16
reagente de tionação[0087] As shown in Scheme 17, compounds of Formula 1g (ie, Formula 1 where R1 is H, R4 and R5 are H and Y1 and Y2 are S) can be prepared by reacting compounds of Formula 1a with at least two equivalents of a thionation reagent such as Lawesson's reagent, tetraphosphorus decasulfide or diphosphorus pentasulfide in solvent such as tetrahydrofuran or toluene. Typically, the reaction is conducted at temperatures ranging from 0 to 115 °C. Those skilled in the art recognize that the use of less than two equivalents of the thionation reagent can provide mixtures comprising products of Formula 1 where Y1 is O and Y2 is S or Y1 is S and Y2 is O, which can be separated by means of of conventional methods such as chromatography and crystallization. tionation reagent
[0088] As shown in Scheme 18, compounds of Formula 1h (i.e., Formula 1 where R1, R4 and R5 are H, Y2 is O and Y1 is NH) can be prepared by alkylating compounds of Formula 1a tetrafluoroborate of triethyloxonium (Meerwein's reagent) followed by treatment of the imino ether resulting from Formula 19 with aqueous ammonia. SCHEME 18
[0089] Those skilled in the art recognize that several functional groups can be converted to others to provide different compounds of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward manner, see Larock, RC, Comprehensive Organic Transformations : A Guide to Functional Group Preparations, Second Edition, Wiley-VCH, New York, 1999. Intermediates for preparing compounds of Formula 1 may contain, for example, aromatic nitro groups, which can be reduced to amino groups and then converted by means of reactions well known in the art, such as the Sandmeyer reaction, on various halides, giving compounds of Formula 1. The above reactions can also be carried out, in many cases, in alternate order.
[0090] It is recognized that some reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these cases, the incorporation of protection and deprotection sequences or functional group interconversions in the synthesis will help to obtain the desired products. The use and selection of protective groups will be evident to those skilled in chemical synthesis (see, for example, Greene, T.W.; Wuts, P.G.M., Protective Groups in Organic Synthesis, second edition; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, after the introduction of a given reagent as illustrated in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. in the subject will also recognize that it may be necessary to carry out combinations of the steps illustrated in the above schemes in an order other than that indicated by the specific sequence shown to prepare the compounds of Formula 1.
[0091] Those skilled in the art will also recognize that the compounds of Formula 1 and the intermediates described herein may be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation and reduction reactions to add substituents or modify existing substituents.
[0092] Without further elaboration, it is believed that those skilled in the art, using the above description, can use the present invention to the fullest extent possible. The following non-limiting examples are illustrative of the present invention. The steps in the Examples below illustrate a procedure for each step in general synthetic transformation, and the starting material for each step may not necessarily have been prepared by means of a specific preparative conduct whose procedure is described in other Examples or Steps. Percentages are by weight, except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise noted. 1H NMR spectra are reported in ppm from tetramethylsilane in CDCl3 at 500 MHz unless otherwise noted; “s” indicates single, “d” indicates double, “t” indicates trio”, “q” indicates quartet, “m” indicates multiple and “d” indicates double. Mass spectra (MS) are reported as the molecular weight of the parent ion with higher isotopic abundance (M+1) formed by the addition of H+ (molecular weight 1) to the molecule or (M-1) formed by the loss of H+ ( 1) molecular weight of the molecule, observed using liquid chromatography coupled to a mass spectrometer (LCMS) using atmospheric pressure chemical ionization (AP+) where “amu” represents unified atomic mass units. SYNTHESIS EXAMPLE 1
[0093] Preparation of N-(2-fluorophenyl)-2-oxo-4-[3-(2-pyridinyloxy)phenyl]-3-pyrrolidinecarboxamide (Compound 34):
[0094] Step A: Preparation of 3-(2-pyridinyloxy)benzaldehyde.
2-Fluoropyridine (20.0 g, 164 mmol) was dissolved in 150 ml of N,N-dimethylformamide and then treated with potassium tert-butoxide (19.9 g, 177 mmol). The reaction was exothermed to 57 °C and then kept cooling to room temperature for one hour. 3-Hydroxybenzaldehyde (13.9 ml, 162 mmol) was added and the mixture was heated at 120 °C overnight. The reaction mixture was kept cooling to room temperature and then partitioned between ethyl acetate and 1 N aqueous HCl solution. The organic layer was washed with brine, dried over magnesium sulfate and concentrated to give a brown slime which was then triturated with diethyl ether. The resulting solid was isolated by filtration and air dried to give 14.9 g of the title compound.
1H NMR (DMSO-d6) δ 10.01 (s, 1H), 8.17 (m, 1H), 7.91 (m, 1H), 7.78 (m, 1H), 7.66 (t, 1H), 7.63 (s, 1H), 7.50 (m, 1H), 7.16-7.20 (m, 1H), 7.13 (d, 1H).
[0097] Step B: preparation of 2-[3-[(1E)-2-nitroethenyl]phenoxy]pyridine.
[0098] To a solution of 3-(pyrid-2-yloxy)benzaldehyde (alternatively known as 3-(2-pyridinyloxy)benzaldehyde, ie the product of Step A, 20.1 g, 101 mmol) in 250 ml of 1-chlorobutane, nitromethane (6.54 ml, 121 mmol), piperidine (0.988 ml, 10.0 mmol) and glacial acetic acid (0.577 ml, 10.0 mmol) were added. The mixture was then heated to reflux for 48 hours with azeotropic removal of water. The reaction was kept cooling to room temperature. The reaction mixture was concentrated onto Celite® diatomaceous filter aid and then purified by medium pressure liquid chromatography (0% to 15% ethyl acetate in hexanes as eluent) to give 19.2 g of the title compound in form of yellow oil.
1H NMR δ 8.19 (m, 1H), 7.99 (d, 1H), 7.74 (m, 1H), 7.56 (m, 1H), 7.48 (t, 1H) 7.36 (m, 2H), 7.29 (m, 1H), 7.05 (m, 1H), 6.99 (d, 1H).
[00100] Step C: Preparation of 1,3-diethyl 2-[2-nitro-1-[3-(2-pyridinyloxy)phenyl]ethyl]propanedioate.
[00101] 2-[3-[(1E)-2-nitroethenyl]phenoxy]pyridine (i.e. the product from Step B, 19.4 g, 105 mmol), diethyl malonate (14.5 ml, 95, 2 mmol) and Ni(II) bis[N,N'-dibenzylcyclohexane-1,2-diamino]dibromide (0.955 g, 1.19 mmol) were refluxed in dichloromethane for 48 hours. The reaction mixture was then cooled to room temperature, concentrated on Celite® diatomaceous filter aid under reduced pressure and then purified by medium pressure liquid chromatography eluting with 0% to 50% ethyl acetate in hexanes to give 30.2 g of the title compound as a colorless oil.
[00102] 1H NMR (500 MHz, DMSO-d6) δ 8.15 (m, 1H), 7.86 (m, 1H) 7.34 (m, 1H) 7.15 (m, 3H) 7.03 (m, 1H) 6.96 (m, 1H) 4.99 (m, 2H) 4.17 (m, 2H) 4.09 (m, 1H) 4.03 (m, 1H) 3.89 (m , 2H) 1.18 (t, 3H) 0.92 (t, 3H).
[00103] Step D: Preparation of ethyl 2-oxo-4-[3-(2-pyridinyloxy)phenyl]-3-pyrrolidinecarboxylate.
[00104] 1,3-Diethyl 2-[2-Nitro-1-[3-(2-pyridinyloxy)phenyl]ethyl]propanedioate (i.e. the product from Step C, 30.1 g, 74.9 mmol ) was dissolved in 500 ml of ethanol at room temperature. NiCl2.6H2O (17.8 g, 74.9 mmol) was added and the mixture was stirred until complete dissolution. The reaction mass was then cooled to 0°C in an ice bath and then sodium borohydride (8.50 g, 225 mmol) was added slowly so that the temperature did not exceed 5°C. Upon complete addition, the ice bath was removed and the reaction mass was stirred at room temperature overnight. Ethanol was then removed under reduced pressure and 500 ml of ethyl acetate and 1.25 l of saturated ammonium chloride solution were added and the reaction was stirred overnight. The organic layer was separated from the aqueous layer and then concentrated onto silica gel under reduced pressure and then purified by MPLC eluting with 0% to 100% ethyl acetate in hexanes to give 7.5 g of the title compound in form of yellow oil.
[00105] 1H NMR δ 8.19 (m, 1H), 7.71 (m, 1H), 7.37 (m, 1H), 7.05 (m, 4H), 6.93 (m, 1H) , 6.37 (bs, 1H), 4.24 (m, 2H), 4.13 (m, 1H), 3.82 (m, 1H), 3.55 (d, 1H), 3.45 ( m, 1H), 1.27 (m, 3H).
[00106] Step E: Preparation of N-(2-fluorophenyl)-2-oxo-4-[3-(2-pyridinyloxy)phenyl]-3-pyrrolidinecarboxamide.
[00107] Ethyl 2-Oxo-4-[3-(2-pyridinyloxy)phenyl]-3-pyrrolidinecarboxylate (i.e. the product from Step D, 0.40 g, 1.2 mmol) was added to 2- fluoroaniline (2.0 ml, 6.8 mmol) and heated in a CEM microwave reactor for 45 minutes at 190 °C. The reaction mixture was cooled to room temperature and then diluted with 200 ml of dichloromethane. This solution was concentrated under reduced pressure on Celite® and then purified by MPLC (0% to 100% ethyl acetate in hexanes as eluent), resulting in 0.23 g of the title compound, product according to the present invention , in solid form.
[00108] 1H NMR δ 10.04 (s, 1H), 8.13 (m, 2H), 8.00 (m, 1H), 7.83 (m, 1H), 7.38 (m, 1H) , 7.12 (m, 8H), 4.00 (m, 2H), 3.70 (t, 1H), 3.25 (t, 1H). SYNTHESIS EXAMPLE 2
[00109] Preparation of N-(2,3-difluorophenyl)-2-oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3-pyrrolidinecarboxamide (Compound 25):
[00110] Step A: Preparation of 3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]benzaldehyde.
[00111] 3-(Trifluoromethyl)pyrazole (0.82 g, 6.0 mmol), 3-(bromomethyl)benzaldehyde (1.0 g, 5.0 mmol) and potassium carbonate (2.1 g, 15 mmol) ) were combined in 50 ml of N,N-dimethylformamide and heated at 80°C for eighteen hours. The reaction mixture was cooled to room temperature and then partitioned between ethyl acetate and brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a green oil which was adsorbed onto silica gel and then purified by MPLC eluting with 0% to 100% ethyl acetate in hexanes to give 0 .82 g of the title compound.
[00112] 1H NMR δ 10.01 (s, 1H), 7.86 (m, 1H), 7.76 (s, 1H), 7.56 (m, 1H), 7.50 (m, 1H) , 7.45 (m, 1H), 6.58 (d, 1H), 5.44 (s, 2H).
[00113] Step B: preparation of 1-[[3-[(1E)-2-nitroethenyl]phenyl]methyl]-3-(trifluoromethyl)-1H-pyrazole (i.e. 1-[[3-[(1E) )-2-nitroethenyl]phenyl]methyl]-3-(trifluoromethyl)-1H-pyrazole.
[00114] To a solution of 3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]benzaldehyde (ie the product of Step A, 16.5 g, 65 mmol) in 100 ml of 1-chlorobutane, nitromethane (4.2 ml, 78 mmol), piperidine (0.64 ml, 6.5 mmol) and glacial acetic acid (0.37 ml, 6.5 mmol) were added. The mixture was then heated to reflux for 48 hours with azeotropic removal of water. The reaction was kept cooling to room temperature. The reaction mixture was concentrated onto Celite® diatomaceous filter aid and then purified by MPLC eluting with 0% to 15% ethyl acetate in hexanes to give 11.2 g of the title compound as a yellow solid.
[00115] 1H NMR (500 MHz, chloroform-d) δ 7.97 (d, 1H), 7.55 (m, 2H), 7.46 (m, 2H), 7.38 (m, 2H), 6.58 (d, 1H), 5.40 (s, 2H).
[00116] Step C: Preparation of 1,3-diethyl 2-[2-nitro-1-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]ethyl]propanedioate.
[00117] 1-[[3-[(1E)-2-Nitroethenyl]phenyl]methyl]-3-(trifluoromethyl)-1H-pyrazole (ie 1-[[3-[(1E)-2-nitroethenyl ]phenyl]methyl]-3-(trifluoromethyl)-1H-pyrazole ie the product from Step B, 11 g, 38 mmol), diethyl malonate (6.9 ml, 45 mmol) and bis[N,N Ni(II) '-dibenzylcyclohexane-1,2-diamino]dibromide (0.46 g, 0.57 mmol) was stirred in dichloromethane for about 16 hours. The reaction mixture was then cooled to room temperature, concentrated on Celite® diatomaceous filter aid under reduced pressure and then purified by MPLC eluting with 0% to 50% ethyl acetate in hexanes to give 11 g of the compound title in the form of yellow oil.
[00118] 1H NMR δ 7.34 (m, 2H), 7.23 (d, 1H), 7.15 (m, 2H), 6.54 (d, 1H), 5.32 (m, 2H) , 4.88 (m, 2H), 4.21 (m, 3H), 3.98 (q, 2H), 3.78 (d, 1H), 1.25 (t, 3H), 1.01 ( t, 3H).
[00119] Step D: Preparation of ethyl 2-oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3-pyrrolidinecarboxylate.
[00120] 1,3-diethyl 2-[2-Nitro-1-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]ethyl]propanedioate (ie the product from Step C, 30.1 g, 74.9 mmol) was dissolved in 500 ml of ethanol at room temperature. NiCl2.6H2O (17.8 g, 74.9 mmol) was added and the mixture was stirred until complete dissolution. The reaction mass was then cooled to 0°C in an ice bath and then sodium borohydride (8.50 g, 225 mmol) was added slowly so that the temperature did not exceed 5°C. Upon complete addition, the ice bath was removed and the reaction mass was stirred at room temperature for three hours. 300 ml of ethyl acetate and 300 ml of saturated ammonium chloride solution were added and the reaction was stirred until the organic layer was clear and the aqueous layer was blue. The organic layer was separated from the aqueous layer and the aqueous layer was extracted again with ethyl acetate. The combined organic layers were washed with ammonium chloride, dried over magnesium sulfate, then concentrated on silica gel under reduced pressure and then purified by MPLC eluting with 0% to 100% ethyl acetate in hexanes to give 3.5 g of the title compound as a yellow oil with some impurities, which was used without further purification. MS (M-1) = 380 amu.
[00121] Step E: Preparation of 2-oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3-pyrrolidinecarboxylic acid.
[00122] Ethyl 2-Oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3-pyrrolidinecarboxylate (ie the product of Step D, 3, 78 g, 9.1 mmol) was dissolved in 65 ml of ethanol and then 1.4 ml of 50% sodium hydroxide solution was added over five minutes. The reaction was then stirred overnight at room temperature. The mixture was diluted with water until the white precipitate dissolved. The organic layer was extracted twice with 125 ml of diethyl ether and then acidified to pH 2 with concentrated hydrochloric acid. The aqueous layer was then extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to give 1.9 g of the title compound as a pink glass.
[00123] 1H NMR (DMSO-d6) δ 12.74 (bs, 1H), 8.09 (d, 2H), 7.33 (m, 3H), 7.12 (m, 1H), 6.74 (d, 1H), 5.41 (s, 2H), 3.83 (m, 2H), 3.51 (m, 2H).
[00124] Step F: preparation of N-(2,3-difluorophenyl)-2-oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3- pyrrolidinecarboxamide.
[00125] 2-Oxo-4-[3-[[3-(trifluoromethyl)-1H-pyrazol-1-yl]methyl]phenyl]-3-pyrrolidinecarboxylic acid (ie the product of Step E, 0.33 g, 0.92 mmol), triethyl amine (0.38 ml, 0.28 mmol) and 2,3-difluoroaniline (0.14 g, 1.1 mmol) were dissolved in 25 ml of dichloromethane, stirred at room temperature for fifteen minutes, then treated with 50% propylphosphonic anhydride (T3P®) in ethyl acetate (1.8 ml, 3.1 mmol) and stirred overnight. The reaction mixture was concentrated under reduced pressure and then purified by MPLC eluting with 0% to 100% ethyl acetate in hexanes to give 0.092 g of the title compound, product according to the present invention, as solid.
[00126] 1H NMR (DMSO-d6) δ 10.22 (s, 1H), 8.21 (s, 1H), 8.07 (d, 1H), 7.77 (m, 1H), 7.34 (m, 3H), 7.16 (m, 3H), 6.71 (d, 1H), 5.42 (s, 2H), 4.02 (m, 1H), 3.92 (m, 1H) , 3.67 (t, 1H), 3.26 (t, 1H). SYNTHESIS EXAMPLE 3
[00127] Preparation of N-(2-fluorophenyl)-4-[3-[(methoxyimino)methyl]phenyl]-1-methyl-2-oxo-3-pyrrolidinecarboxamide (Compound 53):
[00128] Step A: Preparation of 1,3-diethyl 2-[(3-iodophenyl)methylene]propanedioate.
[00129] To a solution of 3-iodobenzaldehyde (10 g, 43 mmol) in benzene (100 ml), diethyl malonate (8.3 g, 52 mmol) and piperidine (0.73 g, 8.6) were added mmol) at 5°C. The reaction mixture was heated at the reflux temperature of the solvent with a Dean-Stark apparatus to remove water for 24 hours. The reaction mixture was evaporated to give the crude product which was purified by silica gel column chromatography eluting with 5% to 20% gradient of ethyl acetate in petroleum ether to give the title product (17 g) .
[00130] 1H NMR (400 MHz) δ 7.80 (s, 1H), 7.60 (s, 1H), 7.40 (m, 1H), 7.30 (s, 1H), 7.10 ( m, 1H), 4.35 (m, 4H), 1.77 (m, 6H).
[00131] Step B: Preparation of 1,3-diethyl 2-[1-(3-iodophenyl)-2-nitroethyl]propanedioate.
[00132] To a solution of 1,3-diethyl 2-[(3-iodophenyl)methylene]propanedioate (i.e. the compound prepared in Step A, 17 g, 45 mmol) in ethanol (170 ml), was added nitromethane (28 g, 450 mmol) and 20% sodium methoxide in methanol (0.25 g, 4.55 mmol) were taken at 5 °C and the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was evaporated to give the crude title compound (16 g) which was used without further purification.
[00133] 1H NMR (400 MHz) δ 7.60 (t, 2H), 7.20 (d, 1H), 7.10 (t, 1H), 4.95 (m, 2H), 4.20 ( m, 3H), 4.00 (m, 2H), 3.75 (d, 1H), 1.20 (m, 6H).
[00134] Step C: Preparation of ethyl 4-(3-iodophenyl)-2-oxo-3-pyrrolidinecarboxylate.
[00135] To a solution of 1,3-diethyl 2-[1-(3-iodophenyl)-2-nitroethyl]propanedioate (ie the compound prepared in Step B, 16 g, 36 mmol) in ethanol (150 ml)/water (32 ml), iron powder (10 g, 180 mmol), ammonium chloride (1.0 g, 18 mmol) was added and the reaction mixture was heated at 110 °C for 24 hours. The reaction mixture was filtered through Celite® diatomaceous earth filter aid and the filtrate was concentrated. Water was added to the crude residue and the mixture was extracted (3x) with ethyl acetate. The combined organic layers were washed with water, brine and then dried over sodium sulfate. The solvent was evaporated to give the title compound as crude intermediate (15g). A 500 mg sample of the crude intermediate was purified by preparative thin layer chromatography to give 250 mg of the title compound.
[00136] 1H NMR (400 MHz) δ 7.60 (m, 2H), 7.20 (m, 1H), 7.10 (m, 1H), 6.10 (s, 1H), 4.20 ( m, 2H), 4.00 (m, 1H), 3.63 (t, 1H), 3.40 (m, 1H), 3.30 (m, 1H), 1.23 (m, 3H).
[00137] Step D: Preparation of 4-(3-iodophenyl)-2-oxo-3-pyrrolidinecarboxylic acid.
To a solution of ethyl 4-(3-iodophenyl)-2-oxo-3-pyrrolidinecarboxylate (ie the compound prepared in Step C, 9.0 g, 25 mmol) in tetrahydrofuran (50 ml ) and water (10 ml), lithium hydroxide monohydrate (1.6 g, 38 mmol) was added at 0 °C and the reaction mixture was stirred at room temperature for four hours. The reaction mixture was then evaporated and the solid was mixed with water. The aqueous mixture was extracted with ethyl acetate and the organic layer was discarded. The aqueous layer was acidified with concentrated hydrochloric acid at 0°C. The resulting solid was collected by filtration and dried in vacuo to give the title compound (5 g) as an off-white solid.
[00139] 1H NMR (400 MHz) δ 12.89 (s, 1H), 8.10 (s, 1H), 7.65 (d, 1H), 7.53 (d, 1H), 7.39 ( d, 1H), 7.18 (t, 1H), 3.81 (m, 1H), 3.50 (m, 2H), 3.20 (m, 1H).
[00140] Step E: Preparation of 4-(3-iodophenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxylic acid.
Potassium t-butoxide (37 ml, 1 M solution in tetrahydrofuran) was cooled to 0°C. To this solution, 4-(3-iodophenyl)-2-oxo-3-pyrrolidinecarboxylic acid (ie, the compound prepared in Step D, 5.0 g, 15 mmol) in tetrahydrofuran was added slowly and stirred for ten. minutes. Methyl bromide (25% in acetonitrile, 14 ml, 38 mmol) was added and the reaction mixture was stirred for four hours. The reaction mixture was diluted with acetonitrile and acidified with 1 N aqueous hydrochloric acid at 0 °C. The reaction mixture was then extracted (3x) with ethyl acetate and the combined organics were washed with brine and dried over sodium sulfate to give crude residue which was washed with diethyl ether to give the title compound (2.3 g) as an off-white solid.
[00142] 1H NMR (400 MHz) δ 12.77 (s, 1H), 7.74 (s, 1H), 7.65 (d, 1H), 7.38 (d, 1H), 7.15 ( t, 1H), 3.81 (m, 2H), 3.62 (m, 1H), 3.45 (d, 1H), 2.80 (s, 3H).
[00143] Step F: Preparation of N-(2-fluorophenyl)-4-(3-iodophenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxamide.
[00144] To a solution of 4-(3-iodophenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxylic acid (ie the compound prepared in Step E, 0.5 g, 1.4 mmol) and 2 -fluoroaniline (0.15 ml, 1.6 mmol) in N,N-dimethylformamide (10 ml), added triethylamine (0.6 ml, 4.3 mmol) and stirred at room temperature for ten minutes. Propylphosphonic anhydride (T3P®) solution (50% in ethyl acetate, 1.7 ml, 2.89 mmol) was then added at 0 °C and stirred for two hours. The reaction mixture was then diluted with water and extracted into ethyl acetate. The combined organic layers were washed with water, brine and then dried over sodium sulfate. The solvent was evaporated to give a crude residue which was washed with diethyl ether and pentane to give the title compound (0.4 g) as an off-white solid.
[00145] 1H NMR (400 MHz) δ 10.08 (s, 1H), 8.00 (m, 1H), 7.75 (s, 1H), 7.63 (d, 1H), 7.37 ( d, 1H), 7.35 (m, 1H), 7.15 (m, 3H), 3.95 (m, 2H), 3.77 (m, 1H), 3.41 (m, 1H), 2.80 (s, 3H).
Step G: Preparation of N-(2-fluorophenyl)-4-(3-formylphenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxamide.
A solution of N-(2-fluorophenyl)-4-(3-iodophenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxamide (ie the compound prepared in Step F, 0.5 g, 1 0.1 mmol) and tetrakis(triphenylphosphine)palladium (0) (0.086 g, 0.075 mmol) in N,N-dimethylformamide (5 ml) in steel bomb was stirred under carbon monoxide gas (100 psi) for thirty minutes at pressure was released, tributyl silane (0.83 ml) was added and the reaction mixture was stirred under carbon monoxide gas (100 psi) at room temperature for 48 hours. The reaction mixture was then diluted with water and extracted with ethyl acetate. The combined organic layers were washed with water, brine and dried over sodium sulfate. The solvent was evaporated to give the crude residue, which was purified by silica gel column chromatography eluting with 20% ethyl acetate in petroleum ether to give the title compound (0.27 g) as a solid. light brown.
[00148] 1H NMR (400 MHz) δ 10.15 (s, 1H), 10.00 (s, 1H), 8.15 (t, 1H), 7.82 (m, 1H), 7.64 ( m, 1H), 7.55 (m, 1H), 7.39 (m, 1H), 7.12 (m, 3H), 4.20 (m, 1H), 3.80 (t, 1H), 3.31 (d, 1H), 3.22 (m, 1H), 3.10 (s, 3H).
[00149] Step H: preparation of N-(2-fluorophenyl)-4-[3-[(methoxyimino)methyl]phenyl]-1-methyl-2-oxo-3-pyrrolidinecarboxamide.
[00150] To a solution of N-(2-fluorophenyl)-4-(3-formylphenyl)-1-methyl-2-oxo-3-pyrrolidinecarboxamide (ie, the compound prepared in Step G, 0.15 g, 0.41 mmol) and methoxylamine hydrochloride (0.054 g, 0.64 mmol) in tetrahydrofuran (10 ml), added sodium acetate (0.047 g, 0.57 mmol) and stirred at room temperature for two hours. The reaction mixture was then diluted with water and extracted into ethyl acetate. The combined organic layers were washed with water, brine and dried over sodium sulfate. The solvent was evaporated to give the crude product which was purified by preparative silica gel thin layer chromatography in 40% ethyl acetate/petroleum ether to give (0.07 g) of the title compound, compound according to present invention, in the form of an off-white solid.
[00151] 1H NMR (400 MHz) δ 9.85 (s, 1H), 8.25 (t, 1H), 8.10 (s, 1H), 7.55 (s, 1H), 7.45 ( s, 1H), 7.25 (s, 2H), 6.99 (m, 3H), 4.25 (m, 1H), 4.10 (s, 3H), 3.75 (d, 1H), 3.50 (m, 1H), 3.33 (m, 1H), 3.00 (s, 3H). SYNTHESIS EXAMPLE 4
[00152] Preparation of (3S,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-1-methyl-2-oxo-N-(2,3,4-trifluorophenyl) -3-pyrrolidinecarboxamide (Compound 87):
[00153] Step A: Preparation of 3-[(5-fluoro-2-pyridinyl)oxy]benzaldehyde.
A solution of 3-hydroxybenzaldehyde (20 g, 164 mmol) in N,N-dimethylformamide (150 ml) was treated with potassium tert-butoxide (23.0 g, 205 mmol) over a period of one hour. The resulting mixture was stirred at 25°C for one hour and then treated with 2,5-difluoropyridine (18.64 g, 162 mmol). The resulting reaction mixture was stirred at 120 °C for 18 hours. The reaction mixture was then cooled and partitioned between ethyl acetate and brine. The organic phase was washed with brine, dried over MgSO4 and concentrated under reduced pressure over Celite® diatomaceous earth filter aid. Purification by solids chromatography gradient eluting with ethyl acetate in hexanes (0 to 35%) provided 10.0 g of the title compound, white solid.
[00155] 1H NMR (DMSO-d6) δ 10.00 (s, 1H), 8.18 (d, 1H), 7.88 (m, 1H), 7.78 (m, 1H), 7.66 (t,1H), 7.62 (m, 1H), 7.50 (m, 1H), 7.23 (m, 1H).
[00156] Step B: preparation of 5-fluoro-2-[3-[(1E)-2-nitroethenyl]phenoxy]pyridine.
[00157] A solution of 3-[(5-fluoro-2-pyridinyl)oxy]benzaldehyde (ie the product obtained in Step A, 10 g, 46.0 mmol) in 1-chlorobutane (250 ml) was treated with nitromethane (3.36 g, 55.2 mmol), followed by piperidine (391 mg, 4.6 mmol) and acetic acid (276 mg, 4.6 mmol). The resulting reaction mass was stirred under reflux, with azeotropic removal of water, for 18 hours. The crude reaction mixture was then concentrated under reduced pressure and purified by chromatography (0 to 25% ethyl acetate in hexanes as eluent) yielding 8.7 g of yellow oil.
[00158] 1H NMR δ 8.02 (d, 1H), 7.98 (d, 1H), 7.55 (d, 1H), 7.49 (m, 2H), 7.38 (d, 1H) , 7.31 (m, 1H), 7.26 (m, 1H), 6.98 (m, 1H).
[00159] Step C: Preparation of 1,3-dimethyl 2-[(1S)-1-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-nitroethyl]propanedioate.
[00160] A stirred mixture of 5-fluoro-2-[3-[(1E)-2-nitroethenyl]phenoxy]pyridine (ie the product obtained in Step B, 8.67 g, 33.3 mmol) and Dimethyl malonate (5.5 g, 41.7 mmol) in toluene (150 ml) was treated with bis[(R,R)-N,N'-dibenzylcyclohexane-1,2-diamino]-Ni( II) (prepared as described in J. Am. Chem. Soc. 2005, 127, 9958-9959; 0.400 g, 0.499 mmol). The reaction mass was stirred at 80 °C for 18 hours. The resulting mixture was cooled to 25°C, filtered and concentrated under reduced pressure to give 13.0 g of amber oil which was used without further purification in the next step.
1H NMR δ 8.05 (d, 1H), 7.45 (m, 1H), 7.35 (t, 1H), 7.06 (m, 2H), 6.99 (m, 1H) , 6.87 (m, 1H), 4.90 (m, 2H), 4.25 (m, 1H), 3.85 (d, 1H), 3.75 (s, 3H), 3.62 ( s, 3H).
Step D: Preparation of methyl (3R,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-oxo-3-pyrrolidinecarboxylate.
A stirred mixture of 1,3-dimethyl 2-[(1S)-1-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-nitroethyl]propanedioate (13.0 g) , 33.1 mmol), nickel(II) chloride hexahydrate (7.88 g, 33.1 mmol) and methanol (300 ml) was cooled in an ice bath and treated with sodium borohydride (ie , the product obtained in Step C, 3.76 g, 99.3 mmol) in 0.5 g portions added over 60 minutes. The resulting mixture was stirred at 25°C for 18 hours. Saturated ethylenediaminetetraacetic acid disodium salt solution (800 ml) and ethyl acetate (500 ml) were then added, the mixture was stirred for 18 hours and then filtered through a pad of Celite® diatomaceous filter aid to remove insoluble particulates. The layers of the filtrate were separated and the aqueous layer was extracted with ethyl acetate (2 x 500 ml). The combined organic extracts were washed with saturated ammonium chloride solution (800 ml) and brine (1000 ml). The organic extract was dried over MgSO4 and concentrated under reduced pressure to give viscous gray oil (8.99 g), which was used without further purification.
[00164] 1H NMR δ 8.02 (d, 1H), 7.45 (m, 1H), 7.37 (t, 1H), 7.09 (m, 1H), 7.02 (m, 2H) , 6.94 (m, 2H), 4.13 (m, 1H), 3.82 (m, 1H), 3.78 (s, 3H), 3.58 (d, 1H), 3.42 ( m, 1H).
[00165] Step E: Preparation of (3R,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-oxo-3-pyrrolidinecarboxylic acid.
[00166] A mixture of methyl (3R,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-oxo-3-pyrrolidinecarboxylate (ie the product obtained in Step D, 8.49g, 25.7mmol) and aqueous sodium hydroxide (50% by weight, 6.16g, 77.2mmol) in methanol (125ml) was stirred at 25°C for 18 hours. The reaction mixture was then diluted with water (250 ml) and extracted with diethyl ether (2 x 150 ml). The ether extract was discarded and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2. The acidic aqueous was extracted with ethyl acetate (2 x 300 ml). The combined organic extracts were washed with brine, dried (MgSO4 ) and concentrated under reduced pressure to give 5.5 g of beige glass, which was carried on to the next step without further purification.
1H NMR (DMSO-d6) δ 12.7 (s, 1H), 8.16 (d, 1H), 8.07 (s, 1H), 7.83 (m, 1H), 7.37 (m, 1H), 7.17 (m, 1H), 7.12 (m, 2H), 7.01 (m, 1H), 3.88 (m, 1H), 3.62 (m, 1H) , 3.51 (d, 1H), 3.21 (t, 1H).
[00168] Step F: Preparation of (3R,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-1-methyl-2-oxo-3-pyrrolidinecarboxylic acid.
To a solution of potassium tert-butoxide (4.75 g, 42.4 mmol) in 42.4 ml of tetrahydrofuran at 0°C was charged a solution of acid (3R,4S)- 4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-2-oxo-3-pyrrolidinecarboxylic acid (ie the product obtained in Step E, 5.5 g, 17.4 mmol) in tetra -hydrofuran (50 ml). The resulting reaction mass was stirred for fifteen minutes at 0 °C. Iodomethane (6.24 g, 44 mmol) in 40 ml of tetrahydrofuran was dropped over twenty minutes. The resulting mixture was heated to 25°C and stirred overnight. The reaction mass was concentrated under reduced pressure and partitioned between ethyl ether and water. The organic phase was discarded and the aqueous was acidified to pH 1 with concentrated hydrochloric acid. The acidified aqueous layer was extracted with ethyl acetate. The organic extract was dried (MgSO4 ) and concentrated under reduced pressure to give 4.0 g of yellow glass which was carried on without further purification.
[00170] 1H NMR δ 9.29 (s, 1H), 8.03 (d, 1H), 7.46 (m, 1H), 7.37 (m, 1H), 7.13 (m, 1H) , 7.06 (m, 1H), 7.02 (m, 1H), 6.92 (m, 1H), 3.96 (m, 1H), 3.79 (m, 1H), 3.57 ( d, 1H), 3.50 (m, 1H), 2.97 (d, 3H).
[00171] Step G: Preparation of (3S,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-1-methyl-2-oxo-N-(2,3,4 -trifluorophenyl)-3-pyrrolidinecarboxamide.
[00172] To a solution of (3R,4S)-4-[3-[(5-fluoro-2-pyridinyl)oxy]phenyl]-1-methyl-2-oxo-3-pyrrolidinecarboxylic acid (i.e., the product obtained in Step F, 500 mg, 1.51 mmol) in 5.0 ml of tetrahydrofuran at 25 °C, was charged triethylamine (632 µl, 4.54 mmol). The reaction mixture was stirred for five minutes and then treated with 2,3,4-trifluoroaniline (208 µl, 1.97 mmol). After stirring an additional five minutes, the mixture was treated with propylphosphonic anhydride (50% in ethyl acetate, 1.63 g, 2.57 mmol). The resulting mixture was stirred overnight at 25°C. The crude mixture was concentrated under reduced pressure and purified by silica gel chromatography eluting with 0 to 15% ethyl acetate in dichloromethane, resulting in 278 mg of the title compound, compound according to the present invention, as viscous yellow oil.
1H NMR δ 9.86 (s, 1H), 8.02 (d, 1H), 7.93 (m, 1H), 7.45 (m, 1H), 7.39 (t, 1H) , 7.19 (m, 1H), 7.12 (m, 1H), 7.03 (m, 1H), 6.93 (m, 1H), 6.90 (m, 1H), 4.11 ( m, 1H), 3.80 (m, 1H), 3.62 (d, 1H), 3.50 (m, 1H), 2.99 (d, 3H).
TABELA 2-360By the procedures described herein, in conjunction with methods known in the art, the compounds of Tables 1 to 6120 below can be prepared. The following abbreviations are used in the following Tables: t indicates tertiary, s indicates secondary, n indicates normal, i indicates iso, c indicates cyclo, Me indicates methyl, Et indicates ethyl, Pr indicates propyl, Bu indicates butyl, i- Pr indicates isopropyl, c-Pr indicates cyclopropyl, t-Bu indicates tertiary butyl, c-Bu indicates cyclobutyl, Ph indicates phenyl, OMe indicates ethoxy, OEt indicates ethoxy, SMe indicates methylthio, NHMe indicates methylamino, CN indicates cyano, NO2 indicates nitro , TMS indicates trimethylsilyl, SOMe indicates methylsulfinyl, C2F5 indicates CF2CF3 and SO2Me indicates methylsulfonyl. TABLE 2-360




TABELA 361[00175] Table 2 is constructed in the same way, except for the replacement of the row header “J2 is -CH2-; A is -CH2-; Q2 is Ph(2-F); and J1 is" by the row header related to Table 2 below (ie, "J2 is -CH2- ; A is -CH2-; Q2 is Ph(2,3-di-F; and J1 is"). The first row of Table 2 is therefore a compound of Formula 1 where J2 is -CH2-; A is -CH2-; Q2 is Ph(2,3-di-F); and J1 is Ph(3-Cl) (i.e., 3-chlorophenyl). Tables 3 to 360 are constructed in a similar way.












TABLE 361
TABELA 362 A 720[00176] Table 361 is constructed in the same way as Table 1 above, except for the replacement of the structure by the one below: TABLE 362 TO 720
[00177] The present invention also includes Tables 362 to 720, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 361 above. TABLE 1081
TABELA 1082 A 1440[00178] Table 1081 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 1082 TO 1440
[00179] The present invention also includes Tables 1082 to 1440, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 1081 above. TABLE 1441
TABELA 1442 A 1800[00180] Table 1441 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 1442 TO 1800
[00181] The present invention also includes Tables 1442 to 1800, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 1441 above. TABLE 1801
TABELA 1802 A 2160[00182] Table 1801 is constructed in the same way as Table 1 above, except for the replacement of the structure by the one below: TABLE 1802 TO 2160
[00183] The present invention also includes Tables 1802 to 2160, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 1801 above. TABLE 2161
TABELA 2162 A 2520[00184] Table 2161 is constructed in the same way as Table 1 above, except for the replacement of the structure by the one below: TABLE 2162 TO 2520
[00185] The present invention also includes Tables 2162 to 2520, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 2161 above. TABLE 2521
TABELA 2522 A 2880[00186] Table 2521 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 2522 TO 2880
[00187] The present invention also includes Tables 2522 to 2880, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 2521 above. TABLE 2881
TABELA 2882 A 3240[00188] Table 2881 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 2882 TO 3240
[00189] The present invention also includes Tables 2882 to 3240, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 7561 above. TABLE 3241
TABELA 3242 A 3600[00190] Table 3241 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 3242 TO 3600
[00191] The present invention also includes Tables 3242 to 3600, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 3241 above. TABLE 3601
TABELA 3602 A 3960[00192] Table 3601 is constructed in the same way as Table 1 above, except for the replacement of the structure with the one below: TABLE 3602 TO 3960
[00193] The present invention also includes Tables 3602 to 3960, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 3601 above. TABLE 3961
TABELA 3962 A 4320[00194] Table 3961 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 3962 TO 4320
[00195] The present invention also includes Tables 3962 to 4320, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 3961 above. TABLE 4321
TABELA 4322 A 4680[00196] Table 4321 is constructed in the same way as Table 1 above, except for the replacement of the structure with the one below: TABLE 4322 TO 4680
[00197] The present invention also includes Tables 4322 to 4680, in which each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 4321 above. TABLE 4681
TABELA 4682 A 5040[00198] Table 4681 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 4682 TO 5040
[00199] The present invention also includes Tables 4682 to 5040, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 4681 above. TABLE 5041
TABELA 5042 A 5400[00200] Table 5041 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 5042 TO 5400
[00201] The present invention also includes Tables 5042 to 5400, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 5041 above. TABLE 5401
TABELA 5402 A 5760[00202] Table 5401 is constructed in the same way as Table 1 above, except for the replacement of the structure by the one below: TABLE 5402 TO 5760
[00203] The present invention also includes Tables 5402 to 5760, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 5401 above. TABLE 5761
TABELA 5762 A 6120[00204] Table 5761 is constructed in the same way as Table 1 above, except that the structure is replaced by the one below: TABLE 5762 TO 6120
[00205] The present invention also includes Tables 5762 to 6120, wherein each Table is constructed in the same manner as Tables 2 to 360 above, except for the replacement of the structure by the structure of Table 5761 above.
[00206] Formulation/utility:
[00207] The compounds according to the present invention will generally be used as an active ingredient herbicide in composition, ie formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as vehicle. The ingredients of the composition or formulation are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
[00208] Useful formulations include liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, fluid concentrates and/or suspoemulsions) and the like, which may optionally be thickened in the form of gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, fluid concentrate and suspoemulsion. The general types of non-aqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
[00209] The general types of solid compositions are dry powders, powders, granules, pellets, pills, pellets, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed with fluid suspensions or film-forming solutions are particularly useful for seed treatment. The active ingredient can be (micro)encapsulated and further molded into a suspension or solid formulation; alternatively, the entire active ingredient formulation can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. Emulsifiable granules combine the advantages of an emulsifiable concentrate formulation and a dry granular formulation. High strength compositions are mainly used as intermediates for further formulation.
[00210] Sprayable formulations are typically rolled into an appropriate medium prior to spraying. These solid and liquid formulations are formulated for easy dilution in the spray medium, usually water, but occasionally another suitable medium such as aromatic or paraffinic hydrocarbon, or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but are more typically found in the range of about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or other suitable medium for foliar treatment by aerial or soil application, or for application to the plant's growing medium. Liquid and dry formulations can be measured directly in drip irrigation systems or measured in the furrow during planting.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the approximate ranges below, which add up to 100% by weight.
[00212] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (such as lactose and sucrose), silica, talc , mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate. Typical solid diluents are described in Watkins et al, Handbook of Insecticide Dust Diluents and Carriers, Second Edition, Dorland Books, Caldwell, New Jersey.
Liquid diluents include, for example, water, N,N-dimethylalkanamides (such as N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (such as N-methylpyrrolidinone), alkyl phosphates (such as such as triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (such as white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerin, triacetate of glycerol, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate , heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl benzoates and a rila and Y-butyrolactone and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethyl hexanol, n- octanol, decanol, isodecyl alcohol, iso-octadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as fruit oils and plant seeds (such as olive, castor, flax, sesame, corn, peanut, sunflower, grape seed oils saffron, cottonseed, soybean, canola, coconut and palm seed), fats from animal sources (such as beef tallow, pork tallow, lard, cod liver oil and fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (such as methylated, ethylated and butylated) where the fatty acids can be obtained through hydrolysis of glycerol esters from plant and animal sources and can be purified through distillation. Typical liquid diluents are described in Marsden, Solvents Guide, second edition, Interscience, New York, 1950.
[00214] Liquid and solid compositions in accordance with the present invention often include one or more surfactants. When added to a liquid, surfactants (also called “surface active agents”) often modify and more often reduce the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoamers.
[00215] Surfactants can be classified as non-ionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alkoxylated alcohols such as alkoxylated alcohols based on natural and synthetic alcohols (which may be linear or branched) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and canola oils, alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates and dodecylphenol ethoxylates (prepared from phenols, ethylene oxide propylene, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers in which the end blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated oils and fatty esters; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin based derivatives, polyethoxylated esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkylated pegylated resins (polyethylene glycol), resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
[00216] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates or carboxylated alcohol; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulphonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; alcohol sulfates; alcohol ethoxylated sulfates; amine and amide sulfonates such as N,N-alkyl taurates; benzene, cumene, toluene, xylene, dodecyl and tridecylbenzene sulfonates; condensed naphthalene sulfonates; naphthalene and alkyl naphthalene sulfonates; fractionated petroleum sulfonates; sulfosuccinamates; and sulfosuccinates and derivatives thereof, such as dialkyl sulfosuccinate salts.
[00217] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines, such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts, such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
[00218] Also useful for the compositions of the present are mixtures of anionic and nonionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants and their recommended uses are described in a series of published references that include McCutcheon's Emulsifiers and Detergents, US and international annual editions published by McCutcheon Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, seventh edition, John Wiley & Sons, New York, 1987.
[00219] The compositions according to the present invention may also contain additives and formulation aids known to those skilled in the art as formulation aids (some of which can be considered also functioning as solid diluents, liquid diluents or surfactants). These additives and formulation aids can control: pH (buffers), foaming during processing (antifoams such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobials) ), product freezing (antifreeze), color (dyes/pigment dispersions), washing (film formers or binders), evaporation (evaporation retardants) and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, vinyl acetate copolymer and polyvinylpyrrolidone, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of additives and formulation aids include those listed in McCutcheon's Volume 2: Functional Materials, US and International Annual Editions published by the McCutcheon Division, The Manufacturing Confectioner Publishing Co., and PCT Patent No. WO 03/024222.
[00220] The compound of Formula 1 and any other active ingredients are typically incorporated into the compositions herein by dissolving the active ingredient in solvents or milling in liquid or dry diluent. Solutions, which include emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active by dilution with water. Active ingredient slurries with particle diameters up to 2000 µm can be wet milled using media mills to obtain particles with average diameters of less than 3 µm. Aqueous slurries can be made into finished suspension concentrates (see, for example, US 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require dry milling processes, which produce average particle diameters in the range of 2 to 10 µm. Powders and dry powders can be prepared through mixing and usually grinding (such as in a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto preformed granular vehicles or by means of agglomeration methods. See Browning, Agglomeration, Chemical Engineering, December 4, 1967, p. 147—48, Perry's Chemical Engineer's Handbook, fourth edition, McGraw-Hill, New York, 1963, p. 8-57 et seq., and WO 91/13546. Pellets can be prepared as described in US 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in US 4,144,050, US 3,920,442 and DE 3,246,493. Pellets can be prepared as taught in US 5,180,587, US 5,232,701 and US 5,208,030. Films can be prepared as taught in GB 2,095,558 and US 3,299,566.
[00221] For additional information regarding the method of formulation, see TS Woods, The Formulator's Toolbox - Product Forms for Modern Agriculture in Pesticide Chemistry and Bioscience, The FoodEnvironment Challenge, T. Brooks and TR Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p. 120-133. See also US 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; US 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Controls as a Science, John Wiley and Sons, Inc., New York, 1961, p. 81-96; Hance et al, Weed Control Handbook, eighth edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in Formulation Technology, PJB Publications, Richmond, Great Britain, 2000.
In the Examples below, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers designate compounds in Index Tables A. Without further elaboration, it is believed that those skilled in the art, using the above description, can utilize the present invention to the fullest extent possible. The following Examples should therefore be interpreted as merely illustrative and not limiting of the descriptive report in any way. Percentages are by weight unless otherwise indicated. EXAMPLE A High Strength Concentrate Compound 20 98.5% Silica airgel 0.5% Synthetic fine amorphous silica 1.0% EXAMPLE B Wettable powder Compound 20 65.0% Dodecylphenol polyethylene glycol ether 2.0% sodium lignin sulfonate 4.0 % Sodium Silicoaluminate 6.0% Montmorillonite (calcined) 23.0% EXAMPLE C Granules Compound 20 10.0% Attapulgite Granules (material with low 90.0% volatility, 0.71/0.30 mm; sieves USS no. ° 25-50) EXAMPLE D Extruded Pellets Compound 20 25.0% Anhydrous Sodium Sulfate 10.0% Crude Calcium Lignine sulfonate 5.0% Sodium alkylnaphthalene sulfonate 1.0% Calcium/magnesium bentonite 59.0% EXAMPLE E Concentrate emulsifiable Compound 20 10.0% Polyoxyethylene sorbitol hexaleate 20.0% C6-C10 fatty acid methyl ester 70.0% EXAMPLE F Microemulsion Compound 20 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkylpolyglycoside 30, 0% Glyceryl Monooleate 15.0% Water 20.0% EXAMPLE G Suspension Concentrate Compound 20 35% Block Copolymer d and butyl 4.0% polyoxyethylene/polypropylene Copolymer of stearic acid and polyethylene glycol 1.0% Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone-based defoamer 0.1% 1 ,2-Benzisothiazolin-3-one 0.1% Water 53.7% EXAMPLE H Emulsion in water Compound 20 10.0% Butyl block copolymer 4.0% polyoxyethylene/polypropylene Copolymer of stearic acid and polyethylene glycol 1.0 % Styrene acrylic polymer 1.0% Xanthan gum 0.1% Propylene glycol 5.0% Silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% Aromatic petroleum based hydrocarbon 20 .0 Water 58.7% EXAMPLE I Dispersion in Oil Compound 20 25% Polyoxyethylene Sorbitol Hexaoleate 15% Organically Modified Bentonite Clay 2.5% Fatty Acid Methyl Ester 57.5%
[00223] The present invention also includes Examples A through I above, except for the replacement of "Compound 20" by "Compound 1", "Compound 2", "Compound 3", "Compound 4", "Compound 5", " Composite 6", "Compound 7", "Compound 8", "Compound 9", "Compound 10", "Compound 11", "Compound 12", "Compound 13", "Compound 14", "Compound 15", " Compost 16", "Compound 17", "Compound 18", "Compound 19", "Compound 21", "Compound 22", "Compound 23", "Compound 24", "Compound 25", "Compound 26", " Compound 27", "Compound 28", "Compound 29", "Compound 30", "Compound 31", "Compound 32", "Compound 33", "Compound 34", "Compound 35", Compound 36, Compound 37, Compound 38,
[00224] Test results indicate that the compounds according to the present invention are highly active pre-emergent and/or post-emergent herbicides and/or plant growth regulators. Compounds according to the present invention generally exhibit higher activity for post-emergence pest control (ie, applied after the herb seedlings emerge from the ground) and pre-emergence herb control (ie, applied before the seedlings of herbs emerging from the soil). Many of them are useful for broad-spectrum pre- and/or post-emergence weed control in regions where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, movie theaters. drive-in, airports, riverbanks, irrigation courses and other waterways, around billboards and structures of highways and railways. Many of the compounds according to the present invention, by virtue of selective metabolism in crops compared to herbs, or through selective activity at the site of physiological inhibition in crops and herbs, or selective placement or into the environment of a mixture of crops and herbs, are useful for selective control of grass and broadleaf grasses in a blend of crop and herbs. Those skilled in the art will recognize that the preferred combination of these selectivity factors in a compound or group of compounds can be easily determined by performing routine biological and/or biochemical tests. Compounds according to the present invention may exhibit tolerance to important agronomic crops, including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn, sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nuts, bananas, pineapple, hops, tea and forests such as eucalyptus and conifers (eg pine) and species of grass (eg, febra grass, St. Augustine grass, Kentucky fescue, and Bermuda grass). The compounds according to the present invention can be used in genetically transformed or cultivated crops to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin) and/or express other useful characteristics. Those skilled in the art will appreciate that not all compounds are equally effective against all herbs. Alternatively, the compounds of the present are useful for modifying plant growth.
The compounds according to the present invention can exhibit surprising selective activity of controlling herb species growing on rice, including, but not limited to, water plantain (Alisma plantago-aquatica L.), purple nutsedge (Cyperus difformis L.) .), bulrush (Cyperus iria L.), rice grass (Echinochloa colonum (L.) LINK), cockscomb (Echinochloa crusgalli (L.) P. BEAUV.), rice millet (two-leaf stage; Echinochloa oryzoides (ARD.) FRITSCH), water grass (two-leaf stage; Echinochloa phyllopogon (STAPF) KOSS./VASC.), water chestnut (Eleocharis dulcis (BURM.f.) TRIN. from HENSCHEL), young herb rice (Heteranthera limosa (SW.) WILLD./VAHL), loofah (Leptochloa fascicularis (LAM.) GRAY), monochoria (Monochoria vaginalis (BURM.f.) C.PRESL from KUNTH), Sagittarius (Sagittaria latifolia WILLD) .), arrow water hyacinth (Sagittaria montevidensis CHAM. & SCHLECHT.), arrow head (Sagittaria rigida PURSH), Japanese rush (Scirpus juncoides ROXB.) and d rush the rice fields (Scirpus mucronatus L.).
The compounds according to the present invention also exhibit specific activities (biological activity) of controlling weed species growing in cereal crops, including, but not limited to, foxtail (Alopecurus myosuroides HUDS.), weed. wind (Apera spica-venti (L.) BEAUV.), wild oats (Avena fatua L.), Italian ryegrass (Lolium multiflorum LAM.), birdseed (Phalaris minor RETEZ.) and green corn (Setaria viridis (L.) P .BEAUV.).
[00227] As the compounds according to the present invention have activity (both pre-emergent and post-emergent herbicide) to control unwanted vegetation by killing or damaging the vegetation, or reducing its growth, the compounds can be usefully applied by by means of a series of methods involving contacting a herbicidal-effective amount of a compound according to the present invention or a composition comprising said compound and at least one of a surfactant, solid diluent or liquid diluent to foliage or other part of the unwanted vegetation, or to the unwanted vegetation environment, such as the soil or water in which the unwanted vegetation is growing or which surrounds the seed or other propagule of the unwanted vegetation.
The herbicidal effective amount of the compounds according to the present invention is determined by a number of factors. These factors include: selected formulation, method of application, type and amount of vegetation present, growing conditions, etc. In general, the herbicidal effective amount of the compounds according to the present invention is about 0.001 to 20 kg/ha, with a preferred range of about 0.004 to 1 kg/ha. Those skilled in the art can easily determine the herbicide-effective amount needed for the desired level of herb control.
[00229] In a common embodiment, a compound in accordance with the present invention is applied, typically in formulated composition, to a locus comprising desired vegetation (e.g., crops) and unwanted vegetation (i.e., grasses), both of which which can be seeds, seedlings and/or larger plants, in contact with a growing medium (eg soil). At that location, a composition comprising a compound according to the present invention can be applied directly to a plant or part thereof, particularly unwanted vegetation, and/or to the growing medium in contact with the plant.
[00230] Plant varieties and cultivars of the desired vegetation at the locus treated with a compound according to the present invention can be obtained by conventional cultivation and propagation methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant genome. A transgene that is defined by its specific location in the plant genome is called a transgenic event or transformation.
[00231] Genetically modified plant cultivars that can be treated in accordance with the present invention include those that are resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi etc.) or abiotic stresses (drought , low temperature, soil salinity, etc.) or that contain other desirable characteristics. Plants can be genetically modified to exhibit characteristics, for example, herbicide tolerance, insect resistance, modified oil profile or drought tolerance. Useful genetically modified plants that contain isolated genetic transformation events or combinations of transformation events are listed in Illustration C. Additional information for the genetic modifications listed in Illustration C can be obtained from publicly available databases maintained, for example, by the US Department of Agriculture.




* Argentina (Brassica napus), ** polonesa (B. rapa).[00232] The following abbreviations, T1 to T37, are used in Illustration C for the characteristics. “-“ indicates that the subscription is not available; "fool." indicates "tolerance" and "res." indicates resistance. Car. Description












* Argentina (Brassica napus), ** Polish (B. rapa).
[00233] Although, more typically, the compounds according to the present invention are used to control unwanted vegetation, contact of unwanted vegetation at the site treated with compounds according to the present invention can result in synergistic or superadditive effects with genetic characteristics in the desired vegetation, including traits incorporated through genetic modification. Resistance to phytophagous insect pests or plant diseases, tolerance to biotic/abiotic stresses or storage stability, for example, may be greater than expected from the genetic characteristics in the desired vegetation.
The compounds according to the present invention may also be mixed with one or more different biologically active agents or compounds, including herbicides, herbicide safety agents, fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators such as insect mating inhibitors and rooting stimulants, chemosterilizers, semiochemicals, repellents, attractants, pheromones, food stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi, to form a multi-component pesticide that provides a spectrum broader scope of agricultural protection. Mixtures of the compounds according to the present invention with other herbicides can broaden the spectrum of activity against additional herb species and suppress the proliferation of any resistant biotypes. The present invention therefore also relates to a composition comprising a compound of Formula 1 (in herbicide effective amount) and at least one additional biologically active agent or compound (in biologically effective amount) and may further comprise at least one of a surfactant, solid thinner or liquid thinner. The other biologically active agents or compounds can be formulated into compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures in accordance with the present invention, one or more biologically active agents or compounds may be formulated together with a compound of Formula 1 to form a premix, or one or more different biologically active agents or compounds may be formulated separately from the compound of Formula 1 and the formulations combined with each other prior to application (such as in a spray tank) or, alternatively, applied successively.
[00235] A mixture of one or more of the following herbicides with a compound according to the present invention may be particularly useful for herb control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor , aloxidim, ametrin, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (eg, methyl and ethyl) and salts (eg, sodium and potassium), aminopyralid, amitrol, ammonium sulfamate, anilophos, assulam, atrazine, azimsulfuron, beflubutamid , benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate,bensulfuron methyl,bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanaphos, bispyribac and its sodium salt, bromacyl, bromobutyl, bromobutyl, bromophenoxy , butaphenacyl, butamiphos, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone-ethyl, catechin, clomethoxyphen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotolu ron, chlorprofam, chlorsulfuron, chlorthal-dimethyl, chlortiamid, cinidon-ethyl, cinmethylin, cinosulfuron, claciphos, clefoxidim, cletodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olumamine, chlorazylamine, methylchlorazine cyclopyrimorate, cyclosulfamuron, cyclooxydim, cyhalofop-butyl, 2,4-D and its butothyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4 -DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetrin, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, diclobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat methylsulfate, diflufenican, diflufenzopyrme, dimefur , dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, difenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, etalfluralin, and tam ulfuron-methyl, etiozin, ethofumesate, ethoxyphen, ethoxysulfuron, ethobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, phenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-isopropyl methyl, flazasulfuron, florassulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, fluketosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron-ethyl, flusulfoxfenyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, phosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate P, glyphosate and its salts such as isopropyl ammonium , potassium, sodium (including sesquisodium) and trimesium (alternatively called sulfosate, halauxifen, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazametabenzo-methyl, imaz amox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxinil, ioxynil octanoate, ioxynil-octanoate, isipoxinil, isipoxinil, isipoxinil isoxachlortol, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (eg MCPA-dimethylammonium, MCPA-potassium and MCPA sodium, esters (eg, MCPA-2-ethylhexyl, MCPA-butothyl) and thioesters ( eg MCPA-thioethyl), MCPB and its salts (eg MCPB-sodium) and esters (eg MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium , metamifop, metamitron, metazachlor, metazosulfuron, metabenzothiazuron, methylarsonic acid and its calcium salts, monoammonium, monosodium and disodium, methyldimron, methobenzuron, methobromuron, metolachlor, S-metolachlor, metossulam, monosodium, metoxuron-methylsulfuron , naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomephone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, petcloxam, penoxamuron, pendoxam, pendoxam, pendoxam, penfamamide, pendoxam , picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxidim, prometon, prometrin, propachlor, propanil, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, prosulfonsulfuron, propirissulfuron , pyraflufen-ethyl, pyrasulfotol, pyrazogyl, pyrazolinate, pyrazoxifen, pyrazosulfuron-ethyl, pyribenzoxim, piributicarb, pyridate, piriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasesulfone, pyributicarb, , quizalofop-P-ethyl, quizalofop-P-tefuril, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetri n, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebutiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthyazine, terbutrin, tenylchlor, tifensulfuron-methyl, thiobencarb, thiafenacil, thiocarbazil, tolpiralate, topramezone, tralkoxydim, triallate, triaphamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butothyl, triclopyr-triethylammonium, tridiphane, trifludisulfazine, trisulfuron methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2 -hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol- 5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin -6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5- [[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (formerly methioxolin), 4-(4-fluorophenyl) )-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl -1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-( trifluoromethyl)benzamide. Other herbicides also include bioherbicides, such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.), Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz), Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos, Schub.
Compounds according to the present invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocoleone, gibberellic acid, gibberellin A4 and A7, hairpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmone, sodium nitrophenolate and trinexapac-methyl, as well as plant growth modifying organisms such as Bacillus cereus strain BP01.
[00237] General references for agricultural protectants (ie herbicides, herbicide safety agents, insecticides, fungicides, nematicides, acaricides and biological agents) include The Pesticide Manual, 13th edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003, and The BioPesticide Manual, second edition, LG Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.
[00238] For embodiments in which one or more of these diverse blending partners are used, the blending partners are typically used in amounts similar to customary amounts when the blending partners are used alone. More particularly in blends, active ingredients are often applied at an application rate of half to the full application rate specified on product labels for use of the active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio between these various blending partners (in total) and the compound of Formula 1 is typically from about 1:3000 to about 3000:1. Weight ratios of about 1:300 to about 300:1 (for example, ratios of about 1:30 to about 30:1) are noteworthy. Those skilled in the art can easily determine, through simple experimentation, the biologically effective amounts of active ingredients needed for the desired spectrum of biological activity. It will be evident that the inclusion of these additional components can expand the spectrum of controlled herbs beyond the spectrum controlled by the compound of Formula 1 alone.
[00239] In certain cases, combinations of a compound according to the present invention with other compounds or biologically active agents (particularly herbicides) (i.e., active ingredients) may result in a greater than additive (i.e., synergistic) effect on the herbs and/or less than additive (ie safety) effect on crops or other desirable plants. Reducing the amount of active ingredients released into the environment while ensuring effective pest control is always desirable. The ability to use larger amounts of active ingredients to provide more effective weed control without excessive crop damage is also desirable. When the synergy of herbicide active ingredients occurs over herbs at application rates that generate agronomically satisfactory levels of weed control, these combinations can be advantageous in reducing crop production costs and reducing the environmental burden. When the safety of active herbicide ingredients on crops occurs, these combinations can be advantageous to increase crop protection by reducing herb competition.
[00240] A combination of a compound according to the present invention with at least one other active ingredient as herbicide is noteworthy. Particularly noteworthy is a combination in which the other active ingredient as herbicide has a different site of action than the compound according to the present invention. In certain cases, a combination with at least one other herbicide active ingredient that has a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. A composition according to the present invention may therefore further comprise (in herbicide effective amount) at least one additional herbicide active ingredient which has similar spectrum of control but different site of action.
The compounds according to the present invention can also be used in combination with herbicide safety agents such as alidochlor, benoxacor, cloquintocet-mexil, cumiluron, ciometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietolate, dimepiperate, fenchlorazol-ethyl, phenchlorim, flurazol, fluxfenin, furilazol, isoxadifen-ethyl, mefempyr-diethyl, mefenate, methoxyphenone, naphthalic anhydride (1,8-naphthalic anhydride) of methoxyphenone, oxabetrinyl, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N -(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]-benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2 -(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2 -hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate 3-oxo-1-cyclohexen-1-yl, 2,2-dichloro-1-(2 ,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]benzamide, to increase the safety of certain crops. Antidote-effective amounts of herbicide safety agents can be applied at the same time as the compounds according to the present invention or applied as seed treatments. One aspect of the present invention, therefore, relates to a herbicide mixture comprising a compound according to the present invention and an antidote effective amount of a herbicide safety agent. Seed treatment is particularly useful for selective weed control as it physically restricts the antidote to crop plants. A particularly useful embodiment of the present invention is therefore a method of selectively controlling the growth of unwanted vegetation in crops, which comprises contacting the crop site with a herbicidal effective amount of a compound according to the present invention, wherein the seed with which the crop is grown is treated with an effective amount as a safety agent antidote. Antidote-effective amounts of security agents can easily be determined by those skilled in the art through simple experimentation.
[00242] The compounds according to the present invention may also be mixed with: (1) polynucleotides, including, but not limited to, chemically modified DNA, RNA and/or nucleotides that influence the amount of a specific target through regulation for low, interference, suppression or silencing of the genetically derived transcript that provides herbicidal effect; or (2) polynucleotides, including, but not limited to, chemically modified DNA, RNA and/or nucleotides that influence the quantity of a specific target through down-regulation, interference, suppression or silencing of the genetically derived transcript that provides a safety effect .
[00243] Noteworthy is a composition comprising a compound according to the present invention (in herbicide effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safety agents (in amount effective) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.




[00244] For better control of unwanted vegetation (eg, slower use speed such as through synergy, broader spectrum of controlled weeds or increased crop safety) or to prevent the development of resistant weeds, are preferred. mixtures of a compound according to the present invention with another herbicide. Table A1 lists specific combinations of Component (a) (i.e. specific compound according to the present invention) with another herbicide as Component (b) illustrative of the mixtures, compositions and methods according to the present invention. Compound 20 in column Component (a) is identified in Table Index A. The second column of Table A1 lists the specific Compound (b) compound (for example, “2,4-D” in the first row). The third, fourth, and fifth columns of Table A1 list ranges of weight ratios for rates at which Component (a) is typically applied to a field-grown crop relative to Component (b) (ie, (a): (B)). Thus, the first line of Table A1, for example, specifically describes that the combination of Component (a) (ie Compound 17 in Index Table A) with 2,4-D is typically applied in a weight ratio of 1: 192 to 6:1. The remaining lines of Table A1 should be interpreted similarly.













[00245] Table A2 is constructed in the same way as Table A1 above, except for the replacement of the rows below the “Component (a)” column header (ie “20”) with the corresponding Component (a) column row shown below. The compound number in column Component (a) is identified in Table Index A. Thus, in Table A2, for example, all rows below the column header “Component (a)” indicate “Compound 1” (ie, Compound 1 identified in Index Table A) and the first row below the column headings in Table A2 specifically describe a mixture of Compound 1 with 2,4-D. Tables A3 through A94 are constructed in a similar way.
[00246] For better control of unwanted vegetation (eg, slower use speed such as through synergy, broader spectrum of controlled weeds or increased crop safety) or to prevent the development of resistant weeds, are preferred. mixtures of a compound according to the present invention with an herbicide selected from the group consisting of chlorimuron-ethyl, nicosulfuron, mesotrione, thifensulfuron-methyl, flupyrsulfuron-methyl, tribenuron, pyrroxasulfone, pinoxaden, tembotrione, pyroxisulam, metolachlor and S - metolachlor.
3-CH3-3-oxetanil indica e naftila indica naftalenila. (R) ou (S) indica a quiralidade absoluta do centro de carbono assimétrico. A abreviação “(d)” indica que o composto aparentemente decompôs-se mediante fusão. A abreviação “Composto n°” indica “Composto número”. A abreviação “Ex.” indica “Exemplo” e é seguida por um número que indica em qual exemplo o composto é preparado. Espectros de massa são relatados com precisão estimada de até ± 0,5 Da como peso molecular do íon parental com abundância isotópica mais alta (M+1) formado pela adição de H+ (peso molecular de 1) à molécula observada utilizando ionização química sob pressão atmosférica (AP+).

1 Vide Exemplo de Síntese 1 para dados de NMR 1H. 2 * Vide Exemplo de Síntese 2 para dados de NMR 1H. 3 ** A ligação livre que se projeta para a direita indica o ponto de conexão de A a Q1 (ou seja, fenila) e a ligação livre que se projeta para a esquerda indica o ponto de conexão de A a J1. 4 Indica que o composto é preparado de forma enantioenriquecida nas posições 3 e 4. 5 Indica que o composto é preparado de forma enantioenriquecida nas posições 3 e 4.[00247] The following Tests demonstrate the control effectiveness of the compounds according to the present invention against specific herbs. Weed control generated by the compounds is not limited to these species, however. See Table Index A for compound descriptions. The following abbreviations are used in the following Index Tables: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl , Bu is butyl, c-Pr is cyclopropyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, -CN is cyano, -NO2 is nitro and TMS is trimethylsilyl; (-CH2O)2CH indicates 3-CH3-3-oxetanil indicates and naphthyl indicates naphthalenyl. (R) or (S) indicates the absolute chirality of the asymmetric carbon center. The abbreviation "(d)" indicates that the compound apparently decomposed upon fusion. The abbreviation “Compound #” indicates “Compound number”. The abbreviation "Ex." indicates "Example" and is followed by a number that indicates in which example the compound is prepared. Mass spectra are reported with estimated accuracy of up to ± 0.5 Da as the molecular weight of the parent ion with the highest isotopic abundance (M+1) formed by the addition of H+ (molecular weight of 1) to the observed molecule using chemical ionization under pressure atmospheric (AP+).





1 See Synthesis Example 1 for 1H NMR data. 2 * See Synthesis Example 2 for 1H NMR data. 3 ** The free bond that projects to the right indicates the connection point from A to Q1 (ie, phenyl) and the free bond that projects to the left indicates the connection point from A to J1. 4 Indicates that the compound is prepared enantioenriched in positions 3 and 4. 5 Indicates that the compound is prepared enantioenriched in positions 3 and 4. BIOLOGICAL EXAMPLES OF THE INVENTION
[00248] Test A:
[00249] Seeds of selected plant species from rice grass (Echinochloa cruss-galli), Kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (Lolium mltiflorum), giant foxtail (Setaria faberii) and amaranth (Amaranthus retroflexus) were planted in a mixture of clayey soil and sand and treated pre-emergence with directed spraying onto the soil, using test substances formulated in a mixture of non-phytotoxic solvents, which included a surfactant.


[00250] At the same time, plants selected from these species of herbs and also foxtail (Alopecurus myosuroides), gallium (aparine, Galium aparine), wheat (Triticum aestivum) and corn (Zea mays) were planted in pots containing the same mixture of clayey soil and sand and treated with post-emergence applications of test substances formulated in the same manner. The height of the plants ranged from 2 to 10 cm and they were at the stage of one to two leaves for post-emergence treatment. Treated plants and untreated controls were kept in a greenhouse for about ten days and, after this period, all treated plants were compared to untreated controls and visually assessed for damage. Plant reaction ratings, summarized in Table A, are based on a scale from 0 to 100, where 0 is no effect and 100 is complete control. Dash (-) indicates no test result. Table A With posts







TEST B
[00251] Plant species in the flooded field test selected from rice (Oryza sativa), rush, umbrella rush (small flower umbrella rush, Cyperus difformis), water hyacinth (Heteranthera limosa) and rice grass (Echinochloa cruss -galli) were grown to the two-leaf stage for testing. At the time of treatment, test pots were flooded to 3 cm above the soil surface, treated by applying test compounds directly to the flooded water, and then maintained at that water depth for the duration of the test. Treated plants and controls were kept in a greenhouse for 13 to 15 days and, after this period, all species were compared with controls and visually evaluated. Plant reaction ratings, summarized in Table B, are based on a scale from 0 to 100, where 0 is no effect and 100 is complete control. Dash (-) indicates no test result.

权利要求:
Claims (15)
[0001]
em que - Q1 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído com um a quatro substituintes independentemente selecionados a partir de R7; ou um anel heteroaromático com cinco a seis membros ou um sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S) e os membros de anéis de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, em que cada anel ou sistema de anéis é opcionalmente substituído com até quatro substituintes independentemente selecionados a partir de R7 no átomo de carbono membro do anel e selecionados a partir de R9 no átomo de nitrogênio membro do anel; - Q2 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído com até cinco substituintes independentemente selecionados a partir de R10; ou um anel heteroaromático com cinco a seis membros, ou um sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S) e os membros de anéis de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, em que cada anel ou sistema de anéis é opcionalmente substituído com até cinco substituintes independentemente selecionados a partir de R10 no átomo de carbono membro do anel e selecionados a partir de R11 no átomo de nitrogênio membro do anel; - T é J1-A-, em que a ligação livre que se projeta para a direita ao lado de A indica o ponto de conexão de J1-A- a Q1; ou - T é R17ON=CR17a-, (R18)2C=NO-, (R19)2NN=CR17a-, (R18)2C=NNR20a-, R20N=CR17a-, (R18)2C=N-, R17ON=CR17aC(R23b)2- ou (R18)2C=NOC(R24a)2-, em que a ligação livre que se projeta para a direita indica o ponto de conexão a Q1; - A é uma cadeia saturada, parcialmente insaturada ou totalmente insaturada que contém de um a três átomos selecionados a partir de até três átomos de carbono, até 1 O, até 1 S e até 2 N, em que a cadeia é opcionalmente substituída com até dois substituintes independentemente selecionados a partir de R15 emátomos de carbono e R16 em átomos de nitrogênio; - Y1 e Y2 são, independentemente entre si, O, S ou NR12; - J1 é um anel fenila ou sistema de anéis naftalenila, em que cada anel ou sistema de anéis é opcionalmente substituído com até cinco substituintes independentemente selecionados a partir de R7’; ou um anel heterocíclico com quatro a seis membros ou sistema de anéis bicíclicos heteroaromáticos com oito a dez membros, em que cada anel ou sistema de anéis contém membros de anéis selecionados a partir de átomos de carbono e um a quatro heteroátomos independentemente selecionados a partir de até 2 átomos de O, até 2 S e até 4 N, em que até três membros de anéis de carbono são independentemente selecionados a partir de C(=O) e C(=S), e os membros de anéis de átomos de enxofre são independentemente selecionados a partir de S(=O)u(=NR8)v, cada anel ou sistema de anéis é opcionalmente substituído com até cinco substituintes independentemente selecionados a partir de R7’ de átomos de carbono membro de anel e selecionados a partir de R9’ de átomos de nitrogênio membro de anel; ou cicloalquilalcóxi C4-C10, cicloalquilalquila C4-C10, alquenilóxi C2-C8, haloalquenilóxi C2-C8, alcoxialcóxi C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, haloalquilsulfonila C1-C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, haloalcoxialcóxi C3-C8, haloalcóxi- haloalquila C2-C8, , halocicloalquila C3-C8, alquilcarbonilóxi C2-C8 ou haloalquilcarbonilóxi C2-C8; - J2 é -CR2R3- ou -CR2R3-CR2aR3a-, em que a porção -CR2R3- é conectada a N; - R1 é H, hidróxi, amino, , , -, alquila C1-C6, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, cianoalquila C2-C6, cicloalquila C3-C6 ou cicloalquilalquila C4-C8; - R2 é H ou CH3; - R3 é H ou CH3; - R2a é H ou CH3; - R3a é H ou CH3; - R4 é H ou CH3; - R5 é H ou CH3; - R6 é H ou CH3; - cada R7 é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C4, cianoalquila C1-C4, cianoalcóxi C1-C4, haloalquila C1-C4, alquenila C2-C4, haloalquenila C2-C4, alquinila C2-C4, haloalquinila C2-C4, nitroalquila C1-C4, nitroalquenila C2-C4, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, haloalcoxialquila C2-C4, cicloalquila C3-C4, halocicloalquila C3-C4, ciclopropilmetila, 1-metilciclopropila, 2-metilciclopropila, alcóxi C1-C4, haloalcóxi C1-C4, alquenilóxi C2-C4, haloalquenilóxi C2-C4, alquinilóxi C3-C4, haloalquinilóxi C3-C4, cicloalcóxi C3-C4, alquiltio C1-C4, haloalquiltio C1-C4, alquilsulfinila C1-C4, haloalquilsulfinila C1-C4, alquilsulfonila C1-C4, haloalquilsulfonila C1-C4, hidróxi, - CHO, alquilcarbonila C2-C4, alquilcarbonilóxi C2-C4, alquilsulfonilóxi C1-C4, haloalquilsulfonilóxi C1-C4, amino, alquilamino C1-C4, dialquilamino C2-C4, formilamino, alquilcarbonilamino C2-C4, -SF5, -SCN, trialquilsilila C3-C4, trimetilsililmetila ou trimetilsililmetóxi; ou - dois R7 adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3-C7; - cada R10 é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C8, haloalquila C1-C8, nitroalquila C1-C8, alquenila C2-C8, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, cianoalquila C1-C4, cianoalcóxi C1C4, haloalquenila C2-C8, nitroalquenila C2-C8, alquinila C2-C8, haloalquinila C2-C8, cicloalquilalquila C4-C10, halocicloalquilalquila C4-C10, alquilcicloalquilalquila C5C12, cicloalquilalquenila C5-C12, cicloalquilalquinila C5-C12, cicloalquila C3-C8, halocicloalquila C3-C8, alquilcicloalquila C4-C10, cicloalquilcicloalquila C6-C12, cicloalquenila C3-C8, halocicloalquenila C3-C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, cicloalcoxialquila C4-C10, alcoxialcoxialquila C3-C10, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilaminoalquila C2-C8, haloalquilaminoalquila C2-C8, cicloalquilaminoalquila C4-C10, dialquilaminoalquila C3-C10, -CHO, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, -C(=O)OH, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, -C(=O)NH2, alquilaminocarbonila C2-C8, cicloalquilaminocarbonila C4-C10, dialquilaminocarbonila C3-C10, hidróxi, alcóxi C1-C8, haloalcóxi C1-C8, alcoxialcóxi C2-C8, alquenilóxi C2-C8, haloalquenilóxi C2C8, alquinilóxi C3-C8, haloalquinilóxi C3-C8, cicloalcóxi C3-C8, halocicloalcóxi C3C8, cicloalquilalcóxi C4-C10, alquilcarbonilalcóxi C3-C10, alquilcarbonilóxi C2-C8, haloalquilcarbonilóxi C2-C8, cicloalquilcarbonilóxi C4-C10, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, alquilsulfonila C1-C8, haloalquilsulfonila C1-C8, cicloalquilsulfonila C3-C8, amino, alquilamino C1-C8, haloalquilamino C1-C6, cicloalquilamino C3-C8, dialquilamino C2-C8, halodialquilamino C2-C8, formilamino, alquilcarbonilamino C2-C8, haloalquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, haloalquilsulfonilamino C1-C6, -SF5, -SCN, trialquilsilila C3-C12, trialquilsililalquila C4-C12, trialquilsililalcóxi C4-C12 ou G2; ou - dois R10 adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3-C7; - cada R7’ é independentemente halogênio, hidroxila, ciano, nitro, alquila C1-C8, alcoxialquila C2-C4, alcoxialcoxialquila C3-C8, cianoalquila C1C4, cianoalcóxi C1-C4, haloalquila C1-C8, nitroalquila C1-C8, alquenila C2-C8, haloalquenila C2-C8, nitroalquenila C2-C8, alquinila C2-C8, haloalquinila C2-C8, cicloalquilalquila C4-C10, halocicloalquilalquila C4-C10, alquilcicloalquilalquila C5C12, cicloalquilalquenila C5-C12, cicloalquilalquinila C5-C12, cicloalquila C3-C8, halocicloalquila C3-C8, alquilcicloalquila C4-C10, cicloalquilcicloalquila C6-C12, cicloalquenila C3-C8, halocicloalquenila C3-C8, alcoxialquila C2-C8, haloalcoxialquila C2-C8, cicloalcoxialquila C4-C10, alcoxialcoxialquila C3-C10, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilaminoalquila C2-C8, haloalquilaminoalquila C2-C8, cicloalquilaminoalquila C4-C10, dialquilaminoalquila C3-C10, -CHO, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, -C(=O)OH, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, -C(=O)NH2, alquilaminocarbonila C2-C8, cicloalquilaminocarbonila C4-C10, dialquilaminocarbonila C3-C10, hidróxi, alcóxi C1-C8, haloalcóxi C1-C8, alcoxialcóxi C2-C8, alquenilóxi C2-C8, haloalquenilóxi C2C8, alquinilóxi C3-C8, haloalquinilóxi C3-C8, cicloalcóxi C3-C8, halocicloalcóxi C3C8, cicloalquilalcóxi C4-C10, alquilcarbonilalcóxi C3-C10, alquilcarbonilóxi C2-C8, haloalquilcarbonilóxi C2-C8, cicloalquilcarbonilóxi C4-C10, alquilsulfonilóxi C1-C8, haloalquilsulfonilóxi C1-C8, alquiltio C1-C8, haloalquiltio C1-C8, cicloalquiltio C3-C8, alquilsulfinila C1-C8, haloalquilsulfinila C1-C8, alquilsulfonila C1-C8, haloalquilsulfonila C1-C8, cicloalquilsulfonila C3-C8, amino, alquilamino C1-C8, haloalquilamino C1-C6, cicloalquilamino C3-C8, dialquilamino C2-C8, halodialquilamino C2-C8, formilamino, alquilcarbonilamino C2-C8, haloalquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, haloalquilsulfonilamino C1-C6, -SF5, -SCN, trialquilsilila C3-C12, trialquilsililalquila C4-C12 ou trialquilsililalcóxi C4-C12; ou - dois R7’ adjacentes são tomados em conjunto com os átomos de carbono aos quais são ligados para formar um anel cicloalquila C3-C7; - cada R8 é, independentemente, H, ciano, alquilcarbonila C2 C3 ou haloalquilcarbonila C2-C3; - cada R9, R9’ e R11 é independentemente ciano, alquila C1 C3, alquenila C2-C3, alquinila C2-C3, cicloalquila C3-C6, alcoxialquila C2-C3, alcóxi C1-C3, alquilcarbonila C2-C3, alcoxicarbonila C2-C3, alquilaminoalquila C2-C3 ou dialquilaminoalquila C3-C4; - cada R12 é independentemente H, ciano, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, -(C=O)CH3 ou -(C=O)CF3; - cada G1 é independentemente fenila, fenilmetila, piridinilmetila, fenilcarbonila, fenóxi, feniletinila, fenilsulfonila, fenilcarbonilalquila ou um anel heteroaromático com cinco ou seis membros, cada qual opcionalmente substituído em membros de anéis com até cinco substituintes independentemente selecionados a partir de R13; - cada G2 é independentemente fenila, fenilmetila, piridinilmetila, fenilcarbonila, fenilcarbonilalquila, fenóxi, feniletinila, fenilsulfonila ou um anel heteroaromático com cinco ou seis membros, cada qual opcionalmente substituído em membros de anéis com até cinco substituintes independentemente selecionados a partir de R14; - cada R13 e R14 é independentemente halogênio, ciano, hidróxi, amino, nitro, -CHO, -C(=O)OH, -C(=O)NH2, -SO2NH2, alquila C1-C6, haloalquila C1-C6, alquenila C2-C6, alquinila C2-C6, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, alcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, cicloalquilalcoxicarbonila C5-C12, alquilaminocarbonila C2-C8, dialquilaminocarbonila C3-C10, alcóxi C1-C6, haloalcóxi C1-C6, alquilcarbonilóxi C2-C8, alquiltio C1-C6, haloalquiltio C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, alquilaminossulfonila C1C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10, alquilamino C1-C6, dialquilamino C2-C8, alquilcarbonilamino C2-C8, alquilsulfonilamino C1-C6, fenila, piridinila ou tienila; - cada R15 é independentemente halogênio, ciano, hidróxi, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R16 é independentemente ciano, alquila C1-C4, haloalquila C1-C4, alcóxi C1-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R17 é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R17a é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, trialquilsilila C3-C10 ou G1; - cada R18 é independentemente H, hidróxi, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquiltio C1-C6, haloalquiltio C1-C6, cicloalquiltio C3-C8, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R19 é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R20 é independentemente H, hidróxi, amino, alquila C1 C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alquilcarbonila C2-C8, haloalquilcarbonila C2-C8, cicloalquilcarbonila C4-C10, alcoxicarbonila C2-C8, haloalcoxicarbonila C2-C8, cicloalcoxicarbonila C4-C10, alquilaminocarbonila C2C8, dialquilaminocarbonila C3-C10, cicloalquilaminocarbonila C4-C10, alcóxi C1-C6, alquilsulfinila C1-C6, haloalquilsulfinila C1-C6, cicloalquilsulfinila C3-C8, alquilsulfonila C1-C6, haloalquilsulfonila C1-C6, cicloalquilsulfonila C3-C8, alquilaminossulfonila C1-C6, dialquilaminossulfonila C2-C8, trialquilsilila C3-C10 ou G1; - cada R20a é independentemente H, alquila C1-C6, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C6, alquenila C2-C6, alquinila C3-C6, alcoxialquila C2-C8, haloalcoxialquila C2-C8, alquiltioalquila C2-C8, alquilsulfinilalquila C2-C8, alquilsulfonilalquila C2-C8, alcóxi C1-C6, trialquilsilila C3C10 ou G1; - cada R23b é independentemente H, halogênio, ciano, hidróxi, alquila C1-C4, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada R24a é independentemente H, alquila C1-C4, cicloalquila C3-C8, cicloalquilalquila C4-C8, haloalquila C1-C4, alcóxi C1-C4, haloalcóxi C1-C4, alcoxialquila C2-C4, alquilcarbonila C2-C4, alcoxicarbonila C2-C4 ou cicloalquila C3-C6; - cada u e v é independentemente 0, 1 ou 2 em cada caso de S(=O)u(=NR8)v, desde que a soma de u e v seja 0, 1 ou 2; desde que, quando: a) J1 for um anel fenila não substituído, A seja diferente de -CH2-, -O-, -CEC-, -C(=O)- ou -SO2-; ou b) J1 for um anel piridinila não substituído, A seja diferente de -CH2-; c) J1 for cicloalquilalquila C4-C10, A seja diferente de alquila; ou d) J1-A- estiver na posição para de Q1, A seja diferente de O e J1 seja diferente de 2-furanilmetila.1. COMPOUND, characterized by being selected from Formula 1, its N-oxides and salts: wherein - Q1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted with one to four substituents independently selected from R7; or a five to six membered heteroaromatic ring or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from of up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the sulfur ring members are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted with up to four substituents independently selected from R7 on the ring member carbon atom and selected from of R9 on the ring member nitrogen atom; - Q2 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted with up to five substituents independently selected from R10; or a five to six membered heteroaromatic ring, or an eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four independently selected heteroatoms a from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S) and the carbon ring members. sulfur are independently selected from S(=O)u(=NR8)v, wherein each ring or ring system is optionally substituted with up to five substituents independently selected from R10 on the ring member carbon atom and selected to from R11 on the ring member nitrogen atom; - T is J1-A-, where the free link protruding to the right beside A indicates the connection point of J1-A- to Q1; or - T is R17ON=CR17a-, (R18)2C=NO-, (R19)2NN=CR17a-, (R18)2C=NNR20a-, R20N=CR17a-, (R18)2C=N-, R17ON=CR17aC( R23b)2- or (R18)2C=NOC(R24a)2-, where the free link projecting to the right indicates the connection point to Q1; - A is a saturated, partially unsaturated or fully unsaturated chain containing one to three atoms selected from up to three carbon atoms, up to 1 O, up to 1 S and up to 2 N, wherein the chain is optionally substituted with up to two substituents independently selected from R15 on carbon atoms and R16 on nitrogen atoms; - Y1 and Y2 are, independently of each other, O, S or NR12; - J1 is a phenyl ring or naphthalenyl ring system, wherein each ring or ring system is optionally substituted with up to five substituents independently selected from R7'; or a four to six membered heterocyclic ring or eight to ten membered heteroaromatic bicyclic ring system, wherein each ring or ring system contains ring members selected from carbon atoms and one to four heteroatoms independently selected from up to 2 O atoms, up to 2 S and up to 4 N, wherein up to three carbon ring members are independently selected from C(=O) and C(=S), and the sulfur ring members are independently selected from S(=O)u(=NR8)v, each ring or ring system is optionally substituted with up to five substituents independently selected from R7' of ring member carbon atoms and selected from R9' of ring member nitrogen atoms; or C4-C10 cycloalkylalkoxy, C4-C10 cycloalkylalkyl, C2-C8 alkenyloxy, C2-C8 haloalkenyloxy, C2-C8 alkoxyalkoxy, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C8 alkylsulfonyloxy C1-C8 alkylsulfonyloxy , C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 haloalkylsulfonyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C3-C8 haloalkoxyalkoxy, C2 haloalkoxy -C8, , C3-C8 halocycloalkyl, C2-C8 alkylcarbonyloxy or C2-C8 haloalkylcarbonyloxy; - J2 is -CR2R3- or -CR2R3-CR2aR3a-, wherein the -CR2R3- portion is N-connected; - R1 is H, hydroxy, amino, , , -, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C6 cyanoalkyl, C3-C6 cycloalkyl or C4-C8 cycloalkylalkyl; - R2 is H or CH3; - R3 is H or CH3; - R2a is H or CH3; - R3a is H or CH3; - R4 is H or CH3; - R5 is H or CH3; - R6 is H or CH3; - each R7 is independently halogen, hydroxyl, cyano, nitro, C1-C4 alkyl, C1-C4 cyanoalkyl, C1-C4 cyanoalkoxy, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2 haloalkynyl -C4, C1-C4 nitroalkyl, C2-C4 nitroalkenyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C4 haloalkoxyalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, cyclopropylmethyl, 1-methylcyclopropyl, 2-methylcyclopropyl, C1 alkoxy -C4, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C4 alkynyloxy, C3-C4 haloalkynyloxy, C3-C4 cycloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, haloalkylsulfinyl -C4, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, hydroxy, -CHO, C2-C4 alkylcarbonyl, C2-C4 alkylcarbonyloxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, amino, C1-C4 alkylamino, C2-C4 dialkylamino, formylamino, C2-C4 alkylcarbonylamino, -SF5, -SCN, C3-C4 trialkylsilyl, trimethylsilylmethyl or trimethylsilylmethoxy; or - two adjacent R7 are taken together with the carbon atoms to which they are attached to form a C3-C7 cycloalkyl ring; - each R10 is independently halogen, hydroxyl, cyano, nitro, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 nitroalkyl, C2-C8 alkenyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkyl, C1-C4 cyanoalkyl, C1C4 cyanoalkoxy , C2-C8 haloalkenyl, C2-C8 nitroalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C5C12 alkylcycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, C5-C12 cycloalkylalkyny C3-C8, C4-C10 alkylcycloalkyl, C6-C12 cycloalkylcycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkyl, C3-C8 alkylthioalkyl C2-C8, C2-C8 alkylsulfonylalkyl, C2-C8 alkylaminoalkyl, C2-C8 haloalkylaminoalkyl, C4-C10 cycloalkylaminoalkyl, C3-C10 dialkylaminoalkyl, -CHO, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, -C( =O)OH, the C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C8 alkoxy, C1-C8 haloalkoxy, C2-C8 alkoxy, C2-C8 alkenyloxy, C2C8 haloalkenyloxy, C3-C8 alkynyloxy, C3-C8 haloalkynyloxy, C3-C8 cycloalkoxy, C3C8 haloalkoxy, C4-C10 cycloalkylalkoxy C4-C10 alkyloxycarbonyloxy , C2-C8 haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl , C1-C8 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, amino, C1-C8 alkylamino, C1-C6 haloalkylamino, C3-C8 cycloalkylamino, C2-C8 dialkylamino, C2-C8 halodialkylamino, formylamino, C2-C8 alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-C6 alkylsulfonylamino, C1-C6 haloalkylsulfonylamino, -SF5, -SCN, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl, C4-C12 or G2 trialkylsilylalkoxy; or - two adjacent R10 are taken together with the carbon atoms to which they are attached to form a C3-C7 cycloalkyl ring; - each R7' is independently halogen, hydroxyl, cyano, nitro, C1-C8 alkyl, C2-C4 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C1C4 cyanoalkyl, C1-C4 cyanoalkoxy, C1-C8 haloalkyl, C1-C8 nitroalkyl, C2-alkenyl C8, C2-C8 haloalkenyl, C2-C8 nitroalkenyl, C2-C8 alkynyl, C2-C8 haloalkynyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C5C12 alkylcycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, C5-C12 cycloalkylalkynyl C3-C8 halocycloalkyl, C4-C10 alkylcycloalkyl, C6-C12 cycloalkylcycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkyl, C2-alkylthio, alkoxy C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylaminoalkyl, C2-C8 haloalkylaminoalkyl, C4-C10 cycloalkylaminoalkyl, C3-C10 dialkylaminoalkyl, -CHO, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl (=O)OH, the C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, -C(=O)NH2, C2-C8 alkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, hydroxy, C1-C8 alkoxy, C1-C8 haloalkoxy, C2-C8 alkoxy, C2-C8 alkenyloxy, C2C8 haloalkenyloxy, C3-C8 alkynyloxy, C3-C8 haloalkynyloxy, C3-C8 cycloalkoxy, C3C8 haloalkoxy, C4-C10 cycloalkylalkoxy C4-C10 alkyloxycarbonyloxy , C2-C8 haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy, C1-C8 alkylsulfonyloxy, C1-C8 haloalkylsulfonyloxy, C1-C8 alkylthio, C1-C8 haloalkylthio, C3-C8 cycloalkylthio, C1-C8 alkylsulfinyl, C1-C8 haloalkylsulfinyl, C1-C8 alkylsulfonyl , C1-C8 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, amino, C1-C8 alkylamino, C1-C6 haloalkylamino, C3-C8 cycloalkylamino, C2-C8 dialkylamino, C2-C8 halodialkylamino, formylamino, C2-C8 alkylcarbonylamino, C2-C8 haloalkylcarbonylamino, C1-C6 alkylsulfonylamino, C1-C6 haloalkylsulfonylamino, -SF5, -SCN, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl or C4-C12 trialkylsilylalkoxy; or - two adjacent R7' are taken together with the carbon atoms to which they are attached to form a C3-C7 cycloalkyl ring; - each R8 is independently H, cyano, C2C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl; - each R9, R9' and R11 is independently cyano, C1 C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl , C2-C3 alkylaminoalkyl or C3-C4 dialkylaminoalkyl; - each R12 is independently H, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -(C=O)CH3 or -(C=O)CF3; - each G1 is independently phenyl, phenylmethyl, pyridinylmethyl, phenylcarbonyl, phenoxy, phenylethynyl, phenylsulfonyl, phenylcarbonylalkyl or a five- or six-membered heteroaromatic ring, each optionally substituted on ring members with up to five substituents independently selected from R13; - each G2 is independently phenyl, phenylmethyl, pyridinylmethyl, phenylcarbonyl, phenylcarbonylalkyl, phenoxy, phenylethynyl, phenylsulfonyl or a five- or six-membered heteroaromatic ring, each optionally substituted on ring members with up to five substituents independently selected from R14; - each R13 and R14 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, -C(=O)OH, -C(=O)NH2, -SO2NH2, C1-C6 alkyl, C1-C6 haloalkyl, alkenyl C2-C6, C2-C6 alkynyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C2-C8 alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C5-C12 cycloalkylalkoxycarbonyl, C2-C8 alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1-C6 alkoxy, haloalkoxy C1-C6, C2-C8 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1C6 alkylaminosulfonyl, C1-C3 dialkylaminosulfonyl, C2-C8 alkylsilyl C10, C1-C6 alkylamino, C2-C8 dialkylamino, C2-C8 alkylcarbonylamino, C1-C6 alkylsulfonylamino, phenyl, pyridinyl or thienyl; - each R15 is independently halogen, cyano, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R16 is independently cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R17 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl, C3-dialkylamino C4-C10 cycloalkylaminocarbonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C3-C8 dialkylaminosulfonyl, C1-C8 alkylsulfonyl G1; - each R17a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C3-C10 or G1 trialkylsilyl; - each R18 is independently H, hydroxy, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkylthioalkyl C2-C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl-dialkylaminocarbonyl C10, C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-haloalkylsulfonyl C6, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C2-C8 dialkylaminosulfonyl, C3-C10 or G1 trialkylsilyl; - each R19 is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2C8 alkylaminocarbonyl, C3-dialkylamino C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C1-C6 alkylaminosulfonyl, dialkylaminosulfonyl C3-C10 or G1 trialkylsilyl; - each R20 is independently H, hydroxy, amino, C1C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkylthioalkyl, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C2-C8 alkylcarbonyl, C2-C8 haloalkylcarbonyl, C4-C10 cycloalkylcarbonyl, C2-C8 alkoxycarbonyl, C2-C8 haloalkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2-C8 alkylcarbonylamino -C10, C4-C10 cycloalkylaminocarbonyl, C1-C6 alkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C8 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C1-C6 alkylaminosulfonyl, C1-C6 alkylaminosulfonyl -C8, C3-C10 or G1 trialkylsilyl; - each R20a is independently H, C1-C6 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C3-C6 alkynyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-alkylthioalkyl C8, C2-C8 alkylsulfinylalkyl, C2-C8 alkylsulfonylalkyl, C1-C6 alkoxy, C3C10 or G1 trialkylsilyl; - each R23b is independently H, halogen, cyano, hydroxy, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2 alkylcarbonyl -C4, C2-C4 alkoxycarbonyl or C3-C6 cycloalkyl; - each R24a is independently H, C1-C4 alkyl, C3-C8 cycloalkyl, C4-C8 cycloalkylalkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-alkoxycarbonyl C4 or C3-C6 cycloalkyl; - each u and v is independently 0, 1 or 2 in each case of S(=O)u(=NR8)v, provided that the sum of u and v is 0, 1 or 2; provided that when: a) J1 is an unsubstituted phenyl ring, A is other than -CH2-, -O-, -CEC-, -C(=O)- or -SO2-; or b) J1 is an unsubstituted pyridinyl ring, A is other than -CH2-; c) J1 is C4-C10 cycloalkylalkyl, A is other than alkyl; or d) J1-A- is in the para position of Q1, A is different from O and J1 is different from 2-furanylmethyl.
[0002]
A COMPOUND according to claim 1, characterized in that Q1 is a phenyl ring optionally substituted with one to two substituents independently selected from R7.
[0003]
A COMPOUND according to any one of claims 1 to 2, characterized in that Q2 is a phenyl ring optionally substituted with one to five substituents independently selected from R10.
[0004]
A COMPOUND according to any one of claims 1 to 3, characterized in that T is J1-A-.
[0005]
A COMPOUND according to any one of claims 1 to 4, characterized in that A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -CEC-, -NH-, -O-, -S -, -SO- or -SO2-.
[0006]
A COMPOUND according to any one of claims 1 to 5, characterized in that A is -CH2-, -CH2O-, -CH2NH-, -CH=CH-, -CEC-, -NH- or -O-.
[0007]
A COMPOUND according to any one of claims 1 to 6, characterized in that A is -CH2-O- or -O-.
[0008]
A COMPOUND according to any one of claims 1 to 7, characterized in that J1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R7'.
[0009]
A COMPOUND according to any one of claims 1 to 7, characterized in that J1 is a four to six membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected from up to 2 carbon atoms. O, up to 2 S atoms and up to 3 N atoms, wherein up to two carbon ring members are independently selected from C (=O) and C (=S), and sulfur atom ring members are selected independently of S(=O)u(=NR8) v, each ring or ring system optionally substituted with up to 3 substituents independently selected from R7' on the carbon atom ring members and selected from R9' on the ring members of the nitrogen atom.
[0010]
A COMPOUND according to claim 9, characterized in that J1 is a five to six membered heteroaromatic ring optionally substituted with a substituent selected from R7' on the carbon atom ring members.
[0011]
11. COMPOUND according to claim 1, characterized in that it is selected from the group consisting of: - N-(2,4-difluorophenyl)-2-oxo-4-[3-(phenoxymethyl)phenyl]-3 - pyrrolidinecarboxamide; and - 2-oxo-4-[3-(2-pyridinyloxy)phenyl]-N-(2,3,4-trifluorophenyl)-3-pyrrolidinecarboxamide.
[0012]
12. HERBICIDAL COMPOSITION, characterized in that it comprises a compound, as defined in any one of claims 1 to 11, and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0013]
13. HERBICIDAL COMPOSITION, characterized in that it comprises a compound, as defined in any one of claims 1 to 11, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safety agents and at least one selected component from the group consisting of surfactants, solid thinners and liquid thinners.
[0014]
14. HERBICIDAL MIXTURE, characterized in that it comprises (a) a compound as defined in any one of claims 1 to 11; and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS), (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enolpyruvylshikimate-3-phosphate synthase (EPSP) inhibitors, (b6) photosystem I electron diversors, (b7) protoporphyrinogene oxidase (PPO) inhibitors, (b8) glutamine synthetase inhibitors (GS), (b9) very long chain fatty acid elongase inhibitors (VLCFA), (b10), auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenylpyruvate inhibitors dioxygenase (HPPD), (b13) homonotisate solenesyltransferase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides, including mitotic switches, organic arsenic, assulam, bromobutide, cinmethylin, cumiluron, dazomet, difenzoquat, dimron, ethobenzanide, flurenol, phosamine, phosamine-ammonium, hydantocid ine, metam, methyldimron, oleic acid, oxaziclomephone, pelargonic acid and pyributicarb; (b16) herbicide safety agents, and salts of compounds (b1) to (b16).
[0015]
15. METHOD OF CONTROLLING THE GROWTH OF UNWANTED VEGETATION, characterized in that it comprises the contact of the vegetation or its environment with an effective amount as herbicide of a compound, as defined in any one of claims 1 to 11.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112017017945B1|2021-06-08|compost, herbicide compositions, herbicide mixture and method of controlling the growth of unwanted vegetation

---

AU2016259529B2|2020-10-01|Aryl substituted bicyclic compounds as herbicides

---

AU2016271374B2|2020-11-26|Substituted cyclic amides and their use as herbicides

---

BR112018000687B1|2021-05-04|compost, herbicide compositions, herbicide mixtures and methods for controlling the growth of unwanted vegetation

---

TWI735345B|2021-08-01|Intermediates to prepare pyrrolidinone herbicides

---

CN107690426B|2021-07-06|Substituted cyclic amides as herbicides

---

TWI691487B|2020-04-21|Piperidinone herbicides

---

BR112017020094B1|2022-01-11|COMPOUND, HERBICIDAL COMPOSITIONS, HERBICIDE MIXTURE AND METHOD FOR CONTROLLING UNWANTED VEGETATION GROWTH

---

TW201835040A|2018-10-01|Nitrone herbicides

---

BR112017012197B1|2021-06-01|COMPOUND, HERBICIDAL COMPOSITIONS, HERBICIDAL MIXTURE AND METHOD TO CONTROL UNWANTED VEGETATION GROWTH

---

TWI713530B|2020-12-21|Pyrimidinyloxy benzene derivatives as herbicides

---

AU2015292521A1|2017-01-19|Pyridones as herbicides

---

JP2020522493A|2020-07-30|Amide for weeding

---

CA3058176A1|2018-10-04|Novel pyridazinone herbicides

---

AU2018277041B2|2021-11-11|Herbicidal 3-substituted lactams

---

BR112021014754A2|2021-09-28|COMPOUND, HERBICIDAL COMPOSITION, HERBICIDAL MIXTURE AND METHOD TO CONTROL THE GROWTH OF UNWANTED VEGETATION

同族专利:

---

公开号 | 公开日

---

BR112017017945A2|2018-04-10|

---

CN107466290B|2021-08-03|

---

JP6956637B2|2021-11-02|

---

WO2016164201A1|2016-10-13|

---

TWI703127B|2020-09-01|

---

TW201639813A|2016-11-16|

---

EP3280709A1|2018-02-14|

---

CA2978014A1|2016-10-13|

---

AR104214A1|2017-07-05|

---

RU2017134986A3|2019-05-21|

---

AU2016246410A1|2017-08-31|

---

US20180049437A1|2018-02-22|

---

EP3280709B1|2021-05-26|

---

US10405547B2|2019-09-10|

---

CN107466290A|2017-12-12|

---

JP2018513857A|2018-05-31|

---

RU2710379C2|2019-12-26|

---

UY36619A|2016-11-30|

---

AU2016246410B2|2020-11-05|

---

RU2017134986A|2019-04-10|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2891855A|1954-08-16|1959-06-23|Geigy Ag J R|Compositions and methods for influencing the growth of plants|

---

US3060084A|1961-06-09|1962-10-23|Du Pont|Improved homogeneous, readily dispersed, pesticidal concentrate|

---

US3235361A|1962-10-29|1966-02-15|Du Pont|Method for the control of undesirable vegetation|

---

DE1262277B|1962-12-05|1968-03-07|Basf Ag|Process for the preparation of pyrrolidones|

---

US3299566A|1964-06-01|1967-01-24|Olin Mathieson|Water soluble film containing agricultural chemicals|

---

US3309192A|1964-12-02|1967-03-14|Du Pont|Method of controlling seedling weed grasses|

---

US4144050A|1969-02-05|1979-03-13|Hoechst Aktiengesellschaft|Micro granules for pesticides and process for their manufacture|

---

US3741989A|1970-10-27|1973-06-26|Abbott Lab|Lactonic acetals|

---

US3920442A|1972-09-18|1975-11-18|Du Pont|Water-dispersible pesticide aggregates|

---

JPS5356288A|1976-10-30|1978-05-22|Matsushita Electric Works Ltd|Preparation of phenolic resin|

---

US4172714A|1976-12-20|1979-10-30|E. I. Du Pont De Nemours And Company|Dry compactible, swellable herbicidal compositions and pellets produced therefrom|

---

JPS5488114A|1977-12-26|1979-07-13|Fuji Photo Film Co Ltd|Manufacturing device for photograph seal|

---

GB2095558B|1981-03-30|1984-10-24|Avon Packers Ltd|Formulation of agricultural chemicals|

---

DE3246493A1|1982-12-16|1984-06-20|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING WATER-DISPERSIBLE GRANULES|

---

US4594094A|1983-04-04|1986-06-10|Shell Oil Company|Oxacycloalkane-alpha-carboxylic acid derivatives and use as plant growth regulators and herbicides|

---

US5180587A|1988-06-28|1993-01-19|E. I. Du Pont De Nemours And Company|Tablet formulations of pesticides|

---

US4874422A|1988-12-27|1989-10-17|Ici Americas Inc.|1-Phenyl-3-carboxyamidopyrrolidones and their use as herbicides|

---

EP0415688B1|1989-08-30|1998-12-23|Aeci Ltd|Dosage device and use thereof|

---

EP0519937B1|1990-03-12|1994-12-28|E.I. Du Pont De Nemours And Company|Water-dispersible or water-soluble pesticide granules from heat-activated binders|

---

DE69122201T2|1990-10-11|1997-02-06|Sumitomo Chemical Co|Pesticides composition|

---

GB9225377D0|1992-12-04|1993-01-27|Ici Plc|Herbicides|

---

JP3487669B2|1995-03-28|2004-01-19|積水化学工業株式会社|Unsaturated polyester resin composition|

---

WO2000009481A1|1998-08-11|2000-02-24|Takeda Chemical Industries, Ltd.|Cyclic amide compounds, process for producing the same, intermediates thereof and herbicides|

---

DE60208808T2|2001-08-15|2006-11-02|E.I. Dupont De Nemours And Co., Wilmington|WITH HETEROCYCLES ORTHO-SUBSTITUTED ARYL AMIDE FOR COMBATING WIRELESS INJURIES|

---

TWI283164B|2001-09-21|2007-07-01|Du Pont|Anthranilamide arthropodicide treatment|

---

HU0401667A2|2001-10-08|2004-12-28|Ucb, S.A.|Use of 2-oxo-1-pyrrolidine derivatives for the preparation of a drug for treatment of dyskinesia and movement disorders|

---

JP4398866B2|2002-10-18|2010-01-13|ビーエーエスエフソシエタス・ヨーロピア|1-phenylpyrrolidin-2-one-3-carboxamide|

---

AU2003277721A1|2002-11-15|2004-06-15|In Kwon Chung|Beta-nitrostyrene compound and telomerase inhibitor having an anticancer activity|

---

US7205318B2|2003-03-18|2007-04-17|Bristol-Myers Squibb Company|Lactam-containing cyclic diamines and derivatives as a factor Xa inhibitors|

---

KR100890696B1|2005-01-28|2009-03-26|아이알엠 엘엘씨|Synthesis of aryl pyrrolidones|

---

US20070123508A1|2005-05-27|2007-05-31|Roger Olsson|PAR2-modulating compounds and their use|

---

US8293926B2|2005-12-09|2012-10-23|Sumitomo Chemical Company, Limited|Method of producing optically active 4-amino-3-substituted phenylbutanoic acid|

---

WO2008013622A2|2006-07-27|2008-01-31|E. I. Du Pont De Nemours And Company|Fungicidal azocyclic amides|

---

ES2304220B1|2007-03-02|2009-09-11|Universidad De Zaragoza|COMPOSITION FOR THE TREATMENT OF INFECTIOUS DISEASES.|

---

EP2065380A1|2007-08-22|2009-06-03|F.Hoffmann-La Roche Ag|Pyridoneamide derivatives as focal adhesion kinase inhibitors and their use for the treatment of cancer|

---

CN101412711A|2007-10-15|2009-04-22|上海恒瑞医药有限公司|Carbamate derivatives and use thereof in medicine|

---

KR101667063B1|2008-09-02|2016-10-17|닛산 가가쿠 고교 가부시키 가이샤|Ortho-substituted haloalkylsulfonanilide derivative and herbicide|

---

US9150591B2|2010-08-10|2015-10-06|Takeda Pharmaceutical Company Limited|Heterocyclic compound and use thereof|

---

EP2613782B1|2010-09-01|2016-11-02|Merck Sharp & Dohme Corp.|Indazole derivatives useful as erk inhibitors|

---

CN102531918B|2012-01-18|2013-10-02|安阳工学院|Method for synthesizing enantiomorphous pure symmetric trans-dialkyl cyclohexylamine|

---

KR20130142477A|2012-06-19|2013-12-30|순천향대학교 산학협력단|Method for preparation of nitrocyclopropane derivatives|

---

US20160137639A1|2012-10-26|2016-05-19|Japan Tobacco Inc.|Triazole-isoxazole compound and medical use thereof|

---

MX2016007259A|2013-12-03|2016-08-04|Du Pont|Pyrrolidinones as herbicides.|

---

GB201321743D0|2013-12-09|2014-01-22|Ucb Pharma Sa|Therapeutic agents|

---

RU2555370C1|2014-02-12|2015-07-10|Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Самарский государственный технический университет"|Method for enanthioselective synthesis of diethyl[3-methyl--butyl]malonate of formula i|

---

WO2016003997A1|2014-07-02|2016-01-07|E. I. Du Pont De Nemours And Company|Piperidinone herbicides|

---

MX2017007087A|2014-12-08|2017-09-05|Du Pont|3-oxo-3-propanoates, a process for their preparation, and their use in preparing pyrrolidinones.|

---

CA2979417A1|2015-04-27|2016-11-03|E I Du Pont De Nemours And Company|Butyrolactones as herbicides|

---

RU2750293C2|2015-05-12|2021-06-25|ЭфЭмСи Корпорейшн|Aryl-substituted bicyclic compounds as herbicides|

---

BR112017022743A2|2015-05-29|2018-07-17|Du Pont|"Compound, herbicidal composition, herbicide mixture and method for controlling unwanted vegetation growth"|

---

RU2017142979A3|2015-06-02|2019-10-11|

---

EP3328836B1|2015-07-31|2021-03-24|FMC Corporation|Cyclic n-carboxamide compounds useful as herbicides|

---

US20200115337A1|2016-12-21|2020-04-16|Fmc Corporation|Nitrone herbicides|

---

KR20190140911A|2017-03-21|2019-12-20|에프엠씨 코포레이션|Pyrrolidinone and its preparation method|

---

RU2019131524A3|2017-03-21|2021-07-16|MX2016007259A|2013-12-03|2016-08-04|Du Pont|Pyrrolidinones as herbicides.|

---

WO2016003997A1|2014-07-02|2016-01-07|E. I. Du Pont De Nemours And Company|Piperidinone herbicides|

---

MX2017007087A|2014-12-08|2017-09-05|Du Pont|3-oxo-3-propanoates, a process for their preparation, and their use in preparing pyrrolidinones.|

---

CA2979417A1|2015-04-27|2016-11-03|E I Du Pont De Nemours And Company|Butyrolactones as herbicides|

---

RU2750293C2|2015-05-12|2021-06-25|ЭфЭмСи Корпорейшн|Aryl-substituted bicyclic compounds as herbicides|

---

BR112017022743A2|2015-05-29|2018-07-17|Du Pont|"Compound, herbicidal composition, herbicide mixture and method for controlling unwanted vegetation growth"|

---

RU2017142979A3|2015-06-02|2019-10-11|

---

EP3328836B1|2015-07-31|2021-03-24|FMC Corporation|Cyclic n-carboxamide compounds useful as herbicides|

---

WO2018010656A1|2016-07-12|2018-01-18|南京明德新药研发股份有限公司|Pyrrolidine derivative serving as ppar agonist|

---

GB201617062D0|2016-10-07|2016-11-23|Syngenta Participations Ag|Herbicidal mixtures|

---

US20200115337A1|2016-12-21|2020-04-16|Fmc Corporation|Nitrone herbicides|

---

KR20190140911A|2017-03-21|2019-12-20|에프엠씨 코포레이션|Pyrrolidinone and its preparation method|

---

WO2018177836A1|2017-03-30|2018-10-04|Bayer Aktiengesellschaft|N-cyclopropyl-2-oxopyrrolidine-3-carboxamide derivatives and related compounds as herbicidal plant protection agents|

---

WO2018177837A1|2017-03-30|2018-10-04|Bayer Aktiengesellschaft|4-cyclopentyl- and 4-cyclopropyl-2-oxopyrrolidine-3-carboxamide derivatives and related compounds as herbicidal plant protection agents|

---

AR111839A1|2017-05-30|2019-08-21|Fmc Corp|LACTAMAS 3-REPLACED HERBICIDES|

---

AR111967A1|2017-05-30|2019-09-04|Fmc Corp|AMIDES HERBICIDES|

---

WO2019025156A1|2017-08-03|2019-02-07|Bayer Aktiengesellschaft|Substituted pyrrolidinones, salts thereof and use thereof as herbicidal agents|

---

WO2020064260A1|2018-09-24|2020-04-02|Bayer Aktiengesellschaft|Substituted 5--3,4-dihydro-2h-pyrrol-4-carboxamides and salts thereof and their use as herbicidal active substances|

---

WO2020113094A1|2018-11-30|2020-06-04|Nuvation Bio Inc.|Pyrrole and pyrazole compounds and methods of use thereof|

---

EP3936192A1|2019-03-06|2022-01-12|Daiichi Sankyo Company, Limited|Pyrrolopyrazole derivative|

法律状态:
2018-08-28| B25A| Requested transfer of rights approved|Owner name: FMC CORPORATION (US) |

---

2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-06-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/03/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201562145598P| true| 2015-04-10|2015-04-10|

---

US62/145,598|2015-04-10|

---

PCT/US2016/024669|WO2016164201A1|2015-04-10|2016-03-29|Substituted cyclic amides as herbicides|

---