compost, herbicide compositions, herbicide mixtures and methods for controlling the growth of unwant

专利摘要:
?COMPOSITE, COMPOSITION AND HERBICIDAL MIXTURE AND METHODS FOR CONTROLLING THE GROWTH OF UNWANTED VEGETATION? The present invention relates to the compounds of Formula 1, including all stereoisomers, N-oxides and salts thereof, wherein A, R1, R2 and R3 are as defined in the present invention. The present invention also relates to compositions containing the compounds of Formula 1 and methods for controlling unwanted vegetation which comprise contacting unwanted vegetation or its environment with an effective amount of a compound or composition of the present invention.
公开号:BR112018000687B1
申请号:R112018000687-4
申请日:2016-07-08
公开日:2021-05-04
发明作者:Thomas Martin Stevenson；Ravisekhara Pochimireddy Reddy
申请人:Fmc Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to certain aryloxypyrimidinyl ethers, their N-oxides, salts and compositions and their methods of use for the control of unwanted vegetation. BACKGROUND OF THE INVENTION
[002] The control of unwanted vegetation is extremely important to achieve high crop efficiency. The realization of selective control of weed growth, especially in useful crops such as rice, soybean, sugar beet, corn, potato, wheat, barley, tomato and plantation crops, among others, is very much desired. Uncontrolled weed growth on such useful crops can cause a significant reduction in productivity and therefore result in increased costs for the consumer. Controlling unwanted vegetation in non-crop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less expensive, less toxic, environmentally safe, or that have different mechanisms of action. BRIEF DESCRIPTION OF THE INVENTION
[003] The present invention relates to the compounds of Formula 1 (including all stereoisomers), (N-oxides and salts thereof), to agricultural compositions containing them and their use as herbicides:
- wherein - A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-alkylcycloalkyl C8, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C4-C8 cycloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C1-C6 nitroalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylthioalkyl C6, C3-C8 cycloalkylthioalkyl, C2-C6 alkylsulfinylalkyl, C2-C6 haloalkylsulfinylalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 haloalkylsulfonylalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkylcarbonylalkylcarbonyl C2-C6 alkylcarbonyl, C6, C2-C6 haloalkoxycarbonylalkyl or C2-C6 alkoxyalkylcarbonyl; or G; or C1-C4 alkyl substituted with Q; - R1 is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2C6 alkenyl, C2-C6 alkynyl, C1-C4 alkoxy or S(O)nR4; - R2 is halogen, cyano, nitro, CHO, C(=O)NH2, C(=S)NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2 haloalkenyl -C4, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C2-C4 alkoxy , C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C62-C6 alkoxyhaloC2-alkoxy, alkoxy , C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C2C4 alkylthioalkyl, C(=O)N(R5a)(R5b), C(=NOR6)H, C(=NR7)H or SOnR4; - R3 is H or F; - G is a non-aromatic 3 to 7 membered heterocyclic ring containing ring members selected from carbon, up to 4 heteroatoms selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, and up to 3 ring members selected from C(=O), C(=S) and S(=O)a(=NR6)b and substituted with up to 3 substituents independently selected from halogen, cyano, C1-alkyl C4, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - Q is a phenyl ring optionally substituted with up to 5 substituents independently selected from R8; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms and optionally substituted with up to 3 substituents independently selected from R9a on the carbon atom ring members and R9b on the nitrogen atom ring members; - each R4 independently is C1-C6 alkyl or C1C6 haloalkyl; - each R5a independently is C1-C4 alkyl or C1-C4 haloalkyl; - each R5b independently is H, C1-C4 alkyl or C1-C4 haloalkyl; - each R6 independently is H or C1-C4 alkyl; - each R7 independently is H, amino, C1-C4 alkyl or C1-C4 alkylamino; - each R8 independently is halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - each R9a independently is halogen, cyano, C1C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - each R9b independently is H, C1-C3 alkyl, C1-C3 alkylcarbonyl, C1-C3 alkoxy or C1-C3 alkoxycarbonyl; - each n independently is 0, 1 or 2; and - a and b independently are 0, 1 or 2, provided that the sum of a and b is 1 or 2; and - provided that when R1 is Cl; R3 is H; and A is o -C(=O)CH2CH2CF3; therefore, R2 is different from Br or cyano.
[004] More particularly, the present invention relates to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof. The present invention also relates to a herbicidal composition comprising a compound of the present invention (i.e., in a herbicidal 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 for controlling the growth of unwanted vegetation which comprises contacting the vegetation or its environment with an herbicidal effective amount of a compound of the present invention (e.g. such as a composition described herein. ).
[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 terms "comprises", "comprises", "includes", "including", "owns", "possessing", "contains", "containing", "characterized by" or any other of its variations are intended to encompass a non-exclusive inclusion, subject to any expressly stated limitations. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to just those elements, but may include other elements that are not expressly listed or inherent in that composition, mixture, process or method.
[007] The transition phrase “consisting of” excludes any unspecified element, step or ingredient. If in the claim, this would restrict the claim to the inclusion of materials other than those cited, except for impurities normally associated with the same materials. When the phrase “consisting of” appears in a clause in the body of a claim, rather than immediately following the preamble, it will only limit the element presented in that clause; other elements are not excluded from the claim as a whole.
[008] The transition phrase "consisting essentially of" is used to define a composition or method that includes the materials, steps, aspects, components or elements, in addition to those described literally, from which these additional materials, steps, aspects , components or elements do not materially affect the basic and innovative feature(s) of the present claimed invention. The term "which consists essentially of" occupies an intermediate position between "which comprises" and "which consists of".
[009] In the event that the Depositors have defined an invention or a part thereof with an open term such as "which comprises" it should be readily understood that (unless otherwise indicated) the description should be interpreted also to describe such invention, using the terms "consisting essentially of" or "consisting of".
[010] Furthermore, unless otherwise indicated, “or” refers to an inclusion and not an exclusion. For example, a condition A or B is satisfied by any of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or not present), and both A and B are true (or present).
[011] Furthermore, the indefinite articles "a" and "an" that precede an element or component of the present invention are intended to be non-restrictive as to the number of cases (i.e., occurrences) of the element or component. Therefore, "a" or "an" must be read to include one or at least one, and the singular word form of the element or component also includes the plural, unless the number obviously means the singular.
[012] As referred to herein, the term "seedling", used alone or in combination of words means a young plant developing from the embryo of a seed.
[013] As referred to herein, the term "broadleaf" used alone or in terms such as "broadleaf weeds" means the dichote or dicotyledon, a term used to describe a group of angiosperms characterized by embryos that have two cotyledons .
[014] As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing radical is attached via a carbon atom to a leaving group such as a halide or sulfonate, which it is displaceable through the attachment of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylation" does not limit the carbon-containing radical to alkyl; carbon-containing radicals in the alkylating agents include the variety of carbon-attached substituent radicals specified for A.
[015] In the above quotes, 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 and hexyl isomers. The term "alkenyl" includes straight or branched chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different isomers of butenyl, pentenyl and hexenyl. The term "alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. The term "alkynyl" includes straight or branched chain alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different isomers of butynyl, pentynyl and hexynyl. The term "alkynyl" can also include those moieties comprised of multiple triple bonds such as 2,5-hexadiinyl.
[016] The term "alkoxy", for example, includes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different isomers of butoxy, pentoxy and hexyloxy. The term "alkoxyalkyl" means the substitution of alkoxy to alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. The term "alkoxyalkoxy" means the substitution of alkoxy to alkoxy. The term "alkenyloxy" includes straight chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O, and CH2=CHCH2CH2O. The term "alkynyloxy" includes straight or branched chain alkynyloxy moieties. Examples of "alkynyloxy" include HC=CHCH2O, CH3C=CCH2O and CH3C=CCH2CH2O. The term "alkylthio" includes straight or branched chain alkylthio moieties such as methylthio, ethylthio, and the different isomers of propylthio, butylthio, pentylthio and hexylthio. The term "alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)- and the different isomers of butylsulfinyl, pentylsulfinyl and hexylsulfinyl. The term "alkylthioalkyl" indicates the substitution of alkylthio to alkyl. Examples of "alkylthioalkyl" include CH3SCH2-, CH3SCH2CH2-, CH3CH2SCH2-, CH3CH2CH2CH2SCH2-, and CH3CH2SCH2CH2-. The terms "alkylamino", "dialkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", "alkylsulfinylalkyl", "alkylsulfonylalkyl" and the like are defined analogously to examples above. The term "cyanoalkyl" refers to an alkyl group substituted with a cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. The term "cyanoalkoxy" indicates an alkoxy group substituted with a cyano group. Examples of "cyanoalkoxy" include NCCH2O, NCCH2CH2O and CH3CH(CN)CH2O. The term "cyanoalkoxyalkyl" indicates an alkoxyalkyl group substituted with a cyano group. Examples of "cyanoalkoxyalkyl" include NCCH2OCH2, NCCH2CH2OCH2 and CH3CH(CN)CH2OCH2. The term "nitroalkyl" indicates an alkyl group substituted with a nitro group. Examples of "nitroalkyl" include O2NCH2, O2NCH2CH2 and CH3CH(NO2)CH2.
[017] The term "cycloalkyl", for example, includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" indicates alkyl substitution in a cycloalkyl moiety and, for example, includes ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" means the replacement of cycloalkyl in an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl and other cycloalkyl moieties linked via straight or branched chain alkyl groups. The term "alkylcycloalkyl" means the replacement of alkyl in a cycloalkyl moiety. Examples of "alkylcycloalkyl" include methylcyclopropyl, ethylcyclopentyl and other alkyl moieties attached to a cycloalkyl group. The term "cycloalkoxy" denotes cycloalkyl bonded through an oxygen atom such as cyclopentyloxy or cyclohexyloxy. The term "cycloalkylcarbonyl" indicates cycloalkyl linked through a carbonyl moiety. The term "cycloalkoxyalkyl" denotes a cycloalkoxy group bonded through an alkyl group such as cyclopentyloxymethyl and cyclohexyloxyethyl. The term "cycloalkylthioalkyl" denotes a cycloalkylthio moiety attached through an alkyl group. The term "cycloalkylalkoxy" denotes a cycloalkyl moiety attached through an alkoxy group. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy and other cycloalkyl moieties attached to straight or branched chain alkoxy groups.
[018] The term "halogen", alone or in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted with 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 with halogen", said alkyl may be partially or fully substituted with halogen atoms, which may be identical or many different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F3C, ClCH2, CF3CH2- and CF3CCl2. The terms "halocycloalkyl", "haloalkoxy", "haloalkoxyalkyl", "haloalkoxyalkoxy", "haloalkylcarbonyl", "haloalkylcarbonylalkyl", "haloalkoxycarbonylalkyl", "alkoxyalkyl", "haloalkylthio", "haloalkylthioalkyl", "haloalkylsulfinyl", "haloalkylsulfinylalkyl" haloalkylsulfonyl", "haloalkylsulfonylalkyl", "haloalkenyl", "haloalkynyl", and the like are defined analogously to the term "haloalkyl". Examples of "halocycloalkyl" include c-Pr(1-Cl)-, c-Bu(2-Br)- and c-hex(4-Cl)-. Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of "haloalkoxyalkyl" include CF3OCH-, CF3CH2OCH2CH2-, CH2ClCH2OCH2- as well as branched haloalkoxy derivatives. Examples of "haloalkoxyalkoxy" include CF3OCH2O-, ClCH2CH2OCH2CH2O-, Cl3CCH2OCH2O- as well as branched alkyl derivatives. Examples of "haloalkylcarbonyl" include CF3C(=O)-, CF3CH2C(=O)- and CF3CF2C(=O)-. Examples of "haloalkylcarbonylalkyl" include CF3C(=O)CH2-, CF3CH2C(=O)CH2- and CF3CF2C(=O)CH2-. Examples of "haloalkoxycarbonylalkyl" include CF3OC(=O)CH2-, CF3CH2OC(=O)CH2- and CF3CF2OC(=O)CH2-. Examples of "alkoxyalkyl" include CH3OCHF-, CH3CH2OCF2CH2-, CH3CH2OCCl2- as well as branched alkoxy derivatives. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S- and ClCH2CH2CH2S-. Examples of "haloalkylthioalkyl" include CCl3SCH2-, CF3SCH2-, CCl3CH2SCH2- and ClCH2CH2CH2SCH2-. Examples of "haloalkylsulfinyl" include CF3S(O)-, CCl3S(O)-, CF3CH2S(O)- and CF3CF2S(O)-. Examples of "haloalkylsulfinylalkyl" include CF3S(O)CH2-, CCl3S(O)CH2-, CF3CH2S(O)CH2- and CF3CF2S(O)CH2-. Examples of "haloalkylsulfonyl" include CF3S(O)2-, CCl3S(O)2-, CF3CH2S(O)2- and CF3CF2S(O)2-. Examples of "haloalkylsulfonylalkyl" include CF3S(O)2CH2-, CCl3S(O)2CH2-, CF3CH2S(O)2CH2- and CF3CF2S(O)2CH2-. Examples of "haloalkenyl" include (Cl)2C=CHCH2- and CF3CH2CH=CHCH2-. Examples of "haloalkynyl" include HC CCHCl-, CF3C C-, CChC C- and FCH2C CCH2-.
[019] The term "alkylcarbonyl" indicates a straight or branched chain alkyl moiety attached to a C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)- and (CH3)2CHC(=O)-. The term "alkoxycarbonyl" denotes a straight or branched chain alkoxy moiety attached to a C(=O) moiety. Examples of "alkoxycarbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)- and the different butoxy or pentoxycarbonyl isomers. The term "alkoxyalkylcarbonyl" denotes a straight or branched chain alkoxyalkyl moiety attached to a C(=O) moiety. Examples of "alkoxyalkylcarbonyl" include CH3OCH2CH2C(=O)- and CH3CH2OCH2C(=O)-. The term "alkoxycarbonylalkyl" denotes a straight or branched chain alkoxycarbonyl moiety linked through alkyl. Examples of "alkoxycarbonylalkyl" include CH3OC(=O)CH2-, CH3CH2CH2OC(=O)CH2- and (CH3)2CHCO(=O)CH2-. The term "alkylcarbonylalkyl" denotes a straight or branched chain alkyl moiety attached to a carbonylalkyl group. Examples of "alkylcarbonylalkyl" include CH3CH2CH2C(=O)CH2- and CH3CH2CH2C(=O)CH2-. The term "alkylcarbonyloxy" denotes a straight or branched chain alkyl moiety attached to a carbonylalkyl group. Examples of "alkylcarbonyloxy" include CH3CH2CH2C(=O) O- and CH3CH2CH2C(=O)O-.
[020] The total number of carbon atoms in a substituent group is indicated by the prefix "Ci-Cj", where i and j are numbers from 1 to 12. For example, C1-C4 alkylsulfonyl indicates from a methylsulfonyl to a butylsulfonyl; C2 alkoxyalkyl indicates CH3OCH2-; C3 alkoxyalkyl indicates, for example, CH3CH(OCH3)-, CH3OCH2CH2-- or CH3CH2OCH2-; and C4 alkoxyalkyl indicates the various isomers of an alkyl group substituted with an alkoxy containing a total of four carbon atoms, examples include CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.
[021] When a group contains a substituent which may be hydrogen, eg R3, therefore, when this substituent is taken as hydrogen, it is recognized that this is equivalent to such a group which is not substituted. When a group of variables is shown optionally attached to a position, for example, [(Rv)r] where r can be 0, therefore, the hydrogen can be in the position even if it is not recited in the definition of the group of variables. When one or more positions in a group are said to be "unsubstituted" or "unsubstituted", therefore, the hydrogen atoms are attached to absorb any free valences.
[022] Unless otherwise indicated, a "ring" as a component of Formula 1 (eg, the Q substituent) is carbocyclic or heterocyclic. The term "ring member" refers to an atom or other moiety (for example, the C(=O), C(=S), S(O) or S(O)2) forming the backbone of a ring . The term "carbocyclic ring" indicates a ring or ring system in which the atoms forming the main chain of the ring are selected from carbon only. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a completely unsaturated carbocyclic ring satisfies Hückel's rule, therefore, that ring is also called an "aromatic ring". The term "saturated carbocyclic" refers to a ring with a main chain made up of carbon atoms linked together through single bonds; unless otherwise indicated, the remaining carbon valences are occupied by hydrogen atoms.
[023] The term "heterocyclic ring" refers to a ring in which at least one of the atoms forming the main chain of the ring is different from carbon, for example, nitrogen, oxygen or sulfur. Typically, a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 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 rule, therefore, that ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". Unless otherwise indicated, heterocyclic rings can be bonded through any available carbon or nitrogen by substituting a hydrogen for said carbon or nitrogen.
[024] The term "aromatic" indicates that each of the atoms in the ring is essentially in the same plane and has a p-orbital plane perpendicular to the plane of the ring and that (4n + 2) π electrons, where n is an integer positive, are associated with the ring to fulfill Hückel's rule. The term "aromatic carbocyclic ring system" indicates a carbocyclic ring system in which at least one ring of the ring system is aromatic. The term "aromatic heterocyclic ring system" indicates a heterocyclic ring system in which at least one ring of the ring system is aromatic. The term "non-aromatic ring system" indicates a carbocyclic or heterocyclic ring system that can be fully saturated as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term "non-aromatic carbocyclic ring system" wherein no ring in the ring system is aromatic. The term "non-aromatic heterocyclic ring system" indicates a heterocyclic ring system in which no ring in the ring system is aromatic.
[025] The term "optionally substituted" in relation to heterocyclic rings refers to groups that are unsubstituted or at least have a substituent other than hydrogen that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions apply unless otherwise noted. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted". Unless otherwise indicated, an optionally substituted group may contain a substituent at each substitution position of the group, and each substitution is independent of the other.
[026] When Q is the heterocyclic ring containing the 5- or 6-membered nitrogen, it may be attached to the remainder of Formula 1 via any available carbon or nitrogen ring atom, unless otherwise described . As noted above, Q may be (among others) phenyl optionally substituted with 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 with one to five substituents is the ring illustrated as U-1 in Exhibit 1, where Rv is R8 as defined in the Brief Description of the Invention for Q and r is an integer from 0 to 5.
[027] As noted above, Q may be (among others) the 5- or 6-membered heteroaromatic, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Short Description of Invention. Examples of a 5- or 6-membered unsaturated heteroaromatic ring optionally substituted with one or more substituents include rings U-2 to U-61 illustrated in Exhibit 1 where Rv is any substituent as defined in the Brief Description of the Invention for Q (ie, R9a or R9b) and r is an integer from 0 to 3, limited by the number of positions available in each U group. Since U-29, U-30, U-36, U-37, U -38, U-39, U-40, U-41, U-42 and U-43 only have one position available, for these U groups, r is limited to the integers 0 or 1 and r where 0 means the U group it is unsubstituted and a hydrogen is present at the position indicated by (Rv)r. SHOW 1



[028] When A is "C1-C4 alkyl substituted with Q", it is understood that Q is linked through a straight or branched alkyl moiety (i.e., the alkylene) with the remainder of Formula 1. The examples of A that are "Q-substituted C1-C4 alkyl" include -CH2Q, -CH2CH2Q and -CH2CH(CH3)Q. Note that when G, among others, is a 5- or 6-membered non-aromatic saturated or unsaturated heterocyclic ring optionally substituted with one or more substituents selected from the group of substituents as defined in the Brief Description of the Invention for G, one or two carbon ring members of the heterocycle optionally may be in the oxidized form of a carbonyl moiety.
[029] Examples of a 5- or 6-membered unsaturated or unsaturated heterocyclic ring (eg when G is a subset of "a 3- to 7-membered non-aromatic heterocyclic ring") containing ring members selected from of up to two O atoms and up to two S atoms, and optionally substituted on the carbon atom ring members by up to 3 substitutes, as defined in the Brief Description of the Invention, includes rings G-1 to G-35 as illustrated in Exhibit 2. Note that when the attachment point on the G group is shown as floating, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by substitution of a hydrogen atom. Optional substituents corresponding to Rv can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these G rings, r is usually an integer from 0 to 3, limited by the number of positions available in each G group.
[030] Note that when G comprises a ring selected from G-28 to G-35, G2 is selected from O, S or N. Note that when G2 is the N, the nitrogen atom can complete its valence by substitution with H or the substituents as defined in the Brief Description of the Invention. SHOW 2


[031] 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 reviews see the eight-volume set of Comprehensive Heterocyclic Chemistry, AR editors-in-chief Katritzky and CW Rees, Pergamon Press, Oxford, 1984 and the twelve-volume set of Comprehensive Heterocyclic Chemistry II, AR Katritzky, editors-in-chief CW Rees and EFV Scriven, Pergamon Press, Oxford, 1996.
[032] The compounds of the present invention may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the 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 single bonds where the rotation barrier is high enough to allow isolation of the isomeric species. A person skilled in the art will consider that a stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s) ). In addition, a person skilled in the art knows how to selectively separate, enrich and/or prepare said stereoisomers. The compounds of the present invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
[033] The compounds of Formula 1 normally 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 essentially represent a single crystal type and embodiments that represent a mixture of polymorphs (i.e., different crystal types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize into different crystalline forms, those forms with different arrangements and/or conformations of the molecules in the crystal structure. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bound in the structure. Polymorphs can differ in such chemical, physical and biological properties as crystal form, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendibility, dissolution rate and bioavailability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 may have beneficial effects (eg, suitability for preparing useful formulations, improved biological performance) over another polymorph or a mixture of polymorphs of the same represented compound by Formula 1. The preparation and isolation of a special 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.
[034] One skilled in the art will consider that not all nitrogen-containing heterocycles can form the N-oxides since nitrogen requires an available pair for oxidation to the oxide; a person skilled in the art will recognize the nitrogen-containing heterocycles that can form the N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are very well known to one 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, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. Such methods for the preparation of N-oxides are extensively described and reviewed in the literature, see, for example: T.L. Gilchrist in Comprehensive Organic Synthesis, volume 7, pages 748 to 750, S.V. Ley, ed., Pergamon Press; Tisler M. and B. Stanovnik in Comprehensive Heterocyclic Chemistry, volume 3, pages 18-20, A.J. Boulton and A. McKillop, Eds., Pergamon Press; M.R. Grimmett and B.R.T. Keene in Advances in Heterocyclic Chemistry, volume 43, pages 149 to 161, A.R. Katritzky, ed., Academic Press; Tisler M. and B. Stanovnik in Advances in Heterocyclic Chemistry, volume 9, pages 285 to 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, volume 22, pages 390 to 392, A.R. Katritzky and A.J. Boulton, Eds., Academic Press.
[035] A person skilled in the art recognizes that because 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. Accordingly, a wide variety of salts of the compounds of Formula 1 are useful for the control of invertebrate pests (i.e., they are agriculturally suitable). Salts of compounds of Formula 1 include acid addition salts with inorganic or organic acids, such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, acids, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric. Salts can also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or sodium, potassium, lithium, calcium, magnesium or barium amides, hydrides, hydroxides or carbonates. Accordingly, the present invention comprises the compounds selected from Formula 1, their N-oxides and agriculturally suitable salts.
[036] Embodiments of the present invention as described in the Brief Description of the Invention include (wherein Formula 1, as used, in the following embodiments, includes its N-oxides and salts):
[037] Embodiment 1. A compound of Formula 1 wherein A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl , C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C4-C8 cycloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-alkylthio , C2-C6 haloalkylthioalkyl, C3-C8 cycloalkylthioalkyl, C2-C6 alkylsulfonylalkyl or C2-C6 haloalkylsulfonylalkyl.
[038] Embodiment 2. A compound of Embodiment 1, wherein A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-cycloalkyl C6, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 alkoxyhaloalkyl.
[039] Embodiment 3. A compound of Embodiment 2, wherein A is C2-C8 alkyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 haloalkoxyalkyl.
[040] Embodiment 4. A compound of Formula 1 or any one of Embodiments 1 to 3, alone or in combination, wherein R1 is halogen, C1-C4 alkyl, or C1-C4 haloalkyl.
[041] Embodiment 5. A compound of Embodiment 4, where R1 is halogen or C1-C4 alkyl.
[042] Embodiment 6. A compound of Embodiment 5, where R1 is halogen or CH3.
[043] Embodiment 7. A compound of Embodiment 6, where R1 is halogen.
[044] Embodiment 8. A compound of Embodiment 7, where R1 is F, Cl, or Br.
[045] Embodiment 9. A compound of Formula 1 or any one of Embodiments 1 to 8, alone or in combination, wherein R2 is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl , C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy , C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or SOnR4.
[046] Embodiment 10. A compound of Embodiment 9, wherein R2 is halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[047] Embodiment 11. A compound of Embodiment 10, where R2 is halogen or cyano.
[048] Embodiment 12. A compound from Embodiment 11, where R2 is cyano.
[049] Embodiment 13. A compound of Embodiment 11, where R2 is halogen.
[050] Embodiment 14. A compound of Formula 1 or any one of Embodiments 1 to 13, alone or in combination, wherein R3 is H.
[051] Embodiment 15. A compound of Formula 1, wherein A is C3-C6 haloalkyl.
[052] Embodiment 16. A compound of Formula 1, wherein A is C4-C6 haloalkyl.
[053] Embodiment 17. A compound of Formula 1, wherein A is C4C5 haloalkyl.
[054] Embodiment 18. A compound of Formula 1, wherein A is CH2CH2CH2CF3.
[055] Embodiment 19. A compound of Formula 1, wherein A is CH2CH2CF2CF3.
[056] Embodiment 20. A compound of Formula 1, wherein A is CH2CH2CF3.
[057] Embodiment 21. A compound of Formula 1, wherein A is CH2CF3.
[058] Embodiment 22. A compound of Formula 1, wherein A is C4-C6 haloalkenyl.
[059] Embodiment 23. A compound of Formula 1, wherein A is other than C2-C6 alkylcarbonyl.
[060] Embodiment 24. A compound of Formula 1, wherein A is other than C2-C6 haloalkylcarbonyl.
[061] Embodiment 25. A compound of Formula 1, wherein A is other than C2-C6 alkylcarbonylalkyl or C2-C6 haloalkylcarbonylalkyl.
[062] Embodiment 26. A compound of Formula 1, wherein R1 is Cl.
[063] Embodiment 27. A compound of Formula 1, wherein R2 is F, Cl, Br or I.
[064] Embodiment 28. A compound of Formula 1, wherein R2 is Cl, Br or I.
[065] Embodiment 29. A compound of Formula 1, wherein R2 is F, Cl, Br, I, cyano, CH3 or CF3.
[066] Embodiment 30. A compound of Formula 1, wherein G is a non-aromatic 5- to 6-membered heterocyclic ring containing ring members selected from carbon, up to 4 heteroatoms selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, and up to 3 ring members selected from C(=O), C(=S) and S(=O)a(=NR6)b and substituted with up to 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.
[067] Embodiment 31. A compound of Formula 1, wherein A is different from G.
[068] Embodiment 32. A compound of Formula 1, wherein A is other than Q-substituted C1-C4 alkyl.
[069] Embodiment 33. A compound of Formula 1, wherein each R4 independently is C1-C3 alkyl or C1-C3 haloalkyl.
[070] Embodiment 34. A compound of Embodiment 33, where R4 is CH3, CH2CH3 or CH2CF3.
[071] Embodiment 35. A compound of Embodiment 34, where R4 is CH3 or CH2CH3.
[072] The embodiments of the present invention, including Embodiments 1 to 35 above as well as any other embodiments described herein, may be combined in any way and descriptions of variables in the embodiments pertain 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 35, as well as any other embodiments described herein, and any combinations thereof, pertain to the compositions and methods of the present invention.
[073] Combinations of Achievements 1 to 35 are illustrated by:
[074] Embodiment A. A compound of Formula 1, wherein - A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3 cycloalkyl -C6, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cycloalkoxyalkyl, C4-C8 cycloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2 alkylthio -C6, C2-C6 haloalkylthioalkyl, C3-C8 cycloalkylthioalkyl, C2-C6 alkylsulfonylalkyl or C2-C6 haloalkylsulfonylalkyl; - R1 is halogen, C1-C4 alkyl or C1-C4 haloalkyl; - R2 is halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or SOnR4; and - R3 is H.
[075] Embodiment B. A compound of Embodiment A, wherein - A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3 cycloalkyl -C6, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 alkoxyhaloalkyl; - R1 is halogen or C1-C4 alkyl; and - R2 is halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.
[076] Embodiment C. A compound of Embodiment B, wherein - A is C2-C8 alkyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 alkoxyhaloalkyl; - R1 is halogen; and - R2 is halogen or cyano.
[077] Specific embodiments include compounds of Formula 1 selected from the group consisting of: - 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine (Compound 13), - 3-[( 5-chloro-2-pyrimidinyl)oxy]-2-[[(2E)-4,4,4-trifluoro-2-buten-1-yl]oxy]benzonitrile (Compound 8) - 2-[3-bromo- 2-(2,2,3,3-tetrafluoropropoxy)phenoxy]-5-chloropyrimidine (Compound 18), - 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(2,2,3,3 ,3-pentafluoropropoxy)benzonitrile (Compound 10) - 2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile (Compound 35), - 3-[(5-chloro-2-pyrimidinyl)oxy] -2-(3,3,3-trifluoropropoxy)benzonitrile (Compound 23), - 3-[(5-fluoro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile (Compound 4) and - 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile (Compound 5).
[078] The present invention also relates to a method for the control of unwanted vegetation which comprises applying, at the locus of vegetation, herbicidally effective amounts of the compounds of the present invention (for example, as a composition described herein). Of interest as embodiments with respect to methods of use are those involving the compounds of the embodiments described above. The compounds of the present invention are especially useful for the selective control of weeds in cereal crops such as wheat, barley, corn, soybean, sunflower, cotton, rapeseed and rice, and special crops such as sugarcane crops. sugar, citrus fruits, fruits and nuts.
[079] Also worthy of interest as embodiments are the herbicidal compositions of the present invention, which comprise the compounds as described in the above embodiments.
[080] The present invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from ( b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics and (b5) 5-enol-pyruvylshikimate-3 inhibitors -phosphate synthase (EPSP), (b6) photosystem I electron deflectors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8), glutamine synthetase (GS) inhibitors, (b9) fatty acid elongase inhibitors of very long chain (VLCFA), (b10) auxin transport inhibitors, (b11), phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltranererase inhibitors (HST), (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including disruptions mitotic agents, organic arsenicals, asulam, bromobutide, cinmethylin, cumilurone, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, phosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxazichlorephone herbicide protective agents; and salts of compounds of (b1) to (b16).
[081] "Photosystem II inhibitors" (b1) are chemical compounds that bind to protein D-1 in the QB binding niche 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 dilation, membrane leakage, and ultimately, cell destruction. The QB binding niche has three different binding sites: the A binding site binds triazines such as atrazine, triazinenes such as hexazinone and uracils such as bromacil, the B binding site binds phenylureas such as diuone , and the C-binding site binds benzothiadiazoles such as bentazone, nitriles such as bromoxynil and phenyl pyridazines such as pyridate. Examples of photosystem II inhibitors include ametrine, amicarbazone, atrazine, bentazone, bromacil, bromophenoxim, bromoxynil, chlorbromurone, chloridazone, chlortolurone, chlorxuron, cumilurone, cyanazine, daimurone, desmedipham, dimethurine, ethphenurine, dimethuron , fluometurone, hexazinone, ioxynil, isoproturone, isourone, lenacil, linuron, metamitrone, metabenzthiazuron, methobromurone, methoxuron, metribuzin, monolinuron, neburone, pentanochlor, phenmedipham, prometon, promethurine, simethazine, pyrazine , tebutyuron, terbacil, terbumetone, terbuthylazine, terbutrin and triethazine.
[082] The "AHAS inhibitors" (b2) are the chemical compounds that inhibit the acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and therefore kill plants by inhibiting the production of amino acids branched-chain aliphatics, such as valine, leucine and isoleucine, which are necessary for DNA synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bemsulfuron-methyl, bispyribac-sodium, chloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, chinosulphuron, cyclosulfamuron, diclosulam, etametsulfuron-methylsulfuron, ethoxylamsulfuron, ethoxysulfurone, ethoxysulfurone flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, halosulfuron-methyl, imazametabenz-methyl, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including the sodium phenidouron-methyl (including the sodium phendourone), iodosulfuron-methyl [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro) -5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazol-5-sulfonamide) , metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium, propirisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amin o]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, -methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron , tribenuron-methyl, trifloxysulfuron (including the sodium salt), triflusulfuron-methyl and trithosulfuron.
[083] The "ACCase inhibitors" (b3) are chemical compounds that inhibit the enzyme acetyl-CoA carboxylase, which is responsible for catalyzing an initial step in the synthesis of lipids and fatty acids in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl-CoA carboxylase and the subsequent lack of lipid production lead to losses in cell membrane integrity, especially in regions of active growth, such as meristems. Eventually, sprouts and rhizome growth ceases, and the sprouts and rhizome bud meristems begin to die. Examples of ACCase inhibitors include aloxidim, butroxydim, clethodim, clodinafop, cyclooxydim, cyhalophop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydime such as resolved and tralkoxydim, fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.
[084] Auxin is a plant hormone that regulates growth in many plant tissues. “Auxin mimics” (b4) are chemical compounds that mimic the plant growth hormone of auxin, therefore causing uncontrolled and disorganized growth leading to plant death in sensitive species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid benazoline acetate, chloramben, claciphos, clmeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-acid) methoxyphenyl)-2-pyridinecarboxylate), methyl (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate methyl halauxfen-methyl), 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 .
[085] The “EPSP inhibitors (b5) are the chemical compounds that inhibit the enzyme, 5-enol-pyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. Herbicide EPSP inhibitors are easily absorbed through 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 ammonium esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively called sulfosate).
[086] The “electron Photosystem I diverters” (b6) are the chemical compounds that accept the electrons from Photosystem I and then several cycles generate the hydroxyl radicals. These radicals are extremely reactive and quickly destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys the integrity of the cell membrane so that the cells and organelles “leak out”, causing the leaf to wilt rapidly and desiccate, and eventually plant death. Examples of this second type of photosynthesis inhibitor include paraquat and diquat.
[087] "PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, resulting in the rapid formation of highly reactive compounds in plants that disrupt cell membranes, causing cell fluids to leak. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butaphenacyl, carfentrazone, carfentrazone-ethyl, clomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazine-ethyl-fluoroglycophene methyl, flumipropene, halosaphen, lactofen, oxadiargyl, oxadiazone, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, tidiazimine, (dihydro-1,5-dimeyl-6-thioxo-3-[2,2, 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) of trifludimoxazine and (N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1( thiaphenacyl 2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).
[088] “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 reduces glutamine levels. 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, ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) glufosinate-P, and bilanaphos.
[089] "VLCFA enlargement 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 vegetables, very long chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation on the leaf surface and provide stability to pollen grains.These herbicides include acetochlor, alachlor, anilophos, butachlor, cafenstrol, dimethachlor , dimethenamid, diphenamide, phenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanophane, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamid-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), petoxamide, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone and ethyl chloride, including resolved forms such as S-methol achlor and chloroacetamides and oxyacetamides.
[090] "Auxin transport inhibitors" (b10) are chemical substances that inhibit the transport of auxin in vegetables, such as through binding with an auxin transporting protein. Examples of auxin transport inhibitors include naptalam (also known as N-(1-naphthyl)phthalomic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).
[091] The “PDS (phytoene desaturase inhibitors) (b11) are the chemical compounds that inhibit the carotenoid biosynthesis pathway in the phytoene desaturase step. Examples of PDS inhibitors include beflubutamide, diflufenican, fluridone, flurochloridone, norflurzone, flurtamone and picolinafen.
[092] "HPPD Inhibitors" (b12) are chemical substances that inhibit the biosynthesis of 4-hydroxyphenyl-pyruvate dioxygenase synthesis. Examples of HPPD inhibitors include benzobicyclone, 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, pyrazoxifene, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl methyl carbonate] -4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl), 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-triazin-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-(methylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.
[093] "HST inhibitors" (b13) unbalance the plant's ability to convert the homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. HST include haloxidine, pyrichlor, 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.
[094] HST inhibitors also include the 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; and Rd6 is OH, or OC(=O)-i-Pr; and 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, or CH2CHF2 C CH; Re7 is OH, OC(=O)Et, OC(=O)-i-Pr or OC(=O)-t-Bu; and Ae8 is N or CH.
[095] Cellulose biosynthesis inhibitors (b14) inhibit cellulose biosynthesis in certain vegetables. They are most effective when using pre-application and early post-application on young or fast-growing vegetables. Examples of inhibitors of cellulose biosynthesis include chlortiamid, 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.
[096] Other herbicides (b15) include herbicides that act through a variety of different modes of action, such as mitotic disruptors (eg flamprop-M-methyl and flamprop-M-isopropyl) organic arsenicals (eg , DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, isoprenoid synthesis inhibitors, and cell wall chloroplast biosynthesis inhibitors. Other herbicides include herbicides with unknown modes of action that either 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 aclonifene, asulam, amitrol, bromobutide, cinmethylin, clomazone, cumilurone, cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), daimuron, difenzoquat , etobenzanid, fluometurone, flurenol, phosamine, phosamine-ammonium, dazometh, dymrone, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1- methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymrone, oleic acid, oxaziclomephone, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl ]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.
[097] “Herbicide protection agents” (b16) are substances added to a herbicide formulation to eliminate or reduce the phytotoxic effects of the herbicide on certain crops. These compounds protect crops from damage by herbicides, but usually do not prevent the herbicide from controlling unwanted vegetation. Examples of herbicide protecting agents include, but are not limited to, benoxacor, cloquintocet-mexyl, cumilurone, ciomethrinil, cyprosulfamide, daimuron, dichlormid, dicyclonone, dietolate, dimepiperate, fenchlorazol-ethyl, phenchlorim, flurazole, flurazol, fluxfen -ethyl, mefenpyr-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.
[098] One embodiment of the present invention is a herbicidal mixture comprising (a) a compound of Formula 1, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) inhibitors acetohydroxy acid synthase (AHAS) (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate synthase (EPSP) inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8), inhibitors of glutamine synthetase (GS), (b9) inhibitors of very long chain fatty acid elongase (VLCFA) and (b12) inhibitors of 4-hydroxyphenyl-pyruvate dioxygenase (HPPD).
[099] The compounds of Formula 1 can be prepared by the general methods known in the state of the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1 to 7 can be used to prepare the compounds of Formula 1. The definitions of A, R 1 and R 2 in the compounds of Formulas 1 to 12 below are as defined above in Brief Description of the Invention, unless otherwise indicated.
[0100] As shown in Scheme 1, a compound of Formula 1 (where R3 is H) can be prepared by nucleophilic substitution, by heating a phenolic intermediate of Formula 2 in a suitable solvent, such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide, in the presence of a base, such as potassium or cesium carbonate, with a compound of Formula 3 (where LG is a nucleophilic reaction leaving group, i.e., nucleofuge, such as halogen or S(O)2CH3). The reaction is normally conducted at temperatures ranging from 50 to 110°C.

[0101] As shown in Scheme 2, compounds of Formula 1 can be prepared by nucleophilic displacement on an alkylating agent with a phenol of Formula 4 in the presence of a suitable acid receptor. Suitable acid receptors include, but are not limited to, sodium hydride, potassium t-butoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide. Suitable solvents include acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide. The reaction is normally conducted at temperatures ranging from 0 to 110°C. SCHEME 2
LG is halogen or S(O)2CH3
[0102] As shown in Scheme 3, compounds of Formula 1 can also be prepared through the Mitsunobu reaction of alcohols of Formula 6 with phenols of Formula 4. This reaction is well known in the prior art and requires the presence of a diazodicarboxylate and a phosphine. Diethyl (DEAD) and diisopropylazodicarboxylate (DIAD) are especially useful reagents in this process. Triphenylphosphine is an especially useful phosphine. The reaction can be carried out in various solvents with tetrahydrofuran being especially useful. The reaction can be carried out at temperatures from 0 to 100°C. A helpful review of this reaction is found in Hughes, Organic Reactions 1992, 42: 335-656. SCHEME 3

[0103] Compounds of Formula 4 can be prepared by dealkylating compounds of Formula 7 with a dealkylating reagent as shown in Scheme 4. A suitable deprotecting agent such as BBr3, AlCl3, Me3SiI and HBr in acid acetic can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature ranging from -80 to 120°C. Other useful phenolic protecting groups suitable for use in the preparation of a compound of Formula 4 can be found in Greene, TW; Wuts, PGM Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, New Jersey, 2012). SCHEME 4

[0104] Compounds of Formula 4 can also be prepared by reacting compounds of Formula 8 with compounds of Formula 3 in the presence of an acid receptor, as shown in Scheme 5. Compound of Formula 4 can be prepared by substitution nucleophilic by heating a catechol intermediate of Formula 8 in a suitable solvent, such as acetone, acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide, in the presence of a base, such as potassium or cesium carbonate, with a compound of Formula 3 (where LG is a nucleophilic reaction leaving group such as halogen or S(O)2CH3). The reaction is normally conducted at temperatures ranging from 50 to 110°C. In cases where mixtures of regioisomeric products are formed, they can be used directly under the conditions of Schemes 2 and 3 and the compounds of Formula 1 can be isolated in pure form by separation techniques known to those skilled in the art such as chromatography and crystallization. SCHEME 5

[0105] Compounds of Formula 9 (where R 2 is an electron withdrawing group) can be prepared by selectively methylating compounds of Formula 8 with a methylating agent of Formula 9 in the presence of an acid acceptor, as shown in Scheme 6. Suitable methylating reagents include methyl iodide, methyl bromide, dimethyl sulfate and methyl triflate. Suitable acid receptors include, but are not limited to, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide and potassium hydroxide. Suitable solvents include acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide. The reaction is normally conducted at temperatures ranging from 0 to 50°C. SCHEME 6
where R2 is an electron withdrawing group
[0106] The compounds of Formula 8, in general, are known in the state of the art or are commercially available. They can also be prepared via the sequence outlined in Scheme 7 by ortholithography of the acetonide compound of Formula 11 and further reacting with an electrophile to introduce the R2 substituent. Examples of electrophilic reagents and the R2 groups they introduce are Br2 (R2 is Br), BrCF2CF2Br (R2 is Br), N,N-dimethylformamide (R2 is CHO), N,N-dimethylacetamide (R2 is COCH3), Cl3CCCl3 (R2 is Cl), CO2 (R2 is CO2H), ClCO2CH2CH3 (R2 is CO2CH2CH3) and CH3SSCH3 (R2 is SCH3). The acetonide of Formula 12 can be deprotected under acidic conditions through the use of reagents such as hydrochloric acid or trifluoroacetic acid in solvents such as dichloromethane, ether, water, methanol or ethanol. Conditions and reagents for Journal of Chemical Research, Synopses, (12), 500-501; 1994. SCHEME 7

[0107] It is recognized by one skilled in the art 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, 2nd Ed., Wiley-VCH, New York, 1999. For example, intermediates for preparing compounds of Formula 1 may contain aromatic nitro groups, which may be reduced to amino and , then be converted through reactions well known in the prior art, such as the Sandmeyer reaction, to various halides, giving the compounds of Formula 1. The above reactions, in many cases, can also be carried out in an alternative order
[0108] 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 such cases, the incorporation of protection/deprotection sequences or functional group interconversions in the synthesis will help to obtain the desired products. The use and selection of protecting groups will be apparent to one skilled in the art in chemical synthesis (see, for example, Greene, TW; Wuts, PG Protective Groups M. in Organic Synthesis, 2nd ed.; Wiley: New York, 1991) . One skilled in the art will recognize that, in some cases, after the introduction of a particular reagent, as described in any individual scheme, it may be necessary to carry out additional routine synthetic steps, not described in detail, to complete the synthesis of compounds from Formula 1. One skilled in the art will also recognize that it may be necessary to carry out a combination of the steps illustrated in the above schemes in a different order than implied by the special shown to prepare the compounds of Formula 1.
[0109] One skilled in the art will also recognize that the compounds of Formula 1 and the intermediates described herein may be subjected to various organometallic, electrophilic, nucleophilic, radical reduction and oxidation reactions to add substituents or modify existing substituents.
[0110] Without further elaboration, it is believed that a technician on the subject, using the previous description, can use the present invention to its fullest extent. The following Examples, therefore, may be interpreted as illustrative only, and not limiting the description in any way. The steps in the following Examples illustrate a procedure for each step in a general synthetic transformation, and the starting material for each step may not necessarily have been prepared by a special preparative operation whose procedure is described in other Steps and Examples. Percentages are by weight, except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages of chromatographic solvent mixtures are by volume, unless otherwise indicated. 1H NMR spectra are reported in ppm from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets, "dt" means doublet of triplets and "br s" means wide singlet. Mass spectra (MS) are reported as the molecular weight of the largest parent ion of isotopic abundance (M+1) formed by the addition of H+ (molecular weight of 1) to the molecule, or (M-1) formed by the loss of H+ (molecular weight of 1) of the molecule, observed using liquid chromatography coupled to a mass spectrometer (LCMS) using atmospheric pressure chemical ionization (AP+) where "amu" represents the unified atomic mass units. EXAMPLE 1 - Preparation of 2-Butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile (Compound 35) STEP A - Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2- methoxybenzonitrile
[0111] 3-hydroxy-2-methoxybenzonitrile (730 mg, 4.9 mmol) and 2,5-dichloropyrimidine (803 mg, 5.4 mmol) were combined in acetonitrile (10 mL) under a nitrogen atmosphere. Powdered potassium carbonate (1.48 g, 10.7 mmol) was added and the resulting mixture was heated at 80°C for 1 hour. The reaction mixture was cooled and concentrated under reduced pressure. The residue was purified by medium pressure liquid chromatography on silica gel eluting with 0 to 20% ethyl acetate in hexanes to give the title compound (1 g).
[0112] MS (AP+) 262 amu (M+1). STEP B - Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2-hydroxybenzonitrile
[0113] 3-[(5-chloro-2-pyrimidinyl)oxy]-2-methoxybenzonitrile (i.e. the product from Step A) (1.00 g, 3.82 mmol) was dissolved in dichloromethane (5 mL ) and cooled to 0°C. Then boron tribromide was added (1M in dichloromethane, 19.1 ml, 19.1 mmol) and the mixture was stirred at room temperature for 3 hours. The reaction mixture was treated with a saturated aqueous solution of sodium hydrogencarbonate at 0°C. The aqueous phase was separated and extracted with dichloromethane. The combined organic phases were washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was used in the next step without further purification.
[0114] MS (AP+) 246 amu (M-1). STEP C - Preparation of 2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile
[0115] À 3-[(5-chloro-2-pyrimidinyl)oxy]-2-hydroxybenzonitrile (ie the product of Step B) 100 mg, 0.4 mmol) and potassium carbonate (170 mg, 1, 2 mmol) in acetonitrile (2 mL) was added the 1-bromobutane (60 mg, 0.44 mmol). The mixture was refluxed for 4 hours. The reaction mixture was partitioned between water (20ml) and ethyl acetate (20ml). The aqueous phase was washed with ethyl acetate (2 x 10 ml). The combined organic phases were washed with brine (20 ml), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by medium pressure liquid chromatography on silica gel (12 g) eluting with a gradient of 0 to 30% ethyl acetate in hexanes to give the title compound, a compound of the present invention, (90 mg).
[0116] 1H NMR (400 MHz, CDCl3) δ 8.49 (s, 2H), 7.51 (d, 1H), 7.41 (d, 1H), 7.19 t, 1H), 4.17 (t, 1H), 1.60 (m, 2H) 1.31 (m, 2H), 0.87 (t, 3H). EXAMPLE 2 - Preparation of 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine (Compound 13) STEP A - Preparation of 2-[3-bromo-2-(methoxy)phenoxy]-5-chloropyrimidine
[0117] 3-Bromo-2-methoxyphenol (5.0 g, 24 mmol) was dissolved in 50 mL of acetonitrile and treated with potassium carbonate (8.5 g, 61 mmol) and 2,5-dichloropyrimidine ( 4.0 g, 27 mmol). The mixture was heated at 80°C for 4 hours. The mixture was cooled and partitioned between water (50ml) and ethyl acetate (50ml). The aqueous phase was extracted with ethyl acetate (50 ml). The combined organic phases were washed with brine (30 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on 80 g of silica gel eluting with 10% ethyl acetate in hexanes to give the title compound as an oil (8.3 g).
[0118] 1H NMR (400 MHz, CDCl 3 ) δ 8.48 (s, 2H), 7.43 (d, 1H), 7.19 (d, 1H), 3.80 (s, 3H). STEP B - Preparation of 2-[3-bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine
[0119] 2-[3-Bromo-2-(methoxy)phenoxy]-5-chloropyrimidine (i.e. step A product) (4.0 g, 12 mmol) was stirred in dichloromethane (60 mL) and cooled with an ice bath. Boron tribromide was added (1M in dichloromethane, 23ml, 23mmol). The cooling bath was removed and the mixture was stirred at 23°C for 14 hours. The mixture was poured into ice water (80 ml). The phases were separated and the aqueous phase was extracted (2x40ml) with dichloromethane. The combined organic phases were dried over magnesium sulphate and concentrated under reduced pressure. The residue was triturated with a mixture of hexanes and diethyl ether (10 to 1.30ml) to give the title compound as a white solid (2.83g).
[0120] 1H NMR (400 MHz, CDCl 3 ) δ 8.50 (s, 2H), 7.41 (d, 1H), 7.17 (d, 1H), 6.88 (t, 1H), 5. 84 (s, 1H). STEP C - Preparation of 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine
[0121] 2-[3-Bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine (ie the product from step B) (0.2 g, 0.66 mmol) was dissolved in acetonitrile (4 mL) ) and treated with potassium carbonate (0.28 g, 1.99 mmol) and 4-bromobutane (0.10 g, 0.73 mmol). The mixture was heated to 70°C for 2 hours and stirred at 23°C for 14 hours. The mixture was poured into water (15ml) and extracted twice with ethyl acetate (10ml). The combined organic phases were washed with brine (10 ml), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (12 g) eluting with a gradient of 0 to 30% ethyl acetate in hexanes to give the title compound, a compound of the present invention, as an oil (140 mg) .
[0122] 1H NMR (400 MHz, CDCl3) δ 8.48 (s, 2H), 7.43 (d, 1H), 7.16 (d, 1H), 7.03 (t, 1H), 3, 99 (t, 2H), 1.59 (m, 2H), 1.31 (m, 2H), 0.87 (t, 3H). EXAMPLE 3 - Preparation of 2-[3-bromo-2-(2,2,3,3,4,4,4-heptafluorobutoxy)phenoxy]-5-chloropyrimidine (Compound 52) STEP A - Preparation of 2-[3 -bromo-2-(2,2,3,3,4,4,4-heptafluorobutoxy)phenoxy]-5-chloropyrimidine
[0123] 2-[3-Bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine (i.e. the product obtained in Example 2, Step B) (0.1 g, 0.332 mmol) was dissolved in 2 mL of acetonitrile under nitrogen atmosphere. Powdered potassium carbonate (0.14 g, 0.995 mmol) was added followed by 2,2,3,3,4,4,4-heptafluoro-1-iodobutane (0.12 g, 0.365 mmol). The resulting reaction mixture was heated at 70°C for 4 h, then warmed to room temperature for 16 h. 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethane sulfonate was added (0.12 g, 0.361 mmol) and heated at 50°C for 2 hours and cooled to room temperature. The mixture was diluted with deionized water and ethyl acetate. The organic layer was decanted and the aqueous layer was extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over magnesium sulfate and concentrated. The resulting oil was purified via silica gel column chromatography eluting with a gradient of hexanes to 25% ethyl acetate in hexanes to isolate the title compound as an oil (45 mg). MS. (ES+) = 483.3 (Br, Cl standard).
[0124] By the procedures described herein, together with the methods known in the state of the art, the following compounds of Tables 1 to 103 can be prepared. The following abbreviations are used in the following Tables: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, i-Pr means isopropyl, Bu means butyl, c-Pr means cyclopropyl, c-Bu means cyclobutyl, Ph stands for phenyl, OMe for methoxy, OEt for ethoxy, SMe for methylthio, SEt for ethylthio, NHMe for methylamino and CN for cyano.

[0125] R1 = Cl, R2 = Br and R3 = H




[0126] The present invention also includes Tables 2 to 103. Each Table is constructed in the same manner as Table 1 above, except that the row title in Table 1 (ie, "R1 = Cl, R2 = Br e R3 = H") is replaced by the respective line title shown below. For example, the first entry in Table 2 is a compound of Formula 1, where R1 = Cl, R2 = Cl, R3 = H and A is n-butyl. Tables 3 through 103 are constructed in a similar way.





[0127] A compound of the present invention, in general, will be used as a herbicide active ingredient in a composition, that is, the formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and diluents liquids, which serve as a vehicle. The formulation or composition ingredients 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.
[0128] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and/or suspension-emulsions) and the like, which optionally may be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspension-emulsion. The general types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrate and oil dispersion.
[0129] The general types of solid compositions include dusts, powders, granules, pellets, pearls, pellets, tablets, filled films (including seed coatings) and the like, which can be dispersible in water ("wettables" ”) or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of the active ingredient can be encapsulated (or “coated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granulate combines the advantages of an emulsifiable concentrate formulation and a dry granulated formulation. High strength compositions are primarily used as intermediates for further formulation.
[0130] Sprayable formulations are normally supplied in a suitable medium prior to spraying. Such solid and liquid formulations are formulated to be easily diluted in the spray medium, generally water, but occasionally another suitable medium, such as an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to about thousands of liters per hectare, but typically range from about ten to about several hundred liters per hectare. Sprayable formulations can be tank mixed with water or other suitable medium for foliar treatment through aerial or land application, or to the vegetable growing medium. Liquid or dry formulations can be directly measured in dip irrigation systems or measured in furrows during planting.
[0131] The formulations will normally contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which total 100% by weight.

[0132] Solid diluents, for example, include clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (for example, lactose, 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 Carries, 2nd Ed., Dorland Books, Caldwell, New Jersey.
[0133] Liquid diluents, for example, include water, N,N-dimethylalkanamides (eg N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (eg N-methylpyrrolidone), alkyl phosphates (eg triethyl phosphate), ethylene glycol, triethylene glycol, polypropylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (eg white mineral oils, normal paraffin, isoparaffins ), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, aromatic hydrocarbons, aliphatic dearomatizers, 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, diba esters sodium, alkyl and aryl benzoates 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-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as vegetable seeds and fruit oils (eg, olive, castor, flax, sesame, corn (millet) oils , peanuts, sunflowers, grape seed, saffron, cottonseed, soybeans, rapeseed, coconut and palm kernels), animal source fats (eg beef tallow, pork tallow, lard, oil of cod liver, fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (eg, methylated, ethylated, butylated) where the fatty acids can be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified through distillation . Liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
[0134] The solid and liquid compositions of the present invention, in general, include one or more surfactants. When added to a liquid, surfactants (also known as “surfactants”), in general, modify, in most cases, reducing 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 foaming agents.
[0135] Surfactants can be classified as non-ionic, anionic or cationic. Nonionic surfactants useful for the present composition include, but are not limited to alkoxylated alcohol, such as alkoxylated alcohol based on natural and synthetic alcohols (which may be branched or linear) 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 soy, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, 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 fatty esters and oils; 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 derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyl PEG resins (polyethylene glycol), graft or comb type polymers and star type polymers; polyethylene glycols (PEGs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
[0136] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated or ethoxylated alkylphenol alcohol; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; 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-alkyltaurates; benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzene sulfonates; condensed naphthalene sulfonates; naphthalene and alkyl naphthalene sulfonates; fractionated petroleum sulfonates; sulfosuccinamates; and sulfosuccinates and derivatives thereof, such as the dialkyl sulfosuccinate salts.
[0137] 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 oxide.
[0138] Also useful for the present composition are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants and their recommended uses are described in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's 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, 7th edition, John Wiley and Sons, New York, 1987.
[0139] The compositions of the present invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation auxiliaries (some of which can be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation aids and additives can control: pH (buffers), foaming during processing (antifoams such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in a container (antimicrobials) ), freezing product (antifreeze), color (dyes / pigment dispersions), washing (film formers or adhesives), evaporation (evaporation retardants) and other formulation attributes. Film formers, for example, include polyvinyl acetates, polyvinyl acetate copolymers, vinyl acetate copolymer-polyvinylpyrrolidone, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT publication WO 2003/024222.
[0140] The compounds of Formula 1 and other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by just mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is immiscible in water, an emulsifier is usually added to emulsify the solvent containing the active on dilution in water. Active ingredient slurries with particle diameters up to 2000 µm can be wet milled using media mills to obtain particles with average diameters less than 3 µm. Aqueous sludges can be manufactured into finished suspension concentrates (see, for example, US patent 3,060,084) or further processed in drying by spraying 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 dusts can be prepared by mixing and generally grinding (such as in a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active material onto preformed granular vehicles or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pages 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 et seq., and the publication WO 1991/13546. Pellets can be prepared as described in US patent 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in US Patents 4,144,050, US 3,920,442 and DE 3,246,493. Tablets 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.
[0141] For more information regarding the formulation technique, see TS Woods, The Formulator's Toolbox - Product Forms for Modern Agriculture in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and TR Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pages 120-133. See also US Patent 3,235,361, column 6, line 16 through column 7, line 19 and Examples 10 to 41; US patent 3,309,192 from column 5, line 43 to column 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, from 138 to 140, from 162 to 164 , 166, 167 and from 169 to 182; US patent 2,891,855, column 3, line 66 to column 5, line 17 and Examples 1 to 4; Klingman, Weed Controls as Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96; and Hance et al., Weed control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.
[0142] In the following Examples, all formulations are prepared in conventional ways. Compound numbers refer to the compounds in Index Tables A. Without further elaboration, it is believed that one skilled in the art using the foregoing description can utilize the present invention to its fullest extent. The following Examples, therefore, are illustrative but not limiting of the present invention in any way. Percentages are by weight unless otherwise noted. EXAMPLE A
EXAMPLE B
EXAMPLE C
EXAMPLE D

EXAMPLE E
EXAMPLE F
EXAMPLE G
EXAMPLE H
EXAMPLE I

[0143] The present invention also includes Examples A to I above, except that "Compound 4" is replaced by "Compound 2", "Compound 3", "Compound 5", "Compound 6", "Compound 7" , "Compound 8", "Compound 9", "Compound 10", "Compound 11", "Compound 12", "Compound 13", "Compound 14", "Compound 15", "Compound 16", "Compound 17" , "Compound 18", "Compound 19", "Compound 20", "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", "Compound 39", "Compound 40", "Compound 41", "Compound 42", "Compound 43", "Compound 44", "Compound 45", "Compound 46", "Compound 47" , "Compound 48", "Compound 49", "Compound 50", "Compound 51", "Compound 52", "Compound 53", "Compound 54", "Compound 55", "Compound 56", "Compound 57" , “Compound 58”, “Compound 59”, “Compound 60”, “Compound 61”, “Compost o 62", "Compound 63", "Compound 64", "Compound 65", "Compound 66", "Compound 67", "Compound 68", "Compound 69", "Compound 70", "Compound 71", " Composite 72”, “Compound 73”, “Compound 74”, “Compound 75”, “Compound 76”, “Compound 77” or “Compound 78”.
[0144] The test results indicate that the compounds of the present invention are highly active pre-emergence and/or post-emergent herbicides and/or plant growth regulators. The compounds of the present invention, in general, show high activity for early post-emergence weed control (i.e., applied after weed seedlings emerge from the soil) and pre-emergence weed control. -emergence (ie, applied before the weed seedlings emerge from the ground). Many of them have utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, car parks, parking in theaters, airfields, riverbanks, irrigation and other waterways, around billboards and road and railway structures. Many of the compounds of the present invention, due to selective metabolism in crops versus weeds, or due to selective activity at the physiological inhibition locus of crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for selective control of grassy and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can be readily determined by performing routine biological and/or biochemical analyses. The compounds of the present invention can show tolerance to agronomic crops, including, among others, alfalfa, barley, cotton, wheat, rapeseed, sugar beet, corn (millet), sorghum, soybean, rice, oats, peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, palm kernel oil, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea and forests such as eucalyptus and conifers (eg loblolly pine) and turfgrass species (eg Kentucky blue grass, St. Augustine grass, Kentucky fescue and bermuda grass). The compounds of the present invention can be used in genetically transformed crops or bred to incorporate herbicide resistance, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will find that not all compounds are equally effective against all weeds. Alternatively, the compounds in question are useful for modifying plant growth.
[0145] Since the compounds of the present invention have pre-emergence and post-emergence activity, for the control of unwanted vegetation, killing or harming the vegetation or reducing its growth, the compounds can be usefully applied through a variety of methods which involve contacting an herbicidal effective amount of a compound of the present invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to foliage or otherwise. part of the unwanted vegetation or to the vegetation environment or to the unwanted vegetation environment, such as soil or water, in which the unwanted vegetation is growing or which surrounds the seed or other propagule of the unwanted vegetation.
[0146] An herbicide-effective amount of the compounds of the present invention is determined by a number of factors. These factors include: the selected formulation, method of application, amount and type of vegetation present, growing conditions, and so on. In general, an herbicidal effective amount of the compounds of the present invention is from about 0.001 to 20 kg/ha with a range preferably from about 0.004 to 1 kg/ha. A person skilled in the art can easily determine the herbicide-effective amount needed for the desired level of weed control.
[0147] In a common embodiment, a compound of the present invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (eg, crops) and unwanted vegetation (ie, weeds), both which can be seeds, seedlings and/or larger plants, in contact with a growing medium (eg soil). At this location, a composition comprising a compound of the present invention can be applied directly to a vegetable or a part thereof, especially unwanted vegetation, and/or to the growing medium in contact with the vegetable.
[0148] The varieties and cultivars of the desired vegetables in the locus treated with a compound of the present invention can be obtained through conventional methods of propagation and reproduction or through the methods of genetic engineering. Genetically modified vegetables (transgenic vegetables) are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant. A transgene that is defined by its special location in the plant genome is called a transgenic transformation or event.
[0149] Cultivars of genetically modified plants 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 and the like ) or abiotic stresses (aridity, cold temperature, soil salinity, and the like), or that contain other desired characteristics. Vegetables can be genetically modified to present aspects, for example, of herbicide tolerance, insect resistance, modified oil profiles or aridity tolerance. Useful genetically modified vegetables that contain the individual genetic transformation events or combinations of transformation events are listed in Display C. Additional information for the genetic modifications listed in Display C can be obtained from publicly available databases maintained, for example , by the US Department of Agriculture.
[0150] The following abbreviations, T1 through T37, are used in View C aspects. A "-" means the entry is not available; "Tol" means "tolerance" and "res" means resistance.


















[0152] Although most commonly, the compounds of the present invention are used for the control of unwanted vegetation, the contact of the desired vegetation at the treated site with the compounds of the present invention can result in superadditive or synergistic effects with the genetic aspects in the desired vegetation, including aspects incorporated through genetic modification. For example, resistance to phytophagic insect pests or plant diseases, tolerance to biotic/abiotic stress or storage stability may be greater than expected from genetic aspects in the desired vegetation.
[0153] One embodiment of the present invention is a method for controlling the growth of unwanted vegetation in genetically modified plants that exhibit the aspects of glyphosate tolerance, glufosinate tolerance, ALS herbicide tolerance, dicamba tolerance, herbicide tolerance of imidazolinone, 2,4-D tolerance, HPPD tolerance, and mesotrione tolerance, which comprises contacting vegetation or its environment with an herbicide-effective amount of a compound of Formula 1.
[0154] The compounds of the present invention can also be mixed with one or more other compounds or biologically active agents, including herbicides, herbicide protection agents, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators, such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feed stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form a multi-component pesticide providing a still spectrum broader range of agricultural protection. Mixtures of the compounds of the present invention with other herbicides can broaden the spectrum of activity against additional weed species and suppress the proliferation of any resistant biotypes. Therefore, the present invention also relates to a composition comprising a compound of Formula 1 (in an herbicidal effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated into compositions that comprise at least one of a surfactant, solid or liquid diluent. For the mixtures of the present invention, one or more other compounds or biologically active agents can be formulated together with a compound of Formula 1 to form a premix, or one or more other compounds or biologically active agents can be formulated separately to from the compound of Formula 1, and the combined formulations prior to application (eg in a spray tank) or, alternatively, applied in succession.
[0155] A mixture of one or more of the following herbicides with a compound of the present invention can be especially useful for the control of weeds: acetochlor, acifluorfen and its sodium salts, aclonifen, acrolein (2-propenal), alachlor, aloxidim, ametrine, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (eg, methyl, ethyl) and its salts (eg, sodium, potassium), aminopyralid, amitrol, ammonium sulfamate, anilophos, asulam, atrazine, azimsulfuone , beflubutamide, benazoline, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bemsulfuron-methyl,bensulide, bentazone, benzobicyclone, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromophenidam, bromacyl,obutanex bromoxynil, butachlor, butaphenacyl, butamiphos, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone-ethyl, catechin, chlormethoxyphene, chloramben, chlorbromurone, chlorflurenol-methyl, chloride zone, chlorimuron ethyl, chlorotoluron, chlorpropam, chlorsulfuron, chlorthal-dimethyl, chlorthiamide, cinidon-ethyl, cinmethylin, cynosulfuron, claciphos, clefoxidim, clethodim, clodinafop-propargyl, clomazone, clomethalid-sulpham, clomethalid-o-pyrilamine cyanazine, cycloate, cyclosulfamuron, cyclooxydim, cyhalofop-butyl, 2,4-D and its butothyl, butyl, isooctyl 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, desmethrin, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat methylsulfate, diflufenican, diflufenzopyr, dimefur dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-p, dimethypine, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamide, diquat dibromide, dithiopyr, diuron, DNOC , endothal, EPTC, esprocarb, ethalfluralin, etamethsulfuron-methyl, ethiozine, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfuron, phenquinotrione, fenpropron-A, fenuron -M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, fluketosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetmiosulam, flumiclorac-pentil , fluoroglycofen acetate, flupoxam, flupyrsulfuron-methyl and its sodium salts, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluoroglycofen-ethyl, fomesafen, foramsulfuron, fosamine ammonium, glufosinate-glufosinate, glufosinate salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively called sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl a, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazametabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, flammoxy-methylsulfuron, indanophane, in ioxynil octanoate, sodium ioxynil, ipfencarbazone, isoproturone, isouron, isoxaben, isoxaflutol, isoxachlortol, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (eg, MCPA-dimethylammonium, 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-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, sodium metam, metamifop, metamitrone, metazachlor, metazosulfuron, metabenzthiazuron, methiozoline, methylarsonic acid and its salts of calcium, monoammonium, methyl and benzurosodium , methobromurone, me tolachlor, S-metolachlor, metosulam, methoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamid-M, naptalam, neburone, nicosulfuron, norflurazone, orbencarb, orthosulfamuron, oxauroxa, oxauroxa, orizaline oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, petoxiamid, phenmedipham, picloram, picloram-potassium, picolinaphene, pinoxaden, prosulfoxazone, promethodiamine, premethylamine , promethrin, propachlor, propanil, propaquizafop, propazine, profam, propisochlor, propoxycarbazone, propizamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazolinate, pyrazoxifene, pyrazolibromide, pyrazolibromide -methyl, pyrimisulfan, pyritiobac, pyritiobac-sodium, pyroxasulfan, piroxsulam, quinclorac, quinmerac, quinocamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuril, rimssulfuron, saflufenacil, sethoxydim, sidurone, simazine, simethrin, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2, 6, sulfosulfuron TCA, Sodium TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, tenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, thiaphenacyl, toprathioprathiocarbazil, triasulfuron, triaziflam, tribenuron-methyl, trichlopyr, triclopyr-butothyl, triclopyr-triethylammonium, tridiphane, triethazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron-methyl, trifloxysulfuron, vernolate, 3-(2-difluoro-phenyl) 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-pyridinecar boxamide, 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 methioxoline), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl ]-2-methyl-1,2,4-triazin-3,5(2H,4H)-dione, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5 methyl -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 gloeosporioides (Penz.) Penz. & Sacc, Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
[0156] The compounds of the present invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocolone, gibberellic acid, gibberellin A4 and A7 , harpin protein, mepiquat chloride, calcium prohexadione, prohydrojasmone, sodium nitrophenolate and methyl trinexapac and plant growth modifying organisms such as the strain Bacillus cereus BP01.
[0157] General references for agricultural protectants (ie, herbicides, herbicide protective agents, insecticides, fungicides, nematocides, 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, 2nd Edition, LG Copping, ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.
[0158] For embodiments, in which one or more of these various mixing partners are used, the mixing partners are typically used in amounts similar to the usual amounts when the mixing partners are used alone. More especially in blends, active ingredients are often applied at an application rate between half and full application rate specified on product labels for the exclusive use of the active ingredient. These values are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various blending partners (in total) to the Formula 1 compound typically ranges from about 1:3,000 to about 3,000:1. Of interest are weight ratios between about 1:300 and about 300:1 (for example, ratios between about 1:30 and about 30:1). A person 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 weeds beyond the spectrum controlled by the compound of Formula 1 alone.
[0159] In certain cases, combinations of a compound of the present invention with other biologically active compounds or agents (i.e., active ingredients) (especially herbicides) may result in a more than additive (i.e., synergistic) effect on weeds and/or a less than additive (i.e. protective agent) effect on crops or other desired vegetables. Reducing the amount of active ingredients released into the environment, ensuring effective pest control is always advantageous. The ability to use greater amounts of active ingredients to provide more effective weed control without undue crop damage is also desired. When the synergism of the herbicide active ingredients occurs with the weeds at application rates providing satisfactory agronomic levels of weed control, such combinations can be advantageous in reducing crop production costs and reducing the environmental burden. When herbicide active ingredient protection occurs in crops, such combinations can be advantageous to increase crop protection by reducing weed competition.
[0160] Of interest is a combination of a compound of the present invention with at least one other herbicide active ingredient. Of special interest is a combination in which the other herbicide active ingredient has a different site of action than the compound of the present invention. In certain cases, a combination of at least one other herbicide active ingredient has a similar spectrum of control, but a different site of action will be especially advantageous for resistance management. Therefore, a composition of the present invention may further comprise (in an herbicide-effective amount) at least one additional herbicide active ingredient that has a similar spectrum of control but a different site of action.
[0161] The compounds of the present invention can also be used in combination with herbicide protecting agents such as allidochlor, benoxacor, cloquintocet-mexyl, ciomethrinil, cyprosulfonamide, dichlormid, dicyclonone, dietolate, dimepiperate, fenchlorazol-ethyl, fenchlorim , flurazol, fluxfenim, furilazol, isoxadiphen-ethyl, mefenpyr-diethyl, mefenate, methoxyphenone naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, 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, and 3-oxo-1-cyclohexen-1-yl of 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl- 5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-me toxi-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide to increase the safety of certain crops. Antidote-effective amounts of the herbicidal protective agents can be applied at the same time as the compounds of the present invention, or applied as seed treatments. Accordingly, one aspect of the present invention relates to a herbicidal mixture comprising a compound of the present invention and an antidote effective amount of the herbicidal protective agents. Seed treatment is especially useful for selective weed control as it physically restricts the antidote to growing vegetables. Therefore, an especially useful embodiment of the present invention is a method for selectively controlling the growth of unwanted vegetation in a crop which comprises contacting the crop locus with a herbicidal effective amount of a compound of the present invention, wherein the seed that the crop is grown is treated with an effective amount as antidotes to the protective agents. Antidote-effective amounts of protective agents can easily be determined by one skilled in the art through simple experimentation.
[0162] The compounds of 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 particular target through regulation, interference, suppression or silencing genetically derived transcripts that produce a herbicidal effect; or (2) polynucleotides including, but not limited to, chemically modified DNA, RNA and/or nucleotides that influence the quantity of a particular target through regulation, interference, suppression or silencing of genetically derived transcription that produce a protective effect.
[0163] Of interest is a composition comprising a compound of the present invention (in an herbicide effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide protection agents (in a effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0164] Preferably for better control of unwanted vegetation (eg a lower utilization rate such as synergism, broader spectrum of controlled weeds or heightened crop safety) or to prevent weed development Resistant weeds are mixtures of a compound of the present invention with an herbicide selected from the group of 2,4-D, acetochlor, alachlor, atrazine, bromoxynil, bentazone, bicyclopyrone, carfentrazone-ethyl, chloransulam-methyl, dicamba, dimethenamid- p, florasulam, flufenacet, flumioxazine, flupyrsulfuron-methyl, fluroxypyr-meptyl, glyphosate, halauxifen-methyl, isoxaflutol, MCPA, mesotrione, metolachlor, metsulfuron-methyl, nicosulfuron, pyrasulfotone, pyrasulfosulfone, tembosulfone methyl, topramazone and tribenuron.
[0165] Table A1 lists the specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 4 in column Component (a) is identified in Index Table A. The second column of Table A1 lists the compound of the specific Component (b) (for example, "2.4 D" in the first row). The third, fourth, and fifth columns of the Table list the ranges of ratio weight ratios where the compound of Component (a) is typically applied to a field-grown crop relative to Component (b) (ie, (a) ):(B)). Therefore, for example, the first row of Table A1 specifically describes the combination of Component (a) (ie Compound 4 in Index Table A) with 2.4 D, normally it is applied in a weight ratio between 1:192 to 6:1. The remaining rows of Table A1 should be constructed similarly. TABLE A1




















[0166] Table A2 is constructed similarly to Table A1 above, except that the entries below the column heading "Component (a)" are replaced by the respective Component Column Entry (a) shown below. Compound 5 in column Component (a) is identified in Index Table A. Therefore, for example, in Table A2, the entries below the column heading "Component (a)" recite "Compound 5" (ie, the Compound 5 identified in Index Table A), and the first row below the column headings in Table A2 specifically describes a mixture of Compound 5 with 2.4 D. Tables A3 through A78 are constructed in a similar manner.




[0167] The compounds of the present invention are useful for controlling weed species that are resistant to herbicides with the AHAS inhibitor or (b2) [chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as mode of action of acetolactate synthase (ALS)].
[0168] The following tests demonstrate the control effectiveness of the compounds of the present invention against specific weeds. The weed control offered by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. The following abbreviations are used in the Index Table that follows: 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 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 and -CN is cyano. The abbreviation "Cmpd. No." stands for "Compound Number". The abbreviation "Ex" means "Example" and is followed by a number indicating in which Example the compound is prepared. Mass spectra are reported with an estimated accuracy to within ± 0.5 Da as the molecular weight of the largest parent ion of isotopic abundance (M+1) formed by adding H+ (molecular weight of 1) to the molecule. The presence of molecular ions containing one or more less abundant higher atomic weight isotopes (eg, 37Cl, 81Br) is not reported. Alternative molecular ion peaks (eg, M+2 or M+4) that occur with compounds containing the multiple halogens are not reported. The reported M+1 peaks were observed by mass spectrometry using atmospheric pressure chemical ionization (AP+) or electrospray ionization (ESI).



- See Index Table B for 1H NMR data. - ** ES+ - E indicates the E isomer as the predominant double bond configuration. INDEX TABLE B
[0169] Cmpd NMR 1H (CDCl3 solution, unless otherwise indicated)


[0170] 1H NMR data are in ppm from tetramethylsilane. Couplings are called (s) singlet, (d) doublet, (t) triplet, (m) multiplet. BIOLOGICAL EXAMPLES OF THE INVENTION TEST A
[0171] Seeds of vegetable species selected from barnyardgrass (Echinochloa crusgalli), kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (Italian ryegrass, Lolium multiflorum), giant foxtail (Giant foxtail, Setaria faberii) and anthill weed (Amaranthus retroflexus), were planted in a mixture of sandy soil and sand and pre-emergence treated with a clayey soil spray and sand and pre-emergence treated with a directed spray. soil using the test chemicals formulated in a non-phytotoxic solvent mixture that included a surfactant.
[0172] At the same time, selected vegetables from these weed species and also wheat (Triticum aestivum), maize (Zea mays), black grass (Alopecurus myosuroides) and gallium (straw bed-trapping weed, Galium aparine) were planted in pots containing the same mixture of clayey soil and sand and treated with post-emergence applications of the test chemicals formulated in the same way. The vegetables varied in height from 2 to 10 cm and were in a stage of one to two leaves for post-emergence treatment. Treated vegetables and untreated controls were kept in a greenhouse for about 10 days, after which all treated vegetables were compared to untreated controls and visually assessed for injury. Plant response ratings, summarized in Table A, are based on a scale of 0 to 100, where 0 is no effect and 100 is complete control. A dash (-) answer means there is no test result. TABLE A













[0173] The plant species in the soaked test selected from rice (Oryza sativa), umbrella sedge (small flower umbrella sedge Cyperus difformis), ducksalad (Heteranthera limosa) and barnyardgrass (Echinochloa crusgalli) were grown to the 2-leaf stage for testing. At the time of treatment, the test pots were soaked to 3 cm above the soil surface, treated by applying the test compounds directly to the rice irrigation water, and then held at that water depth for the duration of the test. Treated vegetables and controls were kept in a greenhouse for 13 to 15 days, after which all species were compared with controls and visually evaluated. The vegetable response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 means no effect and 100 is complete control. A dash (-) answer means that there is no test result. TABLE B

权利要求:
Claims (12)
[0001]
1. COMPOUND, characterized by being selected from Formula 1, N-oxides and salts thereof,
[0002]
A COMPOUND according to claim 1, characterized in that A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C4-C8 cycloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-alkylthioalkyl C2-C6 haloalkylthioalkyl, C3-C8 cycloalkylthioalkyl, C2-C6 alkylsulfonylalkyl or C2-C6 haloalkylsulfonylalkyl.
[0003]
A COMPOUND according to claim 2, characterized in that A is C2-C8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 alkoxyhaloalkyl.
[0004]
A COMPOUND according to claim 3, characterized in that A is C2-C8 alkyl, C2-C8 haloalkyl, C2-C6 haloalkenyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 alkoxyhaloalkyl; R1 is halogen; and R2 is halogen or cyano.
[0005]
5. COMPOUND according to claim 1, characterized in that it is selected from the group consisting of 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine, 3-[(5-chloro-2 -pyrimidinyl)oxy]-2-[[(2E)-4,4,4-trifluoro-2-buten-1-yl]oxy]benzonitrile, 2-[3-bromo-2-(2,2,3, 3-tetrafluoropropoxy)phenoxy]-5-chloropyrimidine, 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(2,2,3,3,3-pentafluoropropoxy)benzonitrile, 2-butoxy-3-[ (5-chloro-2-pyrimidinyl)oxy]benzonitrile, 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(3,3,3-trifluoropropoxy)benzonitrile, 3-[(5-fluoro-2 -pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile and 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile.
[0006]
6. HERBICIDAL COMPOSITION, characterized in that it comprises a compound, as defined in any one of claims 1 to 5, and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0007]
7. HERBICIDAL COMPOSITION, characterized in that it comprises a compound, as defined in any one of claims 1 to 5, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide protection agents and at least one selected component from the group consisting of surfactants, solid thinners and liquid thinners.
[0008]
8. HERBICIDAL MIXTURE, characterized in that it comprises (a) a compound as defined in any one of claims 1 to 5, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate synthase (EPSP) inhibitors, (b6) photosystem I electron deflectors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid elongase (VLCFA) inhibitors, (b10) inhibitors of auxin transport, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltranererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors , (b15) other herbicides including mitotic disruptors, organic arsenics cos, asulam, bromobutide, cinmethylin, cumilurone, dazomet, difenzoquat, dymrone, etobenzanid, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomephone, pelargonic acid, pyributica16, protecting agents and the salts of the compounds of (b1) to (b16).
[0009]
9. HERBICIDAL MIXTURE according to claim 8, characterized in that the at least one additional active ingredient (b) is selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate synthase (EPSP) inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b9) very long chain fatty acid elongase inhibitors (VLCFA) and (b12) 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors.
[0010]
10. HERBICIDAL MIXTURE, characterized in that it comprises (a) a compound as defined in any one of claims 1 to 5, and (b) at least one additional active ingredient selected from the group consisting of 2,4-D, acetochlor , alachlor, atrazine, bromoxynil, bentazone, bicyclopyrone, carfentrazone-ethyl, chloransulam-methyl, dicamba, dimethenamid-p, florasulam, flufenacet, flumioxazine, flupyrsulfuron-methyl, fluroxypyr-meptyl, glyphospalate, methilic, halaximethylic, isso- , metolachlor, metsulfuron-methyl, nicosulfuron, pyrasulfotole, pyraxasulfone, piroxsulam, rimsulfuron, saflufenacil, tembotrione, tifensulfuron-methyl, topramazone, and tribenuron.
[0011]
11. METHOD FOR CONTROLLING THE GROWTH OF UNWANTED VEGETATION, characterized in that it comprises contacting the vegetation or its environment with an herbicide-effective amount of a compound as defined in any one of claims 1 to 5.
[0012]
12. METHOD FOR CONTROLLING UNWANTED VEGETATION GROWTH in genetically modified vegetables that exhibit aspects of glyphosate tolerance, glufosinate tolerance, ALS herbicide tolerance, dicamba tolerance, imidazolinone herbicide tolerance, 2,4-D tolerance HPPD tolerance and mesotrione tolerance, characterized in that it comprises contacting the vegetation or its environment with an herbicidal effective amount of a compound as defined in any one of claims 1 to 5.

类似技术:

---

公开号 | 公开日 | 专利标题

---

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

---

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

---

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

---

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

---

BR112016012584B1|2020-10-20|compost, herbicidal compositions, herbicidal mixtures and method for controlling the growth of unwanted vegetation

---

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

---

BR112016024443B1|2021-08-17|COMPOUNDS, HERBICIDAL COMPOSITION, HERBICIDAL MIXTURES, METHOD FOR CONTROLLING UNWANTED VEGETATION GROWTH AND METHODS FOR PREPARING A COMPOUND

---

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

---

BR112016012819B1|2020-11-17|compost, herbicidal compositions, methods for controlling the growth of unwanted vegetation and herbicidal mixtures

---

JP2018525373A|2018-09-06|Cyclic N-carboxamide compounds useful as herbicides

---

TW202110810A|2021-03-16|Pyrimidinyloxy benzene derivatives as herbicides

---

WO2016014814A1|2016-01-28|Pyridones as herbicides

---

BR112019028016A2|2020-07-07|compost, herbicidal compositions, herbicidal mixture and method to control the growth of unwanted vegetation

---

KR102358945B1|2022-02-08|New pyridazinone herbicide

---

JP2020522493A|2020-07-30|Amide for weeding

---

WO2021183980A1|2021-09-16|Substituted pyrimidines and triazines as 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

---

CA3127789A1|2020-08-06|Diamino-substituted pyridines and pyrimidines as herbicides

---

WO2022026500A1|2022-02-03|Substituted haloalkyl sulfonanilide herbicides

---

IL269625A|2022-01-01|Novel pyridazinone herbicides

同族专利:

---

公开号 | 公开日

---

CA2990839A1|2017-01-19|

---

CN108024537A|2018-05-11|

---

EP3322293A1|2018-05-23|

---

AR105348A1|2017-09-27|

---

AU2016292811B2|2021-02-18|

---

US20180206497A1|2018-07-26|

---

RU2018104971A|2019-08-14|

---

AU2016292811A1|2018-01-18|

---

RU2745802C2|2021-04-01|

---

WO2017011288A1|2017-01-19|

---

EP3322293B1|2021-05-19|

---

MX2018000394A|2018-08-14|

---

RU2018104971A3|2020-01-27|

---

US10485235B2|2019-11-26|

---

BR112018000687A2|2019-05-14|

---

ES2883273T3|2021-12-07|

---

TW201701761A|2017-01-16|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3916678A|1974-01-21|1975-11-04|Warren G Lohoff|Soil moisture detection device|

---

AU535637B2|1977-09-13|1984-03-29|Ici Australia Limited|2-phenoxypyrimidines and their. use as herbicides|

---

NZ188244A|1977-09-13|1981-04-24|Ici Australia Ltd|2-substituted pyrimidines compositions growth regulating processes|

---

JPS6139943B2|1978-03-03|1986-09-06|Sankyo Kk|

---

NZ191078A|1978-08-08|1982-05-31|Ici Australia Ltd|Bis benzenes bisbenzenes and prymidyloxy-pyrimidyl thiobenzens and herbicidal compositions|

---

NZ192708A|1979-02-16|1984-12-14|Ici Australia Ltd|Substituted pyrimidines and compositions|

---

US4371736A|1981-03-27|1983-02-01|E. I. Du Pont De Nemours And Company|Herbicidal pyridinyloxybenzenes|

---

US4432979A|1981-10-26|1984-02-21|William H. Rorer, Inc.|Pyridone compounds|

---

JPS61236766A|1985-04-15|1986-10-22|Sumitomo Chem Co Ltd|O-substituted phenoxy heterocyclic compound, production thereof and herbicide containing said compound as active constituent|

---

AU594098B2|1985-12-11|1990-03-01|Ishihara Sangyo Kaisha Ltd.|N-benzoyl urea compounds, antitumorous compositions containing them, and process for their preparation|

---

GB8917222D0|1989-07-27|1989-09-13|Schering Agrochemicals Ltd|Herbicides|

---

GB8924465D0|1989-10-31|1989-12-20|Ici Plc|Herbicides|

---

JPH04108777A|1990-08-30|1992-04-09|Kumiai Chem Ind Co Ltd|Pyrimidine derivative and herbicide|

---

AU5161193A|1992-10-16|1994-05-09|Nippon Soda Co., Ltd.|Pyrimidine derivative|

---

AU5891494A|1993-01-29|1994-08-15|Nippon Soda Co., Ltd.|Heterocyclic derivative|

---

DE4438824A1|1993-10-16|1995-04-20|Schering Ag|Triazole derivatives, process for their preparation and their use in medicaments|

---

US5962685A|1994-08-02|1999-10-05|Nippon Soda Co., Ltd.|Oxazole derivatives, process for producing the same, and herbicide|

---

WO1996033994A1|1995-04-28|1996-10-31|Nippon Soda Co., Ltd.|Amino-substituted derivatives, process for the preparation thereof, and herbicide|

---

WO1998040379A1|1997-03-11|1998-09-17|E.I. Du Pont De Nemours And Company|Heteroaryl azole herbicides|

---

JPH10251255A|1997-03-14|1998-09-22|Nissan Chem Ind Ltd|Azine derivative|

---

DE19721031A1|1997-05-20|1998-11-26|Bayer Ag|Substituted pyridylpyrazoles|

---

RU2008110949A|2005-08-23|2009-09-27|Айрм Ллк |COMPOUNDS AND COMPOSITIONS-IMMUNOSUPRESSANTS|

---

CN101484433A|2006-02-15|2009-07-15|艾博特公司|Novel acetyl-coA carboxylase inhibitors and their use in diabetes, obesity and metabolic syndrome|

---

GB0614579D0|2006-07-21|2006-08-30|Black James Foundation|Pyrimidine derivatives|

---

CN101279950B|2007-04-06|2010-08-11|中国中化股份有限公司|2-pyrimindinyloxy benzoxy acetamide compound and application thereof|

---

EP2562175A1|2008-01-22|2013-02-27|Dow AgroSciences LLC|5-fluoro pyrimidine derivatives as fungicides|

---

EA201290062A1|2009-08-17|2013-09-30|Мемориал Слоун-Кеттеринг Кэнсэ Сентр|COMPOUNDS, BINDING PROTEINS OF THERMAL SHOCK, COMPOSITIONS AND METHODS OF OBTAINING INDICATED COMPOUNDS|

---

JP2012012299A|2010-06-29|2012-01-19|Nissan Chem Ind Ltd|Solid agrochemical preparation capable of controlling release of agrochemical active ingredient|

---

JP5753178B2|2010-09-24|2015-07-22|クミアイ化学工業株式会社|6-Acylpyridin-2-one derivatives and herbicides|

---

TW201609710A|2013-12-10|2016-03-16|杜邦股份有限公司|Herbicidal substituted pyrimidinyloxy benzene compounds|

---

SG11201604813YA|2014-01-16|2016-07-28|Du Pont|Pyrimidinyloxy benzene derivatives as herbicides|

---

TW201625554A|2014-07-14|2016-07-16|杜邦股份有限公司|Biscatechol derivatives as herbicides|

---

AR101264A1|2014-07-25|2016-12-07|Du Pont|PIRIDONAS AS HERBICIDES|TW202110810A|2015-06-05|2021-03-16|美商艾佛艾姆希公司|Pyrimidinyloxy benzene derivatives as herbicides|

---

EP3416489A1|2016-02-19|2018-12-26|Basf Se|Pesticidally active mixtures comprising anthranilamide compounds|

---

BR112018076951A2|2016-07-12|2019-04-02|Basf Agrochemical Products B.V.|pesticide mixtures, methods for insect control, plant protection and protection of plant propagating material, seed and pesticide composition|

---

WO2018178039A1|2017-03-31|2018-10-04|Basf Se|Crystalline forms of ethyl[3-[2-chloro-4-fluoro-5-phenoxy]-2-pyridyloxy]acetate|

---

CN110461854A|2017-03-31|2019-11-15|巴斯夫欧洲公司|The method for preparing chirality 2,3- thiazoline simultaneously [3,2-A] pyrimidine -4- compound|

---

RU2019138586A3|2017-05-02|2021-05-28|

---

WO2019030100A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and at least one mitosis inhibitor|

---

WO2019030102A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and glyphosate or its salts|

---

US20200359629A1|2017-08-09|2020-11-19|Basf Se|Herbicidal mixtures comprising L-glufosinate or its salt and at least one bleacher herbicide|

---

WO2019030089A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and at least one als inhibitor|

---

WO2019030103A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and at least one auxinic herbicide|

---

WO2019030087A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and at least one lipid biosynthesis inhibitor|

---

WO2019030098A1|2017-08-09|2019-02-14|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and at least one protoporphyrinogen-ix oxidase inhibitor|

---

EP3440937A1|2017-08-09|2019-02-13|Basf Se|Herbicidal mixtures comprising l-glufosinate or its salt and a second herbicide|

---

TW201929671A|2017-08-09|2019-08-01|德商巴地斯顏料化工廠|Herbicidal mixtures comprising L-glufosinate or its salt and at least one photosynthesis inhibitor|

---

CN110996664A|2017-08-09|2020-04-10|巴斯夫欧洲公司|Herbicidal mixture comprising L-spinosad or a salt thereof and at least one VLCFA inhibitor|

---

KR101963770B1|2017-10-17|2019-03-29|주식회사 홍인터내셔날|Dart game apparatus and dart game system with display unit|

---

US20200354337A1|2017-11-27|2020-11-12|Basf Se|Crystalline forms of ethyl 2-[[3-[[3- chloro-5-fluoro-6-[3-methyl-2,6-dioxo- 4-pyrimidin-1-yl]-2-pyridyl]oxy]acetate|

---

WO2019121225A1|2017-12-22|2019-06-27|Basf Se|Aqueous composition comprising 2- succinic acid and ammonia|

---

WO2019121228A1|2017-12-22|2019-06-27|Basf Se|Aqueous composition comprising 2- succinic acid and at least one metal hydroxide|

---

WO2019121226A1|2017-12-22|2019-06-27|Basf Se|Aqueous composition comprising 2- succinic acid and at least one further acid|

---

CN111712131A|2018-02-16|2020-09-25|巴斯夫欧洲公司|Herbicidal mixtures|

---

WO2019175712A1|2018-03-14|2019-09-19|Basf Corporation|New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways|

---

WO2019175713A1|2018-03-14|2019-09-19|Basf Corporation|New catechol molecules and their use as inhibitors to p450 related metabolic pathways|

---

CA3099875A1|2018-06-13|2019-12-19|Basf Se|Crystalline form of ethyl 2-[2-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-pyrimidin-1-yl]phenoxy]phenoxy]acetate|

---

WO2019243104A1|2018-06-20|2019-12-26|BASF Agro B.V.|Method for controlling herbicide resistant or tolerant weeds|

---

WO2019243101A1|2018-06-20|2019-12-26|Basf Se|Method for controlling herbicide resistant or tolerant weeds|

---

AU2019290961A1|2018-06-20|2020-12-24|BASF Agro B.V.|Herbicidal combination|

---

WO2020002089A1|2018-06-25|2020-01-02|Bayer Aktiengesellschaft|Substituted 2-heteroaryloxypyridines and salts thereof and their use as herbicidal agents|

---

CN112384507A|2018-06-25|2021-02-19|拜耳公司|Substituted 4-heteroaryloxypyridines and their salts and their use as herbicides|

---

EP3670505A1|2018-12-18|2020-06-24|Bayer AG|Substituted pyridinyloxybenzenes, their salts and use of said compounds as herbicidal agents|

---

EP3680223A1|2019-01-10|2020-07-15|Basf Se|Mixture comprising an urease inhibitorand a nitrification inhibitorsuch as an ni mixture comprising 2-succinic acidand dicyandiamide |

---

CN113950244A|2019-06-07|2022-01-18|巴斯夫农业公司|Particulate compositions comprising saflufenacil|

---

EP3772514A1|2019-08-08|2021-02-10|Basf Se|Herbicidal amides|

---

GB201911429D0|2019-08-09|2019-09-25|Syngenta Crop Protection Ag|Improvements in or relating to organic compounds|

---

WO2021144195A1|2020-01-16|2021-07-22|Basf Se|Mixtures comprising nitrification inhibitors and carriers|

---

WO2021144193A2|2020-01-16|2021-07-22|Basf Se|Mixtures comprising a solid carrier comprising an urease inhibitor and a further solid carrier comprising a nitrification inhibitor|

---

WO2021148303A1|2020-01-23|2021-07-29|Basf Se|Glufosinate formulations containing amines or ammonium salts|

---

WO2021151733A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and saflufenacil|

---

WO2021151741A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and tiafenacil|

---

WO2021151735A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and carfentrazone-ethyl|

---

WO2021151752A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and selected ppo inhibitors|

---

WO2021151734A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and flumiclorac-pentyl|

---

WO2021151738A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and epyrifenacil|

---

WO2021151737A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and flumioxazin|

---

WO2021151740A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and sulfentrazone|

---

WO2021151745A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and oxadiazon|

---

WO2021151736A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and fluthiacet-methyl|

---

WO2021151739A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and pyraflufen-ethyl|

---

WO2021151753A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and selected ppo inhibitors|

---

WO2021151744A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and oxyfluorfen|

---

WO2021151743A1|2020-01-31|2021-08-05|Basf Se|Herbicide combinations comprising glufosinate and trifludimoxazin|

---

WO2021170464A1|2020-02-28|2021-09-02|Basf Se|Herbicidal malonamides|

---

WO2021175689A1|2020-03-06|2021-09-10|Basf Se|Herbicidal phenyluracils|

---

WO2021191035A1|2020-03-25|2021-09-30|Basf Se|Dioxazolines and their use as herbicides|

---

WO2021198458A1|2020-04-02|2021-10-07|Basf Corporation|Aqueous formulations of dicamba|

---

WO2021206683A1|2020-04-06|2021-10-14|Basf Corporation|High-load solution concentrates of dicamba|

---

WO2021209268A1|2020-04-14|2021-10-21|Basf Se|Beta-lactams and their use as herbicides|

---

WO2021224040A1|2020-05-05|2021-11-11|Basf Se|Condensed isoxazoline derivatives and their use as herbicides|

法律状态:
2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-05-04| 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 08/07/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201562191560P| true| 2015-07-13|2015-07-13|

---

US62/191,560|2015-07-13|

---

PCT/US2016/041444|WO2017011288A1|2015-07-13|2016-07-08|Aryloxypyrimidinyl ethers as herbicides|

---