HETEROBICYCLIC MICROBICIDES DERIVATIVES

专利摘要:
microbicidal heterobicyclic derivatives. compounds of formula i, r5ln 4 r[r7]mr 2 rnn 1 r rs n (1) wherein the substituents are as defined in claim 1. Furthermore, the present invention is directed to agrochemical compositions comprising compounds of formula (I) , w preparation of such compositions and the use of the compounds or compositions in agriculture or horticulture to combat, prevent or control infestation of plants, food crops, seeds or non-living materials by phytopathogenic microorganisms, particularly fungi.
公开号:BR112017020349B1
申请号:R112017020349-9
申请日:2016-03-21
公开日:2021-08-03
发明作者:Farhan BOU HAMDAN；Laura Quaranta；Stephan Trah；Matthias Weiss
申请人:Syngenta Participations Ag；
IPC主号:

专利说明:

HETEROBICYCLIC MICROBICIDES DERIVATIVES
[0001] The present invention is intended for microbicidal heterobicyclic derivatives, e.g. , as active ingredients, which have microbicidal activity, in particular fungicidal activity. The invention is also directed to the preparation of such heterobicyclic derivatives, to intermediates useful in the preparation of such heterobicyclic derivatives, to the preparation of such intermediates, to agrochemical compositions comprising at least one of the heterobicyclic derivatives, to the preparation of such compositions and to the use of heterobicyclic derivatives or compositions of heterobicyclic derivatives in agriculture or horticulture to control or prevent infestation of plants, food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.
[0002] Certain fungicidal heterobicyclic compounds are described in W005070917.
[0003] It has now surprisingly been found that certain new heterobicyclic derivatives have favorable fungicidal properties.
[0004] The present invention therefore provides compounds of formula I
wherein R 1 and R 2 are each independently selected from hydrogen, cyano, C 1 -C 6 alkyl, C 3 -C 2 cycloalkyl, C 2 -C 8 alkenyl and C 1 -C 8 alkynyl, where the alkyl, cycloalkyl, alkenyl groups and alkynyl may be optionally substituted with 1 to 3 substituents independently selected from halogen, C 1 -C 6 alkoxy, and C 1 -C 6 alkylthio; or R 1 and R 2 together with the carbon atom to which they are attached represent a C 3 -C 10 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 6 alkyl, alkoxy C 1 -C 6 and C 1 -C β alkylthio); R3 and R1 are each independently selected from hydrogen, halogen, hydroxyl, C1 -C6 alkyl, C1 -Cβ alkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl and C2-C6 alkynyl, wherein the alkyl groups, alkoxy, cycloalkyl, alkenyl, and alkynyl may optionally be substituted with 1 to 3 substituents independently selected from halogen, C1-CÔ alkoxy, and C1-Cβ alkylthio; or R3 and R1 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rt) (Rc) or C3-C10 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C1 -Cβ alkyl, C1 -Cε alkoxy and C1 -C6 alkylthio; or R2 and R3 together with the carbon atoms to which they are attached represent a C5-C10 cycloalkyl (which may /M5 - tf''h 3/165 y. be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C β alkyl, C 1 -C 8 alkoxy and C 1 -C 6 alkylthio, and additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom); each R5 independently represents halogen, hydroxyl, mercapto, nitro, cyano, formyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3 alkynyloxy -C6, C1 -C6 alkylthio, -C (=NORa) C1 -C3 alkyl, C1 -C6 alkylcarbonyl, aryl, heteroaryl, aryloxy or heteroaryloxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy groups , aryl and heteroaryl may be optionally substituted with 1 to 5 substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, cyano and C 1 -C 6 alkylthio; n is 0, 1, 2, 3 or 4; R is hydrogen, halogen, C1 -Cβ alkyl or C1 -C6 alkoxy; each R independently represents hydroxy, mercapto, cyano, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkenyl, C 3 -C 6 haloalkenyl, C 1 -C 6 alkylthio, haloalkoxy C 1 -C 6 , C 1 -C 6 haloalkylthio, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylcarbonyl, C 3 -C 7 cycloalkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1, 2, 3 or 4; or Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a 2. 4/165% %%, -a,O C5-C7 cycloalkyl (which may optionally be substituted with 1 to 3 independently selected substituents a from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio, and additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom); Ra is selected from hydrogen, C1 -C6 alkyl, C3 -C7 cycloalkyl, C3 -C6 alkenyl and C3 -C6 alkynyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may optionally be substituted with 1 to 3 independently selected substituents from halogen, C1-Cβ alkoxy and C1-C6 alkylthio; Rb and Rc are each independently selected from hydrogen, halogen, cyano, C1-Ce alkyl, C3-C7 cycloalkyl, C2_Ce alkenyl, C∑-Cβ alkynyl, C1-C6 alkoxy, and C1-C6 alkylthio, where alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy and C1-C6 alkylthio; or a salt or N-oxide thereof.
[0005] In a second aspect, the present invention provides an agrochemical composition comprising a compound of formula (I).
[0006] The compounds of formula (I) can be used to control phytopathogenic microorganisms. Thus, in order to control a plant pathogen, a compound of formula (I), or a composition comprising a compound of formula (I), according to the invention can be applied directly to the plant pathogen, or to the locus of a plant pathogen, in particular in a plant susceptible to attack by phytopathogens.
[0007]Therefore, in a third aspect, the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein, to control a phytopathogen.
[0008] In a further aspect, the present invention provides a method of controlling phytopathogens, comprising the application of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein, in the said phytopathogen, or at the locus of said phytopathogen, in particular on a plant susceptible to attack by a phytopathogen.
[0009] The compounds of formula (I) are particularly effective in the control of phytopathogenic fungi.
Thus, in yet another further aspect, the present invention provides the use of a compound of formula (I), or a composition comprising a compound of formula (I), as described herein, to control phytopathogenic fungi.
[0011] In a further aspect, the present invention provides a method of controlling phytopathogenic fungi, comprising applying a compound of formula (I), or a composition comprising a compound of formula (I), as described herein, in said phytopathogenic fungi, or at the site of te % Rus in said phytopathogenic fungi, in particular in a plant susceptible to attack by phytopathogenic fungi.
Where the substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g., one to three substituents. Typically, no more than three of these optional substituents are present at any one time. Where a group is indicated to be substituted, e.g., alkyl, this includes those groups that are part of other groups, e.g., the alkyl in the alkylthio group.
[0013] The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably to fluorine, chlorine or bromine.
Alkyl substituents can be straight chain or branched. Alkyl alone or as part of another substituent is, depending on the number of carbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.
Alkenyl substituents may be in straight-chain or branched form, and alkenyl moieties, where appropriate, may have either the (E) or (Z) configuration. Examples are vinyl and allyl. Alkenyl groups are preferably C2-C6 alkenyl groups, more preferably C2-C4, and most preferably C2C3.
Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl. Alkynyl groups are preferably C2-C6 alkynyl groups, more preferably C2-C4 and most preferably C2-C3.
Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may represent CH2CI, CHCl2, CCI3, CH2F, CHF2, CF3, CF3CH2, CH3CF2, CF3CF2 or CCI3CCI2.
[0018] Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more identical or different halogen atoms and are, for example, 2,2-difluorovinyl or 1,2-dichloro-2-fluorovinyl.
[0019] Haloalkynyl groups are alkynyl groups, respectively, which are substituted with one or more identical or different halogen atoms and are, for example, 1-chloro-prop-2-ynyl.
Alkoxy means an -OR radical, where R is alkyl, e.g., as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.
[0021] Cyan means a -CN group.
[0022] Amino means an -NH2 group.
[0023] Hydroxyl or hydroxy represents an -OH group.
[0024] Aryl groups (either alone or as part of a larger group such as aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, with phenyl being Zv / 8/165 most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is preferably substituted with one to four substituents, most preferably with one to three substituents.
Heteroaryl groups (either alone or as part of a larger group, such as heteroaryloxy, heteroaryl-alkyl) are aromatic ring systems containing at least one heteroatom and consisting of a single ring or two or more fused rings. Preferably single rings will contain up to three heteroatoms and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g., [1,2,4]-triazolyl), furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples of bicyclic groups include purinyl, quinolinyl, cinolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl. Monocyclic heteroaryl groups are preferred, with pyridyl being most preferred. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is preferably substituted with one to four substituents, most preferably with one to three substituents.
[0026] Heterocyclyl groups or heterocyclic rings (either alone or as part of a non-aromatic ring structures containing up to 10 atoms, including one or more heteroatoms (preferably one, two or three) heteroatoms selected from 0, If N Examples of monocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, tietanyl, pyrrolidinyl, tetrahydrofuranyl, [1,3]dioxolanyl, piperidinyl, piperazinyl, [1,4]dioxanyl, imidazolidinyl, [1, 3,5]oxadiazinenyl, hexahydro-pyrimidinyl, [1,3,5]triazinenyl and morpholinyl, or their oxidized versions such as 1-oxo-thietanyl and 1,1-dioxo-thietanyl Examples of bicyclic groups include 2 ,3-dihydro-benzofuranyl, benzo[1,4]dioxolanyl, benzo[1,3]dioxolanyl, cromenyl and 2,3-dihydro-benzo[1,4]dioxinyl Where a heterocyclyl moiety is said is substituted, the heterocyclyl moiety is preferably substituted with one to four substituents, most preferably with one to three substituent. s.
[0027] The presence of one or more possible asymmetric carbon atoms in a compound of formula I means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Atropisomers can also occur, resulting from restricted rotation around a single bond. Formula I is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula I. Likewise, formula I is intended to include all of the present invention includes all possible tautomeric forms for a compound of formula I.
In each case, the compounds of formula I according to the invention are in free form, in oxidized form as an N-oxide, or in salt form, e.g., in the form of an agronomically usable salt.
[0029] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described for example in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.
It is preferred that the compounds of formula I according to the invention are in free form.
[0031] Preferred values of R1, R2, R3, R4, R5, R6, R7, R8, Ra, Rb, Rc, nor are, in any combination thereof, as set forth below:
[0032] Preferably R1 and R2 are each independently selected from hydrogen, C1 -C6 alkyl and C3 -C2 cycloalkyl, wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from of halogen, C1-Cθ alkoxy and C1-Cβ alkylthio; or R 1 and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 alkoxy -C6 and C1 -C6 alkylthio.
[0033] More preferably R1 and R2 are each independently selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C1 alkoxy -C3 θ C1-C3 alkylthio.
[0034] Even more preferably R1 and R2 are each independently selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio ; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C1-C3 alkyl).
[0035] Most preferably R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; or R1 and R2 θm together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group.
[0036] More preferably R1 and R2 are each independently selected from hydrogen and 12/165 C1-C3 alkyl; or R1 and Rj together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group.
[0037] Preferably R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, C1 -Cε alkyl, C1 -Cβ alkoxy and C3 -C7 cycloalkyl, wherein the alkyl, alkoxy and cycloalkyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy, or C1-Cβ alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa, C=C(Rb)(RJ or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 independently selected substituents) from the group consisting of halogen, C1-6 alkyl, C1-6 alkoxy and C1-6 alkylthio); or R' and R3 together with the carbon atom to which they are attached represent a C5-C7 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio, and, in addition, a ring carbon moiety may be replaced by an oxygen atom or of sulfur).
[0038] More preferably R3 and R4 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C3-C4 cycloalkyl, wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 independently selected substituents from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen , C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio ■
[0039] Even more preferably R3 and R4 are each independently selected from hydrogen, halogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R3 θ R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C4 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen and alkyl C1-C3) ■
[0040] Most preferably R3 and R4 are each independently selected from hydrogen, halogen and C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C4 cycloalkyl •
[0041] Most preferably R3 and R4 are each independently selected from hydrogen, fluorine or C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=0 or C3-C4 cycloalkyl.
Preferably each Rs independently represents halogen, cyano, C1 -C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, alkylthio C1-Cβ, -C (=NORa) C1-C6 alkyl, phenyl, heteroaryl (where heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroaryloxy (where heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may optionally be substituted with 1 to 5 substituents independently selected from halogen, C1 -C6 alkyl, C1 -C6 alkoxy, cyano and C1 -C6 alkylthio; n is 0, 1, 2, 3 or 4.
[0043] More preferably each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C3 alkylthio, -C (=NORa ) C1 -C' alkyl, phenyl, heteroaryl (where heteroaryl is pyridyl, thiazolyl or oxazolyl), wherein the alkyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 independently selected substituents a from halogen, C1-C3 alkyl, C1-C3 alkoxy, n is 0, 1 or 2.
[0044] Even more preferably each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl or phenyl, wherein the alkyl, cycloalkyl and phenyl groups may be optionally substituted with 1 to 3 substituents independently selected from of halogen or C1-C3 alkyl; n is 0, 1 or 2.
Most preferably each Rs independently represents halogen, cyano, C1-C3 alkyl, C3-C4 cycloalkyl or phenyl, wherein the alkyl, cycloalkyl and phenyl groups may optionally be substituted with 1 to 3 halogen atoms; n is 0, 1 or 2.
Most preferably each Rs independently represents halogen, C1-C3 alkyl or C3-C4 cycloalkyl, wherein the alkyl and cycloalkyl groups may optionally be substituted with 1 to 3 fluorine atoms; n is 0, 1 or 2.
[0047] Preferably, Re is hydrogen, halogen or C1-Cβ alkyl.
[0048] More preferably, Re is hydrogen or C1-C3 alkyl.
[0049] Even more preferably, R6 is hydrogen or methyl.
[0050] Most preferably, Re is hydrogen.
[0051] Preferably each R independently represents cyano, halogen, C 1 -C β alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 2 -C β haloalkenyl, C 3 -C 6 haloalkynyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkoxy, haloalkylthio C 1 -C 6 , C 3 -C 7 cycloalkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy; m is 0, 1, 2, 3 or 4; or
[0052] Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-6 alkyl , C1 -C6 alkoxy and C1 -C6 alkylthio, and, in addition, a ring carbon moiety may be replaced by an oxygen or sulfur atom).
[0053] More preferably each R independently represents cyano, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkynyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkylthio, C 3 -C 7 cycloalkyl, C 1 -C 6 alkoxy, alkenyloxy C3-C6 or C3-C6 alkynyloxy; m is 0, 1, 2, or 3; or
[0054] Two adjacent R1 substituents together with the carbon atoms to which they are attached represent a Cs-Cε cycloalkyl group;
[0055] Even more preferably, each R7 independently represents cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C3 alkynyl, C1-C4 alkylthio or C3-C4 cycloalkyl; m is 0, 1 or 2.
[0056] More preferably, each R7 independently represents cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C4 cycloalkyl; m is 0, 1 or 2.
[0057] More preferably each R7 independently represents fluorine, chlorine or C1-C3 alkyl; m is 1 or 2 .
[0058] Preferably Ra is selected from hydrogen, C1 -C6 alkyl, C3 -C7 cycloalkyl, C3 -C6 alkenyl and C3 -C6 alkynyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy and C1-Cε alkylthio.
[0059] More preferably Ra is selected from hydrogen, C1-C4 alkyl and C3-C5 cycloalkyl, wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio.
[0060] Even more preferably Ra is selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 halogen atoms.
[0061] Most preferably Ra is selected from hydrogen and C1-C3 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 fluorine atoms.
[0062] Preferably Rb and Rc are each independently selected from hydrogen, halogen, cyano, C1 -C6 alkyl, C3 -C7 cycloalkyl, C2 -C6 alkenyl, C2-C6 alkynyl, C1 -C6 alkoxy and alkylthio C 1 -C 6 , wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen, C 1 -C 6 alkoxy and C 1 -C 6 alkylthio.
[0063] A preferred group of compounds according to the invention are those of formula IA:
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ra , Rb , Rc , neither are as defined for the compounds of formula I, or a salt or N-oxide thereof. Preferred definitions of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ra , Rb , Rc , nor are they as defined for compounds of formula I.
[0064] Another preferred group of compounds according to the invention are those of formula IB which are compounds of formula I wherein R1 and R2 are each independently selected from hydrogen, C1-Cβ alkyl and C3-C7 cycloalkyl , wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C 1 -C β alkoxy and C 1 -C β alkylthio; or R 1 and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 6 alkyl, C 1 alkoxy -Ce and C1 -Cβ alkylthio); R3 and R1 are each independently selected from hydrogen, halogen, hydroxy, C1 -C6 alkyl, C1 -C6 alkoxy and C3 -C7 cycloalkyl, wherein the alkyl, alkoxy and cycloalkyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen, C1 -Cβ alkoxy, and C1 -C6 alkylthio; or R3and R4 together with the carbon atom to which they are attached represent C=0, C=NORa, C=C(Rt>) (Rc) or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy and C 1 -C β alkylthio); or R2and R3together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-Ce alkyl, C1-Cβ alkoxy and C1-C6 alkylthio, and additionally a ring carbon moiety may be substituted by an oxygen or sulfur atom); each R5 independently represents halogen, cyano, C1 -C6 alkyl, C2 -C6 alkenyl, C2 -Ce alkynyl, C3 -C7 cycloalkyl, C1 -C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1 -C6 alkylthio, _C (=NORa) C1 -C6 alkyl, phenyl, heteroaryl (where heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroaryloxy (where heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), where alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may optionally be substituted with 1 to 5 substituents independently selected from halogen, C1 -C4 alkyl, C1 -C6 alkoxy, cyano and C1 -alkylthio Ce; n is 0, 1, 2, 3 or 4; Re is hydrogen, halogen or C1 -C6 alkyl; each R7 independently represents cyano, halogen, C1 -Cβ alkyl, C1 -C6 haloalkyl, C1 -C3 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 haloalkynyl, C1 -C6 alkylthio, C1 -Cβ haloalkoxy C1 -C6 haloalkylthio, C3 -C7 cycloalkyl, C1 -C6 alkoxy, C3 -C6 alkenyloxy or C3 -C6 alkynyloxy; m is 0, 1, 2, 3 or 4; or Two R substituents adjacent together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1 -C6 alkyl, C1 -Cβ alkoxy and C1 -C6 alkylthio s, additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom); Ra is selected from hydrogen, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 8 alkenyl and C 3 -C 8 alkynyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 independently selected substituents from halogen, C1-6 alkoxy and C1-6 alkylthio; Rb and Rc are each independently selected from hydrogen, halogen, cyano, C1 -Ce alkyl, C3 -C7 cycloalkyl, C2 -Ce alkenyl, C2-Ce alkynyl, C1 -Ce alkoxy and C1 -C6 alkylthio, in that the alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1 -C' alkoxy and C1 -C[beta] alkylthio; or a salt or N-oxide thereof. Another preferred group of compounds according to the invention are those of formula IC which are compounds of formula I wherein R1 and R2 are each independently selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C6 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C1 alkoxy -C3 and C1-C3 alkylthio; R3 and R4 are each independently selected from hydrogen, halogen, C1-C4 alkyl θ C3-C4 cycloalkyl, the alkyl and cycloalkyl groups optionally being substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy and C 1 -C 3 alkylthio; each R.5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C3 alkylthio, C(=NORa) C1-alkyl Cβ, phenyl, heteroaryl (where heteroaryl is pyridyl, thiazolyl or oxazolyl), wherein the alkyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C 1 -C 3 Z alkyl, C 1 -C 3 alkoxy, n is 0, 1, or 2; Re is hydrogen or C1-C3 alkyl; each R7 independently represents cyano, halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C2 -C6 alkynyl, C1 -C6 alkylthio, C1 -C6 haloalkoxy, C1 -C6 haloalkylthio, C3 -C7 cycloalkyl, C1 -C6 alkoxy , C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1, 2, or 3; or Two adjacent R 7 substituents together with the carbon atoms to which they are attached represent a C 8 -C 6 cycloalkyl group; Ra is selected from hydrogen, C1-C4 alkyl and C3-C5 cycloalkyl, the alkyl and cycloalkyl groups optionally being substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy θ C1-C3 alkylthio ; or a salt or N-oxide thereof.
[0065] Another preferred group of compounds according to the invention are those of formula IC which are compounds of formula I wherein R 1 and R 2 are each independently selected from hydrogen and C 1 -C 1 -C 1 alkyl, in that the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1 -C3 alkoxy and C1 -C3 alkylthio; or R 1 and R 2 together with the carbon atom to which they are attached represent a C 3 -C 6 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 3 alkyl, alkoxy C1-C3 and C1-C3 alkylthio; R3 and R4 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C3-C4 cycloalkyl, the alkyl and cycloalkyl groups optionally being substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-CF cycloalkyl. (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C1 -C4 alkyl, C1 -C3 alkoxy and C1 -C3 alkylthio; each Rs independently represents halogen, cyano, C1 -alkyl Ca, C3-C4 cycloalkyl, C1-C4 alkoxy;, C3-05 alkenyloxy, C3-C6 alkynyloxy, C1-C4 alkylthio, -C (=NORa ) C1-C8 alkyl, phenyl, heteroaryl (where heteroaryl is pyridyl , thiazolyl or oxazolyl), wherein the alkyl, cycloalkyl, alkoxy, α]chenyloxy, alkynyloxy, phenyl and heteroaryl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen, C1 -C alkyl, C1 alkoxy -C3, n is 0, 1, or 2; R6 is hydrogen or C1-C3 alkyl; each R7 independently represents cyano, halogen, C1-C" alkyl, C1-C6 haloalkyl, C2-C alkynyl, C1-C6 alkylthio, C1-C6 haloalkoxy, C1-C6 haloalkylthio, C3-C6 cycloalkyl, C1-C6 alkoxy C1 -C6 alkenyloxy or C3 -C6 alkynyloxy; m is 0, 1, 2, or 3; or Two R, substituents together with the carbon atoms to which they are attached represent a Cs-Cr cycloalkyl group; Ra is selected from hydrogen, C1 -C3 alkyl and C3-05 cycloalkyl, wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from Halogen, C3 -C3 alkoxy and C alkyritic ;-Ç;; or a salt or N-oxide thereof.
[0066] Another preferred group of compounds according to the invention are those of formula ID which are compounds of formula I wherein R1 and R2 are each independently selected from hydrogen and C1-C4 alkyl, wherein the group alkyl may optionally be substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, and C1-C3 alkyl); R3 and R1 are each independently selected from hydrogen, halogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R3 and R1 together with the carbon atom to which they are attached represent C=0, C=NORa or C3-C4 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, and C1-C3 alkyl; each Rs independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl or phenyl, wherein the alkyl, cycloalkyl and phenyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen or C1-alkyl C3; n is 0, 1 or 2; Re is hydrogen or methyl; each R7 independently represents cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C3 alkynyl, C1-C4 alkylthio or C3-C4 cycloalkyl; m is 0, 1 or 2; and Ra is selected from hydrogen and C1 -C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 halogen atoms; or a salt or N-oxide thereof.
[0067] Another preferred group of compounds according to the invention are those of formula IE which are compounds of formula I wherein R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group; R3 and R4 are each independently selected from hydrogen, halogen and C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C4 cycloalkyl; each R5 independently represents halogen, cyano, C1-C3 alkyl, C3-C4 cycloalkyl or phenyl, wherein the alkyl, cycloalkyl and phenyl groups may optionally be substituted with 1 to 3 halogen atoms; n is 0, 1 or 2. Re is hydrogen or methyl; each R independently represents cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C4 cycloalkyl; m is 0, 1 or 2; and Ra is selected from hydrogen and C1 -C3 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 fluorine atoms; or a salt or N-oxide thereof. A'>
[0068] Another preferred group of compounds according to the invention are those of formula IF which are compounds of formula I wherein R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group; R3 and R4 are each independently selected from hydrogen, fluorine or C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=O, or C3-C4 cycloalkyl; each Rs independently represents halogen, C1-C3 alkyl or C3-C4 cycloalkyl, the alkyl and cycloalkyl groups optionally being substituted with 1 to 3 fluorine atoms; n is 0, 1 or 2; RÉ is hydrogen; and each R7 independently represents fluorine, chlorine or C1-C3 alkyl; m is 1 or 2; or a salt or N-oxide thereof.
[0069] Specific examples of compounds of formula I are illustrated in Tables A1 to A18 below:
[0070] Table Al provides 170 compounds of formula
where Re, R'a and R'b are all H and where the values of Ri, R2, R3, R$, R5 are as defined in Table Z1 below: Table Zl:






xa<0% .SU'D/,
[0071] Table A2 provides 170 compounds of formula Ia where R'a and Fbb are H, Rε is methyl and where the values of R1, R2, R3, R4 and R5 are as defined in Table Z1 above.
[0072] Table A3 provides 170 compounds of formula Ia wherein Ria and R b are H, Rε is Chlorine and wherein the values of Ri, Rz, R3, R4 and R5 are as defined in Table Z1 above.
[0073] Table A4 provides 170 compounds of formula Ia wherein Rε and R b are H, R a is methyl and wherein the values of R, R2, R3, R4 and R5 are as defined in Table Z1 above.
[0074] Table A5 provides 170 compounds of formula Ia wherein Rε and R b are H, R a is fluorine and wherein the values of R, R2, R3, RÍand Rs are as defined in Table Z1 above.
[0075] Table A6 provides 170 compounds of formula Ia where Re and R'b are H, R'a is chlorine and where the values of R1 , R2 , R3 , R1 and R5 are as defined in Table Z1 above.
[0076] Table A7 provides 170 compounds of formula Ia where Re and R'b are H, R'a is ethyl and where the values of R1, R2, R3, R1 and R5 are as defined in Table Z1 above.
Table A8 provides 170 compounds of formula Ia where Re and R'b are H, R'a is bromo and where the values of R1 , R2 , R3 , R1 and Rs are as defined in Table Z1 above.
[0078] Table A9 provides 170 compounds of formula Ia where Re is H, R'a and R'b are methyl and where the values of R1 , R2 , R3 , R1 and R5 are as defined in Table Z1 above.
Table A10 provides 170 compounds of formula Ia where Re is H, R'a and R'b are chlorine and where the values of R1 , R2 , R3 , R1 and Rs are as defined in Table Z1 above.
[0080] Table All provides 170 compounds of formula Ia where Re is H, R'a is methyl R'b is chloro and where the values of R1 , R2 , R3 , R1 and R5 are as defined in Table Z1 above.
[0081] Table A12 provides 170 compounds of formula Ia wherein R6 is H, R'a is fluorine R'b is methyl and wherein the values of R1 , R2 , R3 , R4 and Rs are as defined in Table Z1 above .
[0082] Table A13 provides 170 compounds of formula Ia wherein R6 is H, R7a is fluorine, R7b is chlorine and wherein the values of R1, R2, R3, R4 and Rs are as defined in Table Z1 above.
[0083] Table A14 provides 170 compounds of formula Ia wherein Re is H, R7a is methyl R7b is fluorine and wherein the values of R1 , R2 , R3 , R4 and Rs are as defined in Table Z1 above.
[0084] Table A15 provides 170 compounds of formula Ia where Re. is H, R7a is chloro R7b is methyl and wherein the values of R1, R2, R3, R4 and Rs are as defined in Table Z1 above.
[0085] Table A16 provides 170 compounds of formula Ia wherein R6 is H, R7a is chloro R7b is fluorine and wherein the values of R1, R2, R3, R4 and Rs are as defined in Table Z1 above.
[0086] Table A17 provides 170 compounds of formula Ia wherein Re is H, R7a and R7b are -CH2CH2CH2- and wherein the values of R1, R2, R3, R4 and Rs are as defined in Table Z1 above.
[0087] Table A18 provides 170 compounds of formula Ia wherein R6 and R'a are H, R7b is methyl and wherein the values of R1, R2, R3, R4 θ Rs are as defined in Table Z1 above.
[0088] The compounds according to the invention can possess any number of benefits, including, among others, advantageous levels of biological activity to protect plants against diseases that are caused by fungi, or superior properties for use as agrochemical active ingredients (for example , greater biological activity, an advantageous activity spectrum, a higher safety profile, improved physicochemical properties or greater biodegradability).
The compounds of the present invention may be prepared as shown in the schemes below, wherein, unless otherwise specified, the definition of each variable is as defined above for a compound of formula (I).
Compounds of formula I, in which R1, R2, R3, R4, Rb, RÉ, Rv, men are as defined for compounds of formula I, can be obtained by transforming a compound of formula II into that Rε, R7 and em are as defined for compounds of formula I, with a compound of formula III, wherein R1, R2, R3, R4, Rs and n are as defined for compounds of formula I and Hal is halogen, preferably chloro or bromine, in the presence of an organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper-based catalyst such as copper (I) acetylacetonate or copper(I) bromide-1,10-phenanthroline complex, a nickel catalyst such as Dichloro(1,3-bis(diphenylphosphino)propane) nickel or a palladium based catalyst such as Chloro(2-dicyclohexylphosphine) -2',4',6'-triisopropyl-1,1'-biphenyl)[2—(2'-amino-1,1'-biphenyl)]palladium(II), chloride precatalyst of X-Fos aminobiphenyl palladium or [1,3-Bis(c2>,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl) palladium(II) dichloride in an aprotic solvent such as pyridine, toluene or N,N-dimethylformamide while heating. This is shown in Scheme 1. Scheme 1

[0091] Compounds of formula II, wherein Rs, R and are as defined for the compounds of formula I, are either commercially available or are readily prepared using methods known to those skilled in the art, as described in the literature (Grimmet, MR In Imidazole and Benzimidazole Synthesis; Meth-Cohn, Katritzky, Eds. ; Elsevier Science: Oxford, 1997).
Compounds of formula III, wherein R1, R2, R3, Rn, R5 and n are as defined for compounds of formula I and Hal is halogen, preferably chlorine or bromine, can be obtained by the transformation of a compound of formula IV, wherein R1, R2, Ra, R4, R5 and n are as defined for compounds of formula I, with a halogenating reagent such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier's reagent neat or in the presence of a solvent such as dichloromethane, at various temperatures ranging from cooling to heating. This is shown in Scheme 2.

Compounds of formula IV, wherein R 1 , R 2 , R 3 , Ra , R-- and n are as defined for compounds of formula 1, can be obtained by transformation of a compound of formula V , wherein R 1 , R 2 , R 3 , R 4 , Rs and n are as defined for compounds of formula I and Re is ìC 1 -C quita _, with sodium acetate in acetic acid as described in the literature (Yu. B. Vikharev et al. Pharmaceutical Chemistry Journal, 2005, 39, 405-408). This is shown in Schema 3. Schema_3

Alternatively, compounds of formula III, wherein R 1 , R 2 , R 3 , Ra , R s and n are as defined for compounds of formula I, and Hal is halogen, p j -θ fg is readily chlorine or bromine, can be obtained by transforming a compound of formula V, wherein R 1 , Ra , R 3 , R 4 /Rs and n are as defined for the compounds of formula I and Rs is halogenating alkyl, such as chloride described in literature (Taebo Sim Letters, 2010, 51, 4609).
[0095] The compounds of Rs and n are according to I and Ra is alkyl transformation of one in which Ri, R2, compounds of FIS Rüb — I Ci-Ce, with a sulfuryl reagent according to et al. Tetrahedron This is shown in Scheme 4
formula V, wherein R 1 , R 2 , defined for the compounds of formula C 1 -C 6 , can be obtained by compounding R 3 , R 4 , R 6 in formula I and R' with a thiocyanate of formula VI-a, VI-b or VI-c, are as defined for both H and C1 -Ce alkyl, C1 -Cε alkyl under acidic conditions, e.g., with sulfuric acid as described in the literature (Yu.B. Vikharev et al. Pharmaceutical Chemistry Journal , 2005, 39, 405-408). This is shown in Scheme 5. Scheme5
compounds Os
[0096] of formula VI-a, VI-B or VI-c, wherein R 1 , R 2 , R 3 , R 4 , Rs are as defined for the compounds of formula I and R' is either H or C C C alkyl, or are commercially available or are easily prepared using methods known to persons skilled in the art.
Alternatively, compounds of formula IV, wherein R1, R2, R3, R4, Rs and n are as defined for compounds of formula I, may be obtained by transforming a compound of formula VII, wherein R1 , R 2 , R 3 , R 4 , R 5 and n are as defined for compounds of formula I under acidic conditions, e.g. , with sulfuric acid or polyphosphoric acid as described in the literature (Jun-ichi Minamikawa, Bioorganic & Medicinal Chemistry, 2003, 11, 2205-2209). This is shown in Scheme 6. Scheme 6

Compounds of formula VII, wherein R1, Rz, Rs, R4, R5 and n are as defined for compounds of formula I, can be obtained by transforming a compound of formula VIII, wherein R1, R2 , R3, R4, Rs and n are as defined for compounds of formula I, by treatment with hydroxylamine or hydroxylamine hydrochloride in a solvent such as ethanol or pyridine in the presence or absence of a base such as sodium acetate at temperatures ranging from room temperature until heating. This is shown in Scheme 7. Scheme 7

Compounds of formula VIII, wherein R 1 , R 2 , R 3 , R 1 , R 5 and n are as defined for compounds of formula I, are either commercially available or are readily prepared using methods known to persons skilled in the art .
Alternatively, compounds of formula IV, wherein R 1 , R 2 , R 3 , FU, R 5 and n are as defined for compounds of formula I, may be obtained by transforming a compound of formula IX-a into that R1, R2, R3, R4, Rs and n are as defined for compounds of formula I, by treatment with carbonylating agents such as phosgene, triphosgene or carbonyldiimidazole and subsequent heating, or using directed catalytic CH activation-carbonylation in the presence of carbon monoxide gas, a palladium catalyst such as palladium acetate and an oxidant such as benzoquinone as reported in the literature (Jaume Granell et al. Chem. Commun., 2011, 47, 1054-1056). This is shown in Schema Schema 8

Alternatively, compounds of formula IV, wherein R 1 , R s, R 3 , R 4 , R s and n are as defined for compounds of formula I, can be obtained by transforming a compound of formula IX-b, wherein Ri, R2, R3, R4, Rs and n are as defined for compounds of formula I and Hal is halogen, preferably chlorine, bromine, or iodine, using an intramolecular aminocarbonylation in the presence of carbon monoxide gas, such a palladium catalyst such as Dichlorobis(tricyclohexylphosphine)palladium(II) or Dichlorobis(triphenylphosphine) palladium(II) and an organic base such as a triethyl amine, pyrrolidine or an inorganic base such as cesium carbonate or potassium carbonate as reported in the literature ( Ruimao Hua et al. Tetrahedron Letters, 2013, 54, 5159-5161). This is shown in Schema Schema 9
Alternatively, compounds of formula IV, wherein R 1 , R 2 , R 3 , R 4 , Rs and n are as defined for compounds of formula I, can be obtained by transforming a compound of formula X, wherein R 1 , Ra , Rs, Ra, Rs and n are as defined for compounds of formula I and R' is C1-Cβ alkyl, under acidic conditions, eg sulfuric acid or triflic acid as described in the _C>' literature (Tomohiko Ohwada et al. Journal of Organic Chemistry, 2012, 77, 9313). This is shown in Scheme 10. Scheme 10

Compounds of formula Ib, wherein R3 and R1 are fluorine and R1 , R2 , Rs , Re , R7 , except as defined for compounds of formula I, can be obtained by transforming a compound of formula Ic where R3 and R1 together with the carbon atom to which they are attached represent C=O and R1, R2, Rs, Re, R7, men are as defined for formula I with a fluorinating agent such as diethylaminosulfur trifluoride (DAST) or 2,2-difluoro-1,3-dimethyl-imidazolidine (DFI) neat or in the presence of a solvent while heating. This is shown in Scheme 11. Scheme 11

[00103] Compounds of formula Ic, wherein R3 and R1 together with the carbon atom to which they are attached represent C=0 and R1, R2, R5, Re, R7, men are as defined for formula I, can be obtained by transforming a compound of formula II, wherein Re, R7 and are as defined for compounds of formula I, with a compound of formula III-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R1, R2, R5 and n are as defined for formula I and Hal is halogen, preferably chlorine or bromine, in the presence of a hindered organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6 - lutidine or in the presence of a transition metal catalyst such as a copper based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1,10-phenanthroline complex, a nickel catalyst such as Dichloro(1,3-bis(diphenylphosphino)propane)nickel or a palladium based catalyst such as Clo ro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl) [2-(2'-amino-1,1'-biphenyl)] palladium(II), precatalyst of X-Fos aminobiphenyl palladium chloride or [1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride in an aprotic solvent such as pyridine, toluene or N,N-dimethylformamide while heating. This is shown in Scheme 12. Scheme 12

[00104] Compounds of formula III-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R1, R2, R5 and n are as defined for formula I and Hal is halogen, preferably chlorine or bromine, can be obtained by transforming a compound of formula IV-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R1 , R2 / R5 and n are accordingly defined for formula I, with a halogenating reagent such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide or pure Vilsmeier reagent or in the presence of a solvent such as dichloromethane, at various temperatures ranging from cooling to heating. This is shown in Scheme 13.

[00105] Compounds of formula IV-a, wherein R3 and R4 together with the carbon atom to which they are attached represent C=0 and R1, Rz, Rs, and n are as defined for formula I, can be obtained by transforming a compound of formula IV-b, wherein R3 represents hydrogen, R4 represents OH and R1, R2, Rs and n are as defined for formula I, with an oxidizing agent 1,1,1-triacetoxy-1. ,1-dihydro-1,2-benziodoxol3(1H)-one (Dess-Martin periodinane) or using oxalyl chloride, dimethyl sulfoxide (DMSO) and an organic base such as triethylamine (Swern oxidation). This is shown in Scheme 14. Scheme 14

[00106] The compounds of formula IV-b, wherein R3 represents hydrogen, R4 represents OH and R1, R2, R5 θ n are as defined for formula I, can be obtained by transforming a compound of formula IV- c, wherein R3 represents hydrogen, R4 represents Hal, wherein Hal is halogen, preferably chlorine or bromine, and R1, R2, R5 and n are as defined for formula I, under hydrolysis conditions such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogen carbonate, at temperatures ranging from room temperature to heating. This is shown in Scheme 15. Scheme 15

[00107] Compounds of formula IV-c, wherein R3 represents hydrogen, R1 represents Hal, wherein Hal is halogen, preferably chlorine or bromine, and R1, R2, Rs and n are as defined for formula I, can be obtained by transforming a compound of formula IV-d, wherein R3 and R1 represent hydrogen and R1, Rz, Rs and n are as defined for formula I, with a halogenating agent such as N-chlorosuccinimide (NCS), N- bromosuccinimide (NBS) or 1,3-dibromo-5,5-dimethylhydantoin, in the presence of a radical initiator such as a benzoyl peroxide or an azobisisobutyronitrile (AIBN) as described in the literature ((Jahangir et al Journal of Organic) Chemistry, 1989, 54, 2992). This is shown in Scheme 16. Scheme 16

[00108] Alternatively, compounds of formula IV-a, wherein R3 and R1 together with the carbon atom to which they are attached represent C=O and R1, Ra, Rs and n are as defined for formula I, can be obtained by transforming a compound of formula IV-e, wherein R3 and R4 represent Hal, wherein Hal is halogen, preferably chlorine or bromine, and R1, R2, Rs and n are as defined for formula I, under conditions of hydrolysis, such as heating in a mixture of an organic solvent such as tetrahydrofuran or 1,4-dioxane and water in the presence or absence of an inorganic acid such as hydrochloric acid or an inorganic base such as sodium hydrogencarbonate, at temperatures ranging from room temperature to heating. This is shown in Scheme 17. Scheme 17

Compounds of formula IV-e, wherein R3 and R1 represent Hal, wherein Hal is halogen, preferably chlorine or bromine, and R1, R2, Rs and n are as defined for formula I, can be obtained by means of the transformation of a compound of formula IV-d, wherein R3 and R1 represent hydrogen and R1, R2, Rs and n are as defined for formula I, with a halogenating agent such as N-chlorosuccinimide (NCS), N-bromosuccinimide ( NBS) or 1,3-dibromo-5,5-dimethylhydantoin, in the presence of a radical initiator such as a benzoyl peroxide or an azobisisobutyronitrile (AIBN) as described in the literature ((Jahangir et al Journal of Organic Chemistry, 1989, 54, 2992). This is shown in Scheme 18. Scheme 18

[00110] Compounds of formula IV-d can be obtained according to the method described in Scheme 3.
[00111] Alternatively, compounds of formula Ia, wherein R 3 and R' are fluorine and R 1 , R 2 , Rs , Re , R 7 , men are as defined for compounds of formula I, can be obtained by the transformation of a compound of formula II, wherein Re, R7 and m are as defined for compounds of formula I, with a compound of formula III-b, wherein R3 and R1 are fluorine and R1 , R2 , Rs and n are as defined for formula I and Hal is halogen, preferably chlorine or bromine, in the presence of a hindered organic base such as triethylamine, ethyldiisopropylamine, pyridine or 2,6-lutidine or in the presence of a transition metal catalyst such as a copper-based catalyst such as copper (I) acetylacetonate or copper (I) bromide-1,10-phenanthroline complex, a nickel catalyst such as Dichloro(1,3-bis(diphenylphosphino)propane) nickel or a palladium based catalyst such as Chloro(2-dicyclohexylphosphino-2',4',6' - triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]p aladium(II), palladium chloride precatalyst of X-Fos aminobiphenyl or [1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl) palladium(II) dichloride in a solvent aprotic such as pyridine, toluene or N,N-dimethylformamide while heating. This is shown in Scheme 19.

[00112] Compounds of formula 1II-b, wherein R3 and R, are f:1Lo c and R1, R1 , R5 and n are as defined for the compounds of formula I and Hal is halogen, preferably Chlorine or bromine, may be obtained by transforming a compound of formula IV-f, wherein R3 and R4 are fluorine and R1 , R2 , R2 and n are as defined for compounds of formula I, with a halogenating reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide or Vilsmeier's reagent neat or in the presence of a solvent such as dichloromethane, at various temperatures ranging from cooling to heating. Issc is shown in Scheme 20.

Compounds of formula IVY'-f, wherein R- and R1 , are fluorine and R1 , R2 , R2 and n are as defined for compounds of formula I, can be obtained by the transformation of a compound of formula IV-f, wherein Ra and R4 are Hal and Hal is halogen, preferably chlorine or bromine, and R1, R2, Rs and n are as defined for compounds of formula I, with a source of fluoride, such as potassium fluoride , cesium fluoride or hydrogen fluoride in the presence of an organic base such as pyridine or triethylamine as described in the literature (Hideki Umetani et al. WO 2013047749). This is shown in Scheme 21. Scheme 21

[00114] Alternatively, compounds of formula I, wherein R1, Rz, R3, R1,Rs, Rε, R', and men are as defined for formula I, may be obtained by transformation of a compound of formula Id , wherein R 1 , R 2 , R 3 , R 4 , R 6 , R 2 , men are as defined for formula I and Z represents bromine or iodine in a solvent, in the presence or absence of a base, and in the presence of a coupling reagent and a metallic catalyst. There are no particular limitations on coupling agent, catalyst, solvent and bases as long as it is used in common coupling reactions such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry)", edited by Norio Miyaura und SL Buchwald (Springer editions), or "Metal-Catalyzed . c Cross-Coupling Reactions", edited by Armin de Meijexe and François Diederich (WILEY-VCH editions). This is shown in Scheme 22.

[00115] Alternatively, compounds of formula I, wherein R 1 , R 2 , R 3 , R 4 , Rs , Re , R 2 , men are as defined for formula I, can be obtained by transformation of a compound of formula Ie , wherein R 1 , R 2 , R 3 , R 1 , R 5 , R 3 , men are as defined for formula I and Y represents bromine or iodine in a solvent, in the presence or absence of a base, and in the presence of a coupling reagent and a metallic catalyst. There are no particular limitations on coupling agent, catalyst, solvent and bases as long as it is used in common coupling reactions such as those described in "Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry)", edited by Norio Miyaura und SL Buchwald (Springer editions), or "Metal-Catalyzed Cross-Coupling Reactions", edited by Armin de Meijere and François Diederich (WILEY-VCH editions). This is shown in Scheme 23. Scheme 23

Alternatively, compounds of formula I, wherein R 1 , R 2 , R 3 , R 3 , R 6 , Re , R 2 , and men are as defined above, may be obtained by transformation of another closely related compound of formula I (or an analogue thereof) using standard synthesis techniques known to the person skilled in the art. Non-exhaustive examples include oxidation reactions, reduction reactions, hydrolysis reactions, coupling reactions, nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, nucleophilic addition reactions and halogenation reactions.
[00117] Certain intermediates described in the above schemes are new and as such form a further aspect of the invention.
[00118] Compounds of formula I can be used in the agricultural sector and related areas of use, for example, as active ingredients for the control of plant pests or in non-living materials for the control of microorganisms that cause spoilage or potentially harmful organisms for man. The new compounds are distinguished by excellent activity at low application rates, being well tolerated by plants and being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for the protection of numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy pests occurring on plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting those parts of the plants. plants that grow later, for example, of phytopathogenic microorganisms.
[00119] It is also possible to use the compounds of formula I as a fungicide. The term "fungicide" as used herein means a compound that controls, modifies or prevents the growth of fungi. The term "fungicidal effective amount" means the amount of such a compound or combination of such compounds which is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural development, such as death, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection,
[00120] It is also possible to use the compounds of formula I as disinfecting agents for the treatment of plant propagation material, eg seeds, such as fruits, tubers or grains, or plant cuttings (eg rice), for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula I before planting: a seed, for example, can be treated before being sown. The compounds of formula I can also be applied to grains (coating) either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention also relates to such methods of treating plant propagation material and to the plant propagation material so treated.
[00121] Additionally, the compounds according to the present invention can be used to control fungi in related areas, for example, in the protection of technical materials, including wood and wood-related technical products, in food storage, in hygiene management .
[00122] Additionally, the invention can be used to protect non-living materials from fungal attack, for example, construction timber, wall panels and paints.
The compounds of formula I and the fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of plant fungal pathogens. These are effective in controlling a wide spectrum of plant diseases such as foliar pathogens of ornamental crops, grass, vegetables, field crops, cereals and fruits. is' c. ->o ■S ** ^ '8 55/165 %> v3d3^
[00124] Fungal disease-causing fungi and vectors, as well as phytopathogenic bacteria and viruses, which can be controlled are, for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. including B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium muscingarum, G. , Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum stop, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea, Sclerotheca fuliginea, S. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula hecator-, Urocystis spp, Ustilago spp, Venturia spp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.
[00125] In particular, the compounds of formula I and the fungicidal compositions containing them can be used to control plant diseases caused by a broad spectrum of plant fungal pathogens in the classes of Basidiomycetes, Ascomycetes, Oomycetes and/or Deuteromycetes, Blasocladiomycetes, Critidiomycetes, Glomeromycetes and/or Mucoromycetes.
These pathogens may include: Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora soybeane, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnammytohora e Phytophthora cinnamomiptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola. Ascomycetes, including spot diseases, bruises or molds and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora ta inanensis, Spilocaea oleagmea, Setospha'eXSha turcica, Pyrenochaeta lycoperisici, Pleospora herbarum destructive , Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, cactivora Bipolaris, Venturia inaequalis, Pyrenophora teres, Pyrenophora triticirepentis , Alternaria alternate, Alternaria brassicicola, Alternaria solani and Alternaria toma tophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoi des, Cladosporium carpophilum, Cladosporium effusum, fulva Passalora, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Vitis Pseudocercospora, Pseudocercosporella herpotrichoides, beticola Ramularia, collo-cygni Ramularia, Magnaportales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaportales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium j ugignentis siricumland, Phycognomonia shirkus, phyllose, Phygn. , Waltz Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candidaspp., Capnodium ramosum, Cephaloascusspp., Cephalosporium gramineum, Ceratocystis paradoxacyus, Chaetomium ph. albidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora perenodes pomigena, Glonanes; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crssiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescendios expansionus, P. rhododendri, Petriellidium spp., Peziculaspp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivore, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medica ramginis, Pseudopeziza medica sphyllosporium, Rhisporium sorghum, Pyrenopeziza, R. pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsisis peanuts, e.g. caused by Erisifales such as Blumeria graminis, Erysiphe polygon!, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossylliars such as Dodiopsis gossylliars such as Doidiopsis gossylliar, Phylacte; aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fus icoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta cucurbitacearum; anthracnoses for example those caused by Glomerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilts or molds for example those caused by Hipocreales such as Acremonusa strictum, Clavicerium Fumine, Fpurearium, virguli forme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma vir.
Basidiomycetes, including smuts, for example those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts, for example those caused by Puciniales such as Cerotelium fiei, Chrysomyxa arctostaphyli, Colesporium, Coleosporium Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other decays and diseases such as those caused by Cryptococcusspp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisforma, Laetisaria, Laetisaria, Invismeri, Laetisaria, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries.
[00128] Blastocladiomycetes such as Physoderma maydis.
[00129] Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus,
[00130] As well as diseases caused by other species and genera closely related to those listed above.
[00131] In addition to their fungicidal activity, the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.
Within the scope of the present invention, useful plants and/or target crops to be protected typically comprise perennial and annual crops, such as berries, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (maize), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beet and fodder, coffee, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apple, apricot, avocado, banana, cherry, citrus fruit, nectarine, peach, pear and plum; grasses, for example Bermuda grass, blue grass, agrostis, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; aromatic herbs such as basil, borage, chives, coriander, lavender, levistic, mint, oregano, parsley, rosemary, sage and thyme; vegetables, for example beans, lentils, peas and soya; dried fruit, for example almond, cashew, peanut seed, hazelnut, peanut, pecan, pistachio and walnut; palms, for example palm oil; ornamental plants, for example flowers, shrubs and trees; other trees, for example cocoa, coconut, olive and rubber; vegetables and vegetables, for example asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, pumpkin, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines, for example grapes.
[00133] Useful plants and/or target crops according to the invention include conventional as well as genetically improved or manipulated varieties, such as, for example, insect resistant varieties (e.g. Bt. and VIP varieties) as well as disease resistant , herbicide tolerant (eg glyphosate and glufosinate resistant maize varieties commercially available under the RoundupReady® and LibertyLink® trademarks) and nematode tolerant. As an example, suitable genetically improved or engineered crop varieties include Stoneville 5599BR and Stoneville 4892BR cotton varieties.
The term "useful plants" and/or "target crops" is to be understood as also including useful plants that have been made tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors , for example, primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate synthase) inhibitors, GS (glutamine synthase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) as a result of methods conventional breeding or genetic engineering. An example of a crop that has been made tolerant to imidazolinones, eg imazamox, by conventional breeding methods (mutagenesis) is the Clearfield® summer rape (Canola). Examples of crops that have been made tolerant to herbicides or herbicide classes by genetic engineering methods include glyphosate and glufosinate resistant corn varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
[00135] The term "useful plants" and/or "target crops" is to be understood to include those that naturally are or have been made resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be able to synthesize one or more toxins with selective action, such as are known, for example, from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode colonizing bacteria, and toxins produced by scorpions, arachnids, wasps and fungi. An example of a culture that has been modified to express Bacillus thur ingiens is toxin is Bt Knockout® maize (Syngenta Seeds). An example of a crop comprising more than one gene encoding insecticide resistance and thus expressing more than one toxin is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to various types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant may have the ability to express an insecticidal protein while being tolerant to herbicides, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
[00136] The term "useful plants" and/or "target cultures" should be understood to also include useful plants that have been transformed, using recombinant DNA techniques, so that they are capable of synthesizing antipathogenic substances with a selective action, such as , for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such anti-pathogenic substances and transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as Ô-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins from nematode colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycetes toxins, plant lectins such as pea lectins, barley lectins or white bell lectins; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, plus RIP, abrin, luphine, saporin or briodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
[00138] Furthermore, in the context of the present invention they are to be understood as δ-endotoxins, for example, CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, also expressly hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids from the naturally occurring toxin are replaced. In such amino acid substitutions, recognition sequences from non-naturally present proteases are preferably inserted into the toxin, such as, for example, in the case of Cry3A055, a recognition sequence for cathepsin G is inserted into a Cry3A toxin (see W003/018810) .
Further examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO93/07278, WO95/34656, EP-A-0 427 529, EP-A -451 878 and W003/052073.
[00140] Processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
[00141] The toxin contained in transgenic plants gives plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
[00142] Transgenic plants containing one or more genes that encode an insecticide resistance and express one or more toxins are known, and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (variety of maize that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (variety of maize that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricin-N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a Cry1Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (variety of potato that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (glyphosate tolerant trait GA21), Agrisure® CB Advantage (corn borer (CB) Btll trait) and Protecta®.
[00143] Additional examples of such transgenic crops are: 1. Btll corn from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays that was made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btll maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 2. Maiz Btl76 from Syngenta Seeds SAS, Chemin de I’Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays that was made resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium. 3. Maiz MIR604 from Syngenta Seeds SAS, Chemin de I’Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. MAiz that has been made insect resistant through transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4. Maiz MON 863 of Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects. 5. IPC 531 cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02. 6. Maiz 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein CrylF to achieve resistance to certain Lepidoptera insects and to the PAT protein to achieve tolerance to the herbicide glufosinate ammonium. 7. Maiz NK603 x MON 810 from Monsanto Europe S.A. 270- 272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. It consists of hybrid maize varieties conventionally improved by crossing the genetically modified varieties NK603 and MON 810. Maize NK603 * MON 810 transgenically expresses the CP4 EPSPS protein, obtained from the CP4 strain of Agrobacterium sp., which confers tolerance to the Roundup® herbicide (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki that provides tolerance to certain Lepidoptera, including the European corn borer.
[00144] The term "locus" as used herein means fields in or on which plants are growing, or where the seeds of cultivated plants are sown, or where the seed will be placed in the ground. This includes soil, seeds, and seedlings, as well as established vegetation.
[00145] The term "plants" refers to all physical parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, foliage and fruits.
[00146] The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example, potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil can also be mentioned. These young plants can be protected before transplanting through a total or partial immersion treatment. Preferably, "plant propagation material" is understood to denote seeds.
Pesticide agents referred to herein using their common name are known, for example from "The Pesticide Manual", 15thEd., British Crop Protection Council 2009.
The compounds of formula I can be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulations. For this purpose, they can be conveniently formulated, in a known manner, in emulsifiable concentrates, coating pastes, directly sprayable or dilutable suspensions or solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations, by example, in polymeric substances. As with the type of compositions, the methods of application, such as spraying, atomizing, dusting, dispersing, coating or pouring, are chosen according to the intended objectives and prevailing circumstances. The compositions can also contain other adjuvants such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
[00149] Suitable carriers and adjuvants, for example, for agricultural use, can be solid or liquid and are substances useful in formulation technology, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners , binders or fertilizers. Such carriers are described, for example, in WO 97/33890.
[00150] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may additionally include a wetting agent to enhance activity as well as an antifoam and a crystal growth inhibitor. In use, these concentrates are diluted with water and typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.
[00151] Wettable powders are in the form of finely divided particles that disperse quickly in water or other liquid carriers. The particles contain the active ingredient trapped in a solid matrix. Typical solid matrices include Fuller's earth, kaolin clays, silicas and other organic or inorganic solids that are quickly wetted. Wettable powders typically contain 5% to 95% of the active ingredient and a small amount of wetting, dispersing or emulsifying agent.
[00152] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and which may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquid and usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.
[00153] Granular formulations include both extrudates and relatively coarse particles and are typically applied undiluted to the region where treatment is required. Typical carriers for granular formulations include sand, Fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, cobs crushed corn, ground peanut husks, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with the active compound. Granular formulations typically contain 5% to 25% of active ingredients which may include surface active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or adhesives such as dextrins, glue or synthetic resins.
[00154] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids that act as dispersants and carriers.
[00155] Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous envelope that allows the release of the enclosed material to the surroundings at controlled rates. The diameter of the encapsulated droplets is typically 1 to 50 microns. The enclosed liquid typically constitutes 50 to 95% of the capsule weight and may include a solvent in addition to the active compound. Encapsulated granules are usually porous granules with porous membranes that seal off the granule pore openings, retaining the active species in liquid form within the granule pores. Granules typically range from 1 millimeter to 1 centimeter and preferably from 1 to 2 millimeters in diameter. Granules are formed by extrusion, agglomeration or compression, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular coal. Capsule or membrane materials include synthetic and natural rubbers, cellulosic materials, copolymers of styrene and butadiene, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
[00156] Other formulations useful for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays can also be used, in which the active ingredient is dispersed in a finely divided form due to vaporization of a dispersing solvent carrier having a low boiling point.
Suitable agricultural adjuvants and carriers which are useful in formulating the compositions of the invention in the types of formulations described above are well known to those skilled in the art.
[00158] Liquid carriers that can be used include, for example, water, toluene, xylene, petroleum naphtha, culture oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diroxitol, alkylpyrrolidinone, ethyl acetate, 2-ethyl-hexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, butyl ethylene glycol ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadeca no, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, octane , methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, ether monomethyl propylene glycol, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and molecular weight alcohols higher, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for diluting concentrates.
Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, bark of cottonseeds, wheat flour, soy flour, pumice, wood flour, nutshell flour and lignin.
[00160] A wide variety of surfactants are advantageously used in both said liquid and solid compositions, particularly those designed to be diluted with the carrier prior to application. Such agents, when used normally comprise from 0.1% to 15% by weight of the formulation. These can be anionic, cationic, non-ionic or polymeric in nature and can be used as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; addition products a. to alkylphenol-alkylene oxide such as nonylphenol-ethoxylate C.sub. 18; alcohol-alkylene oxide addition products such as tridecyl alcohol-ethoxylate C.sub. 16; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; sulfosuccinate salts of dialkyl esters such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
[00161] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoaming agents, light blocking agents, compatibilizing agents, defoaming agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavors, dispersing agents, penetration enhancers, micronutrients, emollients, lubricants and adhesive agents.
[00162] Furthermore, additionally, other biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these additional active ingredients can be formulated together with the compositions of the invention or mixed, for example, in the spray tank. These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.
[00163] Additionally, the compositions of the invention can also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described, for example, in United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.
The compounds of formula I are normally used in the form of compositions and can be applied to the region of the crop or plant to be treated, together with additional compounds simultaneously or successively. These additional compounds can be, for example, fertilizers or micronutrient donors or other preparations, which influence plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with additional carriers, surfactants or application-promoting adjuvants commonly employed in the formulation art.
The compounds of formula I can be used in the form of compositions (fungicides) for the control or comprising as active ingredient at least one compound of formula I or at least one preferred individual compound as defined above, in free form or in form of usable salt in the agrochemical domain, and at least one of the aforementioned adjuvants,
Thus, the invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula I, an agriculturally acceptable carrier and, optionally, an adjuvant. An agriculturally acceptable carrier is, for example, a carrier that is suitable for agricultural use. Agricultural conveyors are well known in the art. Preferably, said composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula I.
[00167] The compound of formula (I) can be the only active ingredient of a composition, or it can be mixed with one or more additional active ingredients, such as a pesticide, fungicide, synergist, herbicide or plant growth regulator, when appropriate. An additional active ingredient can, in some cases, result in unexpected synergistic activities.
[00168] Examples of suitable additional active ingredients include the following acycloamino acid fungicides, amide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl-phenylketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithioamide fungicides, furicides of furanilide, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, , pirim fungicides idine, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiophenethiocarbicide fungicides , triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides and zinc fungicides.
Examples of suitable additional active ingredients also include the following: 3-Difluoromethyl1-1-methyl-1H-pyrazole-4-carboxylic acid dichloromethylene-1,2,3,4-tetrahydro-1,4-methane -naphthalen-5-yl)-amide, 3-difluoromethyl-1-methyl)-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide , 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1), 1-methyl acid -3-difluoromethyl-1H-pyrazole-4-carboxylic (4'-methylsulfanyl-biphenyl-2-yl)-amide, 1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid [2-(2,4 -dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide, (5-Chloro-2,4-dimethyl-pyridin-3-yl) -(2,3,4-trimethoxy-6-methyl- phenyl}-methanone, (5-Bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[( E)-3-(2,6-Dichloro-phenyl)-1-methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methyl- acetamide, 3-[5-(4-Chloro-phenyl)-2,3-dimethyl-isoxazolidin-3 - yl]-pyridine, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N,N-dimethyl-6 -trifluoromethylbenzimidazol-1-sulfonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-i-butyrolactone, 4-chloro-2-cyano-N, -dimethyl-5-p- tolylimidazol-1-sulfonamide, N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide, N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide, N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, ()-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, 2',6'-dibromo-2- methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazol-5-carboxanilide, 1-imidazolyl-1-(4'-chlorophenoxy)-(E)-2-[2-[6-{2-cyanophenoxy methyl pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, (E) methyl-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate methyl, (E) methyl-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, (E)—2—[2—[6—(2 methyl ,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, (E)—2—[2—[3—(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E) methyl-2-[2-[3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylate, (E)—2—[2—[3—(phenylsulfonyloxy) methyl phenoxy]phenyl-3-methoxyacrylate, (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl] methyl-3-methoxyacrylate, (E)-2-[2-phenoxyphenyl]- Methyl 3-methoxyacrylate, (E)-2-[2-(3,5-dimethyl-benzoyl)pyrrol-1-yl]-3-methoxymethylacrylate, (E)-2-[2-(3-methoxyphenoxy )phenyl]-3-methoxy methyl acrylate, (E)-2[2-(2-phenylethen-1-yl)-phenyl]-3-methoxy methyl acrylate, (E)-2-[2-(3,5- methyl dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, (E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxymethylacrylate, ( E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3-methoxyacrylate methyl, (E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3- methyl methoxyacrylate, (E)-2-[2-(3-n-propyloxy-phenoxy)phenyl]3-methyl methoxyacrylate, (E)-2-[2-(3-isopropyl methyl loxyphenoxy)phenyl]-3-methoxyacrylate, (E)~ 2-[2-[3-(2-fluorophenoxy)phenoxy]phenyl] methyl-3-methoxyacrylate, (E)-2-[2-(3 methyl-ethoxyphenoxy)phenyl]-3-methoxyacrylate, (E)-2-[2-(4-tert-butyl-pyridin-2-yloxy)phenyl] methyl-3-methoxyacrylate, (E)—2—[ methyl 2-[3—(3- cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, (E)-2-[2-[(3-methyl-pyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate methyl , (E) methyl-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, (E}-2-[2-(5-bromo-pyridin) methyl-2-yloxymethyl)phenyl]-3-methoxyacrylate, (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate methyl, (E)- Methyl 2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, (E), (E)—2—[2—(5,6- methyl dimethylpyrazin-2-ylmethyloximinomethyl)phenyl]-3-methoxyacrylate, (E)-2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy-acrylate of methyl, (E),(E)-2-{ 2-(3-methoxyphenyl)methyloximinomethyl]-phenyl}-3-methoxy methyl acrylate, (E)—2—{2 —(6-(2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate methyl, (E), (E)-2-{2-[6-phenylpyrimidin-4-yl)-methyloximinomethyl] methyl phenyl}-3-methoxyacrylate, (E),(E)-2-{2-[(4-chlorophenyl)-methyloximinomethyl]-phenyl} methyl-3-methoxyacrylate, (E)—2-{2- Methyl [6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate, (E),(E)—2—{2—[(3—nitrophenyl )methyloximinomethyl]phenyl}-3-methoxyacrylate methyl, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine), 2,6-dichloro-N- (4-trifluoromethylbenzyl)-benzamide, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl n-butylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate, 3-iodo-2-propynyl cyclohexylcarbamate, 3-iodo-2-propynyl phenylcarbamate; phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4- chlorophenol, 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenethiazolinone, 4,5-dichloro-(3H)-1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1, 3,5-thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)hexaminium chloride, acibenzolar, acipetaks, alanicarb, albendazole, aldimorph, allicin, allylic alcohol, amethoctradine, amisulbrom, amobam, ampropylphos, anilazine, asomate , aureofungin, azaconazole, azafendine, azithyram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanyl, benomyl, benquinox, bentalurone, bentiavalcarb, bentiazol, benzalkonium chloride, benzamacrylic, benzamacrylic acid, benzamorine biloxazole, binapacryl, biphenyl, bitertanol, bithionol, bixaphene, blasticidin-S, boscalide, bromothalonyl, bromuconazole, bupirimate, butiobate, calcium polysulfide and butylamine,captafol,captan, carbamorph, carbendazim, hydrochloride, carbendazim CGA41396, CGA41397, chinomethionate, chitosan, clobent iazone, chloraniformatane, chloranil, chlorphenazol, chlornebo, chloropicrin, chlorothalonil, chlorozolinate, clozolinate, climbazol, clotrimazole, clozylacon, copper containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, oxychloride of copper, copper oxyquinolate, copper silicate, copper sulfate, copper talate, copper zinc chromate and Bordeaux mixture, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramide, cycloheximide, cyflufenamide, cymoxanil, cipendazole, cyproconazole, cyprodinil, dazomete, debacarb, decafentin, dehydroacetic acid, disulfide 1,1'-di-2-pyridyl dioxide, dichlofluanid, diclomezine, diclone, dichlorane, dichlorophen, diclozoline, diclobutrazol, diclofenazolcarb , difenzoquat, diflumetorime, 0,0-diisopropyl-S-benzyl thiophosphate, dimefluazole, dimethaclone, dimetconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobutone, dinocapo, dinoctone, dinopentone, dinosulfone, dinoterbone, diphenylamine, dipyrithion, disulfiram,dilylphos, dithianone, dithioether, dodecyl dimethyl ammonium chloride, dodemorph, dodicine, dodine, doguadine, drazoxolone, edicontazole, epthanestrone, epoxy, epoxide ethirimol, ethoxyquin, ethylicin, (Z)-N-benzyl-N ([methyl(methyl-thioethylideneamino-oxycarbonyl)amino]thio)-B-ethyl alaninate, etridiazole, famoxadone, fenamidone, phenaminosulfe, fenpanil, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, flupyrazine, fluquinotymazole, stromazol flusilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, furmec iclox, furofanate, gliodine, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiophos, hydrargafen, hydroxyisoxazole, himexazole, imazalyl, imazalyl sulfate, imibenconodine, iprobectadine, iminoctate , iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, isopyrazam, isothianil, isovaledione, izopamphos, casugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozebe, mela, mandipropamide, mebela, mandipropamide, mebela, mandipropamide, mebela mercury, mercurous chloride, meptyldynocap, metalaxyl, metalaxyl-M, metam, metazoxolone, metconazole, metasulfocarb, metfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, metiram, metiramzinc, metominostrobine, metraxfenone , myclobutanil, myclozolin, nabam, natamycin, neoasozine, nickel dimethyldithiocarbamate, nitrate ostyrene, nitrothal-iso-propyl, nuarimol, octylinone, ofurace, organomercury compounds, orysastrobin, ostol, oxadixyl, oxasulfuron, oxine-copper, oxolinic acid, oxpoconazole, oxycarboxin, parinol, pefurazoate, penpyrazoate, penconazole, penconazole , phenamacryl, phenazine oxide, phosdiphene, fosetyl-Al, phosphorus acids, phthalide, picoxystrobin, piperaline, polycarbamate, polyoxin D, polyoxrim, polyrame, probenazol, prochloraz, procymidone, propamidine, propamocarb, propicon, propiconazole, probe prothiocarb, prothioconazole, pyracarbolide, pyraclostrobin, pyrametrostrobin, pyraoxystrobin, pyrazolophos, pyribencarb, pyridinitrile, pyrifenox, pyrimethanil, pyriophenone, pyroquilone, pyroxychlor, pyroxifur, pyrrolnitrine, quinone ammonium compounds, quaternary ammonia, benzinazole, quinzenthion , santonins, sedaxane, silthiofame, simeconazole, sipconazole, sodium pentachlorophenate , solatenol, spiroxamine, streptomycin, sulfur, sultropene, tebuconazole, tebfloquin, teclophthalam, technazene, tecorame, tetraconazole, thiabendazole, thiadifluor, thiciophen, tifluzamide, 2-(thiocyanomethylthio) benzothiazole, thiophanate, thioquine-oxmethyl, thioximide, tolclophos-methyl, tolylfluanid, triadimephone, triadimenol, triamiphos, triarimol, triazbutyl, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazole, triforine, triflumizole, triticonazole, uniconazole, urbacidal, vinbenazine, validamycin ziram, and zoxamide. The compounds of the invention can also be used in combination with anthelmintic agents. Such anthelmintic agents include compounds selected from the class of macrocyclic lactone compounds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP-357460, EP-444964 and EP -594291. Additional anthelmintic agents include semi-synthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxybendazole, parbendazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisol, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintic agents include fluquicides such as triclabendazole and chlorsulone and cestodes such as praziquantel and epsiprantel.
The compounds of the invention can be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintic agents, as well as the antiparasitic oxazolines such as those disclosed in US-5478855, US-4639771 and DE-19520936.
The compounds of the invention can be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO-9615121 and also with anthelmintically active cyclic depsipeptides such as those described in WO-9611945, WO -9319053, WO-9325543, EP-626375, EP-382173, WO-9419334, EP-382173 and EP-503538.
The compounds of the invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like.
The compounds of the invention can be used in combination with terpene alkaloids, for example those described in International Patent Application Publication Numbers WO95/19363 or W004/72086, particularly the compounds disclosed there.
[00174] Other examples of such biologically active compounds with which the compounds of the invention can be used in combination include but are not restricted to the following: Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusaphos, chloroxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demetone, demeton-S-methyl, demeton-S-methyl sulfone, dialyphos, diazinone, dichlorvos, dicrotophos, dimethoate, disulfotone, ethion, ethoprofen, femnitros, famthios, etrim fensulfothione, phenthione, flupyrazophos, phonophos, formotiona, phosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacrylphos, methamidophos, methidathione, methylparathion, mevinphos, monooxidecrotomethonate, paraoxation, naled, oxation methyl, phentoate, phosalone, phospholan, phosphocarb, phosmet, phosphamidone, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenophos, propaphos, proethamphos, prothiophos, pyraclophos, pyridapenthione, quinphos , sulprophos, temephos, terbufos, tebupyrimphos, tetrachlorvinphos, thimethone, triazophos, trichlorphone, vamidothion. Carbamates: alanicarb, aldicarb, carbosulfan methylcarbamate, cloethocarb, ethiofencarb, phenoxycarb, phenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl, pyrolymoxycarb, oxamamate thiodicarb, thiophanox, triazamate, UC-51717. Pyrethroids: acrinatin, allethrin, alphamethrin, (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, 5-benzyl-3-furylmethyl, bifenthrin, beta-cyfluthrin , cyfluthrin, a-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, citythrin, cyphenothrin, deltamethrin, empentrin, esfenvalerate, fentofenprothrin , fenvalerate, flucitrinate, flumethrin, fluvalinate (D-isomer) , imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, pralethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, tefluthrin, t-fluthrin, t-fluthrin, t-fluthrin, t-fluthrin , tralomethrin, Zeta-cypermethrin. Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumurone, lufenuron, novalurone, teflubenzuron, triflumurone, buprofezin, diofenolan, hexazoline, hexazoline; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juveniles: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.
[00175] Other antiparasitics: acequinocilla, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus turingiensis,bensultap, bifenazate, binapacril, bromopropylate, BTG-504, BTG-505, camfechlor, cartap, chlorobenzylate, chlordimeform, chlorfena , clothianidin, cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobutone, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, flufenpyroximate, fluacripropyn, flufenciprofen, flufenciprofen , hydramethylnon, IKI-220, canemite, NC-196, Neemgard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridaryl, propargite, protrifenbute, pymetrozine, pyridaben, pyrimidiphene, NC-1111, R-195, RH-0345 , RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, tebufenpyrad, tetradiphone, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinin, verbutinactin ertalec, YI-5301.
[00176] Biological agents: Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi. Bactericides: chlortetracycline, oxytetracycline, streptomycin.
[00177] Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cephalexin, kanamycin pimobendan, clenbuterol, omeprazole, tiamulin, benazeprila, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, carpentrycyl, cefti.
[00178] The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in A1 to A18 (above) of the present invention"): an adjuvant selected a from the group of substances consisting of petroleum oils (alternative name) (628) + TX, an acaricide selected from the group of substances consisting of 1, 1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) ( 910) + TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N1-naphthylacetamide (IUPAC name) (1295) + TX, 4-sulfone -chlorophenyl and phenyl (IUPAC name) (981) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidoflumete [CCN] + TX, amidothioate (872) + TX, amitone (875) + TX, amitone hydrogen oxalate (875 ) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, nitrogenate (889) + TX, benomyl (62) + TX, benoxaphos (alternative name) [ CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, biphenazate (74) + TX, bifenthrin (76) + TX, binapacril (907) + TX, brofenvalerate (alternative name ) + TX, bromocyclene (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezine (99) + TX, butocarboxim (103) + TX, butoxycarboxim ( 104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfechlor (941) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118 ) + TX, carbophenothione (947) + TX, CGA 50'439 (development code) (125) + TX, quinomethionate (126) + TX, chlorbenside (959) + TX, clo rdimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorphenetol (968) + TX, chlorfensone (970) + TX, chlorophensulfide (971) + TX, chlorfenvinphos (131) + TX , chlorobenzylate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamitone (alternative name) [CCN] + TX, crotoxifos (1010) + TX, cufraneb (1013) + TX, cyanoate (1020) + TX, ciflumethophen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demefione (1037) + TX, demefion-0 (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton- S (1038) TX, demeton-S -methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos (1042) + TX, diazinone (227) + TX, dichlofluanid (230) + TX, dichlorvos (236 ) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dynactin (name alternative) (653) + TX, dinex (1089) + TX, dinex- dinexin (1089) + TX, dinobutone (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinoctone (1090) + TX, dinopentone (1092) + TX, dinosulfone (1097) + TX, dinoterbone (1098) + TX, dioxathion (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfotone (278) + TX, DNOC (282) + TX, dofenapin (1113) + TX, doramectin (alternative name) [CCN] + TX, endosulfan (294) + TX, endothione (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazol (320) + TX, ethrymphos (1 142) + TX, fenazaflor (1147) + TX, phenazaquin (328) + TX, fenbutatin oxide (330) + TX, phenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative none) + TX, fenpyroximate (345) + TX, phensone (1157) + TX, fentriphanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacripyrim (360) + TX, fluazurome (1166) + TX, flubenzimine (1167) + TX, flucycloxuron (366) + TX, flucitrinate (367) + TX, fluenethyl (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate ( 1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) TX, formetanate hydrochloride (405) + TX, formotiona (1192) + TX, formparanate (1193) + TX, gamma-HCH (430) + TX, gliodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/from Chemical Abstracts name) (1216) + TX, hexithiazox (441) + TX , iodomethane (IUPAC name) (542) + TX, isocarbophos (alternative name) (473) + TX, O-(methoxyaminothio) phosphoryl)isopropyl salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodfenphos (1248) + TX, lindane (430) + TX, lufenurome (490) + TX, malathion (492) + TX, malonobene (1254) + TX, mecarbam (502) + TX, mephospholane (1261) + TX, mesulfene (alternative name) [CCN] + TX, methacrylophs (1266) + TX, methamidophos (527) + TX, methidathione (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metholcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifluridide (1309 ) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-010 1 (compound code) + TX, NNI-0250 (compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxideprofos (1324) + TX, oxydisulfotone (1325) + TX, pp' -DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, fencapton (1330) + TX, phentoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phospholane (1338) + TX, phosmet (638) + TX, phosphamidone (639) + TX, phoxim (642) + TX, pyrimiphos-methyl (652) + TX , polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenophos (662) + TX, promacil (1354) + TX, propargite (671) + TX , propetamphos (673) + TX, propoxur (678) + TX, protidathione (1360) + TX, protoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthione (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinphos (711) + TX, quintiophos (1381) + TX, R-1492 (code of development o) (1382) + TX, RA-17 (development code) (1383) + TX, rotenone (722) + TX, escradane (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [ CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX , sulfiram (alternative name) [CCN] + TX, sulfluramide (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradiphone (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiophanox (800) + TX, thiometone (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name ) [CCN] + TX, triamiphos (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, tric lorphone (824) + TX, tripenophos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothione (847) + TX, vaniliprol [CCN] and YI-5302 (compound code) + TX, an algaecide selected from the group of substances consisting of betoxazine [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutrine [CCN] + TX, diclone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinocamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin ( alternate name) [CCN] + TX, milbemycin oxime (alternate name active) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, one avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, phenthione (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX , AOπdL/*e/A. selected from the group of *3 substances consisting of 1-hydroxy-1 H -pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748 ) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [ CCN] + TX, dichlorophen (232) + TX, dipyrithion (1105) + TX, dodicine (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + TX , kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapirin (580) + TX, octylinone (590) + TX, acid oxolinic (606) + TX, oxytetracycline (611) + TX, hydroxyquinoline-potassium sulfate (446) + TX, probenazol (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, teclophthalam (766) + TX, and thiomersal (alternative name) [CCN] + TX, a biological agent s selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseiusspp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani ( alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide ( scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai(scientific name) (51) + TX, Bacillus thuringiensissubsp. israelensis(scientific name) (51) + TX, Bacillus thuringiensissubsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri ( alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (alternative name) scientific) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus cal iginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliaevar. acridum (scientific name) (523) + TX, Metarhizium anisopliaevar. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. leconteiNPV (alternative name) (575) + TX, Oriusspp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis(alternative name) (742) + TX, Steinernema carpocapsae(alternative name) (742) + TX, Steinernema feltiae(alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX, a chemosterilizer selected from the group of substances consisting of afolate [CCN] + TX, alternative bisazir) [CCN] + TX, diflubenzurome (250) + TX, dimatif (name alternative) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl folate [CCN] + TX, morzid [CCN] + TX, penflurone (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX, an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (E)-dec-5-en -1-ol (IUPAC name) (222) + TX, (E)-acetate- tridec-4-en-1-yl (IUPAC name) (829) + TX, (E)-6-methyl-hept-2-en-4-ol (IUPAC name) (541) + TX, (E) acetate ,Z)-tetradeca-4,10-dien-1-yl (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)- hexadec-11-enal (IUPAC name) (436) + TX, (Z) acetate - hexadec-11-en-1-yl (IUPAC name) (437) + TX, (Z) acetate - hexadec-13-en-11-in-1-ila (IUPAC name) (438) + TX, (Z)- icos-13-en-10-one (IUPAC name) (448) + TX, (Z)- tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradec-acetate 9-en-1-yl (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z) acetate ,11E)-tetradeca-9,11-dien-1-yl (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781 ) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin ( alternative name) [CCN] + TX, brevicomine (altern name active) [CCN] + TX, codlelure (alternative none) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, acetate of dodec-8-en-l-ila (IUPAC name) (286) + TX, dodec-9-en-1-ila acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-acetate dien-l-yl (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossiplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) ( 421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (name alternative) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) ) [CCN] + TX, medulre [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl-eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-acetate- 2,13-dien-1-yl (IUPAC name) (588) + TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, orictalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidine (alternative name) (736) + TX, sulcatol (alternative name) [CCN ] + TX, tetradec-ll-en-l-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B2 (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, d adipate ibutyl (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, phthalate of dimethyl [CCN] + TX, ethyl-hexanediol (1137) + TX, hexamide [CCN] + TX, methoquine-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridine [CCN] + TX, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/from Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl) ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX , 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX , 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/do Chemical A name abstracts) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/from Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2 methylcarbamate) -yl)phenyl (IUPAC/Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (name IUPAC) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl methylcarbamate(prop-2- inyl)aminophenyl (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, dimethylcarbamate of 3-methyl-1-phenylpyrazol-5-yl (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX , 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethione (name alternative) [CCN] + TX, acetoprol [CCN] + TX, acrinathrin (9) + TX, acrylon itrile (IUPAC name) (861) + TX, alnicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, alosamidine (alternative name ) [CCN] + TX, alixicarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminum phosphide (640) + TX, amidione (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amitone (875) + TX, amitone hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, atidatione ( 883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, nitrogenate (889) + TX, Bacillus thuringiensis delta-endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide (LUPAC/Chemical Abstracts name) (892) + TX, bartrine [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX,bensultape (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, S-isomer - cyclopentenyl of bioallethrin (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX , bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinphos (914) + TX, bromocyclene (918) + TX, bromo-DDT (alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezine (99) + TX, butacarb (926) + TX, butthiophos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusaphos (109) + TX, arsenate of calcium [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camfechlor (941) + TX, car banolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon tetrachloride (IUPAC name) (946) + TX, carbophenothione (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclene (960) + TX, chlordane ( 128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorideoxiphos (129) + TX, chlorfenapyr (130) + TX, dorfenvinphos (131) + TX, chlorfluazurome (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos- methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin (name alternative) + TX, cismethrin (80) + TX, clocithrin (alternative name) + TX, cloetocarb (999) + TX, closantel (alternative name) tive) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumitoate (1006) + TX, crotamitone (alternative name) [CCN] + TX, crotoxifos (1010) + TX, crufomate (1011) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) ( 1012) + TX, cyanophenphos (1019) + TX, cyanophos (184) + TX, cyanoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196 ) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, citioate (alternative name) [CCN] + TX, d-limonene (alternative name) [CCN] + TX, d -tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazometh (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demefione (1037 ) + TX, demefion-0 (1037) + TX, demefion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O -methyl (224) + TX, demeton-S (1038) + TX, demeton-S-methyl (224) + TX, demeton-S-methylsulfone (1039) + TX, diafenthiuron (226) + TX, dialyphos (1042) + TX, diamidaphos (1044 ) + TX, diazinone (227) + TX, dicaptone (1050) + TX, diclophenthione (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX , dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, 5-methylpyrazol-3-yl diethyl phosphate (IUPAC name) (1076) + TX, diflubenzurome (250) + TX, dilor (alternative radio name) [CCN] + TX, dimefluthrin [CCN] + TX, (1081) + TX, dimethane (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimethylane (1086) + TX, dinex (1089) + TX, dinex-diclexin (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) 4-TX, diophenolane (1099) + TX, dioxabenzophos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfotone (278) + TX, dithychrophos (1108) + TX, DNOC (282) + TX, of the ramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) (1118) + TX, emamectin (291) + TX, benzoate of emamectin (291) + TX, EMPC (1120) + TX, empentrin (292) + TX, endosulfan (294) + TX, endothione (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonan (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, ethaphos (alternative name) [CCN] + TX, ethiofencarb (308) + TX , ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl (1134) + TX, ethoprophos (312) + TX, ethyl format (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name ) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, ethofenprox (319) + TX, ethrymphos (1142) + TX, EXD (1143) + TX, famfur (323) + TX, phenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenetacarb (1149) + TX, fenfluthrin (1150) + TX , fenit rothione (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, phenoxycarb (340) + TX, fenpyritrine (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, phenthione (346) + TX, phenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, flubendiamide (No. CAS Registry: 272451-65-7) + TX, flucofurone (1168) + TX, flucycloxuron (366) + TX, flucitrinate (367) ■+ TX, fluenethyl (1169) + TX, flufenorim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, flumethrin (372) + TX, fluvalinate (1184) + TX, EMC 1137 (development code) (1185) + TX, phonophos (1191) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formotiona (1192) + TX, formparanate (1193) + TX, phosmethylane (1194) + TX, fospirate (1195) + TX, phosthiazate (408) + TX , phosthiethane (1196) + TX, furathiocarb (412) + TX, furethrin (1200) + TX, gamma-cyhalothrin (197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor ( 1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumurome (439) + TX, HHDN (864) + TX, hydramethylnone (443) + TX, hydrogen cyanide (444) + TX, hydroprene (4 45) + TX, hikincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX , isazophos (1231) + TX, isobenzane (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrine (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472 ) + TX, isopropyl (methoxyaminothiophosphoryl)salicylate (name 109/165 IUPAC) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [ CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, iodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN ] + TX, juvenile hormone III (alternative name) [CCN] + TX, colevane (1249) + TX, quinoprene (484) + TX, lambda-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lyrymphos (1251) + TX, lufenurome (490) + TX, litidathione (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) 4-TX, malonobene (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphone (1258) + TX, menazone (1260) + TX, mephospholane (1261) + TX, mercurous chloride (513) + TX, mosulfenphos (1263) + TX, metaflumizone (CCN ) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metham-sodium (519) + TX, methacrylphos (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathione (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquine_butyl ( 1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX, methoxyphenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methyl- chloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, methofluthrin [CCN] + TX, metolcarb (550) + TX, methoxadi azone (1288) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294 ) + TX, monocrotophos (561) + TX, morphothione (1300) + TX, moxidectin (alternative name) [CCN] + TX, naphthalophos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (name IUPAC/from Chemical Abstracts) (1303) + TX, NC-170 (development code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifluridide (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, nitrilacarb (1313) + TX, nitrilacarb complex 1:1 zinc chloride (1313) + TX, NNI-0101 ( compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novalurone (585) + TX, noviflumurone (586) + TX, 0-5-dichloro ethylphosphonothioate -4-iodophenyl O-ethyl (IUPAC name) (1057) + TX, O,O-diethyl 0-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (10 74) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075) + TX, O,0,O',O'-tetrapropyl dithiopyrophosphate (name IUPAC) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxidemeton-methyl (609) + TX, oxideprofos (1324) + TX , oxydisulfotone (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penflurone (alternative name) [CCN ] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (code ( 1339) + TX, phosphamidone (639) + TX, phosphine (IUPAC name) (640) + TX, foxim (642) + TX, foxim-methyl (1340) + TX, pyrimetaphos (1344) + TX, pyrimicarb (651) + TX, pyrimiphos-ethyl (1345) + TX , pyrimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, praletrin (655) + TX, precocious I (alternative name) [CCN] + TX, precocious II (alternative name) [CCN] + TX, precocious III (alternative name) [CCN] + TX, primidone (1349) + TX, profenophos (662) + TX, proflutrin [CCN] + TX, promacil (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX , protidathione (1360) + TX, prothiophos (686) + TX, protoate (1362) + TX, protrifenbuto [CCN] + TX, pymetrozine (688) + TX, pyraclophos (689) + TX, pyrazolophos (693) + TX, Pyresmethrin (1367) + TX, Pyrethrin I (696) + TX, Pyrethrin II (696) + TX, Pyrethrins (696) + TX, Pyridaben (699) + TX, Pyridalyl (700) + TX, Pyridaphenthione (701) + TX , pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX , quinthiophos (711) + TX, quinphos-methyl (1376) + TX, quinothione (1380) + TX, quinthiophos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (development code) (723) + TX, RU 25475 (development code) (1386) + TX, riania (alternative name) ) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, escradano (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [ CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/from Chemical Abstracts name) (1399 ) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (name IUPAC) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramate [CCN] + TX, sulcofurone (746) + TX, sulcofuron-sodium (746) + TX, sulfluramide (750) + TX, sulfotep (753) + TX, sulfuryl fluoride (756) + TX, sulprophos (1408) + TX, tar oils (alternative name) (758 ) + TX, tau-fluvalinate (398) + TX, tazimcarb (1412) + TX, TDE (1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupyrimphos (764) + TX, teflubenzurome ( 768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP (1417) + TX, teralethrin (1418) + TX, terbam (alternative name) + TX, terbuphos (773) + TX, tetrachloroethane [ CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, teta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, ticrophos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogenoxalate (798) + TX, thiodicarb (799) + TX, ti ofanox (800) + TX, thiometone (801) + TX, thionazine (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin (alternative name) [CCN] + TX, tolfenpyrad ( 809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazurone (name alternative) + TX, trichlorphone (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, tripenophos (1455) + TX, triflumurone (835) + TX, trimetacarb (840) + TX, triprene (1459) + TX, vamidothione (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprophos (1469 ) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7 ] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifluquinazone [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0 ] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, flufiprol [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin [ 84937-88-2] + TX, triflumezopyrim (disclosed in WO 2012/092115) + TX, a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [ CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (name IUPAC) (352) + TX, metalaldehyde (518) +• TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide ( 623) + TX, tazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, tr imetacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) ( 1062) + TX, 1,2-dichloropropene with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetra-hydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5- acid thiadiazinen-3-ylacetic (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprol [CCN] + TX, alanicarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (name alternative) + TX, cadusaphos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloetocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomete (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidaphos (1044) + TX, diclophenthione (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [ CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, phenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothione (1158) + TX, phosthiazate (408) + TX, phostiethane (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, isazophos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210 ) + TX, mecarphone (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, isot methyl iocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 ( compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidone (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN ] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IUPAC/from Chemical Abstracts name) (1422) + TX, thiafenox (alternative name) + TX, thionazine (1434) + TX, triazophos (820) + TX, triazurone (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [ 318290-98-1] + TX, a nitrification inhibitor selected from the group of substances such as consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX, a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazol (658 ) and Eynoutria sachalinensis extract (alternative name) (720) + TX, a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-( quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bistiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, diphethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, flocoumaphen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444 ) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, bromide of + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] 4-TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX, a synergistic agent selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol -5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code ment) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (code of development) (724) + TX, sesamex (1393) + TX, sesasmoline (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraguinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinone (227) + TX, dicyclopentadiene (guimeric name) (1069) + TX, guazatine (422) + TX, guazatine acetates ( 422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, tir (804) + TX, trimetacarb (840) + TX, zinc naphthenate [CCN] and ziram ( 856) + TX, a virucide selected from the group of substances consisting of imanine (alternative name) [CCN] and ribavirin (alternative name) [CCN] + TX, a wound protectant selected from the group of substances consisting of oxide mercuric (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX, and biologically active compounds selected from the group consisting of azaconazole [60207-31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazol [116255- 48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX , fenbuconazole [114369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazol [85509-19-9] +TX, flutriafol [76674-21-0] + TX, hexaconazole [79983-71 -4] + TX, imazalyl [35554-44-0] + TX, imibenconazol [86598-92-7] + TX, ipconazol [125225-28-7] + TX, metconazol [125116-23-6] + TX, myclobutanil [88671-89-0] + TX, pefurazoate [101903-30-4] + TX, penconazol [66246-88-6] + TX, prothioconazol [178928-70-6] + TX, pyrifenox [88283-41- 4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1] + TX, simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole [112281-77-3] + TX, triadimephone [43121-43-3] + TX, triadimenol [55219-65-3] + TX, triflumizole [99387-89-0] + TX, triticonazol [131983-72-7] + TX, ancymidol [12771-68-5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284 -71-9] + TX, bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidin [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [118134-30-8] + TX, tridemorph [8141243-3] + TX, cyprodinil [121552-61- 2] + TX, mepanipyrim [110235-47-7] + TX, pyrimethanil [53112-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86-1] + TX, benalaxyl [71626-11-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-170] + TX, ofurace [58810-48-3 ] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazol [ 3878-19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX, dichlozoline [24201-58-9] + TX, iprodione [36734-19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-168] + TX, vinclozoline [50471-44-8] + TX, boscalide [18842585-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-803] + TX , flutolanil [66332-96-5] + TX, mepronil [5581441-0] + TX, oxycarboxine [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thifluzamide [130000-40-7 ] + TX, guazatine [108173-90-6] + TX, dodine [2439-10-3] [112-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [ 131860-33-8] + TX, dimoxystrobin [14996152-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93} + TX, fluoxastrobin [361377-29-9] + TX, kresoxim-methyl [143390-89-0] + TX, metominostrobin [133408-50-1] + TX, trifloxystrobin [141517-21-7] + TX, oryzastrobin [248593-16-0] + TX, picoxystrobin [11742822-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64 -1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, take [137-26-8] + TX, zineb [12122-67- £ 0-4 120/165 & J, § + TX, captafol [2425-06-1] + TX, %v (V.'' dichlofluanid [1085-98-9] + TX, + TX, folpet [133-07-3] + TX, TX, bordeaux mixture [8011- copper [20427-59-2] + TX, 52 — 40 — 71 + TX, copper sulfate [7758-98-7] + TX, copper oxide [1317-39-1] + TX, copper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrotal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphene [36519-00-3] + TX, pyrazolophos [ 13457-18-6] + TX, tolclophos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, bentiavalcarb [ 413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, quinomethionate [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45- 6] + TX, cyflufenamide [180409-60-3] + TX, cymoxanil [57966-95-7] + TX, diclone [117-80-6] + TX, diclocimet [139920-32-4] + TX, diclomezine [62865-36-5] + TX, dichlorane [99-30-9] + TX, diethfencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorf) [ 211867-47-9] + TX, dithianone [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazol [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil [115852-48-7] + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622 —59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52-6] + TX, fenhexamide [126833-17-8] + TX, fosetyl-aluminum [39148-24-8 ] + TX, hyhexazol [10004-44-1] + TX, 5:- & iprova lycarb [140923-17-7] + TX, IKF-916 (Ciazofamidà) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, metasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycurone [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazol [27605-76-1 ] + TX, propamocarb [25606-41-1] + TX, proquinazide [189278-12-4] + TX, pyroquilone [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintazene [ 82-68-8] + TX, sulfur [7704-34-9] + TX, tiadinyl [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamide [374726-62-2] + TX, isopirazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methane-naphthalen-5-yl ) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid-amide (disclosed in WO 2007/048556) + TX, (3',4',5'-trifluoro-biphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyracid amide 4-carboxylic zol (disclosed in WO 2006/087343) + TX, [(35, 4R, 4aR, 65, 6aS, 12R, 12aS, 12b5) -3-[(cyclopropylcarbonyl)oxy]-1,3,4, 4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,HHnaphtho[2, 1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7] + TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl) -N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8 ] + TX, or a biologically active compound selected from the group consisting of N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl -pyrazole-4-carboxamide + TX, 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H , 6H)-tetrone + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX, CAS 850881-30-0 + TX, 3 -(3,4-dichloro-1,2- thiazol-5-ylmethoxy)-1,2-benzothiazole 1,1-dioxide + TX, 2-[2 — [(2,5-dimethylphenoxy)methyl]phenyl]-2-methoxy-N-methyl-acetamide + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl- 3-quinolyl)oxy]phenyl]propan-2-ol + TX, Oxathiapiproline + TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl tert-butyl]carbamate + TX, N-[2-(3,4-difluorophenyl)phenyl]-3-(trifluoromethyl)pyrazine-2-carboxamide + TX, 3-(difluoromethyl)-1-methyl-N-[ (3R)-1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, N-[2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate of 2, 2,2-Trifluoroethyl + TX, (2RS)-2-[4-(4-chlorophenoxy)-α, ot,α-trifluoro-o-tolyl]-1-(1H-1,2,4 -triazol-1-yl)propan-2-ol TX, (2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-3-methyl-1-(1H -1,2,4-triazol-1-yl)butan-2-ol + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl] pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N- methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[ 3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-% ** 123/165% 4-yl]-4.5 -dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl] but-3-ynyl -2-pyridyl]carbamate + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl -pyridazine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl1-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4 - (3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, and

[00179] References in parentheses after active ingredients, eg [3878-19-1] refer to the Chemical Abstracts Registry Number. The mixing partners described above are known. When active ingredients are included in "The Pesticide Manual"[The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CSD TomLin; The British Crop Protection Council], are described in that document with the entry number given in parentheses above in this document for the particular compound; for example, the compound "abamectin" is described under entry number (1). When "[CCN]" is added earlier herein to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprol" is described at the internet address: http://www.alanwood.net/pesticides/acetoprol.html.
[00180] In this document, most of the active ingredients described above are named by a so-called "common name", the relevant "ISO common name" or another "common name" which is used in particular cases. If the designation is not a "common name", the nature of the alternative designation used is given in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" or, if neither of these designations nor a "common name" is used, an "alternative name" is used. "CAS Reg. No" means the Chemical Abstracts Registration Number.
[00181] The mixture of active ingredients of the compounds of formula I selected from Al to A18 (above) with active ingredients described above comprises a compound selected from Al to A18 (above) and an active ingredient as described above preferably in a mixing ratio from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5: 1 and 1:5, with a ratio of 2:1 to 1:2 being especially preferred, and a ratio of 4:1 to 2:1 being likewise preferred, above a ratio of 1:1, or 5: 1, or 5:2, or 5:3, or 5:4, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 3: 5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35 , or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350 , or 4:350, or 1:750, or 2:750 or 4:750. These mixing ratios are by weight.
[00182] Mixtures as described above can be used in a method of controlling pests, comprising applying a composition comprising a mixture as described above to pests or their environment, with the exception of a method of surgical or therapeutic treatment of the body human or animal and diagnostic methods practiced on the human or animal body.
[00183] Mixtures comprising a compound of formula I selected from Al to A18 (above) and one or more active ingredients as described above, can be applied, for example, in a simple "do-mix" form, in a combined spray mixture prepared from separate formulations of the single active ingredient components, such as a "tank mix", and in a combined use of the individual active ingredients when applied sequentially, ie one after the other in a relatively short period of time, such as a few hours or days. The order of application of the compounds of formula I selected from A1 to A18 (above) and the active ingredients as described above is not essential for carrying out the present invention.
The compositions according to the invention may also comprise additional solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (eg coconut oil, rapeseed oil or epoxidized soybean oil), defoamers , for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active principles to achieve specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.
[00185] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example, by grinding, sieving and/or compressing a solid active principle and in the presence of at least one auxiliary, for example by intimate mixing and/or grinding of the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of compounds I for the preparation of these compositions are also an object of the invention.
Another aspect of the invention relates to the use of a compound of formula I or a preferred individual compound as defined above, a composition comprising at least one compound of formula I or at least one preferred individual compound as defined above, or of a fungicide or insecticide mixture comprising at least one compound of formula I or at least one preferred individual compound as defined above, in a mixture with other fungicides or insecticides, as described above, to control or prevent infestation of plants, e.g. ., useful plants, such as crop plants, their propagation material, eg seeds, crops, eg food crops, or materials not alive by insects or by phytopathogenic microorganisms, preferably fungal organisms.
[00187] A further aspect of the invention relates to a method for controlling or preventing an infestation of plants, e.g. useful plants, such as crop plants, their propagation material, e.g., seeds, crops, e.g. ., food crops, or non-living materials by insects or by spoilage or phytopathogenic microorganisms or organisms potentially harmful to humans, in particular fungal organisms, comprising the application of a compound of formula I or a preferred individual compound as defined above as active ingredient in the plants, in parts of the plants or in the place thereof, in the propagation material thereof, or in any part of the non-living material.
[00188] Controlling or preventing means reducing infestation by insects or by spoilage or phytopathogenic microorganisms or organisms potentially harmful to humans, especially fungal organisms, to a level at which an improvement is demonstrated.
[00189] A preferred method for controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms or insects, comprising applying a compound of formula I, or an agrochemical composition containing at least one of said compounds, is the foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula I can also enter the plant through the roots through the soil (systemic action) by soaking the plant locus with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. granular form (soil application). In irrigated rice crops, such pellets can be applied to the irrigated rice field. The compounds of formula I can also be applied to seeds (coating) by impregnating the seeds or tubers with either a liquid formulation of the fungicide or coating them with a solid formulation.
[00190] A formulation, e.g. a composition containing the compound of formula I and, if desired, a solid or liquid adjuvant or monomers to encapsulate the compound of formula I, can be prepared in a known manner, typically by means of intimate mixing and/or grinding the compound with diluents, eg solvents, solid carriers and optionally surface active compounds (surfactants).
[00191] The application methods for the compositions, that is, the pest control methods of the aforementioned type, such as spraying, atomizing, dusting, brushing, covering, dispersing or which are to be selected to suit the intended objectives of the prevailing circumstances - and the use of the compositions for the control of pests of the aforementioned type, are further objects of the invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rate per hectare is preferably from 1g to 2000 g of active ingredient per hectare, more preferably from 10 to 1000 g/ha, most preferably from 10 to 600 g/ha. When used as a seed-soaking agent, convenient dosages range from 10mg to 1g of active substance per kg of seed.
[00192] When the combinations of the present invention are used for seed treatment, rates of 0.001 to 50 g of a compound of formula I per kg of seed, preferably 0.01 to 10 g per kg of seed, are generally sufficient.
Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventively, that is, before the development of a disease, or curatively, that is, after the development of a disease.
The compositions of the invention may be employed in any conventional form, for example in the form of a double pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a seed treatment solution (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment gel for the seed treatment (GF), an emulsifiable concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a microemulsion (ME), a dispersion in oil (OD), an oil miscible fluid (OF), a miscible liquid in oil (OL), a soluble concentrate (SL), an ultra low volume suspension (SU), an ultra low volume liquid (UL), a concentrate. the technical (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically possible formulation in combination with agriculturally acceptable adjuvants.
[00195] Such compositions can be produced in a conventional manner, e.g., by mixing the active ingredients with suitable inert formulating agents (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, antifreeze, adhesives, thickeners and compounds that confer adjuvant effects). Also, conventional slow release formulations may be employed where lasting efficacy is intended. Particularly, formulations to be applied in spray forms such as water dispersible concentrates (eg EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules may contain surfactants such as wetting and dispersing agents and other compounds which provide adjuvant effects, e.g., the condensation product of formaldehyde with naphthalene sulfonate, an alkylaryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.
[00196] A seed dressing formulation is applied in a manner known per se to seeds employing the combination of the invention and a diluent in a suitable form of seed dressing formulation, e.g. , as an aqueous suspension or in a dry powder form having good adhesion to the seeds. Such seed treatment formulations are known in the art. Seed treatment formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, eg as slow release capsules or microcapsules.
[00197] In general, formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% of agriculturally acceptable surfactant and 10 to 99.99% of solid or liquid formulation inerts and adjuvant(s) , the active agent consisting at least of the compound of formula I together with components (B) and (C), and optionally other active agents, particularly microbiocides or preservatives or the like. Concentrated forms of the compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of the formulation may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Although commercial products are preferably formulated as concentrates, the end user will employ standard Imenté'1 diluted formulations.
[00198] While it is preferred to formulate commercial products as concentrates, the end user will typically use diluted formulations. EXAMPLES
[00199] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example , 50ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm or 0.2ppm.
[00200] Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point. LC/MS stands for Liquid Chromatography coupled with Mass Spectroscopy, and the description of the devices and the method is as follows:
[00201] Method G:
[00202] The spectra were recorded on a Waters Mass Spectrometer (ACQUITY UPLC) (SQD, SQDII or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone Range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow : 650 L/Hr, Mass range: 100 to 900 Da) and a Waters UPLC Acquity: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60°C; DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 10-100% B in 1.2 min; Flow (mL/min) 0.85
[00203] Method H:
[00204] The spectra were recorded on a Waters Mass Spectrometer (ACQUITY UPLC) (SQD, SQDII or ZQ single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone Range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150 °C, Desolvation Temperature: 350 °C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow : 650 L/Hr, Mass range: 100 to 900 Da) and a Waters UPLC Acquity: Binary pump, heated column compartment and diode array detector. Solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, Temp: 60°C; DAD wavelength range (nm): 210 to 500, Solvent Gradient: A = water + 5% MeOH + 0.05% HCOOH, B = Acetonitrile + 0.05% HCOOH; gradient: 10-100% B in 2.7 min; Flow (mL/min) 0.85
[00205] Formulation Examples active ingredient [compound of 25% formula (I)] sodium lignosulfonate 5% sodium lauryl sulfate 3% sodium diisobutylnaphthalenesulfonate polyethylene glycol ether (7-8 mol ethylene oxide) acid highly dispersed silica 5% 10% 10% Kaolin 62 % 27%
[00206] The active ingredient is thoroughly mixed with the adjuvants and the mixture is completely ground in a suitable mill, giving wettable powders that can be diluted with water to give suspensions of the desired concentration. Seed treatment powders a a) b) o) dry active ingredient [composed of 25 1: 50 75 1 formula (I)j light mineral oil 5 5 5 highly dispersed silicic acid 5 1 5 - Kaolin 65 1 40 5 20 "Falco
[00207] The active ingredient is thoroughly mixed with the adjuvants and the mixture is completely ground in a suitable mill, yielding powders that can be used directly for seed treatment. Active ingredient emulsifiable concentrate [compound of formula 10% (I) ] polyethylene glycol ether 3% octylphenol (4-5 moles ethylene oxide) calcium dodecylbenzenesulfonate 3% polyglycol ether castor oil (35% moles ethylene oxide) ) Cyclohexanone 30% mixture of xylenes 50%
[00208] Emulsions of any required dilution, which can be used in plant protection, can be obtained from that concentrate by dilution with water. Dust b) c) Active ingredient [composed of 5% 6% 4% formula (I)] talc Kaolin mineral filler
[00209] Ready-to-use dusts are obtained by mixing the active ingredient with the vehicle and grinding the mixture in an o&o suitable mill. Such powders can also be used for dry coatings for seeds. Extruder granules Active ingredient [compound of 15% formula (I)] sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%
[00210] The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredient [compound of formula (I)] % polyethylene glycol (mol. 3 200) % kaolin 89 %
[00211] The finely ground active ingredient is evenly applied, in a mixer, to kaolin moistened with polyethylene glycol. Thereby, non-dusty coated granules are obtained. Suspension concentrate active ingredient [compound of formula (I)] 1(LA >137/165 I propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol 6% ethylene oxide) Sodium lignosulphonate 10% carboxymethylcellulose 1% silicone oil (in form of an emulsion at 1% 75% in water) Water 32%
[00212] The finely ground active ingredient is intimately mixed with the adjuvants, giving a concentrated suspension from which suspensions of any desired dilution can be obtained by diluting with water. Using these dilutions one can treat and protect against infestation by microorganisms by spraying, pouring or dipping live plants as well as plant propagation material. Flowable concentrate for seed treatment active ingredient [compound of formula (I)] 40% propylene glycol 5% butanol copolymer PO/EO 2 % tristyrenephenol with 10-20 moles of EO 2 % 1,2-benzisothiazolin-3- one (as a 0.5% 20% solution in water) calcium salt of monoazo pigment 5% Silicone oil (as a 0.2 % 75% emulsion in water) Water 45.3% • AI' -
The finely ground active ingredient is intimately mixed with the adjuvants, giving a concentrated suspension from which suspensions of any desired dilution can be obtained by diluting with water. Using these dilutions one can treat and protect against infestation by microorganisms by spraying, pouring or dipping live plants as well as plant propagation material.
[00214] Suspension of Slow Release Capsules
28 parts of a combination of the compound of formula I are mixed with 2 parts of an aromatic solvent and 7 parts of the toluene diisocyanate/polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added. The mixture is stirred until the polymerization reaction is complete.
[00216] The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The suspension formulation for capsules contains 28% of the active ingredients. The average diameter of the capsules is 8-15 microns.
[00217] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.
[00218] Preparation examples
The present example illustrates 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.
[00220] Step 1: Preparation of ethyl-2-(2-fluorophenyl)-2-methyl-propanoate
To a suspension of sodium hydride (0.69 mol, 27.4 g) in tetrahydrofuran (220 ml) at room temperature was added dropwise a solution of ethyl-2-(2-fluorophenyl) acetate (0.27 mol, 50.0 g) and iodomethane (0.82 mmol, 117.9 g) in tetrahydrofuran (60 mL, Cone, 1M total) and the mixture was stirred at room temperature overnight . The reaction was quenched by the slow addition of a saturated aqueous ammonium chloride solution and then poured into 300 mL of ice-water mixture. The aqueous phase was extracted with ethyl acetate and the combined organic extracts were dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash chromatography (heptane/ethyl acetate - 19:1) to obtain ethyl-2-(2-fluorophenyl)-2-methyl-propanoate as a pale yellow oil: LC-MS (Method H) Detection UV: 220 nm, Tr = 1.60; MS: (M+1) = 211.2; NMR (400 MHz, CHLOROFORM-d) δ ppm 1.16 - 1.23 (m, 3H) 1.57 (s, 6H) 4.17 (d, J=6.97Hz, 2H) 6 .99 - 7.05 (m, 1H) 7.11 - 7.17 (m, 1H) 7.22 - 7.28 (m, 1H) 7.33 (td, J=7.89, 1.83 Hz, 1H); 19F NMR (377 MHz, CHLOROFORM-d) δppm -113.26 (s, 1F).
[00222] Step 2: Preparation of 3-(2-fluorophenyl)-2,3-dimethyl-butan-2-ol
[00223] A solution of ethyl-2-(2-fluorophenyl)-2-methylpropanoate (0.25 mol, 52.1 g) and lanthanum(III), bis(lithium chloride) chloride complex (0.6 M in THF, 0.50 equiv., 0.12 mol, 207 mL) in tetrahydrofuran (1.2 M) was stirred at room temperature for 1.5 h. The reaction was then cooled to 0 °C and a solution of methyl magnesium bromide (3.0 M in diethyl ether, 3.0 equiv., 0.74 mol, 248 mL) was subsequently added dropwise. The reaction mixture was stirred at room temperature overnight, cooled to 0 °C and then quenched by dropwise addition of a saturated aqueous solution of ammonium chloride. Water was added and the reaction mixture was stirred for an additional 30 min. The reaction mixture was filtered over Celite and the two phases were separated. The aqueous phase was extracted with tert-butylmethyl ether, and the combined organic phases were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give 3-(2-fluorophenyl)-2,3-dimethyl-butan -2-ol as a yellowish solid: LC-MS (Method H) UV detection: 220 nm, Tr = 1.46; MS: (M-OH) = 179.3; mp 42-43°C; NMR (400 MHz, CHLOROFORM-d) δ ppm 1.19 (d, J=1.10 Hz, 6H) 1.50 (d, <7=2.93Hz, 6H) 6.97 - 7, 04 (m, 1H) 7.07 - 7.12 (m, 1H) 7.18 - 7.24 (m, 1H) 7.40 (td, J=8.25, 1.83Hz, 1H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm -104.04 (s, 1F).
[00224] Step 3: Preparation of 5-fluoro-3,3,4,4-tetramethyl-1-methylsulfanyl-isoquinoline.
To cooled sulfuric acid (0°C) (98% w/w, 133 ml, 1M) was added a mixture of C1 , R11'iDi'O methyl thiocyanate (133 mmol, 9.73 g) and 3 -(2-fluorophenyl)-2,3-dimethyl-butan-2-ol (1.00 equiv., 133 mmol, 26.1 g) portion by portion over 15 min, and the mixture was stirred at room temperature for 20 additional min. The reaction mixture was carefully poured into 600 ml of ice water and the pH of the aqueous layer was adjusted to ~8 using an aqueous solution of NaOH (30% w/w). The aqueous phase was extracted with ethyl acetate and the combined organic phases were dried with Na2SO4, filtered and concentrated in vacuo to give (25.1 g, 75%) of 5-fluoro-3,3,4.4 -tetramethyl-1-methylsulfanyl-isoquinoline as a pale yellow oil: LC-MS (Method G) UV detection: 220 nm, Tr=; MS: (M+1) =; TH NMR (400 MHz, CHLOROFORM-d) δ ppm 1.10 (s, 6H) 1.24 (d, <J=2.93 Hz, 6H) 2.34 (s, 3H) 7.00 (ddd, J=12.20, 8.34, 1.10Hz, 1H) 7.07 - 7.21 (m, 1H) 7.32 - 7.42 (m, 1H); NMR (377 MHz, CHLOROFORM-d) δppm -111.06 (s, 1F).
Step 4: Preparation of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1-one.
[00227] To a solution of 5-fluoro-3, 3,4,4-tetramethyl-1-methylsulfanyl-isoquinoline (99.8 mmol, 25.1 g) in a mixture of acetic acid (160 mL, 0.25 M) and water (40 mL) were added sodium acetate (0.10 equiv., 9.98 mmol, 0.818 g) and the mixture was refluxed for 2 h. The reaction mixture was then cooled to room temperature and most of the acetic acid solution was removed under vacuum. The residue was then carefully added to a mixture of saturated aqueous NaHCO solution and ethyl acetate. The two layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic phases were washed with saturated aqueous NaHCOa solution, water and brine, dried with Na 2 SO 3 , filtered and concentrated in vacuo to give 5-fluoro-3,3,4,4-tetramethyl-2H-isoquinolin-1-one (21.4 g, 97%) as a pale yellow oil: LC-MS (Method G) UV detection: 220 nm, Tr = 1.28; MS: (M+1) = 222.2; X H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.21 (s, 6 H) 1.36 (d, J=1.00 Hz, 6 H) 6.19 (s 1, 1 H) 7.12 (ddd, J=12.38, 8.34, 1.28 Hz, 1H) 7.20 - 7.26 (m, 1H) 7.85 (dd, J=7.52, 1.28 Hz , 1H); 19F NMR (377 MHz, CHLOROFORM-d) δppm -111.05 (s, 1F).
[00228] Step 5: Preparation of 1-chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline.
[00229] To a solution of N,N-dimethylformamide (6.3 mmol, 0.49 mL) in dichloromethane (8 mL, 0.8 M) at room temperature was added oxalyl chloride (1.3 equiv., 6 0.01 mmol, 0.53 mL) dropwise, and the white suspension was stirred vigorously for 30 min. A solution of 5-fluoro-3,3,4,4-tetramethyl-2H-isoquino]in-1-one (4.52 mmol, 1.00 g) in dichloromethane (9 mL, 0.5 M) was then added dropwise and the mixture was stirred at room temperature for 2 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCO3 solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2SO, filtered and concentrated to give 1-chloro-5-fluoro-3,3,4,4-tetramethyl- isoquinoline (1.02 g, 94% yield) as a colorless oil: LC-MS (Method G) 0V detection: 220 rim, Tr=1.16; MS: (Mfg-) = 240-242; 1H NMR (400 MHz, Ic 14''_3/165 CLOPOPORMY-d) at ppm 1.27 (s, 6H) 1.38 (s, 6H) 7.15-7.20 (m, 1H) 7.26 - 7.36 (m, 1H) 7.62 (d, 1H).
[00230] Step 6: Preparation of 5-fluoro-3,3,4,4-retramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.
[00231] To a solution of 1-chloro-5-fluoro-3,3,4,4-tetramethyl-isoquinoline (1.67 mmol, 0.430 g) in pyridine (0.20 M, 9.0 mL) at temperature To room 4-methyl-1H-benzimidazole (1.5 equiv., 2.69 mmol, 0.356 g) was added and the mixture was stirred at 90°C for 15 hours. The reaction mixture was allowed to cool to room temperature and then concentrated in vacuo. The obtained residue was purified by flash chromatography to obtain 5-fluoro-3,3,4,4-tetramethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline (0.525 g, 87% yield) as a beige solid. : mp= 118-120°C, LC-MS (Method G) UV detection: 220 nm, Tr = 1.19, MS: (M+1) = 336; 'H NMR (400 MHz, CHLOROFORM-d) at ppm 1.32 (s, 6H) 1.47 (s, 6H) 2.71 (s, 3H) 6.91-6.95 (m, 1 H) 7.10 - 7.25 (m, 5H) 8.18 (s, 1H).
Example 2: This example illustrates the preparation of 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline
[00233] Step 1: Preparation of 3,3-dimethyl-2H-isoquinoline-1,4-dione.
To a solution of 3,3-dimethyl-2,4-dihydroisoquinolin-1-one (57.1 mmol, 10.0 g) in CCI4 (0.20 M, 285 mL) at room temperature was N-bromosuccinimide (3.0 equiv., 171 mmol, 30.5 g) and AIBN (0.15 equiv., 8.5 mmol, 1.43 g) were added and the reaction mixture was stirred at 70 °C for 3 hours. The reaction mixture was allowed to cool to room temperature, concentrated in vacuo and diluted with EtOAc, washed with brine, dried over Na2SCU, filtered and concentrated to give 3,3-dimethyl-2,4-dihydroisoquinolin-1- onamg) as a light yellow solid which was used directly in the next step without further purification: LC-MS (Method H) UV detection: 220 nm, Tr = 1.34; MS: (M+1) - 332-334336; 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.57 (s, 6 H) 7.21 (s 1, 1 H) 7.70 - 7.77 (m, 1H) 7.78 - 7.85 (m, 1H) 8.06 - 8.14 (m, 1H) 8.23 - 8.30 (m, 1H).
[00235] To a solution of 4,4-dibromo-3,3-dimethyl-2H-isoquinolin-1-one (20.0 g) in a mixture of water (450 ml) and tetrahydrofuran (225 ml) was sodium carbonate (3.0 equiv., 135 mmol, 14.3 g) was added and the mixture was stirred at room temperature for 12 h and at 70 °C for 4 h 30 min. The reaction mixture was allowed to cool to room temperature, diluted with water, acidified to pH 3-4 with 90 ml of a 2M hydrochloric acid solution and extracted with dichloromethane. The combined organic extracts were dried over Na 2 SO 4 , filtered and concentrated to obtain 3,3-dimethyl-2H-isoquinolinr-1,4-dione (9.95 g) as a yellow solid: LC-MS (Method H) Detection UV: 220 nm, Tr = 0.81; MS: (M+1) = 190; NMR (400 MHz, CHLOROFORM-d) δ ppm 1.77 (s, 3H) 1.97 (s, 3H) 7.39 (s, 1H) 7.46 - 7.58 (m, 1H) ) 7.60 - 7.71 (m, 1H) 7.98 - 8.22 (m, 2H).
[00236] Step 2: Preparation of 1-chloro-3,3-dimethyl-isoquinolin-4-one.
[00237] To a solution of N,N-dimethylformamide (2.3 mL, 30 mmol) in dichloromethane (52 mL, 0.6 M) at room temperature was added oxalyl chloride (0.67 equiv., 20 mmol, 1.8 ml) dropwise over a period of 35 min and the white suspension was vigorously stirred for 15 min until gas evolution stopped. A solution of 3,3-dimethyl-2H-isoquinoline-1,4-dione (2.5g, 13mmol) in dichloromethane (25ml) was then added dropwise and the mixture stirred at room temperature for 1h . The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCCh solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2SO4, filtered and concentrated to give 1-chloro-3,3-dimethyl-isoquinolin-4-one (2, 5 g, 91% yield) as a yellow solid: LC-MS (Method H) UV detection: 220 nm, Tr= 1.34; MS: (M+1) = 208-210; *H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.47 (s, 6H) 7.62 - 7.69 (m, 1H) 7.73 - 7.81 (m, 1H) 7. 90 (dd, J=8.07, 0.73Hz, 1H) 8.04 (dd, J=7.50, 0.90Hz, 1H).
[00238] Step 3: Preparation of 3,3-Dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one.
To a solution of 1-chloro-3,3-dimethyl-isoquinolin-4-one (3.61 mmol, 0.750 g) in pyridine (0.07 M, 50 mL) at room temperature was added 4-methyl -1H-benzimidazole (1.5 equiv., 0.716 g, 5.42 mmol) and the mixture was stirred at 100°C for 15 hours. The reaction mixture was allowed to cool to room temperature and then concentrated in vacuo. The obtained residue was purified by flash chromatography to obtain 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one (0.569 g, 52% yield) as a brown oil: LC-MS (Method G) UV detection: 220 nm, Tr = 0.98, MS: (M+1) = 305; NMR (400 MHz, CHLOROFORM-d) δ ppm 1.63 (s, 6H) 2.75 (s, 3H) 7.15 - 7.27 (m, 3H) 7.36 - 7.42 ( m, 1H) 7.70 - 7.82 (m, 2H) 8.18 - 8.25 (m, 1H) 8.28 (s, 1H).
Step 4: Preparation of 4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline.
[00241] A solution of 3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinolin-4-one (1.85 mmol, 560 mg) in 2,2-difluoro-1,3-dimethyl- imidazolidine (10.0 equiv., 18.5 mmol, 2.4 mL) was stirred at 105 °C overnight. The reaction mixture was allowed to cool to room temperature, diluted with DCM and then quenched by slow addition to a saturated aqueous solution of NaHCOa. The 2 phases were separated and the aqueous phase was extracted with DCM. The combined organic phases were washed with brine, dried over Na∑SOo, filtered and concentrated. The residue was purified by flash chromatography to obtain 4,4-difluoro-3,3,-dimethyl-1-(4-methylbenzimidazol-1-yl) isoquinoline (36 mg, 60% yield) as a white solid: LC -MS (Method G) UV detection: 220 nm, Tr = 1.12; MS: (M+1) = 326; mp 142 - 149°C; NMR (400 MHz, CHLOROFORM-d) δ ppm 1.49 (s, 6H) 2.76 (s, 3H) 7.15 - 7.27 (m, 2H) 7.34 - 7.42 ( m, 2H) 7.57 - 7.64 (m, 1H) 7.71 - 7.79 (m, 1H) 7.90 - 7.97 (m, 1H) 8.31 (s, 1H); 19F NMR (377 MHz, CHLOROFORM-d) δ ppm-112.38 (s 1.1F).
Example 3: The present example illustrates the--'x3.5'' preparation of 1'-(benzimidazol-1-yl)-3',3'-dimethyl-spiro(cyclopropane-1,4'-isoquinoline )
[00243] Step 1: Preparation of 3,3-dimethylspiro(2H-isoquinoline-4,1'-cyclopropane)-1-one.
[00244] In an autoclave a solution of 2-(1-phenylcyclopropyl)propan-2-amine (120 mg, 0.685 mmol), benzoquinone (2.0 equiv., 1.37 mmol, 153 mg) and acetate was added. palladium (II) (0.05 equiv., 0.034 mmol, 7.6 mg) in acetic acid (4.6 mL, 0.15 M) and the reactor at high pressure was pressurized with carbon monoxide (3 bars) and heated at 110 °C overnight. The reaction vessel was allowed to cool to room temperature, depressurized and the reaction mixture was diluted with dichloromethane and quenched by addition of an aqueous solution of NaOH (2.0M) until pH>9 was reached. The two phases were separated and the aqueous phase was extracted with dichloromethane twice. The combined organic phases were washed with brine, dried over Na2SO4, filtered, concentrated and purified by flash chromatography to give 3,3-dimethylspiro(2H-isoquinoline-4,1'-cyclopropane)-1-one (27 mg, 20% yield) as a yellowish gum: LC-MS (Method G), Tr = 0.80; MS: (M+1) = 202; 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.96 (t, 2H) 1.10 (t, 2H) 1.18 (s, 6H) 6.21 (NH, 1H) 6.91 ( d, 1H) 7.20 (t, 1H) 7.45 (t, 1H) 8.09 (d, 1H).
Step 2: Preparation of 1'-chloro-3',3'-dimethyl-spiro(cyclopropane-1,41-isoquinoline).
[00246] To a solution of N,N-dimethylformamide (0.63 mmol, 0.049 mL) in dichloromethane (1 mL, 0.5 M) at room temperature was added oxalyl chloride (1.3 equiv., 0.63 mmol, 0.056 ml) dropwise, and the white suspension was stirred vigorously for 30 min. A solution of 3,3-dimethylspiro(2H-isoquinoline-4,1'-cyclopropane)-1-one (0.423 mmol, 85 mg) in dichloromethane (0.8 mL, concentration, 0.25 M total) was then added dropwise and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into an ice-cooled mixture of saturated aqueous NaHCOa solution and pentane, and the organic phase was separated. The aqueous phase was then extracted with pentane, and the combined organic phases were washed with brine, dried over Na2SOs, filtered and concentrated to give 1'-chloro-3',3'-dimethyl-spiro(cyclopropane-1 ,4'-isoquinoline) (101 mg, 98% yield) as a beige liquid: LC-MS (Method G), Tr= 1.06; MS: (M+1) = 220-222.
[00247] Step 3: Preparation of 1'-(benzimidazol-1-yl)-3',3'-dimethyl-spiro(cyclopropane-1,4'-isoquinoline).
To a solution of 1'-chloro-33'-dimethyl-spiro(cyclopropane-1,4'-isoquinoline) (0.064 mmol, 14 mg) in pyridine (1.3 ml, 0.05 M) was added benzimidazole (5 equiv., 0.32 mmol, 38 mg) and the mixture was stirred at 90 °C for 1 h. The reaction mixture was allowed to cool to room temperature and then concentrated in vacuo. The obtained residue was purified by flash chromatography to (benzimidazol-1-yl)-3',3'-dimethyl-spiro(cyclopropane-1,4'-isoquinoline) (9 mg, 50% yield) as a yellow gum: LC-MS (Method G), Tr = 1.04; MS: (M+1) = 302; TH NMR (400 MHz, CHLOROFORM-d) δ ppm 1.01 (t, 2H) 1.17 (t, 2H) 1.23 (s, 6H) (m, 2H) 7.27-7.35 (m, 2H) 7.48 (t, 1H) 7.52 (d, 1H) 7.84 (d, 1H) 8.30 (s, 1H).
[00249] Table E: Physical data of compounds of formula I








Biological examples Botryotinia fuckeliana (Botrytis cinerea)/liquid culture (Gray rot)
[00250] Conidia from the cryogenic storage fungus are directly mixed into nutrient broth (Vogeis broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.
[00251] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: E—1, E-2, E —3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15 , E-16, E-17, E-18, E-19, E-20, *NI E-21, E-22, E-23, E-25, E-26, E-27, E-29 , ST-30, ST-31, ST-32, ST-33, ST-34, ST-35, ST-36, ST-37, ST-38, ST-39, ST-40, ST-41, ST -42, P-43, P-44, P-45, P-46, P-47, P-48, P-49, P-50, P-51, P-52, P-53, P-54 , E-55, E-56, E-57, E-58, E-59, E-60, E-61 /liquid culture (fusariosis) Fusa rium culmorum
[00252] Conidia of the cryogenic storage fungus are CBD dextrose). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.
[00253] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: El, E-2, E-4 , E-7, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E -25, ST-26, ST-27, ST-30, ST-31, ST-32, ST-33, ST-34, ST-35, ST-36, ST-41, ST-42, ST-45 , P-46, P-47, P-48, P-49, P-50, P-51, P-55, P-56, P-57, P-58, P-59, P-60, P -61 Gaeumannomyces graminis /liquid culture (Bad culture)
Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.
[00255] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: El, E-3, E-4 , E-7, E-8, E-9, E-14, E-15, E-16, E-17, E-18, E-19, E-21, E-23, E-30, E -31, P-32, P-33, P-37, P-41, P-47, P-48, P-49, P-51, P-58, P-59, P-60, P-61 Glomerella lagenarium (Colletotrichumlagenarium)/liquid culture (Anthracnose)
[00256] Conidia from the cryogenic storage fungus are directly mixed into nutrient broth (potato dextrose CBD broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is measured photometrically 3-4 days after application.
[00257] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: El, E-2, E-3 , E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E -16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31 , P-32, P-33, P-38, P-39, P-40, P-41, P-42, P-43, P-44, P-45, P-46, P-49, P -50, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61 Monographella nivalis (Microdochium nivale) /liquid culture (cereal foot rot):
[00258] Conidia from the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose CBD broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 4-5 days after application.
[00259] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: El, E-2, E-4 , E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E -17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32 , P-33, P-34, P-37, P-38, P-39, P-40, P-41, P-42, P-43, P-44, P-45, P-46, P -47, P-48, P-49, P-50, P-51, P-53, P-54, P-55, P-56, P-57, P-58, P-59, P-60 , E-61 Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria stain)
[00260] Conidia from the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose CBD broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 161/165 ° and growth inhibition is determined photometrically 4-5 days after application.
[00261] The following compounds from Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: E-1, E-18, E -21, P-22, P-30, P-32, P-33, P-34, P-35, P-36, P-50, P-53, P-54, P-55, P-56 , E-57, E-60 Magnaporthe grisea (Pyricularia oryzãe) / rice / leaf disc preventive (rice bruzone):
[00262] Leaf segments of rice from cv. Kanzler are placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments are inoculated with a spore suspension of the fungus 2 days after application. Inoculated leaf segments are incubated at 22°C and u.r. at 80% under a light regime of 24 h of dark followed by 12 h of light/12 h of dark in an air-conditioned chamber and the activity of a compound is evaluated as percent disease control compared to no treatment when a Appropriate level of disease damage appears in untreated control leaf segments (5 - 7 days after application).
[00263] The following compounds in Table E provided at least 80% disease control at 200 ppm compared to untreated control leaf discs under the same conditions, which exhibit extensive disease development: E-21, E-42, E -49, E-50 Magnaporthe grisea (Pyricularia oryzae) liquid (rice bruzone):
Conidia from the cryogenic storage fungus are directly mixed into nutrient broth (CBD potato dextrose broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.
The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm compared to untreated controls under the same conditions, which exhibit extensive disease development:: El, E-4, E-5, E-6 , E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E E-20, E-21, E-22, E-23, E-24, E-25, E-26, E-27, E-30, E-31, E-32, E-33 , P-34, P-35, P-36, P-37, P-38, P-39, P-40, P-41, P-42, P-43, P-44, P-45, P -46, P-47, P-48, P-49, P-50, P-51, P-52, P-53, P-54, P-55, P-56, P-57, P-58 , E-59, E-60, E-61 Fusarium culmorum / wheat / preventive spikelet (Fusarium)
[00266] Spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. Inoculated spikelets are incubated at 20°C and u.r. at 60% under a light regime of 72 h of semi-dark followed by 12 h of light/12 h of darkness in an air-conditioned chamber and the activity of a compound is evaluated as percent disease control compared to no treatment when an appropriate level of disease damage appears in untreated control spikelets (6-8 days after application).
[00267] The following compounds gave at least 80% control of Fusarium culmorum at 200 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: E-20, E-46, E-49, E- 56, E-58 Pyrenophora Ceres / barley / preventive in leaf discs (Reticular stain)
[00268] Leaf segments of barley cv. Hasso are placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments are inoculated with a spore suspension of the fungus 2 days after application. Inoculated leaf segments are incubated at 20°C and u.r. at 65% under a 12 hr light/12 hr dark light regime in an air-conditioned chamber and the activity of a compound is evaluated as percent disease control compared to no treatment when an appropriate level of damage is caused. disease appears in untreated control leaf segments (5-7 days after application).
[00269] The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm compared to untreated controls under the same conditions, exhibited extensive disease development: E-16 Pyrenophora teres/liquid culture (Reticular stain)
[00270] Conidia from the fungus from cryogenic storage are directly mixed into nutrient broth (Vogeis broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.
[00271] The following compounds gave at least 80% control of Pyrenophora teres at 20 ppm compared to untreated controls under the same conditions, which exhibited extensive disease development: E1, E-4, E-5, E-6, ST-7, ST-9, ST-10, ST-11, ST-12, ST-13, ST-14, ST-15, ST-16, ST-17, ST-18, ST-19, ST- 20, ST-21, ST-22, ST-23, ST-25, ST-26, ST-27 Sclerotinia sclerotiorum /liquid culture (white rot)
[00272] Mycelial fragments from a freshly cultivated liquid culture of the fungus are directly mixed into nutrient broth (Vogeis broth). After placing a solution (DMSO) of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. Test plates are incubated at 24°C and growth inhibition is determined photometrically 3-4 days after application.
[00273] The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm compared to untreated controls under the same conditions, which exhibit extensive disease development: El, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-25, E-26, E-27, E-30, E-31, E-32, E- 33, E-37, E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-55, E-56, E-57, E-58, E-61

权利要求:
Claims (14)
[0001]
1. Compound of formula I:
[0002]
A compound according to claim 1, characterized in that R1 and R2 are each independently selected from hydrogen, C1C6 alkyl and C3-C7 cycloalkyl, wherein the alkyl and cycloalkyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy and C1-C6 alkylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3C6 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 alkylthio; or R2 and R3 together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-alkoxy C6 and C1-C6 alkylthio, and additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom).
[0003]
A compound according to claim 1 or 2, characterized in that R3 and R4 are each independently selected from hydrogen, halogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy and C3-C7 cycloalkyl, in that the alkyl, alkoxy and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C6 alkoxy and C1-C6 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa, C=C(Rb)(Rc) or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 alkylthio; or R2 and R3 together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C6 alkyl, C1-alkoxy C6 and C1-C6 alkylthio, and additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom).
[0004]
A compound according to any one of claims 1 to 3, characterized in that each R5 independently represents halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C1-alkoxy C6, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 alkylthio, -C(=NORa)C1C6 alkyl, phenyl, heteroaryl (where the heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), phenoxy or heteroaryloxy ( wherein the heteroaryl is pyridyl, thiophenyl, thiazolyl, imidazolyl or oxazolyl), wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 5 independently selected substituents a from halogen, C1-C6 alkyl, C1-C6 alkoxy, cyano and C1-C6 alkylthio; n be 0, 1, 2, 3 or 4.
[0005]
Compound according to any one of claims 1 to 4, characterized in that R6 is hydrogen, halogen or C1-C6 alkyl.
[0006]
Compound according to any one of claims 1 to 5, characterized in that R7 independently represents cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl , C3C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkoxy, C1C6 haloalkylthio, C3-C7 cycloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy or C3-C6 alkynyloxy; m is 0, 1, 2, 3 or 4; or Two adjacent R7 substituents together with the carbon atoms to which they are attached represent a C5-C7 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy C1-C6 and C1-C6 alkylthio, and additionally a ring carbon moiety may be replaced by an oxygen or sulfur atom).
[0007]
A compound according to any one of claims 1 to 6, characterized in that R1 and R2 are each independently selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3C6 cycloalkyl group (which may be optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio.
[0008]
A compound according to any one of claims 1 to 7, characterized in that R3 and R4 are each independently selected from hydrogen, halogen, C1-C4 alkyl and C3C4 cycloalkyl, wherein the alkyl and cycloalkyl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkoxy and C1-C3 alkylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C6 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 alkylthio.
[0009]
A compound according to any one of claims 1 to 8, characterized in that R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy , C1-C3 alkylthio, - C(=NORa) C1-C6 alkyl, phenyl, heteroaryl (where the heteroaryl is pyridyl, thiazolyl or oxazolyl), where the alkyl, cycloalkyl, alkoxy, alkenyloxy, alkynyloxy, phenyl and heteroaryl groups may be optionally substituted with 1 to 3 substituents independently selected from halogen, C1-C3 alkyl and C1-C3 alkoxy, n being 0, 1 or 2;
[0010]
Compound according to any one of claims 1 to 9, characterized in that R6 is hydrogen or C1-C3 alkyl.
[0011]
A compound according to claim 1, characterized in that R 1 and R 2 are each independently selected from hydrogen and C 1 -C 4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 independently selected substituents a starting from halogen, methoxy and methylthio; or R1 and R2 together with the carbon atom to which they are attached represent a C3C4 cycloalkyl group (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of halogen and C1-C3 alkyl); R3 and R4 are each independently selected from hydrogen, halogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 substituents independently selected from halogen, methoxy and methylthio; or R3 and R4 together with the carbon atom to which they are attached represent C=O, C=NORa or C3-C4 cycloalkyl (which may optionally be substituted with 1 to 3 substituents independently selected from the group consisting of a halogen and C1-C3 alkyl); each R5 independently represents halogen, cyano, C1-C4 alkyl, C3-C4 cycloalkyl or phenyl, wherein the alkyl, cycloalkyl and phenyl groups may optionally be substituted with 1 to 3 substituents independently selected from halogen or C1-alkyl C3; n is 0, 1 or 2; R6 is hydrogen or methyl; each R7 is independently cyano, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C3 alkynyl, C1-C4 alkylthio or C3-C4 cycloalkyl; m is 0, 1 or 2; and Ra is selected from hydrogen and C1-C4 alkyl, wherein the alkyl group may be optionally substituted with 1 to 3 halogen atoms; or a salt or N-oxide thereof.
[0012]
A compound according to claim 1, characterized in that R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; or R1 and R2 together with the carbon atom to which they are attached represent a C3-C4 cycloalkyl group; R3 and R4 are each independently selected from hydrogen, fluorine or C1-C3 alkyl; or R3 and R4 together with the carbon atom to which they are attached represent C=O or C3-C4 cycloalkyl; each R5 independently represents halogen, C1-C3 alkyl or C3-C4 cycloalkyl, the alkyl and cycloalkyl groups optionally being substituted with 1 to 3 fluorine atoms; n is 0, 1 or 2; R6 is hydrogen; and each R7 independently represents fluorine, chlorine or C1-C3 alkyl; m is 1 or 2; or a salt or N-oxide thereof.
[0013]
Composition characterized in that it comprises a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12 and at least one additional active ingredient and/or a diluent.
[0014]
14. Method for combating or controlling phytopathogenic microorganisms, characterized in that it comprises the application to a phytopathogen, to the site of a phytopathogen, or to a plant susceptible to attack by a phytopathogen or its propagation material, of an effective amount from the fungicidal point of view of a compound of formula (I) as defined in any one of claims 1 to 12.

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法律状态:
2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/03/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP15161494|2015-03-27|

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EP15161494.8|2015-03-27|

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PCT/EP2016/056127|WO2016156085A1|2015-03-27|2016-03-21|Microbiocidal heterobicyclic derivatives|

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