# Patent

## Title
Insecticidal compounds

## Abstract

Novel heteroaromatic compounds of formula (I): wherein A1, A2, A3, R1, R2, G1, G2, Q1 and Q2 are as defined in claim 1; or salts or N-oxides thereof. Furthermore, the present invention relates to processes for preparing compounds of formula (I), to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.

## Background
This application is a National Stage Entry under 35 USC §371 of International application serial number PCT/EP2007/003626, filed on Apr. 25, 2007, which claims priority to GB 0608507.0, filed on Apr. 28, 2006, and GB 0618907.0, filed Sep. 25, 2006, the contents of which are incorporated herein by reference.
The present invention relates to heteroaromatic bisamide derivatives, to processes and intermediates for preparing them, to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
Bisamide derivatives with insecticidal properties are disclosed, for example, in EP 1,714,958, JP 2006/306771, WO 06/137376, WO 06/137395 and WO 07/017,075.
Heteroaromatic bisamide derivatives with pharmaceutical properties are disclosed, for example, in WO 05/118579, U.S. Pat. No. 6,747,127 and US 2003/199516.
It has now surprisingly been found that certain heteroaromatic bisamide derivatives have insecticidal properties.
The present invention therefore provides a compound of formula (I)




wherein

A1, A2 and A3 are independently of one another C—X, N—X, nitrogen, oxygen or sulfur, provided that two of A1, A2 or A3 are C—X or nitrogen and that one of A1, A2 or A3 is oxygen, sulfur or N—X;

each X is independently hydrogen, halogen, C1-C4alkyl or trifluoromethyl;

R1 and R2 are independently of one another hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;

G1 and G2 are independently of one another oxygen or sulfur;

Q1 is aryl or aryl substituted by one to five substituents R3, which may be the same or different, or Q1 is heterocyclyl or heterocyclyl substituted by one to five substituents R3, which may be the same or different; wherein

each R3 is independently cyano, nitro, hydroxy, halogen, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkyl-sulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C4alkyl-amino, di-(C1-C4alkyl)amino, C1-C4alkylcarbonyl, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonylamino or phenyl; and

Q2 is a moiety of formula (II) or (III)





wherein

Y1 and Y5 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;

Y3 is C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6 perfluoroalkylsulfonyl;

Y2 and Y4 are independently of each other hydrogen, halogen or C1-C4alkyl;

Y6 and Y9 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;

Y8 is C1-C4haloalkoxy, C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl;

Y7 is hydrogen, halogen or C1-C4alkyl;

or salts or N-oxides thereof.

The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
Each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkoxycarbonyl, alkylcarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. The alkyl groups are preferably C1 to C6 alkyl groups, more preferably C1-C4 and most preferably C1-C3 alkyl groups.
Alkenyl and alkynyl moieties (either alone or as part of a larger group, such as alkenyloxy or alkynyloxy) can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl. The alkenyl and alkynyl groups are preferably C2 to C6 alkenyl or alkynyl groups, more preferably C2-C4 and most preferably C2-C3 alkenyl or alkynyl groups.
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups (either alone or as part of a larger group, such as haloalkoxy or haloalkylthio) are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, —CF3, —CF2Cl, —CH2CF3 or —CH2CHF2. Perfluoroalkyl groups (either alone or as part of a larger group, such as perfluoroalkylthio) are a particular type of haloalkyl group; they are alkyl groups which are completely substituted with fluorine atoms and are, for example, —CF3, —CF2CF3 or —CF(CF3)2.
Haloalkenyl and haloalkynyl groups (either alone or as part of a larger group, such as haloalkenyloxy or haloalkynyloxy) are alkenyl and alkynyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, —CH═CF2, —CCl═CClF or —CHClC≡CH.
Cycloalkyl groups can be in mono- or bi-cyclic form and may optionally be substituted by one or more methyl groups. The cycloalkyl groups preferably contain 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of monocyclic cycloalkyl groups are cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Halocycloalkyl groups are cycloalkyl groups which are substituted with one or more of the same of different halogen atoms and may optionally be substituted by one or more methyl groups. Examples of monocyclic halocycloalkyl groups are 2,2-dichloro-cyclopropyl, 2,2-dichloro-1-methyl-cyclopropyl and 2-chloro-4-fluorocyclohexyl.
In the context of the present specification the term “aryl” refers to a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl (for example, 2-bromo-phenyl, 5-chloro-2-fluoro-phenyl, 3-chloro-2-hydroxy-phenyl, 2-chloro-phenyl, 3-chloro-phenyl, 3-chloro-2,4,5-trifluoro-phenyl, 4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl, 4-N,N-dimethylamino-phenyl, 4-diphenyl, 2-fluoro-phenyl, 4-fluoro-phenyl, 2-fluoro-3-trifluoromethyl-phenyl, 2-fluoro-5-trifluoromethyl-phenyl, 4-fluoro-3-trifluoromethyl-phenyl, 4-iso-propyl-phenyl, 4-methoxycarbonyl-phenyl, 2-methoxy-phenyl, 4-methoxy-phenyl, 2-methyl-phenyl, 4-methylthio-phenyl, 2-methylthio-4-trifluoromethyl-phenyl, 4-nitro-phenyl, phenyl, 2-trifluoromethoxy-phenyl, 4-trifluoromethoxy-phenyl, 2-trifluoromethyl-phenyl and 4-trifluoromethyl-phenyl).
The term “heteroaryl” refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyridyl (for example, 5-bromo-pyrid-3-yl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 2-fluoro-pyrid-3-yl, 3-methyl-pyrid-2-yl, 2-methylthio-pyrid-3-yl, pyrid-3-yl and pyrid-4-yl), pyridazinyl, pyrimidinyl (for example, pyrimidin-5-yl, such as 6-methyl-2-phenyl-pyrimidin-5-yl), pyrazinyl, furanyl (for example, furan-2-yl and furan-5-yl, such as 2-bromo-furan-5-yl), thiophenyl (for example, thiophen-2-yl and thiophen-3-yl, such as 4-methoxy-thiophen-3-yl, and thiophen-5-yl, such as 2-chloro-thiophen-5-yl), oxazolyl (for example, oxazol-4-yl, such as 5-phenyl-oxazol-4-yl), isoxazolyl (for example, isoxazol-4-yl, such as 5-methyl-3-phenyl-isoxazol-4-yl), oxadiazolyl, thiazolyl (for example, thiazol-5-yl, such as 4-methyl-2-phenyl-thiazol-5-yl), isothiazolyl, thiadiazolyl (for example, thiadiazol-4-yl and thiadiazol-5-yl, such as 4-methyl-thiadiazol-5-yl), pyrrolyl (for example, pyrrol-3-yl, such as 1,2,5-trimethyl-pyrrol-3-yl), pyrazolyl (for example, pyrazol-4-yl, such as 5-methyl-1-phenyl-1H-pyrazol-4-yl, and pyrazol-5-yl, such as 1,3-dimethyl-1H-pyrazol-5-yl), imidazolyl (for example, 1H-imidazol-4-yl), triazolyl and tetrazolyl. A preferred heteroaryl group is pyridine. Examples of bicyclic groups are benzothiophenyl (for example, benzo[b]thiophen-5-yl), benzimidazolyl (for example, 1H-benzimidazol-5-yl), benzothiadiazolyl (for example, benzo[1,2,5]thiadiazol-5-yl), quinolinyl (for example, quinolin-2-yl), cinnolinyl (for example, cinnolin-4-yl), quinoxalinyl (for example, quinoxalin-2-yl) and pyrazolo[1,5-a]pyrimidinyl (for example, pyrazolo[1,5-a]pyrimidin-6-yl, such as 2,7-dimethyl-pyrazolo[1,5-a]pyrimidin-6-yl).
The term “heterocyclyl” is defined to include heteroaryl and in addition their unsaturated or partially unsaturated analogues such as 4,5,6,7-tetrahydro-benzothiophenyl (for example, 4,5,6,7-tetrahydro-benzo[c]thiophenyl), chromen-4-onyl (for example, chromen-4-on-2-yl), 9H-fluorenyl (for example, 9H-fluoren-4-yl), 3,4-dihydro-2H-benzo-1,4-dioxepinyl (for example, 3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-yl), 2,3-dihydro-benzofuranyl (for example, 2,3-dihydro-benzofuran-5-yl), piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl, tetrahydrofuranyl and morpholinyl.
Preferred values of A1, A2, A3, X, R1, R2, G1, G2, Q1, Q2, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 are, in any combination, as set out below.
Preferably two of A1, A2 and A3 are C—X and one is sulfur, more preferably A1 and A3 are C—X and A2 is sulfur.
Preferably each X is independently hydrogen, fluoro, chloro, bromo, methyl or trifluoromethyl, more preferably hydrogen, fluoro, chloro, bromo or methyl, even more preferably hydrogen, chloro, bromo or methyl, most preferably hydrogen.
Preferably R1 is hydrogen, methyl, ethyl or acetyl, most preferably hydrogen.
Preferably R2 is hydrogen, methyl, ethyl or acetyl, most preferably hydrogen.
Preferably G1 is oxygen.
Preferably G2 is oxygen.
Preferably Q1 is phenyl, pyridyl, furanyl, thiophenyl, pyrazolyl or 1,2,3-thiadiazolyl, or phenyl, pyridyl, furanyl, thiophenyl, pyrazolyl or 1,2,3-thiadiazolyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro or phenyl. More preferably Q1 is phenyl or pyridyl, or phenyl or pyridyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or phenyl. Even more preferably Q1 is phenyl or pyridyl substituted by one to three substituents independently selected from cyano, fluoro, chloro or methyl. Especially preferred groups for Q1 are 5-bromo-furan-2-yl, 2-bromo-phenyl, 5-bromo-pyrid-3-yl, 2-chloro-phenyl, 3-chloro-phenyl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 5-chloro-thiophen-2-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl, 1,3-dimethyl-pyrazol-5-yl, 2-fluoro-phenyl, 4-fluoro-phenyl, 2-fluoro-pyrid-3-yl, 2-fluoro-3-trifluoromethyl-phenyl, furan-2-yl, 2-methyl-phenyl, 3-methyl-pyrid-2-yl, 4-methylthio-phenyl, 2-methylthio-pyrid-3-yl, 4-nitro-phenyl, phenyl, pyrid-3-yl, pyrid-4-yl, 2-trifluoromethyl-phenyl and 4-trifluoromethyl-phenyl. Most especially preferred groups for Q1 are 5-bromo-furan-2-yl, 2-bromo-phenyl, 5-bromo-pyrid-3-yl, 2-chloro-phenyl, 3-chlorophenyl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 5-chloro-thiophen-2-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl, 1,3-dimethyl-pyrazol-5-yl, 4-fluoro-phenyl, 2-fluoro-pyrid-3-yl, 2-fluoro-3-trifluoromethyl-phenyl, furan-2-yl, 2-methyl-phenyl, 3-methyl-pyrid-2-yl, 4-methylthio-phenyl, 4-nitro-phenyl, phenyl and pyrid-3-yl.
A particularly preferred group of compounds are compounds of formula (I) wherein Q1 is aryl or aryl substituted by one to five substituents R3, which may be the same or different.
Preferably Q1 is phenyl or phenyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro or phenyl. More preferably Q1 is phenyl or phenyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or phenyl. Even more preferably Q1 is phenyl substituted by one to three substituents independently selected from cyano, fluoro, chloro or methyl. Especially preferred groups for Q1 are 2-bromo-phenyl, 2-chloro-phenyl, 3-chloro-phenyl, 4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl, 2-fluoro-phenyl, 4-fluoro-phenyl, 2-fluoro-3-trifluoromethyl-phenyl, 2-methyl-phenyl, 4-methylthio-phenyl, 4-nitro-phenyl, phenyl, 2-trifluoromethyl-phenyl and 4-trifluoromethyl-phenyl. Most especially preferred groups for Q1 are 2-bromo-phenyl, 2-chloro-phenyl, 3-chloro-phenyl, 4-cyano-phenyl, 2,5-dichloro-phenyl, 2,3-difluoro-phenyl, 4-fluoro-phenyl, 2-fluoro-3-trifluoromethyl-phenyl, 2-methyl-phenyl, 4-methylthio-phenyl, 4-nitro-phenyl and phenyl.
Another particularly preferred group of compounds are compounds of formula (I) wherein Q1 is heterocyclyl or heterocyclyl substituted by one to five substituents R3, which may be the same or different. The heterocyclyl group is preferably a heteroaryl group.
Preferably Q1 is pyridyl, furanyl, thiophenyl, pyrazolyl or 1,2,3-thiadiazolyl, or pyridyl, furanyl, thiophenyl, pyrazolyl or 1,2,3-thiadiazolyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro or phenyl. More preferably Q1 is pyridyl or pyridyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or phenyl. Even more preferably Q1 is pyridyl substituted by one to three substituents independently selected from cyano, fluoro, chloro or methyl. Especially preferred groups for Q1 are 5-bromo-furan-2-yl, 5-bromo-pyrid-3-yl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 5-chloro-thiophen-2-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 1,3-dimethyl-pyrazol-5-yl, 2-fluoro-pyrid-3-yl, furan-2-yl, 3-methyl-pyrid-2-yl, 2-methylthio-pyrid-3-yl, pyrid-3-yl and pyrid-4-yl. More especially preferred groups for Q1 are 5-bromo-furan-2-yl, 5-bromo-pyrid-3-yl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 5-chloro-thiophen-2-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 3-dimethyl-pyrazol-5-yl, 2-fluoro-pyrid-3-yl, furan-2-yl, 3-methyl-pyrid-2-yl and pyrid-3-yl. Most especially preferred groups for Q1 are 5-bromo-pyrid-3-yl, 2-chloro-pyrid-3-yl, 2-chloro-pyrid-4-yl, 6-chloro-pyrid-3-yl, 3-chloro-5-trifluoromethyl-pyrid-2-yl, 2-fluoro-pyrid-3-yl, 3-methyl-pyrid-2-yl and pyrid-3-yl.
Preferably Q2 is a moiety of formula (II). Especially preferred groups for Q2 are 4-heptafluoroisopropyl-2,6-dimethyl-phenyl and 4-heptafluoroisopropyl-2,6-diethyl-phenyl.
Preferably Y1 is cyano, chloro, methyl, ethyl or trifluoromethyl, more preferably methyl or ethyl, most preferably methyl.
Preferably Y2 is hydrogen, fluoro, chloro or methyl, most preferably hydrogen.
Preferably Y3 is heptafluoropropyl, heptafluoroprop-2-yl, heptafluoropropylthio, heptafluoropropylsulfinyl, heptafluoropropylsulfonyl, heptafluoroprop-2-ylthio, heptafluoroprop-2-ylsulfinyl, heptafluoroprop-2-ylsulfonyl or nonafluorobut-2-yl, most preferably heptafluoroprop-2-yl.
Preferably Y4 is hydrogen, fluoro, chloro or methyl, most preferably hydrogen.
Preferably Y5 is cyano, chloro, methyl, ethyl or trifluoromethyl, more preferably methyl or ethyl, most preferably methyl.
Preferably Y6 is cyano, chloro, methyl, ethyl or trifluoromethyl, more preferably methyl or ethyl, most preferably methyl.
Preferably Y7 is hydrogen, fluoro, chloro or methyl, most preferably hydrogen.
Preferably Y8 is heptafluoropropyl, heptafluoroprop-2-yl, heptafluoropropylthio, heptafluoropropylsulfinyl, heptafluoropropylsulfonyl, heptafluoroprop-2-ylthio, heptafluoroprop-2-ylsulfinyl, heptafluoroprop-2-ylsulfonyl or nonafluorobut-2-yl, most preferably heptafluoroprop-2-yl.
Preferably Y9 is cyano, chloro, methyl, ethyl or trifluoromethyl, more preferably methyl or ethyl, most preferably methyl.
A particularly preferred group of compounds are compounds of formula (Ia)




wherein R1, R2, G1, G2, Q1 and Q2 are as defined in relation to formula (I) and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof. The preferences for R1, R2, G1, G2, Q1, Q2, X, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I). A group of most particularly preferred compounds are compounds of formula (Ia) wherein X1 and X2 are both hydrogen.

Another group of particularly preferred compounds are compounds of formula (Ib)




wherein R1, R2, G1, G2, Q1 and Q2 are as defined in relation to formula (I) and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof. The preferences for R1, R2, G1, G2, Q1, Q2, X, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I). A group of most particularly preferred compounds are compounds of formula (Ib) wherein X1 and X2 are both hydrogen. A further group of most particularly preferred compounds are compounds of formula (Ib) wherein X1 is bromo and X2 is hydrogen.

A further group of particularly preferred compounds are compounds of formula (Ic)




wherein R1, R2, G1, G2, Q1 and Q2 are as defined in relation to formula (I) and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof. The preferences for R1, R2, G1, G2, Q1, Q2, X, Y1, Y2, Y3, Y4, Y1, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I). A group of most particularly preferred compounds are compounds of formula (Ic) wherein X1 and X2 are both hydrogen. A further group of most particularly preferred compounds are compounds of formula (Ic) wherein X1 is hydrogen and X2 is chloro. Yet a further group of most particularly preferred compounds are compounds of formula (Ic) wherein X1 is hydrogen and X2 is bromo. Another group of most particularly preferred compounds are compounds of formula (Ic) wherein X1 is hydrogen and X2 is methyl.

Certain intermediates are novel and as such form a further aspect of the invention. One such group of novel intermediates are compounds of formula (IX′)




wherein A1, A2, A3, R2, G2 and Q2 are as defined in relation to formula (I); or salts or N-oxides thereof. The preferences for A1, A2, A3, R1, G2, Q2, X, Y1, Y2, Y3, Y4, Y1, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I).

A further group of novel intermediates are compounds of formula (XIII)




wherein A1, A2, A3, R2, G2 and Q2 are as defined in relation to formula (I); or salts or N-oxides thereof. The preferences for A1, A2, A3, R2, G2, Q2, X, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I).

One embodiment the present invention provides a compound of formula (Ix)




wherein

A1, A2 and A3 are independently of one another carbon, nitrogen, nitrogen oxide, oxygen or sulfur with the proviso that at least one of A1, A2 or A3 is not carbon and no more than one of A1, A2 or A3 is oxygen or sulfur;

R1 and R2 are independently of one another hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;

G1 and G2 are independently of one another oxygen or sulfur;

X are independently of one another halogen, C1-C3alkyl or trifluoromethyl;

n is 0, 1, 2 or 3;

Q1 is aryl or aryl substituted by one to five substituents independently selected from R3, or heterocyclyl or heterocyclyl substituted by one to five substituents independently selected from R3; wherein

R3 are independently of one another cyano, nitro, hydroxy, halogen, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C4alkylcarbonyl, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonylamino or phenyl; and

Q2 is a moiety of formula (II) or (D)





wherein

Y1 and Y5 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;

Y3 is C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl;

Y2 and Y4 are independently of each other hydrogen, halogen or C1-C4alkyl;

Y6 and Y9 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;

Y8 is C1-C4haloalkoxy, C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl;

Y7 is hydrogen, halogen or C1-C4alkyl;

or salts or N-oxides thereof.

Preferably two of A1, A2 and A3 are carbon and one is sulfur, most preferably A1 and A3 are carbon and A2 is sulfur.
Preferably X is fluoro, chloro, methyl or trifluoromethyl, most preferably fluoro, chloro or methyl.
Preferably n is 0, 1 or 2, even more preferably 0 or 1, most preferably 0.
The preferences for R1, R2, G1, G2, Q1, Q2, Y1, Y2, Y3, Y4, Y1, Y6, Y7, Y8 and Y9 are the same as the preferences set out for the corresponding substituents of the compounds of the formula (I).
The compounds in Tables 1 to 7 (i.e., Table X where X is 1 to 7) below illustrate the compounds of the invention.










TABLE X







Compound numbers
Q1









X.01
5-bromo-furan-2-yl



X.02
2-bromo-phenyl



X.03
5-bromo-pyrid-3-yl



X.04
2-chloro-phenyl



X.05
3-chloro-phenyl



X.06
2-chloro-pyrid-3-yl



X.07
2-chloro-pyrid-4-yl



X.08
6-chloro-pyrid-3-yl



X.09
5-chloro-thiophen-2-yl



X.10
3-chloro-5-trifluoromethyl-pyrid-2-yl



X.11
4-cyano-phenyl



X.12
2,5-dichloro-phenyl



X.13
2,3-difluoro-phenyl



X.14
1,3-dimethyl-pyrazol-5-yl



X.15
2-fluoro-phenyl



X.16
4-fluoro-phenyl



X.17
2-fluoro-pyrid-3-yl



X.18
2-fluoro-3-trifluoromethyl-phenyl



X.19
furan-2-yl



X.20
2-methyl-phenyl



X.21
3-methyl-pyrid-2-yl



X.22
4-methylthio-phenyl



X.23
2-methylthio-pyrid-3-yl



X.24
4-nitro-phenyl



X.25
phenyl



X.26
pyrid-3-yl



X.27
pyrid-4-yl



X.28
2-trifluoromethyl-phenyl



X.29
4-trifluoromethyl-phenyl

















TABLE 1







Table 1 provides 29 compounds of formula (Ia′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-isopropyl-phenyl.









(Ia′)




















TABLE 2





Table 2 provides 29 compounds of formula (Ib′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ib′)






















TABLE 3





Table 3 provides 29 compounds of formula (Ic′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ic′)






















TABLE 4





Table 4 provides 29 compounds of formula (Ib′′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ib′′)






















TABLE 5





Table 5 provides 29 compounds of formula (Ic′′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ic′′)






















TABLE 6





Table 6 provides 29 compounds of formula (Ic′′′)


wherein Q2 is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ic′′′)






















TABLE 7





Table 7 provides 29 compounds of formula (Ic′′′′)


wherein Q2 . is 2,6-dimethyl-4-perfluoro-


isopropyl-phenyl and Q1 has the values listed in Table 1.

















(Ic′′′′)















The compounds of the invention may be made by a variety of methods.
1) Compounds of formula (I), wherein G1 and G2 are oxygen, may be made by treatment of a compound of formula (V), wherein G1 is oxygen and R is OH, C1-C6alkoxy or Cl, F or Br with an amine of formula NHR2Q2.




When R is OH such reactions are usually carried out in the presence of a coupling reagent, such as DCC (N,N′-dicyclohexylcarbodiimide), EDC (1-ethyl-3-[3-dimethylamino-propyl]-carbodiimide hydrochloride) or BOP-Cl (bis(2-oxo-3-oxazolidinyl)phosphonic chloride), in the presence of a base, such as pyridine, triethylamine, 4-(dimethylamino)-pyridine or diisopropylethylamine, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzotriazole. When R is Cl, such reactions are usually carried out under basic conditions (for example in the presence of pyridine, triethylamine, 4-(dimethylamino)-pyridine or diisopropylethylamine), again optionally in the presence of a nucleophilic catalyst. When R is C1-C6alkoxy it is sometimes possible to convert the ester directly to the amide by heating the ester and amine together in a thermal process.

2) Acid halides of formula (V), wherein G1 is oxygen and R is Cl, F or Br, may be made from a carboxylic acid of formula (V), wherein G1 is oxygen and R is OH, under standard conditions, such as treatment with thionyl chloride or oxalyl chloride.
3) Carboxylic acids of formula (V), wherein G1 is oxygen and R is OH, may be formed from an ester of formula (V), wherein G1 is oxygen and R is C1-C6alkoxy. It is known to a person skilled in the art that there are many methods for the hydrolysis of such esters depending on the nature of the alkoxy group. One widely used method to achieve such a transformation is the treatment of the ester with an alkali hydroxide, such as sodium hydroxide, in a solvent, such as ethanol.
4) Esters of formula (V), wherein G1 is oxygen and R is C1-C6alkoxy, may be made by treatment of a compound of formula (IV), wherein R is C1-C6alkoxy, by acylation with a carboxylic acid of formula Q1-COOH or an acid halide of formula Q1-COHal, wherein Hal is Cl, F or Br, under standard conditions as described in 1).




5) Compounds of formula (IV), wherein R is C1-C6alkoxy, may be made from a compound of formula (VI) by sequential treatment with an alcohol R—OH under acidic conditions and then formation of the N—R1 bond. It is known to a person skilled in the art that there are many methods for the formation of this bond depending on the nature of the substituent R1.




For example, reductive amination may be achieved by treatment of the amine with an aldehyde or ketone and a reducing agent such as sodium cyanoborohydride. Alternatively alkylation may be achieved by treating the amine with an alkylating agent such as an alkyl halide, optionally in the presence of a base. Alternatively arylation may be achieved by treatment of the amine with an aryl halide or sulfonate in the presence of a suitable catalyst/ligand system, often a palladium (0) complex.

6) Alternatively, compounds of formula (IV), wherein R is C1-C6alkoxy, may be made from a compound of formula (VII), wherein R is C1-C6alkoxy and LG is a leaving group, such as fluoro, chloro or sulfonate, via nucleophilic displacement of the leaving group by an amine of formula R1—NH2.




Compounds of formula (VII) and amines of formula R1—NH2 are either known compounds or may be made by methods known to a person skilled in the art.

7) Compounds of formula (I), wherein G1 and G2 are sulfur, may be made from a compound of formula (I), wherein G1 and G2 are oxygen, by treatment with a thio-transfer reagent, such as Lawesson's reagent or phosphorus pentasulfide.
8) Compounds of formula (I), wherein G1 is sulfur and G2 is oxygen, may be made from a compound of formula (V), wherein G1 is oxygen and R is OH or C1-C6alkoxy, by treatment with a thio-transfer reagent, such as Lawessen's reagent or phosphorus pentasulfide, prior to coupling with the amine of formula NHR2Q2.
9) Alternatively, compounds of formula (I), wherein G1 and G2 are oxygen, may be made by the treatment of a compound of formula (IX), wherein G2 is oxygen, with a carboxylic acid of formula Q1-COOH or an acid halide of formula Q1-COHal, wherein Hal is Cl, F or Br, under standard conditions as described in 1).




10) Compounds of formula (IX), wherein G2 is oxygen, may be formed from a compound of formula (VIII), wherein P is a suitable protecting group and R is OH, C1-C6alkoxy or Cl, F or Br by amide bond formation with an amine of formula NHR2Q2 under standard conditions as described in 1), followed by removal of the protecting group P under standard conditions.




11) Compounds of formula (VIII), wherein R is OH, C1-C6alkoxy or Cl, F or Br, may be made by the protection of the amine functionality in a compound of formula (IV), wherein R is OH, C1-C6alkoxy or Cl, F or Br. Suitable protecting groups include carbamates (such as tert-butyloxycarbonyl, allyloxycarbonyl and benzyloxycarbonyl), trialkylsilyl groups (such as tert-butyldimethylsilyl) and acyl groups (such as acetyl). The formation and removal of such groups is widely reported in the literature and is known to a person skilled in the art.
12) For compounds of formula (VIII) and compounds of formula (IV), the esters (wherein R is C1-C6alkoxy) may be hydrolysed to the acids (wherein R is OH) by treatment with an alkali hydroxide, such as sodium hydroxide, in a solvent, such as ethanol. The acids (wherein R is OH) may be converted to the acid halides (wherein R is Cl, F or Br) by treatment with thionyl chloride or oxalyl chloride as described in 2) and 3).
13) Alternatively, it may be possible to convert compounds of formula (IV), wherein R is OH, C1-C6alkoxy or Cl, F or Br, directly to compounds of formula (IX) by amide bond formation with an amine of formula NHR2Q2 under standard conditions as described in 1).
14) Alternatively, compounds of formula (IX), wherein G2 is oxygen, may be made from a compound of formula (X1), wherein G2 is oxygen and LG is a leaving group such as fluoro, chloro or sulfonate, by displacement of the leaving group with a compound of formula R1—NH2. Such reactions are usually performed under basic conditions.
15) Compounds of formula (XI) may be made from a compound of formula (X), wherein R is OH, C1-C6alkoxy or Cl, F or Br and LG is a leaving group as described in 14), via amide bond formation under standard conditions as described in 1). Compounds of formula (VI), formula (VII) and formula (X) are either known compounds or may be made by methods known to a person skilled in the art.




16) Compounds of formula (I), wherein G1 is oxygen and G2 is sulfur, may be made by treatment of a compound of formula (X1), wherein G2 is oxygen and LG is a leaving group, or a compound of formula (IX), wherein G2 is oxygen, with a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide prior to elaborating to compounds of formula (I), wherein G1 is oxygen and G2 is sulfur, as described in 9).
17) An alternative synthesis of compounds of formula (IX), wherein G2 is oxygen and R1 is hydrogen, may be achieved by the reduction of a nitro compound of formula (XIII) wherein G2 is oxygen. There are numerous methods for achieving such a transformation reported in the literature such as treatment with tin chloride under acidic conditions, or hydrogenation catalysed by a noble metal such as palladium on carbon.




18) Compounds of formula (XIII) wherein G2 is oxygen may be derived from a compound of formula (XII), wherein G2 is oxygen and R is OH, C1-C6alkoxy or Cl, F or Br, via acylation with an amine of formula NHR2Q2 under the standard conditions as described in 1).
19) For compounds of formula (XII) wherein G2 is oxygen, the esters (wherein R is C1-C6alkoxy) may be hydrolysed to the acids (wherein R is OH) by treatment with an alkali hydroxide, such as sodium hydroxide, in a solvent, such as ethanol as described in 3). The acids (wherein R is OH) may be converted to the acid halides (wherein R is Cl, F or Br) by treatment with thionyl chloride or oxalyl chloride as described in 2). Compounds of formula (XII) are either known or may be made by methods known to a person skilled in the art.
The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, preferably a plant, or to a plant susceptible to attack by a pest, The compounds of formula (I) are preferably used against insects, acarines or nematodes.
The term “plant” as used herein includes seedlings, bushes and trees.
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per hectare.
When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.
In another aspect the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol ether sulfates (for example sodium laureth-3-sulfate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately diesters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures preferably contain up to 25% by weight of the compound of formula (I).
The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:
a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate;

b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;

c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;

d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron;

e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin;

f) Pyrazoles, such as tebufenpyrad and fenpyroximate;

g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin;

h) Hormones or pheromones;

i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin;

j) Amidines, such as chlordimeform or amitraz;

k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;

l) Neonicotinoid compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran or thiamethoxam;

m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide;

n) Diphenyl ethers, such as diofenolan or pyriproxifen;

o) Indoxacarb;

p) Chlorfenapyr;

q) Pymetrozine;

r) Spirotetramat, spirodiclofen or spiromesifen; or

s) Flubendiamid or rynaxypyr

In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500), N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulfate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulfide 1,1′-dioxide, dichlofluanid, diclomezine, dicloran, dietbofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-A1, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.
The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIXTM.
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The following Examples illustrate, but do not limit, the invention.


PREPARATION EXAMPLES
Example I1
Preparation of 5-nitro-thiophene-3-carbonyl chloride




To a suspension of 5-nitro-thiophene-3-carboxylic acid (5.0 g, 29 mmol) in dichloromethane (60 ml) was added oxalyl chloride (2.93 ml, 35 mmol) at room temperature. The mixture was stirred for 30 minutes at room temperature then for 30 minutes at 50° C. The solvent was evaporated and the residue suspended in tetrahydrofuran (30 ml). The solution was used without purification in the next step.
Example I2
Preparation of 5-nitro-thiophene-3-carboxylic Acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide




To a solution of 4-heptafluoroisopropyl-2,6-dimethylaniline (8.35 g, 28.9 mmol) (prepared as described in EP 1,006,102) in tetrahydrofuran (30 ml) was added pyridine (4.67 ml). The mixture was cooled to 0° C. and the solution of 5-nitro-thiophene-3-carbonyl chloride (29 mmol) in tetrahydrofuran (Example I1) was added. The mixture was stirred at room temperature for 12 hours. Then water (100 ml) was added and the organic phase extracted twice with ethyl acetate (200 ml). The combined organic extracts were dried over sodium sulfate and the solvent evaporated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 5-nitro-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (10.43 g, 81% yield). LC/MS: 445 (MH+).
5-Nitro-thiophene-3-carboxylic acid [2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained in 57% yield when 4-heptafluoroisopropyl-2,6-diethylaniline (prepared as described in EP 1,006,102) was used as reactant; 1H-NMR (CDCl3, 400 MHz): 8.32 (s, 1H), 8.22 (s, 1H), 7.41 (s, 2H), 7.25 (s, 1H), 2.70 (q, 4H), 1.25 (t, 6H) ppm.
5-Nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained in 31% yield when a mixture of 5-nitro-thiophene-2-carboxylic acid and 4-nitro-thiophene-2-carboxylic acid (prepared as described in J. Am. Chem. Soc. 1999, 121, 7751-7759) was used as reactant; LC/MS: 445 (MH+); 1H-NMR (CDCl3, 400 MHz): 8.44 (s, 1H), 8.26 (s, 1H), 7.29 (s, 2H), 2.15 (s, 6H) ppm.
4-Nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained in 18% yield when a mixture of 5-nitro-thiophene-2-carboxylic acid and 4-nitro-thiophene-2-carboxylic acid (prepared as described in J. Am. Chem. Soc. 1999, 121, 7751-7759) was used as reactant; 1H-NMR (CDCl3, 400 MHz): 7.93 (d, 1H), 7.59 (d, 1H), 7.50 (s, 1H), 7.37 (s, 2H), 2.34 (s, 6H) ppm.
5-Methyl-4-nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained in 33% yield when 5-methyl-4-nitro-thiophene-2-carboxylic acid (prepared as described in Bioorganic & Medicinal Chemistry (2004), 12(5), 1221-1230) was used as reactant; 1H-NMR (CDCl3, 400 MHz): 8.12 (s, 1H), 7.38 (s, 2H), 7.33 (s, 1H), 2.91 (s, 3H), 2.37 (s, 6H) ppm.
Example I3
Preparation of 5-amino-thiophene-3-carboxylic Acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide




To a solution of 5-nitro-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (10.10 g, 23 mmol) (Example I2) in isopropanol (120 ml) was added tin chloride (15.52 g, 81.8 mmol). The mixture was cooled to 0° C. and concentrated hydrochloric acid (37%) (23 ml) was added slowly. The mixture was stirred at 80° C. for 2 hours. Then about 1⁄3 of the total volume of isopropanol was evaporated. Water (100 ml) was added to the concentrated mixture followed by aqueous sodium hydroxide (4N) to adjust the pH to 8-9. The aqueous phase was extracted three times with ethyl acetate (200 ml). The combined organic extracts were dried over sodium sulfate and the solvent evaporated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 5-amine-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (4.98 g, 36% yield). LC/MS: 415 (MH+); 1H-NMR (CDCl3, 400 MHz): 7.49 (s, 1H), 7.30 (s, 2H), 7.16 (s, 1H), 6.52 (s, 1H), 3.94 (s, 2H), 2.24 (s, 6H) ppm.
5-Amino-thiophene-3-carboxylic acid [2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 32% yield when 5-nitro-thiophene-3-carboxylic acid [2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I2) was used as reactant; 1H-NMR (CDCl3, 400 MHz): 7.41 (s, 2H), 7.25 (s, 1H), 7.08 (s, 1H), 6.59 (s, 1H), 2.70 (q, 4H), 1.25 (t, 6H) ppm.
4-Amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 31% yield when 4-nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I2) was used as reactant; LC/MS: 415 (MH+); 1H-NMR (CDCl3, 400 MHz): 7.32 (s, 3H), 2.30 (s, 6H) ppm.
5-Amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 30% yield when 5-nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I2) was used as reactant; LC/MS: 415 (MH+); 1H-NMR (MeOD4, 400 MHz): 7.45 (s, 1H), 7.40 (s, 2H), 6.55 (s, 1H), 2.33 (s, 6H) ppm.
4-Amino-5-methyl-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 65% yield when 5-methyl-4-nitro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I2) was used as reactant; 1H-NMR (CDCl3, 400 MHz): 7.34 (s, 2H), 7.23 (m, 2H), 3.45 (s, 2H), 2.32 (s, 6H), 2.29 (s, 3H) ppm.
Example I4
Preparation of 5-bromo-4-amino-thiophene-2-carboxylic Acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide




To a solution of 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (360 mg, 0.87 mmol) (Example I3) in tetrahydrofuran (20 ml) was added N-bromosuccinimide (NBS) (155 mg, 0.87 mmol). The mixture was stirred at room temperature for 1.5 hours. Water (50 ml) was added and the organic phase was extracted twice with ethyl acetate (50 ml). The combined organic extracts were dried over sodium sulfate and the solvent evaporated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 5-bromo-4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (343 mg; 80% yield); 1H-NMR (CDCl3, 400 MHz): 7.26 (s, 2H), 7.10 (s, 1H), 3.8 (s, 2H), 2.24 (s, 6H) ppm.
4-Bromo-5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 64% yield when 5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used as reactant and N-bromosuccinimide (NBS) was used as reagent; 1H-NMR (CDCl3, 400 MHz): 7.24 (s, 2H), 7.15 (s, 1H), 4.3 (s, 2H), 2.20 (s, 6H) ppm.
5-Chloro-4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide was obtained accordingly in 65% yield when 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used as reactant and N-chlorosuccinimide (NCS) was used as reagent; 1H-NMR (CDCl3, 400 MHz): 7.25 (s, 2H), 7.12 (s, 1H), 3.65 (s, 2H), 2.20 (s, 6H) ppm.
Example P1
Preparation of 2-chloro-N-{4-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoro-methyl-ethyl)-phenylcarbamoyl]-thiophen-2-yl}-nicotinamide




To a solution of 5-amino-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (200 mg, 0.45 mmol) (Example I3) in tetrahydrofuran (2 ml) was added pyridine (78 μl). The mixture was cooled to 0° C. and a solution of 2-chloronicotinoyl chloride (0.45 mmol) in dichloromethane was added. The 2-chloronicotinoyl chloride was prepared according to Example I1 using 2-nicotinic acid as starting material and was used directly (i.e. without evaporating the dichloromethane). Upon addition of dimethyl formamide (0.1 ml) the mixture was stirred at room temperature for 40 minutes and then at 45° C. for 1 hour. Then water (50 ml) was added and the organic phase was extracted twice with ethyl acetate (50 ml). The combined organic extracts were dried over sodium sulfate and the solvent evaporated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give Compound No. A1 of Table A (84 mg, 31% yield). M.p. 199-201° C.; LC/MS:554/556 (MH+); 1H-NMR (MeOD, 400 MHz): 8.52 (m, 1H), 8.05 (m, 1H), 7.86 (d, 1H), 7.52 (m, 1H), 7.41 (s, 2H), 7.29 (m, 1H), 2.34 (s, 6H) ppm.
Compound No. A2 of Table A was obtained accordingly in 44% yield using 5-amino-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and isonicotinoyl chloride as reagent; LC/MS: 520/521 (MH+); 1H-NMR (MeOD, 400 MHz): 8.76 (d, 2H), 7.93 (d, 2H), 7.86 (s, 1H), 7.42 (s, 3H), 2.35 (s, 6H) ppm.
Compound No. A3 of Table A was obtained accordingly in 37% yield using 5-amino-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and 4-cyanobenzoyl chloride as reagent; LC/MS: 544/545 (MH+); 1H-NMR (MeOD, 400 MHz): 8.13 (d, 2H), 7.92 (d, 2H), 7.85 (d, 1H), 7.42 (s, 2H), 7.39 (d, 1H), 2.35 (s, 6H) ppm.
Compound No. B1 of Table B was obtained accordingly in 10% yield using 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and 2-chloronicotinoyl chloride as reagent; LC/MS: 554/556 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.53 (d, 1H), 8.06 (d, 1H), 7.78 (d, 1H), 7.53 (m, 1H), 7.41 (s, 2H), 6.88 (d, 1H), 2.36 (s, 6H) ppm.
Compound No. B2 of Table B was obtained accordingly in 15% yield using 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and isonicotinoyl chloride as reagent; LC/MS: 520/521 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.78 (s, 2H), 7.95 (m, 2H), 7.79 (d, 1H), 7.41 (m, 2H), 7.03 (d, 1H), 2.35 (s, 6H) ppm.
Compound No. B3 of Table B was obtained accordingly in 20% yield using 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and 4-cyanobenzoyl chloride as reagent; LC/MS: 544/545 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.14 (d, 2H), 7.92 (d, 2H), 7.79 (d, 1H), 7.41 (s, 2H), 7.01 (d, 1H), 2.35 (s, 6H) ppm.
Compound No C1 of Table C was obtained accordingly in 44% yield using 5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and 2-chloronicotinoyl chloride as reagent; LC/MS: 554/556 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.50 (dd, 1H), 8.12 (s, 1H), 8.03 (dd, 1H), 7.86 (s, 1H), 7.53-7.50 (dd, 1H), 7.42 (s, 2H), 2.35 (s, 6H) ppm.
Compound No. C2 of Table C was obtained accordingly in 37% yield using 5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and isonicotinoyl chloride as reagent; LC/MS: 520/521 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.75 (d, 1H), 8.21 (s, 1H), 7.91 (m, 3H), 7.42 (s, 2H), 2.35 (s, 6H) ppm.
Compound No. C3 of Table C was obtained accordingly in 51% yield using 5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) as reactant and 4-cyanobenzoyl chloride as reagent; LC/MS: 544/545 (MH+); 1H-NMR (MeOD4, 400 MHz): 8.19 (s, 1H), 8.09 (d, 2H), 7.90 (m, 3H), 7.42 (s, 2H), 2.36 (s, 6H) ppm.
Example P2
Preparation of 5-[(thiophene-2-carbonyl)-amino]-thiophene-3-carboxylic Acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide




This method was used to prepare a number of compounds (Compound No. A4 of Table A to Compound No. A46 of Table A) in parallel. The method as detailed below describes the synthesis of Compound No. 13 of Table A; the same conditions were used for the synthesis of the other compounds.
Solution A and solution C were used in all of these reactions, solutions B4-B46 were used only once in the synthesis of the corresponding compound, respectively. Solutions B4-B46 were each prepared from the acid (5 mol) and dimethyl acetamide (30 ml).
Solution A was prepared by dissolving 5-amino-thiophene-3-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (1 mol) (Example I3) in dimethyl acetamide (10 ml). Solution B13 was prepared by dissolving 2-thienylcarboxylic acid (5 mol) in dimethyl acetamide (30 ml). Solution C was prepared by dissolving bis(2-oxo-3-oxazolidinyl)phosphonic chloride (BOP-Cl) (7.5 mol) in dimethyl acetamide (30 ml).
Solution A (0.5 ml) was put in a well and solution B13 (0.3 ml), solution C (0.3 ml) and diisopropylethylamine (Hunig's Base) (50 μl) were added successively. The mixture was stirred at room temperature for 24 hours, then trifluoroacetic acid (100 μl) was added. The mixture was diluted with acetonitrile and purified by HPLC to give Compound No. A13 of Table A (2 mg). LC-MS: 525 (MH+).
Compounds B4-B11 were obtained accordingly when 5-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution A.
Compounds C4-C23 were obtained accordingly when 4-amino-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution A.
Compounds G1-G24 were obtained accordingly when 4-amino-5-methyl-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution A.
Example P3
Preparation of 5-[(furanne-2-carbonyl)-amino]-thiophene-3-carboxylic Acid [2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide




This method was used to prepare a number of compounds (Compound No. A47 of Table A to Compound No. A65 of Table A) in parallel. The method as detailed below describes the synthesis of Compound No. 54 of Table A; the same conditions were used for the synthesis of the other compounds.
Solution D was used in all of these reactions, solutions E47-E65 were used only once in the synthesis of the corresponding compound, respectively. Solutions E47-E65 were each prepared from the acid chloride (1 mol) and toluene (8 ml).
Solution D was prepared by dissolving 5-amino-thiophene-3-carboxylic acid [2,6-diethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (0.187 g, 0.65 mmol) (Example I3) in toluene (7.8 ml). Solution E54 was prepared by dissolving furan-2-carbonyl chloride (99 μl, 1 mmol) in toluene (8 ml).
Solution D (0.3 ml) was put in a well and solution E54 (0.4 ml), diisopropylethyl-amine (Hunig's Base) (25 μl) and dimethylformamide (10 μl) were added successively. The mixture was shaken at 60° C. for 16 hours. The mixture was diluted with acetonitrile and purified by HPLC to give Compound No. A54 of Table A. LC-MS: 537.1 (MH+).
Compounds D1-D17 were obtained accordingly when 5-amino-4-bromo-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution D.
Compounds E1-E18 were obtained accordingly when 4-amino-5-chloro-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution D.
Compounds F1-F19 were obtained accordingly when 4-amino-5-bromo-thiophene-2-carboxylic acid [2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-amide (Example I3) was used in solution D.
The following methods were used for LC-MS analysis:
Method A: Method (Water Alliance 2795 LC) with the following HPLC gradient conditions (Solvent A: 0.1% formic acid in water/acetonitrile (9:1) and Solvent B: 0.1% formic acid in acetonitrile).
















Time


Flow rate



(minutes)
A (%)
B (%)
(ml/min)





















0
90
10
1.7



2.5
0
100
1.7



2.8
0
100
1.7



2.9
90
10
1.7










Type of column: Water atlantis dc18; Column length: 20 mm; Internal diameter of column: 3 mm; Particle Size: 3 micron; Temperature: 40° C.
Method B: Method (Agilent 1100er Series) with the following HPLC gradient conditions (Solvent A: 0.1% formic acid in water/acetonitrile (9:1); Solvent B: 0.1% formic acid in acetonitrile; Solvent C: 0.1% formic acid in water; Solvent D: 0.1% formic acid in water).















Time




Flow rate


(minutes)
A (%)
B (%)
C (%)
D (%)
(ml/min)




















0
90
10
0
0
1.7


2.5
0
100
0
0
1.7


2.8
0
100
0
0
1.7


2.9
90
10
0
0
1.7









Type of column: Water atlantis dc18; Column length: 20 mm; Internal diameter of column: 3 mm; Particle Size: 3 micron; Temperature: 40° C.
The characteristic values obtained for each compound were the retention time (“RT”, recorded in minutes) and the molecular ion, typically the cation MH+ or MH++CH3CN as listed in Tables A, B, C, D, E, F and G. The HPLC-MS method used is indicated in brackets.







TABLE A







Compounds of formula (Ia′):









(Ia′)









 












Com-







pound


RT

MH+ +


No.
Q1
Q2
(min)
MH+
CH3CN















A1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
—




 


A2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
—




 


A3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
—




 


A4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
599.1
640.2


 


A6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
579.1
620.1


 


A7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.85 (A)
588.1
629.2


 


A8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.19 (A)
616.1
657.1


 


A9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.96 (A)
587.1
628.1


 


A10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
570.1
611.1


 


A11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
600.1
641.1


 


A12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.93 (A)
566.1
607.1


 


A13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.93 (A)
525.1
566.1


 


A14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.15 (A)
611.1
652.2


 


A15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
550.1
591.2


 


A16




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.85(A)
537.1
578.1


 


A17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
586.1
627.1


 


A18




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
527.0
568.1


 


A19




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
555.1
596.1


 


A20




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.7 (A)
520.1
561.1


 


A21




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
571.1
612.1


 


A22




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
571.1
612.1


 


A23




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.02 (A)
534.1
575.1


 


A24




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.83 (A)
509.1
550.1


 


A25




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.52 (A)
509.1
550.1


 


A27




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
575.1
616.1


 


A28




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.98 (A)
597.0
638.0


 


A29




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
607.1
648.2


 


A31




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.12 (A)
605.1
646.1


 


A32




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
569.1
610.1


 


A33




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.22 (A)
595.1
636.2


 


A34




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.45 (A)
559.1
600.1


 


A35




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
591.1
632.1


 


A38




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
607.0
648.1


 


A39




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.97 (A)
549.1
590.1


 


A40




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
587.0
628.0


 


A41




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.97 (A)
561.1
602.1


 


A42




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.07 (A)
565.1
606.1


 


A43




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
561.1
602.2


 


A44




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
577.1
618.1


 


A45




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.96 (A)
519.1
560.1


 


A46




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
555.1
596.1


 


A47




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.1 (B)
565.1



 


A48




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
561.1



 


A49




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.13 (B)
581.1



 


A50




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
592.1



 


A51




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.3 (B)
661.1



 


A52




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
590.2



 


A53




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
599.1



 


A54




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.0 (B)
537.1



 


A55




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.3 (B)
631.1



 


A56




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.3 (B)
633.1



 


A57




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.3 (B)
615.1



 


A58




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
631.1



 


A59




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
577.1



 


A60




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.14 (B)
565.1



 


A61




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.2 (B)
615.1



 


A62




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.0 (B)
569.1



 


A63




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.1 (B)
583.1



 


A64




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.1 (B)
605.1



 


A65




4-heptafluoro- isopropyl-2,6- diethyl-phenyl
2.3 (B)
633.1
















TABLE B







Compounds of formula (Ib′):









(Ib′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














B1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.96 (A)
554


 


B2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.90 (A)
520


 


B3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.03 (A)
544


 


B4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
553.1


 


B5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
598


 


B6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
622


 


B7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
566.1


 


B8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
537.1


 


B9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
519.1


 


B10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
534.1


 


B11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
622
















TABLE C







Compounds of formula (Ic′):









(Ic′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














C1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
554


 


C2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.92 (A)
520


 


C3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.05 (A)
544


 


C4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
538.1


 


C5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.06 (A)
553.1


 


C6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.94 (A)
553.1


 


C7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
554


 


C8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.91 (A)
598


 


C9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
587


 


C10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.95 (A)
597


 


C11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
622


 


C12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
566.1


 


C13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
605.1


 


C14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
587


 


C15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.88 (A)
554


 


C16




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.97 (A)
564.1


 


C17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.95 (A)
537.1


 


C18




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.91 (A)
519.1


 


C19




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.97 (A)
555.1


 


C20




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1(A)
559


 


C21




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.81 (A)
537.1


 


C22




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
534.1


 


C23




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.96 (A)
533.1
















TABLE D







Compounds of formula (Ib′′):









(Ib′′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














D1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
615


 


D2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
631


 


D3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
622


 


D4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
642


 


D5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
711


 


D6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.4 (A)
649


 


D7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
587


 


D8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
681


 


D9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
683


 


D10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
665


 


D11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
681


 


D12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
627


 


D13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2(A)
615


 


D14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
665


 


D15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.27 (A)
633


 


D16




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
655


 


D17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.4 (A)
683
















TABLE E







Compounds of formula (Ic′′):









(Ic′′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














E1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.24 (A)
571


 


E2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.17 (A)
567.1


 


E3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.16 (A)
587


 


E4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
578


 


E5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.11 (A)
598


 


E6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.32 (A)
667


 


E7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.02 (A)
543


 


E8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.29 (A)
637


 


E9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.27 (A)
639


 


E10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.25 (A)
621


 


E11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.34 (A)
583.1


 


E12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
553.1


 


E13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.13 (A)
571


 


E14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
621


 


E15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2 (A)
575


 


E16




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.21 (A)
589


 


E17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
611.1


 


E18




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.33 (A)
639
















TABLE F







Compounds of formula (Ic′′′):









(Ic′′′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














F1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
615


 


F2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
611


 


F3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
631


 


F4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
622


 


F5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
642


 


F6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
711


 


F7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
587


 


F8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
681


 


F9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
683


 


F10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
665


 


F11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.4 (A)
627


 


F12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
615


 


F13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
597


 


F14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
665


 


F15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
598


 


F16




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
619


 


F17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.3 (A)
633


 


F18




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
655


 


F19




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.4 (A)
683
















TABLE G







Compounds of formula (Ic′′′′):









(Ic′′′′)









 











Com-






pound


RT



No.
Q1
Q2
(min)
MH+














G1




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.7 (A)
568.1


 


G2




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
552.1


 


G3




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
558.1


 


G4




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
567.1


 


G5




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
567.1


 


G6




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
568.1


 


G7




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
612


 


G8




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
601


 


G9




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
611


 


G10




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
636


 


G11




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9(A)
580.1


 


G12




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.2 (A)
619.1


 


G13




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
601


 


G14




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
568.1


 


G15




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
578.1


 


G17




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
551.1


 


G18




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
533.1


 


G19




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
569.1


 


G20




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
573


 


G21




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.8 (A)
551.1


 


G22




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
1.9 (A)
541.1


 


G23




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.1 (A)
548.1


 


G24




4-heptafluoro- isopropyl-2,6- dimethyl-phenyl
2.0 (A)
547.1









Biological Examples
These Examples illustrate the pesticidal/insecticidal properties of compounds of formula (I). The tests were performed as follows:
Spodoptera littoralis (Egyptian Cotton Leafworm):
Cotton leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200 ppm. After drying, the leaf discs were infested with 5 L1 larvae. The samples were checked for mortality, feeding behaviour, and growth regulation 3 days after treatment (DAT).
The following compounds gave at least 80% control of Spodoptera littoralis: A1, A2, A3, A23, A28, A31, A40, A45, A46, A63, C1, C4, C5, C6, C9, C10, C13, C14, C16, C17, C18, C19, C22, C23, D4, D7, E1, E2, E3, E4, E5, E7, E10, E12, E13, E14, E15, E16, F1, F2, F3, F4, F5, F7, F10, F12, F13, F14, F16, F17, G1, G2, G3, G4, G5, G6, G7, G8, G9, G10, G11, G13, G14, G15, G18, G19, G20, G21, G22, G24.
Heliothis virescens (Tobacco Budworm):
Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation.
The following compounds gave at least 80% control of Heliothis virescens: A1, A3, A13, A15, A20, A22, A23, A28, A31, A35, A38, A39, A40, A41, A42, A45, A46, A63, B4, B5, C1, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C23, D4, D7, D12, D14, E1, E2, E3, E4, E5, E7, E10, E12, E13, E14, E15, E16, E18, F1, F2, F3, F4, F5, F7, F10, F12, F13, F14, F15, F16, F17, F19, G1, G2, G3, G4, G5, G6, G7, G8, G9, G10, G13, G14, G15, G17, G18, G19, G20, G21, G22, G23, G24.
Plutella xylostella (Diamond Back Moth):
A 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying, the MTP's were infested with L2 larvae (7-12 per well). After an incubation period of 6 days, samples were checked for larval mortality and growth regulation.
The following compounds gave at least 80% control of Plutella xylostella: A1, A3, A16, A20, A23, A28, A31, A35, A39, A40, A41, A45, A46, A63, B3, B5, B10, C1, C4, C5, C6, C7, C8, C9, C10, C13, C14, C17, C18, C19, C23, D4, D7, D12, D14, E1, E2, E3, E4, E5, E12, E13, E14, E15, E16, F1, F2, F3, F4, F5, F12, F13, F16, F17, G1, G2, G3, G4, G5, G6, G7, G8, G9, G10, G13, G14, G15, G17, G18, G19, G20, G21.
Diabrotica balteata (Corn Root Worm):
A 24-well microtiter plate (MTP) with artificial diet was treated with test solutions at an application rate of 200 ppm (concentration in well 18 ppm) by pipetting. After drying, the MTP's were infested with larvae (L2) (6-10 per well). After an incubation period of 5 days, samples were checked for larval mortality, and growth regulation.
The following compounds gave at least 80% control of Diabrotica balteata: A1, A3, A10, A31, A45, A46, A47, A49, A50, A53, A56, A57, A62, A63, A65, C1, C3, C4, C5, C6, C7, C8, C9, C10, C15, C16, C17, C18, C19, C20, E1, E2, E3, E4, E5, E10, E12, E13, E16, F2, F3, F4, F5, F10, F14, G1, G2, G3, G4, G5, G6, G7, G9, G10, G11, G14, G15, G17, G18.
Aedes aegypti (Yellow Fever Mosquito):
10-15 Aedes larvae (L2) together with a nutrition mixture are placed in 96-well microtiter plates. Test solutions at an application rate of 2 ppm were pipetted into the wells. 2 days later, insects were checked for mortality and growth inhibition.
The following compounds gave at least 80% control of Aedes aegypti: A1, A2, A3, A4, A10, A11, A13, A16, A17, A20, A22, A23, A24, A28, A31, A35, A40, A41, A42, A45, A46, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C13, C14, C15, C16, C17, C18, C19 and C20.

## Claims

1. A compound of formula (I)



wherein
A1, A2 and A3 are independently of one another C—X, N—X, nitrogen, oxygen or sulfur, provided that two of A1, A2 or A3 are C—X or nitrogen and that one of A1, A2 or A3 is oxygen, sulfur or N—X;
each X is independently hydrogen, halogen, C1-C4alkyl or trifluoromethyl;
R1 and R2 are independently of one another hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;
G1 and G2 are independently of one another oxygen or sulfur;
Q1 is aryl or aryl substituted by one to five substituents R3, which may be the same or different, or Q1 is heteroaryl or heteroaryl substituted by one to five substituents R3, which may be the same or different; wherein
each R3 is independently cyano, nitro, hydroxy, halogen, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3-C6cycloalkyl, C3-C6halocycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C4alkylcarbonyl, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonylamino or phenyl; and

Q2 is a moiety of formula (II) or (III)





wherein
Y1 and Y5 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;
Y3 is C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl;
Y2 and Y4 are independently of each other hydrogen, halogen or C1-C4alkyl;
Y6 and Y9 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;
Y8 is C1-C4haloalkoxy, C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl; and
Y7 is hydrogen, halogen or C1-C4alkyl;

or salts or N-oxides thereof.

2. A compound according to claim 1 wherein two of A1, A2 and A3 are C—X and one is sulfur.

3. A compound according to claim 1 wherein each X is independently hydrogen, fluoro, chloro, bromo, methyl or trifluoromethyl.

4. A compound according to claim 1 wherein each X is hydrogen.

5. A compound according to claim 1 in which R1 is hydrogen, methyl, ethyl or acetyl.

6. A compound according to claim 1 in which R2 is hydrogen, methyl, ethyl or acetyl.

7. A compound according to claim 1 in which G1 is oxygen.

8. A compound according to claim 1 in which G2 is oxygen.

9. A compound according to claim 1 in which Q1 is phenyl, pyridyl, furanyl, thiophenyl or pyrazolyl, or phenyl, pyridyl, furanyl, thiophenyl or pyrazolyl substituted by one to three substituents independently selected from cyano, hydroxy, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro or phenyl.

10. A compound according to claim 1 in which Q2 is a moiety of formula (II).

11. A compound according to claim 1 in which Q2 is 4-heptafluoroisopropyl-2,6-dimethyl-phenyl.

12. A compound according to claim 1 in which Q2 is 4-heptafluoroisopropyl-2,6-diethyl-phenyl.

13. A compound of formula (Ia)



wherein R1, R2, G1, G2, Q1 and Q2 are as defined in claim 1, and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof.

14. A compound of formula (Ib)



wherein R1, R2, G1, G2, Q1 and Q2 are as defined in claim 1, and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof.

15. A compound of formula (Ic)



wherein R1, R2, G1, G2, Q1 and Q2 are as defined in claim 1, and X1 and X2 are independently defined as X in relation to formula (I); or salts or N-oxides thereof.

16. A compound of formula (IX′)



wherein A1, A2, A3, R2, G2 and Q2 are as defined in claim 1; or salts or N-oxides thereof.

17. A compound of formula (XIII)



wherein A1, A2, A3, R2, G2 and Q2 are as defined in claim 1; or salts or N-oxides thereof.

18. A compound of formula (Ix)



wherein
A1, A2 and A3 are independently of one another carbon, nitrogen, nitrogen oxide, oxygen or sulfur with the proviso that at least one of A1, A2 or A3 is not carbon and no more than one of A1, A2 or A3 is oxygen or sulfur;
R1 and R2 are independently of one another hydrogen, C1-C4alkyl or C1-C4alkylcarbonyl;
G1 and G2 are independently of one another oxygen or sulfur;
X are independently of one another halogen, C1-C3alkyl or trifluoromethyl;
n is 0, 1, 2 or 3;
Q1 is aryl or aryl substituted by one to five substituents independently selected from R3, or heterocyclyl or heterocyclyl substituted by one to five substituents independently selected from R3; wherein
R3 are independently of one another cyano, nitro, hydroxy, halogen, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C1-C6cycloalkyl, C3-C6halocycloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl, C1-C3haloalkylsulfonyl, C1-C4alkylamino, di-(C1-C4alkyl)amino, C1-C4alkylcarbonyl, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonylamino or phenyl; and

Q2 is a moiety of formula (II) or (III)





wherein
Y1 and Y5 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;
Y3 is C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl;
Y2 and Y4 are independently of each other hydrogen, halogen or C1-C4alkyl;
Y6 and Y9 are independently of each other cyano, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C3alkylthio, C1-C3haloalkylthio, C1-C3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl or C1-C3haloalkylsulfonyl;
Y8 is C1-C4haloalkoxy, C2-C6perfluoroalkyl, C1-C6perfluoroalkylthio, C1-C6perfluoroalkylsulfinyl or C1-C6perfluoroalkylsulfonyl; and
Y7 is hydrogen, halogen or C1-C4alkyl;

or salts or N-oxides thereof.

19. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1.

20. An insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) as defined in claim 1.

21. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 18.

22. An insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) as defined in claim 18.