PESTICIDALLY ACTIVE HETEROCYCLIC DERIVATIVES WITH SULFUR CONTAINING SUBSTITUENTS
20220132852 · 2022-05-05
Assignee
Inventors
- Amandine KOLLETH KRIEGER (Stein, CH)
- Michel Muehlebach (Stein, CH)
- André STOLLER (Stein, CH)
- Daniel EMERY (Stein, CH)
- Sebastian RENDLER (Basel, CH)
- Anke BUCHHOLZ (Stein, CH)
- Vikas SIKERVAR (Goa, IN)
- Indira SEN (Goa, IN)
Cpc classification
A01N25/00
HUMAN NECESSITIES
C07D213/89
CHEMISTRY; METALLURGY
International classification
A01N43/90
HUMAN NECESSITIES
Abstract
Compounds of the formula (I) wherein the substituents are as defined in claim 1. Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, nematodes, molluscs or representatives of the order Acarina.
##STR00001##
Claims
1. A compound of formula (I) ##STR00203## wherein G.sub.1 and G.sub.2 are, independently from each other, CH or N; R.sub.2 is C.sub.1-C.sub.6haloalkyl; Q is a radical selected from the group consisting of formula Qa and Qb ##STR00204## wherein the arrow denotes the point of attachment to the carbon atom of the bicyclic ring; and wherein A represents CH or N; X is S, SO or SO.sub.2; R.sub.1 is C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.4alkyl; Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6cyanoalkoxy, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl and C.sub.1-C.sub.4alkylsulfonyl; and said ring system can contain 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where said ring system may not contain more than one ring oxygen atom and not more than one ring sulfur atom; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylsulfanyl, C.sub.1-C.sub.4alkylsulfinyl and C.sub.1-C.sub.4alkylsulfonyl; and said ring system contains 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where said ring system contains at least one ring nitrogen atom and may not contain more than one ring oxygen atom and not more than one ring sulfur atom; R.sub.3 is hydrogen, halogen or C.sub.1-C.sub.4alkyl; each R.sub.4 is independently hydrogen, C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl or C.sub.3-C.sub.6cycloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.
2. A compound of formula I according to claim 1, represented by the compounds of formula (I-1) ##STR00205## wherein A, X, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; R.sub.3 is hydrogen or C.sub.1-C.sub.4alkyl; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-1.
3. A compound of formula I according to claim 1, represented by the compounds of formula (I-5) ##STR00206## wherein A, X, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; R.sub.3 is hydrogen or C.sub.1-C.sub.4alkyl; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-5.
4. A compound of formula I according to claim 1, represented by the compounds of formula (I-2) ##STR00207## wherein X, R.sub.1 and R.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the pyridyl substituted by X—R.sub.1, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the pyridyl ring substituted by X—R.sub.1, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-2.
5. A compound of formula I according to claim 1, represented by the compounds of formula (I-6) ##STR00208## wherein X, R.sub.1 and R.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-6.
6. A compound of formula I according to claim 1, represented by the compounds of formula (I-9) ##STR00209## wherein X, R.sub.1 and R.sub.2 are as defined as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-9.
7. A compound of formula I according to claim 1, represented by the compounds of formula (I-12) ##STR00210## wherein X, R.sub.1 and R.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano or C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-12.
8. A compound of formula I according to claim 1, represented by the compounds of formula (I-15) ##STR00211## wherein X, R.sub.1 and R.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-15.
9. A compound of formula I according to claim 1, represented by the compounds of formula (I-18) ##STR00212## wherein X, R.sub.1 and R.sub.2 are as defined under formula I in claim 1, and wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, C.sub.1-C.sub.6haloalkoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, or —N(R.sub.4)CON(R.sub.4).sub.2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; or Q.sub.1 is a five- to six-membered aromatic ring system linked via a ring carbon atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system can contain 1 or 2 ring nitrogen atoms; or Q.sub.1 is a five-membered aromatic ring system linked via a ring nitrogen atom to the ring which contains the substituent A, said ring system is unsubstituted or is mono-substituted by a substituent selected from the group consisting of halogen, cyano and C.sub.1-C.sub.4haloalkyl; and said ring system contains 2 or 3 ring nitrogen atoms; each R.sub.4 is independently hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; preferably R.sub.5 is methyl or cyclopropyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-18.
10. A compound according to claim 1, wherein X is S or SO.sub.2; preferably X is SO.sub.2; and. R.sub.1 is C.sub.1-C.sub.4alkyl or cyclopropyl-C.sub.1-C.sub.4alkyl; preferably R.sub.1 is ethyl or cyclopropylmethyl.
11. A compound according to claim 1, wherein Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkyl, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5 or —N(R.sub.4)CON(R.sub.4).sub.2, in each of which R.sub.4 is independently either hydrogen or C.sub.1-C.sub.4alkyl (preferably hydrogen or methyl) and R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl (preferably methyl or cyclopropyl); or Q.sub.1 is (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which is mono-substituted by chloro or trifluoromethyl; or Q.sub.1 is C-linked pyrimidinyl or N-linked triazolyl; preferably Q.sub.1 is hydrogen, chlorine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, —NH(CH.sub.3), —N(CH.sub.3)COCH.sub.3, —N(CH.sub.3)CO(cyclopropyl), —N(CH.sub.3)CONH(CH.sub.3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, pyrimidin-2-yl or 1,2,4-triazol-1-yl.
12. A compound according to claim 1, wherein R.sub.2 is C.sub.1-C.sub.6fluoroalkyl; preferably R.sub.2 is —CH.sub.2CF.sub.2CHF.sub.2 or —CH.sub.2CF.sub.2CF.sub.3.
13. A compound according to claim 1, wherein Q.sub.1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, —NH(CH.sub.3), —N(CH.sub.3)COCH.sub.3, —N(CH.sub.3)CO(cyclopropyl), —N(H)CONH(CH.sub.3), —N(CH.sub.3)CONH(CH.sub.3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-cyano-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.
14. A compound of formula I as claimed in claim 1, selected from the group consisting of: 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridin-5-yl]pyridin-3-amine (compound P1); N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-acetamide (compound P2); 5-(3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (compound P3); 5-(3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (compound P4); 2-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P5); 2-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P6); 5-(3-ethylsulfinyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P7); 5-(3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P8); 6-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P9); 1-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10); 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P11); N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-2-pyridyl]-N-methyl-acetamide (compound P12); 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-2-pyridyl]-1,3-dimethyl-urea (compound P13); 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-2-amine (compound P14); N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-2-pyridyl]-N-methyl-cyclopropanecarboxamide (compound P15); N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-N-methyl-acetamide (compound P16); 5-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P17); 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-3-amine (compound P18); 2-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P19); 5-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P20); 5-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P21); 5-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P22); 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P23); 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-2-amine (compound P24); 5-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P25); 5-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P26); 3-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-2-pyridyl]oxazolidin-2-one (compound P27); 5-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P28); 2-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P29); 5-[3-ethylsulfanyl-5-(trifluoromethyl)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P30); 5-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P31); 6-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P32); 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-2-pyridyl]-1,3-dimethyl-urea (compound P33); 1-[5-ethylsulfonyl-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P34); 5-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P35); 5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P36); 1-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P37); 1-[5-ethylsulfanyl-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P38); 5-[5-(3-chloropyrazol-1-yl)-3-ethylsulfanyl-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P39); 2-[5-ethylsulfonyl-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P40); 6-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P41); 6-(3-ethylsulfonyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P42); 6-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P43); 6-(3-ethylsulfanyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P44); 5-[3-ethylsulfonyl-5-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P45); 5-[5-(3-chloropyrazol-1-yl)-3-ethylsulfonyl-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P46); 2-[5-ethylsulfanyl-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P47); 5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P48); 5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P49); 5-[3-ethylsulfanyl-5-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P50); 5-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P51); 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P52); 5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P53); and 5-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound P54).
15. A compound of formula I as claimed in claim 1, selected from the group consisting of: 5-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound PN1); 5-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound PN2); 6-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound PN3); 6-(5-cyclopropyl-3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound PN4); 5-(5-cyclopropyl-3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound PN5); 2-[5-ethylsulfanyl-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (compound PN6); 2-[5-ethylsulfanyl-1-oxido-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (compound PN7); 1-[5-ethylsulfanyl-1-oxido-6-[3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridin-6-yl]pyridin-1-ium-3-yl]cyclopropanecarbonitrile (compound PN8); 1-[5-ethylsulfanyl-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]cyclopropanecarbonitrile (compound PN9); 5-[3-ethylsulfanyl-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (compound PN10); and 5-[3-ethylsulfanyl-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound PN11).
16. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in claim 1.
17. 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), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in claim 1.
18. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 16.
19. A compound of formula IXa-1-SP ##STR00213## wherein Q.sub.1SP is 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl or 2-pyridyloxy.
20. A compound of formula VIIa-1-SP′ ##STR00214## wherein Q.sub.1SP′ is cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl or 2-pyridyloxy.
21. A compound of formula VI ##STR00215## wherein G.sub.1, G.sub.2 and R.sub.2 are as defined under formula I above; and X.sub.10 is a halogen or a pseudo-halogen leaving group.
22. A compound of formula II-Qa ##STR00216## wherein X is S; and G.sub.1, G.sub.2, R.sub.2, Q.sub.1, R.sub.3 and R.sub.1 are as defined under formula I in claim 1.
23. A compound of formula III-Qa ##STR00217## wherein G.sub.1, G.sub.2, R.sub.2, Q.sub.1 and R.sub.3 are as defined under formula I in claim 1.
24. A compound of formula IV-Qa ##STR00218## wherein G.sub.1, G.sub.2, R.sub.2, Q.sub.1 and R.sub.3 are as defined under formula I in claim 1.
25. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, as defined in an auxiliary or diluent.
26. 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), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, with a composition as defined claim 16.
Description
PREPARATORY EXAMPLES
[0860] “Mp” means melting point in ° C. Free radicals represent methyl groups. .sup.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated. Either one of the LCMS methods below was used to characterize the compounds. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H).sup.+ or (M−H).sup.−.
LCMS Methods:
Method 1:
[0861] Spectra were recorded on a Mass Spectrometer from Waters (ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.
Method 2:
[0862] Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C., Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5% MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH; gradient: 0 min 0% B, 100% A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.
Method 3:
[0863] Spectra were recorded on a Mass Spectrometer from Agilent Technologies (6410 Triple Quadrupole mass spectrometer) equipped with an equipped with an electrospray source (Polarity: positive or negative ions, MS2 Scan, Capillary: 4.00 kV, Fragmentor: 100 V, Desolvatation Temperature: 350° C., Gas Flow: 11 L/min, Nebulizer Gas: 45 psi, Mass range: 110 to 1000 Da) and a 1200 Series HPLC from Agilent: quaternary pump, heated column compartment and diode-array detector. Column: KINETEX EVO C18, 2.6 μm, 50×4.6 mm, Temp: 40° C., DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A=water+5% Acetonitrile+0.1% HCOOH, B=Acetonitrile+0.1% HCOOH: gradient: 0 min 0% B, 100% A; 0.9-1.8 min 100% B; Flow (mL/min) 1.8.
Method 4:
[0864] Spectra were recorded on a Mass Spectrometer from Waters (SQD Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Full Scan, Capillary: 3.00 kV, Cone range: 41 V, Source Temperature: 150° C., Desolvation Temperature: 500° C., Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 1000 L/Hr, Mass range: 110 to 800 Da) and a H-Class UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3 C18, 1.8 μm, 30×2.1 mm, Temp: 40° C., DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A=water+5% Acetonitrile+0.1% HCOOH, B=Acetonitrile+0.1% HCOOH: gradient: 0 min 10% B; 0-0.2 min 10-50% B; 0.2-0.7 min 50-100% B; Flow (mL/min) 0.8.
Method 5:
[0865] Spectra were recorded on a Mass Spectrometer from Waters (SQD Two mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 41 V, Source Temperature: 150° C., Desolvation Temperature: 500° C., Cone Gas Flow: 50 L/Hr, Desolvation Gas Flow: 1000 L/Hr, Mass range: 110 to 800 Da) and an H-class UPLC from Waters: Quaternary pump, heated column compartment and diode-array detector. Column: Acquity UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 40° C., DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A=water+0.1% HCOOH:Acetonitrile:95:5 v/v, B=Acetonitrile+0.05% HCOOH: gradient: 0-1.0 min 10% B, 90% A; 1.0-5.3 min 10-100% B; 5.3-6.0 min 100-10% B; Flow (ml/min) 0.6.
Example H1: Preparation of N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-acetamide (Compound P2)
[0866] ##STR00057##
Step 1: Preparation of tert-butyl N-(5-fluoro-3-pyridyl)-N-methyl-carbamate (Intermediate I5)
[0867] ##STR00058##
[0868] Methyl iodide (0.877 mL, 14.2 mmol, 2.0 eq.) was added dropwise at room temperature to a solution of tert-butyl N-[5-(trifluoromethyl)-3-pyridyl]carbamate (CAS 342603-20-7) (1.50 g, 7.10 mmol) and cesium carbonate (4.70 g, 14.2 mmol, 2.0 eq.) in N,N-dimethylformamide (30 mL) in a sealed tube under argon. The yellow cloudy suspension was heated at 80° C. and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured over water and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered and concentrated. The crude material was purified by flash chromatography over silica gel (ethyl acetate in cyclohexane) to give the desired product as a brown oil (537 mg). LCMS (method 1): 227 (M+H).sup.+, Rt 0.90 min.
Step 2: Preparation of tert-butyl N-(5-fluoro-1-oxido-pyridin-1-ium-3-yl)-N-methyl-carbamate (Intermediate I6)
[0869] ##STR00059##
[0870] A solution of 3-chloroperbenzoic acid (1.12 g, 4.86 mmol, 2.05 eq.) in dichloromethane (2.0 mL) was added to a solution of tert-butyl N-(5-fluoro-3-pyridyl)-N-methyl-carbamate (intermediate 15 prepared as described above) (537 mg, 2.37 mmol) in dichloromethane (7.0 mL) at 0° C. After stirring for 2 hours at room temperature, the reaction mixture was diluted with tert-butyl methyl ether (25 mL) and washed with a 10% sodium hydrogenosulfite aqueous solution to remove any remaining peroxide (controlled by a starch test). The organic layer was further washed with a saturated sodium hydrogenocarbonate aqueous solution, water and brine, dried over sodium sulfate, filtered and concentrated. Purification of the crude product by flash chromatography over silica gel (methanol in dichloromethane) afforded the desired compound. LCMS (method 1): 243 (M+H).sup.+, Rt 0.71 min.
Step 3: Preparation of tert-butyl N-[5-fluoro-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-1-ium-3-yl]-N-methyl-carbamate (Intermediate I7)
[0871] ##STR00060##
[0872] Obtained according to the procedure described in step 2 of example H2 by reaction of intermediate 11 (prepared as described in step 1 of example H2 below) and intermediate 16 (prepared as described above). LCMS (method 1): 492 (M+H).sup.+, Rt 0.98 min.
Step 4: Preparation of tert-butyl N-[5-ethylsulfanyl-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridin-5-yl]pyridin-1-ium-3-yl]-N-methyl-carbamate (Intermediate I8)
[0873] ##STR00061##
[0874] Obtained according to the procedure described in step 3 of example H2 by reaction of intermediate 17 (prepared as described above). LCMS (method 1): 534 (M+H).sup.+, Rt 1.01 min.
Step 5: Preparation of tert-butyl N-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-carbamate (Intermediate I9)
[0875] ##STR00062##
[0876] Obtained according to the procedure described in step 4 of example H2 by reaction of intermediate 18 (prepared as described above). LCMS (method 1): 518 (M+H).sup.+, Rt 1.16 min.
Step 6: Preparation of tert-butyl N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-carbamate (Intermediate I10)
[0877] ##STR00063##
[0878] Obtained according to the procedure described in example H3 by reaction of intermediate 19 (prepared as described above). LCMS (method 1): 550 (M+H).sup.+, Rt 1.09 min.
Step 7: Preparation of 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-3-amine (Compound P1)
[0879] ##STR00064##
[0880] 2,2,2-trifluoroacetic acid (1.0 mL) was added dropwise to a solution of tert-butyl N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-carbamate (intermediate 110 prepared as described above) (108 mg, 0.200 mmol) in dichloromethane (2.00 mL) at 0° C. After stirring overnight at room temperature, the reaction mixture was concentrated. The crude material was dissolved in ethyl acetate, and the organic phase was washed three times with water, dried over magnesium sulfate, filtered and concentrated. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired compound.
[0881] LCMS (method 1): 450 (M+H).sup.+, Rt 0.89 min.
Step 8: Preparation of N-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]-N-methyl-acetamide (Compound P2)
[0882] ##STR00065##
[0883] Acetyl chloride (0.160 mmol, 1.0 eq.) was added to a 0° C. cooled solution of 5-ethylsulfonyl-N-methyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-3-amine (compound P1 prepared as described above) (72 mg, 0.160 mmol) in dichloromethane (2.0 mL) with triethylamine (0.176 mmol, 1.10 eq.). After stirring for 30 min, the reaction mixture was concentrated. The crude material was dissolved in ethyl acetate, and the organic phase was washed three times with water, dried over magnesium sulfate, filtered and concentrated. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired compound (73 mg) as a solid, mp 189-190° C. LCMS (method 1): 492 (M+H).sup.+, Rt 0.88 min.
Example H2: Preparation of 5-(3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (Compound P3)
[0884] ##STR00066##
Step 1: Preparation of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (Intermediate I1)
[0885] ##STR00067##
[0886] Potassium carbonate (237 mg, 1.72 mmol, 2.0 eq.) and 2,2,3,3,3-pentafluoropropyl trifluoromethane-sulfonate (CAS 6401-00-9) (315 mg, 1.12 mmol, 1.30 eq.) were added to a solution of 5-bromo-1H-pyrazolo[3,4-c]pyridine (CAS 929617-35-6) (170 mg, 0.86 mmol) in N,N-dimethylformamide (4.30 mL). After stirring for 2 hours at room temperature, the reaction mixture was poured over water. The aqueous phase was thoroughly extracted with ethyl acetate, the combined organic phases were dried over sodium sulfate, filtered and concentrated. Purification of the crude material by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as a white solid (150 mg). LCMS (method 1): 330/332 (M+H).sup.+, Rt 0.97 min.
[0887] Similarly, 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (intermediate 13) can be prepared from 5-bromo-1H-pyrrolo[2,3-c]pyridine (CAS 1215387-58-8) and 2,2,3,3,3-pentafluoropropyl trifluoromethane-sulfonate (CAS 6401-00-9). LCMS (method 1): 329/331 (M+H).sup.+, Rt 1.02 min.
[0888] Similarly, 6-bromo-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (intermediate 14) can be prepared from 6-bromo-3H-imidazo[4,5-c]pyridine (CAS 1312440-90-6) and 2,2,3,3,3-pentafluoro-propyl trifluoromethane-sulfonate (CAS 6401-00-9). LCMS (method 1): 330/332 (M+H).sup.+, Rt 0.87 min.
Step 2: Preparation of 5-(3-fluoro-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (Intermediate I2)
[0889] ##STR00068##
[0890] A 1.0 M solution of tetramethylpiperidinyl zinc chloride lithium chloride complex in tetrahydrofuran (3.65 mL, 3.65 mmol, 1.50 eq.) was added dropwise at room temperature to a solution of 3-fluoropyridine N-oxide (CAS 695-37-4) (0.275 g, 2.43 mmol, 1.0 eq.) and 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (intermediate 11 prepared as described above) (0.802 g, 2.43 mmol, 1.0 eq.) in tetrahydrofuran (2.75 mL) under argon. After complete addition, the mixture was degassed for 5 min before adding [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium (complex with dichloromethane) and heating at 60° C. for 4 hours. After cooling to room temperature, the reaction mixture was poured over a saturated aqueous sodium hydrogenocarbonate solution, and the aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed with a saturated sodium hydrogenocarbonate solution, dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography over silica gel (methanol in dichloromethane) to afford the desired product as a brown solid. LCMS (method 1): 363 (M+H).sup.+, Rt 0.76 min.
[0891] Similarly, 6-(3-fluoro-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (intermediate 128) can be prepared from 6-bromo-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (intermediate 14 prepared as described above). LCMS (method 1): 363 (M+H).sup.+, Rt 0.69 min.
Step 3: Preparation of 5-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (Pyridine N-Oxide PN1)
[0892] ##STR00069##
[0893] Sodium ethanethiolate (217 mg, 2.58 mmol, 3.0 eq.) was added in one portion to a solution of 5-(3-fluoro-1-methyl-1-oxido-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (intermediate 12 prepared as described above) (325 mg, 0.86 mmol) in N,N-dimethylformamide (1.0 mL) cooled at 0° C. After stirring for 2 hours at room temperature, the reaction mixture was poured over water, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with water, brine, dried over sodium sulfate, filtered and concentrated. The crude material was used directly without any purification. LCMS (method 1): 405 (M+H).sup.+, Rt 0.83 min.
[0894] Similarly, 6-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (pyridine N-oxide PN3) can be prepared from 6-(3-fluoro-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (intermediate 128 prepared as described above). LCMS (method 1): 405 (M+H).sup.+, Rt 0.77 min.
Step 4: Preparation of 5-(3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (Compound P3)
[0895] ##STR00070##
[0896] Zinc (91 mg, 1.39 mmol, 1.5 eq.) was added at 10° C. to a suspension of 5-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (pyridine N-oxide PN1 prepared as described above) (374 mg, 0.93 mmol) in tetrahydrofuran (10 mL) and a saturated ammonium chloride aqueous solution (5 mL). After stirring for 2 hours at room temperature, the reaction mixture was diluted with ethyl acetate and filtered over Celite. The organic phase was washed with water, brined, dried over sodium sulfate, filtered and concentrated. The crude yellow oil was purified by flash chromatography over silica gel (methanol in dichloromethane) to afford the desired product as a yellow solid (225 mg). LCMS (method 1): 389 (M+H).sup.+, Rt 0.98 min.
Example H3: Preparation of 5-(3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (Compound P4)
[0897] ##STR00071##
[0898] A solution of 3-chloroperbenzoic acid (182 mg, 0.79 mmol, 2.05 eq.) in dichloromethane (2.0 mL) was added to a solution of 5-(3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (compound P3 prepared as described above) (150 mg, 0.39 mmol) in dichloromethane (3.0 mL) at 0° C. After stirring for 30 min at room temperature, the reaction mixture was diluted with tert-butyl methyl ether (25 mL) and washed with a 10% sodium hydrogenosulfite aqueous solution to remove any remaining peroxide (controlled by a starch test). The organic layer was further washed with a saturated sodium hydrogenocarbonate aqueous solution, water and brine, dried over sodium sulfate, filtered and concentrated. Purification of the crude product by flash chromatography over silica gel (methanol in dichloromethane) afforded the desired compound (91 mg).
[0899] LCMS (method 1): 421 (M+H).sup.+, Rt 0.91 min.
Example H4: Preparation of 2-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (Compound P19)
[0900] ##STR00072##
Step 1: Preparation of 2-(5-fluoro-3-pyridyl)-2-methyl-propanenitrile (Intermediate I34)
[0901] ##STR00073##
[0902] To a solution of 2-(5-fluoro-3-pyridyl)acetonitrile (CAS 39891-06-0) (2.77 g, 20.3 mmol) in tetrahydrofuran (102 mL) was added sodium hydride (2.44 g, 61.0 mmol) portionwise at 0° C. The reaction mixture was stirred at 0-5° C. for 30 minutes, then iodomethane (3.88 mL, 61.0 mmol) was added dropwise and the mixture was stirred at room temperature for 2 hour. After completion, the reaction mixture was extracted with ethyl acetate and brine, the combined organic layers were dried over magnesium sulfate, filtered and evaporated. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as yellow solid (2.80 g). LCMS (method 1): 165 (M+H).sup.+, Rt 0.72 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.80 (s, 6H) 7.54 (m, 1H) 8.49 (s, 1H) 8.61 (s, 1H).
Step 2: Preparation of 2-(5-fluoro-1-oxido-pyridin-1-ium-3-yl)-2-methyl-propanenitrile (Intermediate I25)
[0903] ##STR00074##
[0904] To a solution of 2-(5-fluoro-3-pyridyl)-2-methyl-propanenitrile (intermediate 134 prepared as described above) (2.75 g, 16.7 mmol) in acetonitrile (83.7 mL) was added hydrogen peroxide urea complex (4.06 g, 41.9 mmol) at 0° C., followed by dropwise addition of trifluoroacetic anhydride (5.88 mL, 41.9 mmol). The reaction mixture was stirred at 0° C. for 15 minutes and then at room temperature for 1.5 hours. After completion, it was dissolved with ethyl acetate and washed with an aqueous sodium bisulfite solution (˜20%). The aqueous layer was basified at 0-5° C. with sodium hydroxide (4 M) and extracted again with ethyl acetate. The combined organic layers were washed with sat. aq. sodium bicarbonate, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was suspended in diisopropyl ether (˜5-7 mL) and stirred for 30 minutes. The white suspension was filtered and the solid was washed with fresh diisopropyl ether (2×2 mL) and pentane (2×5 mL). The residue was dried under vacuum to afford the desired product as white solid (2.73 g). LCMS (method 1): 181 (M+H).sup.+, Rt 0.34 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.78 (s, 6H) 7.21 (m, 1H) 8.12 (m, 1H) 8.21 (s, 1H).
Step 3: Preparation of 2-[5-fluoro-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (Intermediate I18)
[0905] ##STR00075##
[0906] To a solution of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (intermediate 13 prepared as described above) (350 mg, 1.10 mmol) in tetrahydrofuran (3.50 mL) was added 2-(5-fluoro-1-oxido-pyridin-1-ium-3-yl)-2-methyl-propanenitrile (intermediate 125 prepared as described above) (230 mg, 1.30 mmol), followed by 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.0M in THF, 1.60 mL, 1.60 mmol). The reaction mixture was stirred at room temperature and degassed with argon for 5-10 minutes. Then [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloride dichloromethane adduct (44.0 mg, 0.0530 mmol) was added and the reaction mixture was stirred at 60° C. for 4.5 hours. Another portion of 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.0M in THF, 0.32 mL, 0.32 mmol) was added, the reaction was degassed again with argon for 5 min and the same amount of [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloride dichloromethane adduct (44.0 mg, 0.0530 mmol) was added. The reaction mixture was stirred at 60° C. overnight. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and brine. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by reversed phase chromatography (C-18 column, acetonitrile in water) afforded the desired product as beige solid (216 mg). LCMS (method 1): 429 (M+H).sup.+, Rt 0.86 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.80 (s, 6H) 4.80-4.90 (t, 2H) 6.73 (d, 1H) 7.34 (m, 2H) 8.01 (s, 1H) 8.40 (s, 1H) 8.95 (s, 1H).
Step 4: Preparation of 2-[5-ethylsulfanyl-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (Pyridine N-Oxide PN6)
[0907] ##STR00076##
[0908] To a degassed solution of 2-[5-fluoro-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (intermediate 118 prepared as described above) (150 mg, 0.350 mmol) in N,N-dimethylformamide (3.50 mL) was added sodium ethanethiolate (77.5 mg, 0.876 mmol). The reaction mixture was stirred at room temperature for 30 minutes, then it was extracted with ethyl acetate and brine. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by reversed phase chromatography (C-18 column, acetonitrile in water) afforded the desired product as beige solid (105 mg). LCMS (method 1): 472 (M+H).sup.+, Rt 0.91 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.30 (t, 3H) 1.80 (s, 6H) 2.90-2.99 (q, 2H) 4.78-4.88 (t, 2H) 6.73 (d, 1H) 7.32 (m, 1H) 7.39 (d, 1H) 7.90 (s, 1H) 8.21 (s, 1H) 8.95 (s, 1H).
Step 5: Preparation of 2-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (Compound P29)
[0909] ##STR00077##
[0910] To a solution of 2-[5-ethylsulfanyl-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]pyridin-1-ium-3-yl]-2-methyl-propanenitrile (pyridine N-oxide PN6 prepared as described above) (76.0 mg, 0.160 mmol) in methanol (1.60 mL) was added zinc (activated) (21.0 mg, 0.320 mmol) followed by ammonium formate (31.0 mg, 0.480 mmol) and silica gel (380 mg, 6.30 mmol). The reaction mixture was stirred at room temperature for two nights, the same amounts of zinc and ammonium formate were added twice during this time. The suspension was filtered through a sintered glass filter plate and evaporated. Purification by reversed phase chromatography (C-18 Column, acetonitrile in water) afforded the desired product as a solid (49.0 mg). LCMS (method 1): 455 (M+H).sup.+, Rt 0.94 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.31 (t, 3H) 1.80 (s, 6H) 2.98-3.01 (q, 2H) 4.78-4.88 (t, 2H) 6.73 (d, 1H) 7.32 (m, 1H) 7.81 (d, 1H) 8.27 (s, 1H) 8.55 (s, 1H) 8.92 (s, 1H).
Step 6: Preparation of 2-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (Compound P19)
[0911] ##STR00078##
[0912] To a stirred solution of 2-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridin-5-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P29 prepared as described above) (71.0 mg, 0.160 mmol) in dichloromethane (1.60 mL) was added 3-chloroperbenzoic acid (79.0 mg, 0.340 mmol) at 0° C. The reaction mixture was stirred for 4 hours, then another portion of 3-chloroperbenzoic acid (18.00 mg, 0.078 mmol) was added and stirring continued for 45 minutes. After completion, the reaction mixture was extracted with ethyl acetate and brine, the combined organic layers were dried over magnesium sulfate, filtered and evaporated. Purification by reversed phase chromatography (C-18 Column, acetonitrile in water) afforded the desired product as a beige solid (45.0 mg). LCMS (method 1): 487 (M+H).sup.+, Rt 1.00 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.40 (t, 3H) 1.88 (s, 6H) 4.00 (q, 2H) 4.78-4.88 (t, 2H) 6.73 (d, 1H) 7.32 (m, 1H) 8.17 (s, 1H) 8.55 (d, 1H) 8.80 (s, 1H) 9.08 (s, 1H).
Example H5: Preparation of 5-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoro propyl)pyrrolo[2,3-c]pyridine (Compound P17)
[0913] ##STR00079##
Step 1: Preparation of 3-fluoro-5-(2-pyridyloxy)pyridine (Intermediate I36)
[0914] ##STR00080##
[0915] To a solution of 5-fluoropyridin-3-ol (CAS 209328-55-2) (1.00 g, 8.40 mmol) in N,N-dimethylformamide (10.0 mL) were added potassium carbonate (2.40 g, 17.0 mmol), copper(I) iodide (160 mg, 0.840 mmol) and 2-iodopyridine (2.70 g, 13.0 mmol). The reaction mixture was stirred at 110° C. for 7 hours. After completion, the reaction mixture was extracted with ethyl acetate and brine. Combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as bright yellow solid (1.28 g). LCMS (method 1): 191 (M+H).sup.+, Rt 0.78 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.02 (d, 1H) 7.11 (m, 1H) 7.35 (m, 1H) 7.79 (m, 1H) 8.20 (m, 1H) 8.36 (m, 2H).
Step 2: Preparation of 3-fluoro-1-oxido-5-(2-pyridyloxy)pyridin-1-ium (Intermediate 27)
[0916] ##STR00081##
[0917] To a solution of 3-fluoro-5-(2-pyridyloxy)pyridine (intermediate 136 prepared as described above) (1.20 g, 6.30 mmol) in acetonitrile (32.0 mL) at 0° C. was added hydrogen peroxide urea complex (1.20 g, 13.0 mmol), followed by a dropwise addition of trifluoroacetic anhydride (1.80 mL, 13.0 mmol). The reaction mixture was stirred at 0-5° C. for 1 hour. After completion, the reaction mixture was carefully quenched with sodium bisulfite solution (˜40 mass %) and stirred for 15 minutes. A peroxide test was done before the mixture was basified at 0° C. with sodium hydroxide (4 N) to pH 10. Then it was diluted with ethyl acetate and washed with brine. The combined aqueous layer was extracted again with ethyl acetate and the combined organic layers were dried with sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (methanol in dichloromethane) afforded the desired product as white solid (537 mg). LCMS (method 1): 207 (M+H).sup.+, Rt 0.53 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.02 (m, 2H) 7.16 (m, 1H) 7.80 (m, 1H) 8.01 (m, 1H) 8.10 (m, 1H) 8.22 (m, 1H).
Step 3: Preparation of 5-[3-fluoro-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (Intermediate I32)
[0918] ##STR00082##
[0919] To a solution of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (intermediate 13 prepared as described above) (300 mg, 0.912 mmol) in tetrahydrofuran (3.00 mL) was added 3-fluoro-1-oxido-5-(2-pyridyloxy)pyridin-1-ium (intermediate 27 prepared as described above) (263 mg, 1.28 mmol), followed by slow addition of 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.0 M in THF, 2.30 mL, 2.28 mmol). The reaction mixture was stirred at room temperature and degassed with argon for 5-10 minutes. Then [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloride dichloromethane adduct (37.6 mg, 0.0456 mmol) was added and the reaction mixture was stirred at 75° C. for 2.5 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and brine. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by reversed phase chromatography (C-18 column, acetonitrile in water) afforded the desired product as beige-brown solid (230 mg). LCMS (method 1): 455 (M+H).sup.+, Rt 0.85 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 4.78-4.90 (t, 2H) 6.73 (d, 1H) 7.08 (d, 1H) 7.18 (m, 2H) 7.32 (d, 1H) 7.80-7.85 (m, 1H) 8.01 (s, 1H) 8.28 (m, 2H) 8.94 (s, 1H).
Step 4: Preparation of 5-[3-ethylsulfanyl-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (Pyridine N-Oxide PN10)
[0920] ##STR00083##
[0921] To a degassed solution of 5-[3-fluoro-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (intermediate 132 prepared as described above) (130 mg, 0.286 mmol) in N,N-dimethylformamide (2.86 mL) was added sodium ethanethiolate (27.9 mg, 0.315 mmol) at 0° C. The reaction mixture was stirred at 0-5° C. for 5.5 hours, then sodium ethanethiolate (12.7 mg, 0.143 mmol. 0.500 eq.) was again added and it was stirred two days at room temperature. Another portion of sodium ethanethiolate (12.7 mg, 0.143 mmol) was added and stirring continued for 2.5 hours. The reaction mixture was extracted with ethyl acetate and brine, the combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by reversed phase chromatography (C-18 column, acetonitrile in water) afforded the desired product as yellow foam (96 mg). LCMS (method 1): 498 (M+H).sup.+, Rt 0.90 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.27 (t, 3H) 2.82 (q, 2H) 4.78-4.88 (t, 2H) 6.72 (d, 1H) 7.08 (d, 1H) 7.13 (m, 2H) 7.32 (d, 1H) 7.78-7.83 (m, 1H) 7.91 (s, 1H) 8.20 (d, 1H) 8.23 (m, 1H) 8.92 (s, 1H).
Step 5: Preparation of 5-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl) pyrrolo[2,3-c]pyridine (Compound P54)
[0922] ##STR00084##
[0923] To a solution of 5-[3-ethylsulfanyl-1-oxido-5-(2-pyridyloxy)pyridin-1-ium-2-yl]-1-(2,2,3,3,3-pentafluoropropyl)pyrrolo[2,3-c]pyridine (pyridine N-oxide PN10 prepared as described above) (90.0 mg, 0.180 mmol) in methanol (1.80 mL) were added zinc (activated) (24.0 mg, 0.360 mmol), ammonium formate (35.0 mg, 0.540 mmol) and silica gel (450 mg, 7.40 mmol). The reaction mixture was stirred at room temperature over two days, then another portion of ammonium formate (35.0 mg, 0.540 mmol) and zinc (activated) (24.0 mg, 0.360 mmol) were added, and stirring continued for 4.5 hours. Addition of ammonium formate (35.0 mg, 0.540 mmol) and zinc (activated) (24.0 mg, 0.360 mmol) were repeated, and stirring continued overnight at room temperature. The reaction mixture was filtered through a pad of celite and washed with methanol. The filtrate was evaporated, and the residue was extracted with ethyl acetate and brine. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as white solid (65.0 mg).
[0924] LCMS (method 1): 481 (M+H).sup.+, Rt 0.91 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.31 (t, 3H) 2.89 (q, 2H) 4.78-4.88 (t, 2H) 6.71 (d, 1H) 7.08 (d, 1H) 7.09 (m, 1H) 7.38 (s, 1H) 7.52 (d, 1H) 7.73-7.80 (m, 1H) 8.21 (d, 2H) 8.33 (d, 1H) 8.89 (s, 1H).
Step 6: Preparation of 5-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl) pyrrolo[2,3-c]pyridine (Compound P17)
[0925] ##STR00085##
[0926] To a solution of 5-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-1-(2,2,3,3,3-pentafluoropropyl) pyrrolo[2,3-c]pyridine (compound P54 prepared as described above) (65.0 mg, 0.140 mmol) in dichloromethane (1.40 mL) was added 3-chloroperbenzoic acid (68.0 mg, 0.300 mmol). The reaction mixture was stirred at room temperature for 1 hour, then it was poured onto sat. aq. sodium bicarbonate (60.0 mL) and stirred for 30 minutes. The mixture was extracted with ethyl acetate and sat. aq. sodium bicarbonate and the combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by reversed phase chromatography (C-18 column, acetonitrile in water) afforded the desired product as beige solid (45 mg). LCMS (method 1): 513 (M+H).sup.+, Rt 1.01 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.33 (t, 3H) 3.55-3.62 (m, 1H) 3.82-3.92 (m, 1H) 4.61-4.71 (t, 2H) 6.71 (d, 1H) 7.10-7.17 (m, 2H) 7.29 (s, 1H) 7.69 (s, 1H) 7.80-7.86 (m, 1H) 8.20 (m, 1H) 8.28 (d, 1H) 8.55 (s, 1H) 8.82 (d, 1H).
Example H6: Preparation of 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P11)
[0927] ##STR00086##
Step 1: Preparation of 1-(5-fluoro-3-pyridyl)cyclopropanecarbonitrile (Intermediate I35)
[0928] ##STR00087##
[0929] To a solution of 2-(5-fluoro-3-pyridyl) acetonitrile (CAS 39891-06-0) (4.00 g, 29.38 mmol) in dry acetonitrile (40.0 mL) was added cesium carbonate (28.7 g, 88.1 mmol) and 1,2-dibromoethane (5.06 mL, 58.8 mmol). The reaction mixture was stirred at 80° C. overnight, then cooled to room temperature before being concentrated in vacuo. The residue was diluted with water and extracted with ethyl acetate. The organic layer was washed with water and sat. aq. sodium bicarbonate, dried over magnesium sulfate, filtered and concentrated. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired compound as light yellow solid. LCMS (method 1): 163 (M+H).sup.+, Rt 0.67 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.45-1.55 (m, 2H) 1.83-1.92 (m, 2H) 7.32-7.45 (m, 1H) 8.38-8.55 (m, 2H).
Step 2: Preparation of 1-(5-fluoro-1-oxido-pyridin-1-ium-3-yl)cyclopropanecarbonitrile (Intermediate I26)
[0930] ##STR00088##
[0931] To a solution of 1-(5-fluoro-3-pyridyl)cyclopropanecarbonitrile (intermediate 135 prepared as described above) (150 mg, 0.925 mmol) in tetrahydrofuran (1.85 mL) was added hydrogen peroxide urea complex (182.7 mg, 1.94 mmol) at 0° C., followed by a dropwise addition of 2,2,2-trifluoroacetic-anhydride (0.261 mL, 1.85 mmol). The reaction mixture was stirred at room temperature for 16 hours and was quenched with an aqueous solution of sodium sulfite. It was stirred for 30 minutes, then aq. sat. sodium bicarbonate was added, and it was extracted with ethyl acetate twice. The combined organic layers were washed with aq. sat. sodium bicarbonate, dried over magnesium sulfate, filtered and concentrated. Purification by flash chromatography over silica gel (methanol in ethyl acetate) afforded the desired product as a white solid. LCMS (method 1): 179 (M+H).sup.+, Rt 0.29 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.46-1.55 (m, 2H) 1.86-1.98 (m, 2H) 7.01-7.09 (m, 1H) 7.95-8.02 (m, 1H) 8.05-8.13 (m, 1H)
Step 3: Preparation of 1-[5-fluoro-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-1-ium-3-yl]cyclopropanecarbonitrile (Intermediate I15)
[0932] ##STR00089##
[0933] To a degassed solution of 1-(5-fluoro-1-oxido-pyridin-1-ium-3-yl)cyclopropanecarbonitrile (intermediate 126 prepared as described above) (1.60 g, 9.10 mmol) in tetrahydrofuran (20.0 mL) at 10° C. was added 2,2,6,6-tetramethylpiperidinylzinc chloride LiCl-complex (1.0 mol/L in THF) (9.10 mL, 9.10 mmol) dropwise. The reaction mixture was stirred for 15 minutes, then a degassed solution of 5-bromo-1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridine (intermediate 11 prepared as described above) (2.00 g, 6.1 mmol) in tetrahydrofuran was added, followed by [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (290 mg, 0.390 mmol). The reaction mixture was heated at 60° C. for 17 hours, cooled to room temperature and quenched with aq. sat. sodium bicarbonate, before being extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (methanol in ethyl acetate) afforded the desired product (735 mg). LCMS (method 5): 428 (M+H).sup.+, Rt 0.92 min.
[0934] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.53-1.58 (m, 2H) 1.91-1.96 (m, 2H) 5.15 (t, 2H) 7.18 (dd, 1H) 8.15-8.28 (m, 3H) 9.14 (s, 1H).
Step 4: Preparation of 1-[5-fluoro-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (Intermediate I16)
[0935] ##STR00090##
[0936] To a suspension of 1-[5-fluoro-1-oxido-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]pyridin-1-ium-3-yl]cyclopropanecarbonitrile (intermediate 115 prepared as described above) (820 mg, 1.92 mmol) in tetrahydrofuran (20.0 mL) and sat. ammonium chloride in water (5.00 mL) at 10° C. was added zinc (377 mg, 5.76 mmol). The reaction mixture was stirred overnight at 50° C., cooled to room temperature and dissolved with ethyl acetate. The suspension was filtered to remove the zinc, and the filtrate was washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product. LCMS (method 5): 412 (M+H).sup.+, Rt 1.07 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.55-1.59 (m, 2H) 1.86-1.96 (m, 2H) 5.16 (t, 2H) 7.53 (dd, 1H) 8.26 (s, 1H) 8.40 (s, 1H) 8.53 (s, 1H) 9.16 (s, 1H).
Step 5: Preparation of 1-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P10)
[0937] ##STR00091##
[0938] To a solution of 1-[5-fluoro-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (intermediate 116 prepared as described above) (400 mg, 0.973 mmol) in dry dimethyl formamide (6.0 mL) at 0° C. under nitrogen was added sodium ethanethiolate (90% mass %, 200 mg, 2.14 mmol). The reaction mixture was stirred at room temperature for 3 hours. After completion it was diluted with water and extracted with ethyl acetate. Combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product (190 mg). LCMS (method 5): 454 (M+H).sup.+, Rt 1.14 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.35 (t, 3H) 1.53-1.56 (m, 2H) 1.84-1.89 (m, 2H) 2.97 (q, 2H) 5.14 (t, 2H) 7.72 (d, 1H) 8.23-8.31 (m, 2H) 8.37 (d, 1H) 9.09 (s, 1H).
Step 6: Preparation of 1-[5-ethylsulfonyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P11)
[0939] ##STR00092##
[0940] To a solution of 1-[5-ethylsulfanyl-6-[1-(2,2,3,3,3-pentafluoropropyl)pyrazolo[3,4-c]pyridin-5-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P10 prepared as described above) (175 mg, 0.386 mmol) in dichloromethane (10.0 mL) at 0° C. was added 3-chloroperbenzoic acid (199.8 mg, 0.811 mmol) portionwise. The reaction mixture was stirred for 2 hours warming from 0° C. to room temperature. After completion of reaction, dichloromethane and sodium hydroxide (2 N) were added, the aqueous layer was separated and extracted with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product (148 mg). LCMS (method 5): 486 (M+H).sup.+, Rt 1.05 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.43 (t, 3H) 1.59-1.64 (m, 2H) 1.93-1.98 (m, 2H) 4.00 (q, 2H) 5.15 (t, 2H) 8.25-8.31 (m, 3H) 8.95-9.01 (m, 2H).
Example H7: Preparation of 5-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-1-(2,2,3,3,3-pentafluoro propyl)pyrazolo[3,4-c]pyridine (Compound P25)
[0941] ##STR00093##
Step 1: Preparation of 5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (Compound P53)
[0942] ##STR00094##
[0943] A solution of 5-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (pyridine N-oxide PN1 prepared as described above) (3.50 g, 8.70 mmol) in phosphoryl chloride (35.0 mL, 370 mmol) was stirred at room temperature for 2 hours. The reaction mixture was poured onto ice cold water and neutralized with sat. aq. sodium bicarbonate. Then it was extracted with ethyl acetate (3×50 mL), the combined organic layers were dried over magnesium sulfate, filtered and evaporated. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product (2.00 g). LCMS (method 5): 424/426 (M+H).sup.+, Rt 1.26 min.
[0944] Similarly, 6-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P43) can be prepared from 6-(3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (pyridine N-oxide PN3 prepared as described above). LCMS (method 1): 423/425 (M+H).sup.+, Rt 1.03 min.
Step 2: Preparation of 5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (Compound P49)
[0945] ##STR00095##
[0946] To a solution of 5-(6-chloro-3-ethylsulfanyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (compound P53 prepared as described above) (1.90 g, 4.50 mmol) in dichloromethane (19.0 mL) was added 3-chloroperbenzoic acid (2.30 g, 9.40 mmol) at 0° C. portionwise. The reaction mixture was stirred at room temperature for 2-3 hours, then it was poured onto sat. aq. sodium bicarbonate and extracted with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product (780 mg). LCMS (method 5): 455/457 (M+H).sup.+, Rt 1.16 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.42 (t, 3H) 4.00 (q, 2H) 5.15 (t, 2H) 7.56 (d, 1H) 8.27 (s, 1H) 8.34 (d, 1H) 8.46 (d, 1H) 8.99 (s, 1H).
[0947] Similarly, 6-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P41) can be prepared from 6-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P43 prepared as described above). LCMS (method 1): 455/457 (M+H)+, Rt 0.96 min.
Step 3: Preparation of 5-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (Compound P25)
[0948] ##STR00096##
[0949] In a microwave vial, a solution of 5-(6-chloro-3-ethylsulfonyl-2-pyridyl)-1-(2,2,3,3,3-pentafluoropropyl) pyrazolo[3,4-c]pyridine (compound P49 prepared as described above) (230 mg, 0.506 mmol) in 1,4-dioxane (4.60 mL) was degassed with nitrogen for 10 minutes. Then tributyl(pyrimidin-2-yl)stannane (0.176 mL, 0.556 mmol) and tetrakis(triphenylphosphine)palladium(0) (117 mg, 0.101 mmol) were added, and the reaction mixture was stirred in the microwave at 150° C. for 2 hours. After cooling to room temperature, the reaction mixture was evaporated and the residue was purified by flash chromatography over silica gel (ethyl acetate in cyclohexane) to afford the desired product (130 mg).
[0950] LCMS (method 5): 499 (M+H).sup.+, Rt 1.02 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.44 (t, 3H) 3.97 (q, 2H) 5.16 (t, 2H) 7.42 (t, 1H) 8.27 (s, 1H) 8.43 (d, 1H) 8.68 (d, 1H) 8.77 (d, 1H) 9.00 (d, 3H).
Example H8: Preparation of 6-(5-cyclopropyl-3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (Compound PN4)
[0951] ##STR00097##
Step 1: Preparation of 3-cyclopropyl-5-fluoro-1-oxido-pyridin-1-ium (Intermediate I24)
[0952] ##STR00098##
[0953] To a solution of 3-bromo-5-fluoropyridine 1-oxide (CAS 1221793-60-7) (200 mg, 0.990 mmol) in toluene (3.00 mL) and water (0.089 mL) were added cyclopropylboronic acid (260 mg, 3.00 mmol) and tripotassium phosphate (1.30 g, 5.90 mmol). The reaction mixture was degassed with argon for 5 minutes, then tetrakis(triphenylphosphine)palladium(0) (110 mg, 0.099 mmol) was added, and it was stirred in the microwave for 40 minutes at 120° C. After cooling to room temperature, the reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as beige solid (87.3 mg). LCMS (method 1): 154 (M+H).sup.+, Rt 0.43 min. 1H NMR (400 MHz, CDCl.sub.3) δ ppm 0.82 (s, 2H) 1.10-1.19 (m, 2H) 1.79-1.93 (m, 1H) 6.69-6.78 (m, 1H) 7.85-7.91 (m, 1H) 7.94-8.02 (m, 1H).
Step 2: Preparation of 6-(5-cyclopropyl-3-fluoro-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoro propyl)imidazo[4.5-c]pyridine (Intermediate I29)
[0954] ##STR00099##
[0955] To a solution of 6-bromo-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (intermediate 14 prepared as described above) (1.80 g, 5.45 mmol) in tetrahydrofuran (18.0 mL) was added 3-cyclopropyl-5-fluoro-1-oxido-pyridin-1-ium (intermediate 124) (919 mg, 6.00 mmol), followed by dropwise addition of 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.0M in THF, 24.5 mL, 24.5 mmol). The reaction mixture was stirred at room temperature and degassed with argon for 5-10 minutes. Then [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloride dichloro-methane adduct (156 mg, 0.191 mmol) was added, and the reaction mixture was stirred at 60° C. overnight. Another portion of 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.0M in THF, 5.00 mL) and [1,1′-bis(diphenylphosphino)ferrocene] palladium(II) dichloride dichloromethane adduct (15.0 mg) were added. The reaction mixture stirred again at 65° C. overnight. After cooling to room temperature, the reaction mixture was dissolved with ethyl acetate and aq. sat. sodium bicarbonate was added slowly. The mixture was filtered through hyflo and the filtrate was extracted with ethyl acetate and sat. aq. sodium bicarbonate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (methanol in ethylacetate) afforded the desired product as light brown solid (1.35 g). LCMS (method 1): 403 (M+H).sup.+, Rt 0.80 min. 1H NMR (400 MHz, MeOD) δ ppm 0.90-1.01 (m, 2H) 1.15-1.30 (m, 2H) 2.05-2.17 (m, 1H) 5.40-5.60 (m, 2H) 7.24-7.38 (m, 1H) 8.08-8.18 (m, 1H) 8.21-8.31 (m, 1H) 8.57-8.69 (m, 1H) 9.12-9.24 (m, 1H).
Step 3: Preparation of 6-(5-cyclopropyl-3-ethylsulfanyl-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (Pyridine N-Oxide PN4)
[0956] ##STR00100##
[0957] To a solution of 6-(5-cyclopropyl-3-fluoro-1-oxido-pyridin-1-ium-2-yl)-3-(2,2,3,3,3-pentafluoro propyl)imidazo[4,5-c]pyridine (intermediate 129) (1.34 g, 3.33 mmol) in N,N-dimethylformamide (33.3 mL) was added sodium ethanethiolate (1.09 g, 11.7 mmol) at 10° C. portionwise. The reaction mixture was stirred at room temperature for 4 hours, then additional sodium ethanethiolate (250 mg) was added, and stirring continued for 6 hours. The reaction mixture was poured onto sat. aq. sodium carbonate, the aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with water and sat. aq. sodium carbonate before being dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (methanol in ethyl acetate) afforded the desired product as brown amorph solid (205.6 mg). LCMS (method 1): 445 (M+H).sup.+, Rt 0.86 min. 1H NMR (400 MHz, MeOD) δ ppm 0.87-1.01 (m, 2H) 1.10-1.23 (m, 2H) 1.24-1.32 (m, 3H) 2.04-2.16 (m, 1H) 2.89-3.06 (m, 2H) 5.40-5.59 (m, 2H) 7.32-7.39 (m, 1H) 7.92 (d, 1H) 8.05 (d, 1H) 8.57-8.67 (m, 1H) 9.11-9.20 (m, 1H).
Example H9: Preparation of 6-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (Compound P32)
[0958] ##STR00101##
[0959] To a solution of 6-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-(2,2,3,3,3-pentafluoropropyl)imidazo[4,5-c]pyridine (compound P41 prepared as described above) (255 mg, 0.561 mmol) in pyridine (4.49 mL) was added 1H-1,2,4-triazole (58.1 mg, 0.841 mmol). The reaction mixture was stirred at 120° C. overnight. After cooling to room temperature, it was quenched with ice-water (35 mL) and extracted with ethyl acetate. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography over silica gel (ethyl acetate in cyclohexane) afforded the desired product as a solid (75.8 mg). LCMS (method 1): 488 (M+H).sup.+, Rt 0.89 min. 1H NMR (400 MHz, N,N-DMF-dr) δ ppm 1.26-1.38 (m, 3H) 4.14 (q, 2H) 5.56-5.78 (m, 2H) 8.10-8.19 (m, 1H) 8.41 (d, 1H) 8.47 (d, 1H) 8.69-8.78 (m, 2H) 9.16 (s, 1H) 9.62 (s, 1H).
TABLE-US-00013 TABLE P Examples of compounds of formula (I) LCMS [M + H].sup.+ Mp No. IUPAC name Structures R.sub.t (min) (measured) Method (° C.) P1 5-ethylsulfonyl-N- methyl-6- [1-(2,2,3,3,3- pentafluoropropyl) pyrazolo[3,4-c] pyridin-5-yl]pyridin- 3-amine
TABLE-US-00014 TABLE PN Examples of pyridine N-oxides of compounds of formula (I) LCMS [M + H].sup.+ Mp No. IUPAC name Structures R.sub.t (min) (measured) Method (° C.) PN1 5-(3-ethylsulfanyl-1- oxido-pyridin-1-ium- 2-yl)-1-(2,2,3,3,3- pentafluoropropyl) pyrazolo[3,4-c] pyridine
TABLE-US-00015 TABLE I Examples of intermediates for the preparation of compounds of formula (I) LCMS [M + H].sup.+ Mp No. IUPAC name Structures R.sub.t (min) (measured) Method (° C.) I1 5-bromo-1-(2,2,3,3,3- pentafluoropropyl) pyrazolo[3,4-c]pyridine
[0960] The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other insecticidally, acaricidally and/or fungicidally active ingredients. The mixtures of the compounds of formula I with other insecticidally, acaricidally and/or fungicidally active ingredients may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use. Suitable additions to active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.
[0961] The following mixtures of the compounds of formula I with active ingredients are preferred (the abbreviation “TX” means “one compound selected from the group consisting of the compounds described in Tables A-1 to A-81, Tables B-1 to B-54, Tables C-1 to C-81, Tables D-1 to D-54, Tables E-1 to E-81 and Tables F-1 to F-54, and Table P of the present invention”):
an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,
an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,
an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate (872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin (46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternative name) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate (alternative name)+TX, bromo-cyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (development code) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX, chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate (975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX, chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel (alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermetrin (201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX, dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name) (653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPAC name) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton (278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternative name) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX, eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim (360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin 1 (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternative name) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes (traditional name) (1347)+TX, polynactins (alternative name) (653)+TX, proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite (671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos (711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX, sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam (alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX, tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox (alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternative name) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion (847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,
an algicide selected from the group of substances consisting of bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,
an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,
an avicide selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione (1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,
a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12)+TX, Agrobacterium radiobacter (alternative name) (13)+TX, Amblyseius spp. (alternative name) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX, Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis (alternative name) (33)+TX, Aphidius colemani (alternative name) (34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographa californica NPV (alternative name) (38)+TX, Bacillus firmus (alternative name) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX, Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveria bassiana (alternative name) (53)+TX, Beauveria brongniartii (alternative name) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX, Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonella GV (alternative name) (191)+TX, Dacnusa sibirica (alternative name) (212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alternative name) (300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastix dactylopii (alternative name) (488)+TX, Macrolophus caliginosus (alternative name) (491)+TX, Mamestra brassicae NPV (alternative name) (494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhizium anisopliae var. acridum (scientific name) (523)+TX, Metarhizium anisopliae var. anisopliae (scientific name) (523)+TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp. (alternative name) (596)+TX, Paecilomyces fumosoroseus (alternative name) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741)+TX, Steinernema bibionis (alternative name) (742)+TX, Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae (alternative name) (742)+TX, Steinernema glaseri (alternative name) (742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernema riobravis (alternative name) (742)+TX, Steinernema scapterisci (alternative name) (742)+TX, Steinernema spp. (alternative name) (742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848)+TX,
a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,
a chemosterilant selected from the group of substances consisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid [CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX, thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name) [CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN]+TX,
an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX, (Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX, 14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with 4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin (alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX, codlelure (alternative name) [CCN]+TX, codlemone (alternative name) (167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl 4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name) [CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternative name) (420)+TX, grandlure (421)+TX, grandlure I (alternative name) (421)+TX, grandlure II (alternative name) (421)+TX, grandlure III (alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX, hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol (alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX, lineatin (alternative name) [CCN]+TX, litlure (alternative name) [CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX, megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternative name) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternative name) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX, sordidin (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B.sub.1 (alternative name) (839)+TX, trimedlure B.sub.2 (alternative name) (839)+TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX,
an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX, an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935)+TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/Chemical Abstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX, 2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX, acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX, allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX, aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin (alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl (44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillus thuringiensis delta endotoxins (alternative name) (52)+TX, barium hexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408 (development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate (alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX, bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX, butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate (932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternative name) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX, chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos (131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform [CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos (990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX, chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX, cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternative name)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX, cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX, clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate [CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate (1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos (1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS 708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate (alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX, d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX, dimpropyridaz+TX, dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos (alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron (250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone (alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX, eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX, etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternative name) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX, flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX, flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX, flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code) (1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX, fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX, gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, GY-81 (development code) (423)+TX, halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD (1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos [CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX, hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX, imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX, iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX, isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin (1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name) (473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I (alternative name) [CCN]+TX, juvenile hormone II (alternative name) [CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan (1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternative name) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform (alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin [CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternative name) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170 (development code) (1306)+TX, NC-184 (compound code)+TX, nicotine (578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram (579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron (585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name) (1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyl dithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name) (593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl (609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX, parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX, pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin (626)+TX, petroleum oils (alternative name) (628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name) (1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX, precocene I (alternative name) [CCN]+TX, precocene II (alternative name) [CCN]+TX, precocene III (alternative name) [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin (1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen (708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX, quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX, rafoxanide (alternative name) [CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU 25475 (development code) (1386)+TX, ryania (alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX, sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009 (compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, tar oils (alternative name) (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name) [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX, trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine (alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternative name)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901 (development code) (858)+TX, cyantraniliprole [736994-63-19+TX, chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX, cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX, spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX, sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin [915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim (disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX, epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin [1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin [399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide [1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide [1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole [1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (described in WO2010/060231)+TX, cycloxaprid (described in WO 2005/077934)+TX, spiropidion+TX, Afidopyropen+TX, flupyrimin+TX, Momfluorothrin+TX, kappa-bifenthrin+TX, kappa-tefluthrin+TX, Dichloromezotiaz+TX, Tetrachloraniliprole+TX, benzpyrimoxan+TX
a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX, a nematicide selected from the group of substances consisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene (233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX, abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX, cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX, dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate (262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate (408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX, GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin (alternative name) [CCN]+TX, kinetin (alternative name) (210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrothecium verrucaria composition (alternative name) (565)+TX, NC-184 (compound code)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin (alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternative name)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin (1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX, xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name) (210)+TX, fluensulfone [318290-98-1]+TX, fluopyram+TX,
a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,
a plant activator selected from the group of substances consisting of acibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720)+TX,
a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX, bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX, chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX, coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,
a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599 (development code) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,
an animal repellent selected from the group of substances consisting of anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX, a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,
a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,
and biologically active compounds selected from the group consisting of azaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate [101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX, triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole [99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol [12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX, bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol [23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX, fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph [81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim [110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil [74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl [71626-11-4]+TX, furalaxyl [57646-30-7]+TX, meta-laxyl [57837-19-1]+TX, R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl [77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX, debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole [148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline [24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX, procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid [188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX, flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin [5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide [130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3] [112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin [131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin [361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb [12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX, thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX, captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid [1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX, tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX, copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX, coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper [53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX, nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX, iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen [36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl [57018-04-9]+TX, acibenzo-lar-S-methyl [135158-54-2]+TX, anilazine [101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S [2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX, chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil [57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX, diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb [87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph) [211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone [161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid [126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol [10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid) [120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid [189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX, tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide (disclosed in WO 2007/048556)+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO 2006/087343)+TX, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate [915972-17-7]+TX and 1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide [926914-55-8]+TX; lancotrione [1486617-21-3]+TX, florpyrauxifen [943832-81-3]]+TX, ipfentrifluconazole[1417782-08-1]+TX, mefentrifluconazole [1417782-03-6]+TX, quinofumelin [861647-84-9]+TX, chloroprallethrin [399572-87-3]+TX, cyhalodiamide [1262605-53-7]]+TX, fluazaindolizine [1254304-22-7]+TX, fluxametamide [928783-29-3]+TX, epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin [1065124-65-3]+TX, pydiflumetofen [1228284-64-7]+TX, kappa-bifenthrin [439680-76-9]+TX, broflanilide [1207727-04-5]+TX, dicloromezotiaz [1263629-39-5]+TX, dipymetitrone [16114-35-5]+TX, pyraziflumid [942515-63-1]+TX, kappa-tefluthrin [391634-71-2]+TX, fenpicoxamid [517875-34-2]+TX; fluindapyr [1383809-87-7]+TX; alpha-bromadiolone [28772-56-7]+TX; flupyrimin [1689566-03-7]+TX; benzpyrimoxan [1449021-97-9]+TX; acynonapyr [1332838-17-1]+TX; inpyrfluxam [1352994-67-2]+TX, isoflucypram [1255734-28-1]+TX; rescalure [64309-03-1]+TX; aminopyrifen [1531626-08-0]+TX; tyclopyrazoflor [1477919-27-9]+TX; and spiropidion [1229023-00-0]+TX; and microbials including: Acinetobacter lwoffii+TX, Acremonium alternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremonium diospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84 (Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX, Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX, Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882 (Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX, Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacter chroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural Blooming Blossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacillus pumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808 (Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX, Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strain AQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24 (Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 (Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX, Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki (Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX, Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillus thuringiensis strain BD #32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteria spp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage of Clavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveria bassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA (Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveria brongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX, Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillus thuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderia cepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX, Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes (Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporium cladosporioides+TX, Cladosporium oxysporum+TX, Cladosporium chlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX, Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX, Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX, Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX, Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX, Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydia pomonella granulovirus (Madex®+TX, Madex Plus®+TX, Madex Max/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX, Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslera hawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX, Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccum purpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusarium acuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum (Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX, Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX, Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX, Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillus trueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibrio variabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®)+TX, Isoflavone—formononetin (Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidium giganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX, Lecanicillium muscarium (Vertikil®)+TX, Lymantria dispar nucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX, Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhizium anisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX, Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX, Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus 620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. (AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strain AARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97 (Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus (PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX, Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan C9-1®)+TX, Pantoea spp.+TX, Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicillium aurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX, Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX, Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens (Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonas fluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae (Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens (Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX, Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythium paroecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX, Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia (Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus (Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonas maltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomyces albaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX, Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX, Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108 (ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX, Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX, Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai (Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShield HCO+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39 (Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX, Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX, Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX, Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporon pullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichothecium roseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhiza strain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii (Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementary micronutrients (Natural II®)+TX, various fungi (Millennium Microbes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii (Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillus marismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX, Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and
Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (Plasma Neem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR (Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX, Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemum extract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentials oils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermint and thyme oil (Garden insect Killer®)+TX, Glycinebetaine (Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neem oil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX, oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX, pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis (Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plant extract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil (Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixture of rosemary sesame peppermint thyme and cinnamon extracts (EF 300®)+TX, mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixture of clove peppermint garlic oil and mint (Soil Shot®)+TX, kaolin (Screen®)+TX, storage glucam of brown algae (Laminarin®); and
pheromones including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramount dispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3M MEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC—LR Sprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar Premium Fly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit moth sprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX, Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder (extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11 Tetradecatrienyl acetate+TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX, (E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX, Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX, Lavandulyl senecioate; and
Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi (Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata (Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata (Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX, Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseius californicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris (Thripex®+TX, Bugline Cucumeris®)+TX, Amblyseius fallacis (Fallacis®)+TX, Amblyseius swirskii (Bugline Swirskii®+TX, Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocoris nemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX, Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX, Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae (Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletes aphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX, Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombus terrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperla carnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX, Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX, Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX, Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa (Encarsia Max®+TX, Encarline®+TX, En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus (Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus californicus+TX, Eretmocerus eremicus (Ercal®+TX, Eretline E®)+TX, Eretmocerus eremicus (Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX, Eretline M®)+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiella acarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX, Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis (Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX, Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora (NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX, Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditis megidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline Hm®+TX, Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer (Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline M®+TX, Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline C®+TX, Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis (NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Orius insidiosus (Thripor-I®+TX, Oriline I®)+TX, Orius laevigatus (Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline M®)+TX, Orius strigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX, Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiulus persimilis (Spidex®+TX, Phytoline P®)+TX, Podisus maculiventris (Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline Sf®+TX, Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline Srb®)+TX, Steinernema riobrave (BioVector®+TX, BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernema spp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethorus punctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae (Tricholine B®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX, Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator; and
other biologicals including: abscisic acid+TX, bioSea®+TX, Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichum gloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps (Trapline D®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT Gold CST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline Y®)+TX, Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap (Trapline F®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap (Thripline Ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassium salts of fatty acids (Sanova®)+TX, potassium silicate solution (Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX, SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore Organic Grasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, Rebell Amarillo®)+TX and Traps (Takitrapline y+B®)+TX,
or a biologically active compound or agent selected from: Brofluthrinate+TX, Diflovidazine+TX, Flometoquin+TX, Fluhexafon+TX, Plutella xylostella Granulosis virus+TX, Cydia pomonella Granulosis virus+TX, Imicyafos+TX, Heliothis virescens Nucleopolyhedrovirus+TX, Heliothis punctigera Nucleopolyhedrovirus+TX, Helicoverpa zea Nucleopolyhedrovirus+TX, Spodoptera frugiperda Nucleopolyhedrovirus+TX, Plutella xylostella Nucleopolyhedrovirus+TX, p-cymene+TX, Pyflubumide+TX, Pyrafluprole+TX, QRD 420+TX, QRD 452+TX, QRD 460+TX, Terpenoid blends+TX, Terpenoids+TX, Tetraniliprole+TX, and α-terpinene+TX; or an active substance referenced by a code+TX, such as code AE 1887196 (BSC-BX60309)+TX, code NNI-0745 GR+TX, code IKI-3106+TX, code JT-L001+TX, code ZNQ-08056+TX, code IPPA152201+TX, code HNPC-A9908 (CAS: [660411-21-2])+TX, code HNPC-A2005 (CAS: [860028-12-2])+TX, code JS118+TX, code ZJ0967+TX, code ZJ2242+TX, code JS7119 (CAS: [929545-74-4])+TX, code SN-1172+TX, code HNPC-A9835+TX, code HNPC-A9955+TX, code HNPC-A3061+TX, code Chuanhua 89-1+TX, code IPP-10+TX, code ZJ3265+TX, code JS9117+TX, code ZJ3757+TX, code ZJ4042+TX, code ZJ4014+TX, code ITM-121+TX, code DPX—RAB55 (DKI-2301)+TX, code NA-89+TX, code MIE-1209+TX, code MCI-8007+TX, code BCS-CL73507+TX, code S-1871+TX, code DPX—RDS63+TX, Quinofumelin+TX, mefentrifluconazol+TX, fenpicoxamid+TX, fluindapyr+TX, flufenpyrrolidone+TX, inpyrfluxam+TX or indiflumetpyr+TX, isoflucypram+TX, isocycloseram+TX, pyrapropoyne+TX, florylpicoxamid+TX, metyltetraprole+TX, ipflufenoquin+TX, pyridachlometyl+TX or chlopyridiflu+TX, tetrachlorantraniliprole+TX, tetrachloraniliprole+TX, Tetflupyrolimet+TX, Triflufenpyrrolidone+TX, Tyclopyrazoflor+TX, flupyrimin+TX or pyrifluramide+TX, benzpyrimoxan+TX, beflubutamid-M+TX, Benzosufyl+TX or oxazosulfyl+TX, etpyrafen+TX, acynonapyr+TX or pyrinonafen+TX, oxotrione+TX, bixlozone+TX or clofendizone+TX or dicloroxizone+TX, cyclopyranil+TX or pyrazocyclonil+TX or cyclopyrazonil+TX, alpha-bromadiolone+TX, code AKD-1193+TX, Oxathiapiprolin+TX, Fluopyram+TX, Penflufen+TX, Fluoxopyrosad+TX, fluoxapiprolin+TX, Flupyradifurone+TX, cyetpyrafen+TX, cyclobutrifluram+TX, dimesulfazet+TX, flubeneteram+TX, and flupentiofenox+TX.
[0962] The references in brackets behind the active ingredients, e.g. [3878-19-1] refer to the Chemical Abstracts Registry number. The above described mixing partners are known. Where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound “abamectin” is described under entry number (1). Where “[CCN]” is added hereinabove to the particular compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which is accessible on the internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound “acetoprole” is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.
[0963] Most of the active ingredients described above are referred to hereinabove by a so-called “common name”, the relevant “ISO common name” or another “common name” being used in individual cases. If the designation is not a “common name”, the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditional name”, a “compound name” or a “development code” is used or, if neither one of those designations nor a “common name” is used, an “alternative name” is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.
[0964] The active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-81, Tables B-1 to B-54, Tables C-1 to C-81, Tables D-1 to D-54, Tables E-1 to E-81 and Tables F-1 to F-54, and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-81, Tables B-1 to B-54, Tables C-1 to C-81, Tables D-1 to D-54, Tables E-1 to E-81 and Tables F-1 to F-54, and Table P and an active ingredient as described above preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, special preference being given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.
[0965] The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body.
[0966] The mixtures comprising a compound of formula I selected from Tables A-1 to A-81, Tables B-1 to B-54, Tables C-1 to C-81, Tables D-1 to D-54, Tables E-1 to E-81 and Tables F-1 to F-54, and Table P and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from Tables A-1 to A-81, Tables B-1 to B-54, Tables C-1 to C-81, Tables D-1 to D-54, Tables E-1 to E-81 and Tables F-1 to F-54, and Table P and the active ingredients as described above is not essential for working the present invention.
[0967] The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.
[0968] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.
[0969] The application methods for the compositions, that is the methods of controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring—which are to be selected to suit the intended aims of the prevailing circumstances—and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.
[0970] A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.
[0971] The compounds of the invention and compositions thereof are also be suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
[0972] The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
[0973] The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term “coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
[0974] Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula (I) can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
BIOLOGICAL EXAMPLES
[0975] The Examples which follow serve to illustrate the invention. Certain compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, δ ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
Example B1: Activity Against Diabrotica balteata (Corn Root Worm)
[0976] Maize sprouts placed onto an agar layer in 24-well microtiter plates were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by spraying. After drying, the plates were infested with L2 larvae (6 to 10 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 4 days after infestation.
[0977] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P4, P5, P6, P7, P8, P9, P10, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37, P38, P39, P40, P42, P45, P46, P47, P49, P50, P51, P52.
Example B2: Activity Against Euschistus heros (Neotropical Brown Stink Bug)
[0978] Soybean leaves on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaves were infested with N2 nymphs. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.
[0979] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P4, P5, P6, P8, P10, P11, P12, P14, P15, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P28, P30, P31, P32, P33, P34, P38, P40, P42, P45, P46, P47, P49, P52, PN4 and PN8.
Example B3: Activity Against Plutella xylostella (Diamond Back Moth)
[0980] 24-well microtiter plates with artificial diet were treated with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions by pipetting. After drying, Plutella eggs were pipetted through a plastic stencil onto a gel blotting paper and the plate was closed with it. The samples were assessed for mortality and growth inhibition in comparison to untreated samples 8 days after infestation. The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm: P2, P4, P5, P6, P8, P9, P10, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P38, P39, P40, P42, P45, P46, P47, P49, P50, P51, P52.
Example B4: Activity Against Myzus persicae (Green Peach Aphid) Feeding/Contact Activity
[0981] Sunflower leaf discs were placed onto agar in a 24-well microtiter plate and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying, the leaf discs were infested with an aphid population of mixed ages. The samples were assessed for mortality 6 days after infestation.
[0982] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P2, P4, P5, P6, P7, P8, P11, P12, P14, P15, P16, P17, P21, P22, P23, P24, P25, P26, P27, P32, P33, P34, P40, P42, P44, P46 and PN5.
Example B5: Activity Against Myzus persicae (Green Peach Aphid) Systemic Activity
[0983] Roots of pea seedlings infested with an aphid population of mixed ages were placed directly into aqueous test solutions prepared from 10′000 DMSO stock solutions. The samples were assessed for mortality 6 days after placing seedlings into test solutions.
[0984] The following compounds resulted in at least 80% mortality at a test rate of 24 ppm: P2, P4, P5, P12, P16, P25, P34, P40, P42, P44, P52.
Example B6: Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)
[0985] Cotton leaf discs were placed onto agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with five L1 larvae. The samples were assessed for mortality, anti-feeding effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is given when at least one of the categories mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
[0986] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P2, P4, P5, P6, P8, P10, P11, P12, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P30, P31, P33, P35, P36, P37, P38, P39, P40, P45, P46, P49, P50, P51, P52.
Example B7: Activity Against Bemisia tabaci (Cotton White Fly)
[0987] Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with adult white flies. The samples were checked for mortality 6 days after incubation.
[0988] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P5, P6, P11, P31.
Example B8: Activity Against Frankliniella occidentalis (Western Flower Thrips)
[0989] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from 10′000 DMSO stock solutions. After drying the leaf discs were infested with a Frankliniella population of mixed ages. The samples were assessed for mortality 7 days after infestation.
[0990] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P6, P10, P11, P25, P26, P47.
Example B9: Activity Against Tetranychus urticae (Two-Spotted Spider Mite)
[0991] Bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from 10′000 ppm DMSO stock solutions. After drying the leaf discs were infested with a mite population of mixed ages. The samples were assessed for mortality on mixed population (mobile stages) 8 days after infestation.
[0992] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P26 and PN6.