PESTICIDALLY ACTIVE HETEROCYCLIC DERIVATIVES WITH SULFUR CONTAINING SUBSTITUENTS
20220061324 · 2022-03-03
Assignee
Inventors
- Michel Muehlebach (Stein, CH)
- Sebastian RENDLER (Stein, CH)
- Daniel EMERY (Stein, CH)
- Anke BUCHHOLZ (Stein, CH)
- Indira SEN (Corlim, Ilhas, IN)
- Vikas SIKERVAR (Corlim, Ilhas, IN)
- André STOLLER (Stein, CH)
Cpc classification
C07D213/78
CHEMISTRY; METALLURGY
A01N47/30
HUMAN NECESSITIES
A01N53/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
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, molluscs or representatives of the order Acarina.
##STR00001##
Claims
1. A compound of formula (I) ##STR00132## wherein G.sub.1 and G.sub.2 are, independently from each other, CH or N; R.sub.2 is halogen, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.4haloalkylsulfanyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl or C.sub.1-C.sub.6haloalkoxy; Q is a radical selected from the group consisting of formula Qa and Qb ##STR00133## wherein the arrow denotes the point of attachment to the bicyclic ring; and wherein A represents CH or N; X is S, SO, SO.sub.2 or SO(NH); R.sub.1 is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl 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.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6alkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkoxy, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.6haloalkylsulfonyl, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, —N═S(O)ReRv, —C(R.sub.8)═NO(R.sub.9), —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 ring one oxygen atom and not more than one ring sulfur atom; or Q.sub.1 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; Each R.sub.4 is independently hydrogen, C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl; R.sub.5 is C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl or C.sub.3-C.sub.6cycloalkyl; R.sub.6 and R.sub.7 are, independently from each other, C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.6cycloalkyl; R.sub.8 and R.sub.9 are, independently from each other, hydrogen, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.6haloalkyl; R.sub.3 is hydrogen, halogen or C.sub.1-C.sub.4alkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I.
2. The compound of claim 1, represented by the compounds of formula I-2 ##STR00134## wherein X, Q.sub.1, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1.
3. The compound of claim 1, represented by the compounds of formula I-3 ##STR00135## wherein X, Q.sub.1, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1.
4. The compound of claim 1, represented by the compounds of formula I-6 ##STR00136## wherein X, Q.sub.1, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1.
5. The compound of claim 1, represented by the compounds of formula I-7 ##STR00137## wherein X, Q.sub.1, R.sub.1, R.sub.2, G.sub.1 and G.sub.2 are as defined under formula I in claim 1.
6. The compound according to claim 1, wherein Q.sub.1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, cyanoisopropoxy, trifluoroethoxy, —N(R.sub.4).sub.2, —N(R.sub.4)COR.sub.5, —N(R.sub.4)CON(R.sub.4).sub.2, in each of which R.sub.4 is independently either hydrogen or methyl and R.sub.5 is either methyl or cyclopropyl, or Q.sub.1 is —N═S(O)(CH.sub.3).sub.2, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which is unsubstituted or is mono-substituted by chloro, cyano or trifluoromethyl, or Q.sub.1 is unsubstituted N-linked triazolyl or unsubstituted C-linked pyrimidinyl.
7. The compound according to claim 1, wherein R.sub.2 is C.sub.1-C.sub.6haloalkoxy.
8. The compound according to claim 1, wherein G.sub.1 is CH and G.sub.2 is N; and wherein X is S, SO.sub.2 or S(O)NH.
9. The compound according to claim 1, wherein G.sub.1 is CH and G.sub.2 is CH; and wherein X is S, SO.sub.2 or S(O)NH.
10. The compound of claim 1, represented by the compounds of formula I-4 ##STR00138## wherein A is CH or N; R.sub.2 is C.sub.1-C.sub.6haloalkoxy; G.sub.1 is CH or N; G.sub.2 is CH or N; and Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6alkyl monosubstituted by cyano, 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, —N═S(O)R.sub.6R.sub.7, (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 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; R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; and R.sub.6 and R.sub.7 are, independently from each other, C.sub.1-C.sub.6alkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
11. The compound according to claim 9, wherein Q.sub.1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, —NH.sub.2, —NH(CH.sub.3), —N(CH.sub.3).sub.2, —NHCOCH.sub.3, —N═S(O)(CH.sub.3).sub.2, —N(CH.sub.3)COcyclopropyl, —N(CH.sub.3)COCH.sub.3, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-cyano-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.
12. The compound of claim 1, represented by the compounds of formula I-4 ##STR00139## wherein A is CH or N; R.sub.2 is C.sub.1-C.sub.6haloalkoxy; G.sub.1 is CH or N; G.sub.2 is CH or N; and Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6alkyl monosubstituted by cyano, 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, —N═S(O)R.sub.6R.sub.7, (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 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; R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; and R.sub.6 and R.sub.7 are, independently from each other, C.sub.1-C.sub.6alkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
13. The compound according to claim 11, wherein Q.sub.1 is hydrogen, chlorine, bromine, cyclopropyl, —NH.sub.2, —NH(CH.sub.3), —N(CH.sub.3).sub.2, —NHCOCH.sub.3, —N(CH.sub.3)COCH.sub.3, —N(CH.sub.3)COCH.sub.2CH.sub.3, —NHCO(cyclopropyl), —N(CH.sub.3)CO(cyclopropyl), —N(H)CONH.sub.2, —N(H)CONH(CH.sub.3), —N(H)CON(CH.sub.3).sub.2, —N(CH.sub.3)CONH.sub.2, —N(CH.sub.3)CONH(CH.sub.3), —N(CH.sub.3)CON(CH.sub.3).sub.2, —N(CH.sub.3)COCH.sub.2CH.sub.3, —N(CH.sub.3).sub.2, or (oxazolidin-2-one)-3-yl; or Q.sub.1 is unsubstituted N-linked triazolyl, or is unsubstituted pyrimidinyl.
14. The compound of claim 1, represented by the compounds of formula I-10 ##STR00140## wherein R.sub.2 is C.sub.1-C.sub.6haloalkoxy; G.sub.1 is CH or N; G.sub.2 is CH or N; and Q is a radical selected from the group consisting of formula Qc1 and Qd1 ##STR00141## wherein the arrow denotes the point of attachment to the bicyclic ring; and wherein A is CH or N; and Q.sub.1 is hydrogen, halogen, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6alkyl monosubstituted by cyano, C.sub.1-C.sub.6cyanoalkoxy, —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 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, —N═S(O)(CH.sub.3).sub.2, or 2-pyridyloxy; or Q.sub.1 is unsubstituted N-linked triazolyl, or is unsubstituted pyrimidinyl.
15. The compound of formula I according to claim 1, represented by the compounds of formula I-4S ##STR00142## wherein A is CH or N; R.sub.2 is C.sub.1-C.sub.6haloalkoxy; G.sub.1 is CH or N; G.sub.2 is CH or N; and Q.sub.1 is hydrogen, halogen, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl monosubstituted by cyano, C.sub.1-C.sub.6alkyl monosubstituted by cyano, 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, or —N(R.sub.4)CON(R.sub.4).sub.2, —N═S(O)R.sub.6R.sub.7, (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 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; R.sub.5 is C.sub.1-C.sub.6alkyl or C.sub.3-C.sub.6cycloalkyl; and R.sub.6 and R.sub.7 are, independently from each other, C.sub.1-C.sub.6alkyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.
16. A compound selected from the group consisting of: 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P1); 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P2); 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P3); 3-(5-bromo-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P4); 3-(3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3-tetrafluoropropoxy)imidazo[1,5-a]pyrazine (compound P5); 3-(3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3-tetrafluoropropoxy)imidazo[1,5-a]pyrazine (compound P6); 3-(3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P7); 3-(3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P8); 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-3-methyl-urea (compound P9); 5-ethylsulfonyl-N-methyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]pyridin-2-amine (compound P10); N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-N-methyl-acetamide (compound P11); 3-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P12); N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide (compound P13); 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-1,3-dimethyl-urea (compound P14); 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P15); 2-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P16); [5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P17); [5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P18); 3-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P19); 3-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P20); 3-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P21); 3-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P22); 1-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P23); 2-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P24); 3-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P25); 3-(3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P26); 3-(3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P27); 2-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P28); 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P29); 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P30); 5-ethylsulfonyl-N-methyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]pyridin-2-amine (compound P31); 3-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P32); 3-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P33); 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P34); 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P35); 3-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P36); N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-2-pyridyl]-N-methyl-acetamide (compound P37); N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-2-pyridyl]-N-methyl-cyclopropanecarboxamide (compound P38); N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]-N-methyl-acetamide (compound P39); 3-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P40); N-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]-N-methyl-acetamide (compound P41); 3-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P42); 3-(5-bromo-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (compound P43); [5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P44); [5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P45); 2-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]-2-methyl-propanenitrile (compound P46); 2-[[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P47); 2-[[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P48); 2-[[5-(ethylsulfonimidoyl)-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P49); 2-[[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P50); 2-[[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P51); 2-[[5-(ethylsulfonimidoyl)-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P52); and 1-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridin-3-yl]-3-pyridyl]cyclopropanecarbonitrile (compound P53).
17. 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 and, optionally, an auxiliary or diluent.
18. 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.
19. 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 the composition according to claim 17.
20. A compound of formula XIV ##STR00143## wherein R.sub.1, R.sub.3 and A are as defined under formula I in claim 1, and R.sub.100 is OH, chloro or C.sub.1-C.sub.4alkoxy.
Description
PREPARATORY EXAMPLES
[1053] “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.+.
LCMS and GCMS Methods:
Method 1:
[1054] 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:
[1055] 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:
[1056] Spectra were recorded on a Mass Spectrometer from Waters (Acquity SDS Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch, Capillary: 3.00 kV, Cone Voltage: 41.00 V, Source temperature: 150° C., Desolvation Gas Flow: 1000 L/Hr, Desolvation temperature: 500° C., Gas Flow @Cone: 50 L/hr, Mass range: 110-800 Da, PDA wavelength range: 210-400 nm. Column: Acquity UPLC HSS T3 C.sub.18, length 30 mm, diameter 2.1 mm, particle size 1.8 μm. Column oven temperature 40° C. Solvent gradient: A=Water with 0.1% formic acid: Acetonitrile (95:5 v/v). B=Acetonitrile with 0.05% formic acid. Gradient=0 min 90% A, 10% B; 0.2 min 50% A, 50% B; 0.7-1.3 min 0% A, 100% B; 1.4-1.6 min 90% A, 10% B. Flow rate 0.8 mL/min.
Method 4:
[1057] Spectra were recorded on a Mass Spectrometer from Agilent Technologies (6410 Triple Quadruple Mass Spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch, Capillary: 4.00 kV, Fragmentor: 100.00 V, Gas Temperature: 350° C., Gas Flow: 11 L/min, Nebulizer Gas: 45 psi, Mass range: 110-1000 Da, DAD Wavelength range: 210-400 nm). Column: KINETEX EVO C18, length 50 mm, diameter 4.6 mm, particle size 2.6 μm. Column oven temperature 40° C. Solvent gradient: A=Water with 0.1% formic acid: Acetonitrile (95:5 v/v). B=Acetonitrile with 0.1% formic acid. Gradient=0 min 90% A, 10% B; 0.9-1.8 min 0% A, 100% B, 2.2-2.5 min 90% A, 10% B. Flow rate 1.8 mL/min.
Example H1: Preparation of 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy) imidazo[1,5-a]pyrazine (Compound P1)
[1058] ##STR00044##
Step A: Preparation of 6-chloro-N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide
[1059] ##STR00045##
[1060] To a suspension of 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid (1.57 g, 7.21 mmol; WO17/001314) in toluene (28.3 mL) at room temperature were added one drop of N,N-dimethyl-formamide and oxalyl dichloride (0.818 mL, 9.38 mmol) dropwise, and the mixture was stirred for 3 hours. The reaction mixture was evaporated under reduced pressure to afford 6-chloro-3-ethylsulfanyl-pyridine-2-carbonyl chloride.
[1061] To a solution of (3-chloropyrazin-2-yl)methanamine hydrochloride (1.30 g, 7.21 mmol; CAS 939412-86-9), 4-dimethyl-aminopyridine (9 mg, 0.072 mmol) and triethylamine (2.51 mL, 18.0 mmol) in tetrahydrofuran (20 mL) at 5° C. was added a solution of 6-chloro-3-ethylsulfanyl-pyridine-2-carbonyl chloride (7.21 mmol) in tetrahydrofuran (5.5 mL) dropwise. The reaction mixture was stirred at 0-5° C. for 1 hour, filtered over Hyflo, and the residue washed with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue purified by combiflash (silicagel, 0-100% ethyl acetate gradient in cyclohexane) to afford 6-chloro-N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide as a solid, mp 138-140° C. LCMS (method 1): 343/345 (M+H).sup.+, Rt 0.98 min.
[1062] Similarly, 5-bromo-N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide (solid, mp 127-129° C.) can be obtained from 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid (WO16/030229) and (3-chloropyrazin-2-yl)methanamine hydrochloride. LCMS (method 1): 387/389/391 (M+H).sup.+; Rt 1.03 min.
[1063] Similarly, N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide (white solid) can be obtained from 3-ethylsulfanylpyridine-2-carboxylic acid (WO14/021468) and (3-chloropyrazin-2-yl)methanamine hydrochloride. LCMS (method 1): 309/311 (M+H).sup.+; Rt 0.88 min.
[1064] Similarly, N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxamide can be obtained from 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (WO 18/077565) and (3-chloropyrazin-2-yl)methanamine hydrochloride. LCMS (method 1): 374/376 (M+H).sup.+; Rt 0.93 min.
[1065] Similarly, N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxamide can be obtained from 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (WO 18/077565) and (3-chloropyrazin-2-yl)methanamine hydrochloride. LCMS (method 1): 376/378 (M+H).sup.+; Rt 0.97 min.
[1066] Similarly, N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxamide can be obtained from 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid (see below, Example H11 step 2) and (3-chloropyrazin-2-yl)methanamine hydrochloride. LCMS (method 1): 402/404 (M+H).sup.+; Rt 1.01 min.
Step B: Preparation of 8-chloro-3-(6-chloro-3-ethylsulfanyl-2-pyridyl)imidazo[1,5-a]pyrazine
[1067] ##STR00046##
[1068] To a solution of 6-chloro-N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide (1.95 g, 5.69 mmol) in toluene (19.5 mL) was added phosphorus oxychloride (3.18 mL, 34.14 mmol) and the mixture was stirred at 100° C. overnight. More phosphorus oxychloride (1.0 mL) was added and heating continued at 100° C. for another 1.5 hour. The reaction mixture was diluted with ethyl acetate and added slowly to a cold aqueous saturated sodium carbonate solution. After stirring for one hour at room temperature, the mixture was filtered over Hyflo, the layers separated, the aqueous phase extracted twice with ethyl acetate, the combined organic layers washed with aqueous saturated sodium carbonate, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (0-80% ethyl acetate gradient in cyclohexane) to afford 8-chloro-3-(6-chloro-3-ethylsulfanyl-2-pyridyl)imidazo[1,5-a]pyrazine as a solid. LCMS (method 1): 325/327 (M+H).sup.+, Rt 1.11 min.
[1069] Similarly, 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-chloro-imidazo[1,5-a]pyrazine (solid, mp 152-155° C.) can be obtained from 5-bromo-N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide. LCMS (method 1): 369/371/373 (M+H).sup.+; Rt 1.13 min.
[1070] Similarly, 8-chloro-3-(3-ethylsulfanyl-2-pyridyl)imidazo[1,5-a]pyrazine (solid, mp 126-128° C.) can be obtained from N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-pyridine-2-carboxamide. LCMS (method 1): 291/293 (M+H).sup.+; Rt 0.97 min.
[1071] Similarly, 1-[6-(8-chloroimidazo[1,5-a]pyrazin-3-yl)-5-ethylsulfanyl-3-pyridyl]cyclopropanecarbonitrile can be obtained from N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxamide. LCMS (method 1): 356/358 (M+H).sup.+; Rt 1.03 min.
[1072] Similarly, 2-[6-(8-chloroimidazo[1,5-a]pyrazin-3-yl)-5-ethylsulfanyl-3-pyridyl]-2-methyl-propanenitrile can be obtained from N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxamide. LCMS (method 1): 358/360 (M+H).sup.+; Rt 1.06 min.
[1073] Similarly, 8-chloro-3-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]imidazo[1,5-a]pyrazine can be obtained from N-[(3-chloropyrazin-2-yl)methyl]-3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxamide. LCMS (method 1): 384/386 (M+H).sup.+; Rt 1.10 min.
Step C: Preparation of 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy) imidazo[1,5-a]pyrazine (Compound P1)
[1074] ##STR00047##
[1075] To a solution of 2,2,3,3,3-pentafluoropropan-1-ol (763 mg, 0.507 mL, 5.04 mmol) in tetrahydrofuran (9.7 mL) at 10° C. under argon was added sodium hydride (194 mg, 60 mass % in oil, 4.84 mmol) in portions and the mixture stirred at 10° C. for 5 minutes. To this resulting mixture was added at 10° C. a solution of 8-chloro-3-(6-chloro-3-ethylsulfanyl-2-pyridyl)imidazo[1,5-a]pyrazine (1.26 g, 3.87 mmol) in tetrahydrofuran (19.4 mL) dropwise and stirring continued at 10° C. for 5 minutes, then at room temperature for 21 hours. The reaction mixture was quenched with an aqueous saturated sodium bicarbonate solution, the product extracted twice with ethyl acetate, the combined organic layers dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P1) as a gum. This material was used without further purification step. LCMS (method 1): 439/441 (M+H).sup.+, Rt 1.11 min.
[1076] Compounds P3, P5, P7, P20, P23 and P24 as shown in table P below were prepared following an analoguous sequence as described in example H1.
Example H2: Preparation of 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy) imidazo[1,5-a]pyrazine (Compound P2)
[1077] ##STR00048##
[1078] To a solution of 3-(6-chloro-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (1.99 g, 4.54 mmol) in ethyl acetate (19.9 mL) at 10° C. was added meta-chloroperoxybenzoic acid (2.40 g, 75 mass %, 10.4 mmol) in portions, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with an aqueous ˜10% sodium bisulfite solution and stirred for 10 minutes. An aqueous saturated sodium carbonate solution was added, the product extracted twice with ethyl acetate, the combined organic layers dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (0-30% ethyl acetate gradient in cyclohexane) to afford 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-penta-fluoropropoxy)imidazo[1,5-a]pyrazine (compound P2) as a solid, mp 140-143° C. LCMS (method 1): 471/473 (M+H).sup.+, Rt 1.14 min.
[1079] Compounds P4, P6, P8, P15, P16, P19 and P21 as shown in table P below were prepared following an analoguous sequence as described in example H2.
Example H3: Preparation of 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-3-methyl-urea (Compound P9)
[1080] ##STR00049##
[1081] To a solution of 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (150 mg, 0.3186 mmol) in 1,4-dioxane (4.8 mL) were added cesium carbonate (130 mg, 0.398 mmol), methylurea (28 mg, 0.382 mmol) and Xantphos (15 mg, 0.0255 mmol). The mixture was flushed with argon for 5 minutes, tris(dibenzylideneacetone)dipalladium(0) Pd.sub.2(dba).sub.3 (12 mg, 0.0127 mmol) was added, and the mixture heated at 80° C. for 60 minutes. After dilution with dioxane (20 mL), the mixture was clear filtered through a glass microfiber filter and the filtrate concentrated in vacuo. The residue was purified by combiflash (0-100% ethyl acetate gradient in cyclohexane) to afford 1-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-3-methyl-urea (compound P9) as a solid, mp 280-282° C. LCMS (method 2): 509 (M+H).sup.+, Rt 1.51 min.
[1082] Compound P14 as shown in table P below was prepared following an analoguous sequence as described in example H3.
Example H4: Preparation of 3-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (Compound P12)
[1083] ##STR00050##
[1084] A solution of 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (160 mg, 0.3398 mmol) and 1H-1,2,4-triazole (35 mg, 0.5098 mmol) in pyridine (2.7 mL) was flushed with argon for 5 minutes, the vial was capped and the reaction mixture heated at 120° C. for 100 minutes in the microwave. The reaction mixture was concentrated under reduced pressure and the residue purified by combiflash (0-80% ethyl acetate gradient in cyclohexane) to afford 3-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P12) as a solid, mp 207-208° C. LCMS (method 1): 504 (M+H).sup.+, Rt 1.06 min.
Example H5: Preparation of N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide (Compound P13)
[1085] ##STR00051##
Step A: Preparation of N-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide
[1086] ##STR00052##
[1087] To a solution of 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (391.3 mg, 0.8098 mmol) in 1,4-dioxane (2.35 mL) were added cesium carbonate (369.4 mg, 1.134 mmol), N-methylacetamide (179.4 mg, 0.187 mL, 2.429 mmol) and Xantphos (65.6 mg, 0.1134 mmol). The mixture was flushed with argon for 5 minutes, tris(dibenzylideneacetone) dipalladium(0) Pd.sub.2(dba).sub.3 (7 mg, 0.008 mmol) was added, the vial was capped and the reaction mixture heated at 160° C. for 1 hour in the microwave. After dilution with an aqueous sodium bicarbonate solution, the product was extracted twice with ethyl acetate, the combined organic layers were washed with aqueous saturated sodium bicarbonate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to afford N-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoro-propoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide as a gum. This material was used without further purification step. LCMS (method 1): 476 (M+H).sup.+, Rt 1.09 min.
Step B: Preparation of N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide (Compound P13)
[1088] ##STR00053##
[1089] To a solution of N-[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide (1.172 mmol) in ethyl acetate (5.6 mL) at 10° C. was added meta-chloroperoxybenzoic acid (620.4 mg, 75 mass %, 2.696 mmol) in portions, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with an aqueous ˜10% sodium bisulfite solution and stirred for 10 minutes. An aqueous saturated sodium carbonate solution was added, the product extracted twice with ethyl acetate, the combined organic layers dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (20-100% ethyl acetate gradient in cyclohexane) to afford N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy) imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]-N-methyl-acetamide (compound P13) as a solid, mp 169-173° C.
[1090] LCMS (method 1): 508 (M+H).sup.+, Rt 1.01 min.
[1091] Similarly, N-[5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-2-pyridyl]-N-methyl-acetamide (compound P11) (solid, mp 100-102° C.) can be obtained from 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P2) following an analoguous procedure as described in example H5, step A. LCMS (method 1): 508 (M+H).sup.+; Rt 1.03 min.
Example H6: Preparation of 5-ethylsulfonyl-N-methyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]pyridin-2-amine (Compound P10)
[1092] ##STR00054##
[1093] To a solution of 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (200 mg, 0.4248 mmol) in tetrahydrofuran (4.3 mL) was added an aqueous methylamine solution (41%, 0.652 mL, 8.496 mmol), and the reaction mixture was heated in the microwave at 120° C. for 20 minutes. The clear colorless solution was concentrated in vacuo, the residue dissolved in ethyl acetate, dried over sodium sulfate, filtered and concentrated to dryness under reduced pressure to afford 5-ethylsulfonyl-N-methyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]pyridin-2-amine (compound P10) as a white solid, mp 178-180° C. LCMS (method 1): 466 (M+H).sup.+, Rt 1.03 min.
Example H7: Preparation of [5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.SUP.6.-sulfane (Compound P18)
[1094] ##STR00055##
Step A: Preparation of [5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.SUP.6.-sulfane (Compound P17)
[1095] ##STR00056##
[1096] To a solution of 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (200 mg, 0.414 mmol) in 1,4-dioxane (5 mL) were added cesium carbonate (202 mg, 0.621 mmol), imino-dimethyl-oxo-A.sup.6-sulfane (46 mg, 0.497 mmol) and Xantphos (34 mg, 0.058 mmol). The mixture was flushed with argon for 5 minutes, tris(dibenzylideneacetone) dipalladium(0) Pd.sub.2(dba).sub.3 (4 mg, 0.004 mmol) was added, the vial was capped and the reaction mixture heated at 110° C. for 30 minutes in the microwave. The reaction mixture was filtered over HYFLO and the filtrate evaporated under reduced pressure. The residue was purified by Combiflash over silicagel (methanol gradient in ethyl acetate) to afford [5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P17) as a solid, mp 188-190° C. LCMS (method 1): 496 (M+H).sup.+, retention time 1.03 min.
Step B: Preparation of [5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.SUP.6.-sulfane (Compound P18)
[1097] ##STR00057##
[1098] To a solution of [5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (181 mg, 0.365 mmol) in dichloromethane (3.6 mL) at 0° C. was added meta-chloroperoxybenzoic acid (172 mg, 75 mass %, 0.749 mmol) in two portions over 15 minutes, and the mixture was stirred at room temperature overnight. The reaction mixture was diluted with t-butyl methyl ether, the organic layer washed three times with an aqueous ˜10% sodium bisulfite solution, then with an aqueous sodium hydrogen carbonate solution, water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate gradient in cyclohexane) to afford [5-ethylsulfonyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]imino-dimethyl-oxo-λ.sup.6-sulfane (compound P18) as a solid, mp 199-201° C. LCMS (method 1): 528 (M+H).sup.+, Rt 1.00 min.
Example H8: Preparation of 3-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (Compound P22)
[1099] ##STR00058##
[1100] To a solution of 3-(5-bromo-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (250 mg, 0.517 mmol) in toluene (1.6 mL) were added water (0.05 mL), cyclopropylboronic acid (133 mg, 1.552 mmol) and tripotassium phosphate (659 mg, 3.104 mmol). The mixture was flushed with argon for 5 minutes, tetrakis(triphenylphosphine)palladium(0) Pd(PPh.sub.3).sub.4 (60 mg, 0.052 mmol) was added, the vial was capped and the reaction mixture heated at 120° C. for 40 minutes in the microwave. The reaction mixture was diluted with ethyl acetate and water, the organic layer washed with water and brine, the combined organic phases dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by combiflash (ethyl acetate gradient in cyclohexane) to afford 3-(5-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (compound P22) as a solid, mp 94-96° C. LCMS (method 1): 445 (M+H).sup.+, Rt 1.27 min.
Example H9: Preparation of 3-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (Compound P25)
[1101] ##STR00059##
[1102] A solution of 3-(6-chloro-3-ethylsulfonyl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazine (120 mg, 0.255 mmol) in dimethylformamide (1.5 mL) was flushed with argon for 5 minutes, then tributyl(pyrimidin-2-yl)stannane (0.121 mL, 0.382 mmol) and bis(triphenylphosphine)palladium(II) dichloride Pd(PPh.sub.3).sub.2Cl.sub.2 (18 mg, 0.025 mmol) were added. The vial was capped and the reaction mixture heated at 170° C. for 40 minutes in the microwave. The mixture was quenched with n-hexane, stirred for 10 minutes, decanted and the n-hexane layer carefully discarded (procedure repeated three times). The oily residue was dissolved in ethyl acetate, the solution filtered over a glass microfiber filter and the filtrate concentrated under reduced pressure. The crude product was purified by combiflash (ethyl acetate gradient in cyclohexane) to afford 3-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-8-(2,2,3,3,3-pentafluoropropoxy) imidazo[1,5-a]pyrazine (compound P25) as a white solid, mp 164-166° C. LCMS (method 1): 515 (M+H).sup.+, Rt 1.05 min.
Example H10: Preparation of 2-[[5-(ethylsulfonimidoyl)-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (Compound P52)
[1103] ##STR00060##
Step 1: Preparation of methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate
[1104] ##STR00061##
[1105] To a solution of methyl 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylate (prepared as described in WO 2016/026848) (10.0 g, 36.21 mmol) in acetonitrile (72 ml) were added cesium carbonate (25.96 g, 79.67 mmol) and (E)-benzaldehyde oxime (5.7 g, 47.08 mmol), and the suspension was heated to 80° C. overnight. The solvent was evaporated in vacuo and the residue dissolved with ethyl acetate and water. The separated aqueous layer was acidified with 1M aqueous hydrochloric acid and extracted with ethyl acetate (3×) and once with dichloromethane. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel (gradient 0-10% methanol in dichloromethane) to afford methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate. LCMS (method 1): m/z 214 [M+H].sup.+; retention time: 0.68 min.
Step 2: Preparation of methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate
[1106] ##STR00062##
[1107] To a solution of methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate (2.5 g, 11.72 mmol) in acetonitrile (59 ml) were added cesium carbonate (5.7 g, 17.49 mmol), and 2-bromo-2-methyl-propanamide (3.1 g, 18.67 mmol) after 5 minutes. The reaction mixture was stirred at room temperature overnight, poured into water and ethyl acetate. The separated aqueous layer was extracted with ethyl acetate (3×), the combined organic layers dried over sodium sulfate, filtered and evaporated to afford crude methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate. This material was used without further purification into the next step. LCMS (method 1): m/z 299 [M+H].sup.+; retention time: 0.71 min.
Step 3: Preparation of methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate
[1108] ##STR00063##
[1109] To a mixture of crude methyl 5-(2-amino-1,1-dimethyl-2-oxo-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (4.18 g, 14.0 mmol) and triethylamine (5.73 g, 7.89 ml, 56.0 mmol) in dichloromethane (140 ml) at 0° C. was added trifluoroacetic anhydride (8.92 g, 5.90 ml, 42.0 mmol) dropwise. The resulting suspension was stirred at room temperature for two hours. The reaction mixture was carefully quenched with methanol, then with an aqueous sodium hydrogen carbonate solution. The aqueous layer was extracted twice with dichloromethane, the combined organic layers dried over sodium sulfate, filtered and evaporated. The residue was purified by combiflash (0-45% gradient ethyl acetate in cyclohexane) to afford methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate. LCMS (method 1): m/z 281 [M+H].sup.+; retention time: 0.90 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 1.43 (t, J=7.40 Hz, 3H), 1.80 (s, 6H), 2.95 (q, J=7.40 Hz, 2H), 3.99 (s, 3H), 7.58 (d, J=2.32 Hz, 1H), 8.22 (d, J=2.32 Hz, 1H).
Step 4: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid
[1110] ##STR00064##
[1111] To a solution of methyl 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylate (6.0 g, 21.41 mmol) in tetrahydrofuran (60 ml) were added lithium hydroxide hydrate (1.8 g, 42.81 mmol) and water (10 ml). The reaction mixture was stirred at room temperature until complete (TLC monitoring), then concentrated under reduced pressure. The residue was diluted with water (100 ml), acidified with a 2N aqueous hydrochloric acid solution and the aqueous phase extracted with ethyl acetate (3×100 ml). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo.
[1112] The crude product was washed twice with n-pentane (50 ml), filtered and evaporated to dryness to give 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid as a solid. LCMS (method 3): m/z 267 [M+H].sup.+ and m/z 265 [M−H].sup.−; retention time: 0.82 min. .sup.1H NMR (400 MHz, DMSO-de) 5 ppm 1.27 (t, J=7.21 Hz, 3H), 1.78 (s, 6H), 2.97 (q, J=7.21 Hz, 2H), 7.58 (d, J=2.32 Hz, 1H), 8.24 (d, J=2.32 Hz, 1H).
Step 5: Preparation of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride
[1113] ##STR00065##
[1114] To a solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxylic acid (771 mg, 2.90 mmol) and N,N-dimethylformamide (one drop) in tetrahydrofuran (19 ml) at 0-5° C. was added oxalyl chloride (0.328 ml, 3.76 mmol) and the mixture was stirred at room temperature for 2 hours. The solution was concentrated under reduced pressure, diluted twice with tetrahydrofuran and evaporated to dryness. LCMS data of an aliquot quenched with dimethylamine consistent with 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-N,N-dimethyl-pyridine-2-carboxamide (C.sub.14H.sub.19N.sub.3O.sub.2S, 293.38): LCMS (method 1): m/z 294 [M+H].sup.+; retention time: 0.83 min.
Step 6: Preparation of N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide
[1115] ##STR00066##
[1116] To a solution of (3-chloropyrazin-2-yl)methanamine hydrochloride (0.548 g, 3.05 mmol; CAS 939412-86-9) in tetrahydrofuran (12 mL) were added at room temperature 4-(dimethylamino)pyridine (3.5 mg, 0.029 mmol) and triethylamine (1.01 mL, 7.25 mmol) dropwise. A solution of 5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carbonyl chloride (0.826 g, 2.90 mmol) in tetrahydrofuran (12 mL) was further added dropwise and under cooling. The reaction mixture was stirred at room temperature for 1 hour. It was then slowly diluted with sodium bicarbonate sat. aq. and extracted twice with ethyl acetate. The combined organic layers were washed with sodium bicarbonate sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product (0.469 g). LCMS (method 1): m/z 392/394 [M+H].sup.+; retention time: 1.01 min.
Step 7: Preparation of 2-[[6-(8-chloroimidazo[1,5-a]pyrazin-3-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile
[1117] ##STR00067##
[1118] To a solution of N-[(3-chloropyrazin-2-yl)methyl]-5-(1-cyano-1-methyl-ethoxy)-3-ethylsulfanyl-pyridine-2-carboxamide (prepared as described above; 0.454 g, 1.15 mmol) in toluene (4.5 mL) was added phosphorus(V) oxychloride (0.648 mL, 6.95 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirred overnight. After cooling to room temperature, it was diluted with ethyl acetate, and slowly added to cold sodium hydroxide sat. aq. and stirred for 1 hour. The reaction mixture was then extracted twice with ethyl acetate, the combined organic layers washed with sodium hydroxide sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product (0.350 g). LCMS (method 1): m/z 374/376 [M+H].sup.+; retention time: 1.11 min.
Step 8: Preparation of 2-[[5-ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (Compound P50)
[1119] ##STR00068##
[1120] To a solution of 2-[[6-(8-chloroimidazo[1,5-a]pyrazin-3-yl)-5-ethylsulfanyl-3-pyridyl]oxy]-2-methyl-propanenitrile (prepared as described above; 0.336 g, 0.899 mmol) in acetonitrile (4 mL) were added 2,2,3,3,3-pentafluoro-1-propanol (0.109 mL, 1.08 mmol) and potassium carbonate (0.149 g, 1.08 mmol) at room temperature. The reaction mixture was heated to 50° C. and stirred for one day. To reach full conversion, additional 2,2,3,3,3-pentafluoro-1-propanol (0.080 mL, 0.79 mmol) and potassium carbonate (0.100 g, 0.72 mmol) were added and stirring continued at 50° C. for 2 more days. After cooling to room temperature, the reaction mixture was filtered, the solvent removed under reduced pressure and the residue diluted with ethyl acetate. The organic layer was washed twice with sodium bicarbonate sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product as a white solid (0.389 g). LCMS (method 1): m/z 488 [M+H].sup.+; retention time: 1.25 min.
Step 9: Preparation of 2-[[5-(ethylsulfonimidoyl)-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (Title Compound P52)
[1121] ##STR00069##
[1122] 2-[[5-Ethylsulfanyl-6-[8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyrazin-3-yl]-3-pyridyl]oxy]-2-methyl-propanenitrile (compound P50 prepared as described above; 77 mg, 0.16 mmol), (diacetoxyiodo)benzene (0.13 g, 0.39 mmol) and ammonium carbamate (25 mg, 0.32 mmol) were charged into a flask equipped with a magnetic stirrer. To this mixture was added methanol (1.15 mL) dropwise at room temperature, and the reaction mass then stirred at room temperature for 2.5 hours. After addition of Isolute, the volatiles were removed under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product as a white solid (45 mg), mp 121-123° C. LCMS (method 1): m/z 519 [M+H].sup.+; retention time: 1.06 min.
Example H11: Preparation of 3-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (Compound P32)
[1123] ##STR00070##
Step 1: Preparation of methyl 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylate
[1124] ##STR00071##
[1125] A mixture of methyl 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylate (prepared as described above; 2.00 g, 9.4 mmol), potassium carbonate (2.6 g, 19 mmol), 2-iodopyridine (1.5 mL, 14.0 mmol), and copper iodide (0.187 g, 0.94 mmol) in N,N-dimethylformamide (20 mL) was stirred at 110° C. for 6 hours. The reaction mixture was neutralized with aqueous 2M hydrochloric acid (50 mL), diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford methyl 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylate. This material was used without further purification into the next step. LCMS (method 4): m/z 291 [M+H].sup.+; retention time: 1.37 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ/ppm: 1.38 (t, 3H), 2.87 (q, 2H), 3.98 (s, 3H), 7.03 (d, 1H), 7.10 (m, 1H), 7.52 (d, J=2.3 Hz, 1H), 7.77 (m, 1H), 8.16 (m, 1H), 8.29 (d, 0=2.3 Hz, 1H).
Step 2: Preparation of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid
[1126] ##STR00072##
[1127] To a solution of methyl 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylate (prepared as described above; 0.900 g, 3.10 mmol) in tetrahydrofuran (10 mL) were added lithium hydroxide monohydrate (0.0951 g, 4.65 mmol) and water (2 mL). The reaction mixture was stirred at room temperature for 2 hours, then acidified with aqueous 2M hydrochloric acid (25 mL) and extracted with ethyl acetate (3×25 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid as a solid. LCMS (method 4): m/z 277 [M+H].sup.+; retention time: 1.26 min.
Step 3: Preparation of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carbonyl chloride
[1128] ##STR00073##
[1129] To a solution of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid (prepared as described above; 0.50 g, 1.8 mmol) in tetrahydrofuran (10 mL) were added under argon one drop of N,N-dimethylformamide and oxalyl chloride (0.21 mL, 2.4 mmol) dropwise. The reaction mixture was stirred at room temperature for 2 hours, then concentrated under reduced pressure to afford quantitatively the desired product as an oil. This material was used without further purification into the next step.
Step 4: Preparation of 3-(2,2,3,3,3-pentafluoropropoxy)pyridine-2-carbonitrile
[1130] ##STR00074##
[1131] To a solution of 2-cyano-3-fluoropyridine (10.0 g, 77.8 mmol; CAS 97509-75-6) in acetonitrile (120 mL) were added 2,2,3,3,3-pentafluoro-1-propanol (9.40 mL, 93.4 mmol) and potassium carbonate (12.9 g, 93.4 mmol) at room temperature. The reaction mixture was heated to 50° C. and stirred for 5 hours. After cooling to room temperature, the reaction mixture was filtered, the solvent removed under reduced pressure and the residue diluted with ethyl acetate. The organic layer was washed twice with sodium bicarbonate sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford the desired product as a white solid (19.5 g). This material was used without further purification into the next step. LCMS (method 1): m/z 253 [M+H].sup.+; retention time: 0.91 min. .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm: 4.63 (m, 2H), 7.42 (m, 1H), 7.56 (m, 1H) 8.45 (m, 1H).
Step 5: Preparation of [3-(2,2,3,3,3-pentafluoropropoxy)-2-pyridyl]methanamine hydrochloride
[1132] ##STR00075##
[1133] To a solution of 3-(2,2,3,3,3-pentafluoropropoxy)pyridine-2-carbonitrile (prepared as described above; 19.5 g, 77.3 mmol) in methanol (195 mL) under argon was added palladium (activated, 10% on charcoal, 2.47 g) and the reaction mixture stirred under a hydrogen atmosphere for two days. The mixture was filtered through Celite and the filtrate concentrated under reduced pressure. The resulting oil was diluted with diethyl ether, hydrochloric acid (4N in dioxane, 23.2 mL, 92.8 mmol) was added under cooling and the suspension stirred for 15 minutes. The precipitate was filtered, washed with diethyl ether and dried under reduced pressure to afford the desired product as a white solid (19.15 g). This material was used without further purification into the next step. LCMS (method 1): m/z 257 [M+H].sup.+; retention time: 0.51 min of the free base.
Step 6: Preparation of 3-ethylsulfanyl-N-[[3-(2,2,3,3,3-pentafluoropropoxy)-2-pyridyl]methyl]-5-(2-pyridyloxy)pyridine-2-carboxamide
[1134] ##STR00076##
[1135] To a solution of [3-(2,2,3,3,3-pentafluoropropoxy)-2-pyridyl]methanamine hydrochloride (prepared as described above in step 5; 0.53 g, 1.8 mmol) in tetrahydrofuran (7.3 mL) were added at room temperature 4-(dimethylamino)pyridine (2.2 mg, 0.018 mmol) and triethylamine (0.88 mL, 6.3 mmol) dropwise. A solution of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carbonyl chloride (prepared as described above in step 3; 0.53 g, 1.8 mmol) in tetrahydrofuran (7.3 mL) was further added dropwise and under cooling. The reaction mixture was stirred at room temperature for 2 hours, slowly diluted with sodium bicarbonate sat. aq. and extracted twice with ethyl acetate. The combined organic layers were washed with sodium bicarbonate sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product (0.25 g). LCMS (method 1): m/z 515 [M+H].sup.+; retention time: 1.13 min.
Step 7: Preparation of 3-[3-ethylsulfanyl-5-(2-pyridyloxy)-2-pyridyl]-8-(2,2,3,3,3-pentafluoropropoxy)imidazo[1,5-a]pyridine (Title Compound P32)
[1136] ##STR00077##
[1137] To a solution of 3-ethylsulfanyl-N-[[3-(2,2,3,3,3-pentafluoropropoxy)-2-pyridyl]methyl]-5-(2-pyridyloxy)pyridine-2-carboxamide (prepared as described above; 0.23 g, 0.45 mmol) in toluene (2.3 mL) was added phosphorus(V) oxychloride (0.42 mL, 4.5 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirred for 18 hours. After cooling to room temperature, it was diluted with ethyl acetate and sodium hydroxide sat. aq. was added slowly at 10° C. The reaction mixture was then extracted twice with ethyl acetate, the combined organic layers washed with sodium hydroxide sat. aq., dried over magnesium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography over silica gel (gradient ethyl acetate in cyclohexane) afforded the desired product (0.15 g) as a solid. LCMS (method 1): m/z 497 [M+H].sup.+; retention time: 1.19 min.
TABLE-US-00013 TABLE P Examples of compounds of formula (I) LCMS R.sub.t [M + H].sup.+ Mp No. IUPAC name Structures (min) (measured) Method (° C.) P1 3-(6-chloro-3-ethylsulfanyl- 2-pyridyl)-8-(2,2,3,3,3- pentafluoropropoxy)imi- dazo[1,5-a]pyrazine
[1138] 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.
[1139] 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-93, AA-1 to AA-81, AB-1 to AB-93 and AC-1 to AC-81, and Tables B-1 to B-66, BB-1 to BB-54, BC-1 to BC-66 and BD-1 to BD-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 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, bromocyclen (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 0-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (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 nobrave (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 0-(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, Myrothedum 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 ametoctradin [865318-97-4]+TX, amisulbrom [348635-87-0]+TX, azaconazole (60207-31-0]+TX, benzovindiflupyr [1072957-71-1]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, coumoxystrobin [850881-70-8]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX, enoxastrobin [238410-11-2]+TX, epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fenpyrazamine [473798-59-3]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, fluxapyroxad [907204-31-3]+TX, fluopyram [658066-35-4]+TX, fenaminstrobin [366815-39-6]+TX, isofetamid [875915-78-9]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, ipfentrifluconazole [1417782-08-1]+TX, isotianil [224049-04-1]+TX, mandestrobin [173662-97-0] (can be prepared according to the procedures described in WO 2010/093059)+TX, mefentrifluconazole [1417782-03-6]+TX, metconazole [125116-23-6]+TX, myclobutanil [88671-89-0]+TX, paclobutrazol [76738-62-0]+TX, pefurazoate [101903-30-4]+TX, penflufen [494793-67-8]+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, metalaxyl [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, flutianil [958647-10-4]+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, pyraoxystrobin [862588-11-2]+TX, fluoxapiprolin [1360819-11-9]+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, acibenzolar-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]+IK, 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, picarbutrazox [500207-04-5]+TX, polyoxins [11113-80-7]+TX, probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid [189278-12-4]+TX, pydiflumetofen [1228284-64-7]+TX, pyrametostrobin [915410-70-7]+TX, pyroquilon [57369-32-1]+TX, pyriofenone [688046-61-9]+TX, pyribencarb [799247-52-2]+TX, pyrisoxazole [847749-37-5]+TX, quinoxyfen [124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX, Timorex Gold™ (plant extract containing tea tree oil from the Stockton Group)+TX, tebufloquin [376645-78-2]+TX, tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tolprocarb [911499-62-2]+TX, triclopyricarb [902760-40-1]+TX, tricyclazole [41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX, valifenalate [283159-90-0]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, phenamacril+TX, sedaxane [874967-67-6]+TX, trinexapac-ethyl [95266-40-3]+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,11H-naphtho[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, Acremoriium alternatum+TX+TX, Acremoriium cephalosporium+TX+TX, Acremoriium diospyri+TX, Acremoriium obclavatum+TX, Adoxophyes orarta granulovirus (AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84 (Galltrol-A®)+TX, Aiternana alternate+TX, Alternaria cassia+TX, Aiternana 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 I-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 Cry1 Ab+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 (VertikiI®)+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, Myrothedum 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, Periicilium billai (Jumpstart®+TX, TagTeam®)+TX, Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicillium griseofulvum+TX, Penicillium purpurogertum+TX, Penicillium spp.+TX, Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX, phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthora cryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomaia+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, Pseudomonas 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 HC®+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, Trichothedum 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 pepermint thyme and cinnamon extracts (EF 300®)+TX, mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixture of clove pepermint 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 nobrave (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,
[1140] or a biologically active compound selected from Quinofumelin+TX, mefentrifluconazol+TX, fenpicoxamid+TX, fluindapyr+TX, inpyrfluxam+TX or indiflumetpyr+TX, isoflucypram+TX, pyrapropoyne+TX, florylpicoxamid+TX, metyltetraprole+TX, ipflufenoquin+TX, pyridachlometyl+TX or chlopyridiflu+TX, tetrachlorantraniliprole+TX, tetrachloraniliprole+TX, Tyclopyrazoflor+TX, flupyrimin+TX or pyrifluramide+TX, benzpyrimoxan+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, dimpropyridaz+TX, tetflupyrolimet+TX, beflubutamid-M+TX, isocycloseram+TX, Flupyradifurone+TX, tetflupyrolimet+TX, N-[(1,2 cis)-2-[2-fluoro-4-(trifluoromethyl)phenyl]cyclobutyl]-3-(trifluoromethyl)pyrazine-2-carboxamide+TX, 2-(trifluoromethyl)-N-[(2,3 cis)-2-(2,4,6-trifluorophenyl)oxetan-3-yl]benzamide+TX, 2,6-difluoro-N-[(2,3 cis)-2-(2,4,6-trifluorophenyl)oxetan-3-yl]benzamide+TX, N-[(1,2 cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide+TX, N-[(1,2 cis)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide+TX, N-[(1,2 cis)-2-(2,4-difluorophenyl)cyclobutyl]-2-(trifluoromethyl)benzamide+TX, N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2010/130767)+TX, 2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone (can be prepared according to the procedures described in WO 2011/138281)+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (can be prepared according to the procedures described in WO 2012/031061)+TX, 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2012/084812)+TX, CAS 850881-30-0+TX, 3-(3,4-dichloro-1,2-thiazol-5-ylmethoxy)-1,2-benzothiazole 1,1-dioxide (can be prepared according to the procedures described in WO 2007/129454)+TX, 2-[2-[(2,5-dimethylphenoxy)methyl]phenyl]-2-methoxy-N-methyl-acetamide+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone (can be prepared according to the procedures described in WO 2005/070917)+TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol (can be prepared according to the procedures described in WO 2011/081174)+TX, 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (can be prepared according to the procedures described in WO 2011/081174)+TX, oxathiapiprolin+TX [1003318-67-9], tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX, N-[2-(3,4-difluorophenyl)phenyl]-3-(trifluoromethyl)pyrazine-2-carboxamide (can be prepared according to the procedures described in WO 2007/072999)+TX, 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2014/013842)+TX, 2,2,2-trifluoroethyl N-[2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate+TX, (2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol+TX, (2RS)-2-[4-(4-chlorophenoxy)-α,α,α-trifluoro-o-tolyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol+TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (can be prepared according to the procedures described in WO 2007/031513)+TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate (can be prepared according to the procedures described in WO 2012/025557)+TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (can be prepared according to the procedures described in WO 2010/000841)+TX, 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl]-4H-1,2,4-triazole-3-thione (can be prepared according to the procedures described in WO 2010/146031)+TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate+TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (can be prepared according to the procedures described in WO 2005/121104)+TX, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (can be prepared according to the procedures described in WO 2013/024082)+TX, 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine (can be prepared according to the procedures described in WO 2012/020774)+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile (can be prepared according to the procedures described in WO 2012/020774)+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2011/162397)+TX, 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide (can be prepared according to the procedures described in WO 2012/084812)+TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (can be prepared according to the procedures described in WO 2013/162072)+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one (can be prepared according to the procedures described in WO 2014/051165)+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX, (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate+TX, N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxamide [1255734-28-1] (can be prepared according to the procedures described in WO 2010/130767)+TX, 3-(difluoromethyl)-N-[(R)-2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl]-1-methylpyrazole-4-carboxamide [1352994-67-2]+TX, N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX, N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX, N′-[4-(4,5-dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX,
##STR00131##
(fenpicoxamid [517875-34-2] (as described in WO 2003/035617))+TX, (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-{[3-(acetyloxy)-4-methoxy-2-pyridyl]carbonyl}-L-alaninate [1961312-55-9]+TX; (as described in WO 2016/122802)+TX, 2-(difluoromethyl)-N-(1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, and spiropidion [1229023-00-0]+TX; and 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide+TX, wherein each of these carboxamide compounds can be prepared according to the procedures described in WO 2014/095675 and/or WO 2016/139189.
[1141] 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.
[1142] 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.
[1143] The active ingredient mixture of the compounds of formula I selected from Tables A-1 to A-93, AA-1 to AA-81, AB-1 to AB-93 and AC-1 to AC-81, and Tables B-1 to B-66, BB-1 to BB-54, BC-1 to BC-66 and BD-1 to BD-54 and Table P with active ingredients described above comprises a compound selected from Tables A-1 to A-93, AA-1 to AA-81, AB-1 to AB-93 and AC-1 to AC-81, and Tables B-1 to B-66, BB-1 to BB-54, BC-1 to BC-66 and BD-1 to BD-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.
[1144] 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.
[1145] The mixtures comprising a compound of formula I selected from Tables A-1 to A-93, AA-1 to AA-81, AB-1 to AB-93 and AC-1 to AC-81, and Tables B-1 to B-66, BB-1 to BB-54, BC-1 to BC-66 and BD-1 to BD-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-93, AA-1 to AA-81, AB-1 to AB-93 and AC-1 to AC-81, and Tables B-1 to B-66, BB-1 to BB-54, BC-1 to BC-66 and BD-1 to BD-54 Table P and the active ingredients as described above is not essential for working the present invention.
[1146] 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.
[1147] 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.
[1148] 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.
[1149] 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.
[1150] 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.
[1151] 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.
[1152] 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).
[1153] 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
[1154] 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, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.
Example B1: Activity Against Diabrotica balteata (Corn Root Worm)
[1155] 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.
[1156] 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: P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P25, P27, P28, P31, P33, P35, P36, P37, P38, P40, P42, P43, P47, P49, P50, P51, P52, P53.
Example B2: Activity Against Euschistus heros (Neotropical Brown Stink Bug)
[1157] 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.
[1158] 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: P8, P10, P11, P12, P13, P15, P17, P18, P19, P21, P25, P28, P35, P36, P39, P45, P47, P50, P51.
Example B3: Activity Against Plutella xylostella (Diamond Back Moth)
[1159] 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.
[1160] 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: P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P25, P26, P27, P28, P30, P31, P33, P35, P36, P37, P38, P39, P40, P41, P42, P43, P45, P46, P47, P49, P50, P51, P52, P53.
Example B4: Activity Against Myzus persicae (Green Peach Aphid) Feeding/Contact Activity
[1161] 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.
[1162] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P4, P5, P6, P7, P8, P10, P11, P12, P13, P14, P15, P16, P18, P19, P21, P25, P28, P31, P36, P37, P39, P40, P45, P47, P51, P52.
Example B5: Activity Against Spodoptera littoralis (Egyptian Cotton Leaf Worm)
[1163] 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.
[1164] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P4, P5, P6, P8, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P25, P28, P30, P31, P33, P35, P38, P50, P51, P52.
Example B6: Activity Against Bemisia tabaci (Cotton White Fly)
[1165] 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.
[1166] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P12, P27, P51, P52.
Example B7: Activity Against Frankliniella occidentalis (Western Flower Thrips)
[1167] 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.
[1168] The following compounds resulted in at least 80% mortality at an application rate of 200 ppm: P11, P17, P18, P51.
Example B8: Activity Against Myzus persicae (Green Peach Aphid) Systemic Activity
[1169] 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.
[1170] The following compounds resulted in at least 80% mortality at a test rate of 24 ppm: P13.