Patent EA-000645-B1 (EA)
Title: Pesticidal sulfur compounds
Inventor: LOWDER PATRICK DOYLE
IPC: C12N5/00
Filed: 1996-05-31
Abstract: 1. A compound of Formula (I) or Formula (II):   wherein: =X is =NR<3>, =O or an electron pair; R<1> is C1-C6 alkyl, C3-C6 cycloalkyl, or C4-C8 (cycloalkyl)alkyl, each of which is optionally substituted by one or more halogen; R<2> and R<3> are independently selected from hydrogen, C1-C6 alkyl; C1-C6 haloalkyl; COR<4>; S(O)PR<4>; cyano, nitro, COOR<4>; CONR<4>R<5>; -C(O)SR<4>; -C(S)OR<4>; -SO2NR<4>R<5>; -P(O)qR<4>R<5>; -P(O)q(OR<4>)R<5>; -P(O)q(OR<4>)(OR<5>); C=(NR<4>)NR<5>R<6>; CH=NR<4>; C=(NR<4>)(OR<5>); C(S)N(R<4>)(R<5>); C(O)C(O)R<4>; C(O)C(O)OR<4>; C(O)C(O)NR<4>R<5>; and CONR<4>SO2R<5>; p is 0, 1 or 2; q is 0 or l; R<4>, R<5> and R<6> are independently selected from hydrogen; nitro-, cyano-, CHO; R<14>; phenyl optionally substituted by one or more of R<14>, halogen, nitro-, cyano-, OR<14>, SR<14>, COR<14>, COOR<14>, or OR<14>; halogen; COR<14>; COOR<14>; CHO; and hydroxyl, Q is Q-1, Q-2 or Q-3 as designated below:   R<7> is hydrogen, cyano-, nitro-, C1-C4 alkyl, C1-C4 haloalkyl, halogen, CHO, or COR<20>; R<8> is hydrogen, halogen, cyano- S(O)pR<14>, OR<4>, NR<16>R<17>. N(R<16>)CON(R<17>)(R<18>), N3 or NH(C1-C5 alkyl) substituted by one or more hydroxyl, cyano-, nitro, OR<14>. S(O)pR<14>, COOR<14> or CON(R<16>)(R<17>); R<9> and R<11> are independently selected from hydrogen, halogen, OR<14>, SR<14> and R<14>; R<10> is cyano; R<12> is hydrogen, halogen, R<14>, OR<14>, S(O)pR<14> or   R<13> is hydrogen, halogen or R<14>; Ar is phenyl, optionally bearing one or more substituents selected from the group consisting of halogen, R<15>, OR<15>, SF5 and S(O)pR<15>; or Ar is 2-pyridyl, optionally bearing one or more substituents selected from the group consisting of halogen, R<15>, OR<15>, SF5 and S(O)pR<14>; R<14> and R<19> are independently selected from C1-C6 alkyl, C3-C6 cycloalkyl, and C4-C8 (cycloalkyl)alkyl, each of which is optionally substituted by one or more halogen; R<15> is C1-C6 alkyl, optionally substituted by one or more halogen; R<16>, R<17> and R<18> are independently selected from hydrogen, nitro-, cyano-, CHO, R<19>, COR<19>, and COOR<19>; R<20> is selected from C1-C6 alkyl, optionally substituted by one or more halogen. 2. A compound according to Claim 1 wherein R<1> is optionally halogenated C1-C6 alkyl, preferably methyl or ethyl. 3. A compound according to Claim 1 wherein R<2> is hydrogen, COOR<4>, S(O)pR<4> cyano-,CONR<4> R<5>, -COR<4>, P(O)q(OR<4>) OR<5>) or P(O)qR<4>R<5>. 4. A compound according to Claim 3 wherein R<2> is hydrogen, or cyano or COOR<4> (in which p is two and R<4> is C1-C6 alkyl or optionally substituted phenyl) 5. A compound according to Claim 3 wherein R<2> is S(O)pR<4> (in which p is two and R<4> is C1-C6 alkyl or optionally substituted phenyl). 6. A compound according to Claim 4 wherein R<2> is CONR<4>R<5> (in which R<4> is hydrogen or C1-C6, alkyl and R<5> is C1-C6 alkyl, or in which R<4> is hydrogen and R<5> is COR<14> in which R<14> is optionally halogenated C1-C6 alkyl. 7. A compound according to Claim 4 wherein R<2> is COR<4> (in which R<4> is hydrogen or C1-C6 alkyl); or R<2> is P(O)q(OR<4>)(OR<5>) or P(O)qR<4>R<5> (in which q is one and R<4> and R<5> are each C1-C6 alkyl). 8. A compound according to Claim 1 wherein Q is Q-1, more preferably wherein R<7> is cyano- or hydrogen. or C1-C4 alkyl and/or when R<8> is NR<16>R<17>. 9. A compound according to Claim 8 wherein R<8> is amino. 10. A compound according to Claim 1 wherein Ar is phenyl substituted in the 2 and 6 positions by halogen and in the 4 position by halogenated C1-C6 alkyl or SF5 or OR<15>, preferably when Ar is 2,6-dichloro-4-trifluoromethylphenyl; or Ar is 2-pyridyl substituted in the 3 position by halogen and in the 5 position by halogenated C1-C6 alkyl or SF5 or OR<15>, preferably when Ar is 3-chloro-5-trifluoromethylpyrid-2-yl. 11. The compound according to Claim 1, which is: S-((5-amino-3-cyano-1 -(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(tert-butoxycarbonyl)sulfilimme; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-acetylsulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(methoxycarbonyl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(methylsulfonyl)sulfilinune; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-ethyl-N-(methylcarbamoyl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-ethyl-N-(cyano)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-ethyl-N-(formyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-ttifIuoromethyl)phenyl]-4-(lH-pyrazolyl))-S-methyl-N-acetylsulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(diethylphosphoryl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifiuoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(dimethylcarbamoyl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-(dimethylphosphinyl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-((trichloroacetylamino)-carbonyl)-sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S-ethyl-N-((chloroacetylamino)carbonyl)sulfilimine; S-((5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl)phenyl.|-4-(1H-pyrazolyl)) -S-ethyl-N-(methylthiocarbamoyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl)) -S -ethyl-N-((ethoxycarbonylmethyl)aminocarbonyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-inethyl-N-(methylthiocarbamoyl)su]filimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyI]-4-(1H-pyrazolyl))-S-ethyl-N-(ethoxycarbonylaminocarbonyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-methyl-N-(fonyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-methyl-N-(cyano)sulfilimine; S-((5-amino-3-cyano-1 -(2,6-dichloro-4-trifluoromethyl)pbenyl]-4-(1H-pyrazolyl)) -S-methyl-N-(l,2-dioxopropyl)sulfilimine; S-((5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(lH-pyrazolyl))-S-methyl-N-(tert-butoxycarbonyl)sulfilimine; S-((5-amino-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-methyl-N-(formyl)sulfilimine; S-((5-amino- 1-(2.6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-methyl-N-(acetyl)sulfilimine; S-((5-amino-l-(2,6-dichloro-4-trifluoromethyl)phenyl]-4-(1H-pyrazolyl))-S-methyl-N-(cyano)sulfilimine; S-((5-amino-l-(2,6-dichloro-4-trifluoromethyl)phenyl-3-methyl]-4-(lH-pyrazolyl))-S-ethyl-N-(formyl)sulfilimine; S-((5-amino-l-(2,6-dichloro-4-trifluoromethyl)phenyl-3-methy]]-4-(lH-pyrazolyl)}-S-ethyl-N-(cyano)sulfilimine; N-(tert-butoxycarbonyl)-S-4-[5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenylpyrazolyl)-S-ethylsulfoximine; N-acetyl-S-4-[5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenylpyrazolyl)-S-ethylsulfoximine; S-4-(5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenylpyrazolyl)-S-ethyl sulfoximine; S-(5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl)phenyl-4-(lH-pyrazolyl))-S-methyl-N-((4-methylphenyl)sulfonylsulfilimine; S-4-(5-amino-3-cyano-l-(2-(3-chloro-5-trifluoromethyl)pyridyl)pyrazolyl)-S-ethylsulfoxide 12. Sulfur containing derivatives of heterocyclic compounds of formula (II)   R<1> is C1-C6 alkyl, C3-C6 cycloalkyl, or C4-C8 (cycloalkyl)alkyl, each of which is optionally substituted by one or more halogen; M is 1 or 2, Q is Q-1, Q-2 or Q-3 as designated below:   R<7> is hydrogen, cyano-, nitro-, C1-C4 alkyl, C1-C4 haloalkyl, halogen, CHO, or COR<20>; R<8> is hydrogen, halogen, cyano-, S(O)pR<14>, OR<4>, NR<16>R<17>, N(R<16>)CON(R<17>)(R<18>), N3 or NH(C1-C5 alkyl) substituted by one or more hydroxyl, cyano-, nitro, OR<14>, S(O)pR<14>, COOR<14> or CON(R<16>)(R<17>); R<9> and R<11> are independently selected from hydrogen, halogen, OR<14>, SR<14> and R<14>; R<10> is cyano; R<12> is hydrogen, halogen, R<14>, OR<14>, S(O)pR<14> or   R<13> is hydrogen, halogen or R<14>; Ar is phenyl, optionally bearing one or more substituents selected from the group consisting of halogen, R<15>, OR<15>, SF5 and S(O)pR<15>; or Ar is 2-pyridyl, optionally bearing one or more substituents selected from the group consisting of halogen, R<15>, OR<15>, SF5 and S(O)pR<14>; R<14> and R<19> are independently selected from C1-C6 alkyl, C1-C6 cycloalkyl, and C4-C8 (cycloalkyl)alkyl, each of which is optionally substituted by one or more halogen; R<15> is C1-C6 alkyl, optionally substituted by one or more halogen; R<16>, R<17> and R<18> are independently selected from hydrogen, nitro-, cyano-, CHO, R<19>, COR<19>, and COOR<19>; R<20> is selected from C1-C6 alkyl, optionally substituted by one or more halogen. Z is an anionic counter ion, such as Cl<->, Br<->, I<->, F<->, OSO2R<4->, C104<->, OCOR<4->, BF4<->, SbF6<->, SO3<-> or HSO4<->, a phosphate anion or a hydrogenophosphate anion or other agriculturally acceptable anion. 13. A compound according to Claim 12 wherein R<1> is optionally halogenated C1-C6 alkyl, preferably methyl or ethyl. 14. A compound according to Claim 12 wherein Q is Q-1, more preferably wherein R<7> is cyano- or hydrogen. or C1-C4 alkyl and/or when R<8> is NR<16>R<17>. 15. A compound according to Claim 14 wherein R<8> is amino-. 16. A compound according to Claim 1 wherein Ar is phenyl substituted in the 2 and 6 positions by halogen and in the 4 position by halogenated C1-C6 alkyl or SF5 or OR<15>, preferably when Ar is 2,6-dichloro-4-trifluoromethylphenyl; or Ar is 2-pyridyl substituted in the 3 position by halogen and in the 5 position by halogenated C1-C6 alkyl or SF5 or OR<15>, preferably when Ar is 3-chloro-5-trifluoromethylpyrid-2-yl. 17. A compound according to Claim 12 which