PESTICIDALLY ACTIVE SEMI-CARBAZONES AND THIOSEMICARBAZONES DERIVATIVES
20180007907 · 2018-01-11
Assignee
Inventors
Cpc classification
C07D209/50
CHEMISTRY; METALLURGY
C07D277/66
CHEMISTRY; METALLURGY
C07D215/227
CHEMISTRY; METALLURGY
C07D231/56
CHEMISTRY; METALLURGY
A01N47/34
HUMAN NECESSITIES
C07D487/00
CHEMISTRY; METALLURGY
C07D235/18
CHEMISTRY; METALLURGY
C07D277/68
CHEMISTRY; METALLURGY
C07D209/48
CHEMISTRY; METALLURGY
International classification
A01N47/34
HUMAN NECESSITIES
C07D277/66
CHEMISTRY; METALLURGY
C07D215/227
CHEMISTRY; METALLURGY
C07D235/18
CHEMISTRY; METALLURGY
C07D231/56
CHEMISTRY; METALLURGY
C07D209/50
CHEMISTRY; METALLURGY
C07D277/68
CHEMISTRY; METALLURGY
Abstract
Compounds of formula (I), wherein the substituents are as defined in claim 1, and agrochemically acceptable salts and enantiomers thereof, can be used as insecticides.
##STR00001##
Claims
1. A compound of formula I, ##STR00141## wherein, Ar.sub.1 and Ar.sub.2 are independently of each other phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl, wherein said phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl can be substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, cyano-C.sub.1-C.sub.4alkyl, cyano-C.sub.3-C.sub.6cycloalkyl nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6haloalkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.2-C.sub.6haloalkylaminocarbonyl or C.sub.2-C.sub.6 dialkylaminocarbonyl; X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.6 or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, or C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl; provided that when R.sub.2 and R.sub.3 are different from hydrogen, R.sub.2 and R.sub.3 can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, and C.sub.2-C.sub.8 dialkylaminocarbonyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; J is an aromatic or a non-aromatic bicyclic ring system selected from J.sub.1, J.sub.2 and J.sub.3 ##STR00142## wherein indicates that the ring is aromatic or non-aromatic; in which the arrows show the connectivity as depicted in formula (I) wherein A.sub.1 is nitrogen, N—R.sub.7a, sulfur, oxygen or C—R.sub.7b; A.sub.2 is nitrogen, N—R.sub.8a, sulfur, oxygen or C-R.sub.8b; A.sub.3 is nitrogen, N—R.sub.9a, sulfur, oxygen or C—R.sub.9b; B.sub.1 is nitrogen or C—R.sub.10; B.sub.2 is nitrogen or C—R.sub.11; B.sub.3 is nitrogen or C—R.sub.12; B.sub.4 is nitrogen or C—R.sub.13; B.sub.5 is nitrogen or C—R.sub.14; B.sub.6 is nitrogen or C—R.sub.15; C.sub.1 is nitrogen, C or C—R.sub.16; C.sub.2 is nitrogen, C or C—R.sub.17; with the provisos that a) not more than two substituents A can be oxygen or sulfur, b) when two substituents A are oxygen and/or sulphur, these substituents are A.sub.1 and A.sub.3, and A.sub.2 is C—R.sub.8b, and c) when C.sub.1 is N, then C.sub.2 is C or C—R.sub.16 and when C.sub.2 is N, then C.sub.1 is C or C—R.sub.17; each of R.sub.7a, R.sub.7b, R.sub.8a, R.sub.8b, R.sub.9a, R.sub.9b, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15, R.sub.16 and R.sub.17 are independently from each other hydrogen, halogen, nitro, cyano, hydroxy, ═O, CHO, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfonyl-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylsulfoximino-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.4dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl, —CONHSO.sub.2—C.sub.1-C.sub.6-alkyl, —CONHSO.sub.2N(C.sub.1-C.sub.6-alkyl).sub.2, or C.sub.3-C.sub.6trialkylsilyl; or an agrochemically acceptable salt, stereoisomer, tautomer and N-oxide of the compounds of formula I.
2. A compound according to claim 1, ##STR00143## wherein, Ar.sub.1 and Ar.sub.2 are independently of each other phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl, wherein said phenyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl can be substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, cyano-C.sub.1-C.sub.4alkyl, cyano-C.sub.3-C.sub.6cycloalkyl nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6haloalkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.2-C.sub.6haloalkylaminocarbonyl or C.sub.2-C.sub.6dialkylaminocarbonyl; X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5 or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, or C.sub.1-Caalkoxyimino-C.sub.1-C.sub.4alkyl; provided that when R.sub.2 and R.sub.3 are different from hydrogen, R.sub.2 and R.sub.3 can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, and C.sub.2-C.sub.8 dialkylaminocarbonyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; J is an aromatic bicyclic ring system selected from J.sub.1, J.sub.2 and J.sub.3 ##STR00144## wherein indicates that the ring is aromatic; in which the arrows show the connectivity as depicted in formula (I) wherein A.sub.1 is nitrogen, N—R.sub.7a, sulfur, oxygen or C—R.sub.7b; A.sub.2 is nitrogen, N—R.sub.8a, sulfur, oxygen or C—R.sub.8b; A.sub.3 is nitrogen, N—R.sub.9a, sulfur, oxygen or C—R.sub.9b; B.sub.1 is nitrogen or C—R.sub.10; B.sub.2 is nitrogen or C—R.sub.11; B.sub.3 is nitrogen or C—R.sub.12; B.sub.4 is nitrogen or C—R.sub.13; B.sub.5 is nitrogen or C—R.sub.14; B.sub.6 is nitrogen or C—R.sub.15; C.sub.1 is nitrogen or C; C.sub.2 is nitrogen or C; with the provisos that a) not more than two substituents A can be oxygen or sulfur, b) when two substituents A are oxygen and/or sulphur, these substituents are A.sub.1 and A.sub.3, and A.sub.2 is C—R.sub.8b, and c) when C.sub.1 is N, then C.sub.2 is C and when C.sub.2 is N, then C.sub.1 is C; each of R.sub.7a, R.sub.7b, R.sub.8a, R.sub.8b, R.sub.9a, R.sub.9b, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are independently from each other hydrogen, halogen, nitro, cyano, hydroxy, ═O, CHO, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.4talkoxy, C.sub.1-C.sub.1alkoxy-C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfonyl-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylsulfoximino-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.4dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl, —CONHSO.sub.2—C.sub.1-C.sub.6-alkyl, —CONHSO.sub.2N(C.sub.1-C.sub.6-alkyl).sub.2, or C.sub.3-C.sub.6trialkylsilyl; or an agrochemically acceptable salt, stereoisomer, tautomer and N-oxide of the cornpound of formula I.
3. A compound according to claim 1, wherein Ar.sub.1 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, or C.sub.2-C.sub.6haloalkoxycarbonyl; Ar.sub.2 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, or C.sub.2-C.sub.6haloalkoxycarbonyl; X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5, or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, or C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl; provided that when R.sub.2 and R.sub.3 are different from hydrogen, R.sub.2 and R.sub.3 can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, and C.sub.2-C.sub.8 dialkylaminocarbonyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; J is a group selected from J.sub.1′ to J.sub.1: ##STR00145## ##STR00146## R.sub.9a is hydrogen, halogen, nitro, cyano, hydroxy, ═O, CHO, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfonyl-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylsulfoximino-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.4dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl, —CONHSO.sub.2—C.sub.1-C.sub.6-alkyl, —CONHSO.sub.2N(C.sub.1-C.sub.6-alkyl).sub.2, or C.sub.3-C.sub.6trialkylsilyl.
4. A compound according to claim 1, wherein: Ar.sub.1 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, or C.sub.2-C.sub.6haloalkoxycarbonyl; Ar.sub.2 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, or C.sub.2-C.sub.6haloalkoxycarbonyl; X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5, or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, or C.sub.1-C.sub.6-alkyl, R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylarninocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, provided that when R.sub.2 and R.sub.3 groups are different from hydrogen, said R.sub.2 and R.sub.3 groups can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, and C.sub.1-C.sub.4alkylthio; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen or C.sub.1-C.sub.6-alkyl; J is a group selected from J.sub.1′ to J.sub.14: ##STR00147## ##STR00148## wherein R.sub.9a is C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.6haloalkyl.
5. A compound according to claim 1, wherein: Ar.sub.1 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6haloalkoxycarbonyl; Ar.sub.2 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.2-C.sub.4alkylcarbonyl, CHO, C.sub.2-C.sub.6alkoxycarbonyl, and C.sub.2-C.sub.6haloalkoxycarbonyl; X is a direct bond, or O; Y is oxygen or sulfur; R.sub.1 is hydrogen, or C.sub.1-C.sub.6-alkyl, R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, provided that when R.sub.2 and R.sub.3 groups are different from hydrogen, said R.sub.2 and R.sub.3 groups can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, and C.sub.1-C.sub.4alkylthio; J is a group selected from J.sub.1′ to J.sub.14: ##STR00149## ##STR00150## each of R.sub.7a, R.sub.7b, R.sub.8a, R.sub.8b, R.sub.9a, R.sub.9b, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.16, are independently from each otherhydrogen, halogen, nitro, cyano, hydroxy, ═O, CHO, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfonyl-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylsulfoximino-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.4dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl, —CONHSO.sub.2—C.sub.1-C.sub.6-alkyl, —CONHSO.sub.2N(C.sub.1-C.sub.6-alkyl).sub.2, or C.sub.3-C.sub.6trialkylsilyl.
6. A compound according to claim 1, wherein: Ar.sub.1 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, C.sub.1-C.sub.4alkoxy, and C.sub.1-C.sub.4haloalkoxy; Ar.sub.2 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio. X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5, or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.2-C.sub.4alkylcarbonyl, C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, or C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl; provided that when R.sub.2 and R.sub.3 are different from hydrogen, R.sub.2 and R.sub.3 can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylarnino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, and C.sub.2-C.sub.8 dialkylaminocarbonyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; J is a group selected from: ##STR00151##
7. A compound according to claim 1, wherein: Ar.sub.1 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, C.sub.1-C.sub.4alkoxy, and C.sub.1-C.sub.4haloalkoxy.; Ar.sub.2 is phenyl or phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.3haloalkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkoxy, halogen, cyano, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio. X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5, or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, or C.sub.1-C.sub.6-alkyl; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen or C.sub.1-C.sub.6-alkyl; J is a group selected from: ##STR00152##
8. A compound according to claim 1, wherein: Ar.sub.1 is phenyl substituted by C.sub.1-C.sub.4haloalkoxy; Ar.sub.2 is phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, halogen, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy; X is a direct bond, O, S, SO.sub.2, CR.sub.4R.sub.5, or NR.sub.6; Y is oxygen or sulfur; R.sub.1 is hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, halo-C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, C.sub.3-C.sub.6dialkylaminocarbonyl, C.sub.2-C.sub.6alkoxycarbonyloxy, C.sub.2-C.sub.6alkylaminocarbonyloxy, C.sub.3-C.sub.6dialkylaminocarbonyloxy, or C.sub.1-C.sub.4alkoxyimino-C.sub.1-C.sub.4alkyl; provided that when R.sub.2 and R.sub.3 are different from hydrogen, R.sub.2 and R.sub.3 can be substituted by one to three substituents independently selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.4haloalkenyl, C.sub.2-C.sub.4haloalkynyl, C.sub.3-C.sub.6halocycloalkyl, halogen, cyano, nitro, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.1-C.sub.4alkylsulfoximino, C.sub.1-C.sub.4alkylamino, C.sub.2-C.sub.6dialkylamino, C.sub.3-C.sub.6cycloalkylamino, C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkylamino, C.sub.2-C.sub.4alkylcarbonyl, C.sub.2-C.sub.6alkoxycarbonyl, C.sub.2-C.sub.6alkylaminocarbonyl, and C.sub.2-C.sub.8 dialkylaminocarbonyl; R.sub.4, R.sub.5 and R.sub.6 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, halo-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl or C.sub.1-C.sub.3-alkoxy; J is a group selected from: ##STR00153##
9. A compound according to claim 1, wherein: Ar.sub.1 is phenyl substituted by C.sub.1-C.sub.4haloalkoxy; Ar.sub.2 is phenyl substituted by one to three substituents independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, halogen, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy; X is a direct bond or O; Y is oxygen or sulfur; R.sub.1 is hydrogen or C.sub.1-C.sub.6-alkyl, R.sub.2 and R.sub.3 are independently from each other hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl J is a group selected from: ##STR00154##
10. A pesticidal composition, which comprises at least one compound of formula I according to claim 1, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary.
11. A method for controlling pests, which comprises applying a compound according to claim 1, optionally with at least on auxiliary, 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.
12. A method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a composition according to claim 10.
13. The pesticidal composition of claim 10, further including a propagation material, wherein the composition is coating the propagation material.
Description
PREPARATORY EXAMPLES
[0292] “Mp” means melting point in ° C. .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.
[0293] LC MS Method: Standard:
[0294] 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: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; Flow (ml/min) 0.85.
Example P1
Preparation of N-(2,6-dimethylphenyl)-2-((2-(4-(trifluoromethoxy)phenyl)-2H-indazol-6-yl)methylene)hydrazinecarbothioamide (compound P1)
[0295] ##STR00048##
Step A-1: Preparation of 6-methyl-2-[4-(trifluoromethoxy)phenyl]indazole
[0296] ##STR00049##
[0297] A solution of 2-bromo-4-methyl-benzaldehyde (30.0 g, 0.15 mol) and 4-(trifluoromethoxy)aniline (32.0 g, 0.180 mol) in dimethylformamide (300 mL) was charged with sodium azide (18.9 g, 0.30 mol) followed by tetramethylethylenediamine (1.74 g, 0.015 mol) at room temperature followed stirring for 10 minutes. Copper iodide (2.85 g, 0.015 mol) was added to the reaction mixture and heated to 120° C. for 16 hours. The reaction mixture was cooled to 0° C., diluted with water (300 mL) and extracted into ethyl acetate (2×500 mL). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate and concentrated under the reduced pressure. The residue was purified by column chromatography to afford 6-methyl-2-[4-(trifluoromethoxy)phenyl]indazole (5.00 g) as light brown solid.
[0298] MS m/z: 293 [M+H].sup.+.
[0299] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.31 (s, 1H), 7.92 (dd, 2H), 7.59 (d, 1H), 7.51 (s, 1H), 7.37 (d, 2H), 6.96 (dd, 1H), 2.46(s, 3H).
Step A-2: Preparation of 2-[4-(trifluoromethoxy)phenyl]indazole-6-carbaldehyde
[0300] ##STR00050##
[0301] A solution of 6-methyl-2-[4-(trifluoromethoxy)phenyl]indazole (5.0 g, 0.017 mol) in 1, 4-dioxane (100 mL) was charged with selenium oxide (5.65 g, 0.514 mol) at room temperature and heated to 110° C. for 72 hours. The reaction mixture was cooled to 0° C., diluted with water (100 mL) and extracted with ethyl acetate (2×300 mL). The combined organics was washed with brine (50 mL), dried over anhydrous sodium sulfate and concentrated under the reduced pressure. The residue was purified by column chromatography to afford 2-[4-(trifluoromethoxy)phenyl]indazole-6-carbaldehyde (3.00 g) as pale yellow solid.
[0302] MS m/z:307 [M+H].sup.+.
[0303] .sup.1H NMR (300 MHz, CDCl.sub.3): δ 10.10 (s, 1H), 8.46 (d, 1H), 8.30 (d, 1H), 7.95-7.99 (m, 2H), 7.80 (d, 1H), 7.66 (dd, 1H),7.42(d, 2H).
Step A-3: Preparation of 2-isothiocyanato-1,3-dimethyl-benzene
[0304] ##STR00051##
[0305] A solution of 2,6-dimethylaniline (5.00 g, 0.04 mol) in acetonitrile (100 mL) was charged with 1,1′-thiocarbonyldiimidazole (14.7 g, 0.08 mol) drop wise at 0° C. over 10 min and stirred at room temperature for 16 hours. The reaction mixture was cooled to 0° C., quenched with water (200 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with water (100 mL) and brine (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash column chromatography to afford 2-isothiocyanato-1,3-dimethyl-benzene (4.50 g) as a colorless liquid.
[0306] .sup.1H NMR (300 MHz, CDCl.sub.3): δ 7.09-7.01 (m, 3H), 2.37 (s, 6H).
Step A-4: Preparation of 1-amino-3-(2,6-dimethylphenyl)thiourea
[0307] ##STR00052##
[0308] A solution of 2-isothiocyanato-1,3-dimethyl-benzene (2.00 g, 0.01 mol) in ethanol (40 mL) was charged with hydrazine hydrate (5.80 mL, 0.12 mol) drop wise at 0° C. over 10 min and stirred at room temperature for 16 hours. The reaction mixture was concentrated under reduced pressure and treated with MTBE (50 mL) and was dried under vacuum to afford to afford 1-amino-3-(2,6-dimethylphenyl)thiourea (2.20 g) as an off white solid.
[0309] MS m/z: 196 [M+H].sup.+.
[0310] .sup.1H NMR (300 MHz, CDCl.sub.3): δ 9.09 (bs, 1H), 8.90 (bs, 1H), 7.05-7.04 (m, 3H), 4.69 (bs, 2H), 2.14 (s, 6H).
Step A-5: Preparation of 1-(2,6-dimethylphenyl)-3-[[2-[4-(trifluoromethoxy)phenyl]indazol-6-yl]methylene-amino]thiourea
[0311] ##STR00053##
[0312] A solution of 2-[4-(trifluoromethoxy)phenyl]indazole-6-carbaldehyde (1.00 g, 3.26 mmol, and 1-amino-3-(2,6-dimethylphenyl)thiourea (0.64 g, 3.26 mmol) in ethanol (25 mL) was charged with acetic acid (40 mg, 0.65 mmol) at room temperature and heated to 90° C. for 16 hours. The reaction mixture was cooled to room temperature and the solids were filtered, washed with ethanol (10 mL) and dried under vacuum to afford 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-6-yl]methyleneamino]thiourea (0.71 g) as pale yellow solid.
[0313] MS m/z: 484 [M+H].sup.+.
Example P2
Preparation of N-(2-isopropylphenyl)-2-((2-(4-(trifluoromethoxy)phenoxy)quinolin-6-yl)methylene)hydrazinecarbothioamide (compound P2)
[0314] ##STR00054##
Step B-1: Preparation of 6-bromo-2-[4-(trifluoromethoxy)phenoxy]quinoline
[0315] ##STR00055##
[0316] A suspension of sodium hydride (0.25 g, 6.16 mmol) in dimethylformamide (5 mL) was charged with a solution of 4-(trifluoromethoxy)phenol (1.00 g, 5.60 mmol) in dimethylformamide (5 mL) at 0° C. and stirred at same temperature for 30 minutes. A solution of 6-bromo-2-chloro-quinoline (1.36 g, 5.60 mmol) in dimethylformamide (5 mL) was added to the reaction mixture drop wise over 15 minutes at 0° C. The reaction mixture was heated to 90° C. for 16 hours. The reaction mixture was cooled to 0° C., diluted with water (20 mL) and extracted into ethyl acetate (2×50 mL). The combined organics was washed with brine (20 mL), dried over anhydrous sodium sulfate, concentrated under the reduced pressure. The residue was triturated with ethanol (20 mL) and filtered, dried under vacuum to afford 6-bromo-2-[4-(trifluoromethoxy)phenoxy]quinoline (1.10 g) as brown solid.
[0317] MS m/z: 384 [M+H].sup.+
[0318] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.05 (d, 1H), 7.92 (d, 1H), 7.62-7.70 (m, 2H), 7.27(d, 1H), 7.13 (d, 1H).
Step B-2: Preparation of 2-[4-(trifluoromethoxy)phenoxy]quinoline-6-carbaldehyde
[0319] ##STR00056##
[0320] A solution of 6-bromo-2-[4-(trifluoromethoxy)phenoxy]quinoline (0.80 g, 2.08 mmol) in tetrahydrofuran (20 mL) was charged with n-buthyllithium (1.0 mL, 2.5 M in hexanes) drop wise over 5 minutes at −78° C. and stirred at the same temperature for 1 hour. Dimethylformamide (25 mg, 4.16 mmol) in tetrahydrofuran (1.0 mL) was added drop wise over 2 minutes at −78° C. The reaction mixture was stirred at same temperature for another 2 hours. The reaction mixture was diluted with 2 N HCl (10 mL) and extracted with ethyl acetate (2×50 mL). The combined organics was washed with brine (20 mL), dried over anhydrous sodium sulfate and concentrated under the reduced pressure. The residue was purified by column chromatography to afford 2-[4-(trifluoromethoxy)phenoxy]quinoline-6-carbaldehyde (0.20 g) as an off white solid.
[0321] MS m/z: 334 [M+H].sup.+
[0322] .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ 10.1 (s, 1H), 8.67 (d, 1H), 8.62 (d, 1H), 8.07 (dd, 1H), 7.77(d, 1H), 7.44-7.51 (m, 5H).
Step B-3: Preparation of 1-amino-3-(2-isopropylphenyl)thiourea
[0323] ##STR00057##
[0324] A solution of 1-isopropyl-2-isothiocyanato-benzene (1.00 g, 5.64 mmol) in ethanol (10 mL) was charged with hydrazine monohydrochloride (1 mL) at room temperature and stirred 16 hours. The resulted solids were filtered, washed with ethanol (5 mL) and dried under vacuum to afford 1-amino-3-(2-isopropylphenyl)thiourea (0.60 g) as an off white solid.
[0325] .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ 9.01 (bs, 1H), 7.35 (s, 1H), 7.29 (dd, 1H), 7.12-7.27 (m, H), 4.30-5.30 (bs, 2H), 3.08 (m, 1H), 1.16 (d, 6H).
Step B-4: Preparation of 1-(2-isopropylphenyl)-3-[[2-[4-(trifluoromethoxy)phenoxy]-6-quinolyl]-methylene-amino]thiourea
[0326] ##STR00058##
[0327] A solution of 2-[4-(trifluoromethoxy)phenoxy]quinoline-6-carbaldehyde (0.20 g, 0.60 mmol) and 1-amino-3-(2-isopropylphenyl)thiourea (0.126 g, 0.60 mmol) in ethanol (10 mL) was charged with acetic acid (7.0 mg, 0.12 mmol) at room temperature and heated at 90° C. for 16 hours. The reaction mixture was cooled to room temperature and the solids were filtered, washed with ethanol (5 mL) and dried under vacuum to afford 1-(2-isopropylphenyl)-3-[(E)-[2-[4-(trifluoromelhoxy)phenoxy]-6-quinolyl]methyleneamino]thiourea (0.20 g) as pale yellow solid.
[0328] MS m/z: 525 [M+H].sup.+.
[0329] .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ 11.8 (s, 1H), 10.10 (s, 1H), 8.44-8.51 (m, 2H), 8.29 (s, 1H), 8.21 (d, 1H), 7.62 (d, 1H), 7.40-7.50 (m, 4H), 7.17-7.37 (m, 5H).
Example P3
Preparation of 1-(2-isopropylphenyl)-3-[[2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazol-6-yl]methyleneamino]thiourea (compound P3)
[0330] ##STR00059##
Step C-1: Preparation of 6-bromo-2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole
[0331] ##STR00060##
[0332] A suspension of sodium hydride (0.25 g, 6.16 mmol) in dimethylformamide (5 mL) was charged with a solution of 4-(trifluoromethoxy)phenol (1.0 g, 5.60 mmol) in dimethylformamide (5 mL) at 0° C. and stirred for 30 minutes. 6-bromo-2-chloro-1,3-benzothiazole (1.40 g, 5.60 mmol) in dimethylformamide (5 mL) was added to the reaction mixture drop wise over 15 minutes at 0° C. The reaction mixture was heated to 90° C. for 16 hours. The reaction mixture was cooled to 0° C., diluted with water (20 mL) and extracted with ethyl acetate (2×50 mL). The combined organics was washed with brine (20 mL), dried over anhydrous sodium sulfate, concentrated under the reduced pressure. The residue was triturated with ethanol (20 mL) and filtered, dried under vacuum to afford 6-bromo-2-[4-(trifluoromelhoxy)phenoxy]-1,3-benzothiazole (1.00 g) as off white solid.
[0333] MS m/z: 392.0 [M+H].sup.+.
[0334] .sup.1H NMR (300 MHz, DMSO-d.sub.6): δ 8.26 (d, 1H), 7.53-7.67 (m, 6H).
Step C-2: Preparation of 2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole-6-carbaldehyde
[0335] ##STR00061##
[0336] A solution of 6-bromo-2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole (1.00 g, 2.56 mmol) in tetrahydrofuran (20 mL) was charged with n-buthyllithium (1.1 mL, 2.50 M in hexanes) drop wise over 5 minutes at −78° C. and stirred at same temperature for 1 hour. Dimethylformamide (370 mg, 5.12 mmol) in tetrahydrofuran (1.0 mL) was added drop wise over 2 minutes at −78° C. The reaction mixture was stirred at same temperature for another 2 hours. The reaction mixture was diluted with HCl (2 N, 10 mL) and extracted with ethyl acetate (2×50 mL). The combined organics was washed with brine (20 mL), dried over anhydrous sodium sulfate and concentrated under the reduced pressure. The residue was purified by column chromatography to afford 2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazole-6-carbaldehyde (0.10 g) as an off white solid.
[0337] MS m/z: 340 [M+H].sup.+.
[0338] .sup.1H NMR (300 MHz, DMSO-d.sub.6): δ 10.03 (s, 1H), 8.59 (d, 1H), 7.96 (dd, 1H), 7.88 (d, 1H), 7.59-7.69 (m, 2H), 7.57 (d, 2H).
Step C-3: Preparation of 1-(2-isopropylphenyl)-3-[[2-[4-(trifluoromethcw)phenoxy]-1,3-benzothiazol-6-yl]methyleneamino]thiourea
[0339] ##STR00062##
[0340] A solution of 2-[4-(trifluoromelhoxy)phenoxy]-1,3-benzothiazole-6-carbaldehyde (0.10 g, 0.295 mmol) and 1-amino-3-(2-isopropylphenyl)thiourea (62 mg, 0.295 mmol, described in step B-3) in ethanol (5 mL) was charged with acetic acid (3.50 mg, 0.06 mmol) at room temperature and heated to 90° C. for 16 hours. The reaction mixture was cooled to room temperature and the solids were filtered, washed with ethanol (2 mL) and dried under vacuum to afford 1-(2-isopropylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenoxy]-1,3-benzothiazol-6-yl]methyleneamino]thiourea (40 mg) as pale yellow solid.
[0341] MS m/z: 531 [M+H].sup.+.
[0342] .sup.1H NMR (300 MHz, DMSO-d.sub.6): δ 11.81 (s, 1H), 10.00 (s, 1H), 8.48 (s, 1H),8.19 (s, 1H), 8.04 (dd, 1H), 7.72 (d, 1H), 7.66-7.62 (m, 2H), 7.54 (d, 2H), 7.17-7.37(m, 4H).
Example P4
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindolin-5-yl]methyleneamino]thiourea (compound P4)
[0343] ##STR00063##
Step D-1: Preparation of 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carboxylic acid
[0344] ##STR00064##
[0345] Under Argon a mixture of 1,3-dioxoisobenzofuran-5-carboxylic acid (200 mg, 1.04 mmol) and 4-(trifluoromethoxy)aniline (0.184 mg, 1.04 mmol)) in acetic acid (5 ml) was heated to reflux for 2 hours. The reaction was quenched with ice water and the precipitate was filtered off and washed with water and tert-butylmethylether to give 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carboxylic acid (206 mg) as beige crystals.
[0346] LC-MS: t.sub.R=1.51 min, m/z=350 [M−1].
[0347] .sup.1H NMR (400 MHz, DMSO) δ ppm 7.55-7.65 (m, 4H) 8.11 (d, J=7.70 Hz, 1H) 8.32-8.33 (m, 1H) 8.43 (dd, J=7.70, 1.47 Hz, 1H) 13.76 (br. s., 1H).
Step D-2: Preparation of 5-(hydroxymethyl)-2-[4-(trifluoromethoxy)phenyl]isoindoline-1,3-dione
[0348] ##STR00065##
[0349] Under Argon a mixture of 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carboxylic acid (190 mg, 0.541 mmol) in tetrahydrofuran (3 ml) was cooled to 0° C., then a solution of borane in tetrahydrofuran (0.65 ml, 1 M) was added. The mixture was stirred at ambient temperature overnight. After completion, the reaction mixture was diluted with a solution of hydrochloridric acid, extracted with ethyl acetate and washed with brine. The combined organic layers were dried over magnesium sulfate and evaporated under vacuo to give 5-(hydroxymethyl)-2-[4-(trifluoromethoxy)phenyl]isoindoline-1,3-dione (163 mg) as a beige solid.
[0350] LC-MS: t.sub.R=1.43 min, m/z=338 [M+1].
[0351] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 4.79-4.97 (m, 2H) 7.34-7.38 (m, 2H) 7.50-7.53 (m, 2H) 7.78-7.82 (m, 1H) 7.92-7.99 (m, 2H).
Step D-3: Preparation of 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carbaldehyde
[0352] ##STR00066##
[0353] To a solution of 5-(hydroxymethyl)-2-[4-(trifluoromethoxy)phenyl]isoindoline-1,3-dione (0.3 g, 0.89 mmol) in dichloromethane (10 ml) was added manganese dioxide (0.85 g, 9.80 mmol) and the reaction mixture was stirred at ambient temperature overnight. It was then filtered through a pad of celite, and washed with dichloromethane, the combined filtrate and washing were concentrated under reduced pressure. The crude product was purified by flash chromatography to give 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]iso-indoline-5-carbaldehyde (246 mg) as beige crystals.
[0354] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.38 (dd, J=9.17, 0.73 Hz, 2H) 7.51-7.56 (m, 2H) 8.15 (d, J=7.70 Hz, 1H) 8.33-8.37 (m, 1H) 8.46 (d, J=0.73 Hz, 1H) 10.21 (s, 1H).
Step D-4: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindolin-5-yl]methyleneamino]thiourea
[0355] ##STR00067##
[0356] To a suspension of 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carbaldehyde (85 mg, 0.253 mmol) in methanol (10 ml) was added at room temperature 1-amino-3-(2,6-dimethylphenyl)thiourea (849 mg, 0.253 mmol). This mixture was heated at reflux for 3 h. After complete conversion, the solution was concentrated under vaccum, and the crude product was purified by flash chromatography to give 1-(2,6-dimethylphenyl)-3-[(E)-[1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindolin-5-yl]methyleneamino]thiourea (77 mg) as a yellow solid.
[0357] LC-MS: t.sub.R=2.02 min, m/z=511 [M−1], 513 [M+1].
[0358] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 2.34 (s, 6H) 7.18 (s, 1H) 7.18-7.18 (m, 1H) 7.37 (d, J=8.07 Hz, 2H) 7.51-7.54 (m, 2H) 8.01-8.04 (m, 3H) 8.31 (s, 1H) 8.69 (s, 1H) 10.01 (s, 1H).
Example P5
Preparation of 1-(2,6-dimethylphenyl)-3-[[1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindolin-5-yl]methyleneamino]urea (compound P5)
[0359] ##STR00068##
Step E-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindolin-5-yl]methyleneamino]urea
[0360] ##STR00069##
[0361] To a suspension of 1,3-dioxo-2-[4-(trifluoromethoxy)phenyl]isoindoline-5-carbaldehyde (200 mg, 0.596 mmol, example P4, step D-3) in methanol (10 ml) was added at room temperature 1-amino-3-(2,6-dimethylphenyl)urea (106 mg, 0.596 mmol). This mixture was heated at reflux for 3 h. After complete conversion, the solution was concentrated under vaccum, and the crude product was purified by crystallisation to give 1-(2,6-dimethylphenyl)-3-[(E)-[1,3-dioxo-2-[4-(trifluoromelhoxy)phenyl]isoindolin-5-yl]methyleneamino]urea (244 mg) as a white solid.
[0362] LC-MS: t.sub.R=1.92 min, m/z=495 [M−1], 497 [M+1].
[0363] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 6H) 7.54-7.66 (m, 4H) 7.97 (d, J=7.70 Hz, 1H) 8.09 (s, 1H) 8.21 (dd, J=8.07, 1.10 Hz, 1H) 8.65 (s, 1H) 8.89 (s, 1H) 10.91 (s, 1H).
Example P7
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]thiourea (compound P7)
[0364] ##STR00070##
Step F-1: Preparation of 2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazole-5-carbonitrile
[0365] ##STR00071##
[0366] A three necked round bottom flask was charged with 2-bromo-1,3-benzoxazole-5-carbonitrile (0.700 g, 2.82 mmol), tripotassium phosphate (1.85 g, 8.47 mmol) and [4-(trifluoromethoxy)phenyl]boronic acid (0.712 g, 3.39 mmol), 1,4-dioxane (28.2 mL) and water (11.3 mL). The reaction mixture was purged with argon for 30 min. Subsequently, PdCl.sub.2(dppf) (0.109 g, 0.141 mmol) was added and the reaction mixture was purged with argon again.The orange reaction mixture was stirred at 90° C. for 1 hour, then cooled to 0-10° C. and diluted with water (20 mL), filtered over celite and washed with ethyl acetate. The mother liquor was diluted in ethyl acetate (300 mL). The organic layer was extracted with water (2×150 mL), brine (150 mL), dried with magnesium sulfate anhydrous, filtered of and evaporated. The crude product was purified by flash-chromatography to give 2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazole-5-carbonitrile (453 mg) as a white solid.
[0367] LC-MS: t.sub.R=1.12 min, m/z=305 [M+1].
[0368] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 7.67 (d, J=8.44 Hz, 2H) 7.95 (dd, J=8.44, 1.47 Hz, 1H) 8.07 (d, J=8.44 Hz, 1H) 8.37 (d, J=8.80 Hz, 2H) 8.47 (s, 1H).
Step F-2: Preparation of 2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazole-5-carbaldehyde
[0369] ##STR00072##
[0370] A solution of 2-[4-(trifluoromelhoxy)phenyl]-1,3-benzoxazole-5-carbonitrile (0.100 g, 0.322 mmol) in dichloromethane (3.22 mL) was cooled to 0° C. under Argon. A solution of DIBAL-H in dichloromethane (1N, 0.436 g, 0.354 mmol, 0.354 mL) was added and the reaction mixture was stirred at 0° C. for 30 min. The reaction mixture was quenched by the dropwise addition of water at 0° C. It was then diluted in dichloromethane and the organic layer was washed with brine, dried with magnesium sulfate anhydrous, filtered of and evaporated to give 90 mg 2-[4-(trifluoromethoxy)phenyI]-1,3-benzoxazole-5-carbaldehyde.
[0371] LC-MS: t.sub.R=1.16 min, m/z=308 [M+1].
Step F-3: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]thiourea
[0372] ##STR00073##
[0373] A 5 ml vial was charged with 2-[4-(trifluoromelhoxy)phenyl]-1,3-benzoxazole-5-carbaldehyde (0.090 g, 0.26 mmol) and methanol (1.3 mL). 1-Amino-3-(2,6-dimethylphenyl)thiourea (0.051 g, 0.26 mmol) was added and the reaction mixture was stirred at room temperature overnight. The reaction mixture was filtered of, washed with methanol and twice with pentane.The crude product was purified by flash-chromatography to give 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]thiourea (30 mg) as a white solid.
[0374] LC-MS: t.sub.R=1.25 min, m/z =483 [M−1], 485 [M+1].
[0375] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 6H) 7.12-7.17 (m, 3H) 7.65 (d, J=8.80 Hz, 2H) 7.85 (d, J=8.44 Hz, 1H) 8.02 (d, J=8.80 Hz, 1H) 7.99-8.04 (m, 1H) 7.99-8.04 (m, 1H) 8.27 (s, 1H) 8.23-8.29 (m, 1H) 8.33 (d, J=8.80 Hz, 2H) 8.52 (s, 1H) 10.01 (s, 1H) 11.82 (s, 1H).
Example P10
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]urea (compound P10)
[0376] ##STR00074##
Step G-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]urea
[0377] ##STR00075##
[0378] A vial was charged with 2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazole-5-carbaldehyde (0.070 g, 0.21 mmol, example P7, step F-2) and methanol (2.1 mL). 1-Amino-3-(2,6-dimethylphenyl)urea (0.035 g, 0.19 mmol) was added and the reaction mixture was stirred at room temperature overnight. The reaction mixture was filtered of, washed with methanol and twice with pentane to give 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzoxazol-5-yl]methyleneamino]urea (830 mg) as a white solid.
[0379] LC-MS: t.sub.R=1.23 min, m/z=467 [M−1], 469 [M+1].
[0380] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.24 (s, 6H) 7.11 (s, 3H) 7.65 (d, J=8.07 Hz, 2H) 7.83 (d, J=8.80 Hz, 1H) 7.98 (d, J=8.80 Hz, 1H) 8.06 (s, 1H) 8.34 (d, J=8.44 Hz, 2H) 8.40 (s, 1H) 8.67 (s, 1H) 10.65 (s, 1H).
Example P13
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]melhyleneamino]thiourea (compound P13)
[0381] ##STR00076##
Step H-1: Preparation of 2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazole-5-carbaldehyde
[0382] ##STR00077## [0383] a) A dried vial was charged with copper(I) iodide (0.120 g, 0.630 mmol) and dichloromethane (7.93 g, 92.5 mmol, 5.99 mL). XANTPHOS (0.401 g, 0.693 mmol) was added and the reaction mixture was stirred at room temperature for 15 min. The solvent was removed by bubbling through with argon. The remaining solid was directly used for the next step. [0384] b) A vial was set under argon and charged with Cu(Xantphos)I (0.0471 g, 0.0613 mmol) (procedure step a), dichloro-bis(tricyclohexylphosphine)palladium(II) (0.119 g, 0.153 mmol), cesium carbonate (2.50 g, 7.66 mmol) and toluene (6.13 mL). To the resulting mixture was added 1,3-benzothiazole-5-carbaldehyde (0.500 g, 3.06 mmol) and 1-bromo-4-(trifluoromethoxy)benzene (1.11 g, 4.60 mmol, 0.683 mL). The reaction mixture was stirred at 100° C. overnight. After cooling to room temperature, it was diluted with ethyl acetate and quenched with a solution of ammonium chloride saturated/water (1/1). The resulting suspension was filtered over celite and washed several times with ethyl acetate. The organic layer was separated and washed with water, brine, dried over anhydrous magnesium sulfate, filtered of and evaporated. The crude product was purified over flash-chromatography to give 2-[4-(trifluoromethoxy)phenyI]-1,3-benzothiazole-5-carbaldehyde (352 mg) as a white solid.
[0385] LC-MS: t.sub.R=1.82 min, m/z=323 [M+1].
[0386] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 7.62 (d, J=8.07 Hz, 2H) 8.00 (dd, J=8.25, 1.28 Hz, 1H) 8.30 (d, J=8.80 Hz, 2H) 8.42 (d, J=8.44 Hz, 1H) 8.63 (d,J=1.10 Hz, 1H) 10.18 (s, 1H).
Step H-2: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]methyleneamino]thiourea
[0387] ##STR00078##
[0388] A vial was charged with 2-[4-(trifluoromethoxy)phenyI]-1,3-benzothiazole-5-carbaldehyde (0.060 g, 0.18 mmol) and methanol (1.8 mL). 1-Amino-3-(2,6-dimethylphenyl)thiourea (0.034 g, 0.17 mmol) was added and the reaction mixture was stirred at room temperature overnight. To improve the solubility of the reaction mixture acetonitrile/water (1:1, 1 ml) was added and reaction was further heated at 65° C. After cooling, the reaction mixture was filtered, the cake was washed with methanol and diethyl ether to give 1-(2,6-d imethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]methyleneamino]thiourea (59 mg) as a yellow solid.
[0389] LC-MS: t.sub.R=1.26 min, m/z=499 [M−1], 501 [M+1].
[0390] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 6H) 7.13 (br. s., 3H) 7.59 (d, J=8.07 Hz, 2H) 8.04 (d, J=8.07 Hz, 1H) 8.14-8.33 (m, 4H) 8.70 (s, 1H) 10.06 (br. s., 1H) 11.85 (br. s., 1H).
Example P16
Preparation of 1-(2,6-dimethylphenyI)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]melhyleneamino]thiourea (compound P16)
[0391] ##STR00079##
Step 1-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]methyleneamino]thiourea
[0392] ##STR00080##
[0393] A vial was charged with 2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazole-5-carbaldehyde (0.060 g, 0.18 mmol, example P13, step H-1) and methanol (1.8 mL). 1-Amino-3-(2,6-dimethylphenyl)urea (0.031 g, 0.17 mmol) was added and the reaction mixture was stirred at room temperature overnight. In order to complete the conversion, the reaction mixture was further heated at 65° C. for 3 hours. The reaction mixture was filtered, the cake was washed with methanol to give 1-(2,6-dimelhylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazol-5-yl]methyleneamino]thiourea (69 mg) as a yellow solid.
[0394] LC-MS: t.sub.R=1.21 min, m/z =483 [M−1], 485 [M+1].
[0395] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.23 (s, 6H) 7.10 (s, 3H) 7.59 (d, J=8.07 Hz, 2H) 8.00-8.08 (m, 2H) 8.17-8.25 (m, 3H) 8.57 (s, 1H) 8.71 (s, 1H) 10.68 (s, 1H).
Example P17
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]methyleneamino]thiourea (compound P17)
[0396] ##STR00081##
Step J-1: Preparation of 2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridine-6-carbonitrile
[0397] ##STR00082##
[0398] To a solution of 6-aminopyridine-3-carbonitrile (5.1 g, 42.0 mmol) in 190 ml of ethanol was added 2-bromo-1-[4-(trifluoromethoxy)phenyl]ethanone (12.1 g, 42.0 mmol) and the mixture was heated at reflux for 24 hours. After concentration to about 100 ml the precipitated salt was filtered, suspended in water and neutralized with an aqueous NaHCO.sub.3 solution. The precipitated free base was filtered, and dried in vacuo. The crude solid was purified by flash-chromatography to give 2-[4-(trifluoromethoxy)phenyl]-imidazo[1,2-a]pyridine-6-carbonitrile (7.43 g) as a white solid.
[0399] LC-MS: t.sub.R=1.05 min, m/z=304 [M+1].
[0400] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.29-7.34 (m, 3H) 7.71 (d, J=9.17 Hz, 1H) 7.95 (s, 1H) 7.97-8.01 (m, 2H) 8.59 (dd, J=1.65, 0.92 Hz, 1H).
Step J-2: Preparation of 2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazole-5-carbaldehyde
[0401] ##STR00083##
[0402] Under Argon, 2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridine-6-carbonitrile (1.0 g, 3.1 mmol) was solved in 10 ml tetrahydrofuran and 10 ml dichloromethane, and cooled to −20° C. using dry ice/EtOH. To this solution, a solution of DIBAL-H in toluene (1M, 4.7 ml, 4.7 mmol) was added dropwise at −20° C. and further stirred for 30 min. The mixture was allowed to warm to room temperature and was carefully quenched with 10 ml methanol/ethyl acetate 2:1 at 0° C. The reaction mixture was stirred for 30 min at 0° C. and 10 ml of water was added dropwise at 0° C. The organic phase was separated, and the water was extracted with 2×100 ml dichloromethane. The organic layer was washed with water, brine, dried over sodium sulfate, filtrated and evaporated. Crude product was purified by chromatography to give (2-[4-(trifluoromethoxy)phenyl]-1,3-benzothiazole-5-carbaldehyde (354 mg) as orange crystals.
[0403] LC-MS: t.sub.R=1.00 min, m/z=307 [M+1].
[0404] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 7.31 (dd, J=8.80, 1.10 Hz, 2H) 7.68-7.74 (m, 2H) 7.97-8.03 (m, 3H) 8.69 (t, J=1.28 Hz, 1H) 9.97 (s, 1H).
Step J-3: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]methyleneamino]thiourea
[0405] ##STR00084##
[0406] To a suspension of 2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridine-6-carbaldehyde (200 mg, 0.653 mmol) in 5 ml methanol was added at room temperature 1-amino-3-(2,6-dimethylphenyl)thiourea. The mixture was heated to reflux and stirred for 3 h. The reaction was almost complete and concentrated under vacuo.
[0407] The crude product was purified by flash chromatography to give 1-(2,6-dimelhylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]methyleneamino]thiourea (84 mg) as a yellow solid.
[0408] LC-MS: t.sub.R=1.82 min, m/z=483 [M-1], 484 [M+1].
[0409] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.21 (s, 6H) 7.11-7.15 (m, 3H) 7.46 (d, J=8.07 Hz, 2H) 7.60 (d, J=9.54 Hz, 1H) 8.07-8.11 (m, 2H) 8.16 (s, 1H) 8.21 (dd, J=9.54, 1.83 Hz, 1H) 8.42 (s, 1H) 8.90 (s, 1 H) 9.95 (s, 1H) 11.85 (s, 1H).
Example P18
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]methyleneamino]urea (compound P18)
[0410] ##STR00085##
Step K-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]methyleneamino]urea
[0411] ##STR00086##
[0412] To a suspension of 2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridine-6-carbaldehyde (200 mg, 0.653 mmol, example P17, step J-2) in 5 ml methanol was added at room temperature 1-amino-3-(2,6-dimethylphenyl)urea (0.117 mg, 0.653 mmol). The mixture was heated at reflux for 3 hours. The mixture was concentrated under vacuo and purified by flash chromatography to give 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]imidazo[1,2-a]pyridin-6-yl]melhyleneamino]urea (84 mg) as a yellow solid.
[0413] LC-MS: t.sub.R=1.82 min, m/z=483 [M−1], 484 [M+1].
[0414] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.23 (s, 6H) 7.11 (s, 3H) 7.45 (d, J=8.07 Hz, 2H) 7.60 (d, J=9.17 Hz, 1H) 7.96 (s, 1H) 8.08-8.16 (m, 3H) 8.42 (s,1H) 8.62 (s, 1H) 8.82 (s, 1H) 10.69 (s, 1H).
Example P21
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea (compound P21)
[0415] ##STR00087##
Step L-1: Preparation of methyl 1-[4-(trifluoromethoxy)phenyl]indazole-5-carboxylate and methyl 2-[4-(trifluoromethoxy)phenyl]indazole-5-carboxylate.
[0416] ##STR00088##
[0417] A dried vial was charged with methyl 1H-indazole-5-carboxylate (1.00 g, 5.68 mmol), copper(I) iodide (0.108 g, 0.568 mmol), cesium carbonate (1.85 g, 5.68 mmol) and 5.7 mL DMSO. The reaction mixture was evacuated and flushed with argon again. After addition of 1-iodo-4-(trifluoromethoxy)benzene (0.843 g, 2.84 mmol), the reaction mixture was heated at 100° C. After cooling, the reaction mixture was diluted with ethyl acetate. It was filtrated over celite and washed several times with ethyl acetate. The organic layer was extracted with water, brine, dried with anhydrous MgSO.sub.4, filtered of and evaporated. The crude product was purified by flash-chromatography to give a mixture of methyl 1-[4-(trifluoromethoxy)-phenyl]indazole-5-carboxylate and methyl 2-[4-(trifluoromethoxy)phenyl]indazole-5-carboxylate (610 mg) as a yellow solid.
[0418] LC-MS: t.sub.R=1.15 min, m/z=337 [M+1].
[0419] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 3.91 (s, 3H) 7.63 (d, J=8.44 Hz, 2H) 7.92-7.99 (m, 3H) 8.07 (dd, J=8.80, 1.47 Hz, 1H) 8.61 (d, J=2.20 Hz, 2H).
Step L-2: Preparation of [1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methanol and [2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methanol
[0420] ##STR00089##
[0421] A vial under argon was charged with a mixture of methyl 1-[4-(trifluoromethoxy)phenyl]indazole-5-carboxylate and (methyl 2-[4-(trifluoromethoxy)phenyl]indazole-5-carboxylate (0.610 g, 1.72 mmol) and with diethyl ether (8.62 mL). The reaction mixture was cooled to −70° C. and a solution of DIBAL-H in dichloromethane (1N, 1.7 mL, 1.7 mmol) was added dropwise. After 1 hat this temperature, the reaction mixture was warmed to 0° C. and another 1 equivalent (1.7 mL) DIBAL-H in dichloromethane was added. The reaction mixture was stirred at 0° C. for another 30 min. After quenching at 0° C. with Rochelle salt (10 mL), the mixture was extracted twice with dichloromethane, dried over anhydrous MgSO.sub.4, filtered and evaporated to give a mixture of [1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methanol and [2-[4-(trifluoro-methoxy)phenyl]indazol-5-yl]methanol (0.849 mg) as a yellow oil.
[0422] LC-MS: t.sub.R=0.97 min, m/z =308 [M+1].
[0423] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 4.64 (d, J=5.50 Hz, 2H) 7.49 (d, J=8.44 Hz, 1H) 7.59 (d, J=8.80 Hz, 2H) 7.81-7.88 (m, 2H) 7.93 (d, J=8.80 Hz, 2H) 8.39 (s, 1H).
Step L-3: Preparation of 1-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde and 2-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde.
[0424] ##STR00090##
[0425] A 25 mL round bottom flask was set under argon and charged with Dess-Martin period inane (0.707 g, 1.67 mmol) suspended in dichloromethane (9.00 mL). A mixture of [1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methanol and [2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methanol (0.476 g, 1.39 mmol) in dichloro-methane (4 mL) was added dropwise at room temperature. The reaction mixture was stirred at this temperature overnight. After dilution with 15 mL ethyl acetate, the mixture was poured into a mixture of saturated NaHCO.sub.3and saturated Na.sub.2S.sub.2O.sub.3 (˜40 mL, 1:1) and stirred for 10 min at 0° C. (pH˜9). The solution was then extracted with ethyl acetate (100 mL), washed with saturated NaHCO.sub.3 (80 mL), water (80 mL), brine (80 mL), dried over anhydrous MgSO.sub.4, filtered and evaporated. The crude mixture was separated by flash-chromatography to give 1-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.265 mg) and 2-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.046 mg).
1-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde
[0426] LC-MS: t.sub.R=1.07 min, m/z =307 [M+1].
[0427] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 7.65 (d, J=8.44 Hz, 2H) 7.94-8.07 (m, 4H) 8.54-8.74 (m, 2H) 10.07-10.16 (m, 1H).
2-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde
[0428] LC-MS: tR=1.05 min, m/z=307 [M+1].
[0429] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 7.67 (d, J=8.80 Hz, 2H) 7.74-7.79 (m, 1H) 7.84-7.89 (m, 1H) 8.29 (d, J=9.17 Hz, 2H) 8.57 (s, 1H) 9.52 (s, 1H) 10.05 (s, 1H).
Step L-4: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea
[0430] ##STR00091##
[0431] To a solution of 1-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.050 g, 0.16 mmol) in methanol (1.6 mL) was added 1-amino-3-(2,6-dimethylphenyl)thiourea (0.029 g, 0.15 mmol) and the reaction mixture was heated at 65° C. overnight. The reaction mixture was filtered, the solid was washed with methanol and diethyl ether to give 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea (49 mg) as a yellow solid.
[0432] LC-MS: t.sub.R=1.24 min, m/z=482 [M−1], 484 [M+1].
[0433] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 6H) 7.12-7.16 (m, 3H) 7.63 (d, J=8.44 Hz, 2H) 7.87 (d, J=8.80 Hz, 1H) 7.96 (d, J=9.17 Hz, 2H) 8.26-8.32 (m, 3H) 8.47 (s, 1H) 9.94 (s, 1H) 11.75 (s, 1H).
Example P24
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]urea (compound P24)
[0434] ##STR00092##
Step M-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]urea.
[0435] ##STR00093##
[0436] To a solution of 1-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.050 g, 0.16 mmol, example P21, step L-3) in methanol (1.6 mL) was added 1-amino-3-(2,6-dimethylphenyl)urea (0.026 g, 0.15 mmol) and the reaction mixture was stirred 3 h at 65° C. The mixture was filtered of, washed with methanol and diethyl ether to give 1-(2,6-dimethylphenyl)-3-[(E)-[1-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methylene-amino]urea (27 mg) as a white solid.
[0437] LC-MS: t.sub.R=1.19 min, m/z=467 [M−1], 468 [M+1].
[0438] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.23 (s, 6H) 7.10 (s, 3H) 7.61 (d, J=8.44 Hz, 2H) 7.87 (d, J=9.17 Hz, 1H) 7.92-7.97 (m, 2H) 8.08 (s, 1H) 8.18-8.22 (m, 2H) 8.45 (d, J=0.73 Hz, 1H) 8.57 (s, 1H) 10.57 (s, 1H).
Example P25
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea (compound P25)
[0439] ##STR00094##
Step N-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea
[0440] ##STR00095##
[0441] To a solution of 2-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.023 g, 0.075 mmol, example P21, step L-3) in methanol (0.75 mL) was added 1-amino-3-(2,6-dimethylphenyl)thiourea (0.014 g, 0.071 mmol) and the reaction mixture was heated 3 h at 65° C. After cooling, it was filtered, washed with methanol and diethyl ether to give 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]thiourea (14 mg) as a yellow solid.
[0442] LC-MS: t.sub.R=1.23 min, m/z =482 [M−1], 484 [M+1].
[0443] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 6H) 7.10-7.15 (m, 3H) 7.63 (d, J=8.44 Hz, 2H) 7.71 (d, J=9.17 Hz, 1H) 8.00 (s, 1H) 8.22-8.30 (m, 4H) 9.19 (s, 1H) 9.91 (s, 1H) 11.72 (s, 1H).
Example P26
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]urea (compound P26)
[0444] ##STR00096##
Step O-1: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]methyleneamino]urea
[0445] ##STR00097##
[0446] To a solution of 2-[4-(trifluoromethoxy)phenyl]indazole-5-carbaldehyde (0.023 g, 0.075 mmol, example P21, step L-3) in methanol (0.75 mL) was added 1-amino-3-(2,6-dimethylphenyl)urea (0.013 g, 0.071 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was filtered and the cake was washed twice with methanol. The crude product was suspended in diethyl ether and filtered to give 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]indazol-5-yl]melhylene-amino]urea (8.5 mg) as a white solid.
[0447] LC-MS: t.sub.R=1.23 min, m/z=482 [M−1], 484 [M+1].
[0448] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.24 (s, 6H) 7.11 (s, 3H) 7.63 (d, J=8.44 Hz, 2H) 7.72 (d, J=9.17 Hz, 1H) 7.94 (s, 1H) 8.04 (s, 1H) 8.17-8.30 (m,4H) 8.57 (s, 1H) 9.18 (s, 1H) 10.56 (s, 1H).
Example P27 and P28
Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[2-[4-(trifluoromethoxy)phenyl]-indazol-5-yl]methyleneamino]urea (compound P27) and 1-(2,6-dimelhylphenyl)-3-[(E)-[3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methyleneamino]urea (compound P28)
[0449] ##STR00098##
Step P-1: Preparation of methyl 3-amino-4-[[4-(trifluoromethoxy)benzoyl]amino]benzoate
[0450] ##STR00099##
[0451] Under Argon, a solution of methyl 3,4-diaminobenzoate (5.0 g, 29.2 mmol), triethylamine (10.3 ml, 73.0 mmol) in 90 ml tetrahydrofuran was cooled to 0°-5° C. A solution of 4-(trifluoromethoxy)benzoyl chloride (4.98 ml, 30.6 mmol) in 60 ml tetrahydrofuran was added dropwise at 0°-5° C. The mixture was stirred for 2 h at 0°-5° C. and 1 h at RT. After completion of the reaction, the mixture was diluted with tent-butyl methyl ether, quenched with a saturated NH.sub.4Cl-solution and extracted with 2×300 ml tert-butyl methyl ether. The combined organic layers were washed with brine and dried over Na.sub.2SO.sub.4, filtrated and evaporated to give methyl 3-amino-4-[[4-(trifluoromethoxy)benzoyl]amino]benzoate (11.2 g) as beige crystals.
[0452] LC-MS: t.sub.R=0.95 min, m/z=353 [M−1], 355 [M+1].
[0453] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 3.76 (s, 3H) 5.89 (s, 2H) 6.76-6.80 (m, 1H) 7.50-7.54 (m, 2H) 7.60 (dd, J=8.44, 1.83 Hz, 1H) 7.78 (d, J=1.83 Hz,1H) 8.13 (d, J=8.80 Hz, 2H) 9.75 (s, 1H).
Step P-2: Preparation of methyl 3-amino-4-[[4-(trifluoromethcw)benzoyl]amino]benzoate
[0454] ##STR00100##
[0455] A solution of methyl 3-amino-4-[[4-(trifluoromethoxy)benzoyl]amino]benzoate (2.5g, 6.7 mmol) in 15 ml acetic acid was irradiated in the microwave for 30 min at 140° C. The reaction mixture was then poured into water (30 mL) and the precipitate formed was filtered to give methyl 3-amino-4-[[4-(trifluoromethoxy)-benzoyl]amino]benzoate (2.7 g) as beige crystals.
[0456] LC-MS: t.sub.R=1.01 min, m/z=335 [M−1], 337 [M+1].
[0457] .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 3.89 (s, 3H) 7.60 (d, J=8.07 Hz, 2H) 7.71 (d, J=8.44 Hz, 1H) 7.86-7.90 (m, 1H) 8.22 (s, 1H) 8.31-8.35 (m, 2H).
Step P-3: Preparation of methyl 1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carboxylate and methyl 3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carboxylate
[0458] ##STR00101##
[0459] Under argon, sodium hydride (60 mg, 1.48 mmol) was suspended in 5 ml DMF and cooled to 5°-10° C. To this suspension, methyl 3-amino-4-[[4-(trifluoromethoxy)benzoyl]amino]benzoate (500 mg, 1.41 mmol) in 7 ml DMF was added dropwise at 5°-10° C. and further stirred 30 min at room temperature. lodomethane (98 μl, 1.55 mmol) was then added dropwise at 25°-32° C. and the colourless solution was heated at 70° C. overnight. After cooling, the mixture was poured into 40 ml water, and extracted with 3×20 ml of tert-butyl methyl ether. The organic layer was washed with brine, dried over Na.sub.2SO.sub.4, filtrated and evaporated to give a mixture of methyl 1-methyl-2-[4-(trifluoromethcw)phenyl]benzimidazole-5-carboxylate and methyl 3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carboxylate (400 mg) as a white solid.
Step P-4: Preparation of [1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methanol and [3-methyl-2-[4-(trifluoromethoxy)phenyl]-1H-benzimidazol-5-yl]methanol
[0460] ##STR00102##
[0461] Under argon, a mixture of methyl 1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carboxylate and methyl 3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carboxylate (400 mg, 1.08 mmol) was dissolved in 8 ml tetrahydrofuran and 8 ml dichloromethane and cooled to −70° C. To this yellow solution, DIBAL-H in toluene (25%, 1.46 ml, 2.17 mmol) was added dropwise at −70°-65° C. The mixture was stirred at −70° C. for 3 hours and was allowed to warm to room temperature overnight. In order to complete the reaction, the mixture was cooled to −70° C. and additional DIBAL-H in toluene (25%, 1.46 ml, 2.17 mmol) was added dropwise at −70°-65° C. After carefully quenching with 3 ml methanol at −70° C. and 30 min stirring at −70° C., 3 ml water was added dropwise. The mixture was stirred for 30 min at −70° C. and then allowed to warm to room temperature. The organic phase was separated, and the water phase was extracted with 2×10 ml dichloromethane. The organic layer was washed with water, brine, dried over Na.sub.2SO.sub.4, filtrated and evaporated. The crude product was purified by flash-chromatography to give a mixture of [1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methanol and [3-methyl-2-[4-(tri-fluoromethoxy)phenyl]-1H-benzimidazol-5-yl]methanol as an orange wax.
[0462] LC-MS: t.sub.R=0.75 min, m/z=321 [M−1], 323 [M+1].
Step P-5: Preparation of 1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carbaldehyde and 3-methyl-2-[4-(trifluoromethoxy)phenyl]-1H-benzimidazole-5-carbaldehyde
[0463] ##STR00103##
[0464] To a solution of [1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methanol and [3-methyl-2-[4-(trifluoromethoxy)phenyl]-1H-benzimidazol-5-yl]methanol (1.97 g, 5.81 mmol) in 100 ml dichloromethane was added manganese dioxide (5.61 g, 58.1 mmol) and the mixture was stirred at rt overnight. The mixture was filtrated over a pad of celite, and the filtrate was evaporated to give a mixture of 1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carbaldehyde and 3-methyl-2-[4-(trifluoromethoxy)phenyl]-1H -benzimidazole-5-carbaldehyde (1.58 g).
[0465] LC-MS: t.sub.R=0.98 min, m/z=321 [M−1].
[0466] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 3.96 (d, J=14.67 Hz, 6H) 7.26 (s, 2H) 7.40-7.45 (m, 4H) 7.50-7.54 (m, 1H) 7.82-7.98 (m, 7H) 8.01 (d, J=0.73 Hz, 1H) 8.31 (d, J=0.73 Hz, 1H) 10.12 (d, J=5.14 Hz, 2H).
Step P-6: Preparation of 1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-2-[4-(trifluoromethcw)phenyl]benzimidazol-5-yl]methyleneamino]urea and 1-(2,6-dimethylphenyl)-3-[(E)-[3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methyleneamino]urea
[0467] ##STR00104##
[0468] To a solution of a mixture of 1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazole-5-carbaldehyde and 3-methyl-2-[4-(trifluoromethoxy)phenyl]-1H-benzimidazole-5-carbaldehyde (120 mg, 0.356 mmol) in 10 ml ethanol was added 1-amino-3-(2,6-dimethylphenyl)urea (71 mg, 0.374 mmol) and the reaction mixture was heated to 65° C. for 3 h. After evaporation, the crude product was purified by flash-chromatography to give 1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methylene-amino]urea (P27) (64 mg) and 1-(2,6-dimethylphenyl)-3-[(E)-[3-methyl-2-[4-(trifluoromethoxy)phenyl]-benzimidazol-5-yl]melhyleneamino]urea (P28) (64 mg) as white crystals.
1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methyleneamino]urea (P27):
[0469] LC-MS: t.sub.R=1.05 min, m/z=480 [M−1], 482 [M+1].
[0470] 1H NMR (400 MHz, CDCl.sub.3) δ ppm 2.36 (s, 6H) 3.90 (s, 3H) 7.13 (s, 3H) 7.26 (s, 1H) 7.41 (t, J=8.07 Hz, 3H) 7.62 (s, 1H) 7.74 (dd, J=8.44, 1.47 Hz, 1H) 7.81-7.86 (m, 2H) 7.94 (s, 1H) 8.01 (d, J=0.73 Hz, 1H) 9.02 (s, 1H).
1-(2,6-dimethylphenyl)-3-[(E)-[3-methyl-2-[4-(trifluoromethoxy)phenyl]benzimidazol-5-yl]methyleneamino]urea (P28):
[0471] LC-MS: t.sub.R=1.05 min, m/z=480 [M−1], 482 [M+1].
[0472] .sup.1H NMR (400 MHz, CDCl.sub.3) δ ppm 2.37 (s, 6H) 3.93 (s, 3H) 7.14 (s, 3H) 7.26 (s, 2H) 7.41 (d, J=8.07 Hz, 2H) 7.58-7.69 (m, 3H) 7.82-7.89 (m, 3H) 7.94 (s, 1H) 8.96 (br. s., 1H).
[0473] The compounds listed in Table 14 are either prepared as disclosed herein or may be prepared in a similar manner as disclosed for the compounds above. Generally, the compounds may be prepared according to schemes 1 to 7 above or according to known methods.
TABLE-US-00003 TABLE 14 Examples of compounds of formula (I) Com- pound Melting No. Structures Point MS/NMR P1
[0474] Formulation examples (% =percent by weight)
TABLE-US-00004 Example F1: Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6% Castor oil polyethylene glycol ether 5% — — (36 mol of EO) Tributylphenoxypolyethylene glycol ether — 12% 4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
TABLE-US-00005 Example F2: Solutions a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% — — — Polyethylene glycol MW 400 — 70% — — N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1% 5% Petroleum ether — — 94% — (boiling range: 160-190°)
The solutions are suitable for use in the form of microdrops.
TABLE-US-00006 Example F3: Granules a) b) c) d) Active ingredient 5% 10% 8% 21% Kaolin 94% — 79% 54% Highly disperse silica 1% — 13% 7% Attapulgite — 90% — 18%
The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
TABLE-US-00007 Example F4: Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97% — Kaolin — 90%
Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
TABLE-US-00008 Example F5: Wettable powders a) b) c) Active ingredient 25% 50% 75% Sodium lignosulfonate 5% 5% — Sodium lauryl sulfate 3% — 5% Sodium diisobutyl-naphthalenesulfonate — 6% 10% Octylphenoxypolyethylene glycol ether — 2% — (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin 62% 27% —
[0475] The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
TABLE-US-00009 Example F6: Extruder granules Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87%
The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
TABLE-US-00010 Example F7: Coated granules Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94%
In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
TABLE-US-00011 Example F8: Suspension concentrate Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil (75% aqueous emulsion) 0.8%
Water 32
[0476] The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
TABLE-US-00012 Example F9: Powders for dry seed treatment a) b) c) active ingredient 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% — Kaolin 65% 40% — Talcum — — 20%
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
TABLE-US-00013 Example F10: Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (35 mol of ethylene oxide) Cyclohexanone 30% xylene mixture 50%
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
TABLE-US-00014 Example F11: Flowable concentrate for seed treatment active ingredients 40% propylene glycol 5% copolymer butanol PO/EO 2% Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (in the form of a 20% 0.5%.sup. solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup. Water 45.3%
[0477] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
[0478] The activity of compositions comprising compounds according to the invention can be broadened considerably, and adapted to prevailing circumstances, by including other active substances. The active substances can be of chemical or biological in type, and in the case of biological could be further modified from the biological species derived in nature. Active substances include substances that control, repel or attract pests that damage or harm useful plants in general, but also substances that improve the growth of a useful plant, such as plant growth regulators, and substances that improve the performance of the active substance, such as synergists. Examples are insecticides, acaricides, nematicides, molluscicides, aligicides, virusicides, rodenticide, bactericides, fungicides, chemosterilants, anthelmintics. Examples of a biological active substance include baculovirus, plant extract, and bacteria.
[0479] The mixtures of the compounds of formula I with other active substances 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 relating to production, for example grinding or mixing, storage or use.
[0480] Individual active substances can occur in more than one group or class, and at more than one place within a group or class: information about the active substances, their spectrum, sources and classifications can be found from Compendium of Pesticide Common Names (see http://www.alanwood.net/pesticides/index.html) or from the Pesticide Manual created by the British Crop Production Counci (see http://bcpcdata.com/pesticide-manual.html).
[0481] Preferred mixtures are indicated below where a compound of formula I according to the invention is indicated as “I”.
[0482] Compositions comprising an adjuvant include I+compounds selected from the group of substances consisting of petroleum oils;
[0483] Compositions comprising an acaricide include I+1,1-bis(4-chlorophenyl)-2-ethoxyethanol, I+2,4-dichlorophenyl benzenesulfonate, I+2-fluoro-N-methyl-N-1-naphthylacetamide, I+4-chlorophenyl phenyl sulfone, I+abamectin, I+acequinocyl, I+acetoprole, I+acrinathrin, I+aldicarb, I+aldoxycarb, I+alpha-cyperrneihrin, I+amidithion, I+amidoflumet, I+amidothioate, I+amiton, I+amiton hydrogen oxalate, I+amitraz, I+aramite, I+arsenous oxide, I+AVI 382, I+AZ 60541, I+azinphos-ethyl, I+azinphos-methyl, I+azobenzene, I+azocyclotin, I+azothoate, I+benomyl, I+benoxafos, I+benzoximate, I+benzyl benzoate, I+bifenazate, I+bifenthrin, I+binapacryl, I+brofenvalerate, I+bromocyclen, I+bromophos, I+bromophos-ethyl, I+bromopropylate, I+buprofezin, I+butocarboxim, I+butoxycarboxim, I+butylpyridaben, I+calcium polysulfide, I+camphechlor, I+carbanolate, I+carbaryl, I+carbofuran, I+carbophenothion, I+CGA 50′439, I+chinomethionat, I+chlorbenside, I+chlordimeform, I+chlordimeform hydrochloride, I+chlorfenapyr, I+chlorfenethol, I+chlorfenson, I+chlorfensulfide, I+chlorfenvinphos, I+chlorobenzilate, I+chloromebuform, I+chloromethiuron, I+chloropropylate, I+chlorpyrifos, I+chlorpyrifos-methyl, I+chlorthiophos, I+cinerin I, I+cinerin II, I+cinerins, I+clofentezine, I+closantel, I+coumaphos, I+crotamiton, I+crotoxyphos, I+cufraneb, I+cyanthoate, I+cyflumetofen, I+cyhalothrin, I+cyhexatin, I+cypermethrin, I+DCPM, I+DDT, I+demephion, I+demephion-O, I+demephion-S, I+demeton, I+demeton-methyl, I+demeton-O, I+demeton-O-methyl, I+demeton-S, I+demeton-S-methyl, I+demeton-S-methylsulfon, I+diafenthiuron, I+dialifos, I+diazinon, I+dichlofluanid, I+dichlorvos, I+dicliphos, I+dicofol, I+dicrotophos, I+dienochlor, I+dimefox, I+dimethoate, I+dinactin, I+dinex, I+dinex-diclexine, I+dinobuton, I+dinocap, I+dinocap-4, I+dinocap-6, I+dinocton, I+dinopenton, I+dinosulfon, I+dinoterbon, I+dioxathion, I+diphenyl sulfone, I+disulfiram, I+disulfoton, I+DNOC, I+dofenapyn, I+doramectin, I+endosulfan, I+endothion, I+EPN, I+eprinomectin, I+ethion, I+ethoate-methyl, I+etoxazole, I+etrimfos, I+fenazaflor, I+fenazaquin, I+fenbutatin oxide, I+fenothiocarb, I+fenpropathrin, I+fenpyrad, I+fenpyroximate, I+fenson, I+fentrifanil, I+fenvalerate, I+fipronil, I+fluacrypyrim, I+fluazuron, I+flubenzimine, I+flucycloxuron, I+flucythrinate, I+fluenetil, I+flufenoxuron, I+flumethrin, I+fluorbenside, I+fluvalinate, I+FMC 1137, I+formetanate, I+formetanate hydrochloride, I+formothion, I+formparanate, I+gamma-HCH, I+glyodin, I+halfenprox, I+heptenophos, I+hexadecyl cyclopropanecarboxylate, I+hexythiazox, I+iodomethane, I+isocarbophos, I+isopropyl O-(methoxyaminothiophosphoryl)salicylate, I+ivermectin, I+jasmolin I, I+jasmolin II, I+jodfenphos, I+lindane, I+lufenuron, I+malathion, I+malonoben, I+mecarbam, I+mephosfolan, I+mesulfen, I+methacrifos, I+methamidophos, I+methidathion, I+methiocarb, I+methomyl, I+methyl bromide, I+metolcarb, I+mevinphos, I+mexacarbate, I+milbemectin, I+milbemycin oxime, I+mipafox, I+monocrotophos, I+morphothion, I+moxidectin, I+naled, I+NC-184, I+NC-512, I+nifluridide, I+nikkomycins, I+nitrilacarb, I+nitrilacarb 1:1 zinc chloride complex, I+NNI-0101, I+NNI-0250, I+omethoate, I+oxamyl, I+oxydeprofos, I+oxydisulfoton, I+pp′-DDT, I+parathion, I+permethrin, I+petroleum oils, I+phenkapton, I+phenthoate, I+phorate, I+phosalone, I+phosfolan, I+phosmet, I+phosphamidon, I+phoxim, I+pirimiphos-methyl, I+polychloroterpenes, I+polynactins, I+proclonol, I+profenofos, I+promacyl, I+propargite, I+propetamphos, I+propoxur, I+prothidathion, I+prothoate, I+pyrethrin I, I+pyrethrin II, I+pyrethrins, I+pyridaben, I+pyridaphenthion, I+pyrimidifen, I+pyrimitate, I+quinalphos, I+quintiofos, I+R-1492, I+RA-17, I+rotenone, I+schradan, I+sebufos, I+selamectin, I+SI-0009, I+sophamide, I+spirodiclofen, I+spiromesifen, I+SSI-121, I+sulfiram, I+sulfluramid, I+sulfotep, I+sulfur, I+SZI-121, I+tau-fluvalinate, I+tebufenpyrad, I+TEPP, I+terbam, I+tetrachlorvinphos, I+tetradifon, I+tetranactin, I+tetrasul, I+thiafenox, I+thiocarboxime, I+thiofanox, I+thiometon, I+thioquinox, I+thuringiensin, I+triamiphos, I+triarathene, I+triazophos, I+triazuron, I+trichlorfon, I+trifenofos, I+trinactin, I+vamidothion, I+vaniliprole and I+YI-5302;
[0484] Compositions comprising an anthelmintic include I+abamectin, I+crufomate, I+doramectin, I+emamectin, I+emamectin benzoate, I+eprinomectin, I+ivermectin, I+milbemycin oxime, I+moxidectin, I+piperazine, I+selamectin, I+spinosad and I+thiophanate;
[0485] Compositions comprising an avicide include I+chloralose, I+endrin, I+fenthion, I+pyridin-4-amine and I+strychnine;
[0486] Compositions comprising a biological control agent include I+Adoxophyes orana GV, I+Agrobacterium radiobacter, I+Amblyseius spp., I+Anagrapha falcifera NPV, I+Anagrus atomus, I+Aphelinus abdominalis, I+Aphidius colemani, I+Aphidoletes aphidimyza, I+Autographa californica NPV, I+Bacillus firmus, I+Bacillus sphaericus Neide, I+Bacillus thuringiensis Berliner, I+Bacillus thuringiensis subsp. aizawai, I+Bacillus thuringiensis subsp. israelensis, I+Bacillus thuringiensis subsp. japonensis, I+Bacillus thuringiensis subsp. kurstaki, I+Bacillus thuringiensis subsp. tenebrionis, I+Beauveria bassiana, I+Beauveria brongniartii, I+Chlysoperla carnea, I+Cryptolaemus montrouzieri, I+Cydia pomonella GV, I+Dacnusa sibirica, I+Diglyphus isaea, I+Encarsia formosa, I+Eretmocerus eremicus, I+Helicoverpa zea NPV, I+Heterorhabditis bacteriophora and H. megidis, I+Hippodamia convergens, I+Leptomastix dactylopii, I+Macrolophus caliginosus, I+Mamestra brassicae NPV, I+Metaphycus helvolus, I+Metarhizium anisopliae var. acridum, I+Metarhizium anisopliae var. anisopliae, I+Neodiprion sertifer NPV and N. lecontei NPV, I+Orius spp., I+Paecilomyces fumosoroseus, I+Phytoseiulus persimilis, I+Spodoptera exigua multicapsid nuclear polyhedrosis virus, I+Steinernema bibionis, I+Steinernema carpocapsae, I+Steinernema feltiae, I+Steinernema glaseri, I+Steinernema riobrave, I+Steinernema riobravis, I+Steinernema scapterisci, I+Steinernema spp., I+Trichogramma spp., I+Typhlodromus occidentalis and I+Verticillium lecanii;
[0487] Compositions comprising a soil sterilant include I+iodomethane and methyl bromide;
[0488] Compositions comprising a chemosterilant include I+apholate, I+bisazir, I+busulfan, I+diflubenzuron, I+dimatif, I+hemel, I+hempa, I+metepa, I+methiotepa, I+methyl apholate, I+morzid, I+penfluron, I+tepa, I+thiohempa, I+thiotepa, I+tretamine and I+uredepa;
[0489] Compositions comprising an insect pheromone include I+(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, I+(E)-tridec-4-en-1-yl acetate, I+(E)-6-methylhept-2-en-4-ol, I+(E,Z)-tetradeca-4,10-dien-1-yl acetate, I+(Z)-dodec-7-en-1-yl acetate, I+(Z)-hexadec-11-enal, I+(Z)-hexadec-11-en-1-yl acetate, I+(Z)-hexadec-13-en-11-yn-1-yl acetate, I+(Z)-icos-13-en-10-one, I+(Z)-tetradec-7-en-1-al, I+(Z)-tetradec-9-en-1-ol, I+(Z)-tetradec-9-en-1-yl acetate, I+(7E,9Z)-dodeca-7,9-dien-1-yl acetate, I+(9Z,11E)-tetradeca-9,11-dien-1-yl acetate, I+(9Z,12E)-tetradeca-9,12-dien-1-yl acetate, I+14-methyloctadec-1-ene, I+4-methylnonan-5-ol with 4-methylnonan-5-one, I+alpha-multistriatin, I+brevicomin, I+codlelure, I+codlemone, I+cuelure, I+disparlure, I+dodec-8-en-1-yl acetate, I+dodec-9-en-1-yl acetate, I+dodeca-8, I+10-dien-1-yl acetate, I+dominicalure, I+ethyl 4-methyloctanoate, I+eugenol, I+frontalin, I+gossyplure, I+grandlure, I+grandlure I, I+grandlure II, I+grandlure III, I+grandlure IV, I+hexalure, I+ipsdienol, I+ipsenol, I+japonilure, I+lineatin, I+litlure, I+looplure, I+medlure, I+megatomoic acid, I+methyl eugenol, I+muscalure, I+octadeca-2,13-dien-1-yl acetate, I+octadeca-3,13-dien-1-yl acetate, I+orfralure, I+oryctalure, I+ostramone, I+siglure, I+sordidin, I+sulcatol, I+tetradec-11-en-1-yl acetate, I+trimedlure, I+trimedlure A, I+trimedlure B.sub.1, I+trimedlure B.sub.2, I+trimedlure C and I+trunc-call;
[0490] Compositions comprising an insect repellent include I+2-(octylthio)ethanol, I+butopyronoxyl, I+butoxy(polypropylene glycol), I+dibutyl adipate, I+dibutyl phthalate, I+dibutyl succinate, I+diethyltoluamide, I+dimethyl carbate, I+dimethyl phthalate, I+ethyl hexanediol, I+hexamide, I+methoquin-butyl, I+methylneodecanamide, I+oxamate and I+picaridin;
[0491] Compositions comprising an insecticide include I+1-dichloro-1-nitroethane, I+1,1-dichloro-2,2-bis(4-ethylphenyl)ethane , I+, I+1,2-dichloropropane, I+1,2-dichloropropane with 1,3-dichloropropene, I+1-bromo-2-chloroethane, I+2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, I+2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, I+2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, I+2-(2-butoxyethoxy)ethyl thiocyanate, I+2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, I+2-(4-chloro-3,5-xylyloxy)ethanol, I+2-chlorovinyl diethyl phosphate, I+2-imidazolidone, I+2-isovalerylindan-1,3-dione, I+2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, I+2-thiocyanatoethyl laurate, I+3-bromo-1-chloroprop-1-ene, I+3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, I+4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, I+5,5-dimethyl-3-oxocyclohex-1-enyl dimelhylcarbamate, I+abamectin, I+acephate, I+acetamiprid, I+acethion, I+acetoprole, I+acrinathrin, I+acrylonitrile, I+alanycarb, I+aldicarb, I+aldoxycarb, I+aldrin, I+allethrin, I+allosamidin, I+allyxycarb, I+alpha-cypermethrin, I+alpha-ecdysone, I+aluminium phosphide, I+amidithion, I+amidothioate, I+aminocarb, I+amiton, I+amiton hydrogen oxalate, I+amitraz, I+anabasine, I+athidathion, I+AVI 382, I+AZ 60541, I+azadirachtin, I+azamethiphos, I+azinphos-ethyl, I+azinphos-methyl, I+azothoate, I+Bacillus thuringiensis delta endotoxins, I+barium hexafluorosilicate, I+barium polysulfide, I+barthrin, I+Bayer 22/190, I+Bayer 22408, I+bendiocarb, I+benfuracarb, I+bensultap, I+beta-cyfluthrin, I+beta-cypermethrin, I+bifenthrin, I+bioallethrin, I+bioallethrin S-cyclopentenyl isomer, I+bioethanomethrin, I+biopermethrin, I+bioresmethrin, I+bis(2-chloroethyl) ether, I+bistrifluron, I+borax, I+brofenvalerate, I+bromfenvinfos, I+bromocyclen, I+bromo-DDT, I+bromophos, I+bromophos-ethyl, I+bufencarb, I+buprofezin, I+butacarb, I+butathiofos, I+butocarboxim, I+butonate, I+butoxycarboxim, I+butylpyridaben, I+cadusafos, I+calcium arsenate, I+calcium cyanide, I+calcium polysulfide, I+camphechlor, I+carbanolate, I+carbaryl, I+carbofuran, I+carbon disulfide, I+carbon tetrachloride, I+carbophenolhion, I+carbosulfan, I+cartap, I+cartap hydrochloride, I+cevadine, I+chlorbicyclen, I+chlordane, I+chlordecone, I+chlordimeform, I+chlordimeform hydrochloride, I+chlorethoxyfos, I+chlorfenapyr, I+chlorfenvinphos, I+chlorfluazuron, I+chlormephos, I+chloroform, I+chloropicrin, I+chlorphoxim, I+chlorprazophos, I+chlorpyrifos, I+chlorpyrifos-methyl, I+chlorthiophos, I+chromafenozide, I+cinerin I,I+cinerin II, I+cinerins, I+cis-resmethrin, I+cismethrin, I+clocythrin, I+cloethocarb, I+closantel, I+clothianidin, I+copper acetoarsenite, I+copper arsenate, I+copper oleate, I+coumaphos, I+coumithoate, I+crotamiton, I+crotoxyphos, I+crufomate, I+cryolite, I+CS 708, I+cyanofenphos, I+cyanophos, I+cyanthoate, I+cyclethrin, I+cycloprothrin, I+cyfluthrin, I+cyhalothrin, I+cypermethrin, I+cyphenothrin, I+cyromazine, I+cythioate, I+d-limonene, I+d-tetramethrin, I+DAEP, I+dazomet, I+DDT, I+decarbofuran, I+deltamethrin, I+demephion, I+demephion-O, I+demephion-S, I+demeton, I+demeton-methyl, I+demeton-O, I+demeton-O-methyl, I+demeton-S, I+demeton-S-methyl, I+demeton-S-methylsulphon, I+diafenthiuron, I+dialifos, I+diamidafos, I+diazinon, I+dicapthon, I+dichlofenthion, I+dichlorvos, I+dicliphos, I+dicresyl, I+dicrotophos, I+dicyclanil, I+dieldrin, I+diethyl 5-methylpyrazol-3-yl phosphate, I+diflubenzuron, I+dilor, I+dimefluthrin, I+dimefox, I+dimetan, I+dimethoate, I+dimethrin, I+dimethylvinphos, I+dimetilan, I+dinex, I+dinex-diclexine, I+dinoprop, I+dinosam, I+dinoseb, I+dinotefuran, I+diofenolan, I+dioxabenzofos, I+dioxacarb, I+dioxathion, I+disulfoton, I+dithicrofos, I+DNOC, I+doramectin, I+DSP, I+ecdysterone, I+El 1642, I+emamectin, I+emamectin benzoate, I+EMPC, I+empenthrin, I+endosulfan, I+endothion, I+endrin, I+EPBP, I+EPN, I+epofenonane, I+eprinomectin, I+esfenvalerate, I+etaphos, I+ethiofencarb, I+ethion, I+ethiprole, I+ethoate-methyl, I+ethoprophos, I+ethyl formate, I+ethyl-DDD, I+ethylene dibromide, I+ethylene dichloride, I+ethylene oxide, I+etofenprox, I+etrimfos, I+EXD, I+famphur, I+fenamiphos, I+fenazaflor, I+fenchlorphos, I+fenethacarb, I+fenfluthrin, I+fenitrothion, I+fenobucarb, I+fenoxacrim, I+fenoxycarb, I+fenpirithrin, I+fenpropathrin, I+fenpyrad, I+fensulfothion, I+fenthion, I+fenthion-ethyl, I+fenvalerate, I+fipronil, I+flonicamid, I+flubendiamide, I+flucofuron, I+flucycloxuron, I+flucythrinate, I+fluenetil, I+flufenerim, I+flufenoxuron, I+flufenprox, I+flumethrin, I+fluvalinate, I+FMC 1137, I+fonofos, I+formetanate, I+formetanate hydrochloride, I+formothion, I+formparanate, I+fosmethilan, I+fospirate, I+fosthiazate, I+fosthietan, I+furathiocarb, I+furethrin, I+gamma-cyhalothrin, I+gamma-HCH, I+guazatine, I+guazatine acetates, I+GY-81, I+halfenprox, I+halofenozide, I+HCH, I+HEOD, I+heptachlor, I+heptenophos, I+heterophos, I+hexaflumuron, I+HHDN, I+hydramethylnon, I+hydrogen cyanide, I+hydroprene, I+hyquincarb, I+imidacloprid, I+imiprothrin, I+indoxacarb, I+iodomethane, I+IPSP, I+isazofos, I+isobenzan, I+isocarbophos, I+isodrin, I+isofenphos, I+isolane, I+isoprocarb, I+isopropyl O-(methoxy-aminothiophosphoryl)salicylate, I+isoprothiolane, I+isothioate, I+isoxathion, I+ivermectin, I+jasmolin I, I+jasmolin II, I+jodfenphos, I+juvenile hormone I, I+juvenile hormone II, I+juvenile hormone III, I+kelevan, I+kinoprene, I+lambda-cyhalothrin, I+lead arsenate, I+lepimectin, I+leptophos, I+lindane, I+lirimfos, I+lufenuron, I+lythidathion, I+m-cumenyl methylcarbamate, I+magnesium phosphide, I+malathion, I+malonoben, I+mazidox, I+mecarbam, I+mecarphon, I+menazon, I+mephosfolan, I+mercurous chloride, I+mesulfenfos, I+metaflumizone, I+metam, I+metam-potassium, I+metam-sodium, I+methacrifos, I+methamidophos, I+methanesulfonyl fluoride, I+methidathion, I+methiocarb, I+methocrotophos, I+methomyl, I+methoprene, I+methoquin-butyl, I+methothrin, I+methoxychlor, I+methoxyfenozide, I+methyl bromide, I+methyl isothiocyanate, I+methylchloroform, I+methylene chloride, I+metofluthrin, I+metolcarb, I+metoxadiazone, I+mevinphos, I+mexacarbate, I+milbemectin, I+milbemycin oxime, I+mipafox, I+mirex, I+monocrotophos, I+morphothion, I+moxidectin, I+naftalofos, I+naled, I+naphthalene, I+NC-170, I+NC-184, I+nicotine, I+nicotine sulfate, I+nifluridide, I+nitenpyram, I+nithiazine, I+nitrilacarb, I+nitrilacarb 1:1 zinc chloride complex, I+NNI-0101, I+NNI-0250, I+nornicotine, I+novaluron, I+noviflumuron, I+O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, I+O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, I+O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, I+O,O,O′,O′-tetrapropyl dithiopyrophosphate, I+oleic acid, I+omethoate, I+oxamyl, I+oxydemeton-methyl, I+oxydeprofos, I+oxydisulfoton, I+pp′-DDT, I+para-dichlorobenzene, I+parathion, I+parathion-methyl, I+penfluron, I+pentachlorophenol, I+pentachlorophenyl laurate, I+permethrin, I+petroleum oils, I+PH 60-38, I+phenkapton, I+phenothrin, I+phenthoate, I+phorate+TX, I+phosalone, I+phosfolan, I+phosmet, I+phosnichlor, I+phosphamidon, I+phosphine, I+phoxim, I+phoxim-methyl, I+pirimetaphos, I+pirimicarb, I+pirimiphos-ethyl, I+pirimiphos-methyl, I+polychlorodicyclopentadiene isomers, I+polychloroterpenes, I+potassium arsenite, I+potassium thiocyanate, I+prallethrin, I+precocene I, I+precocene II, I+precocene III, I+primidophos, I+profenofos, I+profluthrin, I+promacyl, I+promecarb, I+propaphos, I+propetamphos, I+propoxur, I+prothidathion, I+prothiofos, I+prothoate, I+protrifenbute, I+pymetrozine, I+pyraclofos, I+pyrazophos, I+pyresmethrin, I+pyrethrin I, I+pyrethrin II, I+pyrethrins, I+pyridaben, I+pyridalyl, I+pyridaphenthion, I+pyrimidifen, I+pyrimitate, I+pyriproxyfen, I+quassia, I+quinalphos, I+quinalphos-methyl, I+quinothion, I+quintiofos, I+R-1492, I+rafoxanide, I+resmethrin, I+rotenone, I+RU 15525, I+RU 25475, I+ryania, I+ryanodine, I+sabadilla, I+schradan, I+sebufos, I+selamectin, I+SI-0009, I+SI-0205, I+SI-0404, I+SI-0405, I+silafluofen, I+SN 72129, I+sodium arsenite, I+sodium cyanide, I+sodium fluoride, I+sodium hexafluorosilicate, I+sodium pentachlorophenoxide, I+sodium selenate, I+sodium thiocyanate, I+sophamide, I+spinosad, I+spiromesifen, I+spirotetrmat, I+sulcofuron, I+sulcofuron-sodium, I+sulfluramid, I+sulfotep, I+sulfuryl fluoride, I+sulprofos, I+tar oils, I+tau-fluvalinate, I+tazimcarb, I+TDE, I+tebufenozide, I+tebufenpyrad, I+tebupirimfos, I+teflubenzuron, I+tefluthrin, I+temephos, I+TEPP, I+terallethrin, I+terbam, I+terbufos, I+tetrachloroethane, I+tetrachlorvinphos, I+tetramethrin, I+theta-cypermethrin, I+thiacloprid, I+thiafenox, I+thiamethoxam, I+thicrofos, I+thiocarboxime, I+thiocyclam, I+thiocyclam hydrogen oxalate, I+thiodicarb, I+thiofanox, I+thiometon, I+thionazin, I+thiosultap, I+thiosultap-sodium, I+thuringiensin, I+tolfenpyrad, I+tralomethrin, I+transfluthrin, I+transpermethrin, I+triamiphos, I+triazamate, I+triazophos, I+triazuron, I+trichlorfon, I+trichlormetaphos-3, I+trichloronat, I+trifenofos, I+triflumuron, I+trimethacarb, I+triprene, I+vamidothion, I+vaniliprole, I+veratridine, I+veratrine, I+XMC, I+xylylcarb, I+YI-5302, I+zeta-cypermethrin, I+zetamethrin, I+zinc phosphide, I+zolaprofos and ZXI 8901, I+cyantraniliprole, I+chlorantraniliprole, I+cyenopyrafen, I+cyflumetofen, I+pyrifluquinazon, I+spinetoram, I+spirotetramat, I+sulfoxaflor, I+flufiprole, I+meperfluthrin, I+tetramethylfluthrin, I+triflumezopyrim;
[0492] Compositions comprising a molluscicide include I+bis(tributyltin) oxide, I+bromoacetamide, I+calcium arsenate, I+cloethocarb, I+copper acetoarsenite, I+copper sulfate, I+fentin, I+ferric phosphate, I+metaldehyde, I+methiocarb, I+niclosamide, I+niclosamide-olamine, I+pentachlorophenol, I+sodium pentachlorophenoxide, I+tazimcarb, I+thiodicarb, I+tributyltin oxide, I+trifenmorph, I+trimethacarb, I+triphenyltin acetate and triphenyltin hydroxide, I+pyriprole;
[0493] Compositions comprising a nematicide include I+AKD-3088, I+1,2-dibromo-3-chloropropane, I+1,2-dichloropropane, I+1,2-dichloropropane with 1,3-dichloropropene, I+1,3-dichloropropene, I+3,4-dichlorotetrahydrothiophene 1,1-dioxide, I+3-(4-chlorophenyl)-5-methylrhodanine, I+5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, I+6-isopentenylaminopurine, I+abamectin, I+acetoprole, I+alanycarb, I+aldicarb, I+aldoxycarb, I+AZ 60541, I+benclothiaz, I+benomyl, I+butylpyridaben, I+cadusafos, I+carbofuran, I+carbon disulfide, I+carbosulfan, I+chloropicrin, I+chlorpyrifos, I+cloethocarb, I+cytokinins, I+dazomet, I+DBCP, I+DCIP, I+diamidafos, I+dichlofenthion, I+dicliphos, I+dimethoate, I+doramectin, I+emamectin, I+emamectin benzoate, I+eprinomectin, I+ethoprophos, I+ethylene dibromide, I+fenamiphos, I+fenpyrad, I+fensulfothion, I+fosthiazate, I+fosthietan, I+furfural, I+GY-81, I+heterophos, I+iodomethane, I+isamidofos, I+isazofos, I+ivermectin, I+kinetin, I+mecarphon, I+metam, I+metam-potassium, I+metam-sodium, I+methyl bromide, I+methyl isothiocyanate, I+milbemycin oxime, I+moxidectin, I+Myrothecium verrucaria composition, I+NC-184, I+oxamyl, I+phorate, I+phosphamidon, I+phosphocarb, I+sebufos, I+selamectin, I+spinosad, I+terbam, I+terbufos, I+tetrachlorothiophene, I+thiafenox, I+thionazin, I+triazophos, I+triazuron, I+xylenols, I+YI-5302 and zeatin, I+fluensulfone;
[0494] Compositions comprising a synergist include I+2-(2-butoxyethoxy)ethyl piperonylate, I+(5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, I+farnesol with nerolidol, I+MB-599, I+MGK 264, I+piperonyl butoxide, I+piprotal, I+propyl isomer, I+S421, I+sesamex, I+sesasmolin and I+sulfoxide;
[0495] Compositions comprising an animal repellent include I+anthraquinone, I+chloralose, I+copper naphthenate, I+copper oxychloride, I+diazinon, I+dicyclopentadiene, I+guazatine, I+guazatine acetates, I+methiocarb, I+pyridin-4-amine, I+thiram, I+trimethacarb, I+zinc naphthenate and I+ziram;
[0496] Further compositions include I+Brofluthrinate, I+Cycloxaprid, I+Diflovidazine, I+Flometoquin, I+Fluhexafon, I+Guadipyr, I+Plutella xylostella Granulosis virus, I+Cydia pomonella Granulosis virus, I+Harpin, I+Imicyafos, I+Heliothis virescens Nucleopolyhedrovirus, I+Heliothis punctigera Nucleopolyhedrovirus, I+Helicoverpa armigera Nucleopolyhedrovirus, I+Helicoverpa zea Nucleopolyhedrovirus, I+Spodoptera frugiperda Nucleopolyhedrovirus, I+Plutella xylostella Nucleopolyhedrovirus, I+Pasteuria nishizawae, I+p-cymene, I+Pyflubumide, I+Pyrafluprole, I+pyrethrum, I+QRD 420, I+QRD 452, I+QRD 460, I+Terpenoid blends, I+Terpenoids, I+Tetraniliprole, and I+α-terpinene;
[0497] Composition also include mixtures of compound of formula I and an active substance referenced by a code, such as I+code AE 1887196 (BSC-BX60309), I+code NNI-0745 GR, I+code IKI-3106, I+code JT-L001, I+code ZNQ-08056, I+code IPPA152201, I+code HNPC-A9908 (CAS: [660411-21-2]), I+code HNPC-A2005 (CAS: [860028-12-2]), I+code JS118, I+code ZJ0967, I+code ZJ2242, I+code JS7119 (CAS: [929545-74-4]), I+code SN-1172, I+code HNPC-A9835, I+code HNPC-A9955, I+code HNPC-A3061, I+code Chuanhua 89-1, I+code IPP-10, I+code ZJ3265, I+code JS9117, I+code SYP-9080, I+code ZJ3757, I+code ZJ4042, I+code ZJ4014, I+code ITM-121, I+code DPX-RAB55 (DKI-2301), I+code Me5382, I+code NC-515, I+code NA-89, I+code MIE-1209, I+code MCI-8007, I+code BCS-CL73507, I+code S-1871, I+code DPX-RDS63, and I+code AKD-1193.
[0498] The active ingredient mixture of the compounds of formula I selected from Tables 1 to 13 with active ingredients described above comprises a compound selected from Tables 1 to 13 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.
[0499] 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.
[0500] The mixtures comprising a compound of formula I selected from Tables 1 to 13 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 1 to 13 and the active ingredients as described above is not essential for working the present invention.
[0501] 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.
[0502] 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.
[0503] 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.
[0504] 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.
[0505] 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.
[0506] The invention therefore relates to a method for the protection of plant propagation material from the attack by pests, which comprises treating the propagation material or the site, where the propagation material is planted, with a compound of formula (I) or with a composition as defined above, which comprises at least one compound of formula I or, where appropriate, a tautomer thereof, in each case in free form or in agrochemically utilizable salt form, as active ingredient and at least one auxiliary composition.
[0507] 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.
[0508] 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).
[0509] 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
%=Percent by Weight, Unless Otherwise Specified
Example B1
Spodoptera littoralis (Egyptian Cotton Leaf Worm)
[0510] 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 five L1 larvae. The samples were assessed for mortality, anti-feedant effect, and growth inhibition in comparison to untreated samples 3 days after infestation. Control of Spodoptera littoralis by a test sample is when at least one of mortality, anti-feedant effect, and growth inhibition is higher than the untreated sample.
[0511] The following compounds resulted in at least 80% control at an application rate of 200 ppm: P1, P2, P3, P17, P18, P19, P21, P27, P29, P31, P32, P33, P34, P35 and P36.
Example B2
Plutella xylostella (Diamond Back Moth)
[0512] 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, the plates were infested with L2 larvae (10 to 15 per well). The samples were assessed for mortality and growth inhibition in comparison to untreated samples 5 days after infestation.
[0513] 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: P1, P2, P3, P4, P12, P13, P14, P15, P17, P18, P19, P22, P29, P30, P31, P32, P33, P34, P35 and P36.
Example B3
Diabrotica balteata (Corn Root Worm)
[0514] Maize sprouts, placed on 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.
[0515] 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: P1, P2, P3, P13, P14, P15, P17, P21, P29, P35 and P36.