Alpha-cyanophenoxybenzylamine derivatives, processes for preparing them, and their use as intermediates for the preparation of pyrethroid insecticides

Claim 2

A compound of formula I wherein: A, B, D and E are independently chosen from the group consisting of hydrogen, halogen, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl and C 1 to C 6 alkoxy; and Z is chosen from NR 1 R 2 and R 1 R 2 R 3 wherein: R 1 and R 2 are independently chosen from the group consisting of C 1 to C 6 alkyl, phenyl, benzyl, and the groups phenyl and benzyl wherein in each group the phenyl ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, hydroxy, C 1 to C 6 alkyl, C 1 to C 6 alkoxy and C 1 to C 6 haloalkyl, or R 1 and R 2 are linked to form a three to seven membered heterocyclic ring; R 3 is chosen from the group consisting of C 1 to C 6 alkyl, phenyl, benzyl, and the groups phenyl and benzyl wherein in each group the phenyl ring is substituted with from one to three substituents chosen from the group consisting of halogen, nitro, cyano, hydroxy, C 1 to C 6 alkyl, C 1 to C 6 alkoxy and C 1 to C 6 haloalkyl, or R 1 R 2 R 3 is a pyridinium, pyrazinium, pyrimidinium or pyridazinium ring; and is the anion of an organic or an inorganic acid.

Claim 3

A compound according to claim 1 wherein: A, B, D and E are independently chosen from the group consisting of hydrogen, halogen, methyl, trifluoromethyl and methoxy; and Z is chosen from the groups NR 1 R 2 and NR 1 R 2 R 3 wherein: wherein: R 1 and R 2 are independently chosen from the group consisting of C 1 to C 4 alkyl, phenyl and benzyl or R 1 and R 2 are 'linked together to form a heterocyclic ring chosen from the group consisting of 1-pyrrolyl, 1-imidazolyl, 1-pyrrolidinyl, 1-pyrrolinyl, 1-imidazolinyl, piperidino, 1-piperazinyl and morpholino; R 3 is chosen from the group consisting of C 1 to C 4 alkyl, phenyl and benzyl or R 1 R 2 R 3 is a pyridinium, pyrazinium, pyrimidinium or pyridazinium ring; and is the anion of a strong acid.

Claim 4

A compound according to claim 1 or claim 2 wherein: A, B, D and E are independently chosen from hydrogen and halogen; and Z is chosen from the groups NR 1 R 2 and R 1 R 2 R 3 wherein: R 1 and R 2 are independently chosen from C 1 to C 4 alkyl or R 1 and R 2 are linked to form a heterocyclic ring chosen from the group consisting of 1-pyrrolyl, 1-pyrrolidinyl, piperidino and morpholino; R 3 is chosen from C 1 to C 4 alkyl; and is the anion of a strong acid.

Claim 5

A compound according to any one of claims 1 to 3 inclusive wherein in the compound of formula I the phenyl ring of the benzyl group is substituted in the 3- position by the phenoxy group to give a compound of formula II

Claim 6

A compound according to any one of claims 1 to 4 inclusive wherein Z is the group - R 1 R 2 R 3 .

Claim 7

A compound according to any one of claims 1 to 4 inclusive wherein: A, B, D and E are hydrogen; and Z is chosen from the group consisting of N,N-dimethyl- mino, 1-pyrrolidinyl, N,N-di(n-propyl)amino, N-isobutyl-N-methylamino, N,N,N-trimethylammonio methyl sulfate, and N-isobutyl-N,N-dimethylammonio methyl sulfate.

Claim 8

A process for the preparation of a compound of formula I as defined according to any one of claims 1 to 6 inclusive which process comprises either: reacting an a-cyanophenoxybenzyl derivative of formula IV, wherein L is a leaving group, with an amine of formula V, wherein R 26 is hydrogen or R 1 and R 27 is hydrogen or R 2 , and, if R 26 and/or R 27 is hydrogen, alkylating the product as required to give a compound of formula I or reacting a phenoxybenzaldehyde derivative of formula VI with hydrocyanic acid or a salt thereof and an amine of formula V, as hereinbefore defined, and, if R 26 and/ or R 27 is hydrogen, alkylating the product as required to give a compound of formula I

Claim 9

A process for the synthesis of pyrethroid esters which process comprises reacting a compound of formula I, as defined according to any one of claims 1 to 6 inclusive and wherein Z is the group - R 1 R 2 R 3 , with a pyrethrin acid or pyrethroid acid or a salt thereof.

Claim 10

A process according to claim 8 wherein said pyrethrin or pyrethroid acid has the formula IX wherein J is chosen from the groups of the formula: wherein V represents a substituted aromatic group or an unsaturated alicyclic group or an alkenyl group and is selected from the group consisting of the formulae in which R g and R 10 are independently chosen from hydrogen, halogen, cyano, nitro, C 1 to C 6 alkyl optionally substituted with halogen atoms or C 1 to C 6 alkoxy, C2 to C 6 alkenyl optionally substituted with halogen atoms, C 2 to C 6 alkynyl optionally substituted with halogen atoms, C 1 to C 6 alkoxy optionally substituted with halogen atoms, C 1 to C 6 alkylthio, C 1 to C 6 alkylsulfinyl, acyl, acyloxy, C 1 to C 6 -(alkoxy)carbonyl, C 2 to C 6 -(alkenyloxy)carbonyl and C 2 to C 6 -(alkynyloxy)-carbonyl, or R 9 and R 10 may jointly form a methylene dioxy, tetramethylene or trimethylene group; R 11 and R 12 are independently chosen from hydrogen, halogen, cyano, nitro, C 1 to C 6 alkyl optionally substituted with halogen atoms or C 1 to C 6 alkoxy, C 2 to C 6 alkenyl optionally substituted with halogen atoms, C 2 to C 6 alkynyl optionally substituted with halogen atoms, C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, C 1 to C 6 alkylsulfinyl, acyl, acyloxy, C 1 to C 6 -(alkoxy)carbonyl, C 2 to C 6 -(alkenyloxy)carbonyl and C 2 to C 6 -(alkynyloxy)-carbonyl; T represents an oxygen atom or a sulfur atom; R 13 is chosen from hydrogen, halogen, cyano, nitro and C 1 to C 6 alkyl; m and n are independently integers of from 1 to 3; the dotted line in formula XX represents a double bond present at a position either conjugated with or non-conjugated with the ketone group ( C = O ); R14, R 15 and R 16 are independently chosen from hydrogen, C 1 to C 6 alkyl, C2 to C 6 alkenyl, C 2 to C 6 alkynyl, halogen, acyl and acyloxy; W represents a straight or branched chain C 1 to C 6 alkyl group optionally substituted with halogen, a straight or branched chain C 2 to C 6 alkenyl group optionally substituted with halogen, a straight or branched chain C 2 to C 6 alkynyl group, C 1 to C 6 alkoxy, cyano or a C 3 to C 7 alicyclic group; G is hydrogen or fluorine; Y is the group R 18 R 19 C=CR 17 in which R 17 is hydrogen or C1 to C 6 alkyl; R 18 is hydrogen, halogen or C 1 to C 6 alkyl optionally substituted with halogen atoms; R 19 is chosen from the group consisting of hydrogen, halogen, C l to C 6 alkyl optionally substituted with halogen atoms, C 1 to C 6 alkyl substituted with C 1 to C 6 alkoxy, C 1 to C 6 alkyl substituted with C 2 to C 6 alkenyloxy, C 1 to C 6 alkyl substituted with C 2 to C 6 alkynylox y , C 1 to C 6 -(alkoxy)carbonyl, acyl, a substitutent of the formula R 21 R 22 C=CR 20 - wherein R 20 , R 21 and R 22 are individually hydrogen or C 1 to C 6 alkyl, and a substituent of the formula R 23 ON=CH- wherein R 23 is hydrogen or C 1 to C alkyl or C 2 to C 6 alkenyl or C 2 to C 6 alkynyl; or R 18 and R 19 jointly may form a cycle of formula wherein U is -CH 2 -, and p is an integer of from 2 to 5; R 6 is hydrogen or C 1 to C 6 alkyl; R 4 and R 5 are independently chosen from hydrogen, halogen and C1 to C 6 alkyl, or R 4 and R 5 jointly form an ethylene, trimethylene, tetramethylene or pentamethylene bridging group; R 7 and R 8 are independently chosen from hydrogen, C 1 to C6 alkyl, C 1 to C 6 haloalkyl, halogen and phenyl optionally substituted with one or more groups or atoms chosen from halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl and C 1 to C 6 alkoxy or R 7 and R 8 jointly form a bridging group selected from ethylene, trimethylene, tetramethylene, pentamethylene and groups of the formulae Q is selected from Cl to C6 alkyl, C2 to C 6 alkenyl, C 2 to C 6 alkynyl and the group in which R 24 is chosen from hydrogen, C 1 to C 3 alkoxy, C 1 to C 3 alkylthio, C 1 to C 2 alkyl, nitro, fluoro, chloro, bromo and amino; R 25 is chosen from hydrogen and methyl; or R 24 and R 25 jointly is a methylenedioxy bridging group.

Claim 11

A process according to claim 9 wherein J is the group wherein: V is chosen from the groups and in which R 9 , R 10 and R 11 are independently chosen from hydrogen, halogen and C 1 to C 6 alkoxy optionally substituted with halogen; W is chosen from C 1 to C 6 alkyl; and G is chosen from hydrogen and fluorine.

Claim 12

ll. A process according to claim 9 wherein J is chosen from the groups wherein: Y is the group R 18 R 19 C=CR 17 - in which R 17 is hydrogen and R 18 and R 19 are independently chosen from halogen, and C 1 to C 6 alkyl optionally substituted with halogen, R 4 and R 5 are methyl R 6 and R are hydrogen and R 8 is chosen from C 1 to C 6 haloalkyl.

Claim 13

A process according to claim 9 or claim 10 wherein J is the group wherein: V is chosen from the group phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-methoxyphenyl, 2-chloro-4-trifluoro- methylanilino and 4-(difluoromethoxy)phenyl; W is isopropyl; and G is hydrogen.

Claim 14

A process according to claim 9 or claim 11 wherein J is chosen from the groups 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl, 3-(2,2- dibromovinyl)-2,2-dimethylcyclopropyl, 2,2-dimethyl-3-(2,2-dimethylvinyl)-cyclopropyl and 3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropyl.

Claim 15

A process according to claim 9, claim 10 or claim 12 wherein J is the group wherein: V is 4-chlorophenyl; W is isopropyl; and G is hydrogen.

Claim 16

A process according to claim 9, claim 11 or claim 13 wherein J is chosen from the groups 3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropyl and 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl.