Patent EA-001751-B1 (EA)
Title: 1,4-diaryl-2,3-difluoro-2 buteneinsecticidal and acaricidal agents
Inventor: BENTLEY TERENCE JAMES
IPC: C07C41/30
Filed: 1998-11-11
Abstract: 1. 1,4-diaryl-2,3-difluoro-2-butenes of general formula   wherein Ar is phenyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4alkoxy and C1-C4haloalkoxy groups, R is hydrogen, C1-C4alkyl or C3-C6cycloalkyl; R1 is hydrogen; Ar1 is phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups. 2. A compound according to Claim 1 wherein R is isopropyl, trifluoromethyl or cyclopropyl; R1 is hydrogen; and Ar1 is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups. 3. A compound according to Claim 2 wherein R is isopropyl. 4. A compound according to Claim 3 selected from the group consisting of 4-(p-chlorophenyl)-2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; 4-(p-chlorophenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(m-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 2,3-difluoro-4-(p-fluorophenyl)-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; and 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-4-(p-fluorophenyl)-5-methyl-2-hexene, (E)-isomer. 5. A method for the control of insect or acarid pests which comprises contacting said pests or their food supply, habitat or breeding grounds with a pesticidally effective amount of a compound according to Claim 1. 6. A method according to Claim 5 wherein R is isopropyl, trifluoromethyl or cyclopropyl; R1 is hydrogen; and Ar1 is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups. 7. A method according to Claim 6 wherein R is isopropyl. 8. A method according to Claim 7 wherein a compound is selected from the group consisting of 4-(p-chlorophenyl)-2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; 4-(p-chlorophenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(m-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 2,3-difluoro-4-(p-fluorophenyl)-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; and 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-4-(p-fluorophenyl)-5-methyl-2-hexene, (E)-isomer. 9. A method for the protection of growing plants from attack or infestation by insect or acarid pests which comprises applying to the foliage of the plants, or to the soil or water in which they are growing, a pesticidally effective amount of a compound according to Claim 1. 10. A method according to Claim 9 wherein a compound is selected from the group consisting of 4-(p-chlorophenyl)-2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; 4-(p-chlorophenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-5-methyl-1-(m-phenoxyphenyl)-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(m-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 4-(p-ethoxyphenyl)-2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-2-hexene, (E)-isomer; 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-5-methyl-4-[p-(trifluoromethoxy)phenyl]-2-hexene, (E)-isomer; 2,3-difluoro-4-(p-fluorophenyl)-5-methyl-1-(m-phenoxyphenyl)-2-hexene, (E)-isomer; and 2,3-difluoro-1-(4-fluoro-3-phenoxyphenyl)-4-(p-fluorophenyl)-5-methyl-2-hexene, (E)-isomer. 11. A method according to Claim 10 wherein the compound is applied to the plants, or to the soil or water in which they are growing, at a rate of about 0.1 kg/ha to 4.0 kg/ha. 12. A composition for the control of insect or acarid pests which comprises an agronomically acceptable carrier and a pesticidally effective amount of a compound according to Claim 1. 13. A composition according to Claim 12 wherein R is isopropyl, trifluoromethyl or cyclopropyl; R1 is hydrogen; and Ar1 is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups. 14. A composition according to Claim 13 wherein R is isopropyl. 15. 3-aryl-1,2-difluoro-1-propenes of general formula   wherein Ar is phenyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups; 1- or 2-naphthyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups, or 5- or 6-membered heteroaromatic ring optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups; R is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; Z1 is hydrogen or F, and the optical isomers thereof, and the (E)- and (Z)-isomers thereof. 16. A compound according to Claim 15 wherein Ar is phenyl optionally substituted with any combination of from one to three halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups; and R is C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl or C3-C6halocycloalkyl. 17. A compound according to Claim 16 wherein R is isopropyl. 18. A process for the preparation of a compound having the structural formula   wherein Ar, Ar1 and R are as defined in Claim 1, which process comprises reacting a 3-aryl-1,1,2-trifluoro-1-propene compound having the structural formula   wherein Ar and R are as described above with sodium bis(2-methoxyethoxy)-aluminum hydride and a mineral acid to form a 3-aryl-1,2-difluoro-1-propene compound having the structural formula   wherein Ar and R are as described above, and sequentially reacting the 3-aryl-1,2-difluoro-1-propene compound with an alkyllithium compound, zinc chloride, tetrakis(triphenylphosphine)palladium(0) and a substituted methyl halide compound having the structural formula ZCH2Ar1 wherein Z is Cl, Br or I and Ar1 is as described above. 19. A process according to Claim 18 wherein R is isopropyl; and Ar1 is 3-phenoxyphenyl optionally substituted with any combination of from one to six halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups.