US008487115B2

(12) United States Patent (10) Patent No.: US 8.487,115 B2 Matsuo (45) Date of Patent: Jul. 16, 2013

(54) HYDANTOIN DERIVATIVES OF (56) References Cited CYANO-SUBSTITUTED CHRYSANTHEMIC ACD ESTERS AND THEIR USE IN PEST U.S. PATENT DOCUMENTS CONTROL 4,176,189 A * 1 1/1979 Itaya et al...... 514/389 (75) Inventor: Noritada Matsuo, Amagasaki (JP) FOREIGN PATENT DOCUMENTS JP 57-158765 A 9, 1982 (73) Assignee: Sumitomo Chemical Company, W. 3. A. 3. Limited, Tokyo (JP) WO WO 2010O87419 A2 * 8, 2010 OTHER PUBLICATIONS (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 Int'l Search Report and Written Opinion issued Jun. 17, 2011 in Int’l U.S.C. 154(b) by 0 days. Application No. PCT/JP2011/057504. Tomlin, “473 imiprothrin'. The e-Pesticide Manual, Version 4.0, pp. 1-2 (Jul. 1, 2006). (21) Appl. No.: 13/637,788 Int’l Preliminary Report on Patentability issued Oct. 2, 2012 in Int’l Application No. PCT/JP2011/057504. (22) PCT Filed: Mar. 18, 2011 * cited by examiner (86). PCT No.: PCT/UP2011/057504 Primary Examiner — Joseph K. McKane S371 (c)(1), Assistant Examiner — Amanda L. Aguirre (2), (4) Date: Dec. 12, 2012 (74) Attorney, Agent, or Firm — Panitch Schwarze Belisario & Nadel LLP (87) PCT Pub. No.: WO2011/122509 (57) ABSTRACT PCT Pub. Date: Oct. 6, 2011 An ester compound represented by formula (1): wherein R represents hydrogen or methyl, R' represents hydrogen or (65) Prior Publication Data C1-C4 alkyl, andR represents hydrogen or C1-C4 alkyl; has US 2013/0090363 A1 Apr. 11, 2013 an excellent pest control effect and is therefore useful as an active ingredient of a pest control agent. (30) Foreign Application Priority Data Mar. 31, 2010 (JP) ...... 2010-08 1657 O H3C CH3 R3 R4 (51) Int. Cl. AOIN 53/00 (2006.01) l 5 C07D 233/72 (2006.01) e1) \ CHEC R (52) U.S. Cl. USPC ...... 548/319.5: 548/318.5: 514/389 is, O O YN (58) Field of Classification Search USPC ...... 548/3001: 334.5 See application file for complete search history. 30 Claims, No Drawings US 8,487,115 B2 1. 2 HYDANTON DERVATIVES OF 5 The ester compound according to 1, wherein a relative CYANO-SUBSTITUTED CHRYSANTHEMIC configuration of the Substituent of the 1'-position existing on ACDESTERS AND THEIR USE IN PEST the Substituent at the 3-position of the cyclopropane ring is CONTROL Z-configuration in formula (1): 6The ester compound according to 1, wherein an absolute CROSS-REFERENCE TO RELATED configuration of the 1-position of the cyclopropane ring is an APPLICATION R configuration and a relative configuration of the Substituent of the 1'-position existing on the substituent at the 3-position This application is a Section 371 of International Applica of the cyclopropane ring is Z-configuration in formula (1): tion No. PCT/JP2011/057504, filed Mar 18, 2011, which was 10 7The ester compound according to 1, wherein an absolute published in the English language on Oct. 6, 2011, under configuration of the 1-position of the cyclopropane ring is an International Publication No. WO 2011/122509 A1, and the R configuration, a relative configuration of the Substituent at disclosure of which is incorporated herein by reference. the 1-position of the cyclopropane ring and the Substituent at 15 the 3-position of the cyclopropane ring is a trans configura TECHNICAL FIELD tion, and a relative configuration of the substituent of the 1'-position existing on the substituent at the 3-position of the The present invention relates to an ester compound and use cyclopropane ring is Z-configuration in formula (1): thereof. 8. The ester compound according to any one of 1 to 7. wherein R is hydrogen in formula (1): BACKGROUND ART 9. The ester compound according to any one of 1 to 7. wherein R is hydrogen or methyl in formula (1): Heretofore, various compounds have been synthesized so 10 The ester compound according to any one of 1 to 7. as to control pests. For example, a certain ester compound is wherein R is hydrogen in formula (1): described in JP-A-57-158765. 25 11 The ester compound according to any one of 1 to 7. wherein R is methyl in formula (1): DISCLOSURE OF INVENTION 12 The ester compound according to any one of 1 to 7. wherein R is hydrogen in formula (1): An object of the present invention is to provide a novel 13 The ester compound according to any one of 1 to 7. compound having an excellent pest control effect. 30 wherein R is hydrogen and R is hydrogen or methyl in The present inventors have intensively studied and found formula (1): that an ester compound represented by formula (1) shown 14 The ester compound according to any one of 1 to 7. below has an excellent pest control effect, and led to the wherein R is hydrogen and R is hydrogen in formula (1): present invention. 15 The ester compound according to any one of 1 to 7. That is, the present invention is directed to the following 35 wherein R is hydrogen and R is methyl in formula (1): invention: 16. The ester compound according to any one of 1 to 7. 1. An ester compound represented by formula (1): wherein R is hydrogen and R is hydrogen in formula (1): 17 The ester compound according to any one of 1 to 7. 40 wherein R is hydrogen or methyl, and R is hydrogen in formula (1): 18 The ester compound according to any one of 1 to 7. wherein R is hydrogen and R is hydrogen in formula (1): 19. The ester compound according to any one of 1 to 7. 45 wherein R is methyl and R is hydrogen in formula (1): e1) - \ 3 ci 20. The ester compound according to any one of 1 to 7. N.Y. O wherein R is hydrogen, R is hydrogen or methyl, and R is hydrogen in formula (1): 21. The ester compound according to any one of 1 to 7. wherein R represents hydrogen or methyl, R' represents 50 wherein R is hydrogen, Rishydrogen, and Rishydrogenin hydrogen or C1-C4 alkyl, and R represents hydrogen or formula (1): C1-C4 alkyl 22 The ester compound according to any one of 1 to 7. (hereinafter referred to as the compound of the present inven wherein R is hydrogen, R is methyl; and R is hydrogen in tion); formula (1): 2 The ester compound according to 1, wherein a relative 55 23 A pest control agent comprising the ester compound configuration of the Substituent at the 1-position of the cyclo according to any one of 1 to 22 and an inert barrier; propane ring and the Substituent at the 3-position of the cyclo 24A method of controlling pests, which comprises a step of propane ring is a trans configuration in formula (1); applying an effective amount of the ester compound accord 3 The ester compound according to 1, wherein an absolute ing to any one of 1 to 22 to pests or a place where pests configuration of the 1-position of the cyclopropane ring is an 60 habitat; R configuration in formula (1): 25 A method of controlling pests, which comprises the step 4The ester compound according to 1, wherein an absolute of applying an effective amount of the ester compound configuration of the 1-position of the cyclopropane ring is an according to any one of 1 to 22 to cockroaches or a place R configuration, and a relative configuration of the Substitu where cockroaches inhabits: ent at the 1-position of the cyclopropane ring and the Sub 65 26. The method of controlling pests according to 25. stituent at the 3-position of the cyclopropane ring is a trans wherein the cockroach is American cockroach (Periplaneta configuration in formula (1): Americana); US 8,487,115 B2 3 4 27 The method of controlling pests according to 25, Substituent at the 1-position of the cyclopropane ring and the wherein the cockroach is German cockroach (Blattella ger Substituent at the 3-position of the cyclopropane ring is a trans manica); configuration, and a relative configuration of the Substituent 28 A method of controlling pests, which comprises a step of of the 1'-position existing on the substituent at the 3-position spraying an effective amount of the ester compound accord 5 of the cyclopropane ring is Z-configuration. ing to any one of 1 to 22 to cockroaches or a place where Anester compound represented by formula (1) in which R is cockroaches inhabit; hydrogen. 29. The method of controlling pests according to 28. An ester compound represented by formula (1) in which a wherein the cockroach is American cockroach (Periplaneta relative configuration of the substituent at the 1-position of 10 the cyclopropane ring and the Substituent at the 3-position of Americana); the cyclopropane ring is a trans configuration, and R is 30 The method of controlling pests according to 28. hydrogen. wherein the cockroach is German cockroach (Blattella ger An ester compound represented by formula (1) in which an manica). absolute configuration of the 1-position of the cyclopropane The compound of the present invention has an excellent 15 ring is an R configuration, and R is hydrogen. pest control effect and is therefore useful as an active ingre An ester compound represented by formula (1) in which an dient of a pest control agent. absolute configuration of the 1-position of the cyclopropane In the compound of the present invention, there are isomers ring is an R configuration, a relative configuration of the derived from two asymmetric carbon atoms at the 1-position Substituent at the 1-position of the cyclopropane ring and the and the 3-position on the cyclopropane ring, and isomers Substituent at the 3-position of the cyclopropane ring is a trans derived from the double bond present in the substituent at the configuration, and R is hydrogen. 3-position of the cyclopropane ring. Each isomer having pest Anester compound represented by formula (1) in which R is control activity or a mixture of those isomers in an arbitrary hydrogen and a relative configuration of the Substituent of the ratio which has pest control activity are included in the 1'-position existing on the substituent at the 3-position of the present invention. 25 cyclopropane ring is Z-configuration. An ester compound represented by formula (1) in which R is hydrogen and an absolute configuration of the 1-position of the cyclopropane ring is an R configuration and a relative O H3C CH3 R3 R4 configuration of the Substituent of the 1'-position existing on 30 the Substituent at the 3-position of the cyclopropane ring is ls )=( Z-configuration. An ester compound represented by formula (1) in which Ris e1) \, ci- R hydrogen, an absolute configuration of the 1-position of the O O cyclopropane ring is an R configuration, a relative configu 35 ration of the substituent at the 1-position of the cyclopropane ring and the Substituent at the 3-position of the cyclopropane Examples of the C1-C4 alkyl represented by R' include ring is a trans configuration, and a relative configuration of the methyl, ethyl, propyl, butyl and isopropyl, and the C1-C4 substituent of the 1'-position existing on the substituent at the alkyl represented by Rinclude methyl, ethyl, propyl, butyl 3-position of the cyclopropane ring is Z-configuration. and isopropyl. 40 An ester compound represented by formula (1) in which R is Examples of the compound of the present invention hydrogen or methyl. include the following compounds. An ester compound represented by formula (1) in which a An ester compound represented by formula (1) in which a relative configuration of the substituent at the 1-position of relative configuration of the substituent at the 1-position of the cyclopropane ring and the Substituent at the 3-position of the cyclopropane ring and the Substituent at the 3-position of 45 the cyclopropane ring is a trans configuration, and R is the cyclopropane ring is a trans configuration. hydrogen or methyl. An ester compound represented by formula (1) in which an An ester compound represented by formula (1) in which an absolute configuration of the 1-position of the cyclopropane absolute configuration of the 1-position of the cyclopropane ring is an R configuration. ring is an R configuration, and R is hydrogen or methyl. An ester compound represented by formula (1) in which an 50 An ester compound represented by formula (1) in which an absolute configuration of the 1-position of the cyclopropane absolute configuration of the 1-position of the cyclopropane ring is an R configuration, and a relative configuration of the ring is an R configuration, a relative configuration of the Substituent at the 1-position of the cyclopropane ring and the Substituent at the 1-position of the cyclopropane ring and the Substituent at the 3-position of the cyclopropane ring is a trans Substituent at the 3-position of the cyclopropane ring is a trans configuration. 55 configuration; and R is hydrogen or methyl. An ester compound represented by formula (1) in which a An ester compound represented by formula (1) in which R is relative configuration of the substituent of the 1'-position hydrogen or methyl, and a relative configuration of the Sub existing on the Substituent at the 3-position of the cyclopro stituent of the 1'-position existing on the substituent at the pane ring is Z-configuration. 3-position of the cyclopropane ring is Z-configuration. An ester compound represented by formula (1) in which an 60 Anester compound represented by formula (1) in which Ris absolute configuration of the 1-position of the cyclopropane hydrogen or methyl, and an absolute configuration of the ring is an R configuration and a relative configuration of the 1-position of the cyclopropane ring is an R configuration and substituent of the 1'-position existing on the substituent at the a relative configuration of the substituent of the 1'-position 3-position of the cyclopropane ring is Z-configuration. existing on the Substituent at the 3-position of the cyclopro An ester compound represented by formula (1) in which an 65 pane ring is Z-configuration. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which R is ring is an R configuration, a relative configuration of the hydrogen or methyl, an absolute configuration of the 1-posi US 8,487,115 B2 5 6 tion of the cyclopropane ring is an R configuration, a relative Anester compound represented by formula (1) in which Ris configuration of the Substituent at the 1-position of the cyclo methyl, an absolute configuration of the 1-position of the propane ring and the Substituent at the 3-position of the cyclo cyclopropane ring is an R configuration, a relative configu propane ring is a trans configuration, and a relative configu ration of the substituent at the 1-position of the cyclopropane ration of the substituent of the 1'-position existing on the 5 ring and the Substituent at the 3-position of the cyclopropane Substituent at the 3-position of the cyclopropane ring is ring is a trans configuration, and a relative configuration of the Z-configuration. substituent of the 1'-position existing on the substituent at the An ester compound represented by formula (1) in which Ris 3-position of the cyclopropane ring is Z-configuration. hydrogen. An ester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which a 10 hydrogen. relative configuration of the substituent at the 1-position of An ester compound represented by formula (1) in which a the cyclopropane ring and the Substituent at the 3-position of relative configuration of the substituent at the 1-position of the cyclopropane ring is a trans configuration, and R is the cyclopropane ring and the Substituent at the 3-position of hydrogen. the cyclopropane ring is a trans configuration, and R is An ester compound represented by formula (1) in which an 15 hydrogen. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which an ring is an R configuration, and R is hydrogen. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which an ring is an R configuration, and R is hydrogen. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which an ring is an R configuration, a relative configuration of the absolute configuration of the 1-position of the cyclopropane Substituent at the 1-position of the cyclopropane ring and the ring is an R configuration, a relative configuration of the Substituent at the 3-position of the cyclopropane ring is a trans Substituent at the 1-position of the cyclopropane ring and the configuration, and R is hydrogen. Substituent at the 3-position of the cyclopropane ring is a trans An ester compound represented by formula (1) in which Ris configuration, and R is hydrogen. hydrogen and a relative configuration of the Substituent of the 25 Anester compound represented by formula (1) in which Ris 1'-position existing on the substituent at the 3-position of the hydrogen and a relative configuration of the Substituent of the cyclopropane ring is Z-configuration. 1'-position existing on the substituent at the 3-position of the An ester compound represented by formula (1) in which R is cyclopropane ring is Z-configuration. hydrogen and an absolute configuration of the 1-position of Anester compound represented by formula (1) in which Ris the cyclopropane ring is an R configuration and a relative 30 hydrogen and an absolute configuration of the 1-position of configuration of the Substituent of the 1'-position existing on the cyclopropane ring is an R configuration and a relative the substituent at the 3-position of the cyclopropane ring is configuration of the substituent of the 1'-position existing on Z-configuration. the Substituent at the 3-position of the cyclopropane ring is An ester compound represented by formula (1) in which Ris Z-configuration. hydrogen, an absolute configuration of the 1-position of the 35 An ester compound represented by formula (1) in which R is cyclopropane ring is an R configuration, a relative configu hydrogen, an absolute configuration of the 1-position of the ration of the substituent at the 1-position of the cyclopropane cyclopropane ring is an R configuration, a relative configu ring and the Substituent at the 3-position of the cyclopropane ration of the substituent at the 1-position of the cyclopropane ring is a trans configuration, and a relative configuration of the ring and the Substituent at the 3-position of the cyclopropane substituent of the 1'-position existing on the substituent at the 40 ring is a trans configuration, and a relative configuration of the 3-position of the cyclopropane ring is Z-configuration. substituent of the 1'-position existing on the substituent at the An ester compound represented by formula (1) in which R is 3-position of the cyclopropane ring is Z-configuration. methyl. Anester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which a hydrogen and R is hydrogen or methyl. relative configuration of the substituent at the 1-position of 45 An ester compound represented by formula (1) in which a the cyclopropane ring and the Substituent at the 3-position of relative configuration of the substituent at the 1-position of the cyclopropane ring is a trans configuration, and R is the cyclopropane ring and the Substituent at the 3-position of methyl. the cyclopropane ring is a trans configuration, R is hydrogen An ester compound represented by formula (1) in which an and R is hydrogen or methyl. absolute configuration of the 1-position of the cyclopropane 50 An ester compound represented by formula (1) in which an ring is an R configuration, and R is methyl. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which an ring is an R Configuration, and R is hydrogen and R is absolute configuration of the 1-position of the cyclopropane hydrogen or methyl. ring is an R configuration, a relative configuration of the An ester compound represented by formula (1) in which an Substituent at the 1-position of the cyclopropane ring and the 55 absolute configuration of the 1-position of the cyclopropane Substituent at the 3-position of the cyclopropane ring is a trans ring is an R configuration, a relative configuration of the configuration, and R is methyl. Substituent at the 1-position of the cyclopropane ring and the An ester compound represented by formula (1) in which Ris Substituent at the 3-position of the cyclopropane ring is a trans methyl and a relative configuration of the substituent of the configuration, R is hydrogen and R is hydrogen or methyl. 1'-position existing on the substituent at the 3-position of the 60 Anester compound represented by formula (1) in which R is cyclopropane ring is Z-configuration. hydrogen and R is hydrogen or methyl, and a relative con An ester compound represented by formula (1) in which Ris figuration of the substituent of the 1'-position existing on the methyl and an absolute configuration of the 1-position of the Substituent at the 3-position of the cyclopropane ring is cyclopropane ring is an R configuration and a relative con Z-configuration. figuration of the substituent of the 1'-position existing on the 65 Anester compound represented by formula (1) in which R is Substituent at the 3-position of the cyclopropane ring is hydrogen, R is hydrogen or methyl, and an absolute configu Z-configuration. ration of the 1-position of the cyclopropane ring is an R US 8,487,115 B2 7 8 configuration and a relative configuration of the Substituent of substituent of the 1'-position existing on the substituent at the the 1'-position existing on the substituent at the 3-position of 3-position of the cyclopropane ring is Z-configuration. the cyclopropane ring is Z-configuration. Anester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which R is hydrogen, R is methyl, and an absolute configuration of the hydrogen, R is hydrogen or methyl, an absolute configura 1-position of the cyclopropane ring is an R configuration and tion of the 1-position of the cyclopropane ring is an R con a relative configuration of the substituent of the 1'-position figuration, a relative configuration of the Substituent at the existing on the Substituent at the 3-position of the cyclopro 1-position of the cyclopropane ring and the Substituent at the pane ring is Z-configuration. 3-position of the cyclopropane ring is a trans configuration, An ester compound represented by formula (1) in which R is 10 hydrogen, R is methyl, an absolute configuration of the 1-po and a relative configuration of the substituent of the 1'-posi sition of the cyclopropane ring is an R configuration, a rela tion existing on the Substituent at the 3-position of the cyclo tive configuration of the substituent at the 1-position of the propane ring is Z-configuration. cyclopropane ring and the Substituent at the 3-position of the An ester compound represented by formula (1) in which R is cyclopropane ring is a trans configuration, and a relative hydrogen and R is hydrogen. 15 configuration of the Substituent of the 1'-position existing on An ester compound represented by formula (1) in which a the Substituent at the 3-position of the cyclopropane ring is relative configuration of the substituent at the 1-position of Z-configuration. the cyclopropane ring and the Substituent at the 3-position of Anester compound represented by formula (1) in which R is the cyclopropane ring is a trans configuration, R is hydrogen hydrogen and R is hydrogen. and R is hydrogen. An ester compound represented by formula (1) in which a An ester compound represented by formula (1) in which an relative configuration of the substituent at the 1-position of absolute configuration of the 1-position of the cyclopropane the cyclopropane ring and the Substituent at the 3-position of ring is an R configuration, and R is hydrogen and R is the cyclopropane ring is a trans configuration, R is hydrogen hydrogen. and R is hydrogen. An ester compound represented by formula (1) in which an 25 An ester compound represented by formula (1) in which an absolute configuration of the 1-position of the cyclopropane absolute configuration of the 1-position of the cyclopropane ring is an R configuration, a relative configuration of the ring is an R configuration, R is hydrogen and R is hydrogen. Substituent at the 1-position of the cyclopropane ring and the An ester compound represented by formula (1) in which an Substituent at the 3-position of the cyclopropane ring is a trans absolute configuration of the 1-position of the cyclopropane configuration, R is hydrogen and R is hydrogen. 30 ring is an R configuration, a relative configuration of the An ester compound represented by formula (1) in which R is Substituent at the 1-position of the cyclopropane ring and the hydrogen, R is hydrogen, and a relative configuration of the substituent at the 3-position of the cyclopropane ring is a trans substituent of the 1'-position existing on the substituent at the configuration, R is hydrogen and R is hydrogen. 3-position of the cyclopropane ring is Z-configuration. Anester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which R is 35 hydrogen, R is hydrogen and a relative configuration of the hydrogen, R is hydrogen, and an absolute configuration of substituent of the 1'-position existing on the substituent at the the 1-position of the cyclopropane ring is an R configuration 3-position of the cyclopropane ring is Z-configuration. and a relative configuration of the substituent of the 1'-posi Anester compound represented by formula (1) in which R is tion existing on the Substituent at the 3-position of the cyclo hydrogen, R is hydrogen, and an absolute configuration of propane ring is Z-configuration. 40 the 1-position of the cyclopropane ring is an R configuration An ester compound represented by formula (1) in which R is and a relative configuration of the substituent of the 1'-posi hydrogen, R is hydrogen, an absolute configuration of the tion existing on the Substituent at the 3-position of the cyclo 1-position of the cyclopropane ring is an R configuration, a propane ring is Z-configuration. relative configuration of the substituent at the 1-position of Anester compound represented by formula (1) in which R is the cyclopropane ring and the Substituent at the 3-1-5 position 45 hydrogen, R is hydrogen, an absolute configuration of the of the cyclopropane ring is a trans configuration, and a rela 1-position of the cyclopropane ring is an R configuration, a tive configuration of the Substituent of the 1'-position existing relative configuration of the substituent at the 1-positioned of on the Substituent at the 3-position of the cyclopropane ring is the cyclopropane ring and the Substituent at the 3-position of Z-configuration. the cyclopropane ring is a trans configuration, and a relative An ester compound represented by formula (1) in which R is 50 configuration of the Substituent of the 1'-position existing on hydrogen and R is methyl. the Substituent at the 3-position of the cyclopropane ring is An ester compound represented by formula (1) in which a Z-configuration. relative configuration of the substituent at the 1-position of Anester compound represented by formula (1) in which Ris the cyclopropane ring and the Substituent at the 3-position of hydrogen or methyl, and R is hydrogen. the cyclopropane ring is a trans configuration, R is hydrogen 55 An ester compound represented by formula (1) in which a and R is methyl. relative configuration of the substituent at the 1-position of An ester compound represented by formula (1) in which an the cyclopropane ring and the Substituent at the 3-position of absolute configuration of the 1-position of the cyclopropane the cyclopropane ring is a trans configuration, R is hydrogen ring is an R configuration, R is hydrogen and R is methyl. or methyl, and R is hydrogen. An ester compound represented by formula (1) in which an 60 An ester compound represented by formula (1) in which an absolute configuration of the 1-position of the cyclopropane absolute configuration of the 1-position of the cyclopropane ring is an R configuration, a relative configuration of the ring is an R configuration, R is hydrogen or methyl, and R' Substituent at the 1-position of the cyclopropane ring and the is hydrogen. Substituent at the 3-position of the cyclopropane ring is a trans An ester compound represented by formula (1) in which an configuration, R is hydrogen and R is methyl. 65 absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which R is ring is an R configuration, a relative configuration of the hydrogen, R is methyl and a relative configuration of the Substituent at the 1-position of the cyclopropane ring and the US 8,487,115 B2 10 Substituent at the 3-position of the cyclopropane ring is a trans An ester compound represented by formula (1) in which an configuration, R is hydrogen or methyl, and R is hydrogen. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which Ris ring is an R configuration, a relative configuration of the hydrogen or methyl, R is hydrogen, and a relative configu Substituent at the 1-position of the cyclopropane ring and the ration of the substituent of the 1'-position existing on the Substituent at the 3-position of the cyclopropane ring is a trans Substituent at the 3-position of the cyclopropane ring is configuration, R is methyl and R is hydrogen. Z-configuration. An ester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which Ris methyl, R is hydrogen, and a relative configuration of the hydrogen or methyl, R is hydrogen, and an absolute configu substituent of the 1'-position existing on the substituent at the ration of the 1-position of the cyclopropane ring is an R 10 3-position of the cyclopropane ring is Z-configuration. configuration and a relative configuration of the Substituent of Anester compound represented by formula (1) in which Ris the 1'-position existing on the substituent at the 3-position of methyl, R is hydrogen and an absolute configuration of the the cyclopropane ring is Z-configuration. 1-position of the cyclopropane ring is an R configuration and An ester compound represented by formula (1) in which R is a relative configuration of the substituent of the 1'-position hydrogen or methyl, R is hydrogen, an absolute configura 15 existing on the Substituent at the 3-position of the cyclopro tion of the 1-position of the cyclopropane ring is an R con pane ring is Z-configuration. figuration, a relative configuration of the Substituent at the Anester compound represented by formula (1) in which Ris 1-position of the cyclopropane ring and the Substituent at the methyl, R is hydrogen, an absolute configuration of the 1-po 3-position of the cyclopropane ring is a trans configuration, sition of the cyclopropane ring is an R configuration, a rela and a relative configuration of the substituent of the 1'-posi tive configuration of the substituent at the 1-position of the tion existing on the Substituent at the 3-position of the cyclo cyclopropane ring and the Substituent at the 3-position of the propane ring is Z-configuration. cyclopropane ring is a trans configuration, and a relative An ester compound represented by formula (1) in which R is configuration of the Substituent of the 1'-position existing on hydrogen and R is hydrogen. the Substituent at the 3-position of the cyclopropane ring is An ester compound represented by formula (1) in which a 25 Z-configuration. relative configuration of the substituent at the 1-position of An ester compound represented by formula (1) in which R is the cyclopropane ring and the Substituent at the 3-position of hydrogen, R is hydrogen or methyl, and R is hydrogen. the cyclopropane ring is a trans configuration, R is hydrogen An ester compound represented by formula (1) in which a and R is hydrogen. relative configuration of the substituent at the 1-position of An ester compound represented by formula (1) in which an 30 the cyclopropane ring and the Substituent at the 3-position of absolute configuration of the 1-position of the cyclopropane the cyclopropanering is a trans configuration, R is hydrogen, ring is an R configuration, R is hydrogen and R is hydrogen. R" is hydrogen or methyl, and R is hydrogen. An ester compound represented by formula (1) in which an An ester compound represented by formula (1) in which an absolute configuration of the 1-position of the cyclopropane absolute configuration of the 1-position of the cyclopropane ring is an R configuration, a relative configuration of the 35 ring is an R configuration, R is hydrogen, R is hydrogen or Substituent at the 1-position of the cyclopropane ring and the methyl, and R is hydrogen. Substituent at the 3-position of the cyclopropane ring is a trans An ester compound represented by formula (1) in which an configuration, R is hydrogen and R is hydrogen. An ester absolute configuration of the 1-position of the cyclopropane compound represented by formula (1) in which R is hydro ring is an R configuration, a relative configuration of the gen, R is hydrogen, and a relative configuration of the Sub 40 Substituent at the 1-position of the cyclopropane ring and the stituent of the 1'-position existing on the substituent at the Substituent at the 3-position of the cyclopropane ring is a trans 3-position of the cyclopropane ring is Z-configuration. configuration, R is hydrogen, R is hydrogen or methyl, and An ester compound represented by formula (1) in which Ris R is hydrogen. hydrogen, R is hydrogen and an absolute configuration of the Anester compound represented by formula (1) in which R is 1-position of the cyclopropane ring is an R configuration and 45 hydrogen, R is hydrogen or methyl, R is hydrogen, and a a relative configuration of the substituent of the 1'-position relative configuration of the substituent of the 1'-position existing on the Substituent at the 3-position of the cyclopro existing on the Substituent at the 3-position of the cyclopro pane ring is Z-configuration. pane ring is Z-configuration. An ester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which R is hydrogen, R is hydrogen, an absolute configuration of the 50 hydrogen, R is hydrogen or methyl, R is hydrogen, and an 1-position of the cyclopropane ring is an R configuration, a absolute configuration of the 1-position of the cyclopropane relative configuration of the substituent at the 1-position of ring is an R configuration and a relative configuration of the the cyclopropane ring and the Substituent at the 3-position of substituent of the 1'-position existing on the substituent at the the cyclopropane ring is a trans configuration, and a relative 3-position of the cyclopropane ring is Z-configuration. configuration of the Substituent of the 1'-position existing on 55 An ester compound represented, by formula (1) in which R the Substituent at the 3-position of the cyclopropane ring is is hydrogen, R is hydrogen or methyl, R is hydrogen, an Z-configuration. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which Ris ring is an R configuration, a relative, configuration of the methyl and R is hydrogen. Substituent at the 1-position of the cyclopropane ring and the An ester compound represented by formula (1) in which a 60 Substituent at the 3-position of the cyclopropane ring is a trans relative configuration of the substituent at the 1-position of configuration, and a relative configuration of the Substituent the cyclopropane ring and the Substituent at the 3-position of of the 1'-position existing on the substituent at the 3-position the cyclopropane ring is a trans configuration, R is methyl of the cyclopropane ring is Z-configuration. and R is hydrogen. Anester compound represented by formula (1) in which R is An ester compound represented by formula (1) in which an 65 hydrogen, R is hydrogen, and R is hydrogen. absolute configuration of the 1-position of the cyclopropane An ester compound represented by formula (1) in which a ring is an R configuration, R is methyl and R is hydrogen. relative configuration of the substituent at the 1-position of US 8,487,115 B2 11 12 the cyclopropane ring and the Substituent at the 3-position of 1-position of the cyclopropane ring and the Substituent at the the cyclopropanering is a trans configuration, R is hydrogen, 3-position of the cyclopropane ring is a trans configuration, R" is hydrogen, and R is hydrogen. and a relative configuration of the substituent of the 1'-posi An ester compound represented by formula (1) in which an tion existing on the Substituent at the 3-position of the cyclo absolute configuration of the 1-position of the cyclopropane propane ring is Z-configuration. ring is an R configuration, R is hydrogen, Rishydrogen, and The process for producing the compound of the present R is hydrogen. invention will be described below. An ester compound represented by formula (1) in which an The compound of the present invention can be produced, absolute configuration of the 1-position of the cyclopropane for example, by the production process described below. ring is an R configuration, a relative configuration of the 10 Substituent at the 1-position of the cyclopropane ring and the A process of reacting an alcohol compound represented by Substituent at the 3-position of the cyclopropane ring is a trans the formula (2): configuration, R is hydrogen, R is hydrogen, and R is hydrogen. (2) An ester compound represented by formula (1) in which R is 15 O hydrogen, R is hydrogen, R is hydrogen, and a relative configuration of the Substituent of the 1'-position existing on the Substituent at the 3-position of the cyclopropane ring is Z-configuration. An ester compound represented by formula (1) in which R is -ric hydrogen, R is hydrogen, R is hydrogen, and an absolute configuration of the 1-position of the cyclopropane ring is an with a carboxylic acid compound represented by the formula R configuration and a relative configuration of the Substituent of the 1'-position existing on the substituent at the 3-position (3): of the cyclopropane ring is Z-configuration. 25 An ester compound represented by formula (1) in which R is (3) hydrogen, R is hydrogen, R is hydrogen, an absolute con H3C CH3 R3 R4 figuration of the 1-position of the cyclopropane ring is an R configuration, a relative configuration of the Substituent at the 1-position of the cyclopropane ring and the Substituent at the 30 CHEC R5 3 V 3-position of the cyclopropane ring is a trans configuration, HO CN and a relative configuration of the substituent of the 1'-posi tion existing on the Substituent at the 3-position of the cyclo O propane ring is Z-configuration. An ester compound represented by formula (1) in which R is 35 (wherein R, R and R have the same meanings as defined hydrogen, R is methyl, and R is hydrogen. above), An ester compound represented by formula (1) in which a or a reactive derivative thereof. relative configuration of the substituent at the 1-position of Examples of the reactive derivative include an acid halide the cyclopropane ring and the Substituent at the 3-position of of the carboxylic acid compound represented by the formula the cyclopropanering is a trans configuration, R is hydrogen, 40 R" is methyl, and R is hydrogen. (3), an acid anhydride of the carboxylic acid compound, and An ester compound represented by formula (1) in which an methyl and ethyl esters of the carboxylic acid compound. absolute configuration of the 1-position of the cyclopropane Examples of the acid halide include an acid chloride com ring is an R configuration, R is hydrogen, R is methyl, and pound. R is hydrogen. 45 The reaction is usually, carried out in the presence a con An ester compound represented by formula (1) in which an densing agent or a base in a solvent. absolute configuration of the 1-position of the cyclopropane Examples of the condensing agent include dicyclohexyl ring is an R configuration, a relative configuration of the carbodiimide and 1-ethyl-3-(3-dimethylaminopropyl)carbo Substituent at the 1-position of the cyclopropane ring and the diimide hydrochloride. Substituent at the 3-position of the cyclopropane ring is a trans 50 Examples of the base include organic bases Such as triethy configuration, R is hydrogen, R is methyl, and R is hydro lamine, pyridine, N,N-diethylaniline, 4-dimethylaminopyri gen. dine and diisopropylethylamine. An ester compound represented by formula (1) in which R is Examples of the solvent include hydrocarbons such as hydrogen, R is methyl, R is hydrogen, and a relative con benzene, toluene and hexane; ethers such as diethylether and figuration of the substituent of the 1'-position existing on the 55 tetrahydrofuran; halogenated hydrocarbons such as chloro Substituent at the 3-position of the cyclopropane ring is form, dichloromethane, 1,2-dichloroethane and chloroben Z-configuration. Zene; and a mixed solvent thereof. An ester compound represented by formula (1) in which R is The reaction time is usually within a range from 5 minutes hydrogen, R is methyl, R is hydrogen, and an absolute to 72 hours. configuration of the 1-position of the cyclopropane ring is an 60 The reaction temperature is usually within a range from R configuration and a relative configuration of the Substituent –20° C. to 100° C. (from -20° C. to a boiling point of the of the 1'-position existing on the substituent at the 3-position Solvent in a case a boiling point of the solvent used is lower of the cyclopropane ring is Z-configuration. than 100° C.), and preferably -5°C. to 100° C. (from -5°C. An ester compound represented by formula (1) in which R is to a boiling point of the Solvent in a case a boiling point of the hydrogen, R is methyl, R is hydrogen, an absolute configu 65 solvent used is lower than 100° C.). ration of the 1-position of the cyclopropane ring is an R In the reaction, a use molar ratio of the alcohol compound configuration, a relative configuration of the Substituent at the represented by the formula (2) to the carboxylic acid com US 8,487,115 B2 13 14 pound represented by the formula (3) or the reactive deriva (wherein R, R and R have the same meanings as defined tive thereof can be optionally set, but is preferably an equimo above), in the presence of a base to obtain the compound lar or near equimolar ratio. represented by the formula (6-1): The condensing agent or base can be usually used in any amount within a range from 0.25 mol to an excess amount, and preferably from 0.5 mol to 2 mol, based on 1 mol of the alcohol compound represented by the formula (2). These condensing agents or bases are appropriately selected accord ing to the kind of the carboxylic acid compound represented (6-1) by the formula (3) or the reactive derivative thereof. 10 After completion of the reaction, the reaction mixture is usually subjected to a post-treatment operation offiltering the reaction mixture and concentrating the filtrate, or pouring water into the reaction mixture, followed by extraction with an organic solvent and further concentration, and thus the 15 RO compound of the present invention can be obtained. The obtained compound of the present invention can be purified by operations such as chromatography and distillation. The alcohol compound represented by the formula (2) is a compound described in JP-A-05-255271. The intermediate of the present invention can be produced, for example, by the following process. (wherein R. R. R. and R have the same meanings as Among the carboxylic acid compound represented by the defined), and further hydrolyzing the obtained compound in formula (3), the carboxylic acid compound represented by the the presence of a base. formula (3-1) in which relative configuration of the substitu 25 The compound represented by the formula (6-1) can be ent at the 1-position of the cyclopropane ring and the Sub usually produced by reacting in a polar solvent at a tempera stituent at the 3-position of the cyclopropane ring is trans ture within a range from 0°C. to 80°C., and preferably from configuration can be produced, for example, by the following 0°C. to 30°C., using the nitrile compound represented by the process. formula (5) in the amount of 1.0 to 1.5 mol and a base in the That is, a carboxylic acid compound represented by the 30 mount of 1 to 10 mol, based on 1 mol of the caronaldehyde formula (3-1): ester derivative represented by the formula (4-1). Examples of the base include carbonates such as potassium carbonate and Sodium carbonate; and alkali metal compounds Such as (3-1) sodium hydride. Examples of the polar solvent include acid 35 amides such as N,N-dimethylformamide; and sulfoxide such as dimethyl sulfoxide. After completion of the reaction, the reaction mixture is Subjected to a post-treatment operation of adding water, fol 40 lowed by extraction with an organic solvent and further dry HO ing and concentration of the organic layer, and thus the com pound represented by the formula (6-1) can be obtained. In the step of hydrolyzing the compound represented by the (wherein R, R and R have the same meanings as defined formula (6-1), the carboxylic acid compound represented by above), can be produced by reacting a caronaldehyde ester 45 the formula (3-1) can be usually produced by reacting in a derivative represented by the formula (4-1): solvent at a temperature of 0°C. to 80°C., and preferably 0° C. to 30°C., using a base in the amount of 1 to 10 mol based on mol of the compound represented by the formula (6-1). (4-1) Examples of the base include carbonic acid alkali metal salts H3C CH3 50 Such as potassium carbonate and Sodium carbonate; and alkali metal compounds such as sodium hydride. Examples of CHO the solvent include ethers such as tetrahydrofuran; alcohols RO Such as methanol; water, and a mixture thereof. After completion of the reaction, the reaction solution is O 55 Subjected to a post-treatment operation of acidifying, fol lowed by extraction with an organic solvent and further dry (wherein R represents a C1-C4 alkyl group), with a nitrile ing and concentration of the organic layer, and thus the car compound represented by the formula (5): boxylic acid compound represented by the formula (3-1) can 60 be obtained. Among the carboxylic acid compound represented by the (5) formula (3), a carboxylic acid compound represented by the formula (3-2) in which relative configuration of the substitu ent at the 1-position of the cyclopropane ring and the Sub 65 stituent at the 3-position of the cyclopropane ring is cis con figuration can be produced, for example, by the following process. US 8,487,115 B2 15 16 That is, the carboxylic acid compound represented by the ing and concentration of the organic layer, and thus the com formula (3-2): pound represented by the formula (6–2) can be obtained. In the step of producing the compound represented by the formula (3-2) from the compound represented by the formula (3-2) 5 (6–2), the reaction is carried out at a reaction temperature of H3C CH3 usually 50° C. to 150° C. (50° C. to a boiling point of the R3 R4 Solvent in a case a boiling point of the solvent is lower than 150° C.), using an acid catalyst in the amount of 0.005 to 0.05 3 ) ( mol based on 1 mol of the compound represented by the HO ch= R5 10 formula (6-2), and thus the carboxylic acid compound repre O CN sented by the formula (3-2) can be produced. Examples of the acid catalyst include p-toluenesulfonic acid and the like. Examples of the solvent include ethers such as tetrahydrofu (wherein R, R and R have the same meanings as defined ran; hydrocarbons such as toluene; and a mixture thereof. above), can be produced by reacting a caronaldehyde ester 15 After completion of the reaction, the carboxylic acid com derivative represented by the formula (4-2): pound represented by the formula (3-2) can be obtained by Subjecting to a post-treatment operation of drying and con centrating of the organic layer. (4-2) H3C CH3 The caronaldehyde ester derivative represented by the for mula (4-1) is compound described in Tetrahedron 45, 3039 3052 (1989). HC 3 The caronaldehyde ester derivative represented by the for mula (4-2) is a compound described in Journal of American Hic)—o CHO Chemical Society, 1982, 104, 4282-4283. H3C O 25 The nitrile compound represented by the formula (5) can be synthesized according to a known method such as described in Journal of American Chemical Society, 2008, 130, 3734. with the nitrile derivative represented by the formula (5): Examples of pests on which the compound of the present invention has a control effect include harmful arthropod pests 30 Such as harmful insects and harmful acarines, and more spe (5) cifically, the following pests. Hemiptera: planthoppers such as Laodelphax striatellus, Nilaparvata lugens, and Sogatella furcifera, leafhopperS Such as Nephotettix cincticeps, and Nephotettix virescens, aphids 35 Such as Aphis gossypii, and Myzus persicae, plant bugs such (wherein R, R and R have the same meanings as defined as Nezara antennata, Riptortus clavetus, Eysarcoris lewisi, above), in the presence of a base to obtain a compound rep Eysarcoris parvus, Plautia Stali, and Halyomorpha mista, resented by the formula (6–2): white flies such as Trialeurodes vaporariorum, Bemisia tabaci, and Bemisia argentifolii, Scales such as Aonidiella 40 aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplas (6–2) tes rubens, and Icerya purchasi, lace bugs, bed bugs such as HC CH3 Cimex lectularius, jumping plantlice and so on; R3 R4 Lepidoptera: Pyralidae Such as Chilo suppressalis, Cnaphalocrocis medinalis, Notarcha derogata, and Plodia H3C 3 )–( 45 interpunctella, Spodoptera litura, Pseudaletia separata, Noctuidae Such as Trichoplusia spp., Heliothis spp., and Ear Hic)—o CHEC R5 ias spp., Pieridae Such as Pieris rapae, Tortricidae Such as HC O YN Adoxophey's spp., Grapholita molesta, Adoxophyes Orana fasciata, and Cydia pomonella, Carposinidae Such as Carpo (wherein R, R and R have the same meanings as defined 50 sina niponensis, Lyonetiidae Such as Lyonetia spp., Lyman above), and heating the obtained compound in the presence of triidae Such as Lymantria spp., Lymantriidae such as Euproc an acid catalyst. tis spp., Yponameutidae such as Plutella xylostella, The compound represented by the formula (6–2) can be Gelechiidae Such as Pectinophora gossypiella, Arctiidae Such usually produced by reacting in a polar solvent at a tempera as Hyphantria cunea, Tineidae Such as Tinea translucens, and ture of 0°C. to 80°C., and preferably 0°C. to 30°C., using the 55 Tineola bisselliella, and so on; nitrile compound represented by the formula (5) in the Diptera: Culex spp. Such as Culex pipiens pallens, Culex amount of 1.0 to 1.5 mol and a base in the amount of 1 to 10 tritaeniorhynchus, and Culex quinquefasciatus, Aedes spp. mol, based on 1 mol of the caronaldehyde ester derivative Such as Aedes aegypti, and Aedes albOpictus, Anopheles spp. represented by the formula (4-2). Examples of the base Such as Anopheles sinensis, and Anopheles gambiae, Chi include carbonates such as potassium carbonate and sodium 60 ronomidae, Muscidae such as Musca domestica, and Muscina carbonate; and alkali metal compounds such as sodium stabulans, Calliphoridae, Sarcophagidae, little housefly, hydride. Examples of the polar solvent include acid amides Anthomyiidae such as Delia platura, and Delia antiqua, such as N,N-dimethylformamide; and sulfoxides such as Tephritidae, Drosophilidae, Phoridae such as Megaselia spi dimethylsulfoxide. racularis, Cloginia albipunctata, Psychodidae, Simuliidae, After completion of the reaction, the reaction mixture is 65 Tabanidae, Stomoxyidae, Agromyzidae, and so on; Subjected to a post-treatment operation of adding water, fol Coleoptera: Diabrotica spp. Such as Diabrotica virgifera lowed by extraction with an organic solvent and further dry virgifera, and Diabrotica undecimpunctata howardi, Scara US 8,487,115 B2 17 18 baeidae Such as Anomala cuprea, and Anomala rufocuprea, lipede (Parafontaria laminate), train millipede (Parafontaria Curculionidae Such as Sitophilus zeanais, Lissorhoptrus laminata armigera), Parafontaria acutidens, Epanerchodus Oryzophilus, and Callosobruchuys chienensis, Tenebrionidae Orientalis, etc.; Such as Tenebrio molitor, and Tribolium Castaneum, Chry Isopoda: Sow bugs such as Porcellionides pruinosus somelidae such as Oulema Oryzae, Aulacophora femoralis, (Brandt), Porcellio scaber Latreille, pill bugs such as com Phyllotreta Striolata, and Leptinotarsa decemlineata, Derm mon pill bug (Armadillidium vulgare), sea louses such as estidae Such as Dermestes maculates, Anobiidae, Epillachna wharf roach (Ligia exotica), etc.; spp. Such as Epilachna vigintioctopunctata, Lyctidae, Bos Gastropoda: tree slug (Limax marginiatus), yellow slug trychidae, Ptinidae, Cerambycidae, Paederus fiscipes, and so (Limax flavus), etc. On; 10 The pest control agent of the present invention contains the Blattodea: Blattella germanica, Periplaneta fuliginosa, compound of the present invention and an inert carrier. The Periplaneta americana, Periplaneta brunnea, Blatta Orienta pest control agent of the present invention is usually formed lis, and so on; into formulations described below. Examples of the formula Thysanoptera: Thrips palmi, Thrips tabaci, Frankliniella tion include an oil solution, an emulsifiable concentrate, a occidentalis, Frankliniella intonsa, and so on; 15 wettable powder, a flowable formulation (e.g., an aqueous Hymenoptera: Formicidae Such as Monomorium pharao Suspension, or an aqueous emulsion), a microcapsule, a dust, sis, Formica fisca japonica, Ochetellus glaber, Pristo a granule, a tablet, an aerosol, a carbon dioxide formulation, myrmex pungens, Pheidole noda, and Linepithema humile, a heat transpiration formulation (e.g., an insecticidal coil, an long-legged wasps such as Polistes chinensis antennalis, electric insecticidal mat, or a liquid absorbing core-type heat Polistes jadwigae, and Polistes rothneyi, Vespidae Such as transpiration pesticide), a piezo insecticidal formulation, a Vespa mandarinia japonica, Vespa simillima, Vespa analis heat fumigant (e.g., a self combustion-type fumigant, a insularis, Vespa crabro flavofasciata, and Vespa ducalis, chemical reaction-type fumigant, or a porous ceramic plate Bethylidae, Xylocopa, Pompilidae, Sphecoidae, mason fumigant), an unheated transpiration formulation (e.g., a resin wasp, and so on; transpiration formulation, a paper transpiration formulation, Orthoptera: mole crickets, grasshoppers, etc.; 25 an unwoven fabric transpiration formulation, a knit fabric Shiphonaptera: Ctenocephalides felis, Ctenocephalides transpiration formulation, or a Sublimating tablet), an aerosol canis, Pulex irritans, Xenopsylla cheopis, and so on; formulation (e.g., a fogging formulation), a direct contact Anoplura: Pediculus humanus corporis, Phthirus pubis, formulation (e.g., a sheet-shaped contact formulation, a tape Haematopinus eurysternus, Dalmalinia ovis, and so on; shaped contact formulation, or a net-shaped contact formu Isoptera: Reticulitermes spp. Such as Reticuliterinesspera 30 lation), an ULV formulation and a poison bait tus, Coptotermes formosanus, Reticulitermes flavipes, Reti Examples of the method for formulation include the fol culitermes hesperus, Reticulitermes virginicus, Reticuliter lowing methods. mes tibialis, and Heterotermes aureus, Incisitermes spp. Such (1) A method comprising mixing the compound of the present as Incisitermes minor, and Zootermopsis spp. Such as Zooter invention with a solid carrier, a liquid carrier, a gaseous car mopsis nevadensis, and so on; 35 rier or a poison bait, followed by addition of a surfactant and Acarina: Tetranychidae such as Tetranychus urticae, Tet other auxiliary agents for formulation, and if necessary, fur ranychus kanzawai, Panonychus citri, Panonychus ulmi, and ther processing. Oligonychus spp., Eriophyidae Such as Aculops pelekassi, (2.) A method comprising impregnation of a base material and Aculus Schlechtendali, Tarsonemidae such as Polyphago containing no active ingredient with the compound of the tarisonemus latus, Tenuipalpidae, Tuckerellidae, Ixodidae 40 present invention. Such as Haemaphysalis longicornis, Haemaphysalis flava, (3) A method comprising mixing the compound of the present Dermacentor variabilis, Ixodes ovatus, Ixodes persulcatus), invention and a base material, followed by Subjecting the Ixodes scapularis, Boophilus microplus, Amblyomma ameri mixture to mold processing. canum, and Rhipicephalus sanguineus, Acaridae such as These formulations usually contain 0.001 to 98% by Trophagus putrescentiae, Dermanyssidae Such as Der 45 weight of the compound of the present invention, depending matophagoides farinae, Dermatophagoides ptrenyssinus, on formulation forms. Cheyletidae Such as Cheyletus eruditus, Cheyletus malaccen Examples of the solid carrier used in the formulation sis, and Cheyletus moorei, chicken mite Such as Ornithonys include fine powders or granules of clays (e.g., kaolin clay, sus bacoti, Ornithonyssus Sylvairum, and Dermanyssus galli diatomaceous earth, bentonite, Fubasami clay, or acid white nae, Trombiculidae such as Leptotrombidium akamushi, and 50 clay), synthetic hydrated silicon oxide, talc, ceramics, other So on; inorganic minerals (e.g., sericite, quartz, Sulfur, active car Araneae: Japanese foliage spider (Chiracanthium japoni bon, calcium carbonate, or hydrated silica) and fine powder cum), redback spider (Latrodectus hasseltii), Nephila clavata and granulated Substances such as chemical fertilizers (e.g., (Tetragnathidae), CycloSa Octotuberculata, St. Andrew's ammonium Sulfate, ammonium phosphate, ammonium cross spider (Argiope amoena), Wasp spider (Argiope bruen 55 nitrate, ammonium chloride, or urea); Substances that are nichii), orb-weaving spider (Araneus ventricosus), grass spi Solid at room temperature (e.g., 2,4,6-triisopropyl-1,3,5-tri der (Agelena Silvatica), Wolfspider (Pardosa astrigera), dock oxane, naphthalene, p-dichlorobenzene, or camphor, ada spider (Dolomedes sulfurous), Carrhotus xanthogramma, mantine); as well as felt, fiber, fabric, knit, sheet, paper, common house spider (Achaearanea tepidariorum), thread, foam, porous material and multi-filament comprising Coelotes insidiosus, jumping spider (Salticidae), huntsman 60 one or more substances selected from the group consisting of spider (Heteropoda venatoria), etc.; wool, silk, cotton, hemp, pulp, synthetic resins (e.g., polyeth Chilopoda: centipedes Such as house centipede (There ylene resins such as low density polyethylene, Straight chain uonema hilgendorfi), Scolopendra subspinipes, Scolopendra low density polyethylene and high density polyethylene; eth subspinipes japonica, Scolopocryptops rubiginosus, Bothro ylene-vinyl ester copolymers such as an ethylene-vinyl polys asperatus, etc.; 65 acetate copolymer, ethylene-methacrylate copolymers such Diplopoda: millipedes Such as garden millipede (Oxidus as an ethylene-methyl methacrylate copolymer and an ethyl gracilis), garden millipede (Nedyopus tambanus), train mil ene-ethyl methacrylate copolymer, ethylene-acrylate copoly US 8,487,115 B2 19 20 merS Such as an ethylene-methyl acrylate copolymer and an lose, ethylcellulose and wood flour, thermal decomposition ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic stimulants such as alkali metal salt, alkaline earth metal salt, acid copolymers such as an ethylene-acrylic acid copolymer; dichromate and chromate, oxygen carriers such as potassium ethylene-tetracyclododecene copolymers; polypropylene nitrate, combustion-Supporting agents such as melamine and resins such as a propylene homopolymer and a propylene flour starch, extenders such as diatomaceous earth, and bind ethylene copolymer, poly-4-methylpentene-1, polybutene-1, erS Such as Synthetic glue. polybutadiene, polystyrene; acrylonitrile-styrene resin; acry Examples of a base material for the chemical reaction-type lonitrile-butadiene-styrene resins; styrene elastomers such as fumigant include exothermic agents such as alkali metal Sul a styrene-conjugated diene block copolymer and a hydroge fide, polysulfide, hydrosulfide and calcium oxide, catalytic nated Styrene-conjugated diene block copolymer; fluorine 10 agents such as a carbonaceous material, iron carbide and resins; acrylic resins such as methyl polymethacrylate; polya active white clay, organic foaming agents such as aZodicar mide resins such as nylon 6 and nylon 66; polyester resins bonamide, benzenesulfonylhydrazide, dinitropentamethyl Such as polyethylene terephthalate, polyethylene naphtha enetetramine, polystyrene and polyurethane, and fillers such late, polybutylene terephthalate and polycyclohexylene dim as strips of natural fiber and synthetic fiber. ethylene terephthalate; or porous resins such as polycarbon 15 Examples of a resin used as a base material of the resin ate, polyacetal, polyacryl Sulfone, polyarylate, transpiration formulation include polyethylene resins such as hydroxybenzoic acid polyester, polyetherimide, polyester low density polyethylene, straight chain low density polyeth carbonate, polyphenylene ether resins, polyvinyl chloride, ylene and high density polyethylene; ethylene-vinyl ester polyvinylidene chloride, polyurethane, foamed polyure copolymers such as an ethylene-vinyl acetate copolymer; thane, foamed polypropylene and foamed ethylene), glass, ethylene-methacrylate copolymers such as an ethylene-me metal and ceramics. thyl methacrylate copolymer and an ethylene-ethyl meth Examples of the liquid carrier include aromatic oraliphatic acrylate copolymer, ethylene-acrylate copolymers such as an hydrocarbons (e.g., Xylene, toluene, alkylnaphthalene, phe ethylene-methyl acrylate copolymer and an ethylene-ethyl nylxylylethane, kerosene, light oil, hexane, or cyclohexane), acrylate copolymer, ethylene-vinylcarboxylic acid copoly halogenated hydrocarbons (e.g., chlorobenzene, dichlo 25 merS Such as an ethylene-acrylic acid copolymer; ethylene romethane, dichloroethane, or trichloroethane), alcohols tetracyclododecene copolymers; polypropylene resins such (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, as a propylene copolymer and a propylene-ethylene copoly benzyl alcohol, or ethylene glycol), ethers (e.g., diethyl ether, mer, poly-4-methylpentene-1, polybutene-1, polybutadiene, ethylene glycol dimethyl ether, diethylene glycol monom polystyrene, acrylonitrile-styrene resins; acrylonitrile-buta ethyl ether, diethylene glycol monoethyl ether, propylene 30 diene-styrene resins; styrene elastomers such as a styrene glycol monomethyl ether, tetrahydrofuran, or dioxane), esters conjugated diene block copolymer and a hydrogenated Sty (e.g., ethyl acetate, or butyl acetate), ketones (e.g., acetone, rene-conjugated diene block copolymer; fluorine resins: methyl ethyl ketone, methyl isobutyl ketone, or cyclohex acrylic resins such as methyl polymethacrylate; polyamide anone), nitriles (e.g., acetonitrile, or isobutyronitrile), Sulfox resins such as nylon 6 and nylon 66; polyester resins such as ides (e.g., dimethyl sulfoxide), acid amides (e.g., N,N-dim 35 polyethylene terephthalate, polyethylene naphthalate, poly ethylformamide, N,N-dimethylacetamide, or N-methyl butylene butalate and polycyclohexylene dimethylene pyrrolidone), alkylidene carbonate (e.g., propylene terephthalate; polycarbonate, polyacetal, polyacryl Sulfone, carbonate), vegetable oils (e.g., soybean oil, or cottonseed polyarylate, hydroxybenzoic acid polyester, polyetherimide, oil), plant essential oils (e.g., orange oil, hyssop oil, or lemon polyester carbonate, polyphenylene ether resin, polyvinyl oil), and water. 40 chloride, polyvinylidene chloride and polyurethane. These Examples of the gaseous carrier include butane gas, chlo base materials may be used alone or as a combination of two rofluorocarbon, liquefied petroleum gas (LPG), dimethyl or more kinds. If necessary, a plasticizer Such as phthalate ether and carbon dioxide. esters (e.g., dimethyl phthalate, dioctyl phthalate, etc.), adipic Examples of the surfactant include alkyl sulfate, alkylsul acid esters and Stearic acid may be added to these base mate fonate, alkylaryl Sulfonate, alkylaryl ethers, polyoxyethyl 45 rials. The resin transpiration formulation can be prepared by enated alkylaryl ethers, polyethylene glycol ethers, polyhy mixing the compound of the present invention with the base dric alcohol esters and Sugar alcohol derivatives. material, kneading the mixture, followed by molding it by Examples of the other auxiliary agents for formulation injection molding, extrusion molding or pressure molding. include a binder, a dispersant and a stabilizer. The resultant resin formulation can be subjected to further Specifically, there are, for example, casein, gelatin, 50 molding or cutting procedure, if necessary, to be processed polysaccharides (e.g., starch, gum arabic, cellulose deriva into shapes such as a plate, film, tape, net or string shape. tives, or alginic acid), lignin derivatives, bentonite, saccha These resin formulations can be processed into animal col rides, synthetic water-soluble polymers (e.g., polyvinyl alco lars, animal ear tags, sheet products, trap strings, gardening hol, or polyvinyl pyrrolidone), polyacrylic acid, BHT (2,6- Supports and other products. di-tert-butyl-4-methylphenol) and BHA (a mixture of 2-tert 55 Examples of a base material for the poisonbait include bait butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol). ingredients such as grain powder, vegetable oil, saccharide Examples of a base material for the insecticidal coil and crystalline cellulose, antioxidants such as dibutylhy include a mixture of vegetable powder such as wood flour and droxytoluene and nordihydroguaiaretic acid, preservatives lees powder, and a binder Such as incense material powder, Such as dehydroacetic acid, accidentalingestion inhibitors for starch and gluten. 60 children and pets such as a chili powder; insect attraction Examples of a base material for the electric insecticidal fragrances such as cheese flavor, onion flavor and peanut oil. mat include a plate obtained by hardening cotton linter and a The pest control method of the present invention usually plate obtained by hardening fibrils of a mixture of cotton conducted by applying an effective amount of the compound linter and pulp. of the present invention to apest or a habitat thereof (e.g. plant Examples of a base material for the self combustion-type 65 bodies, soil, the interior of a house, animal bodies, the interior fumigant include combustible exothermic agents such as of a car, or outdoor open space) in a form of a pest control nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellu agent of the present invention. US 8,487,115 B2 21 22 A method for applying the pest control agent of the present area, application method and other factors, and is usually in invention includes the following methods, and appropriately the range from 1 to 10,000 g in terms of the compound of the selected depending on the form of the pest control agent of the present invention per 10,000 m. When the pest control agent present invention, the application area and so on. of the present invention is formulated into an emulsifiable (1) A method comprising applying a pest control agent of the concentrate, a wettable powder, a flowable formulation and so present invention as it is to a pest of a habitat of the pest. on, the pest control agent is usually applied after diluting with (2) A method comprising diluting a pest control agent of the water so that the concentration of the active ingredient present invention with a solvent such as water, and then becomes 0.01 to 10,000 ppm, and a granule or a dust is usually spraying the dilution to a pest or a habitat of the pest. In this applied as it is. method, the pest control agent of the present invention is 10 These formulations or water dilutions of the formulations usually formulated into an emulsifiable concentrate, a wet may be directly sprayed over pests or plants such as crop table powder, a flowable formulation, a microcapsule or the plants to be protected from pests, or may be used in the soil like. The formulation is usually diluted so that the concentra treatment for the control of pests which inhabit the soil of the tion of the compound of the present invention can be 0.1 to cultivated land. 10,000 ppm. 15 Application can also be conducted by a method of directly (3) A method comprising heating a pest control agent of the winding the resin formulation formed into sheet-shaped, or present invention at a habitat of a pest, thereby allowing an string- or cord-shaped formulation around plants, disposing active ingredient to volatilize and diffuse from the pest con the formulation in the neighborhood of plants, or spreading trol agent. the formulation on the soil surface at the root. In this case, any of the amount and concentration of applica The compound of the present invention can be used as a tion of the compound of the present invention can be appro pest control agent in cultivating field Such as farm, paddy priately determined depending on the form, application field, lawn or orchard, or non-cultivating field. The compound period, application area, application method, kind of a pest, of the present invention can control pests inhabiting the cul damage to be incurred and so on. tivating field in the cultivating field where the following When the compound of the present invention is used for 25 “plant crops are cultivated. prevention of epidemics, the amount to be applied is usually Agricultural crops: corn, rice, wheat, barley, rye, oat, Sor from 0.0001 to 1,000 mg/m of the compound of the present ghum, cotton, soybean, peanut, Sarrazin, Sugar beet, rapeseed, invention in the case of applying to a space, and from 0.0001 Sunflower, Sugar cane, tobacco, etc.; to 1,000 mg/m of the compound of the present invention in Vegetables: Solanaceae vegetables (eggplant, tomato, the case of applying to a plane. An insecticidal coil or an 30 green pepper, hot pepper, potato etc.), Cucurbitaceae Veg electric insecticidal mat is applied by heating to Volatilize and etables (cucumber, pumpkin, Zucchini, watermelon, melon diffuse an active ingredient, depending on the form of the etc.). Cruciferae vegetables (Japanese radish, turnip, horse formulation. A resin transpiration formulation, a paper tran radish, kohlrabi, Chinese cabbage, cabbage, brown mustard, spiration formulation, an unwoven fabric transpiration for broccoli, cauliflower etc.), Compositae vegetables (burdock, mulation, a knit fabric transpiration formulation or a Subli 35 garland chrysanthemum, artichoke, lettuce etc.), Liliaceae mating tablet are allowed to stand as it is in a space to be Vegetables (Welsh onion, onion, garlic, asparagus etc.), applied, and placed under air blowing. Umbelliferae vegetables (carrot, parsley, celery, parsnip etc.), When the pest control agent of the present invention is Chenopodiaceae vegetables (spinach, Swiss chard etc.), applied to a space for the purpose of prevention of epidemics, Labiatae vegetables (Japanese basil, mint, basil etc.), Straw examples of the space include a closet, a Japanese cabinet, a 40 berry, Sweat potato, yam, aroid, etc.; Japanese chest, a cupboard, a toilet, a bathroom, a shed, a Fruit trees: pomaceous fruits (apple, common pear, Japa living room, a dining room, a garage, the interior of a car and nese pear, Chinese quince, quince etc.), stone fleshy fruits so on. The pest control agent can be also applied to outdoor (peach, plum, nectarine, Japanese plum, cherry, apricot, open Space. prune etc.), citrus plants (Satsuma mandarin, orange, lemon, When the pest control agent of the present invention is used 45 lime, grapefruit etc.), nuts (chestnut, walnut, hazel nut, for controlling external parasites of livestock Such as cows, almond, pistachio, cashew nut, macadamia nut etc.), berry horses, pigs, sheep, goats and chickens and Small animals fruits (blueberry, cranberry, blackberry, raspberry etc.), Such as dogs, cats, rats and mice, the pest control agent of the grape, persimmon, olive, loquat, banana, coffee, date, coco present invention can be applied to the animals by a known nut palm, oil palm, etc.; method in the veterinary field. Specifically, when systemic 50 Trees other than fruit trees: tea, mulberry, woody plants control is intended, the pest control agent of the present (azalea, Camelia, hydrangea, Sasanqua, Illicium religiosum, invention is administered to the animals as a tablet, a mixture cherry tree, tulip tree, crape myrtle, fragrant olive etc.), Street with feed or a Suppository, or by injection (including intra trees (ash tree, birch, dogwood, eucalyptus, ginkgo, lilac, muscular, Subcutaneous, intravenous and intraperitoneal maple tree, oak, poplar, cercis, Chinese Sweet gum, plane injections). On the other hand, when non-systemic control is 55 tree, Zelkova, Japanese arborvitae, fir tree, Japanese hemlock, intended, the pest control agent of the present invention is needle juniper, pine, spruce, yew, elm, horse-chestnut etc.), applied to the animals by means of spraying of the oil solution Sweet viburnum, Podocarpus macrophyllus, Japanese cedar, oraqueous Solution, pour-on or spot-ontreatment, or washing Japanese cypress, croton, spindle tree, Chainese howthorn, of the animal with a shampoo formulation, or by putting a etc. collar or eartag made of the resin transpiration formulation to 60 Lawn: Zoysia (Japanese lawn grass, mascarene grass, etc.). the animal. In the case of administering to an animal body, the Bermudagrass (Cynodon dactylon, etc.), bentgrass (creeping dosage of the compound of the present invention is usually in bent grass, Agrostis stolonifera, Agrostis tenuis, etc.), blue the range from 0.1 to 1,000 mg per 1 kg of an animal body grass (Kentucky bluegrass, rough bluegrass, etc.), fescue (tall weight. fescue, chewing fescue, creeping fescue, etc.), ryegrass (dar When the pest control agent of the present invention is used 65 nel, perennial ryegrass, etc.), cockSfoot, timothy grass, etc.; for controlling a pest in the agricultural field, the amount can Others: flowers (rose, carnation, chrysanthemum, Eustoma widely vary depending on the application period, application grandiflorum Shinners (prairie gentian), gypsophila, ger US 8,487,115 B2 23 24 bera, pot marigold, Salvia, petunia, verbena, tulip, aster, (7) Phenylpyrazole Compounds: gentian, lily, pansy, cyclamen, orchid, lily of the valley, lav acetoprole, ethiprole, fipronil, Vaniliprole, pyriprole, ender, Stock, ornamental kale, primula, poinsettia, gladiolus, pyrafluprole, and so on; cattleva, daisy, verbena, Cymbidium, begonia, etc.), bio-fuel (8) Bt Toxin Insecticides: plants (Jatropha, Safflower, gold-of-pleasure, Switchgrass, Live spores derived from and crystal toxins produced from Miscanthus, ribbon grass, giant reed, kenaf, cassava, willow, Bacillus thuringiesis and a mixture thereof; etc.), foliage plant; etc. (9) Hydrazine Compounds: The above “plant crops include gene transgenic plant chromafenozide, halofenozide, methoxyfenozide, crops. tebufenozide, and so on; The compound of the present invention can be mixed with 10 (10) Organic Chlorine Compound: or can be used in combination with other insecticide, acari aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, cide, nematocide, Soil pest control agent, fungicide, herbi and so on; cide, plant growth regulating agent, repellent, synergist, fer (11) Natural Insecticides: tilizer, or soil modifier. machine oil, nicotine-Sulfate; 15 (12) Other Insecticides: Examples of active ingredient of Such the insecticide and avermectin-B, bromopropylate, buprofezin, chlor acaricide include: phenapyr. cyromazine, D-D(1,3-Dichloropropene), emamec (1) Synthetic Pyrethroid Compounds: tin-benzoate, fenaZaquin, flupyrazofos, hydroprene, methop acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cyclopro rene, indoxacarb, metoxadiaZone, milbemycin-A, thrin, cyfluthrin, cyhalothrin, cypermethrin, empenthrin, del pymetrozine, pyridalyl pyriproxyfen, spinosad, Sulfluramid, tamethrin, esfenvalerate, ethofenproX, fempropathrin, fenval tolfenpyrad, triazamate, flubendiamide, lepimectin, Arsenic erate, flucythrinate, flufenoprox, flumethrin, fluvalinate, acid, benclothiaz, Calcium cyanamide, Calcium polysulfide, halfenproX, imiprothrin, permethrin, prallethrin, pyrethrins, chlordane, DDT, DSP, flufenerim, flonicamid, flurimfen, resmethrin, sigma-cypermethrin, Silafluofen, tefluthrin, tral formetanate, metam-ammonium, metam-Sodium, Methyl omethrin, transfluthrin, tetramethrin, phenothrin, cypheno 25 bromide, Potassium oleate, protrifenbute, spiromesifen, Sul thrin, alpha-cypermethrin, Zeta-cypermethrin, lambda-cyha fur, metaflumizone, spirotetramat, pyrifluquinaZone, spineto lothrin, gamma-cyhalothrin, furamethrin, tau-fluvalinate, ram, chlorantraniliprole, tralopyril, and so on. metofluthrin, 2,3,5,6-tetrafluoro-4-methylbenzyl-2,2-dim Examples of the active ingredient of the repellent include ethyl-3-(1-propenyl)cyclopropane carboxylate, 2.3.5,6-tet N,N-diethyl-m-toluamide, limonene, linalool, citronellal, rafluoro-4-(methoxymethyl)benzyl-2,2-dimethyl-3-(2-me 30 menthol, menthone, hinokitiol, geraniol, eucalyptol, indoX thyl-1-propenyl)cyclopropane carboxylate, 2,3,5,6- acarb, carane-3,4-diol, MGK-R-326, MGK-R-874 and BAY tetrafluoro-4-(methoxymethyl)benzyl-2,2,3,3- KBR-3O23. tetramethylcyclopropane carboxylate, and so on; Examples of the active ingredient of the synergist include (2) Organic Phosphorous Compounds: 5-2-(2-butoxyethoxy)ethoxymethyl-6-propyl-1,3-benzo acephate, Aluminium phosphide, butathiofos, cadusafos, 35 dioxol, N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicar chlorethoxyfos, chlorfenvinphos, chlorpyrifos, chlorpyrifos boxylmide, octachlorodipropylether, thiocyanoacetic acidis methyl, cyanophos: CYAP, diazinon, DCIP (dichlorodiiso obornyl, N-(2-ethylhexyl)-1-isopropyl-4-methylbicyclo propyl ether), dichlofenthion:ECP, dichlorvos:DDVP. 2.2.2]oct-5-ene-2,3-dicarboxylmide. dimethoate, dimethylvinphos, disulfoton, EPN, ethion, etho prophos, etrimfos, fenthion: MPP, fenitrothion:MEP fosthi 40 EXAMPLES azate, formothion, Hydrogen phosphide, isofenphos, isox athion, malathion, mesulfenfos, methidathion:DMTP, Hereinafter, the present invention will be described in more monocrotophos, naled:BRP, oxydeprofos:ESP. parathion, detail by way of Production Examples, Formulation phosalone, phosmet:PMP. pirimiphos-methyl, Examples and Test Examples, but the present invention is not pyridafenthion, quinalphos, phenthoate:PAP profenofos, 45 limited thereto. propaphos, prothiofos, pyraclorfos, salithion, Sulprofos, First, Production Examples of the compound of the present tebupirimfos, temephos, tetrachlorvinphos, terbufos, thiome invention will be described. ton, trichlorphon: DEP, vamidothion, phorate, cadusafos, and So on; Production Example 1 (3) Carbamate Compounds: 50 alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, car To a chloroform solution (10 mL) of 3-hydroxymethyl-1- bofuran, carbosulfan, cloethocarb, ethiofencarb, fenobucarb, (2-propynyl)imidazolidine-2,4-dione (450 mg, 2.68 mmol) fenothiocarb, fenoxycarb, furathiocarb, isoprocarb:MIPC, and (1R)-trans-3-(1Z)-2-cyano-1,3-butadienyl-2,2-dimeth metolcarb, methomyl, methiocarb, NAC, oxamyl, pirimicarb, ylcyclopropanecarboxylic acid (478 mg, 2.50 mmol), propoxur:PHC, XMC, thiodicarb, xylylcarb, aldicarb, and so 55 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochlo On; ride (516 mg, 2.70 mmol) and 4-dimethylaminopyridine (15 (4) Nereistoxin Compounds: mg) were added. After stirring at room temperature for 3 cartap, benSultap, thiocyclam, monosultap, bisultap, and hours, water was poured into the reaction Solution and the So on; Solution was extracted with ethyl acetate. The organic layer (5) Neonicotinoid Compounds: 60 was dried over magnesium sulfate and then concentrated imidacloprid, nitenpyram, acetamiprid, thiamethoxam, under reduced pressure condition, and the residue was Sub thiacloprid, dinotefuran, clothianidin, and so on; jected to silica gel column chromatography to obtain 240 mg (6) Benzoylurea Compounds: of 2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl-(1R)- chlorfluaZuron, bistrifluoron, diafenthiuron, diflubenzu trans-3-(1Z)-2-cyano-1,3-butadienyl-2,2-dimethylcyclo ron, fluaZuron, flucycloXuron, flufenoXuron, hexaflumuron, 65 propane carboxylate (hereinafter referred to as the present lufenuron, novaluron, noviflumuron, teflubenzuron, triflu invention compound (1)) represented by the following for muron, triaZuron, and so on; mula: US 8,487,115 B2 25 26

-( H3C CH3 " O HC3 CH3 o CH3.

O O O Sk \, O O

10 Paleyellow liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.22 2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl-(1R)- (s.3H), 1.36 (s.3H), 1.79 (d. 1H, J=5.3 Hz), 2.37 (t, 1H, J=2.5 trans-3-(1Z)-2-cyano-3-methyl-1,3-butadienyl-2,2-dim Hz), 2.54 (dd. 1H, J=9.5, 5.3 Hz), 4.06 (s. 2H), 4.27 (d. 2H, ethylcyclopropane carboxylate represented by the following J=2.5 Hz), 5.31 (d. 1H, J=10.4 Hz), 5.52 (d. 1H, J=10.4 Hz), formula: 5.60 (dd, 2H), 5.94 (d. 1H, J=10.4 Hz), 6.24 (dd. 1H, J=10.4 15 HZ, 17.2 Hz)

Production Example 2 3-hydroxymethyl-1-(2-propynyl)imidazolidine-2,4-dione (450 mg, 2.68 mmol) was dissolved in tetrahydrofuran (10 mL), and 0.35 mL of pyridine was added. To the mixed solution, a tetrahydrofuran solution (5 mL) of (1R)-trans-3- 25 (1Z.3E)-2-cyano-1,3-pentadienyl-2,2-dimethylcyclopro Reference Production Examples will be described below panecarboxylic acid chloride (599 mg, 2.68 mmol) was added with respect to the production of the carboxylic acid com under ice cooling. After stirring at room temperature for 12 pound (3). hours, water was poured into the reaction solution and the 30 Solution was extracted with ethyl acetate. The organic layer Reference Production Example 1 was washed in turn with 5% hydrochloric acid, saturated Methyl-(1R)-trans-3-formyl-2,2-dimethylcyclopropane sodium bicarbonate water and saturated brine, and then dried carboxylate (2.53 g, 16.2 mmol), 3-pentenonitrile (1.90 g, over magnesium sulfate. After concentration under reduced 23.5 mmol) and anhydrous potassium carbonate (3.22g, 23.3 pressure condition, the residue was Subjected to silica gel 35 mmol) were added to 30 mL of N,N-dimethylformamide and column chromatography to obtain 771 mg of 2,5-dioxo-3-(2- the mixture was stirred at room temperature for 24 hours. The propynyl)imidazolidinylmethyl-(1R)-trans-3-(1Z.3E)-2- reaction solution was added to 100 mL of ice water and the cyano-1,3-pentadienyl-2,2-dimethylcyclopropane carboxy solution was extracted twice with each 100 mL of ethyl late (hereinafter referred to as the present invention acetate. The obtained ethyl acetate layers were combined, compound (2)) represented by the following formula: 40 washed once with 50 mL of saturated brine and then dried over magnesium sulfate. After concentration under reduced pressure condition, the residue was Subjected to silica gel column chromatography to obtain 0.94 g of methyl-(1R)- trans-3-(1Z.3E)-2-cyano-1,3-pentadienyl-2,2-dimethylcy 45 clopropane carboxylate represented by the following for -( H3C CH3 ( ,CH3. mula:

i: A CN CH3 O O 50

CN H3CO Paleyellow liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.20 55 (s, 3H), 1.34 (s, 3H), 1.74 (d. 1H, J=5.6 Hz), 1.83 (d. 3H, O J=6.8 Hz), 2.37 (t, 1H, J=2.5 Hz), 2.50 (dd. 1H, J=9.5, 5.3 Hz), 4.06 (s. 2H), 4.27 (d. 2H, J–2.5 Hz), 5.51 (d. 1H, J=10.4 Colorless liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.22 (s, Hz), 5.59 (d. 1H, J=10.4 Hz), 5.78 (d. 1H), 5.95 (d. 1H), 6.10 3H), 1.35 (s.3H), 1.75 (d. 1H, J=5.2 Hz), 1.82 (d. 3H, J=5.2 (dd. 1H) 60 Hz), 2.5 (m, 1H, J=10.0, 5.2 Hz), 3.7 (s, 3H), 5.82 (d. 1H, Specific examples of the compound of the present inven J=10.0 Hz), 5.96 (d. 1H, J=16.8 Hz), 6.10 (m, 1H) tion will be described below. Reference Production Example 2 2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl-(1R)- trans-3-(1Z)-2-cyano-4-methyl-1,3-pentadienyl-2,2-dim 65 Methyl-(1R)-trans-3-(1Z.3E)-2-cyano-1,3-pentadienyl ethylcyclopropane carboxylate represented by the following 2,2-dimethylcyclopropane carboxylate (502 mg, 2.29 mmol) formula: was dissolved in a mixed liquid of 3 mL of methanol and 1 mL US 8,487,115 B2 27 28 of water, and then potassium hydroxide (300 mg, 5.36 mmol) mmol) was added and the Solution was stirred at room tem was added and the mixed solution was stirred at room tem perature for 24 hours. The reaction solution was added to 20 perature for 24 hours. The reaction solution was added to 20 mL of ice water, and the solution was extracted with 20 mL of mL of ice water and the solution was extracted with 20 mL of ethyl acetate. To the obtained aqueous layer, 5% hydrochloric ethyl acetate. To the obtained aqueous layer, 5% hydrochloric 5 acid was added until the pH became 2, and then the solution acid was added until the pH became 2, and then the solution was extracted with 30 mL of ethyl acetate. The ethyl acetate was extracted with 30 mL of ethyl acetate. The ethyl acetate layer washed twice with 20 mL of saturated brine and then layer was washed twice with 20 mL of saturated brine and dried over magnesium sulfate. After concentration under then dried over magnesium Sulfate. After concentration under reduced pressure condition, 440 mg of (1R)-trans-3-(1Z)-2- reduced pressure condition, 452 mg of (1R)-trans-3-(1Z. 10 cyano-1,3-butadienyl-2,2-dimethylcyclopropanecarboxylic 3E)-2-cyano-1,3-pentadienyl-2,2-dimethylcyclopropan acid represented by following formula: ecarboxylic acid represented by the following formula:

CH3 15

CN HO CN HO was obtained. Colorless liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.25 (s, was obtained. 3H), 1.38 (s, 3H), 1.82 (d. 1H, J=5.2 Hz), 2.56 (dd. 1H, Colorless liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.23 (s, 25 J=10.4, 5.2 Hz), 5.32 (d. 1H, J=10.8 Hz), 5.62 (d. 1H, J=17.2 3H), 1.38 (s.3H), 1.76 (d. 1H, J=5.2 Hz), 1.82 (d. 3H, J=6.4 Hz), 6.01 (d. 1H, 10.4 Hz), 6.25 (dd. 1H, J=10.4, 17.2 Hz) Hz), 2.54 (dd. 1H, J=10.0, 5.2 Hz), 5.82 (d. 1H, J=10.0 Hz), 5.97 (d. 1H, J=15.6 Hz), 6.11 (m. 1H) Reference Production Example 5 Reference Production Example 3 30 (1R)-trans-3-(1Z)-2-cyano-1,3-butadienyl-2,2-dimeth ylcyclopropanecarboxylic acid (440 mg, 2.30 mmol) was Methyl-(1R)-trans-3-formyl-2,2-dimethylcyclopropane dissolved in 3 mL of tetrahydrofuran and then thionyl chlo carboxylate (2.53 g, 16.2 mmol),3-butenonitrile (3.62g, 54.0 ride (301 mg, 2.53 mmol) and 10 mg of N,N-dimethylforma mmol) and anhydrous potassium carbonate (3.22 g, 23.3 mide were added and the solution was stirred at room tem mmol) were added to 30 mL of N,N-dimethylformamide and 35 perature for 1 hours, and further at 60° C. of 3 hours. The the mixture was stirred at room temperature for 24 hours. The reaction Solution was concentrated under reduced pressure reaction solution was added to 100 mL of ice water and the condition to obtain 460 mg of (1R)-trans-3-(1Z)-2-cyano-1, solution was extracted twice with each 100 mL of ethyl 3-butadienyl-2,2-dimethylcyclopropanecarboxylic acid acetate. The ethylacetate layers were combined, washed once chloride represented by the following formula: with 50 mL of saturated brine and then dried over magnesium 40 Sulfate. After concentration under reduced pressure condi tion, the residue was Subjected to silica gel column chroma tography to obtain 0.37 g of methyl-(1R)-trans-3-(1Z)-2- cyano-1,3-butadienyl-2,2-dimethylcyclopropane carboxylate represented by the following formula: 45 CN C

50 as a pale yellow liquid. CN Formulation Examples are shown below. Parts are by mass. H3CO Formulation Example 1 O 55 Twenty (20) parts of each of the compounds (1) to (2) of the Colorless liquid: 'H-NMR (CDC1, TMS) 8 (ppm): 1.24 (s, present invention is dissolved in 65 parts of xylene and 15 3H), 1.35 (s, 3H), 1.81 (d. 1H, J=5.2 Hz), 2.54 (dd. 1H, parts of SOLPOL 3005X (a registered trademark of TOHO J=10.4, 5.2 Hz), 3.71 (s.3H), 5.30 (d. 1H, J=10.8 Hz), 5.61 (d. Chemical Industry Co., Ltd.) is added thereto and thoroughly 1H, J=17.2 Hz), 5.98 (d. 1H, 10.4 Hz), 6.26 (dd. 1H, J=10.4, mixed with stirring to obtain emulsifiable concentrates. 17.2 Hz) 60 Formulation Example 2 Reference Production Example 4 Five (5) parts of SORPOL 3005X is added to 40 parts of Methyl-(1R)-trans-3-(1Z)-2-cyano-1,3-butadienyl-2.2- each of the compounds (1) to (2) of the present invention and dimethylcyclopropane carboxylate (483 mg, 2.36 mmol) was 65 the mixture is thoroughly mixed, and 32 parts of CARPLEX dissolved in a mixed liquid of 3 mL of tetrahydrofuran and 1 #80 (synthetic hydrated silicon oxide, a registered trademark mL of water, and then potassium hydroxide (215 mg, 3.84 of SHIONOGI & CO.,LTD.)and 23 parts of 300-mesh diato US 8,487,115 B2 29 30 maceous earth are added thereto, followed by mixing with romethane and the solution is mixed with 89.9 parts of stirring by a mixer to obtain wettable powders. deodorized kerosine to obtain oil solutions. Formulation Example 3 Formulation Example 8 Zero point one (0.1) part of each of the compounds (1) to A mixture of 1.5 parts of each of the compounds (1) to (2) (2) of the present invention and 39.9 parts of deodorized of the present invention, 1 part of TOKUSILGUN (synthetic kerosine are mixed and dissolved, and the solution is filled hydrated silicon oxide, manufactured by Tokuyama Corpo into an aerosol container and a valve portion is installed. ration), 2 parts of REAX 85A (sodium lignin sulfonate, Then, 60 parts of power propellant (liquefied petroleum gas) manufactured by West Vaco Chemicals), 30 parts of BENTO 10 is filled therein under pressure through the valve portion to NITE FUJI (bentonite, manufactured by Houjun) and 65.5 obtain oil-based aerosol formulations. parts of SHOUKOUZANA clay (kaoline clay, manufactured by Shoukouzan Kougyousho) is thoroughly pulverized and Formulation Example 9 mixed, and water is added thereto. The mixture is thoroughly 15 Zero point six (0.6) part of each of the compounds (1) to (2) kneaded, granulated by an extruding granulator, and then of the present invention, 5 parts of xylene, 3.4 parts of deodor dried to obtain 1.5% granules. ized kerosine and 1 part of Reodol MO-60 (emulsifier, a registered trademark of Kao Corporation) are mixed and dis Formulation Example 4 solved, and the solution and 50 parts of water are filled into an aerosol container, and then 40 parts of power propellant (liq To a mixture of 10 parts of each of the compounds (1) to (2) uefied petroleum gas) is filled therein under pressure through of the present invention, 10 parts of phenylxylylethane and a valve portion to obtain aqueous aerosol formulations. 0.5 part of SUMIDURL-75 (tolylene diisocyanate, manufac tured by Sumitomo Bayer Urethane Co., Ltd.) is added 20 Formulation Example 10 parts of 10% aqueous solution of gum arabic, and the mixture 25 Zero point three (0.3) g of each of the compounds (1) to (2) is stirred with a homomixer to obtain an emulsion having an of the present invention is dissolved in 20 ml of acetone and average particle diameter of 20 Jum. To the emulsion, 2 parts the solution is uniformly mixed with stirring with 99.7 g of a of ethylene glycol is added and the mixture is further stirred in base material for a coil (obtained by mixing Tabu powder, a warm bath at a temperature of 60°C. for 24 hours to obtain Pyrethrum marc and wooden powder at a ratio of 4:3:3). microcapsule slurry. On the other hand, 0.2 part of Xanthan 30 Then, 100 ml of water is added thereto, and the mixture is gum and 1.0 part of VEEGUM R (aluminum magnesium thoroughly kneaded, dried and molded to obtain insecticidal silicate, manufactured by Sanyo Chemical Industries, Ltd.) coils. are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. Then, 42.5 parts of the above-mentioned Formulation Example 11 microcapsule slurry and 57.5 parts of the above-mentioned 35 thickener solution are mixed to obtain microcapsules. A mixture of 0.8g of each of the compounds (1) to (2) of the present invention and 0.4 g of piperonyl butoxide is dis Formulation Example 5 solved in acetone and the total volume is adjusted to 10 ml. Then, 0.5 ml of this solution is uniformly impregnated into a A mixture of 10 parts of each of the compounds (1) to (2) 40 base material for an insecticidal mat for electric heating (a of the present invention and 10 parts of phenylxylylethane is plate obtained by hardening fibrils of a mixture of cotton added to 20 parts of a 10% aqueous solution of polyethylene linters and pulp) having a size of 2.5 cmx 1.5 cm and a thick glycol, and the mixture is stirred by a homomixer to obtain an ness of 0.3 cm to obtain insecticidal mats for electric heating. emulsion having an average particle diameter of 3 Jum. On the 45 other hand, 0.2 part of xanthan gum and 1.0 part of VEEGUM Formulation Example 12 R (aluminum magnesium silicate, manufactured by Sanyo A solution obtained by dissolving 3 parts of each of the Chemical Industries, Ltd.) are dispersed in 58.8 parts of ion compound (1) to (2) of the present invention in 97 parts of exchanged water to obtaina thickener Solution. Then, 40 parts deodorized kerosine is poured into a vessel made of vinyl of the above-mentioned emulsion solution and 60 parts of the 50 chloride. A liquid absorptive core whose upper part can be above-mentioned thickener solution are mixed to obtain heated by a heater (an inorganic pulverized powder is hard flowable formulations. ened with a binder and sintered) is inserted thereinto to obtain parts to be used for a liquid absorptive core type thermal Formulation Example 6 transpiring apparatus. 55 To 5 parts of each of the compounds (1) to (2) of the present Formulation Example 13 invention, 3 parts of CARPLEX #80 (synthetic hydrated sili con oxide, a registered trademark of SHIONOGI & CO., One hundred (100) mg of each of the compound (1) to (2) LTD.), 0.3 part of PAP (a mixture of monoisopropyl phos of the present invention is dissolved in an appropriate amount phate and diisopropyl phosphate) and 91.7 parts of talc (300 60 of acetone and the solution is impregnated into a porous mesh) are added and the mixture is stirred by a mixer to obtain ceramic plate having a size of 4.0 cmx4.0 cm and a thickness dusts. of 1.2 cm to obtain thermal fumigants. Formulation Example 7 Formulation Example 14 65 Zero point one (0.1) part of each of the compounds (1) to One hundred (100)ug of each of the compound (1) to (2) of (2) of the present invention is dissolved in 10 parts of dichlo the present invention is dissolved in an appropriate amount of US 8,487,115 B2 31 32 acetone and the solution is uniformly applied to filter paper having a size of 2 cmx2 cm and a thickness of 0.3 mm, and air-dried to remove acetone, and thus Volatile agents for using -( H3C CH3 o at room temperature are obtained. e1) -( 5 Formulation Example 15 i: A CH3 O O Ten (10) parts of each of the compound of the present inventions (1) to (2), 35 parts of white carbon containing 50 10 were used. parts of a polyoxyethylene alkyl ether Sulfate ammonium salt, The results after 2 minutes are shown in Table 1. and 55 parts of water are mixed and then finely ground by a wet grinding method to obtain 10% formulations. TABLE 1

Next, it will be demonstrated by Test Examples that the 15 Knockdown rate (%) compound of the present invention is effective as an active Test compounds after 2 minutes ingredient of a pest controlling agent. Present invention compound (1) 95 Present invention compound (2) 1OO Comparative compound (1) 45 Test Example 1 comparative compound (2) 10 Each of the present invention compounds (1) and (2) (0.00156 parts) produced in the aforementioned Production INDUSTRIAL APPLICABILITY Examples was dissolved in 10 parts of dichloromethane and the resulting solution was mixed with 89.99844 parts of 25 The compound of the present invention has an excellent deodorized kerosine to prepare a 0.00156% (w/v) oil solu pest control effect and is therefore useful as an active ingre tion. dient of a pest control agent. Ten German cockroaches (5 of each male and female) were The invention claimed is: released in a test container (measuring 8.75 cm in diameter 1. An ester compound represented by formula (1): and 7.5 cm in height, bottom area covered with a 16 mesh wire 30 netting) coated with butter at an inner wall, and the container was disposed on the bottom of a test chamber (bottom surface measuring 46 cm and 46 cm, 70 cm in height). From 60 cm in height above the container, 1.5 ml of the oil Solution of each of the present invention compounds (1) and (2) was sprayed using a spray gun (spray pressure: 0.4 kg/cm). Thirty seconds after spraying, the container was removed from the test chamber. After a given time, the num ber of knockdowned cockroaches was counted and a knock down rate was determined (repeated twice). The knockdown rate was calculated by the following equation. wherein R represents hydrogen or methyl, R' represents hydrogen or C1-C4 alkyl, and R represents hydrogen or Knockdown rate (%)=(number of knockdowned cock roaches/number of test cockroaches)x100 C1-C4 alkyl. 45 2. The ester compound according to claim 1, wherein a For comparison, a test was carried out in the same manner relative configuration of the substituent at the 1-position of as described above, except that 2,5-dioxo-3-(2-propynyl)imi the cyclopropane ring and the Substituent at the 3-position of dazolidinylmethyl-(1R)-trans-3-(2-methyl-1-propenyl)-2.2- the cyclopropane ring is a trans configuration in formula (1). dimethylcyclopropane carboxylate (compound described in 3. The ester compound according to claim 1, wherein an “Pestiside Science', 1979, 10, p. 291, hereinafter referred to 50 absolute configuration of the 1-position of the cyclopropane as the comparative compound (1)) represented by the follow ring is an R configuration in formula (1). ing formula: 4. The ester compound according to claim 1, wherein an absolute configuration of the 1-position of the cyclopropane ring is an R configuration, and a relative configuration of the 55 Substituent at the 1-position of the cyclopropane ring and the Substituent at the 3-position of the cyclopropane ring is a trans configuration in formula (1). 5. The ester compound according to claim 1, wherein a relative configuration of the substituent of the 1'-position 60 existing on the Substituent at the 3-position of the cyclopro pane ring is Z-configuration in formula (1). 6. The ester compound according to claim 1, wherein an and 2,5-dioxo-3-(2-propynyl)imidazolidinylmethyl-(1R)- absolute configuration of the 1-position of the cyclopropane trans-3-(1E)-2-methyl-1-butadienyl)-2,2-dimethylcyclo ring is an R configuration and a relative configuration of the propane carboxylate (compound described in JP-A-49 65 substituent of the 1'-position existing on the substituent at the 11854, hereinafter referred to as the comparative compound 3-position of the cyclopropane ring is Z-configuration in for (2)) represented by the following formula: mula (1). US 8,487,115 B2 33 34 7. The ester compound according to claim 1, wherein an 20. The ester compound according to claim 1, wherein R absolute configuration of the 1-position of the cyclopropane is hydrogen, R is hydrogen or methyl, and R is hydrogen in ring is an R configuration, a relative configuration of the formula (1). Substituent at the 1-position of the cyclopropane ring and the 21. The ester compound according to claim 1, wherein R Substituent at the 3-position of the cyclopropane ring is a trans is hydrogen, R is hydrogen, and R is hydrogen in formula (1). configuration, and a relative configuration of the Substituent 22. The ester compound according to claim 1, wherein R of the 1'-position existing on the substituent at the 3-position is hydrogen, R is methyl, and R is hydrogen in formula (1). of the cyclopropane ring is Z-configuration in formula (1). 23. A pest control agent comprising the ester compound 8. The ester compound according to claim 1, wherein R is according to claim 1 and an inert carrier. hydrogen in formula (1). 10 24. A method of controlling pests, which comprises a step 9. The ester compound according to claim 1, wherein R is of applying an effective amount of the ester compound hydrogen or methyl in formula (1). according to claim 1 to pests or a place where pests habitat. 10. The ester compound according to claim 1, wherein R' 25. A method of controlling pests, which comprises the is hydrogen in formula (1). step of applying an effective amount of the ester compound 15 according to claim 1 to cockroaches or a place where cock 11. The ester compound according to claim 1, wherein R' roaches inhabits. is methyl in formula (1). 26. The method of controlling pests according to claim 25, 12. The ester compound according to claim 1, wherein R wherein the cockroach is American cockroach (Periplaneta is hydrogen in formula (1). Americana). 13. The ester compound according to claim 1, wherein R 27. The method of controlling pests according to claim 25, is hydrogen and R is hydrogen or methyl in formula (1). wherein the cockroach is German cockroach (Blattella ger 14. The ester compound according to claim 1, wherein R manica). is hydrogen and R is hydrogen in formula (1). 28. A method of controlling pests, which comprises a step 15. The ester compound according to claim 1, wherein R of spraying an effective amount of the ester compound is hydrogen and R is methyl in formula (1). 25 according to claim 1 to cockroaches or a place where cock 16. The ester compound according to claim 1, wherein R roaches inhabit. is hydrogen and R is hydrogen in formula (1). 29. The method of controlling pests according to claim 28, 17. The ester compound according to claim 1, wherein R' wherein the cockroach is American cockroach (Periplaneta is hydrogen or methyl, and R is hydrogen in formula (1). Americana). 18. The ester compound according to claim 1, wherein R' 30 30. The method of controlling pests according to claim 28, is hydrogen and R is hydrogen in formula (1). wherein the cockroach is German cockroach (Blattella ger 19. The ester compound according to claim 1, wherein R' manica). is methyl and R is hydrogen in formula (1).