(19) TZZ ZZ_T (11) EP 2 840 078 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 317/32 (2006.01) C07C 323/12 (2006.01) 03.01.2018 Bulletin 2018/01 C07C 323/18 (2006.01) C07C 323/25 (2006.01) C07C 317/14 (2006.01) C07C 321/28 (2006.01) (2006.01) (2006.01) (21) Application number: 13777766.0 A01N 31/16 A01N 33/20 A01N 37/00 (2006.01) A01N 39/00 (2006.01) A01N 43/00 (2006.01) A01N 47/02 (2006.01) (22) Date of filing: 11.04.2013 A01N 47/48 (2006.01) A01N 55/00 (2006.01) A01N 41/10 (2006.01) C07C 317/22 (2006.01) C07C 317/46 (2006.01) C07C 323/62 (2006.01) C07C 331/10 (2006.01) C07C 323/20 (2006.01) (86) International application number: PCT/JP2013/002459 (87) International publication number: WO 2013/157229 (24.10.2013 Gazette 2013/43) (54) ALKYLPHENYLSULPHIDE DERIVATIVE AND PEST CONTROL AGENT ALKYLPHENYLSULPHIDDERIVAT UND SCHÄDLINGSBEKÄMPFUNGSMITTEL DÉRIVÉ DE SULFURE D’ALKYLPHÉNYLE ET AGENT DE LUTTE CONTRE LES ORGANISMES NUISIBLES (84) Designated Contracting States: • KAWAMOTO, Kei AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Iwata-shi GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Shizuoka 437-1213 (JP) PL PT RO RS SE SI SK SM TR • WATANABE, Akira Iwata-shi (30) Priority: 20.04.2012 JP 2012096356 Shizuoka 437-1213 (JP) • KOMATSU, Masaaki (43) Date of publication of application: Tokyo 110-0008 (JP) 25.02.2015 Bulletin 2015/09 • MATSUDA, Takeshi Tokyo 110-0008 (JP) (73) Proprietor: Kumiai Chemical Industry Co., Ltd. • ITO, Seisuke Tokyo 110-0008 (JP) Tokyo 110-0008 (JP) (72) Inventors: (74) Representative: Vossius & Partner • DOMON, Kei Patentanwälte Rechtsanwälte mbB Iwata-shi Siebertstrasse 3 Shizuoka 437-1213 (JP) 81675 München (DE) • TORIYABE, Keiji Iwata-shi (56) References cited: Shizuoka 437-1213 (JP) WO-A2-2007/064553 CN-A- 1 456 549 • OGAWA, Yutaka JP-A- S6 341 451 JP-A- S60 158 162 Iwata-shi US-A- 3 388 167 US-A- 3 962 345 Shizuoka 437-1213 (JP) US-A- 4 005 148 • BESSHO, Junichiro Iwata-shi • HELVETICA CHIMICA ACTA vol. 86, no. 7, 2003, Shizuoka 437-1213 (JP) pages 2610 - 2619, XP055173750 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 840 078 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 840 078 B1 • ZHURNAL ORGANICHESKOI KHIMII vol. 7, no. 7, • SYNTHETIC COMMUNICATIONS vol. 11, no. 12, 1971, pages 1466 - 1469 (1518-1520), 1981, pages 957 - 968, XP008175263 XP008175262 • ZHURNALORGANICHESKOI KHIMII vol. 5, no. 10, • ’TERT-BUTANESULFINYLTHIOETHER 1969, pages 1813 - 1815 (1760-1762), LIGANDS: SYNTHESIS AND APPLICATION IN XP008175261 PALLADIUM-CATALYZED ASYMMETRIC • JOURNAL OF THE CHEMICAL SOCIETY 1945, ALLYLIC ALKYLATION’ TETRAHEDRON: pages 14 - 18, XP008175260 ASYMMETRY vol. 22, no. 5, 2011, pages 575 - 579, • DATABASE CAS REGISTRY [Online] 16 XP055173255 November 1984 XP055185528 Retrieved from • ’N-TOSYL-S-DIFLUOROMETHYL-S-PHENYLSULF STN Database accession no. 85292-33-7 OXIMI NE: A NEW DIFLUOROMETHYLATION REAGENT FOR S-, N-, AND C-NUCLEOPHILES’ ORGANIC LETTERS vol. 11, no. 10, 2009, pages 2109 - 2112, XP055173258 2 EP 2 840 078 B1 Description TECHNICAL FIELD 5 [0001] The present invention relates to a novel alkyl phenyl sulfide derivative or an agriculturally acceptable salt thereof, as well as to a pest control agent containing the derivative or the salt thereof as an active ingredient. BACKGROUND ART 10 [0002] Alkyl phenyl sulfide derivatives having a pest control effect are described in patent literatures 1, 2, 3, 4, 5 and 6. However, the compounds described in the patent literatures 1, 2, 3 and 4 are restricted to alkyl phenyl sulfide derivatives having no substituent group on the alkylthio group; the compounds described in the patent literature 5 are restricted to alkyl phenyl sulfide derivatives having certain substituents on the phenyl ring; and the compounds described in the patent literature 6 are restricted to alkyl phenyl sulfide derivatives having a 2-bromoethylthio group as a substituent group. 15 Thus, these patent literatures make no mention of an alkyl phenyl sulfide derivative having a substituent group other than bromine atom on the alkylthio group. [0003] The follow-up experiment made on the compounds described in the above patent literatures revealed that, despite the description made therein, the compounds have an insufficient effect to spider mites, have no effect to spider mites which have acquired chemical resistance, and accordingly have no sufficient control effect. 20 PRIOR ART LITERATURES Patent Literatures 25 [0004] Patent literature 1: JP-A-1975-29744 Patent literature 2: JP-A-1976-19121 Patent literature 3: JP-B-1982-35162 30 Patent literature 4: JP-A-1988-41451 Patent literature 5: JP-A-1992-312566 Patent literature 6: US Patent 3388167 DISCLOSURE OF THE INVENTION 35 Task to Be Achieved by the Invention [0005] Pest control agent applied to useful crops is desired to be a chemical agent which exhibits a sufficient pest control effect at a low dose when applied to soil or stem and leaf. Also, development of safer pest control agent is desired 40 because requirements for safety of chemical substance and its influence to environment are becoming stronger. Further, in recent years, the use of pest control agents such as insecticide, miticide and the like over many years have invited the appearance of pests which have acquired resistance to such pest control agents, and complete control of pests have become difficult. Furthermore, the use of pest control agents having high toxicity to humans and livestock has become a problem from the safety to workers and others. 45 [0006] Under such circumstances, the task of the present invention is to solve the above-mentioned problems of conventional pest control agents and provide a pest control agent superior in safety, control effect, residual effect, etc. (Means to solve the problems) 50 [0007] In order to develop a pest control agent having the above-mentioned desirable properties, the present inventors synthesized various alkyl phenyl sulfide derivatives and investigated their physiological activities earnestly. As a result, it was found that an alkyl phenyl sulfide derivative represented by the following general formulas [I] or [I’] (the derivative is hereinafter referred to as the present compound) has an excellent effect on various pests, particularly on spider mites represented by Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, etc. A further research has led to the 55 completion of the present invention. [0008] The present invention is as follows. (1) An alkyl phenyl sulfide derivative represented by the general formula [I] or an agriculturally acceptable salt thereof 3 EP 2 840 078 B1 5 10 [in the formula [I], 15 n is an integer of 0, 1 or 2, 1 R is a C1∼C6 haloalkyl group (the group excludes 2-bromoethyl group), a 2C∼C8 alkenyl group (the group excludes allyl group), a C 2∼C8 haloalkenyl group, a C 2∼C6 alkynyl group, a C 2∼C6 haloalkynyl group, a branched C4∼C6 alkyl group (the group excludes isobutyl group), a 3∼CC6 cycloalkyl C1∼C6 alkyl group or a C3∼C6 halocycloalkyl C1∼C6 alkyl group, 20 2 R is a halogen atom, a C1∼C6 alkyl group, a C1∼C6 haloalkyl group, a C3∼C6 cycloalkyl group, a C3∼C6 halocycloalkyl group, a C1∼C6 alkoxy group, a C1∼C6 haloalkoxy group, a cyano group or a nitro group, 3 R is a halogen atom, a C1∼C6 alkyl group or a C1∼C6 haloalkyl group, 5 R4 is a C1∼C12 alkyl group (the group may be mono- or poly-substituted with R ), a C 3∼C6 cycloalkyl group (the 5 group may be mono- or poly-substituted with R), a C2∼C8 alkenyl group (the group may be mono- or poly- 25 5 5 substituted with R ), a C2∼C6 alkynyl group (the group may be mono- or poly-substituted with R ) or a benzoyl group (the group may be mono- or poly-substituted with R 6), 5 R is a halogen atom, a C 1∼C6 alkyl group, a C1∼C6 haloalkyl group, a C3∼C6 cycloalkyl group (the group may 6 be mono- or poly-substituted with R ),a C3∼C6 halocycloalkyl group, a hydroxyl group, a C1∼C6 alkoxy group, a C1∼C6 haloalkoxy group, a C 3∼C6 cycloalkoxy group, a C 3∼C6 halocycloalkoxy group, a C 1∼C6 alkoxy C1∼C6 30 alkoxy group, a C1∼C6 haloalkoxy C1∼C6 alkoxy group, a C1∼C6 haloalkoxy C1∼C6 haloalkoxy group, a C1∼C6 alkylsulfinyloxy group, a C1∼C6 haloalkylsulfinyloxy group, a C3∼C6 cycloalkylsulfinyloxy group, a C3∼C6 halo- cycloalkylsulfinyloxy group, a C1∼C6 alkylsulfonyloxy group, a C1∼C6 haloalkylsulfonyloxy group, a C3∼C6 cy- cloalkylsulfonyloxy group, a C3∼C6 halocycloalkylsulfonyloxy group, a thiol group, a C1∼C6 alkylthio group, a C1∼C6 haloalkylthio group, a C2∼C6 alkenylthio group, a C2∼C6 haloalkenylthio group, a C3∼C6 cycloalkylthio 35 group, a C3∼C6 halocycloalkylthio group, a C3∼C6 cycloalkyl C1∼C6 alkylthio group, a C3∼C6 halocycloalkyl C1∼C6alkylthio group,a tri(C 1∼C6alkyl)silyl C 1∼C6 alkylthio group, a C 1∼C6alkylsulfinyl group, a C 1∼C6 haloalkyl- sulfinyl group, a C3∼C6 cycloalkylsulfinyl group, a C3∼C6 halocycloalkylsulfinyl group, a C1∼C6 alkylsulfonyl group, a C 1∼C6 haloalkylsulfonyl group, a C 3∼C6 cycloalkylsulfonyl group, a C 3∼C6 halocycloalkylsulfonyl group, a C1∼C6 alkylcarbonyl group, a C 1∼C6 haloalkylcarbonyl group, a formyl group, a C 1∼C6 alkylcarbonyloxy group, 40 a C1∼C6 haloalkylcarbonyloxy