(19) TZZ _T (11) EP 2 427 427 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 255/60 (2006.01) 25.12.2013 Bulletin 2013/52 (86) International application number: (21) Application number: 10713937.0 PCT/EP2010/054862 (22) Date of filing: 14.04.2010 (87) International publication number: WO 2010/127926 (11.11.2010 Gazette 2010/45) (54) 4-CYANO-3-BENZOYLAMINO-N-PHENYL-BENZAMIDES FOR USE IN PEST CONTROL 4-CYANO-3-BENZOYLAMINO-N-PHENYL-BENZAMIDE ZUR VERWENDUNG IN DER SCHÄDLINGSBEKÄMPFUNG 4-CYANO-3-BENZOYLAMINO-N-PHÉNYL-BENZAMIDES DESTINÉS À ÊTRE UTILISÉS DANS LA LUTTE ANTIPARASITAIRE (84) Designated Contracting States: • HUETER, Ottmar Franz AT BE BG CH CY CZ DE DK EE ES FI FR GB GR CH-4332 Stein (CH) HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL • MAIENFISCH, Peter PT RO SE SI SK SM TR CH-4332 Stein (CH) (30) Priority: 06.05.2009 GB 0907822 (74) Representative: Herrmann, Jörg et al 18.12.2009 GB 0922234 Syngenta Crop Protection Münchwilen AG (43) Date of publication of application: Intellectual Property Department 14.03.2012 Bulletin 2012/11 Schaffhauserstrasse CH-4332 Stein (CH) (73) Proprietor: Syngenta Participations AG 4058 Basel (CH) (56) References cited: EP-A1- 1 714 958 WO-A1-2008/000438 (72) Inventors: WO-A1-2008/074427 • JUNG, Pierre Joseph Marcel CH-4332 Stein (CH) Remarks: • GODFREY, Christopher Richard Ayles Thefile contains technical information submitted after CH-4332 Stein (CH) the application was filed and not included in this specification 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 2 427 427 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 427 427 B1 Description [0001] The present invention relates to novel bis-amide derivatives having insecticidal activity, to methods of using them to control insect, acarine, nematode and mollusc pests and to insecticidal, acaricidal, nematicidal and molluscicidal 5 compositions comprising them. It also describes processes and intermediates for preparing them. [0002] Compounds having insecticidal properties are disclosed in EP 1,714,958, JP 2006/306771, WO 2006/137376, EP 1,916,236, WO 2007/017075, WO 2008/000438, WO 2008/074427 and WO 2009/049845. There exists a need for alternative methods of control of pests. Preferably, new compounds may possess improved insecticidal properties, such as improved efficacy, improved selectivity, lower tendency to generate resistance or activity against a broader range of 10 pests. Compounds may be more advantageously formulated or provide more efficient delivery and retention at sites of action, or may be more readily biodegradable. [0003] It has now surprisingly been found that bis-amide derivatives having a particular substitution pattern on a terminal phenyl group have excellent insecticidal properties that are unexpectedly superior to previously disclosed compounds. 15 [0004] Accordingly, the present invention provides a compound of formula (I) 20 25 wherein 30 1 R is hydrogen, C1-C8alkyl, C1-C8alkylcarbonyl, or C1-C8alkoxycarbonyl; 2 R is hydrogen, C1-C8alkyl, C1-C8alkylcarbonyl, or C1-C8alkoxycarbonyl; each R3 is independently halogen; n is 0, 1, 2 for 3; Q2 is a group of formula (II) 35 40 45 1 5 Y and Y are each independently selected from halogen, cyano,1-C C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, 1-CC4alkoxy-C1-C4alkyl, 1-CC3alkythio, 1-CC3haloalkylthio, 1-CC3alkylsulfinyl, C1-C3haloalkylsulfinyl, C1-C3alkylsulfonyl and C1-C3haloalkylsulfonyl; 3 Y is selected from2-C6 perfluoroalkyl,C 2-CC 6perfluorocycloalkyl, hydroxy-C2-C6perfluoroalkyl, C1-C4alkylcarbonyloxy-C2-C6perfluoroalkyl, C1-C4haloalkylcarbonyloxy-C2-C6perfluoroalkyl, 50 C1-C6perfluoroalkylthio, 1-C6Cperfluoroalkylsulfinyl, 1-C6Cperfluoroalkylsulfonyl, arylcarbonyloxy- C2-C6perfluoroalkyl and arylcarbonyloxy-C2-C6perfluoroalkyl in which the aryl group may be substituted by one to five R4 groups, which may be the same or different; 2 4 Y and Y are each independently selected from hydrogen, halogen and C 1-C4alkyl; and 4 R is halogen, cyano, nitro, C 1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy; 55 or an agrochemically acceptable salt or N-oxides thereof. [0005] The compounds of formula (I) may exist in different geometric or optical isomers (enantiomers and/or diaster- oisomers) ortautomeric forms. This invention covers allsuch isomers and tautomers and mixturesthereof in all proportions 2 EP 2 427 427 B1 as well as isotopic forms such as deuterated compounds. [0006] Unless otherwise indicated, alkyl, on its own or as part of another group, such as alkoxy, alkylcarbonyl or alkoxycarbonyl, may be straight or branched chain and may contain from 1 to 8 carbon atoms, preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3. Examples of alkyl include methyl, ethyl,n-propyl, iso-propyl, n-butyl, 5 sec-butyl, iso-butyl and tert-butyl. [0007] Hydroxyalkyl are alkyl groups, which are substituted by one or more hydroxy groups, and includes, for example, hydroxymethyl and 1,3-dihydroxypropyl. [0008] Halogen means fluorine, chlorine, bromine or iodine. [0009] Haloalkyl groups may contain one or more identical or different halogen atoms, and include, for example, 10 difluoromethyl, trifluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl and 2,2-difluoroethyl. Perfluoroalkyl groups are alkyl groups which are completely substituted with fluorine atoms and include, for example, trifluoromethyl, pentafluor- oethyl, heptafluoroprop-2-yl and nonafluorobut-2-yl.. [0010] Hydroxyperfluoroalkyl groups are hydroxyalkyl groups which are substituted in every available position by a fluorine atom, and include, for example, hexafluoro-2-hydroxyprop-2-yl and octafluoro-2-hydroxybut-2-yl. 15 [0011] Cycloalkyl groups may be monocyclic or bicyclic and may preferably contain from 3 to 8 carbon atoms, more preferably 4 to 7, and most preferably 5 to 6, and include, for example, cyclopropyl, cyclobutyl, cyclohexyl and bicyclo [2.2.1]heptan-2-yl. [0012] Perfluorocycloalkyl groups are cycloalkyl groups which are substituted in every available position by a fluorine atom, and include, for example, undecafluorocyclohexyl. 20 [0013] Aryl includes phenyl, naphthyl, anthracenyl, indenyl, phenanthrenyl and biphenyl, with phenyl being preferred. [0014] Preferred values of R1, R2, R3, n, Q2, Y1, Y2, Y3, Y4, Y5 and R4 are, in any combination, as set out below. [0015] Preferably, R1 is hydrogen. [0016] Preferably, R2 is hydrogen. [0017] Preferably, R3 is fluoro. 25 [0018] In one preferred aspect, n is 0. [0019] In another preferred aspect, n is 1. When n is 1, the R 3 group is preferably substituted in the 2- position of the phenyl ring. 1 [0020] Preferably, Y is halogen, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl or C1-C3alkylthio. More preferably, Y1 is fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, methylthio, or methoxymethyl. Most preferably, 30 Y1 is chloro, bromo, methyl, ethyl, or cyano. [0021] Preferably, Y2 is hydrogen, chloro, fluoro or methyl. More preferably, Y 2 is hydrogen or fluoro. Most preferably, Y2 is hydrogen. 3 [0022] Preferably, Y is C2-C6perfluoroalkyl, C2-C6perfluorocycloalkyl, hydroxy-C2-C6perfluoroalkyl, arylcarbonyloxy- C2-C6perfluoroalkyl, or arylcarbonyloxy-C2-C6perfluoroalkyl in which the aryl group may be substituted by one to five 35 R4 groups, which may be the same or different. More preferably, Y 3 is heptafluoropropyl, nonafluorobutyl, undecafluor- ocyclohexyl, heptafluoropropylthio, heptafluoropropylsulfinyl, or heptafluoropropylsulfonyl. Yet more preferably, 3Y is heptafluoroprop-1-yl, heptafluoroprop-2-yl, nonafluorobut-2-yl or undecafluorocyclohexyl. Most preferably, Y3 is hep- tafluoroprop-2-yl, nonafluorobut-2-yl or undecafluorocyclohexyl. [0023] Preferably, Y4 is hydrogen, chloro, fluoro or methyl. More preferably, Y 4 is hydrogen or fluoro. Most preferably, 40 Y4 is hydrogen. 5 [0024] Preferably, Y is halogen, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl or C1-C3alkylthio. More preferably, Y5 is fluoro, chloro, bromo, cyano, methyl, ethyl, methoxy, methylthio, or methoxymethyl. Most preferably, Y5 is chloro, bromo, methyl, ethyl, or cyano. [0025] Preferably, R4 is chloro, fluoro, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, or trifluoromethoxy. 45 [0026] Most preferably, Q2 is selected from 2-bromo-6-chloro-4-(hexafluoro-2-benzoyloxyprop-2-yl)phenyl, 2-bromo-6-chloro-4-(hexafluoro-2-hydroxyprop-2-yl)phenyl, 2-bromo-6-chloro-4-(nonafluorobut-2-yl)phenyl, 50 2-bromo-6-ethyl-4-(nonafluorobut-2-yl)phenyl, 2-chloro-6-cyano-4-(nonafluorobut-2-yl)phenyl, 2-chloro-6-methylthio-4-(nonafluorobut-2-yl)phenyl, 2,6-dibromo-4-(heptafluoroprop-2-yl)phenyl, 2,6-dibromo-4-(nonafluorobut-2-yl)phenyl, 55 2,6-dichloro-3-fluoro-4-(heptafluoroprop-2-yl)phenyl, 2,6-dichloro-4-(nonafluorobut-2-yl)phenyl, 2,6-dimethyl-4-(nonafluorobut-2-yl)phenyl, 2,6-dimethyl-4-(undecafluorocyclohexyl)phenyl, 3 EP 2 427 427 B1 2-ethyl-6-methyl-4-(nonafluorobut-2-yl)phenyl, 2-ethyl-6-methyl-4-(octafluoro-2-hydroxybut-2-yl)phenyl, 2-methoxymethyl-6-methyl-4-(nonafluorobut-2-yl)phenyl, and 2-methoxy-6-methyl-4-(nonafluorobut-2-yl)phenyl. 5 [0027] In a preferred embodiment of the invention, R1 and R2 are