(19) TZZ _¥_ 4B_T (11) EP 2 193 124 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 261/04 (2006.01) A01N 43/80 (2006.01) 19.12.2012 Bulletin 2012/51 A61K 31/42 (2006.01) (21) Application number: 08835800.7 (86) International application number: PCT/US2008/078254 (22) Date of filing: 30.09.2008 (87) International publication number: WO 2009/045999 (09.04.2009 Gazette 2009/15) (54) NAPHTHALENE ISOXAZOLINE COMPOUNDS FOR CONTROL OF INVERTEBRATE PESTS NAPHTHALEN-ISOXAZOLIN-VERBINDUNGEN ZUR BEKÄMPFUNG WIRBELLOSER SCHÄDLINGE COMPOSÉS DE NAPHTALÈNE ISOXAZOLINE DESTINÉS À LA LUTTE CONTRE LES ORGANISMES NUISIBLES INVERTÉBRÉS (84) Designated Contracting States: • SELBY, Thomas, Paul AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Hockessin HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT Delaware 19707 (US) RO SE SI SK TR •XU,Ming Newark (30) Priority: 03.10.2007 US 997504 P Delaware 19702 (US) (43) Date of publication of application: (74) Representative: Beacham, Annabel Rose et al 09.06.2010 Bulletin 2010/23 Dehns St Bride’s House (73) Proprietor: E. I. du Pont de Nemours and Company 10 Salisbury Square Wilmington, DE 19898 (US) London EC4Y 8JD (GB) (72) Inventors: • LONG, Jeffrey, Keith (56) References cited: Wilmington WO-A-2007/079162 WO-A-2008/122375 Delaware 19803 (US) 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 2 193 124 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 193 124 B1 Description FIELD OF THE INVENTION 5 [0001] This invention relates to certain naphthalene isoxazolines, their N-oxides, salts and compositions suitable for agronomic and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments. BACKGROUND OF THE INVENTION 10 [0002] The control ofinvertebrate pests isextremely importantin achieving high cropefficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. 15 Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action. [0003] PCT Patent Publication WO 07/079162 discloses isoxazoline derivatives of Formula i as insecticides 20 25 30 1 6 4 5 10 wherein, inter alia, A through A are independently C or N; W is O or S; R is H or C1-C6 alkyl; and R is H, OR , NR11R12 or Q1. [0004] The naphthalene isoxazolines of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION 35 [0005] This invention is directed to compounds of Formula 1 (including all geometric and stereoisomers), N-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests: 40 45 50 wherein 1 R is halogen, C1-C3 haloalkyl or C1-C3 haloalkoxy; 55 2 R is H, halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl; 3 R is H, halogen, C1-C3 haloalkyl or C1-C3 haloalkoxy; 4 R is H, halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl; 5 R is H, CH3, C2-C7 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C7 alkoxycarbonyl or CH2O(C1-C3 alkyl); 2 EP 2 193 124 B1 6 11 12 13 14 R is C1-C6 alkyl group optionally substituted with halogen, OR , S(O)nR or NR C(O)R ; or 6 R is C3-C6 cycloalkyl or C4-C7 cycloalkylalkyl, each optionally substituted with 1 to 4 substituents selected from the group consisting of halogen, C 1-C2 alkyl, C1-C2 haloalkyl and up to 1 cyclopropyl; or 6 R is (CH2)mQ; or 5 R6 is OR8 or NR9aR9b; Q is a 4- to 6-membered saturated ring containing carbon atoms and one O or S(O)n as ring members and optionally substituted with 1 or 2 R 10; 8 R is C1-C4 alkyl or C1-C4 haloalkyl; 9a R is C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl; 10 9b R is H, C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl; 10 each R is independently halogen, cyano or C1-C2 alkyl; 11 R is H, C1-C4 alkyl or C1-C4 haloalkyl; 12 R is C1-C4 alkyl or C1-C4 haloalkyl; 13 R is H or C1-C4 alkyl; 15 14 R is C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl; m is 0 or 1; and each n is independently 0, 1 or 2. [0006] This invention also provides a composition comprising a compound of Formula 1, an N-oxide or a salt thereof, 20 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, this invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula1 , an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. 25 [0007] This invention further discloses a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, or the composition described above, and a propellant. This invention also provides a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, or the compositions described in the em- bodiments above, one or more food materials, optionally an attractant, and optionally a humectant. 30 [0008] This invention further discloses a trap device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest. 35 [0009] This invention provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula1 , an N-oxide or a salt thereof, (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, 40 solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. [0010] This invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula1, an N-oxide or a salt thereof, (e.g., as a composition described herein). This invention also relates to the treated seed. This invention further provides a method 45 for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein). DETAILS OF THE INVENTION 50 [0011] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or "containing," or any other variation thereof, are intended to cover a non- exclusive inclusion. For example, a composition, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive 55 or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). [0012] Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or 3 EP 2 193 124 B1 "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. [0013] As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests.