NZ617429B2 - Pesticidal mixtures including isoxazoline derivatives - Google Patents

Abstract

Disclosed are pesticidal mixtures comprising a component A and a component B, wherein component A is a compound of formula (I) wherein the substituents are as defined in the specification, and component B is an additional insecticide. Also disclosed are methods of controlling insects, acarines, nematodes or molluscs which comprises applying said pesticidal mixtures to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest. todes or molluscs which comprises applying said pesticidal mixtures to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest.

Description

IDAL ES INCLUDING ISOXAZOLINE DERIVATIVES The present invention relates to mixtures of pesticidally active ingredients and to s ofusing the mixtures in the field of agriculture.

EPl731512 discloses that certain isoxazoline compounds have insecticidal activity.

The present invention provides pesticidal mixtures comprising a component A and a component B, wherein component A is a compound of formula I wherein L is a direct bond or methylene; A1 and A2 are OH, or one ofAI and A2 is OH and the other is N; R1 is hydrogen, cyano, cyano-Cl-Cgalkyl, C1-Cgalkyl, C1-Cghaloalky1, Cg-Cgcycloalkyl, Cg-Cgcycloalkyl where one carbon atom is replaced by O, S, 8(0) or 802, or C3-Cgcycloalkyl-Cl-Cgalkyl, C3- Cgcycloalkyl—Cl—Cgallql where one carbon atom in the cycloalkyl group is replaced by O, S, 8(0) or $02, or Cg-Cgcycloalkyl—C1—Cghaloalkyl, C1-Cghydroxyalkyl, C1-Cgalkoxy-C1—Cgalkyl, Cg—Cgalkenyl, C2- Cghaloalkenyl, Cg—Csalkynyl, C2-Cghaloalkynyl, phenyl, phenyl substituted by one to three R6 , - C1—C4alky1, phenyl—CI—C4alky1 wherein the phenyl moiety is substituted by one to three R6, 5—6 ed heteroaryl—CI—C4alkyl or 5—6 membered heteroaryl—Cl-C4a1ky1 n the heteroaryl moiety is substituted by one to three R6, or C1~C4all<yl-(C1-C4alkyl-O-N=)C—CH2-; R2 is chlorodifluoromethyl or romethyl; each R3 is independently bromo, chloro, fluoro or tn'fluoromethyl; R4 is hydrogen, halogen, methyl, halomethyl or cyano; R5 is hydrogen; or R4 and R5 together form a bridging 1,3-butadiene group; each R6 is ndently halogen, cyano, nitro, C1—Cgalky1, C1-Cghaloa1kyl, C1-Cgalkoxy, or C1- Cghaloalkoxy; p is 2 or 3; and component B is a compound selected from a) a pyrethroid including those selected from the group consisting of permethrin, cypennethn'n, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothiin, gamma—cyhalothrin, bifenthrin, fenpropathrin, cyfluthrin (including beta rin), tefluthrin, ethofenprox, l pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, thrin and -benzyl-3—fi1rylmethyl-(E)-(l R,3S)-2,2—dimethyl- 3~(2-oxothiolanylidenemethyl)cyclopropane ylate; b) an organophosphate including those selected from the group consisting of sulprofos, acephate, methyl parathion, azinphos-methyl, demeton—s—methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, oate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos—methyl, pirimiphos-ethyl, fenitrothion, fosthiazate and diazinon; c) a carbamate including those selected from the group consisting of pirimicarb, triazamate, cloethocarb, carbofuran, fiirathiocarb, ethiofencarb, rb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl, thiodicarb and oxamyl; d) a benzoyl urea including those ed from the group consisting of diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron; e) an organic tin nd including those selected from the group ting of cyhexatin, fenbutatin oxide and azocyclotin; f) a pyrazole including those selected from the group consisting of tebufenpyrad and fenpyroximate; g) a macrolide including those selected from the group consisting of abamectin, emamectin (e.g. emamectin te), ivermectin, milbemycin, ad, azadirachtin and spinetoram; h) an organochlorine compound ing those selected from the group consisting of endosulfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane and dieldrin; i) an amidine ing those selected from the group consisting of chlordimeform and amitraz; j) a fumigant agent including those selected from the group consisting of chloropicrin, dichloropropane, methyl bromide and metam; k) a otinoid compound including those ed from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, furan, thiamethoxam, clothianidin, nithiazine and flonicainid; l) a diacylhydrazine including those selected from the group consisting of tebufenozide, chromafenozide and methoxyfenozide; m) a diphenyl ether including those selected from the group consisting of olan and pyriproxyfen; n) indoxacarb; 0) chlorfenapyr; p) pymetrozine; q) etramat, spirodiclofen and spiromesifen; r) a diamide including those selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; s) sulfoxaflor; t) metaflurnizone; u) fipronil and ethiprole; v) pyrifluqinazon; w) buprofezin; x) diafenthiuron; y) 4—[(6—Chloro—pyridin—3~ylrnethy1)—(2,2-difluoro—ethyl)-arnino] —5H—furan—2—0ne; z) Bacillus species, and Pasteuria species; aa) difurone; ab) CAS: 915972—17—7 (WO 2006129714; WOZOl 1/147953; WO2011/147952); ac) CAS: 26914-55—8 (WO 2007020986); ad) a nd selected from novaluron, noviflumuron, tolfenpyrad, pyriprole, milbemectin, lepimectin, metaflumizone, ial oils such as Bugoil® - (Plantlmpact), acequinocyl, bifenazate, yrafen, cyflumetofen, etoxazole, flometoquin, fluacrypyrirn, fluensulfone, flufenerim, flupyradifuone, harpin, l5 thane, dodecadienol, pyridaben, pyridalyl, difen, flupyradifurone.

In addition, component B may be a nematicidally active biological agent. The nematicidally active biological agent refers to any biological agent that has nematicidal activity. The biological agent can be any type known in the art including bacteria and fungi. The wording “nernaticidally active” refers to having an effect on, such as reduction in damage caused by, agricultural-related nematodes. The nematicidally active biological agent can be a bacterium or a fungus. Preferably, the biological agent is a bacterium. Examples of nematicidally active bacteria include Baciullus species, e.g. Bacillusfirmus, Bacillus cereus, Bacillus subtilis, and n‘a species such as Pasteuria penetrcms and Pasteuria nishizawae. A suitable Bacillusfirmus strain is strain CNCM 1-1582 which is cially available as BioNemTM. A suitable Bacillus cereus strain is strain CNCM 1—1562. Of both Bacillus s more details can be found in US 6,406,690. Other biological organisms that may be included in the compositions of the invention are bacteria such as Streptomyces spp. such as S. avermitilis, and fungi such as Pochonia Spp. such as P. chlamydosporia. Also of interest are izium Spp. such as M. anisopliae; Pochonia Spp. such as P. chlamydospofla.

It has now been found, surprisingly, that the active ingredient mixture according to the invention 3O not only delivers about the additive enhancement of the spectrum of action with respect to the pest to be controlled that was in principle to be ed but achieves a synergistic effect which can extend the range of action of the ent A and of the component B in two ways. Firstly, the rates of application of the component A and of the component B are lowered whilst the action remains equally good.

Secondly, the active ingredient mixture still achieves a high degree ofpest control, mes even where the two individual components have become totally ineffective in such a low application rate range. This allows increased safety in use.

However, besides the actual synergistic action with respect to pest control, the pesticidal compositions according to the invention can have further surprising advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: a broadening of the spectrum of pest control to other pests, for example to resistant strains; a reduction in the rate of ation of the active ingredients; te pest control with the aid of the compositions according to the invention, even at a rate of application at which the individual compounds are totally ineffective; advantageous behaviour during formulation and/or upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageuos degradability; improved toxicological and/or ecotoxicological our; improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leafblade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds , more productive tillers, r flowering, early grain maturity, less plant verse ng), increased shoot growth, improved plant vigor, and early germination; or any other advantages familiar to a person d in the art.

The compounds of formula I have outstanding icidal properties as described in . The components B are known, e.g. from “The Pesticide Manual”, Fifteenth Edition, Edited by Clive Tomlin, British Crop Protection Council. The compound under y) is known from DE 102006015467. Reference to the above components B includes reference to their salts and any usual derivatives, such as ester derivatives.

The combinations according to the invention may also comprise more than one of the active components B, if, for e, a broadening of the spectrum of pest control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components B with any of the compounds of formula I, or with any preferred member of the group ofcompounds of a I. The mixtures ofthe ion may also se other active ients in on to components A and B.

In other ments the mixtures of the invention may include only components A and B as pesticidally active ingredients, e.g. no more than two pesticidally active ingredients.

Preferred substituents are, in any combination, as set out below.

A1 and A2 are preferably C—H.

R1 is preferably hydrogen, cyano~C1-Cgalkyl, C1—Cgalkyl, C3—Cgcycloalkyl, Cg-Cgcycloalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, 8(0) or 802, or C3—Cgcycloalkyl-C1—Cgalkyl, C3-CgCYClOEIlky1-C1-Cgalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, 8(0) or 802, or C1-Cshaloalkyl, ydroxyalkyl, C1-Cghydroxyalkyl, Cg-Cgalkenyl, C2-Cgalkynyl, phenyl-C1- C4alkyl or phenyl-Cl-C4alkyl wherein the phenyl moiety is tuted by one to three R6, 5-6 membered heteoaryl-CI-C4alkyl or 5-6 membered heteroaryl—Cl-C4alkyl wherein the heteroaryl moiety is substituted by one to three R6; more preferably R1 is hydrogen, cyano-Cl—Cgalkyl—, lkyl, Cg—Cgcycloalkyl, C3- Cgcycloalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, 8(0) or 802, or C1-Cghaloalkyl, C1-Cghydroxyalkyl, Cg-Cgalkenyl, C2—Cgalkynyl, —Cl—C4alkyl or phenyl-Cl-C4alkyl wherein the phenyl moiety is substituted by one to three R6, 5-6 membered heteroaryl—Cl—C4alkyl or 5—6 membered heteroaryl—C1—C4alkyl wherein the heteroaryl moiety is substituted by one to three R6; even more preferably R1 is hydrogen, Cl-Csalkyl, C1—C6alkyl, C3-C6cycloalkyl, C3-C5cycloalkyl where one carbon atom in the cycloalkyl group is replaced by O, S, 8(0) or 802, or C1—C6haloalkyl, C1- C5hydroxyalkyl, C1—C6alkoxy—C1—C6alkyl, C2—C6alkenyl, lkynyl, phenyl—CHg-alkyl or phenyl—CH2— wherein the phenyl moiety is substituted by one to three R6, furanyl or furanyl substituted by one to three R6, triazolyl or triazolyl ally substituted by one to three R6; yet even more preferably R1 is hydrogen, C1-C4alkyl, C3—Cacycloalkyl, C1—C4haloalkyl, C1-C4hydroxyalkyl, lkoxy—C1-C4alkyl, phenyl-CHg—alkyl- or phenyl-CH2— wherein the phenyl moiety is substituted by one to three R6, furanyl or furanyl substituted by one to three R6, thietanyl, oxetanyl, oxo-thietanyl, or thietanyl; yet even more preferably R1 is hydrogen, methyl, ethyl, propyl, butyl, cyclopropyl, cyclopropyl—methyl, cyclobutyl, cyclobutyl—methyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl, cyanoethyl, benzyl, benzyl substituted by one to three R6, or R1 is pyridyl—methyl— or pyridyl—methyl- substituted by one to three R6; yet even more preferably R1 is methyl, ethyl, ropyl, cyclobutyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, propargyl, cyanomethyl, cyanoethyl, benzyl, benzyl substituted by one to three R6, or pyridine—methyl- or pyridine-methyl- substituted by one to three R6, even more preferably methyl, ethyl, cyclopropyl, utyl, oxetanyl, thietanyl, trifluoroethyl, difluoroethyl, allyl, gyl, cyanomethyl, cyanoethyl, benzyl, or pyridine-methyl-. Ethyl and roethyl are particularly preferred. Heteroaryl preferably refers to pyridyl, zinyl, pyrimidinyl, pyrazinyl, pyrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl or thiazolyl, more ably l, pyrazolyl, furanyl, thiophenyl or thiazolyl, most preferably pyridyl.

R2 is preferably trifluoromethyl.

Preferably each R3 is independently chlorine or fluorine, most ably chlorine.

R4 is preferably chloro or methyl, most preferably methyl.

R5 is preferably en.

Each R6 is preferably independently halogen, cyano, C1-Cghaloalkyl, C1—Cgalkoxy or C1- Cghaloalkoxy, most preferably fluoro, chloro, bromo, trifluoromethyl, trifluoromethoxy, cyano or methoxy. p is preferably 2.

L is preferably a direct bond.

In one ment Al and A2 are OH; R2 is trifluoromethyl, and R5 is hydrogen.

In one embodiment Al and A2 are OH; R2 is trifluoromethyl, R4 is methyl, R5 is hydrogen, each R3 is chlorine, p is 2.

Compounds of formula I include at least one chiral centre and may exist as compounds of formula 1* or compounds of formula I**.

W0 2012I163960 \ 1 \ 1 (l**) nds of formula I** are more biologically active than compounds of formula 1*. Component A may be a mixture of compounds 1* and I** in any ratio 6.g. in a molar ratio of 1 :99 to 99: 1, e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. Preferably component A is a racemic mixture of the compounds of formula 1** and 1* or is omerically enriched for the compound of formula I**. For example, when ent A is an enantiomerically ed mixture of formula I**, the molar proportion of compound I** compared to the total amount of both enantiomers (in component A and therefore the mixture of the invention per se) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. In one embodiment component A is a compound of formula 1** in substantially pure form, e.g. it is ed substantially in the e ofthe alternative enantiomer.

Preferred compounds of formula 1 are shown in the Tables below.

Table A: Com ounds of formula I-a F3C O\IN Table A provides 354 compounds and mixtures of formula (I-a) wherein R1 has the values listed in table X below. The symbols * and ** indicate the location of the chiral centres.

Table B: Com ounds of formula I—b FC O\IN ( l-b ) O N Table B provides 354 compounds and mixtures of formula (I-b) wherein R1 has the values listed in table X below. The symbols * and ** indicate the on of the chiral centres.

Table C: Compounds of a (Lo) Table C provides 354 compounds and mixtures of formula (1-0) wherein R1 has the values listed in table X below. The symbols * and ** indicate the location of the chiral centres.

Table D: Corn ounds of formula l—d 0. 1“]th ( ) O R1 Table D provides 354 compounds and mixtures of formula (I—d) wherein R1 has the values listed in table X below. The symbols * and ** indicate the on of the chiral centres.

Table E: Com ounds of formula I-e a O 0 N ()I-e H P Cl Cl 0 N\ O R1 Table B provides 354 compounds and mixtures of formula (l-e) wherein R1 has the values listed in table X below. The symbols * and ** indicate the location of the chiral centres.

Table F: Corn ounds of formula I— * Cl a O O N (H) H P CI Cl 0 N\ O R1 Table F provides 354 compounds and mixtures of formula (1-1) wherein R1 has the values listed in table X below. The symbols * and ** te the location of the chiral centres.

Table X represents Table A when X is A, Table B when X is B, Table C when X is C, Table D when X is D, Table E when X is B, Table F when X is F.

Compound Stereochemistry at Stereochemistry at R1 numbers * ** X.l Racemic mixture Racemic mixture ethyl- l X.2 Racemic mixture Racemic mixture butyl- X.3 Racemic e Jjkigcemic mixture but-Z-yl- X.4 Racemic mixture Racemic mixture 3—bromo—propyl— Racemic e Racemic e 2,2,2—trifluoro—ethyl- X.6 Racemic mixture c mixture 3,3,3-t1ifluoro-propyl— X.7 Racemic mixture Racemic mixture 2-methoxy-ethyl— J Racemic mixture Racemic mixture 1-methoxy-propyl- Racemic mixture Racemic mixture cyclobutyl- X. 10 Racemic e Racemic e 2-methyl-cyclohex-1 -yl- X.11 Racemic mixture Racemic e phenyl—methyl— X. 12 Racemic e J Racemic mixture 1-phenyl—eth—1 —yl— X. l 3 Racemic mixture Racemic mixture 2—phenyl-eth—l -yl- nd chemistry at Stereochemistry at R numbers * * * X. 14 Racemic e Racemic mixture (3 —chloro—pheny1)—methyl- i x15 Racemic mixture (2-fluor0-pheny1)-methyl— X. 16 Racemic mixture Racemic mixture (4-methoxy-phenyl)-methyl- X. 17 Racemic mixture Racemic mixture flu0r0methyI-phenyl)- methyl- X. 1 8 Racemic mixture Racemic mixture (Z—trifluoromethoxy-phenyl)- methyl- X. 19 Racemic mixture c mixture (pyrid—Z-yl)—methyl— X20 Racemic mixture Racemic mixture (pyrid-3 -y1)-methyl— X21 Racemic mixture Racemic mixture (2—ch10r0-pyridyl)—methy1- X22 Racemic mixture Racemic e (1 —methyl— 1H—imidazol—4—y1)— methyl- X23 Racemic mixture Racemic mixture (furan—Z—yl)—methyl— X24 Racemic mixture Racemic mixture 2-(thi0phen—2'-y1)-eth—1-yl— X25 Racemic mixture Racemic mixture 2~(ind01—3 '—y1)-eth-1 -y1- X26 Racemic mixture Racemic e (1H—benzimidazol—Z—yl)—methyl- X27 Racemic mixture Racemic mixture (oxetan-Z—yl)-methyl- X28 Racemic mixture Racemic mixture (tetrahydrofiiran-Z-yl)-methyl— X29 Racemic e Racemic mixture 2-([1 ',3 '] dioxolan—2'—yl)—eth- 1 ~y1— Racemic mixture Racemic mixture pholin-4'-yl)—eth-l -yl— X.31 Racemic mixture Racemic mixture 2-(benzo[1',3']dioxol-5'-yl)-eth X32 Racemic mixture Racemic mixture (2,3 —dihydr0—benzo[1,4]dioxin yl)-methy1— Racemic mixture Racemic mixture 2-chlor0-pheny1— X.34 Racemic mixture Racemic mixture 3-fluoro-pheny1— X.35 Racemic mixture c e 2—methy1—pheny1— X.36 Racemic mixture Racemic mixture ro—6-methyl—phenyl— X.37 Racemic mixture Racemic mixture 2-triflu0r0methyl-phenyl— X.38 Racemic mixture c mixture 2,4-dimethoxy—phenyl— X.39 Racemic mixture Racemic mixture yl-pyrid—2-yl— X.40 Racemic mixture c mixture 1,3—dimethy1—lH-pyrazol-S-yl— X.41 Racemic e Racemic mixture 4~methy1-thiazolyl- X42 Racemic mixture Racemic mixture 5-methy1-thiadiazolyl- X43 Racemic mixture Racemic mixture quinolin-Z—yi— Racemic mixture Racemic mixture quinolin—S—yl— X.45 Racemic e Racemic mixture benzothiazoly1— X.46 Racemic mixture Racemic mixture 4—methy1—benzothiazol—2—y1— X47 Racemic mixture Racemic e thietan-3 -y1- X48 Racemic mixture Racemic e 1-oxo-thietanyl- X49 Racemic mixture Racemic mixture 1,1—dioxo-thietan—3—yl— X.50 Racemic mixture Racemic mixture 3-methyl-thietan-3—y1— X.51 Racemic mixture Racemic mixture 0xetan—3yl Racemic mixture Racemic mixture tetrahydropyranyl WO 63960 Compound Stereochemistry at Stereochemistry at R numbers * ** X.53 Racemic mixture Racemic mixture hydrogen X.54 Racemic mixture Racemic e methyl X-ss prowl Azimumhyt X.57 Racemic mixture Racemic e 2—fluoro—ethyl— X.58 S c mixture ethyl— X.59 S Racemic mixture butyl— X.60 S Racemic e but—Z-yl— X. 61 S Racemic mixture 3—brom0-pr0pyl- X.62 S Racemic e 2,2,2—trifluoro-ethyl— X.63 S Racemic mixture 3,3,3—t1iflu0r0-propyl— X.64 S Racemic mixture 2-methoxy—ethy1— X.65 S Racemic mixture 1—meth0xy—prop-2—y1— X.66 S Racemic mixture cyclobutyl— X.67 S Racemic mixture 2—methy1-cyclohex-1—yl- X.68 S Racemic mixture phenyl-methyl— S Racemic mixture 1—phenyI—ethyl- X.70 S Racemic mixture y1-eth— 1 -yl- X.71 S Racemic mixture (3-ch10ro-pheny1)-methyl- X.72 c mixture (2-fluoro-phenyI)-methyl- X.73 S Racemic mixture (4-methoxy-phenyl)-methyl- X.74 S Racemic mixture (2-triflu0r0methyl—phenyl)— methyl— X.75 S Racemic mixture (2—trifluoromethoxy—phenyl)- methyl- X.76 S Racemic mixture (pyrid—Z-yl)—methyl— X.77 S Racemic mixture (pyrid—B—yl)—methyl— X.78 S Racemic e (2—chloro—pyrid-5—yl)—methy1— fl x79 3 Racemic mixture (1-methyl—1H—imidazol—4—yl)— methxl- X. 80 S Racemic mixture (fiiran-Z-yl)-methyl— XS] S Racemic mixture 2—(thiophen—2'—yl)-ethyl— X.82 S Racemic mixture 2-(ind01—3'—yl)—eth—1 —yl— X. 83 S Racemic mixture (1H-benzimidazol-Z-yl)—methy1— X.84 S Racemic mixture (oxetan-Z-yl)-methyl- X.85 S Racemic mixture (tetrahydrofuran—Z-yl)—methy1— X.86 S Racemic mixture 2—([1',3']dioxolan—2'—yl)—eth—1 —yI- X.87 S Racemic mixtureW X.88 S Racemic mixture 2-(benzo[1',3']dioxol-5’-yl)~eth—1 - X.89 S Racemic mixture ‘i {2,3—dihydr0-benzofl ,4]dioxin-6— yl)-methy1— X.9O S c mixture ro—phenyl- S Racemic mixture 3-fluoro—pheny1— Compound Stereochemistry atW numbers * ** X92 S Racemic mixture 2—methy1-pheny1- X93 S c mixture 2-chloromethy1-phenyl~ X94 S Racemic mixture 2-trifluor0methy1—phenyl- X95 Racemic mixture 2,4—dimeth0xy-phenyl- X96 S Racemic mixture 3-methy1—pyrid-2—yl- X97 S Racemic mixture 1,3-dimethyl— 1 H-pyrazol—S—yl- X98 S Racemic mixture y1-thiazol—2-yl- X99 S Racemic mixture 5-methy1—thiadiazolyl- X. 100 S Racemic mixture quinolin—Z—yl— X. 101 S Racemic mixture quinolin—S—yl— X. 102 S Racemic mixture benzothiazol—6—y1— X. 103 S Racemic mixture 4—methy1—benzothiazol—2—y1— X. 104 S Racemic mixture thietan—3-y1— X. 1 05 S Racemic mixture 1-0x0-thietan—3 —y1— X. 106 S Racemic mixture ox0—thietan—3-yl— X. 107 S Racemic e 3-methy1—thietan-3—yl- X. 108 S Racemic mixture oxetan-3y1 X. 109 S Racemic e tetrahydropyran—4-y1 S Racemic mixture hydrogen X.111 S c mixture methyl X.112 S Racemic mixture propyl X. 1 13 S Racemic mixture 2,2-difluor0-ethyl— XI 14 S Racemic mixture 2-fluoro-ethyl— X.115 Racemic mixture Racemic e isopropyl : X. 1 16 Racemic mixture c mixture cyclopropyl XI 17 S Racemic mixture isopropyl X] 18 S Racemic mixture cyclopropyl X1 19 Racemic mixture S ethyl— X. 120 Racemic mixture S butyl- X. 121 Racemic e S but—2—y1- X. 122 Racemic mixture S 3-bromo-pr0py1— X. 123 Racemic e S 2,2,2—trifluoro—ethy1- Racemic mixture S 3,3,3-trifluoro-pr0pyl- X. 125 Racemic mixture S 2—methoxy—ethyl- X. 1 26 Racemic mixture S 1 —methoxy—prop—2-yl— X. 127 Racemic mixture S utyl- X. 129 Racemic mixture S phenyl-methyl- X. 130 Racemic mixture S 1—pheny1—eth—1 —yl— X. 13 1 Racemic mixture S 2-phenyl-eth—1 ~yl— X. 132 Racemic mixture S oro-pheny1)—methy1— X. 133 Racemic mixture S (2—flu0r0—phenyl)—methy1— ___J W0 2012!163960 nd Stereochemistry at Stereochemistry at Rr numbers * ** X. 134 Racemic mixture S (4—methoxy—pheny1)-methy1— X. 135 Racemic e 5 (2-trifluor0methy1-phenyl)- methyl- X. 136 Racemic mixture S (2-trifluoromethoxy-phenyl)- methyl- X. 137 Racemic mixture S —Z-y1)-methyl— X. 139 Racemic mixture S (2-chloro-pyrid-5—y1)—methyl- X. 140 Racemic mixture S (1 -methy1—1H—imidazol—4—y1)— methyl- X. 1 4 1 Racemic e S (furan—Z-yl)-methy1- X. 142 Racemic mixture S ophen—2'—yl)—eth-l-yl- X. 143 Racemic mixture S 2~(ind01—3'~y1)-eth—1—yl— X. 1 44 Racemic mixture S (1 H~benzimidazol-Z—yl)-methy1- X. 145 c mixture S (oxetan—Z—y1)-methyl- X. 146 Racemic mixture S (tetrahyW X. 147 Racemic mixture S 2-([1',3’]dioxolan-2'-yl)—eth-1—y1— X.148 s 2—(morpholin-4‘-yl)-eth—1-yl— X. 149 Racemic mixture S 2—(benzo[1',3‘]dioxol—5'—yl)—eth—1 - X. 150 Racemic mixture S 2,2,3 ro-benzo[1,4]dioxin yl)-methyl- X. 15 1 Racemic mixture S 2-chloro-phenyl- X. 152 Racemic e S 3-fluoro—phenyl— X. 1 53 Racemic mixture S 2-methy1—phenyl— X. 154 Racemic e S 2—chloro—6—methy1-phenyl— X. 155 Racemic mixture S 2—trifluoromethyI-pheny1— X. 1 56 Racemic mixture S L methoxy—phenyl- X. 1 57 Racemic mixture S 3—methy1-pyridy1— X. 1 5 8 Racemic mixture S 1 ,3 -dimethy1- 1 H-pyrazoly1— X. 159 Racemic mixture S y1—thiazol-2—y1— X. 160 Racemic mixture S 5-methy1—thiadiazol~2—yl— X. 1 61 Racemic mixture S quinolin—Z—yi— X. 1 62 Racemic mixture S quinolin—S—yl— X. 1 63 Racemic mixture S benzothiazol-6—yl— X. 164 Racemic mixture S 4—methy1—benzothiazo1y1— ...__1—__.

X. 1 65 Racemic mixture S thietan—3 —y1- X. 1 66 Racemic mixture S l-oxo-thietany1- x167 Racemic mixture S 3 -methy1-thietanyl- X. 169 Racemic mixture S 0xetan—3y1 X. 170 Racemic mixture S tetrahydropyranyl X. 1 71 c mixture S hydrogen 1_X' 172 Racemic mixture S methyl W0 2012/163960 Compound Stereochemistry at Stereochemistry at 1 RI s * ** X. 173 Racernic mixture S propyl X.174 s 2,2-difluor0-ethy1— X. 175 Racemic mixture S 2-fluoro-ethy1— X. 176 S S ethyl- X. 1 77 S S buty1— X. 178 S S buty1— S S 3 -bromo—propy1— X. 1 80 S S 2,2,2-triflu0ro-ethy1- X. 1 81 S S 3,3,3-triflu0r0-propyl— X. 1 82 S S 2-methoxy—ethyl- X. 1 83 S S 1 -methoxy—prop—2-yl— X. 1 84 S S cyclobutyl— X. 1 85 S S 2-methyl-cyclohex-1 —y1— X. 1 86 S ~——_+S_-‘——_——— phenyl—methyl- X. 1 87 S S 1 —pheny1—ethy1— X. 188 S S yl-eth—1 -y1- X. 1 89 S S (3—chloro-pheny1)-methyl— X. 1 90 S S (2—flu0ro—phenyl)-methy1— X. 1 9 1 S S (4-methoxy-phenyl)-methyl- S S (2-trifluoromethyl-phenyl)- methyl- X. 193 S S (2~trifluoromethoxy—phenyl)— methyl— 3 s (pyfid—Z—yl)—methy1— X. 195 S S (pyrid-S—yl)-methyl— X.196 s s L(Z—chloro-pyrid-5—yl)-methyl— X. 1 97 S S (1 -methy1—1H—imidazol—4—y1)— methyl- X. 1 9 8 S S (furan—Z—yl)—methy1— X. 199 S S 2—(thiophen-2'—y1)-eth-1—yl- X.200 S S 2—(ind01-3 ethy1- X.201 S S (1H—benzimidazol—Z-yI)—methyl- J X.202 S S (oxetan-Z—y1)-methyl- X.203 S S (tetrahydrofuran-Z-yD-methyl— X.204 S S 2—([1’,3']dioxolan—2'—yl)-ethyl- S S pholin-4'—yl)-eth—1 -yl- X.206 S S 2—(benzo[1',3‘]di0xol-5'—yl)-eth—1 — 2,2,3-dihydro—benzo[1 ,4] 1- X207 S S yl)-methyl- S S 2-chloro-pheny1— X.209 S S 3—fluor0—phenyl— X2 1 0 S S 2—methyl—phenyl- X.21 1 S S 2—chloro-6~methyl—phenyl— Compound Stereochemistry at Stereochemistry at R numbers * ** X212 S S 2-trifluoromethy1-phenyl- X21 3 S S 2,4-dimethoxy-phenyl- X214 3-methyI-pyridyl- X215 S S 1,3-dimethyl- 1 H—pyrazoI—S-yl- X216 5 ethy1—thiazolyl- X21 8 S S quinolin-Z—yl— X219 S s W X220 S S benzothiazol-6—yl- X221 S S 4—methyl~benzothiazol—2-yl— X222 S S thietan—3-yl— X223 S S 1—0x0-thietan—3—yl— X224 S S 1,1—diox0—thietan—3—yl— X225 S S 3-methy1—thietan—3—yl— X226 S S oxetan—3y1 X227 S S tetrahydropyran—4-yl X228 S S hydrogen X229 S S methyl X230 S S propyl X23 1 S S 2,2—difluoro-ethyl- X232 S S 2—fluoro-ethyl- r-X233 Racemic mixture S isopropyl X234 Racemic mixture S cyclopropyl X235 S S isopropyl X236 S S cyclopropyl X237 Racemic e R ethyl~ X23 8 c mixture R butyl— X239 Racemic mixture R buty1- X240 Racemic mixture R 3-brom0-pr0pyl— X241 Racemic mixture R 2,2,2—triflu0ro-ethyl— X242 Racemic mixture ’1—R 3,3,3—triflu0ro-propyl— X243 Racemic mixture R oxy—ethyl- X244 Racemic mixture R 1—methoxy-prop-2—yl— X245 Racemic mixture R cyclobutyl- X246 c mixture R 2—methy1-cyclohex—1-yl— X247 Racemic mixture R phenyl-methyl- X248 Racemic mixture R 1-phenyl-eth-1 -y1— X249 Racemic mixture R yl-eth-1 -yl- X250 Racemic e R (3 —chloro-phenyl)—methyl- X251 Racemic mixture RW X252 Racemic mixture R (4-methoxy-phenyl)—methyl— Compound Stereochemistry at Stereochemistry at R1 numbers * ** X253 c mixturem meth 1- X.254 Racemic mixture R (2-t1ifluoromethoxy-pheny1)- methyl- X.255 Racemic mixture R (pyrid—Z-yl)—methyl- Racemic e R —3—y1)—methy1— X257 Racemic mixture R (2-ch10ro-pyrid—5-y1)—methyl— X258 Racemic mixture R (1 -methy1—1H—imidazol-4—y1)— meth 1- X259 c mixture R (furai—2-yl)-methy1— X260 Racemic e R 2-(thiophen—2'—y1)—eth— 1 —yl— X261 Racemic mixture R 2—(indol-3’-yl)—eth— 1 —y1- X262 Racemic mixture R (1H~benzimidazol-Z—yl)-methy1- X263 Racemic mixture R (oxetan-Z-y1)-methy1- X264 Racemic mixture R W X265 Racemic mixture R ,3']dioxolan—2'-yl)-eth—1 -y1— X266 Racemic mixture R 2—(morpholin—4’—yl)-eth— 1 -y1— X267 Racemic mixture R 2—(benzo[1 ',3']dioxol-5'—y1)-eth—1 - X268 Racemic e R W yl)-methy1- Racemic mixture R 2-chloro-pheny1- X270 Racemic mixture R 3-fluoro-phenyl- X271 Racemic mixture R 2-methyl-phenyl— X272 Racemic mixture R 2-chloro~6-methy1-phenyl- X273 Racemic mixture R 2—trifluoromethy1—phenyl— X274 Racemic mixture R 2,4-dimethoxy-phenyl— X275 Racemic mixture R 3-methy1-pyridyl— X.276 Racemic mixture R 1 3 —dimethy1- 1 H—pyrazol-S-yl— X277 Racemic mixture R 4-methy1-thiazol-2—y1- X278 Racemic mixture R 5—methyl—thiadiazol—2—y1- X279 Racemic mixture R quinolin—Z-yl— X280 c e R quinolin—S—yl— X281 Racemic mixture R benzothiazol-6—y1— X282 Racemic mixture R 4—methyI—benzothiazolyl— X283 Racemic mixture R thietan-3—y1— X284 Racemic mixture R 1-oxo-thietanyl— X285 Racemic mixture R 1,1-dioxo-thietan—3—yl— X286 Racemic mixture R 3-methy1-thietanyl- X287 Racemic mixture R oxetan-3yl X288 Racemic mixture R ydropyran—4-yl X289 Racemic mixture R hydrogen X290 Racemic mixture methyl X291 Racemic mixture WP“ propyl W0 2012/163960 Compound Stereochemistry at Stereochemistry at RF numbers * ** X292 Racemjc mixture R 2,2-difluor0-ethy1- X293 Racemic mixture R 2-fluoro-ethyl- X294 S R ethyl- X.295 S R butyl- X296 S R buty1— X297 S R 3 -brom0-pr0py1— X298 S m X299 S R 3 ,3,3 ~triflu0ro-pr0py1— X300 S R oxy-ethy1- X. 3 01 S R 1—meth0xy-prop-2—yl— X.302 S R cyclobutyl- X303 S R 2~methy1-cyclohex-1 —yl— X304 S R pheny1~methy1- X305 S —I—R 1—pheny1—eth—1 —yl- X306 S R yl-eth—1-yl- X307 S R (3-ch10r0-phenyl)—methy1- X. 3 08 R (2—flu0ro—pheny1)-methyl- X309 S R (4-methoxy—phenyl)-mcthyl- X. 3 1 0 S R (2-tfifluoromethy1-phenyl)- methyl- X31 1 S R (2-trifluoromethoxy—pheny1)- methyl- __I X. 3 12 S R (pyrid-Z—yl)-methyl— X. 3 1 3 S R (pyrid-3 -y1)-methy1— X3 14 S R (2—chloro-pyrid—5—yl)—methyl— X. 3 1 5 S R (1 ~methy1—1H—imidazol—4—yl)— methyl- __J X. 3 1 6 S R (fumn—Z—yl)—methy1— X3 17 S R 2-(thi0phen—2'-y1)—eth—1 -y1— X3 1 8 S R 2-(ind01—3'—yl)~eth—1 -y1— X3 1 9 S R (1H-benzimidazol—2-yl)-methy1- X320 S R ny1)-methy1— X321 S R (tetrahydrofilran—Z—yl)—methy1- X.322 S R 2-([1',3']dioxolan—2'—y1)—eth—1—y1— X323 S R 2-(m0rpholin-4'-y1)-eth~1 -y1- X324 S R W X325 S R {23-dihydIo-benzo[1,4]dioxin—6— y1)-methyl- X.327 S R 3—fluoro-phenyl— X328 S R 2-methy1—pheny1- X329 S _*R— ro~6-methyl—pheny1- X330 S R 2—trifluoromethyl-phenyl— Compound Stereochemistry at Stereochemistry at RI numbers * ** X33 1 S R 2,4-dimethoxy—phenyl- X332 3 R l 3-methyl-pyridyl- X. 3 3 3 S R 1,3-dimethyl-1 zol-S-yl- X334 S R 4-methyl-thiazoly1- X335 S R 5—methyl—thiadiazol—2-yl— X336 S R quinolin-Z-yl— X337 S R quinolin-S-yl— X338 S R benzothiazol—6—yl- X339 S R 4-methyl-benzothiazol—Z—yl- X340 S R thietan-3 -yl— X341 8 R —_‘ l-oxo-thietan—3-yl— X.342 S R l, l —dioxo-thietan—3—yl— X343 S R 3—methyl-thietanyl— X344 S R oxetan—3yl X345 S R tetrahydropyran—4—yl X346 S R hydrogen X347 S R methyl X348 S R propyl X349 S R 2,2-difluoro-ethyl- X350 S R 2-fluor0-ethyl- X351 Racemic mixture R isopropyl X352 Racemic mixture R cyclopropyl J X353 S R isopropyl X354 S R cyclopropyl The present invention includes all isomers of compounds of a (I), salts and N—oxides thereof, including enantiomers, diastereomers and tautomers. Component A may be a mixture of any type of isomer of a compound of formula I, or may be substantially a single type of isomer.

In one embodiment of the invention component B is a nd selected from pymetrozine and flonicamid; an organophosphate selected from the group consisting of sulprofos, te, methyl parathion, azinphos—methyl, demeton—s—methyl, heptenophos, thiometon, fenamiphos, monocrotophos, ofos, triazophos, methamidophos, dimethoate, phosphamidon, ion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthjazate and diazinon; a roid selected from the group consisting of permethrin, ethrin, erate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma—cyhalothrin, bifenthrin, fenpropathrin, hrin, tefluthrin, ethofenprox, natural pyrethrin, tetramethrin, S—bioallethrin, fenfluthrin, thrin and 5-benzyl—3—furylmethyl—(§)-(l R,3S)—2,2-dimethyl— 3-(2-oxothiolan—3—ylidenemethyl)cyclopropane carboxylate; a ide selected from the group consisting of abamectin, emamectin benzoate, ctin, milbemycin, spinosad, azadirachtin and spinetoram; a diamide selected from the group consisting of flubendiamide, chlorantraniliprole (Rynaxypyr®) and cyantraniliprole; a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nithiazine and mid; spirotetramat, spirodiclofen and spiromesifen; and sulfoxaflor, lufeneron, diafenthiuron, and fipronil.

In one ment ent B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, chlorantraniliprole, flonicamid, sulfoxaflor, lufeneron, diafenthiuron, flubendiamide, tefluthrin, diafenthiuron and fipronil.

In one embodiment ent B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid, diafenthiuron and flonicamid.

In one embodiment component B is a compound ed from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda cyhalothrin, diafenthiuron, pymetrozine, spirotetramat, thiamethoxam, clothianidin, imidacloprid and chlorantraniliprole.

In one embodiment component B is a compound selected from the group consisting of abamectin, chlorpyrifos, cyantraniliprole, emamectin, lambda thrin, diafenthiuron, pymetrozine, spirotetramat, and thiamethoxam.

In one embodiment component B is a compound selected from the group consisting of a pyrethroid ing those selected from the group consisting of permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin, lambda-cyhalothrin, gamma—cyhalothrin, hrin, fenpropathrin, cyfluthrin (including beta cyfluthrin), tefluthrin, ethofenprox, natural pyrethrin, ethrin, S—bioallethrin, fenfluthrin, prallethrin and -benzylfi1rylmethyl—(EH1 R,3 S)—2,2—dimethyl— 3 —(2—oxothiolan~3~ylidenemethyl)cyclopropane ylate; a neonicotinoid compound including those selected from the group consisting of loprid, thiacloprid, acetamiplid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nithiazine and flonicamid; and diafenthiuron.

In one embodiment component B is a nd selected from the group consisting of thiamethoxam, lambda cyhalothrin and diafenthiuron, preferably thiamethoxam and lambda cychalothrin.

In one embodiment, and of particular interest for seed care, component B is a nd selected from teflluthrin, abamectin, spinosad, spinetoram, yrifos, thiodicarb, chlorantraniliprole, cyantraniliprole, usfirmus, Bacillus is, Pasteuria spp. (e.g. P. penetrans, P. nishizawae), imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thoxam, clothianidin, nithiazine, flonicamid, l, quinazone, pymetrozine, sulfoxaflor and spirotetramat.

The ion also includes the following combinations: A mixture of a nd of formulal selected from Tables A, B, C, D, E and F + tin.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + chlorpyrifos.

A mixture of a nd of formula I selected from Tables A, B, C, D, E and F + cyantraniliprole.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + emamectin.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + cyhalothrin.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + lambda cyhalothrin.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + gamma cyhalothrin.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + pymetrozine.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + spirotetramat.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiamethoxam.

A mixture of a compound of a I selected from Tables A, B, C, D, E and F + chlorantraniliprole.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + profenofos.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + acephate.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + azinphos—methyl.

A mixture of a compound of formulaI selected from Tables A, B, C, D, E and F + methamidophos.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + spinosad.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + spinetoram.

A e of a compound of formulaI ed from Tables A, B, C, D, E and F + flonicamid.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + indoxacarb.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + iclofen.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + spiromesifen.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + sulfoxaflor.

A mixture of a compound of al selected from Tables A, B, C, D, E and F + fipronil.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + imidacloprid.

A mixture of a nd of formula I selected from Tables A, B, C, D, E and F + thiacloprid.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + acetamjprid.

A mixture of a compound of formula 1 selected from Tables A, B, C, D, E and F + nitenpyram.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + dinotefuran.

A mixture of a compound of a I selected from Tables A, B, C, D, E and F + clothianidin.

A mixture of a compound of al ed from Tables A, B, C, D, E and F + nithiazine.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + pyriproxyfen.

A mixture of a compound of formulaI selected from Tables A, B, C, D, E and F + buprofezin.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + pyrifluqinazon.

W0 20121163960 A e of a compound of formulaI selected from Tables A, B, C, D, E and F + thiamethoxam and cyantraniliprole.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + thiamethoxam and chlorantraniliprole.

A mixture of a compound of formulal selected from Tables A, B, C, D, E and F + sulfoxaflor.

A mixture of a compound of formulaI ed from Tables A, B, C, D, E and F + lufeneron.

A e of a compound of formula I selected from Tables A, B, C, D, E and F + diafenthiuron.

A mixture of a compound of forrnulal selected from Tables A, B, C, D, E and F + flubendiamide.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + tefluthrin.

A mixture of a nd of formula I selected from Tables A, B, C, D, E and F + fipronil.

A mixture of a nd of formula I selected from Tables A, B, C, D, E and F + thiodicarb.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + Bacillusfirmus.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + Bacillus subtilis.

A mixture of a compound of formula I selected from Tables A, B, C, D, E and F + P. penetrans.

A mixture of a nd of formula I selected from Tables A, B, C, D, E and F + P. nishizawae.

In one embodiment the ratio of the compound of a I to abamectin by weight in the composition may be 120.05 to 1:1. Examples of ratios falling within this range include 120.1, 120.2, 120.3, 1:0.4, 120.5, 120.6, 120.7, 120.8, 120.9. Where used for soil application the ratio of nd of formulaI to abamectin may be up to 1:13.

In one embodiment the ratio of the compound of formula I to chlorpyrifos by weight in the composition may be 1:1 to 1:10. Examples of ratios falling within this range e 1:2, 1:3, 1:4, 1:5, 1:6,1:7,1:8,1:9.

In one embodiment the ratio of the compound of formula I to cyantraniliprole by weight in the composition may be 120.2 to 1:4. Examples of ratios falling within this range include 120.5, 121, 121.5, 1:2, 122.5, 1:3, 123.5.

In one embodiment the ratio of the nd of formula I to emamectin by weight in the composition may be 1:0.05 to 1:1. Examples of ratios falling within this range include 120.1, 120.2, 120.3, 120.4, 120.5, 120.6, 120.7, 120.8, 120.9.

In one embodiment the ratio of the compound of formula I to lambda cyhalothrin by weight in the composition may be 1:01 to 1:2. es of rates falling within this range e 120.2, 120.4, 120.6, 120.8, 1:], 1:1.2, 1:1.4, 121.6, 121.8. In another embodiment the ratio ofthe compound of a I to lambda cyhalothrin is at least 121000, at least 12500, at least 12100. For example that ratio of the compound offormula I to lamda cyhalothrin is e.g. 12250 to 25021, e.g. 12250 to 1021 to e.g.] :250 to 1:1.

In one embodiment the ratio of the compound of formula I to pymetrozine by weight in the composition may be 1:1 to 1:6. Examples of rates falling within this range include 122, 1:3, 1:4, 1:5.

Where used for soil application the ratio of compound of a I to pymetrozine may be up to 1210, additional examples include 127, 128, 1:9.

In one embodiment the ratio of the compound of formula I to spirotetramat by weight in the composition may be 120.5 to 1:4. Examples of ratios falling within this range include 1:], 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5.

In one embodiment the ratio of the compound of formula I to thiamethoxam by weight in the composition may be 1: 0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4 and 1:5. In another embodiment the ratio of the compound of formula I to thiamethoxam by weight in the composition may be at least 124000, at least 1:1000, at least 1:100. For e the ratio of the compound of formula I to thoxam is e.g. 1:250 to 250:1, e.g. 1:250 to 10:1 to e.g.1:250 to 1:].

In one embodiment the ratio of the compound of formula I to clothianidin by weight in the composition may be 1: 0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4 and 1:5.

In one embodiment the ratio of the compound of formula I to imidacloprid by weight in the ition may be 1: 0.5 to 1:6. Examples of ratios falling within this range e 1:1, 1:2, 1:3, 1:4 and 1:5.

In one embodiment the the ratio of the compound of formula I to ntraniliprole by weight in the composition may be 1:02 to 1:4. es of ratios g within this range include 120.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3,1:3.5.

In one embodiment the ratio of the compound of formula I to sulfoxaflor by weight in the composition may be 1: 0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4 and 1:5.

In one embodiment the ratio of the compound of formula I to diafenthiuron by weight in the composition may be 1: 1.5 to 1:80, e.g. 1: 0.5 to 1:6. Examples of ratios falling within this range include 1:1, 1:2, 1:3, 1:4 and 1:5. . In another embodiment the ratio of the nd of formula I to diafenthiuron by weight in the composition may be at least 1:500, at least 1:250, at least 1:100. For example that ratio of the compound of formula I to diafenthiuron is e.g. 1:250 to 250:1, e.g. 1:250 to 10:1 to e.g.1:250 to 1:1.

The compounds of the invention may be made by a variety ofmethods as shown in Schemes 1 to Scheme 1 1) Compounds of formula (I), can be ed by reacting a compound of formula (11) wherein R is OH, C1-C6alkoxy or C1, F or Br, with an amine of a (III) as shown in Scheme 1. When R is OH such reactions are usually carried out in the presence of a coupling reagent, such as N,N'—dicyclohexyl- carbodiimide (“DCC”), 1-ethyl(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) or bis(2-oxo-3—oxazolidinyl)phosphonic de (“BOP—C1”), in the presence of a base, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzotriazole (“HOBT”). When R is C1, such reactions are y carried out in the presence of a base, and optionally in the presence of a nucleophilic catalyst. Alternatively, it is le to conduct the on in a biphasic system comprising an organic solvent, preferably ethyl acetate, and an s solvent, preferably a solution of sodium hydrogen carbonate. When R is C1—C6alkoxy it is sometimes possible to convert the ester directly to the amide by heating the ester and amine together in a thermal process. Suitable bases include pyridine, triethylamine, 4—(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base). Preferred solvents are MN—dimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, ethyl acetate and toluene. The reaction is carried out at a temperature of from 0°C to 100°C, preferably from 15°C to 30°C, in particular at t temperature. Amines of a (III) are either known in the literature or can be prepared using methods known to a person skilled in the art. 2) Acid halides of a (II), wherein R is Cl, F or Br, may be made from carboxylic acids of formula (II), wherein R is OH, under standard ions, as bed for example in W02009/080250. 3) Carboxylic acids of formula (II), wherein R is OH, may be formed from esters of formula (II), n R is C1-C5alkoxy as described for example in W02009/O80250. 4) Compounds of formula (I) can be prepared by reacting a compound of formula (IV) wherein XB is a leaving group, for example a halogen, such as bromo, with carbon monoxide and an amine of formula (III), in the presence of a catalyst, such as palladium(ll) acetate or bis— (triphenylphosphine)palladium(II) dichloride, optionally in the presence of a ligand, such as triphenylphosphine, and a base, such as sodium carbonate, pyridine, triethylamine, 4—(dimethylamino)— pyridine (“DMAP”) or diisopropylethylamine (Hunig’s base), in a t, such as water, N,N— dimethylformamide or tetrahydrofuran. The reaction is carried out at a ature of from 50°C to 200°C, preferably from 100°C to 150°C. The reaction is carried out at a pressure of from 50 to 200 bar, preferably from 100 to 150 bar.

) Compounds of formula (IV) wherein XB is a leaving group, for example a halogen, such as bromo, can be made by a various of methods, for example as described in W02009/080250.

Scheme 2 \ 1 \ 1 6) Alternatively, compounds of formula (I), can be prepared by various methods from an intermediate of formula (V) as shown in Scheme 2 wherein XB is a leaving group, for e a halogen, such as bromo, or XB is cyano, formyl or acetyl according to similar methods to those described in WOO9080250. An intermediate of formula (V) can be ed for example from an ediate of formula (VI) as described in the same reference.

Scheme 3 7) Alternatively, compounds of formula (I) can be prepared by various methods from an intermediate of formula (VII) as shown in Scheme 3 n XC is XC—l or XC-Z R2 R2 H # H / H H 3 3 (R >, (R ), XC—1 XC—2 according to similar methods to those described in W02009/080250. 8) Compounds of formula (VII) wherein XC is XC is XC-l or XC-Z can be prepared from a compound of formula (Va) from a compound of formula (VII) wherein XC is CHg-halogen using similar methods to those described in W02009/O80250. 9) Compounds of formula (VII) wherein XC is CHz—halogen, such as bromo or chloro, can be prepared by reacting a methyl ketone of formula (Va) with a halogenating agent, such as bromine or ne, in a solvent, such as acetic acid, at a temperature of from 0°C to 50°C, preferably from ambient temperature to 40°C.

Other methods for the preparation of compounds of formula I are bed in 2010/068605, which is incorporated herein by reference.

The present ion also relates to a method of controlling insects, es, nematodes or molluscs which comprises ng to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination of components A and B; seeds comprising a mixture of components A and B; and a method comprising coating a seed with a mixture of components A and B.

Components A and B may be provided and/or used in amounts such that they are capable of synergistic pest control. For example, For example, the present invention includes pesticidal mixtures comprising a component A and a component B in a synergistically effective amount; agricultural compositions comprising a mixture of component A and B in a synergistically effective amount; the use of a e of component A and B in a synergistically effective amount for combating animal pests; a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or nment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a mixture of component A and B in a synergistically effective ; a method for protecting crops from attack or ation by animal pests which comprises contacting a crop with a mixture of component A and B in a synergistically effective amount; a method for the protection of seeds from soil insects and of the seedlings’ roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pie—germination with a mixture of component A and B in a synergistically effective amount; seeds comprising, e.g. coated with, a mixture ofcomponent A and B in a synergistically effective amount; a method comprising coating a seed with a mixture of component A and B in a synergistically effective amount; a method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination ofcomponents A and B in a synergistically effective amount. es ofA and B will normally be applied in an insecticidally, acan'cidally, nematicidally or molluscicidally effective .

In application components A and B may be applied aneously or separately.

According to the invention “useful plants” typically comprise the following species of plants: grape Vines; s, such as wheat, barley, rye or cats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, rries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil , cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or ; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, ruit or mandarins; vegetables, such as h, e, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; Vines; hops; durian; bananas; natural rubber plants; turf or omamentals, such as flowers, shrubs, leaved trees or evergreens, for example conifers. This list does not represent any limitation. It may be noted that nd of formula I may also be used for controlling insect, acaricide, mollusc and/or de pests on turf in the e of mixing partners.

The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example ulfuron, prosulfuron and trifloxysulfuron, EPSPS (S—enol— pyrovyl—shikimate—3—phosphate-synthase) tors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods ofbreeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of ides by genetic ering methods include glyphosate— and glufosinate-resistant maize varieties cially available under the trade names RoundupReady® Herculex I® and LibertyLink®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin—producing bacteria, especially those of the genus Bacillus.

Compounds of formula I and es of the ion may be used on transgenic plants (including cultivars) obtained by genetic engineering methods and/or by conventional s. These are understood as meaning plants having novel ties ("traits") which have been obtained by conventional breeding, by nesis or by recombinant DNA techniques. Depending on the plant s or plant cultivars, their location and growth conditions (soils, climate, vegetation , diet), the treatment according to the invention may also result in superadditive "synergistic") effects.

Thus, for e, d application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the ted products, better storage stability and/or sability of the harvested products are possible, which exceed the effects which were actually to be expected. Such synergistic effects with the transgenic crop can be ed when applied for control of soil pests (e.g. seed care or in—furrow treatments) as well as after nce, in particular for corn and soybean.

Use of the compounds of formula I and the es of the invention can also be applied as a seed care treatment with transgenic crops in resistance management strategies for the trait (particularly inseciticidal traits), e.g. including in corn and soybean.

The preferred transgenic plants or plant cultivars which are to be treated according to the invention include all plants which, by Virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. es of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products.

WO 63960 Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against s, mites, phytopathogenic fungi, bacteria and/or viruses, and also sed tolerance of the plants to certain herbicidally active nds.

Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soybean, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes).

Compounds offormula I and mixtures ofthe invention may be used on transgenic plants that are capable of producing one or more idal proteins which confer upon the transgenic plant tolerance or resistance to harmful pests, e.g. insect pests, nematode pests and the like. Such pesticidal proteins include, t limitation, Cry proteins from Bacillus thuringiensis CrylAb, CrylAc, CrylF, Cry2Ab, Cry2Ae, Cry3A, Cry3Bb, or Cry9C; engineered ns such as modified Cry3A ( US Patent 7,030,295) or CrylA.105; or vegetative insecticidal proteins such as Vipl, Vip2 or Vip3. A full list of Bt Cry proteins and VIPs usefi11 in the invention can be found on the worldwide web at Bacillus thuringiensis Toxin Nomenclature Database maintained by the University of Sussex (see also, Crickmore et al. (1998) Microbiol. Mol. Biol. Rev. 62:807—813). Other pesticidal proteins useful in the invention include proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion , arachnid toxins, wasp toxins, or other insect—specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome—inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3—hydroxysteroid oxidase, eroid—IDP—glycosyl— transferase, terol oxidases, ecdysone inhibitors or HMG-CoA—reductase; ion channel blockers, such as blockers of sodium or calcium channels; le e esterase; diuretic hormone ors (helicokinin ors); stilben synthase, bibenzyl synthase, chitinases or ases. Further examples of such pesticidal proteins or transgenic plants capable of sizing such proteins are disclosed, e.g., in EP—A 374753, WO 93/007278, WO 95/34656, EP—A 427529, EP-A 451878, W0 03/18810 and W0 03/52073. The methods for producing such transgenic plants are generally known to the person skilled in the art and some ofwhich are commercially available such as Agrisure®CB (P1) (corn ing CrylAb), Agrisure®RW (P2) (corn producing mCry3A), Agrisure® Viptera (P3) (corn s producing ); Agrisure300GT (P4) (corn s producing CrylAb and mCry3A); YieldGard® (P5) (corn hybrids producing the CrylAb protein), YieldGard® Plus (P6) (corn hybrids producing CrylAb and Cry3Bb1), Genuity® SmartStax® (P7) (corn s with CrylA.105, Cry2Ab2, CrylF, Cry34/35, Cry3Bb) ; Herculex® I (P8) (corn hybrids producing CryiFa) and ex®RW (P9) (corn hybrids producing Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin-N—Acetyltransferase [PAT]) ; NuCOTN®33B (P10) (cotton cultivars producing CrylAc), Bollgard®I (P11) (cotton cultivars ing CrylAc), Bollgard®ll (P12) (cotton cultivars producing CrylAc and Cry2Ab2) and VIPCOT® (P13) W0 20121163960 2012/060126 (cotton cultivars producing a Vip3Aa). Soybean Cyst Nematode resistance soybean (SCN® - ta (P14)) and soybean with Aphid ant trait (AMT® (P15)) are also of interest.

Further examples of such transgenic crops are: 1. Btll Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-3l 790 St. Sauveur, France, registration number C/FR/96/05/10 (P16). Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a ted b) toxin. Btll maize also transgenically expresses the enzyme PAT to achieve tolerance to the ide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10 (P17). Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrim'a nubilalis and Sesamia nonagrioides) by enic expression of a CryIA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F—31 790 St. Sauveur, France, registration number C/FR/96/05/ 1 0 (P18). Maize which has been rendered insect-resistant by transgenic sion of a modified CryIIlA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin—D- protease recognition sequence. The preparation of such transgenic maize plants is described in WC 03/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B—1150 Brussels, Belgium, registration number C/DE/02/9 (P19). MON 863 expresses a CryIIIB(b1) toxin and has ance to certain Coleoptera insects.

. IPC 531 Cotton from Monsanto Europe S.A. 270—272 Avenue de Tervuren, B—1150 ls, Belgium, registration number C/ES/96/02. (P20) 6. 1507 Maize from Pioneer as Corporation, Avenue Tedesco, 7 B—1160 Brussels, Belgium, registration number C/NL/OO/l 0. (P21) cally modified maize for the expression of the protein Cry1F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium. 7. NK603 X MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03 (P22). Consists of conventionally bred hybrid maize varieties by crossing the cally modified varieties NK603 and MON 810. NK603 >< MON 810 Maize enically expresses the n CP4 EPSPS, ed from Agrobacterium Sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CryIA(b) toxin obtained from Bacillus thuringiensis subsp. kursraki which brings about tolerance to certain Lepidoptera, e the European corn borer.

Further examples of transgenic plants, and of very high interest, are those carrying traits conferring resistance to 2.4D (e.g. Enlist®) (e. g. WO 2011066384) (P23), glyphosate (e.g. Roundup Ready®, Roundup Ready 2 Yield® (P25)), ylurea (e.g. STS®), glufosinate (e.g. Liberty Link®, Ignite®, W0 63960 Dicamba (Monsanto), HPPD tolerance (e.g. isoxaflutole herbicide, mesotrione herbicide — US7312379) (Bayer CropScience, ta). Double or triple stacks of any of the traits described here are also of interest, ing glyphosate and sulfonyl—urea tolerance ((e.g. Optimum GAT®), plants stacked with STS® and Roundup Ready® or plants stacked with STS® and p Ready 2 , dicamba and glyphosate tolerance (Monsanto). Of particular interest are n plants carrying trains conferring resistance to 2.4D (e.g. Enlist®), glyphosate (e. g. Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. y Linl<®, Ignite®), a (Monsanto) HPPD tolerance (e.g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stack in soybean plants of any of the traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance (e.g. Optimum GAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2 Yield®), dicamba and glyphosate tolerance (Monsanto).

Transgenic crops of insect-resistant plants are also described in BATS um fiir Biosicherheit und Nachhaltigkeit, m BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (hflpJ/batsch).

The term “locus” of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term “plant propagation material” is understood to denote generative parts of a plant, such as seeds, which can be used for the lication of the latter, and vegetative material, such as cuttings or tubers, for example es. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. ably “plant propagation material” is understood to denote seeds. Insecticides that are of particular interest for treating seeds include thiamethoxam, imidacloprid and clothianidin. Accordingly, in one ment component B is ed from thiamethoxam, imidacloprid and clothianidin.

Methods for applying or treating active ingredients on to plant ation material, especially seeds, are known in the art, and include dressing, coating, pelleting and soaking application methods of the propagation material. Conventional treating techniques and es can be used, such as fluidized beds, roller mills, rotostatic seed treaters, drum coaters, and spouted beds.

Methods of applying to the soil can be Via any suitable method, which ensures that the combination penetrates the soil, for example, nursery tray ation, in furrow application, soil drenching, soil injection, drip irrigation, application through sprinklers or central pivot, incorporation into soil (broad cast or in band) are such methods. Alternatively or in addition one or more materials may be applied on a suitable substrate, for example a seed which is not intended for germination, and “sowing” the treated substrate with the plant propagation material.

Even distribution of ingredients and good nce is particularly desired for seed treatment.

Treatment could vary from a thin film or dressing of the formulation, for e, a mixture of active ingredients, on a plant propagation material, such as a seed, where the al size and/or shape are recognizable to an intermediary state to a thicker film such as pelleting with many layers of different materials (such as carriers, for example, clays; different formulations, such as of other active ingredients; polymers; and colourants) where the original shape and/or size of the seed is no longer recognisable.

Application onto plant propagation al can include controlled release coatings, wherein the ingredients of the combinations are incorporated into materials that release the ingredients over time. es of controlled release logies are generally known in the art and include polymer films and waxes, wherein the ingredients may be incorporated into the controlled release material or applied between layers of materials, or both.

A further aspect ofthe instant invention is a method ofprotecting natural substances ofplant and/or animal origin, which have been taken from the l life cycle, and/or their sed forms t attack of pests, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a ation of components A and B in a synergistically effective amount.

Such applications include use of the mixtures of the invention as a treatment, for example a fumigant, for stored grain to protect against attack of invertabrate pests and or fungi. It may be noted that compounds of formula I may be used alone as a treatment for stored grain to protect against attack of invertabrate pests.

According to the instant invention, the term “natural substances of plant origin, which have been taken from the natural life cycle” denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form. Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term ssed form of a natural substance of plant origin” is understood to denote a form of a natural substance ofplant origin that is the result of a modification process. Such modification processes can be used to transform the natural substance ofplant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre—drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also falling under the definition of a processed form of a natural substance ofplant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and rs, or in the form of finished articles, such as ure or objects made from wood.

According to the instant invention, the term “natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms” is tood to denote material of animal origin such as skin, hides, r, furs, hairs and the like.

A preferred ment is a method of protecting natural substances of plant , which have been taken from the natural life cycle, and/or their processed forms against attack of pests, which comprises applying to said natural nces of plant and/or animal origin or their processed forms a combination of components A and B in a synergistically effective amount.

W0 2012/163960 A fiirther preferred embodiment is a method of protecting fruits, preferably pomes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a combination of components A and B in a synergistically effective amount.

The compounds of formula (I) and mixtures of the invention can be used to combat and control infestations of insect pests such as Lepidoptera, Dipz‘era, Hemiptera, Thysanoprera, Orthoptera, Diclyoptera, tera, Sz'p/ionaptera, Hymenoptera and Isoptera and also other invertebrate pests, for e, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively ed to as pests. The pests which may be ed and controlled by the use ofthe compounsd ofthe invention include those pests ated with agriculture (which term includes the growing of crops for food and fiber products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man—made structures and the transmission of diseases ofman and animals; and also nuisance pests (such as flies). The compounds ofthe ion may be used for e on turf, omamentals, such as , shrubs, broad-leaved trees or evergreens, for e conifers, as well as for tree injection, pest management and the like. Compositions comprising the compound of formula I may be used on ornamental garden plants (e.g. , shrubs, broad-leaved trees or evergreens), e.g. to control , whitefly, scales, meelybug, beetles and caterpillars. Compositions sing the compound of formula I may be used on garden plants (e.g. flowers, shrubs, broad-leaved trees or evergreens), on indoor plants (e. g. flowers and shrubs) and on indoor pest e. g. to control aphids, whitefly, scales, meelybug, beetles and caterpillars.

Furthermore, the compounds of formula (I) and mixtures ofthe invention may be effective against harmful insects, without substantially imposing any harmful side effects to cultivated plants.

Application ofthe compounds of the invention may increase the harvest , and may e the quality ofthe harvested material. The compounds of the invention may have favourable properties with respect to amount appled, residue formulation, selectivity, ty, production methodology, high activity, wide spectrum of control, safety, control of resistant sms, e.g. pests that are resistant to organic phosphorus agents and/or carbamate agents.

Examples of pest species which may be controlled by compounds of formula (I) and mixtures of 3O the invention include: coleopterans, for example, Callosobmchus chinensis, Sitophilus zeamais, Tribolz‘um castaneum, Epilachna vigintioctomaculata, Agriotesfuscicollis, Anomala rufocuprea, Lepz‘inotarsa decemlz‘neata, Diabrotica 3191)., Monochamus tus, Lissorhoptrus oryzophilus, Lyctus bruneus, phorafemoralis; optemns, for example, Lymam‘rz’a dispar, Malacosoma neustria), Pieris rapae, Spodopzera , Mamestra brassz‘cae, Chilo supplr'essalz's), Pyrausta nubilalis, Ephestz‘a cautella, Adoxophyes orana, apsa pomonella, Agroz‘iflucosa, Galleria mellonez’z’a, Plutella pennis, Heliotlzis Virescens, Phyllocnistis citrella; hemipterans, for example, Nephotettix cincticeps, Nilaparvaza lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzuspersicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp., Trialeurodes vaporarz'orm, Psylla spp.; thysanopterans, for example, Thrips palmi, Franklinella occidental; orthoprerans, for example, Blatella ica, Periplaneta americana, Grylloralpa Africana, Locusta migratoria orz'odes; isopterans, for example, Reticulitermes speratus, Capratemzesformosanus; dipterans, for example, Musca domestica, Aedes aegypti, Hylemia a, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, Liriomyza trifolii; acari, for example, Tetranychus cianabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp.; nematodes, for e, Meloidogyne incognito, Bursaphelenchus lignicolus Mamiya et m, Apheienchoides besseyi, Heterodem glycines, Pratylenchus spp.. es of further pest species which may be controlled by nds of formula (I) and mixture ofthe invention include: from the order of the ra (Phthiraptera), for example, Damah’nia spp., Haematopinus spp., Linognaz‘hus spp., lus spp., dectes spp.; from the class of the Arachnida, for example, Acarus siro, Aceria sheldom', Aculops spp., Aculus spp., Amblyomma spp., Argos spp., Boophifus spp., Brevipalpus spp., ‘a praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetmnychus spp., Epitrimems pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, tranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., coptmta. oleivom, Polyphagotarsonemus lotus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio mourns, Stenotarsonemus spp., Tarsonemus spp., ychus spp., Vasates lycopersicz'; from the class of the Bivalva, for e, Dreissena spp.; from the order of the Chilopoda, for example, Geophz'lus spp., Scutigera spp.; from the order of the tera, for example, Acanthoscehdes obtecrus, Adoretus spp., tica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., 'a spp., Atomaria spp., Altagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., ytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus orator, Ib/Zamm‘pha elegans, [fizlotrupes bajulus, Hypem postica, Hypothenemus spp., Lachnostema consanguinea, Leptinotarsa decemlineaz‘a, Lissorhoptrus ozyzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthogmphus, Niptus ucus, Olya‘es rhinoceros, Oryzaephilus surinamensis, 3O Otiowhynchus sulcatus, Omzcetoniajucunda, Phaedon cochleariae, Phyllophaga spp., Popilliajaponica, Premnonjypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Triboh'um spp., Trogodemza spp., Tychius spp., Xylotrechus spp., Zabrus spp.; from the order of the CoZZembola, for e, Onychiurus armatus; from the order ofthe Demzapz‘era, for example, Forficula auricularz'a; from the order ofthe oda, for example, Blaniulus guttulaz‘us; from the order of the Diprem, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora eiythrocephala, Ceratz'tis capitata, Chin/somyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus W0 2012!]63960 oleae, Dennatobia hominis, Drosophila Spp., Fannia spp., Gastrophilus spp., Hylemyz‘a Spp., osca Spp., I-bgpoderma spp., Liriomyza Spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinellafiit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tanm'a Spp., Tipula sa, Wohlfahrtia spp.; from the class of the Gastropoda, for example, Arion Spp., Biomphalaria spp., Bulinus , Derocems spp., Galba $1919., Lymnaea Spp., Oncomelam'a Spp., Succinea Spp.; from the class ofthe helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma Spp., Ascaris lubricoides, Ascaris Spp., Bmgia malayi, Brugz'a timori, Bunostomum Spp., Chabertia Spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dichocaulusfilaria, Dz'p/zylloborhrium latum, Dracunculus medilzensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., chus spp., Heterakis Spp., Hymenolepis nana, Hyostrongulus Spp., Loa Loa, dims spp., Oesophagostomum spp., Opisthorchis spp., Oizclzocerca valvulus, Ostertagz'a Spp., Paragonimus spp., Schistosomen spp., Slrongyloidesfuellebami, Strong/[aides stercoralis, Stronyloides spp., Taem'a saginata, Taenia solium, Trichinella spiralis, Trichinella naliva, fi‘ichz'nella britovi, nella ', Triclzinella pseudopsiralis, Trichostrongulus Spp., Triclmris trichurz‘a, Wuclzereria bancrofti; ft may be furthermore possible to control protozoa, such as Eimeria; from the order of the Heteroptera, for example, Anasa tristis, Antestiopsis Spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cz'mex Spp., Creontiades dilutus, Dasynus piperz’s, Dic/telopsfurcatus, coris i, Dysdercus Spp., Euschz'stus spp., Eurygaster spp., Heliopeltis Spp., Horcias nobilez’lus, Leptocorisa 3121)., Leptoglossus phyllopus, Lygus Spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, cysta persea, Rhodnius Spp., Sahlbergella singularis, Scorinophora spp., nitis nashi, Tibraca spp., Triatoma Spp.; from the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia Spp., Agonoscena spp., Aleurodes , Aleurolobus barodensis, Aleurothrixus spp., Amrasca Spp., Anuraphis cardui, Aonidiella Spp., Aphanostigma piri, Aphis Spp., Arboridia apicalis, Aspidielz’a spp., Aspidiotus spp., Atanus spp., Aulacm'thum solani, Bemisia 519p, Brackycaudus helichlysii, Brackycolus spp., Brevicoryne brassicae, zpona marginam, ep/zalafulgida, vacuna Zam'gem, Cercopidae, Ceroplastes spp., Chaetosz'phonfi‘agaefolii, Chionaspi-S nsis, Chlorita onukii, C12romaphisjuglandicola, Chigvsomphalusficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., rina Spp., s spp., Doraz'is Spp., Drosicha Spp., Dysapkis spp., Dysmicoccus Spp., Empoasca spp., Eriosoma Spp., Erythrorzeura spp., Euscelis bilobatus, Geococcus cofleae, disca coagulata, Hyalopterus ai‘undinis, Icerya spp., Idiocems spp., Idioscopus Spp., Laodelphax striatellus, Leccmium spp., Lepidosaphes spp., Lz‘paphis i, Macrosiphum Spp., Mahanamlafimbriolata, Melanaphis sacchari, fiella Spp., Metopolopkium dirizodum, Monellia costalis, Monelliopsis pecam‘s, Myzus spp., Nasonovia ribisnigri, ettix Spp., Nilaparvata lugens, Oncomeropia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza Spp., oria spp., Pemphigus Spp., Peregrinus maidz's, Phenacoccus spp., Phloeomyzus passerinii, Pkorodon kumuli, Plzylloxem spp., pis aspidistrae, Planococcus Spp., Protopulvinaria pyrifonnis, Pseudaulacaspis pentagona, coccus spp., Psylla spp., alus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rlzopalosiphum spp., Saissez‘ia spp., Scaplzoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatellafurcifera, Sogatodes spp., Sticz‘ocephalafestina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariomm, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolz'i; from the order of the Hymenoptem, for e, Diprion spp., Hoplocampa spp., Lasius spp., Mono- m pkaraonis, Vespa spp.; from the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of the Isoptera, for example, litermes spp., Odontotermes spp.; from the order of the ptem, for example, Acronicta major, Aedia leucomelas, Agroz‘is spp., Alabama argillacea, Anticarsia spp., Barathra brassz'cae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua lum, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneurafumifemna, Clysia ambiguella, Cnap/zalocerus spp., Earias insulana, Ephestia kuehm‘ella, Euproctis chrysorrlwea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoveipa spp., Heléothis spp., Hofinannoplzila pseudospretella, Homona magnanima, meuta padella, Laphygma spp., Lithocoiletis blancardella, Lithophane antennata, Loxagrotis albicosta, ria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema Olyzae, Panolisflammea, Pectinophora gossypiella, Phyllocnisz‘is citrella, Pieris spp., Plutella xylosz‘ella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyr‘austa nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellz’onella, Tineola liella, Tortrix viridana, Tric/zoplusia spp.; from the order of the Orthoptera, for example, Acheta domesticus, Blatta alis, Blattella germanica, Grjylloz‘alpa spp., Leucop/zaea e, a spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria; from the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla s. From the order of the Symphyla, for example, Scutigerella immaculata; from the order of the Thysanoptera, for example, Baliothrips bifieris, Enneothrépsflavens, Frankliniella spp., Heliotlzrzps spp., Hercinoz‘hripsfemoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips oni, TImps S1911; from the order ofthe Thysanum, for example, a saccharina. The phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocogilenchus spp., Heterodem spp., Longidorus spp., ogyne spp., Pralylenchus spp., Radopholus Similis, Rogxlenchus spp., Trichodorus spp., 3O Elenchorhynchus spp., Tylenchulus spp., Tylenchulus semzpenetrans, Xiphz'nema spp.

The combinations according to the present invention are rmore particularly effective against the following pests: Myzus persicae (aphid), Aphis gossyaii (aphid), Aphisfabae (aphid), Lygus spp. ds), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc inctz‘ceps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs),Le1)tocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlz‘neata (Colorado potato beetle), Anthonomus s (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), ia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothz‘s virescens (tobacco budworm), Helicovema armigera (cotton bollworm), verpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (White fly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta_migratoria (locust), Chortiocetes tezmirzifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citrz’ (citrus red mite), Tetranychus urticae (two—spotted spider mite), ychus cinnabarinus (carmine spider mite), Pityllocoptmta oleivora (citrus rust mite), Fob/p/zagotarsonemus lotus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenoceplzalidesfelis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. ies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the rmitidae (for example Neotermes spp.), the Rhinotermitidae (for e Coptotermesformosanus, Reticulitermesflavipes, R. Speratu, R. virginicus, R. hespems, and R. ensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminata (fire ant), Monomorium pharaom's oh’s ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogzne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Prazfylenc/zus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing des), Tylenchulus itrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabdz‘tz‘s s_(vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).

The nd of formula I and mixtures ofthe invention may be used for pest control on various plants, ing soybean (e.g. in some cases lO—70g/ha), corn (e.g. in some cases /ha), sugarcane (e.g. in some cases 20—200g/ha), alfalfa (e.g. in some cases lO—70g/ha), cas (e.g. in some cases 10- SOg/ha), oilseed rape (e.g. ) (e. g. in some cases 20-70g/ha), potatoes (including sweet potatoes) (e.g. in some cases 10—70g/ha), cotton (e. g. in some cases lO—70g/ha), rice (e.g. in some cases 10—70g/ha), coffee (e.g. in some cases 30—150g/ha), citrus (e.g. in some cases 60—200g/ha), almonds (e. g. in some cases 40-180g/ha), fruiting bles, cucurbits and pulses (e.g. tomatoes, pepper, chili, eggplant, cucumber, squash etc.) (e.g. in some cases lO—80g/ha), tea (e.g. in some cases 20-150g/ha), bulb vegetables (e.g. onion, leek etc.) (e. g. in some cases /ha), grapes (e.g. in some cases 30-180g/ha), pome fruit (e.g. apples, pears etc.) (e. g. in some cases 30—180g/ha), and stone fruit (e.g. pears, plums etc.) (e.g. in some cases 30—180g/ha).

The mixtures of the invention may be used for pest control on various plants, including soybean, corn, sugarcane, alfalfa, brassicas, oilseed rape (e.g. canola), potatoes (including sweet potatoes), cotton, rice, coffee, citrus, s, fruiting vegetables, cucurbits and pulses (e.g. tomatoes, pepper, chili, eggplant, cucumber, squash etc), tea, bulb vegetables (6.g. onion, leek etc.), grapes, pome fruit (e. g. apples, pears etc), stone fruit (e.g. pears, plums etc.), and cereals.

The mixtures ofthe invention may be used on soybean to l, for example, Elasmopalpus lignosellus, Dilobodems abderus, Diabrotica Speciosa, Trialeurodes spp., Bemisia spp., aphids, W0 63960 Sternechus subsignatus, Formicidae, Agratis ypsilon, Julus Spp., Murgantia Spp., Halyomorpha spp., Thyanra spp., Megascelz‘s ssp., Procornitermes ssp., Gijzllotalpidae, Nezara viridula, orus Spp., Acrosternum 3191)., Neomegaloromus spp., Cerotoma trifurcata, Popilliajaponica, Edessa 5101)., Liogenys fuscus, Euschistus Izeros, stalk borer, Scapz‘ocoris castanea, phyllophaga spp., Migdolus spp., Pseudoplusia includens, Anticarsia gemmaz‘alis, ia Spp., Rachz'plusia 5171)., rera S1311, Bemisia tabaci, Tetranychus spp., Agriotes spp.

, Euscnz'stus spp.. The mixtures of the invention are preferably used on soybean to l Diloboderus s, Diabrotica Speciosa, Trialeurodes spp., ’a spp., Nezara la, Piezodorus Spp., Acrosternum spp., Cerotoma trzfurcata, Popillia japonica, Euschistus news, Scaptocoris castanea, plzylloplzaga Spp., Migdolus S1211, Agriotes spp., Euschz’stus 3171)..

The mixtures of the invention may be used on corn to control, for e, Euschistus Izei‘os, Euschistus spp., Dichelopsfurcatus, Diloboderus abderus, Thyanta spp., Elasmopabous lignosellus, orpha 3171)., Spodoptera frugiperda, Nezara viridula, Cerotoma trzfurcata, Papilliajaponica, Agratis ypsilon, Diabrotica speciosa, aphids, Heteroptera, Procornitermes spp., Scaptocoris castanea, Formicidae, Julus 331)., Dalbulus maidis, Diabrotica virgifera, Diabrotica spp., Mocis lafipes, Bemisia tabaci, heliotlzz‘s 3121)., Tetranychus Spp., Ikflps Spp., phylloplzaga Spp., Migdolus spp., coris Spp., Liogenysfuscus, Spodoptera Spp., Osm'nia spp., Sesamia Spp., Wireworms, Agriotes spp., Halolydeus destructor. The mixtures ofthe invention are preferably used on corn to control Euschistus heros, Euschistus spy, Dicnelopsfurcatus, Diloboderus abderus, Nezara viridula, Cerotoma cata, ia japonica, Diabrotica speciosa, Diabrotica em, Diabrotica 5171)., Tetranycims Spp., anz’ps Spp., Phyllophaga S1011, Migdolus spp., Scaptocoris Spp., Agriotes 5131)..

The mixtures of the invention may be used on sugar cane to control, for example, Sphenophorus $1112., tennites, Migdolus spp., Diloboderus spp., Telcnin licus, Diatrea saccharalis, Mananarva spp., Mealybugs.

The mixtures of the invention may be used on alfalfa to control, for e, Hypera brunneipennis, Hypera postica, Colias eme, Collops $1913., Empoasca , Epitrix Spp., Geocoris 51917., Lygus hesperus, Lygns Zineolaris, Spissz‘stilus Spp., Spodoptera S1711, Aphids, Trichoplusia ni. The es of the invention are preferably used on alfalfa to control Hypera brunneipennis, Hypera a, Empoasca solana, Epitrix spp., Lygus hesperus, Lygus lineolaris, Trichoplusia mi.

The mixtures of the invention may be used on brassicas to control, for example, Plutella ella, Pieris Spp., Mamestra spp., Plusia S1711, Trichoplusia ni, Phyllotreta Spp., Spodoptem 3191)., Empoasca spp. , thrips Spp., Delia spp. , Murgann’a Spp., Trialeurodes Spp., ia Spp., Microtheca Spp., Aphids.The mixtures of the invention are preferably used on brassicas to control Plutella xylostella, Pieris Spp., Plusia $1717., Trichoplusia ni, Phylloz‘reta Spp., Thrips 5131)..

The mixtures of the invention may be used on oil seed rape, e.g. canola, to l, for example, Meliget/zes spp., Ceutorhynchus napi, Halotydeus destructor, Psylloides spp..

The mixtures of the invention may be used on potatoes, including sweet potatoes, to control, for example, Empoasca spp., Leptinotarsa spp., Diabrotz'ca speciosa, Phthorimaea Spp., Paratrioza spp., Maladera matrida, Agriotes spp., Aphids, wireworms. The mixtures of the invention are preferably used on potatoes, including sweet potatoes, to control Empoasca spp., Leptinotarsa spp., tica Speciosa, Pitt/torimaea spp., Paratrioza spp., Agriotes spp..

The mixtures ofthe invention may be used on cotton to l, for example, Anthonomus grandis, Pectinoplzora spp., heliothis Spp., Spodoptem spp., Tetranyc/ms 5171)., Empoasca spy, Thrips Spp., Bemisia tabaci, Trialeurodes Spp., Aphids, Lygus spp., phyllophaga spp., Scaptocoris spp., Austroasca grisea, Creontiades spp., Nezara Spp., Piezodorus spp., Halogideus tor, lO Oxycaraenus hyalim'pennis, Dysdercus cingulatus. The mixtures of the invention are preferably used on cotton to control Ant/tonomus grandis, ychus spp., ca spp., thn'pS spp., Lygus Spp., phyllophaga spp., Scaptocoris Spp..

The mixtures of the invention may be used on rice to control, for example, Leptocorisa spp., Cnaphalocrosis spp., Chile spp., Scirpophaga spp., Lissorhoptms spp., Oebaluspugnax, Scorinophara Spp., Nep/zotettix malayanus, Nephotettllx nigropictus, Nephotettix parvus, Nepfzottetix virescens, ettzlx spp., Mealybugs, Sogatellafurcz'fera, Nilapawam lugens, Orseolia spp., Cnaphalocrocis medinalis, ia Spp., Stenchaetothrzps is, T[trips spp., Hydrellia philippina, Grasshoppers, Pomacea canaliculata, Scirpophaga innotata, Chilo suppressalis, Chile auricilius, Chilo pobzchrysus, Sesamia iry’erens, Laodelphax striatellus, Nymphuia depunctalis, Oulema , Stinkbugs. The mixtures ofthe invention are preferably used on rice to control Leptocorisa spp., Lissorkoptrus spp., Oebalus pugnax, Nephotettix malayanus, Nep/zotettix nigropictus, ettix paivus, Nephottetix virescens, ettix Spp., Sogatellafurcifera, Stenchaetothrzps is, Thrips spp., Hydrellia philippina, Grasshoppers, Pomacea canaliculata, Scirpophaga innolata, Chilo suppressaz’is, Chilo polycluysus, Oulema oryzae.

The mixtures of the invention may be used on coffee to control, for e, Hypothenemus , Perileucoptera Cofleella, Tetranyc/zus spp., alpus spp., Mealybugs. The mixtures ofthe invention are preferably used on coffee to control Hypothenemus Hamper", Perileucoptera Cofleella.

The mixtures ofthe invention may be used on citrus to control, for e, Panonychus citri, Phyllocoptruta oleivom, Brevz'palpus Spp., Diaphorina citri, Scirtothrips 31317., T[trips spp., Unaspis 5131)., Ceratilz‘s capitata, Phyllocnistis spp., Aphids, Hardscales, Softscales, Mealybugs. The mixtures of the invention are preferably used on citrus to l chus citri, coptmta olez‘vora, Brevz'palpus Spp., Diaphorina cim‘, Scirtothrips spp., thrz'ps spp., cnistis spp..

The mixtures ofthe invention may be used on almonds to control, for example, Amyeloz’s transitella, Tetranychus Spp..

The mixtures of the invention may be used on fruiting vegetables, cucurbits and pulses, including tomatoes, pepper, chili, eggplant, cucumber, squash etc., to control, for example, s 5191)., Tetranychus spp., agotarsonemus spp., Aculops Spp., Empoasca Spp., Spodoptera 5131)., heliothis spp., Tum absoluta, Liriomyza Spp., Bemisia tabaci, Trialeurodes Spp., Aphids, Paratrioza spp., Frankliniella occidentalis, Frankliniella Spp., Anthonomus spp., Phyllotreta Spp., Amrasca spp., Epilacima Spp., Halyomorpha spp., Scirtothrips spp., Leucinodes Spp., Neoleucinodes Spp. Mama: spp., Fruit flies, Stinkbugs, Lepidopteras, Coleopz‘ems. The mixtures of the invention are ably used on fruiting vegetables, cucurbits and pulses, including tomatoes, pepper, chili, eggplant, cucumber, squash etc, to control Thrips spp., Tetranychus Spp., Fob/phagotarsonemus spp., Aculops , ca Spp., tera spp., heliothis 8171)., Tuta absoluta, Liriomyza Spp., Paratrioza spp., Frankliniella occidentalis, Frankliniella spp., Amrasca spp., Scirtothrips spp., Leucinodes 3171)., Neoleucinodes Spp..

The mixtures ofthe invention may be used on tea to control, for example, Pseudaulacaspis Spj)., Empoasca. spp., Scirtothrzps Spp., Caloptilia Ilzez'vom, Tetranychus spp..The mixtures of the invention are preferably used on tea to control Empoasca spp., thrszs $1219..

The es ofthe ion may be used on bulb vegetables, including onion, leek etc. to control, for example, Thrips spp., Spodoptera spp., heliot/zz's spp.. The mixtures of the invention are preferably used on bulb vegetables, including onion, leek etc. to control T[trips Spp..

The mixtures ofthe invention may be used on grapes to control, for example, Empoasca Spp., Lobesia , Eupoecz‘lia ella, Franklim'ella spp., Thrips spp., Tetranycitus spp., Rhipévhorothrzps Cruenratus, Eatetmnychus ettei, Erythroneum Elegantula, Scaphoz‘des spp., Scelodonta strigicollis, Mealybugs. The mixtures of the invention are preferably used on grapes to control Fmnklinz'ella spp., Thrips spp., ychus spp., Rhipzphorothrips Cruentatus, Scaphoides Spp..

The mixtures ofthe invention may be used on pome fi‘uit, ing apples, pears etc., to control, for example, Cacopsyz’z’a spp., Psylla spp., Panonychus ulmi, Cydz'a pomonella, Lepidopteras, Aphids, Hardscales, Softscales. The es ofthe invention are preferably used on pome fruit, ing , pears etc., to control Cacopsylla spp., Psylla spp., Panonychus ulmi.

The mixtures of the ion may be used on stone fruit to control, for example, Grapholita molesta, Scirtothrips Spp., T[trips spp., Fran/cliniella Spp., Telranychus spp., Aphids, Hardscales, Softscales, Mealybugs. The mixtures of the invention are preferably used on stone fruit to control Scirtoz‘lzrips spp., TImps spp., Fran/diniella Spp., Tetranychus Spp..

The mixtures of the invention may be used on s to control, for example, Aphids, Stinkbugs, earthmites, Ewygaster integriceps, Zabrus tenebrioides, Anisoplia austriaca, Ckaetocnema aridula, treta Spp., Oulema melanopus, Oscinella spp., Delia spp., Mayetiola Spp., Contarinia spp., Cephus spp., Steneotarsonemus spp., Apamea spp..

In another ment compounds of formula I and es of the invention may be used on rice to control Baliot/zrips biformis (Thrips), Chilo spp. (e.g. Chilo polychiysus (Dark headed striped borer), Chilo suppressalis (Rice stemborer), Chilo indicus (Paddy stem borer), Clzz’lo polychzysus (Dark- headed rice borer), Cizilo suppressalis (Stripe stem ), Cnaphalocrocis medinalis (Rice leaf folder), Dicladispa amzigera ), Hydrellia philipina (Rice whorl—maggot), Laodelphax spp. (Smaller brown planthopper) (e. g. Laodelphax striatellus ), Lema myzae (Rice leatbeetle), Leptocorsia acuta (Rice bug), Leptocorsia oratorius (rice bug), Lissorhoptms oryzophilus (rice water weevil), Mythemz‘na ta (armyworm), Neplzottetz‘x spp. (Green leaflropper ) (e. g. Nephotetrz‘x cincticeps, Nephotettix malayanus, Nephotettz’x nigropz‘ctus, Nephotetlix parvus, Nephottetix virescens), Nilaparvata lugens (Brown opper), Nyngphula depunctalis (Rice caseworm), Orseolz‘a oryzae (Rice Gall midge), Oulema oryzae (Rice etle), Scirpoplzaga incertulas (Yellow Stemborer), Scirpophaga ta (White Stemborer), Scotinophara coarctata (Rice black bug), Sogaellafrucifem (White—backed opper), Steneoz‘arsonemus Spinki.

The compounds of formula I and mixtures of the invention may be used to control animal g pests including: Ants, Bedbugs (adult), Bees, Beetles, Boxelder Bugs, Carpenter Bees, Carpet s, Centipedes, Cigarette, Beetles, Clover Mites, Cockroaches, ed Flour Beetle, Crickets, Earwigs, Firebrats, Fleas, Flies, Lesser Grain Borers, Millipedes, Mosquitoes, Red Flour Beetles, Rice s, Saw-toothed Grain Beetles, Silverfish, Sowbugs, Spiders, Termites, Ticks, Wasps, Cockroaches, Crickets, Flies, Litter Beetles (such as Darkling, Hide, and Carrion), Mosquitoes, Pillbugs, Scorpions, s, Spider Mites (Twospotted, Spruce), Ticks.

The compounds of formula I and mixtures of the invention may be used to control ornamental pests including: Ants (Including Imported fire ants), Armyworms, Azalea caterpillars, Aphids, Bagworms, Black vine weevils (adult), Boxelder bugs, Budwonns, California oakworms, Cankerworms, Cockroaches, Crickets, ms, Eastern tent caterpillars, Elm leaf beetles, European sawflies, Fall webworms, Flea beetles, Forest tent illars, Gypsy moth larvae, Japanese beetles (adults), June beetles (adults), Lace bugs, Leaf-feeding caterpillars, Leafhoppers, Leafminers (adults), Leaf rollers, Leaf skeletonizers, Midges, Mosquitoes, Oleander moth larvae, Pillbugs, Pine sawflies, Pine shoot beetles, Pinetip moths, Plant bugs, Root weevils, Sawflies, Scale insects (crawlers), Spiders, ebugs, d s, Striped oakworms, Thrips, Tip moths, Tussock moth larvae, Wasps, ites, Brown softscales, California les (crawlers), Clover mites, Mealybugs, Pineneedlescales (crawlers), Spider mites, Whiteflies.

The compounds of formula I and mixtures of the invention may be used to control turf pests including: Ants (Including Imported fire ants, Armyworms, Centipedes, Crickets, Cutworrns, Earwigs, Fleas (adult), Grasshoppers, Japanese beetles ), Millipedes, Mites, Mosquitoes (adult), Pillbugs, Sod webworms, Sow bugs, Ticks (including species which transmit Lyme e), Bluegrass billbugs (adult), Black turfgrass us (adult), Chiggers, Fleas (adult), Grubs (suppression), Hyperodes weevils ), Mole crickets (nymphs and young adults), Mole Crickets (mature adults), Chinch Bugs.

The compounds of formula (I) and mixture of the invention, in particular those in the tables above, may be used for soil applications, ing as a seed application, to target at least the following: sucking pests such as aphids, , brown plant hopper (e.g. on rice), sting bugs, white flies (eg. on cotton and vegetables), mites; on soil pests such as corn root worm, Wireworms, white grabs, zabrus, termites (e.g. on sugar cane, soy, pasture), maggots, cabbage root fly, red legged earth mite; on lepidoptera, such as spodoptera, cutworrns, elasmoplpus, plutella (e.g. brassica), stem borers, leaf miners, flea beetle, Stemeckus; on nematicides, such as Heterodera glycines (e.g. on soybean), Pratylenchus brachyums (e.g. on corn), P. zeae (e. g. oncom), P. penetrans (e.g. on corn), Meloidogyne ita (e.g. on vegetables), Heterodera schachtii (e.g. on sugar beet), Rotylenclms reniformz‘s (e.g. on cotton), Heterodera avenae (e.g. on cereals), enchus neglectus (e.g. on cereals), thornei (e.g. on cereals).

The compounds of formula (I) and mixture of the ion, in particular those in the tables above may be used for seed applications at least on the following: soil grubs for corn, soybeans, sugarcane: Migdolus Spp; phaga spp.; derus Spp; Cyclocephala spp; Lyogenysfuscus; sugarcane weevils: Spkenophoms Ievis &Metamasius erus; termites for soybeans, sugarcane, pasture, others: Heterotermes tenuis; Heterotermes longiceps; Comitermes cumulans; Procomitemzes triacifer ; Neocaprz'termes opacus; Neocapritemzes parvus; corn root worms for corn and potatoes: Diabrozica $1312., seed Maggot: Delia platura; soil stinkbugs: Scaptocoris castanea; Wireworms: Agriotes Spp,‘ Athous spp Hipnodes bicolor; era destructor; Limonius calm; Limonius calz' ornicus; rice water weevil: Lissorltoplrus onvzophilus; Red Legged earth mites: Halolydeus destructor.

For soil applications using compounds of formula I on sugar cane, including application on sugar cane propogation material such as buds, the following mixing partners are of ular interest: insecticides selected from neonicotinoids, in particular thiamethoxarn, imidacloprid and anidin, aflor, tin, carbofuran, tefluthrin, fipronil, ethiprole, spinosad, lamda-cyhalothrin, bisamides, in particular chlorantraniliprole, cyantraniliprole, flubendiamide; optionally with fungicides ed from azoxystrobin, cyproconazole, thiabendazole, fluazinam, fludioxonil, mefenoxam, Sedaxane. For foliar applications using compounds of formula I on sugar cane, the following mixing partners are of particular st: insecticides selected from thoxam, Lambda cyhalothrin, spirotetramat, spinetoran, chlorantraniliprole, lufenuron; optionally with fungicides selected from N-[9-(dichloromethylene)— l ,2,3 ,4—tetrahydro—l ,4—methanonaphthalen—5-yl]—3~(difluoromethyl)—l —methyl— 1 H—pyrazole—4— amide [CAS 1072957—71-1], azoxystrobin, cyproconazole, protioconazole. Combinations with glyphosate are also of interest.

Particular combinations of interest for sugar cane, particularly on sugar cane propogation al such as buds, include a compound of formula I with thiamethoxam and abamectin, a compound of formula I with thiamethoxam and cyantraniliprole, a compound of a I with thiamethoxam and chlorantraniliprole. Further ations of particular interestfor sugar cane e a compound of formulal + thiamethoxam + abamectin + mefenoxam + fludioxonil + azoxystrobin + thiabendazole; a compound of formula I + abamectin + mefenoxam + onil + azoxystrobin + thiabendazole, a compound of formula I + thiamethoxam + mefenoxam + fludioxonil + azoxystrobin + ndazole, a compound of formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + trobin + thiabendazole, a compound of formula I + thiamethoxam + abamectin + fludioxonil + azoxystrobin + thiabendazole, a compound of formula] + thiamethoxam + abamectin + mefenoxam + azoxystrobin + thiabendazole, a compound of formula I + thiamethoxam + abamectin + mefenoxam + fludioxonil + thiabendazole, a compound of formula I + thiamethoxam + abamectin + xam + fludioxonil + azoxystrobin. Example of ratios are below.

The amount of a combination ofthe invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example lactic or therapeutic; the type of pest to be controlled or the application time.

The es comprising a nd of formula I, e. g. those ed from table A, and one or more active ingredients as bed above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank—mix”, and in a combined use of the single active ingredients when applied in a tial manner, i.e. one after the other with a reasonably short period, such as a few hours or days.

The order of applying the compounds of formula I ed from table A and the active ingredients as described above is not essential for working the present ion.

The synergistic activity of the combination is apparent from the fact that the pesticidal activity of the composition ofA + B is greater than the sum of the pesticidal activities ofA and B.

The method of the invention comprises applying to the useful plants, the locus thereof or propagation material thereof in admixture or separately, a synergistically effective aggregate amount of a ent A and a component B.

Some of said combinations according to the invention have a systemic action and can be used as foliar, soil and seed treatment pesticides.

With the combinations according to the invention it is possible to inhibit or destroy the pests which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by pests.

The compound of formula I are understood to represent a new mode of action. Accordingly, it may be noted that compounds of formula I may be used to control acarides, insects and des, preferably insects, that are resistant to active ingredients having other modes of action, e.g. it may be included in resistant management programs.

The combinations of the t invention are of particular interest for controlling pests in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, ane, fruit and omamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

The combinations according to the invention are d by treating the pests, the useful , the locus f, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the rial als threatened by pests, attack with a combination of components A and B in a synergistically effective amount.

The combinations according to the invention may be applied before or after infection or contamination of the useful plants, the propagation al thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the rial materials by the pests.

The combinations according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur on useful plants in agriculture, in horticulture and in forests, or on organs of usefiil plants, such as fruits, , e, , tubers or roots, and in some cases even on organs of useful plants which are formed at a later point in time remain protected against these pests.

When applied to the useful plants the compound of formula I is generally applied at a rate of 1 to 500 g a.i./ha in association with 1 to 2000 g a.i./ha, of a compound ofcomponent B, depending on the class of chemical ed as component B.

Generally for plant propagation material, such as seed treatment, application rates can vary from 0.001 to 10g / kg of seeds of active ingredients. When the combinations of the present invention are used for treating seed, rates of 0.001 to 5 g of a compound of formula I per kg of seed, preferably from 0.01 to 1 g per kg of seed, and 0.001 to 5 g of a compound ofcomponent B, per kg of seed, preferably from 0.01 to 1 g per kg of seed, are generally sufficient.

The weight ratio ofA to B may generally be between 1000 : 1 and 1 : 1000. In other embodiments that weight ratio ofA to B may be between 500 : 1 to 1 : 500, for e between 100 : 1 to 1 : 100, for example between 1 : 50 to 50 : 1, for example 1 : 20 to 20 : 1. Other embodiments of weight ratios of component (B) to component (A) range from 500: 1 to 1:250, with one embodiment being from 200:] to 1:150, another embodiment being from 150:1 to 1:50 and another embodiment being from 50:1 to 1:10. Also ofnote are weight ratios of component (B) to component (A) which range from 450:1 to 1:300, with one embodiment being from 150:1 to 1:100, another embodiment being from 30:1 to 1:25 and r embodiment being from 10:1 to 1:10. Other embodiemnts include 1:5 to 5:1, for example 4:1, 3:1.2:1,1:1,1:2,1:3,1:4,1:5 The invention also provides idal mixtures comprising a combination of components A and B as mentioned above in a synergistically effective , together with an lturally acceptable carrier, and optionally a surfactant.

Spodoptera preferably means Spodoptera alis. Heliothis preferably means Heliothis virescens. Tetranychus preferably means Tetranychus urticae.

The compositions of the invention may be employed in any conventional form, for e in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS) (e.g. with high active ingredient tration), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GP), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (E0), an emulsion, oil in water (EW), a micro- on (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical trate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingre- dients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, reeze, stickers, thickeners and compounds that e adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e. g. the condensation product of formaldehyde with naphthalene sulphonate, an rylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated henol and an ethoxylated fatty alcohol.

A seed dressing formulation is d in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed ng formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. A typical a tank—mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75 %, of the desired ingredients, and 99.75 to 20 %, ally 99 to 25 %, of a solid or liquid aries ding, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40 %, especially 0.5 to 30 %, based on the tank-mix formulation. A typical pre-mix formulation for seed treatment application comprises 0.5 to 99.9 %, especially 1 to 95 %, of the desired ingredients, and 99.5 to 0.1 %, especially 99 to 5 %, of a solid or liquid nt (including, for example, a solvent such as water), where the auxiliaries can be a tant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre—mix formulation.

The rates of application of a plant propagation material treatment varies, for example, according 3O to type of use, type of crop, the specific compound(s) and/or agent(s) used, and type of plant propagation material. The suitable rate is an effective amount to provide the d action (such as disease or pest control) and can be determined by trials and routine experimentation known to one of ordinary skill in the art.

Generally for soil treatments, application rates can vary from 0.05 to 3 kg per hectare (g/ha) of ients. Generally for seed treatments, application rates can vary from 0.5 to 1000g/ lOOkg of seeds of ingredients.

WO 63960 In general, the ations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with a compound of component B, and optionally other active agents, ularly microbiocides or conservatives or the like.

Concentrated forms of compositions generally n in between about 2 and 80%, preferably between about 5 and ?0% by weight of active agent. Application forms of ation may for example contain from 0.01 to 20% by , preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ d formulations.

Formulation Examples Powders for d5; seed treatment c) light mineral oil 5 5 5% highly dispersed silicic acid 5 5 0 —--20 The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment. —--- __-- _--- Ready-for—use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Suspension concentrate silicone oil (in the form of a 75 % emulsion in water) W0 2012I163960 The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired on can be obtained by dilution with water. Using such dilutions, seeds can be treated and protected against infestation by ng, pouring or immersion.

Flowable concentrate for seed treatment The finely ground combination is tely mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such ons, seeds can be treated and protected against infestation by spraying, pouring or ion.

The invention further pertains to a product for use in agriculture or horticulture comprising a capsule wherein at least a seed treated with the inventive compound is located. In another ment, the t comprises a e wherein at least a treated or untreated seed and the inventive compound are Slow Release Capsule Suspension 28 parts ofthe inventive compound are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene—polyphenylisocyanate—mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts ofpolyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this on a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts ofwater is added.

The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension ation contains 28% of the active ingredient. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in a suitable apparatus.

Examples The Examples in 2010/068605, in corporated herein by reference, demonstrates that compounds of formula I have inseciticidal activity.

W0 20121163960 A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions ofthe individual components.

The action to be ed E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20—22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray e X = % action by active ient A) using p ppm of active ingredient Y = % action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected ive) action of active ingredients A)+B) using p+q ppm of active ingredient is E = X + Y ~ —)—(-——Y— 1 00 If the action ly observed (0) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms the synergism factor SF corresponds to O/E. In the agricultural practice an SF of 2 1.2 indicates significant improvement over the purely complementary addition of activities (expected activity), while an SF of S 0.9 in the practical application routine signals a loss of activity compared to the expected activity.

Tables 1 to 3 show mixtures of the present invention demonstrating notable synergistic effects. As the percent of mortality cannot exceed 100 t, the unexpected increase in icidal activity can be greatest only when the separate active ingredient components alone are at application rates providing considerably less than 100 t control. Synergy may not be evident at low application rates where the individual active ingredient components alone have little activity. However, in some instances high activity was observed for combinations wherein individual active ingredient alone at the same application rate had essentially no activity. The synergism is remarkable.

Tetranvchus urticae (Two spotted spider mite) (contact/feeding activity) Bean plants are ed with mite populations ofmixed ages. 1 day after infestation, plants are treated in a spray chamber with diluted test solutions. 1 and 8 days later, samples are checked for adult mortality. 2 replicates per treatment were ted.

Table 1 Mixtures ound A58 and thiamethoxam A58 TMX A58 + TMX Application observed observed oberved expected ppm l % control % control % control % difference 0.4 + 200 80 0 85 80 +5 _—-_ —__-—-_-_ ___M ___M ___M Table 2 Mixtures of compound A58 and lambda cyhalothrin A58 LCYH A58 + LCYH Application observed observed oberved expected ppm control % l % control % control % difference A58 + LCYH 0.4 + 25 80 80 95 96 —1 A58 + LCYH 0.2 + 12.5 40 75 100 85 +15 A58 + LCYH 0.2 + 25 40 80 95 88 +7 A58 + LCYH 0.1 + 100 O 95 95 95 0 A58 + LCYH 0.1 + 50 0 85 95 85 +10 A58 + LCYH 0.1 + 25 0 80 90 80 +10 A58 + LCYH 0.1 + 12.5 0 75 90 75 +15 A58 + LCYH 0.1 + 6.25 O 25 60 25 +35 A58 + LCYH 0.05 + 50 0 85 95 85 +10 A58 + LCYH 80 85 80 +5 A58 + LCYH 0 75 0 +75 A58 + LCYH 0.05 + 12.5 0 75 75 75 0 A58 + LCYH 0.05 + 6.25 0 25 75 +50 A58 + LCYH 0.025 + 25 0 80 85 80 +5 A58 + LCYH 0.025 + 12.5 0 75 85 75 +10 A58 + LCYH 0.025 + 6.25 0 25 60 25 +35 0.025 + A58 + LCYH 3.125 0 O 55 0 +55 0.025 + A58 + LCYH 1.562 O 0 25 0 +25 0.0125 + A58 + LCYH 12.5 0 75 75 75 0 0.0125 + A58 + LCYH 6.25 0 25 75 25 +50 0.0125 + A58 + LCYH 3.125 0 0 65 0 +65 0.0062 + A58 + LCYH 1.562 0 0 45 0 +45 0.0062 + A58 + LCYH 3.125 0 0 15 0 +15 0.0031 + A58 + LCYH 1.562 0 0 15 0 +15 0.0031 + F658 + LCYH 0.781 0 0 3O 0 +30 A58 + LCYH 0.006 + 6.25 0 25 25 25 0 Table 3 Mixtures ofcompound A58 and diafenthiuron A58 DFN A58 + DFN Application observed observed oberved expected ppm control % control % control % control % difference A58 + DFN 0.4 + 25 85 95 95 99.25 —4.25 A58 + DFN 0.2 + 25 60 95 90 98 -8 A58 + DFN 0.2 + 12.5 60 6O 90 84 +6 A58 + DFN 0.1 + 25 0 95 80 95 -15 A58 + DFN 0.1 + 12.5 0 60 75 60 +15 A58 + DFN 0.1 + 6.25 O 25 25 25 0 A58 + DFN 0.05 + 25 0 95 90 95 —5 A58 + DFN 0.05 + 12.5 0 60 80 60 +20 A58 + DFN 0.05 + 6.25 [ o 25 7o 25 +45 A58 + DFN 0.05 + 3.125 0 0 4O 0 +40 A58 + DFN 0.025 + 25 O 95 85 95 ~10 A58 + DFN 0.025 + 12.5 0 6O 75 60 +15 A58 + DFN 0.025 + 6.25 0 25 35 25 +10 0.025 + A58 + DFN 3.125 0 0 65 0 +65 J 0.025 + A58 + DFN 1.562 0 0 25 0 +25 0.0125 + A58 + DFN 12.5 0 60 80 60 +20 0.0125 + A58 + DFN 6.25 O 25 90 25 +65 0.0125 + A58 + DFN 3.125 0 0 25 0 +25 0.0125 + A58 + DFN 1.562 0 0 15 0 +15 0.0062 + A58 + DFN 6.25 0 25 25 25 0 0.0062 + A58 + DFN 3.125 0 0 65 0 +65 In the above tables column 2 shows the application rates used, where the first rate given ponds to the nd in column 3 and the second rate given corresponds to the compound in column 4. Columns 3 and 4 show the control ed from the compounds alone. Column 5 shows the control observed from the combined application of both nds. Data is not shown for experiments where there was no insect mortality when the compounds were applied alone and in combination. When a compound applied alone gave no control at a particular rate, it is assumed that lower rates of that compound alone also give no control.

Claims (12)

Claims 1.

1. A pesticidal mixture comprising a component A and a component B, wherein component A is a compound of formula I wherein L is a direct bond; AI and A2 are C—H; R1 is ethyl or trifluoroethyl ; 10 R2 is trifluoromethyl; each R3 is independently chloro or fluoro; R4 is methyl; R5 is hydrogen; p is 2 or 3; 15 and component B is a nd selected fromthe group consisting of thiamethoxam, lambda cyhalothrin and diafenthiuron.

2. A pesticidal mixture according to claim 1, wherein A1 and A2 are OH; R2 is trifluoromethyl, R4 is methyl, R5 is hydrogen, each R3 is chlorine, p is 2.

3. A pesticidal mixture ing to claim 1 or 2, wherein ent A is a mixture of compounds 1* and I** wherein the molar proportion of compound I** compared to the total amount of both enantiomers is greater than 50%.

4. A pesticidal mixture according to any one of claims 1 to 3, wherein component B is a compound selected from the group consisting of thiamethoxam and lambda cyhalothrin.

5. A idal e according to any one of claims 1 to 4, wherein the mixture comprises an agricultural able carrier and optionally a surfactant. 10

6. A pesticidal mixture according to any one of claims 1 to 5, wherein the weight ratio ofA to B is 1000:1t0111000.

7. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest a combination of components A and B, n ents A and B are as defined in any one of claims 1 to 6.

8. A seed comprising a mixture as defined in any one of claims 1 to 6. 15

9. A pesticidal mixture according to claim 1, substantially as herein described with reference to any one of the Examples thereof.

10. A pesticidal e according to any one of claims 1 to 6, substantially as herein described. 20

11. A method according to claim 7, substantially as herein described.

12. A seed according to claim 8, substantially as herein described.