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WO2015172938A1 - Agrochemical composition hydrophilic and hydrophobic coated metal oxide submicron particles - Google Patents

Agrochemical composition hydrophilic and hydrophobic coated metal oxide submicron particles Download PDF

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Publication number
WO2015172938A1
WO2015172938A1 PCT/EP2015/057143 EP2015057143W WO2015172938A1 WO 2015172938 A1 WO2015172938 A1 WO 2015172938A1 EP 2015057143 W EP2015057143 W EP 2015057143W WO 2015172938 A1 WO2015172938 A1 WO 2015172938A1
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WO
WIPO (PCT)
Prior art keywords
metal oxide
submicron
coated metal
alkyl
composition according
Prior art date
Application number
PCT/EP2015/057143
Other languages
French (fr)
Inventor
Wen Xu
Original Assignee
Basf Se
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Filing date
Publication date
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Publication of WO2015172938A1 publication Critical patent/WO2015172938A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients

Definitions

  • Agrochemical compositions generally comprise pesticides. Some pesticidal active ingredients (a.i.) are susceptible to ultraviolet radiation (UV) breakdown (e.g. photodegradation), which reduces the efficacy of the active ingredient. Some pesticidal active ingredients are also poorly water soluble.
  • UV ultraviolet radiation
  • the disadvantage of the known agrochemical compositions is the poor pesticidal stability and the low pesticide concentration. An additional disadvantage is that water-insoluble, photodegradable pesticides can be unstable when exposed to light.
  • Subject matter of the present invention relates to an agrochemical composition
  • an agrochemical composition comprising a) a pesticide,
  • the present invention relates to agrochemical compositions that are used to stabilize a photodegradable pesticidal active ingredient (a.i.). More specifically, this invention relates to an agrochemical aqueous emulsion, wherein the photodegradable active ingredient is dissolved in the oil phase, said oil phase is encircled by a polymer matrix formed by a film of submicron particles encapsulating the oil droplet surface, wherein the submicron particles are comprised of hydrophilic- and hydrophobic-coated metal oxide particles.
  • the invention further relates to a process for the preparation of said composition; and to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • the present invention comprises combinations of certain features with other additional features.
  • an object of the present invention to provide an agrochemical composition which stabilizes pesticides which are sensitive to sunlight.
  • Another object of the invention was to increase the stability of photodegradable pesticides in an agrochemical composition during storage and/or after application to the environment.
  • the objects were achieved by the agrochemical composition according to the invention.
  • an aqueous emulsion is taken to mean compositions which maintains an oil-in-water emulsion upon mixing with water (e.g. in a weight ratio of 1 part concentrate to 99 parts water).
  • the emulsion usually forms under shear mixing.
  • the resulting emulsion may have an average oil droplet size around 1 - 3 pm, 0.5 to 10 pm or 0.1 to 50 pm.
  • the average droplet size may be determined by laser diffraction, e.g. with a Malvern Mastersizer 2000.
  • pesticides refer to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators. Pesticides include fungicides, insecticides, herbicides and growth regulators. In one embodiment, pesticides are insecticides. Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in
  • Pesticide Manual 15th Ed. (2009), The British Crop Protection Council, London, the entire contents of which are hereby incorporated by reference.
  • the following pesticides are suitable, by way of example (pesticides A) to K) are fungicides):
  • Inhibitors of complex III at Q 0 site e.g. strobilurins: azoxystrobin, coumethoxystrobin,
  • coumoxystrobin dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone; inhibitors of complex III at Q, site: cyazofamid, amisulbrom
  • carboxamides benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-[re (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluoroph
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl; others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine;
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine; other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
  • methionine synthesis inhibitors anilino-pyrimidines: cyprodinil, mepanipyrim, pyrimethanil; protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
  • G protein inhibitors quinoxyfen;
  • Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)- but-2-yl) carbamic acid-(4-fluorophenyl) ester; compounds affecting cell membrane permeability and fatty acides: propamocarb, propamocarb-hydrochlorid; fatty acid amide hydrolase inhibitors: oxathiapiprolin;
  • inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; organochlorine compounds (e.g.
  • inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • acibenzolar-S-methyl probenazole, isotianil, tiadinil, prohexadione-calcium
  • phosphonates fosetyl, fosetyl-aluminum, phosphorous acid and its salts
  • N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide 5-chloro-1-(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
  • abscisic acid amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6- dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iod
  • acetamides acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
  • aryloxyphenoxypropionates clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; Bipyridyls: diquat, paraquat;
  • (thio)carbamates asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxyn
  • imazamethabenz imazamox, imazapic, imazapyr, imazaquin, imazethapyr
  • phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop
  • pyrazines chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
  • pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron,
  • metazosulfuron metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3- yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn
  • amicarbazone aminotriazole, anilofos, beflubutamid, benazolin,
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos- methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; carbamates: alanycarb, aldica
  • the pesticide is an isothiazoline insecticide of the formula I:
  • A is a group A 1 , A 2 , A 3 or A 4 ;
  • a 2 is a group of following formula:
  • W is selected from O and S;
  • Y is selected from hydrogen, -N(R 5 )R 6 and -OR 9 ;
  • a 3 is a group of following formula:
  • a 4 is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, or is a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring is optionally substituted with one or more substituents R ;
  • B , B 2 and B 3 are each independently selected from the group consisting of N and CR 2 , with the proviso that at most two of B , B 2 and B 3 are N;
  • G , G 2 , G 3 and G 4 are each independently selected from the group consisting of N and CR 4 , with the proviso that at most two of G , G 2 , G 3 and G 4 are N;
  • each R 2 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF 5 , Ci-C6-alkyl, Cs-Cs-cycloalkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R 8 ,
  • R 3a , R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, -C0 2 R 3d , Ci-C 3 -alkyl, CrC 3 -haloalkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, Ci-C 3 -alkoxy, Ci-C 3 -haloalkoxy, CrC 3 -alkylthio, CrC 3 -haloalkylthio, CrC 3 -alkylsulfonyl and Ci-C 3 -haloalkylsulfonyl; or
  • each R 3c is independently selected from the group consisting of hydrogen, halogen, CH 3 and CF 3 ;
  • R 3d is selected from the group consisting of hydrogen, CrC6-alkyl and Ci-C 3 -alkyloxy-CrC 3 -alkyl-;
  • each R 4 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF 5 , Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R 8 , C 3 -C8-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R 8 , C 2 -C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R 8 , C 2 -C6-alkynyl which may be partially or fully halogenated and/or may be substitute
  • phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R , and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10- membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S0 2 , as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted by one or more radicals R ;
  • each R 5 is independently selected from the group consisting of hydrogen, Ci-Cio-alkyl, C 3 -C 3 - cycloalkyl, C 2 -Cio-alkenyl, C 2 -Cio-alkynyl, wherein the four last-mentioned aliphatic and
  • cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more substituents R 8 , and
  • each R 6 is independently selected from the group consisting of hydrogen, cyano, Ci-Cio-alkyl, C 3 - Ce-cycloalkyl, C 2 -Cio-alkenyl, C 2 -Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R 8 ,
  • R 7a , R 7b are each independently selected from the group consisting of hydrogen, halogen, cyano, d-d-alkyl, d-d-cycloalkyl, d-d-alkenyl and C 2 -C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R 8 ;
  • each R 8 is independently selected from the group consisting of cyano, azido, nitro, -SCN, -SF 5 , d- d-cycloalkyl, d-d-halocycloalkyl, where the cycloaliphatic moieties in the two last-mentioned radicals may be substituted by one or more radicals R 3 ;
  • heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6 ,
  • R 8 together with the carbon atoms of an alkyl, alkenyl, alkynyl or cycloalkyl group which they are bonded to, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring, where the heterocyclic ring comprises 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, and where the carbocyclic or heterocyclic ring is optionally substituted with one or more substituents R 16 ; and
  • each R 9 is independently selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, d- Ce-haloalkyl, d-d-cycloalkyl, C3-C8-cycloalkyl-CrC 4 -alkyl-, d-d-halocycloalkyl, d-d-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the nine last-mentioned radicals may be substituted by one or more radicals R 3 ,
  • heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S,
  • R 9 in the groups -S(0) n R 9 and -OSO2R 9 is additionally selected from the group consisting of d-d- alkoxy and Ci-C6-haloalkoxy;
  • R 0a , R 0 are selected independently from one another from the group consisting of hydrogen, d- Ce-alkyl, d-d-haloalkyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-alkenyl, d-d-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the eight last- mentioned radicals may be substituted by one or more radicals R 3 ;
  • heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S,
  • R 0a and R 0 form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, d-d- haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d-cycloalkyl, d-d-halocycloalkyl, d-Ce- alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C6-hal
  • R is independently selected from the group consisting of halogen, cyano, azido, nitro, -SCN, -SF 5 , Ci-Cio-alkyl, d-Ce-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more radicals R 8 ,
  • phenyl optionally substituted with 1 , 2, 3, 4, or 5 substituents selected independently from R 6 ; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated aromatic heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents selected independently from R 6 ;
  • each R 2 is independently selected from the group consisting of hydrogen, halogen, CrC6-alkyl, Ci- Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, d-Ce-alkenyl, d-Ce-haloalkenyl, d-Ce-alkynyl, C 2 - Ce-haloalkynyl, d-Ce-cycloalkyl, d-Ce-halocycloalkyl, CrCe-alkoxy-d-Ce-alkyl, d-Ce-haloalkoxy- d-Ce-alkyl, and
  • phenyl optionally substituted with 1 , 2, 3, 4, or 5 substituents R 6 ;
  • each R 3 is independently selected from the group consisting of cyano, nitro,
  • C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy and oxo;
  • phenyl, benzyl, phenoxy where the phenyl moiety in the three last-mentioned radicals may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents R 6 ; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by 1 , 2 or 3 substituents R 6 ;
  • R 3 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of C1-C6- alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from CN, C3-C4-cycloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy and oxo;
  • each R 4 is independently selected from the group consisting of hydrogen, cyano, Ci-C6-alkoxy, Ci- C6-haloalkoxy, Ci-C6-alkylthio, CrC6-haloalkylthio, CrC6-alkylsulfinyl, CrC6-haloalkylsulfinyl, Cr C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from CN , Ci-C4-alkoxy, CrC4-haloalkoxy, CrC4-alky
  • C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, Ci-C4-alkylthio, C1-C4- alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4-cycloalkyl, C3-C4-cycloalkyl-Ci-C4-alkyl-, where the cycloalkyl moiety in the two last-mentioned radicals may be substituted by 1 or 2 substituents selected from halogen and cyano; and oxo;
  • cyclic moieties in the four last-mentioned radicals may be unsubstituted and/or carry 1 , 2 or 3 substituents selected from halogen, Ci-C6-alkyl, C1-C6- haloalkyl, d-Ce-alkoxy, d-Ce-haloalkoxy and (CrC6-alkoxy)carbonyl; and a 3-, 4-, 5- or 6- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6 ;
  • R 4a and R 4 independently of each other, have one of the meanings given for R 4 ;
  • R 4a and R 4 together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and d-d- haloalkoxy;
  • each R 5 is independently selected from the group consisting of hydrogen, cyano, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
  • C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, d-d- alkylthio, C 1 -C4-al ky Isu If i nyl , Ci-C4-alkylsulfonyl and oxo;
  • each R 6 is independently selected from the group consisting of halogen, nitro, cyano, -OH, -SH, d-Ce-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d-alkylsulfinyl, d-d- haloalkylsulfinyl, d-C6-alkylsulfonyl, d-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf- butyldimethylsilyl;
  • d-d-alkyl d-d-alkenyl, d-d-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from d- d-cycloalkyl, d-d-alkoxy, d-d-haloalkoxy and oxo;
  • d-d-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from d-d-alkyl, d-d-cycloalkyl, d-d-alkoxy, d-d-haloalkoxy and oxo; phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from d-d- alkyl, d-Ce-haloalkyl, d-d-alkoxy, d-d-haloalkoxy and (d-C6-alkoxy)carbonyl;
  • the ring optionally carries one or more substituents selected from halogen, d-d-haloalkyl, d-d-alkoxy and d-d-haloalkoxy;
  • each n is independently 0, 1 or 2;
  • each m is independently 0 or 1 ;
  • the isothiazoline insecticide is a compound of formula 1.1 :
  • R is d-d-haloalkyl and is in particular CF 3 ;
  • R 2a , R 2 and R 2c are selected independently from one another from hydrogen, halogen and d-d- haloalkyl, preferably from hydrogen, F, CI, Br and CF 3 ;
  • R 4 is selected from hydrogen, halogen, cyano, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, C 1 -C4- haloalkoxy, d-d-alkylthio and d-d-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH 3 , CF 3 , OCH 3 , OCF 2 H, OCF 3 , SCH 3 , SCF 2 H, and SCF 3 ;
  • R 0a and R 4a independently from each other are selected from hydrogen, Ci-d-alkyl, d-d- haloalkyl, preferably from hydrogen and CH 3 ;
  • R 4 is selected from hydrogen, d-d-alkyl, d-d-haloalkyl, d-d-alkenyl, d-d-haloalkenyl, d- d-alkynyl, d-d-haloalkynyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-cycloalkyl-d-d-alkyl-, where the cycloalkyl moieties in the three last-mentioned groups may be substituted by a cyano group; Ci-d-alkyl substituted with a cyano group, Ci-d-alkoxy, Ci-d-haloalkoxy, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC 4 -alk
  • k 0, 1 , 2 or 3;
  • n 0, 1 or 2;
  • each R is independently selected from the group consisting of halogen, cyano, nitro, CrC 4 -alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, CrC4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkylsulfinyl, CrC 4 -haloalkylsulfinyl, CrC 4 -alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C 2 -C4-alkenyl, C 2 -C4-haloalkenyl, C 2 -C4-alkynyl and C 2 -C4-haloalkynyl, C 1 -C4- alkylcarbonyl, Ci-C4-alkylaminocarbon
  • the present invention relates to agrochemical compositions comprising an isothiazoline insecticide of formula 1.1 and the submicron particles b) and c) as defined herein below.
  • the isothiazoline insecticide is a compound of formula I.2:
  • R is Ci-C4-haloalkyl and is in particular CF 3 ;
  • R 2a , R 2 and R 2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF 3 ;
  • R 4 is selected from hydrogen, halogen, cyano, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH 3 , and CF 3 ;
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, -CH 2 -CN and Ci-C6-alkoxy- methyl-, and preferably from hydrogen and CrC 4 -alkyl; and
  • phenyl optionally substituted with 1 , 2, 3, 4 or 5 substituents R ; and a heteromonocyclic ring selected from rings of formulae D-1 to D-181 as defined above;
  • R 9 is selected from hydrogen, CrC6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more CN;
  • R 0a is selected from the group consisting of hydrogen and Ci-C6-alkyl
  • each R is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4-haloalkylthio, Ci-C4-alkylsulfinyl, CrC4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl, CrC4-alkylcarbonyl, Ci-C4-alkylaminocarbonyl; or
  • each R 4a is selected from the group consisting of hydrogen and Ci-C6-alkyl
  • each R 14b is selected from the group consisting of hydrogen, d-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkylmethyl, C 2 -C4-alkynyl, C 2 -C4-alkenyl, Ci-C4-alkoxy, wherein the six last-mentioned radicals may be partially or fully halogenated and/or may be substituted with one cyano group.
  • the present invention relates to agrochemical compositions comprising a) an
  • the isothiazoline insecticide is a compound of formula 1.2a:
  • R is Ci-C4-haloalkyl and is in particular CF 3 ;
  • R 2a , R 2 and R 2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF 3 ;
  • R 4 is selected from hydrogen, halogen, cyano, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH 3 , and CF 3 ;
  • R 5 is selected from hydrogen, Ci-C6-alkyl, C 2 -C3-alkenyl, C 2 -C3-alkynyl, CH 2 -CN and Ci-C6-alkoxy- methyl-, and preferably from hydrogen and CrC4-alkyl; and
  • R 6a is selected from -X-R 6b and -N(R 5a )R 6c ;
  • X is selected from -C(R a ) 2 -, -C(R a ) 2 -C(R a ) 2 -,
  • n 0, 1 or 2
  • each R a is independently selected from the group consisting of hydrogen, halogen, Ci-C3-alkyl, and CrC3-haloalkyl and is preferably hydrogen;
  • R 5a is selected from hydrogen, and Ci-C6-alkyl, and is preferably hydrogen;
  • R 6 is selected from the group consisting of C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R 8 ;
  • each R 4a is selected from the group consisting of hydrogen and Ci-C6-alkyl
  • each R 4 is selected from the group consisting of hydrogen, d-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkylmethyl, C 2 -C4-alkynyl, C 2 -C4-alkenyl, Ci-C4-alkoxy, wherein the six last-mentioned radicals may be partially or fully halogenated and/or may be substituted with one cyano group; where in case that R 5 is hydrogen, R 6a is further selected from hydrogen, 1-cyanocyclopropyl, 1 - cyanocyclobutyl and 1-cyanocyclopentyl.
  • the present invention relates to agrochemical compositions comprising a) an isothiazoline insecticide of formula 1.2a, and b) submicron particles as defined herein below.
  • the isothiazoline insecticide is a compound of formula I.3:
  • R is CrC4-haloalkyl and is in particular CF 3 ;
  • R 2a , R 2b and R 2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
  • R 4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH 3 , CF 3 , OCH3, OCF2H , OCF3, SCH 3 , SCF 2 H, and SCF 3 ;
  • R 5 is selected from hydrogen, Ci-C4-alkyl, C2-C3-alkynyl, -CH 2 -CN and Ci-C6-alkoxy-methyl-, and preferably from hydrogen and Ci-C4-alkyl;
  • R 7 is hydrogen or methyl
  • R 9 is selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more cyano group;
  • R 0a is selected from the group consisting of hydrogen and Ci-C6-alkyl
  • each R is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4-haloalkylthio, Ci-C4-alkylsulfinyl, CrC4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6- cycloalkyl, Cs-Ce-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl, CrC4-alkylcarbonyl, Ci-C4-alkylaminocarbonyl; or
  • each R 4a is selected from the group consisting of hydrogen and d-d-alkyl
  • each R 4b is selected from the group consisting of hydrogen, d-d-alkyl, d-d-alkynyl, d-d- alkenyl, -CH2-CN, d-d-haloalkyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-alkoxy and d-d- haloalkoxy, d-d-cycloalkylmethyl.
  • the present invention relates to agrochemical compositions comprising a) an isothiazoline insecticide of formula 1.3, and b) submicron particles as defined herein below.
  • the isothiazoline insecticide is a compound of formula I.4:
  • R is d-d-haloalkyl and is in particular CF 3 ;
  • R 2a , R 2b and R 2c are selected independently from one another from hydrogen, halogen and d-d- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
  • R 4 is selected from hydrogen, halogen, cyano, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, d-d- haloalkoxy, d-d-alkylthio and d-d-haloalkylthio;
  • A is A 4 and selected from rings of formulae D-1 to D-181 as defined above, preferably selected from D-59, D-65 and D-66 and in particular D-59.
  • the composition can comprise at least 0.1 % by weight, at least 20% by weight, at least 35% by weight, or at least 45% by weight of pesticide (e.g. the isothiazoline insecticide of formula I). In other embodiments, the composition can comprise not more than 80% by weight, not more than 70% by weight, or not more than 60% by weight of the pesticide(e.g. the isothiazoline insecticide).
  • the pesticide is usually water-insoluble. Usually, it is soluble in water to not more than 1 g/l, preferably not more than 200 mg/l and in particular to not more than 50 mg/l at 25°C. Examples of water-insoluble pesticides include isothiazolines as described herein.
  • the skilled worker can select a pesticide with a suitable water-solubility from the above pesticide list.
  • the pesticide can have a melting point of more than 50°C, more than 70°C, or more than 90°C.
  • the pesticide can be present in the composition in dissolved form.
  • the skilled worker can select, from the above pesticide list, a pesticide with a suitable solubility.
  • the composition may comprise from 0.1 to 70% by weight, from 10 to 50% by weight, or from 15 to 40% by weight, of pesticide, the basis being the total of all the pesticides present in the composition.
  • the submicron particles are metal oxides coated with hydrophilic or hydrophobic surface active agents wherein the particles have an average particle size of less than 1000 nm.
  • the particle size is less than 300 nm. In another emobodiment, the particle size is less than 100 nm. In another form the average particle may be in the range from 1 nm to 1000 nm, preferably 1 nm to 100 nm, more preferably 10 nm to 20 nm, determined by means of X-ray diffraction spectroscopy.
  • the agrochemical composition usually comprises 0.1 to 15 wt%, preferably 0.5 to 10 wt% and in particular 1 to 8 wt% of the submicron hydrophilic-coated metal oxide.
  • the agrochemical composition usually comprises 0.1 to 15 wt%, preferably 0.5 to 10 wt% and in particular 1 to 8 wt% of the submicron hydrophobic-coated metal oxide particles.
  • the agrochemical composition usually comprises 0.5 to 25 wt%, preferably 1 to 15 wt% and in particular 3 to 12 wt% of the sum of the submicron hydrophobic-coated metal oxide particles and the submicron hydrophilic-coated metal oxide particles.
  • the weight ratio of submicron hydrophilic-coated metal oxide particles and submicron hydrophobic-coated metal oxide particles is between 10:1 and 1 :10, preferably between 5:1 and 1 :5, and in particular 3: 1 and 1 :3.
  • the use of titanium dioxide in agrochemistry is known: WO 2007/014826 discloses the use of a preparation containing a UV radiation absorbing metal oxide powder and a superspreading agent for the reduction of sunburn damage to useful plants.
  • EP 1 139 763 B1 discloses the use of a particulate material such as titanium dioxide to reduce physiological disorders of a plant without diminishing photosynthesis.
  • WO 2005/072680 discloses a particle of T1O2 or ZnO, which has been doped with one or more other elements such that the concentration of dopant in a surface of the particle is greater than that at a core of the particle.
  • a positive effect of titanium dioxide on plants was described, a severe disadvantage of titanium dioxide is known: Topalov et al. Water Research 1999, 33:1371 -1376 disclose the photocatalytic activity of titanium dioxide towards the decomposition of the fungicide metalaxyl.
  • Kuer and Nunez, Pest Management Science, 2007, 63:491-494 disclose the degradation of nitrogen heterocycles, the basic structural units of a large number of commercial herbicides and fungicides, using titanium dioxide as photocatalyst.
  • JP2004323501 discloses that titanium dioxide is disclosed as a photocatalyst for decomposing residual agrochemicals used for the agricultural products. Thus, the photocatalytic activity of titanium dioxide would contraindicate its use with pesticides which are susceptible to light.
  • submicron metal oxides including titanium dioxide ( ⁇ 2)
  • ⁇ 2 titanium dioxide
  • Hydrophilic- and hydrophobic- coated submicron metal oxides are of particular advantage.
  • coated means, that the metal oxide submicron particles have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (e.g. titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, inorganic oxides, silicon oxides, metal oxides, sodium hexametaphosphate, alumina or glycerol.
  • Such a surface treatment results in a coating of the metal oxide submicron particle.
  • Submicron hydrophilic-coated metal oxide submicron particles may be selected from metal oxides submicron particles coated with inorganic oxides.
  • the inorganic oxide is substantially free of fatty acids.
  • the inorganic oxide is substantially free of silicon or silicon polymers.
  • the term “substantially free” refers to coatings which contain less than 1 % of compounds which are not inorganic oxides. In an embodiment, “substantially free” refers to coatings which contain less than 0.5% of compounds which are not inorganic oxides. In another embodiment, “substantially free” refers to coatings which contain less than 0.1 % of compounds which are not inorganic oxides.
  • the coating of the metal oxide submicron particles comprises at least one inorganic oxide.
  • inorganic oxide refers to oxides and hydroxides of inorganic elements, such as of silicon (e.g. silica Si02), aluminum (e.g. alumina AI203, or aluminum hydroxide
  • the metal oxide submicron particles comprise one inorganic oxide.
  • suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with silica and alumina (such as the products "Micro-titanium Dioxide MT 500 SA” and “Microtitanium dioxide MT 100 SA” from the company Tayca, and the products “Tioveil Fin”, “Tioveil OP”, “Tioveil MOTG” and “Tioveil IPM” from the company Tioxide).
  • suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with alumina (such as TTO-55(B) from Ishihara Corp. USA).
  • Submicron hydrophobic-coated metal oxide particles may be selected from metal oxides coated with:
  • silicon containing polymer and an inorganic oxide silicon containing polymer and an inorganic oxide
  • inorganic oxide and a fatty acid or salts thereof.
  • the submicron hydrophobic-coated metal oxide particles may be selected from metal oxides coated with inorganic oxide and a fatty acid or salts thereof.
  • the coating of the metal oxide submicron particles comprises a silicon containing polymer.
  • the coating may comprise at least one silicon containing polymer. Preferably, it comprises one silicon containing polymer.
  • Suitable examples include, but are not limited to titanium dioxides submicron particles treated with octyltrimethylsilane (such as "T 805", by the company Degussa), with a polydimethylsiloxane (such as the product sold under the trade name "70250 Cardre UF Ti02SI3", by the company Cardre), with a polydimethylhydrogenosiloxane (such as the product sold under the trade name "Microtitanium Dioxide USP Grade Hydrophobic", by the company Color Techniques).
  • octyltrimethylsilane such as "T 805", by the company Degussa
  • a polydimethylsiloxane such as the product sold under the trade name "70250 Cardre UF Ti02SI3", by the company Cardre
  • a polydimethylhydrogenosiloxane such as the product sold under the trade name "Microtitanium Dioxide USP Grade Hydrophobic", by the company Color Techniques).
  • coated zinc oxide submicron particles which are sold under the name "Zinc Oxide CS-5", by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane), "SPD-ZI”, by the company Shin-Etsu (ZnO coated with silicone- grafted acrylic polymer, dispersed in cyclodimethylsiloxane).
  • Further coated zinc oxide particles are commercially available from BASF SE as Z-COTE HP1 (98 wt% zinc oxide and 2 wt% triethoxy- caprylylsilane) or Z-COTE MAX (96-99 wt% zinc oxide and 1-4 wt% dimethoxydiphenylsilane / triethoxycaprylylsilane crosspolymer).
  • Z-COTE HP1 98 wt% zinc oxide and 2 wt% triethoxy- caprylylsilane
  • Z-COTE MAX 96-99 wt% zinc oxide and 1-4 wt% dimethoxydiphenylsilane / triethoxycaprylylsilane crosspolymer.
  • silicon containing polymer refers to synthetic polymeric compounds comprising silicon atoms, which are linked via oxygen atoms to polymers and wherein the residual valences of the silicon atoms are saturated by hydrogen and/or organic residues.
  • silicon containing polymers are
  • the coating of the metal oxide submicron particles comprises a silicon containing polymer and an inorganic oxide.
  • Suitable examples include, but are not limited to coated titanium dioxide submicron particles, which were surface-treated with silica, alumina and silicone (such as the products "Microtitanium Dioxide MT 100 SAS", “Microtitanium Dioxide MT 600 SAS” and “Microtitanium Dioxide MT 500 SAS” from the company Tayca) or alumina and silicone (such as the product "UVT-M262" from the company Kemira).
  • coated titanium dioxide submicron particles are available from BASF SE as T-Lite SF (titanium dioxide coated with aluminum hydroxide and dimethicone/methicone copolymer; titanium dioxide content 79-89 wt%), T-Lite SF-S (titanium dioxide coated with hydrated silica, dimethicone/methicone copolymer and aluminum hydroxide; titanium dioxide content 73-83 wt%) or T-lite MAX (titanium dioxide coated with dimethoxydiphenylsilane/triethoxycaprylylsilane crosspolymer, hydrated silica and aluminum hydroxide; titanium dioxide content 69-73 wt%).
  • T-Lite SF titanium dioxide coated with aluminum hydroxide and dimethicone/methicone copolymer
  • T-Lite SF-S titanium dioxide coated with hydrated silica, dimethicone/methicone copolymer and aluminum hydroxide
  • Each of the aforementioned T-Lite products has a crystallite size of 14-16 nm, an average particle length of 50 nm and width of 10 nm.
  • Further examples of coated zinc oxide submicron particles are those sold under the name "Daitopersion ZN-30" and “Daitopersion ZN-50", by the company Daito (dispersions in cyclopolymethylsiloxane /oxyethylenated polydime-thylsiloxane, containing 30% or 50% of nanozinc oxides coated with silica and polymethylhydrogenosiloxane), or those sold under the name "Fuji ZNO-SMS-10", by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane).
  • the coating of the metal oxide submicron particles comprises an inorganic oxide and a fatty acid or salts thereof.
  • suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with alumina and aluminium stearate (such as the product "Microtitanium Dioxide MT 100 T” from the company Tayca), alumina and aluminum laurate (such as the product "Microtitanium Dioxide MT 100 S” from the company Tayca), iron oxides and iron stearate (such as the product "Microtitanium Dioxide MT 100 F", from the company Tayca), alumina and stearic acid (such as the product "UVT-M160", from the company Kemira; or Solaveil XT-300, XT-100 or XT-40W, from Croda).
  • the submicron sized metal oxides of the present invention include titanium dioxide (amorphous or crystallized in rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide. Preferred metal oxides are T1O2 and ZnO. In an embodiment, the submicron sized metal oxide is T1O2. In another embodiment, the submicron sized metal oxide is ZnO.
  • the hydrophilic submicron metal oxides are easily dispersed into the aqueous phase of an emulsion.
  • the hydrophobic submicron metal oxides are dispersible in the oil phase of an emulsion.
  • hydrophilic surface active T1O2 particles include Eusolex ® T-ECO, Eusolex ® T-AVO and Eusolex ® T-Aqua (Merck); STR-100W (Kowa); and TTO-55B and TTO-55A (Ishihara Sangyo Kaisha, Ltd).
  • hydrophobic surface active T1O2 include SolaveilTM AT-300 and SolaveilTM CT-300 (Croda); and Eusolex ® T and Eusolex ® OLED (Merck).
  • a photodegradable active ingredient such as an isothiazoline insecticide as described supra, formulated for example in an oil-in-water emulsion, can be photochemically stabilized when encircled by a polymer matrix formed by a film of submicron particles encapsulating the oil droplet surface, with the submicron particles being hydrophilic- and hydrophobic-coated metal oxides.
  • the aforementioned film forming polymeric matrix capsules may have surface activity and behave as an emulsifier and a stabilizer for such an agrochemical composition.
  • agrochemical composition may related to any customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • the present invention particularly relates to emulsifiable concentrates (e.g. EC) and emulsions (e.g. EW, EO, ES, ME).
  • agrochemical composition is emulsion.
  • the agrochemical compositions may be prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • the oil-in-water emulsion or agrochemical composition can furthermore comprise auxiliaries conventionally used for crop protection products. Suitable auxiliaries are solvents, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetrants, protective colloids, stickers, thickeners, bactericides, antifreeze agents, antifoam agents, colorants, adhesives and binders.
  • solvents examples are water-immiscible solvents and water-soluble solvents.
  • the water- immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l.
  • the water-soluble solvent may be soluble in water at 20 °C more than 50 g/l, preferably more than 100 g/l.
  • Suitable solvents are organic solvents such as mineral oil fractions with medium to high boiling point, for example kerosene, diesel oil; oils of vegetable or animal origin; aliphatic and cyclic hydrocarbons, for example toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes;
  • alcohols for example ethanol, propanol, butanol, cyclohexanol; glycols; ketones, for example cyclohexanone; esters, for example carbonates, fatty acid esters; fatty acids; phosphonates;
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetrant, protective colloid, or auxiliary. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.), the entire contents of which are incorporated by reference.
  • the solvent is a water-immiscible solvent.
  • the water-immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l.
  • the concentration of the water-immiscible solvent in the agrochemical composition is from 10 to 90 wt%, preferably from 20 to 60 wt% and most preferably from 30 to 60 wt%.
  • the agrochemical composition of the present invention may comprise a solvent selected from hydrocarbons.
  • the hydrocarbon may be used to dissolve the water-insoluble pesticide for the oil- in-water emulsion of the present invention.
  • Hydrocarbons can include aromatic petroleum derivatives (aromatic hydrocarbons) with a solubility in water ⁇ 0.1 % (w/w) and a distillation range from 130 °C to 300 °C (commercially available under the following brand names: SolvessoTM 100, SolvessoTM 150, SolvessoTM 200, SolvessoTM 150ND, SolvessoTM 200ND, Aromatic 150, Aromatic 200, Hydrosol A 200, Hydrosol A 230/270, CaromaxTM 20, CaromaxTM 28, Aromat K 150, Aromat K 200, ShellsolTM A 150, ShellsolTM A 100, Fin FAS-TX 150, Fin FAS-TX 200).
  • the hydrocarbon is an aromatic hydrocarbon.
  • the composition may comprise further solvents (e.g. the organic solvents listed below) in addition to the hydrocarbon.
  • the composition can comprise not more than 30% by weight, not more than 10% by weight, or not more than 1 % by weight of the further solvents.
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • phosphates are phosphate esters.
  • carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • anionic surfactants include sulfates and sulfonates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Nonionic surfactants can include alkoxylates. Nonionic surfactants such as alkoxylates may also be employed as adjuvants.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases.
  • Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers.
  • Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds which have negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol.
  • Suitable antifoam agents are silicones, long-chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • examples are inorganic colorants (e.g. iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants).
  • the composition may comprise at least one anionic surfactant.
  • the composition comprises not less than 0.5% by weight of anionic surfactants, not less than 2% by weight, or not less than 3% by weight.
  • the composition can comprise not more than 30% by weight, not more than 15% by weight, or not more than 10% by weight of anionic surfactants.
  • the composition preferably comprises at least one nonionic surfactant (such as alkoxylates).
  • the composition can comprise not less than 1 % by weight, not less than 5% by weight, or not less than 10% by weight of nonionic surfactants.
  • the composition can comprise not more than 65% by weight, not more than 45% by weight, or not more than 35% by weight of nonionic surfactants.
  • the composition comprises a nonionic surfactant and an anionic surfactant.
  • the invention furthermore relates to a process for the preparation of the agrochemical composition according to the invention by mixing the water-insoluble pesticide and submicron hydrophilic- and hydrophobic-coated metal oxide particles.
  • the water-insoluble pesticide is an isothiazoline insecticide as described herein.
  • the invention furthermore relates to an emulsion obtainable (preferably obtained) by mixing water, the water-insoluble pesticide, and submicron hydrophilic- and hydrophobic-coated metal oxide particles according to the invention.
  • the emulsion normally arises upon shear mixing.
  • the mixing ratio of water to composition can be in the range of from 1000 to 1 up to 1 to 1 , preferably 200 to 1 up to 3 to 1.
  • the invention furthermore relates to a method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the agrochemical composition according to the invention is allowed to act on the respective pests, their environment or on the crop plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on the crop plants and/or their environment.
  • the therapeutic treatment of humans and animals is excluded from the method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants.
  • the application rates of the pesticides amount to from 0.001 to 2 kg per ha, from 0.005 to 2 kg per ha, from 0.05 to 0.9 kg per ha, or from 0.1 to 0.75 kg per ha, depending on the nature of the desired effect.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, from 1 to 100 g, or from 5 to 100 g, per 100 kg of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, or 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizers or micronutrients may be added to the emulsion in the form of a premix or optionally only shortly before use (tank mix).
  • These agents can be admixed to the compositions according to the invention at a weight ratio of from 1 : 100 to 100:1 , or from 1 :10 to 10: 1.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, or 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • compositions are highly stable; that the pesticide does not precipitate, cream or crystallize in the composition; that the pesticide does not precipitate, cream or crystallize in the emulsion; that high pesticide concentrations in the composition can be employed; that the composition is capable of being stored over prolonged periods (e.g. 3 months to 3 years; that adjuvants can be included in the composition formulation; that the pesticide in the emulsion is photostable; that the pesticide exhibits a greater effect over time.
  • Hydrophilic Particles Rutile type titanium dioxide particles, post-treated with alumina, primary particle size 30-50 nm, titanium dioxide content 88-94 %, oil absorption 29-38 g/100 g, specific surface area 35-45 m2/g (BET method), commercially available as TT-55B from Ishihara Corp. USA.
  • Hydrophobic Particles titanium dioxide dispersion in carrier oil (caprylic/capric triglyceride) with polyhydroxystearic acid as dispersing agent, coated with alumina and stearic acid, commercially available as SolaveilTM AT-300 from Croda USA.
  • Solvent A Aromatic hydrocarbon solvent, initial boiling point about 230 °C; aromatic content above
  • Solvent B ⁇ , ⁇ -Dimethyl C8/C10 fatty acid amide, liquid, density about 0.88 g/cm 3 .
  • Surfactant A Ethoxylated castor oil, melting point about 32 °C, HLB 14-15 (Griffin).
  • Surfactant B Solution of calcium salt of dodecylbenzenesulfonic acid (60 wt%) in organic solvent, flash point 78 °C.
  • Isothiazoline 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl-N-(2- pyridylmethyl)benzamide.
  • Example 1 An isothiazoline oil-in-water emulsion B having the following composition was prepared (cf Table 1 ):
  • the pesticidal oil-in-water emulsion was prepared by the following procedure: 1 ) Isothiazoline and Hydrophobic Particles are added to Solvent A, stirred until dissolved / uniform (oil phase). 2) Hydrophilic Particles, Surfactant A, Propylene Glycol, Acticide MBS, Silicon Antifoamer were mixed with D.I. water until uniform (aqueous phase). 3) Poured oil phase into the above aqueous phase with agitation. 4) Homogenized the above mixture for 2 minutes at 7000 rpm using a
  • Formulations were diluted to the same concentration using D.I. water. 5 drops of 1 ⁇ I dilution deposited on glass plate. 2 glass plates per sample per time point. After application, glass plates were put in the UV chamber. 1 and 24 hours after application, glass plates were taken out of UV chamber and washed off with 10 ml water/MEOH at ratio of 50/50. Wash off liquid was analyzed for active ingredient (a.i.) concentration via HLPC/MS/MS. Active ingredient recovery was calculated as a percentage of a.i. applied.
  • Emulsifer Surfactant A 6.25
  • the pesticidal emulsifiable composition was prepared by the following procedure:
  • the glass plate testing result is summarized in following Table 3.
  • Photodegradation of the isothiazoline was reduced in emulsion B (cf Table 1 ) when compared to a conventional EC of Table 2.

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Abstract

Subject matter of the present invention relates to an agrochemical composition comprising a) a pesticide, and b) submicron hydrophilic-metal oxide particle and c) hydrophobic-coated metal oxide particles. The invention further relates to a process for the preparation of said composition;and to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or ontheir environment.

Description

Agrochemical composition hydrophilic and hydrophobic coated metal oxide submicron particles
BACKGROUND OF THE INVENTION
Many pesticides are sensitive to sunlight and as a result are capable of decomposing. The decomposition might take place during storage or after application to the environment. As a result, the pesticidal activity decreases, higher amounts of pesticides have to be applied, and the pesticides have to be applied in shorter intervals or applied more often. Agrochemical compositions generally comprise pesticides. Some pesticidal active ingredients (a.i.) are susceptible to ultraviolet radiation (UV) breakdown (e.g. photodegradation), which reduces the efficacy of the active ingredient. Some pesticidal active ingredients are also poorly water soluble. The disadvantage of the known agrochemical compositions is the poor pesticidal stability and the low pesticide concentration. An additional disadvantage is that water-insoluble, photodegradable pesticides can be unstable when exposed to light.
SUMMARY OF THE INVENTION
Subject matter of the present invention relates to an agrochemical composition comprising a) a pesticide,
b) submicron hydrophilic-coated metal oxide particles, and
c) submicron hydrophobic-coated metal oxide particles.
In an embodiment, the present invention relates to agrochemical compositions that are used to stabilize a photodegradable pesticidal active ingredient (a.i.). More specifically, this invention relates to an agrochemical aqueous emulsion, wherein the photodegradable active ingredient is dissolved in the oil phase, said oil phase is encircled by a polymer matrix formed by a film of submicron particles encapsulating the oil droplet surface, wherein the submicron particles are comprised of hydrophilic- and hydrophobic-coated metal oxide particles. The invention further relates to a process for the preparation of said composition; and to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment. The present invention comprises combinations of certain features with other additional features.
DETAILED DESCRIPTION OF THE INVENTION
It was an object of the present invention to provide an agrochemical composition which stabilizes pesticides which are sensitive to sunlight. Another object of the invention was to increase the stability of photodegradable pesticides in an agrochemical composition during storage and/or after application to the environment. The objects were achieved by the agrochemical composition according to the invention. Usually, an aqueous emulsion is taken to mean compositions which maintains an oil-in-water emulsion upon mixing with water (e.g. in a weight ratio of 1 part concentrate to 99 parts water). The emulsion usually forms under shear mixing. In various embodiments, the resulting emulsion may have an average oil droplet size around 1 - 3 pm, 0.5 to 10 pm or 0.1 to 50 pm. The average droplet size may be determined by laser diffraction, e.g. with a Malvern Mastersizer 2000.
The term pesticides refer to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators. Pesticides include fungicides, insecticides, herbicides and growth regulators. In one embodiment, pesticides are insecticides. Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in
Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London, the entire contents of which are hereby incorporated by reference. The following pesticides are suitable, by way of example (pesticides A) to K) are fungicides): A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin,
coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone; inhibitors of complex III at Q, site: cyazofamid, amisulbrom,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- 1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4- methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-ben- zodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate; inhibitors of complex II (e. g. carboxamides): benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-
3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3- dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-(1 ,1 ,3-trimethylindan- 4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1-methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)- 1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide; other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine^ nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-[re (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[re (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1 ,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine; Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine; Inhibitors of 3-keto reductase: fenhexamid;
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl; others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine; other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil; protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil; G protein inhibitors: quinoxyfen; G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)- but-2-yl) carbamic acid-(4-fluorophenyl) ester; compounds affecting cell membrane permeability and fatty acides: propamocarb, propamocarb-hydrochlorid; fatty acid amide hydrolase inhibitors: oxathiapiprolin;
H) Inhibitors with Multi-Site Action
inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide; guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3- c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defense inducers
acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, 2-[3,5-bis(difluoromethyl)-1 H- pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2- yl)piperidin-1-yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2- yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone, 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro- 1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2methoxy-acetic acid 6-tert-butyl- 8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole),
N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
L) Growth regulators
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6- dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
M) Herbicides
acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor; amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl; Bipyridyls: diquat, paraquat;
(thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; imidazolinones:
imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron,
metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3- yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron.tebuthiuron; other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho- sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin,
bencarbazone.benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr,
Drec slera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen- ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione,
sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4- fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2- yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro- phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy- phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino- 2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester.
P) Insecticides
organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos- methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfen vale rate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5- dimethyl-[1 ,3,5]triazinane; GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3- carbothioic acid amide; macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; METI II and III compounds:
acequinocyl, fluacyprim, hydramethylnon; Uncouplers: chlorfenapyr; oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; mixed function oxidase inhibitors: piperonyl butoxide; sodium channel blockers: indoxacarb, metaflumizone; ryanodine receptor inhibitors: chlorantraniliprole, cyantraniliprole, flubendiamide, N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro- 2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dichloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2- pyridyl)-5-(difluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-dibromo-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, pyrifluquinazon and 1 ,1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]- 1 ,3,4, 4a, 5, 6, 6a, 12, 12a, 12b-decahydro-12-hydroxy-4,6a, 12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)- 21-1,11 H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester.
Preferably, the pesticide is an isothiazoline insecticide of the formula I:
Figure imgf000008_0001
wherein
A is a group A1 , A2, A3 or A4;
wherein A1 is selected from the group consisting of -C(=NR6)R8, -S(0)nR9 and
-N(R5)R6;
A2 is a group of following formula:
Figure imgf000009_0001
wherein
# denotes the bond to the aromatic ring of formula (I);
W is selected from O and S;
Y is selected from hydrogen, -N(R5)R6 and -OR9;
A3 is a group of following formula:
Figure imgf000009_0002
wherein
# denotes the bond to the aromatic ring of formula (I);
A4 is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, or is a 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromonocyclic or heterobicyclic ring is optionally substituted with one or more substituents R ; B , B2 and B3 are each independently selected from the group consisting of N and CR2, with the proviso that at most two of B , B2 and B3 are N;
G , G2, G3 and G4 are each independently selected from the group consisting of N and CR4, with the proviso that at most two of G , G2, G3 and G4 are N;
R is selected from the group consisting of Ci-C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-CrC4-alkyl-, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl and -C(=0)OR15;
each R2 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the four last mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR 0aR 0 , phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R , and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10- membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heteromono- or heterobicyclic ring may be substituted by one or more radicals R ;
R3a, R3 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, -C02R3d, Ci-C3-alkyl, CrC3-haloalkyl, C2-C3-alkenyl, C2-C3-alkynyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, CrC3-alkylthio, CrC3-haloalkylthio, CrC3-alkylsulfonyl and Ci-C3-haloalkylsulfonyl; or
R3a and R3b together form a group =0, =C(R3c)2, =NOH or =NOCH3;
each R3c is independently selected from the group consisting of hydrogen, halogen, CH3 and CF3; R3d is selected from the group consisting of hydrogen, CrC6-alkyl and Ci-C3-alkyloxy-CrC3-alkyl-; each R4 is independently selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, -SCN, -SF5, Ci-C6-alkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C3-C8-cycloalkyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C2-C6-alkenyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8, C2-C6-alkynyl which may be partially or fully halogenated and/or may be substituted by one or more radicals R8,
-Si(R12)3, -OR9, -S(0)nR9, -NR 0aR 0 ,
phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R , and a 3-, 4-, 5-, 6- 7-, 8-, 9- or 10- membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S02, as ring members, where the heteromonocyclic or heterobicyclic ring may be substituted by one or more radicals R ;
each R5 is independently selected from the group consisting of hydrogen, Ci-Cio-alkyl, C3-C3- cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and
cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more substituents R8, and
-S(0)nR9,
each R6 is independently selected from the group consisting of hydrogen, cyano, Ci-Cio-alkyl, C3- Ce-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R8,
-OR9, -NR 0aR 0 , -S(0)nR9, -C(=O)NR10aN(R10a)R10b, -Si(R12)3, -C(=0)R8,
phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R , and
a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or maximally unsaturated heteromonocyclic or heterobicyclic ring containing 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and S02, as ring members, where the
heteromonocyclic or heterobicyclic ring may be substituted with one or more substituents R ; or R5 and R6, together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, where the ring may further contain 1 , 2, 3 or 4 heteroatoms or heteroatom-containing groups selected from O, S, N, SO, SO2, C=0 and C=S as ring members, wherein the heterocyclic ring may be substituted with 1 , 2, 3, 4 or 5 substituents independently selected from the group consisting of halogen, cyano, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-alkenyl, d-d-haloalkenyl, d-d-alkynyl, d-d- haloalkynyl, wherein the aliphatic or cycloaliphatic moieties in the twelve last-mentioned radicals may be substituted by one or more radicals R8, and phenyl which may be substituted with 1 , 2, 3, 4 or 5 substituents R ;
or R5 and R6 together form a group =C(R8)2, =S(0)m(R9)2, =NR10a or =NOR9;
R7a, R7b are each independently selected from the group consisting of hydrogen, halogen, cyano, d-d-alkyl, d-d-cycloalkyl, d-d-alkenyl and C2-C6-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted by one or more radicals R8;
each R8 is independently selected from the group consisting of cyano, azido, nitro, -SCN, -SF5, d- d-cycloalkyl, d-d-halocycloalkyl, where the cycloaliphatic moieties in the two last-mentioned radicals may be substituted by one or more radicals R 3;
-Si(R12)3, -OR9, -OSO2R9, -S(0)nR9, -N(R10a)R10b, -C(=O)N(R10a)R10b,
-C(=S)N(R10a)R10b, -C(=0)OR9,
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R 6, and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated
heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6,
or
two R8 present on the same carbon atom of an alkyl, alkenyl, alkynyl or cycloalkyl group together form a group =0, =C(R13)2; =S; =S(0)m(R15)2, =S(0)mR15N(R14a)R14b, =NR10a, =NOR9; or
=NN(R10a)R10b;
or
two radicals R8, together with the carbon atoms of an alkyl, alkenyl, alkynyl or cycloalkyl group which they are bonded to, form a 3-, 4-, 5-, 6-, 7- or 8-membered saturated or partially unsaturated carbocyclic or heterocyclic ring, where the heterocyclic ring comprises 1 , 2, 3 or 4 heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2, as ring members, and where the carbocyclic or heterocyclic ring is optionally substituted with one or more substituents R16; and
R8 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of d-d- alkyl, d-d-haloalkyl, d-d-alkenyl, d-d-haloalkenyl, d-d-alkynyl and d-d-haloalkynyl, where the aliphatic moieties in these six radicals may be substituted by one or more radicals R 3; and R8 in the groups -C(=NR6)R8, -C(=0)R8 and =C(R8)2 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, CrC6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, d- C6-alkynyl and C2-C6-haloalkynyl, where the aliphatic moieties in the six last-mentioned radicals may be substituted by one or more radicals R 3;
each R9 is independently selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, d- Ce-haloalkyl, d-d-cycloalkyl, C3-C8-cycloalkyl-CrC4-alkyl-, d-d-halocycloalkyl, d-d-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the nine last-mentioned radicals may be substituted by one or more radicals R 3,
-CrC6-alkyl-C(=0)OR15, -Ci-C6-alkyl-C(=0)N(R14a)R14b,
-CrC6-alkyl-C(=S)N(R14a)R14b, -CrC6-alkyl-C(=NR14)N(R14a)R14b,
-Si(R12)3, -S(0)nR15, -S(0)nN(R1 a)R1 b, -N(R10a)R10b, -N=C(R13)2, -C(=0)R13,
-C(=0)N(R1 a)R1 b, -C(=S)N(R1 a)R1 b, -C(=0)OR15,
phenyl, optionally substituted with one or more substituents R 6; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated
heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S,
NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6; and
R9 in the groups -S(0)nR9 and -OSO2R9 is additionally selected from the group consisting of d-d- alkoxy and Ci-C6-haloalkoxy;
R 0a, R 0 are selected independently from one another from the group consisting of hydrogen, d- Ce-alkyl, d-d-haloalkyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-alkenyl, d-d-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, where the aliphatic and cycloaliphatic moieties in the eight last- mentioned radicals may be substituted by one or more radicals R 3;
-CrC6-alkyl-C(=0)OR15, -CrC6-alkyl-C(=0)N(R1 a)R1 b, -d-d-alkyl-C(=S)N(R1 a)R1 b, -d-d-alkyl- C(=NR14)N(R14a)R14 , CrC6-alkoxy, CrC6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio,
-S(0)nR15, -S(0)nN(R1 a)R1 b, -C(=0)R13, -C(=0)OR15, -C(=0)N(R1 a)R1 b,
-C(=S)R13, -C(=S)SR15, -C(=S)N(R1 a)R1 b, -C(=NR1 )R13;
phenyl, optionally substituted with 1 , 2, 3 or 4, substituents R 6; and
a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated
heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S,
NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6;
or
R 0a and R 0 form together with the nitrogen atom they are bonded to a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain one or two heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, d-d- haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d-cycloalkyl, d-d-halocycloalkyl, d-Ce- alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R 6, and a 3-, 4-, 5-, 6,- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents R 6;
or R10a and R10b together form a group =C(R13)2, =S(0)m(R15)2, =S(0)mR15N(R14a)R14b, =NR14 or =NOR15;
R is independently selected from the group consisting of halogen, cyano, azido, nitro, -SCN, -SF5, Ci-Cio-alkyl, d-Ce-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the four last-mentioned aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or may be substituted with one or more radicals R8,
-OR9, -NR 0aR 0 , -S(0)nR9, -Si(R12)3;
phenyl, optionally substituted with 1 , 2, 3, 4, or 5 substituents selected independently from R 6; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated aromatic heterocyclic ring comprising 1 , 2, 3 or 4 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents selected independently from R 6;
or two R present on the same ring carbon atom of an unsaturated or partially unsaturated heterocyclic ring may together form a group =0, =C(R13)2; =S; =S(0)m(R 5)2; =S(0)mR 5N(R14a)R14 , =NR14, =NOR15, or =NN(R14a)R14 ;
or two R bound on adjacent ring atoms form together with the ring atoms to which they are bound a saturated 3-, 4-, 5-, 6-, 7-, 8- or 9-membered ring, wherein the ring may contain 1 or 2
heteroatoms or heteroatom groups selected from O, S, N, NR 4, NO, SO and SO2 and/or 1 or 2 groups selected from C=0, C=S and C=NR14 as ring members, and wherein the ring may be substituted by one or more radicals selected from the group consisting of halogen, CrC6-alkyl, Ci- Ce-haloalkyl, d-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, d-Ce-cycloalkyl, C3-C8-halocycloalkyl, d-Ce-alkenyl, d-Ce-haloalkenyl, d-Ce-alkynyl, d-Ce-haloalkynyl, phenyl which may be substituted by 1 , 2, 3, 4 or 5 radicals R 6, and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by one or more radicals R 6;
each R 2 is independently selected from the group consisting of hydrogen, halogen, CrC6-alkyl, Ci- Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, d-Ce-alkenyl, d-Ce-haloalkenyl, d-Ce-alkynyl, C2- Ce-haloalkynyl, d-Ce-cycloalkyl, d-Ce-halocycloalkyl, CrCe-alkoxy-d-Ce-alkyl, d-Ce-haloalkoxy- d-Ce-alkyl, and
phenyl, optionally substituted with 1 , 2, 3, 4, or 5 substituents R 6;
each R 3 is independently selected from the group consisting of cyano, nitro,
-OH, -SH, -SCN, -SF5, d-Ce-alkoxy, Ci-Ce-haloalkoxy, Ci-Ce-alkylthio, Ci-Ce-haloalkylthio, Ci-C6- alkylsulfinyl, CrC6-haloalkylsulfinyl, CrC6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy and oxo;
phenyl, benzyl, phenoxy, where the phenyl moiety in the three last-mentioned radicals may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents R 6; and a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may be substituted by 1 , 2 or 3 substituents R 6;
or
two R 3 present on the same carbon atom of an alkyl, alkenyl, alkynyl or cycloalkyl group may together be =0, =CH(CrC4-alkyl), =C(CrC4-alkyl)Ci-C4-alkyl, =N(CrC6-alkyl) or =NO(CrC6-alkyl); and
R 3 as a substituent on a cycloalkyl ring is additionally selected from the group consisting of C1-C6- alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from CN, C3-C4-cycloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy and oxo;
and
R13 in the groups =C(R13)2, -N=C(R13)2, -C(=0)R13, -C(=S)R13 and
-C(=NR 4)R13 is additionally selected from the group consisting of hydrogen, halogen, Ci-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from CN, C3- C4-cycloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy and oxo;
each R 4 is independently selected from the group consisting of hydrogen, cyano, Ci-C6-alkoxy, Ci- C6-haloalkoxy, Ci-C6-alkylthio, CrC6-haloalkylthio, CrC6-alkylsulfinyl, CrC6-haloalkylsulfinyl, Cr C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from CN , Ci-C4-alkoxy, CrC4-haloalkoxy, CrC4-alkylthio, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4- cycloalkyl which may be substituted by 1 or 2 substituents selected from halogen and cyano; and oxo;
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, Ci-C4-alkylthio, C1-C4- alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C4-cycloalkyl, C3-C4-cycloalkyl-Ci-C4-alkyl-, where the cycloalkyl moiety in the two last-mentioned radicals may be substituted by 1 or 2 substituents selected from halogen and cyano; and oxo;
phenyl, benzyl, pyridyl, phenoxy, wherein the cyclic moieties in the four last-mentioned radicals may be unsubstituted and/or carry 1 , 2 or 3 substituents selected from halogen, Ci-C6-alkyl, C1-C6- haloalkyl, d-Ce-alkoxy, d-Ce-haloalkoxy and (CrC6-alkoxy)carbonyl; and a 3-, 4-, 5- or 6- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring comprising 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring is optionally substituted with one or more substituents R 6;
R 4a and R 4 , independently of each other, have one of the meanings given for R 4; or
R 4a and R 4 , together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and d-d- haloalkoxy;
or
R 4a and R 4 or R 4 and R 4, together with the nitrogen atoms to which they are bound in the group -C(=NR14)N(R14a)R14b, form a 3-, 4-, 5-, 6- or 7-membered partially unsaturated or maximally unsaturated heterocyclic ring, wherein the heterocyclic ring may additionally contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2, as ring members, where the heterocyclic ring optionally carries one or more substituents selected from halogen, d- C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
each R 5 is independently selected from the group consisting of hydrogen, cyano, trimethylsilyl, triethylsilyl, ferf-butyldimethylsilyl,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C3- C4-cycloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4-alkylsulfinyl, d-d- alkylsulfonyl and oxo;
C3-C8-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C4-alkyl, C3-C4-cycloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, d-d- alkylthio, C 1 -C4-al ky Isu If i nyl , Ci-C4-alkylsulfonyl and oxo;
phenyl, benzyl, pyridyl and phenoxy, wherein the four last-mentioned radicals may be
unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from d-d- alkyl, d-d-haloalkyl, d-d-alkoxy, d-d-haloalkoxy and (Ci-C6-alkoxy)carbonyl;
each R 6 is independently selected from the group consisting of halogen, nitro, cyano, -OH, -SH, d-Ce-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d-alkylsulfinyl, d-d- haloalkylsulfinyl, d-C6-alkylsulfonyl, d-C6-haloalkylsulfonyl, trimethylsilyl, triethylsilyl, ferf- butyldimethylsilyl;
d-d-alkyl, d-d-alkenyl, d-d-alkynyl, wherein the three last-mentioned aliphatic radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from d- d-cycloalkyl, d-d-alkoxy, d-d-haloalkoxy and oxo;
d-d-cycloalkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from d-d-alkyl, d-d-cycloalkyl, d-d-alkoxy, d-d-haloalkoxy and oxo; phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from d-d- alkyl, d-Ce-haloalkyl, d-d-alkoxy, d-d-haloalkoxy and (d-C6-alkoxy)carbonyl;
or
two R 6 present together on the same atom of an unsaturated or partially unsaturated ring may be =0, =S, =N(d-C6-alkyl), =NO(d-C6-alkyl), =CH(d-C4-alkyl) or =C(d-d-alkyl)d-d-alkyl;
or
two R 6 on two adjacent carbon atoms form together with the carbon atoms they are bonded to a 4-
, 5-, 6-, 7- or 8-membered saturated, partially unsaturated or maximally unsaturated ring, wherein the ring may contain 1 or 2 heteroatoms or heteroatom groups selected from N, O, S, NO, SO and
SO2, as ring members, and wherein the ring optionally carries one or more substituents selected from halogen, d-d-haloalkyl, d-d-alkoxy and d-d-haloalkoxy;
each n is independently 0, 1 or 2; and
each m is independently 0 or 1 ;
and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.
In one form, the isothiazoline insecticide is a compound of formula 1.1 :
Figure imgf000016_0001
wherein
R is d-d-haloalkyl and is in particular CF3;
R2a, R2 and R2c are selected independently from one another from hydrogen, halogen and d-d- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
R4 is selected from hydrogen, halogen, cyano, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, C1-C4- haloalkoxy, d-d-alkylthio and d-d-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH3, CF3, OCH3, OCF2H, OCF3, SCH3, SCF2H, and SCF3;
R 0a and R 4a independently from each other are selected from hydrogen, Ci-d-alkyl, d-d- haloalkyl, preferably from hydrogen and CH3;
R 4 is selected from hydrogen, d-d-alkyl, d-d-haloalkyl, d-d-alkenyl, d-d-haloalkenyl, d- d-alkynyl, d-d-haloalkynyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-cycloalkyl-d-d-alkyl-, where the cycloalkyl moieties in the three last-mentioned groups may be substituted by a cyano group; Ci-d-alkyl substituted with a cyano group, Ci-d-alkoxy, Ci-d-haloalkoxy, phenyl which is optionally substituted with 1 , 2, 3 or 4, substituents each independently selected from the group consisting of halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-alkylthio, Ci-C4-haloalkylthio, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl; and a heteromonocyclic ring selected from rings of formulae D-1 to D-181
Figure imgf000017_0001
D-1 D-2 D-3 D-4 D-5
Figure imgf000017_0002
D- D-7 D-8 D-9 D-10
Figure imgf000017_0003
D-1 1 D-12 D-13 D-14
Figure imgf000017_0004
D-20 -21 D-22 D-23 D-24
Figure imgf000017_0005
D-30 D-31 D-32 D-33 D-34
Figure imgf000018_0001
D-40 D-41 D-42 D-43 D-44
Figure imgf000018_0002
D-45 D-46 D-47 D-48 D-49
Figure imgf000018_0003
D-50 D-51 D-52 D-53 D-54
Figure imgf000018_0004
D-65 D-66 D-67 D-68 D-69
Figure imgf000018_0005
Figure imgf000019_0001
Figure imgf000020_0001
D-110 D-111 D-112 D-113 D-114
Figure imgf000020_0002
D-115 D-116 D-117 D-118 D-119
Figure imgf000020_0003
D-120 D-121 D-122 D-123 D-124
Figure imgf000020_0004
D-125 D-126 D-127 D-128 D-129
Figure imgf000020_0005
D-130 D-131 D-132 D-133 D-134
Figure imgf000020_0006
D-135 D-136 D-137 D-138 D-139
Figure imgf000020_0007
D-140 D-141 D-142 D-143 D-144
Figure imgf000021_0001
D-145 D-147 D-148 D-149
Figure imgf000021_0002
D-155 D-156 D-157 D-158 D-159
Figure imgf000021_0003
D-160 D-161 D-162 D-163 D-164
Figure imgf000021_0004
D-175 D-176 D-177 D-178 D-179
Figure imgf000022_0001
D-180 D-181
wherein
k is 0, 1 , 2 or 3;
n is 0, 1 or 2; and
each R is independently selected from the group consisting of halogen, cyano, nitro, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, CrC4-haloalkoxy, CrC4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkylsulfinyl, CrC4-haloalkylsulfinyl, CrC4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4-haloalkynyl, C1-C4- alkylcarbonyl, Ci-C4-alkylaminocarbonyl, or
two R present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S.
Thus, the present invention relates to agrochemical compositions comprising an isothiazoline insecticide of formula 1.1 and the submicron particles b) and c) as defined herein below. In another form, the isothiazoline insecticide is a compound of formula I.2:
Figure imgf000022_0002
wherein
R is Ci-C4-haloalkyl and is in particular CF3;
R2a, R2 and R2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
R4 is selected from hydrogen, halogen, cyano, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH3, and CF3;
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, -CH2-CN and Ci-C6-alkoxy- methyl-, and preferably from hydrogen and CrC4-alkyl; and
R6 is selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C4-alkyl which carries one radical R8, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl which may be substituted by 1 to 4 substituents selected from halogen, cyano; N(R 0a)R 0 , -CH=NOR9; phenyl which may be substituted with 1 , 2, 3, 4, or 5 substituents R , and a heteromonocyclic ring selected from rings of formulae D-1 to D-181 as defined above; R8 is selected from hydrogen, OH, CN, Cs-Cs-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more cyano group; Ci-C6-alkoxy, Ci-C6-alkylthio, CrC6-alkylsulfinyl, CrC6-alkylsulfonyl, wherein the four last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more substituents selected from cyano, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl;-C(=0)N(R14a)R14b;
phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R ; and a heteromonocyclic ring selected from rings of formulae D-1 to D-181 as defined above;
R9 is selected from hydrogen, CrC6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more CN;
R 0a is selected from the group consisting of hydrogen and Ci-C6-alkyl;
R 0 is selected from the group consisting of hydrogen, C(=0)N(R 4a)R 4 ; phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R ; and a heteromonocyclic ring selected from rings of formulae D-1 to D-181 as defined above;
each R is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4-haloalkylthio, Ci-C4-alkylsulfinyl, CrC4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl, CrC4-alkylcarbonyl, Ci-C4-alkylaminocarbonyl; or
two R present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S;
each R 4a is selected from the group consisting of hydrogen and Ci-C6-alkyl;
each R14b is selected from the group consisting of hydrogen, d-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkylmethyl, C2-C4-alkynyl, C2-C4-alkenyl, Ci-C4-alkoxy, wherein the six last-mentioned radicals may be partially or fully halogenated and/or may be substituted with one cyano group.
[001 ] Thus, the present invention relates to agrochemical compositions comprising a) an
isothiazoline insecticide of formula 1.2, and b) submicron particles as defined herein below.
[002] In yet another form, the isothiazoline insecticide is a compound of formula 1.2a:
Figure imgf000023_0001
wherein
R is Ci-C4-haloalkyl and is in particular CF3; R2a, R2 and R2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
R4 is selected from hydrogen, halogen, cyano, CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH3, and CF3;
R5 is selected from hydrogen, Ci-C6-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, CH2-CN and Ci-C6-alkoxy- methyl-, and preferably from hydrogen and CrC4-alkyl; and
R6a is selected from -X-R6b and -N(R5a)R6c; wherein
X is selected from -C(Ra)2-, -C(Ra)2-C(Ra)2-,
-C(Ra)2-C(=O)-NR10a-C(Ra)2-, -C(Ra)2S(0)n-C(Ra)2-,
-C(Ra)2-C(Ra)2-S(0)n-C(Ra)2-, -C(Ra)2-0-C(Ra)2-, and
-C(Ra)2-C(Ra)2-0-C(Ra)2-, and preferably from -C(Ra)2-,
-C(Ra)2-C(=0)-NH-C(Ra)2-, -C(Ra)2-C(Ra)2-S(0)2-C(Ra)2-, and
-C(Ra)2-C(Ra)2-0-C(Ra)2-, wherein
n is 0, 1 or 2, and
each Ra is independently selected from the group consisting of hydrogen, halogen, Ci-C3-alkyl, and CrC3-haloalkyl and is preferably hydrogen;
R5a is selected from hydrogen, and Ci-C6-alkyl, and is preferably hydrogen;
R6 is selected from the group consisting of C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R8;
R6c is -C(=0)N(R14a)R14b
R8 is selected from, cyano, Ci-C6-alkoxy, CrC6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci- C6-alkylsulfinyl, CrC6-haloalkylsulfinyl, Ci-C6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, - C(=0)N(R14a)R14 ;
each R 4a is selected from the group consisting of hydrogen and Ci-C6-alkyl;
each R 4 is selected from the group consisting of hydrogen, d-Ce-alkyl, Cs-Ce-cycloalkyl, C3-C6- cycloalkylmethyl, C2-C4-alkynyl, C2-C4-alkenyl, Ci-C4-alkoxy, wherein the six last-mentioned radicals may be partially or fully halogenated and/or may be substituted with one cyano group; where in case that R5 is hydrogen, R6a is further selected from hydrogen, 1-cyanocyclopropyl, 1 - cyanocyclobutyl and 1-cyanocyclopentyl.
Thus, the present invention relates to agrochemical compositions comprising a) an isothiazoline insecticide of formula 1.2a, and b) submicron particles as defined herein below.
In another form, the isothiazoline insecticide is a compound of formula I.3:
Figure imgf000025_0001
wherein
R is CrC4-haloalkyl and is in particular CF3;
R2a, R2b and R2c are selected independently from one another from hydrogen, halogen and C1-C2- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
R4 is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkylthio, and preferably from hydrogen, F, CI, Br, CH3, CF3, OCH3, OCF2H , OCF3, SCH3, SCF2H, and SCF3;
R5 is selected from hydrogen, Ci-C4-alkyl, C2-C3-alkynyl, -CH2-CN and Ci-C6-alkoxy-methyl-, and preferably from hydrogen and Ci-C4-alkyl;
R7 is hydrogen or methyl;
R8 is selected from the group consisting of hydrogen, d-Ce-alkyl, Cs-Ce-cycloalkyl, C3-Ce-alkenyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more substituents R 3; C3-C8- alkynyl, -N(R10a)R10b,-C(=O)N(R14a)R14b, -CH=NOR9; phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R ; and a heterocyclic ring selected from rings of formulae D-1 to D-181 as defined above;
R9 is selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, wherein the three last-mentioned radicals may be partially or fully halogenated and/or may be substituted by one or more cyano group;
R 0a is selected from the group consisting of hydrogen and Ci-C6-alkyl;
R 0 is selected from the group consisting of hydrogen, Ci-C6-alkyl, CrC6-cycloalkyl, wherein the two last-mentioned radicals may be partially or fully halogenated and/or are optionally substituted by one cyano group; -C(=0)N(R14a)R14 ; phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R ; and a heteromonocyclic ring selected from rings of formulae D-1 to D-181 as defined above;
each R is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-C4-alkyl, CrC4-haloalkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, CrC4-haloalkylthio, Ci-C4-alkylsulfinyl, CrC4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C3-C6- cycloalkyl, Cs-Ce-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl and C2-C4- haloalkynyl, CrC4-alkylcarbonyl, Ci-C4-alkylaminocarbonyl; or
two R present on the same carbon atom of a saturated heterocyclic ring may form together =0 or =S; R 3 is selected from cyano, Ci-C6-alkoxy, CrC6-haloalkoxy, CrC6-alkylthio, Ci-C6-haloalkylthio, d- C6-alkylsulfinyl, CrC6-haloalkylsulfinyl, CrC6-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, - C(=0)N(R14a)R14b, phenyl, optionally substituted with 1 , 2, 3, 4 or 5 substituents R11 and a heterocyclic ring selected from rings of formulae D-1 to D-181 as defined above; and is preferably selected from d-d-alkoxy, d-d-haloalkoxy, d-d-alkylthio, d-d-haloalkylthio, d-d- alkylsulfonyl and Ci-C6-haloalkylsulfonyl;
each R 4a is selected from the group consisting of hydrogen and d-d-alkyl; and
each R 4b is selected from the group consisting of hydrogen, d-d-alkyl, d-d-alkynyl, d-d- alkenyl, -CH2-CN, d-d-haloalkyl, d-d-cycloalkyl, d-d-halocycloalkyl, d-d-alkoxy and d-d- haloalkoxy, d-d-cycloalkylmethyl.
Thus, the present invention relates to agrochemical compositions comprising a) an isothiazoline insecticide of formula 1.3, and b) submicron particles as defined herein below.
In another form, the isothiazoline insecticide is a compound of formula I.4:
Figure imgf000026_0001
wherein
R is d-d-haloalkyl and is in particular CF3;
R2a, R2b and R2c are selected independently from one another from hydrogen, halogen and d-d- haloalkyl, preferably from hydrogen, F, CI, Br and CF3;
R4 is selected from hydrogen, halogen, cyano, d-d-alkyl, d-d-haloalkyl, d-d-alkoxy, d-d- haloalkoxy, d-d-alkylthio and d-d-haloalkylthio; and
A is A4 and selected from rings of formulae D-1 to D-181 as defined above, preferably selected from D-59, D-65 and D-66 and in particular D-59.
In various embodiments, the composition can comprise at least 0.1 % by weight, at least 20% by weight, at least 35% by weight, or at least 45% by weight of pesticide (e.g. the isothiazoline insecticide of formula I). In other embodiments, the composition can comprise not more than 80% by weight, not more than 70% by weight, or not more than 60% by weight of the pesticide(e.g. the isothiazoline insecticide). The pesticide is usually water-insoluble. Usually, it is soluble in water to not more than 1 g/l, preferably not more than 200 mg/l and in particular to not more than 50 mg/l at 25°C. Examples of water-insoluble pesticides include isothiazolines as described herein. Using simple preliminary experiments, the skilled worker can select a pesticide with a suitable water-solubility from the above pesticide list. In various embodiments, the pesticide can have a melting point of more than 50°C, more than 70°C, or more than 90°C. The pesticide can be present in the composition in dissolved form. Using simple preliminary experiments, the skilled worker can select, from the above pesticide list, a pesticide with a suitable solubility.
In various embodiments, the composition may comprise from 0.1 to 70% by weight, from 10 to 50% by weight, or from 15 to 40% by weight, of pesticide, the basis being the total of all the pesticides present in the composition.
The submicron particles are metal oxides coated with hydrophilic or hydrophobic surface active agents wherein the particles have an average particle size of less than 1000 nm. In an
embodiment, the particle size is less than 300 nm. In another emobodiment, the particle size is less than 100 nm. In another form the average particle may be in the range from 1 nm to 1000 nm, preferably 1 nm to 100 nm, more preferably 10 nm to 20 nm, determined by means of X-ray diffraction spectroscopy. The agrochemical composition usually comprises 0.1 to 15 wt%, preferably 0.5 to 10 wt% and in particular 1 to 8 wt% of the submicron hydrophilic-coated metal oxide.
The agrochemical composition usually comprises 0.1 to 15 wt%, preferably 0.5 to 10 wt% and in particular 1 to 8 wt% of the submicron hydrophobic-coated metal oxide particles.
The agrochemical composition usually comprises 0.5 to 25 wt%, preferably 1 to 15 wt% and in particular 3 to 12 wt% of the sum of the submicron hydrophobic-coated metal oxide particles and the submicron hydrophilic-coated metal oxide particles.
Typically, the weight ratio of submicron hydrophilic-coated metal oxide particles and submicron hydrophobic-coated metal oxide particles is between 10:1 and 1 :10, preferably between 5:1 and 1 :5, and in particular 3: 1 and 1 :3. The use of titanium dioxide in agrochemistry is known: WO 2007/014826 discloses the use of a preparation containing a UV radiation absorbing metal oxide powder and a superspreading agent for the reduction of sunburn damage to useful plants. EP 1 139 763 B1 discloses the use of a particulate material such as titanium dioxide to reduce physiological disorders of a plant without diminishing photosynthesis. WO 2005/072680 discloses a particle of T1O2 or ZnO, which has been doped with one or more other elements such that the concentration of dopant in a surface of the particle is greater than that at a core of the particle. Although a positive effect of titanium dioxide on plants was described, a severe disadvantage of titanium dioxide is known: Topalov et al. Water Research 1999, 33:1371 -1376 disclose the photocatalytic activity of titanium dioxide towards the decomposition of the fungicide metalaxyl. Kuer and Nunez, Pest Management Science, 2007, 63:491-494, disclose the degradation of nitrogen heterocycles, the basic structural units of a large number of commercial herbicides and fungicides, using titanium dioxide as photocatalyst.
JP2004323501 discloses that titanium dioxide is disclosed as a photocatalyst for decomposing residual agrochemicals used for the agricultural products. Thus, the photocatalytic activity of titanium dioxide would contraindicate its use with pesticides which are susceptible to light.
Surprisingly, the inventors have found that submicron metal oxides, including titanium dioxide (ΤΊΟ2), can help stabilize pesticides sensitive to UV degradation. Hydrophilic- and hydrophobic- coated submicron metal oxides are of particular advantage.
The term "coated" means, that the metal oxide submicron particles have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (e.g. titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, inorganic oxides, silicon oxides, metal oxides, sodium hexametaphosphate, alumina or glycerol. Such a surface treatment results in a coating of the metal oxide submicron particle.
Submicron hydrophilic-coated metal oxide submicron particles may be selected from metal oxides submicron particles coated with inorganic oxides. In an embodiment, the inorganic oxide is substantially free of fatty acids. In another embodiment, the inorganic oxide is substantially free of silicon or silicon polymers. The term "substantially free" refers to coatings which contain less than 1 % of compounds which are not inorganic oxides. In an embodiment, "substantially free" refers to coatings which contain less than 0.5% of compounds which are not inorganic oxides. In another embodiment, "substantially free" refers to coatings which contain less than 0.1 % of compounds which are not inorganic oxides.
In an embodiment, the coating of the metal oxide submicron particles comprises at least one inorganic oxide. The term "inorganic oxide" refers to oxides and hydroxides of inorganic elements, such as of silicon (e.g. silica Si02), aluminum (e.g. alumina AI203, or aluminum hydroxide
AI(OH)3), zirconium or iron, preferably aluminum and silicon. Preferred inorganic oxides are alumina, aluminum hydroxide and silica, in particular alumina. Preferably, the metal oxide submicron particles comprise one inorganic oxide. Suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with silica and alumina (such as the products "Micro-titanium Dioxide MT 500 SA" and "Microtitanium dioxide MT 100 SA" from the company Tayca, and the products "Tioveil Fin", "Tioveil OP", "Tioveil MOTG" and "Tioveil IPM" from the company Tioxide). In a preferred form suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with alumina (such as TTO-55(B) from Ishihara Corp. USA).
Submicron hydrophobic-coated metal oxide particles may be selected from metal oxides coated with:
a silicon containing polymer;
silicon containing polymer and an inorganic oxide; or
inorganic oxide and a fatty acid or salts thereof.
Preferably, the submicron hydrophobic-coated metal oxide particles may be selected from metal oxides coated with inorganic oxide and a fatty acid or salts thereof. In another embodiment, the coating of the metal oxide submicron particles comprises a silicon containing polymer. The coating may comprise at least one silicon containing polymer. Preferably, it comprises one silicon containing polymer. Suitable examples include, but are not limited to titanium dioxides submicron particles treated with octyltrimethylsilane (such as "T 805", by the company Degussa), with a polydimethylsiloxane (such as the product sold under the trade name "70250 Cardre UF Ti02SI3", by the company Cardre), with a polydimethylhydrogenosiloxane (such as the product sold under the trade name "Microtitanium Dioxide USP Grade Hydrophobic", by the company Color Techniques). Further examples are those of coated zinc oxide submicron particles, which are sold under the name "Zinc Oxide CS-5", by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane), "SPD-ZI", by the company Shin-Etsu (ZnO coated with silicone- grafted acrylic polymer, dispersed in cyclodimethylsiloxane). Further coated zinc oxide particles are commercially available from BASF SE as Z-COTE HP1 (98 wt% zinc oxide and 2 wt% triethoxy- caprylylsilane) or Z-COTE MAX (96-99 wt% zinc oxide and 1-4 wt% dimethoxydiphenylsilane / triethoxycaprylylsilane crosspolymer). The term "silicon containing polymer" refers to synthetic polymeric compounds comprising silicon atoms, which are linked via oxygen atoms to polymers and wherein the residual valences of the silicon atoms are saturated by hydrogen and/or organic residues. Examples of silicon containing polymers are silicones, such as methicone or a copolymer of methicone and dimethicone.
In one embodiment, the coating of the metal oxide submicron particles comprises a silicon containing polymer and an inorganic oxide. Suitable examples include, but are not limited to coated titanium dioxide submicron particles, which were surface-treated with silica, alumina and silicone (such as the products "Microtitanium Dioxide MT 100 SAS", "Microtitanium Dioxide MT 600 SAS" and "Microtitanium Dioxide MT 500 SAS" from the company Tayca) or alumina and silicone (such as the product "UVT-M262" from the company Kemira). Further examples of coated titanium dioxide submicron particles are available from BASF SE as T-Lite SF (titanium dioxide coated with aluminum hydroxide and dimethicone/methicone copolymer; titanium dioxide content 79-89 wt%), T-Lite SF-S (titanium dioxide coated with hydrated silica, dimethicone/methicone copolymer and aluminum hydroxide; titanium dioxide content 73-83 wt%) or T-lite MAX (titanium dioxide coated with dimethoxydiphenylsilane/triethoxycaprylylsilane crosspolymer, hydrated silica and aluminum hydroxide; titanium dioxide content 69-73 wt%). Each of the aforementioned T-Lite products has a crystallite size of 14-16 nm, an average particle length of 50 nm and width of 10 nm. Further examples of coated zinc oxide submicron particles are those sold under the name "Daitopersion ZN-30" and "Daitopersion ZN-50", by the company Daito (dispersions in cyclopolymethylsiloxane /oxyethylenated polydime-thylsiloxane, containing 30% or 50% of nanozinc oxides coated with silica and polymethylhydrogenosiloxane), or those sold under the name "Fuji ZNO-SMS-10", by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane).
In another embodiment, the coating of the metal oxide submicron particles comprises an inorganic oxide and a fatty acid or salts thereof. Suitable examples include, but are not limited to titanium dioxide submicron particles, which were surface-treated with alumina and aluminium stearate (such as the product "Microtitanium Dioxide MT 100 T" from the company Tayca), alumina and aluminum laurate (such as the product "Microtitanium Dioxide MT 100 S" from the company Tayca), iron oxides and iron stearate (such as the product "Microtitanium Dioxide MT 100 F", from the company Tayca), alumina and stearic acid (such as the product "UVT-M160", from the company Kemira; or Solaveil XT-300, XT-100 or XT-40W, from Croda).
Usually, the metal oxide submicron particles are entirely covered by the coating. The submicron sized metal oxides of the present invention include titanium dioxide (amorphous or crystallized in rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide. Preferred metal oxides are T1O2 and ZnO. In an embodiment, the submicron sized metal oxide is T1O2. In another embodiment, the submicron sized metal oxide is ZnO. The hydrophilic submicron metal oxides are easily dispersed into the aqueous phase of an emulsion. The hydrophobic submicron metal oxides are dispersible in the oil phase of an emulsion. Commercially available hydrophilic surface active T1O2 particles include Eusolex® T-ECO, Eusolex® T-AVO and Eusolex® T-Aqua (Merck); STR-100W (Kowa); and TTO-55B and TTO-55A (Ishihara Sangyo Kaisha, Ltd). Commercially available hydrophobic surface active T1O2 include Solaveil™ AT-300 and Solaveil™ CT-300 (Croda); and Eusolex® T and Eusolex® OLED (Merck). Surprisingly, a photodegradable active ingredient, such as an isothiazoline insecticide as described supra, formulated for example in an oil-in-water emulsion, can be photochemically stabilized when encircled by a polymer matrix formed by a film of submicron particles encapsulating the oil droplet surface, with the submicron particles being hydrophilic- and hydrophobic-coated metal oxides. The aforementioned film forming polymeric matrix capsules may have surface activity and behave as an emulsifier and a stabilizer for such an agrochemical composition.
The term "agrochemical composition" may related to any customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. Thus, the present invention particularly relates to emulsifiable concentrates (e.g. EC) and emulsions (e.g. EW, EO, ES, ME). In another form agrochemical composition is emulsion. The agrochemical compositions may be prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The oil-in-water emulsion or agrochemical composition can furthermore comprise auxiliaries conventionally used for crop protection products. Suitable auxiliaries are solvents, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetrants, protective colloids, stickers, thickeners, bactericides, antifreeze agents, antifoam agents, colorants, adhesives and binders. Examples for solvents are water-immiscible solvents and water-soluble solvents. The water- immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l. The water-soluble solvent may be soluble in water at 20 °C more than 50 g/l, preferably more than 100 g/l.
Suitable solvents are organic solvents such as mineral oil fractions with medium to high boiling point, for example kerosene, diesel oil; oils of vegetable or animal origin; aliphatic and cyclic hydrocarbons, for example toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes;
alcohols, for example ethanol, propanol, butanol, cyclohexanol; glycols; ketones, for example cyclohexanone; esters, for example carbonates, fatty acid esters; fatty acids; phosphonates;
amines; amides, for example N-methylpyrrolidone; and their mixtures. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetrant, protective colloid, or auxiliary. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.), the entire contents of which are incorporated by reference.
Preferably, the solvent is a water-immiscible solvent. The water-immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l.
The concentration of the water-immiscible solvent in the agrochemical composition is from 10 to 90 wt%, preferably from 20 to 60 wt% and most preferably from 30 to 60 wt%.
The agrochemical composition of the present invention may comprise a solvent selected from hydrocarbons. The hydrocarbon may be used to dissolve the water-insoluble pesticide for the oil- in-water emulsion of the present invention. Hydrocarbons can include aromatic petroleum derivatives (aromatic hydrocarbons) with a solubility in water < 0.1 % (w/w) and a distillation range from 130 °C to 300 °C (commercially available under the following brand names: Solvesso™ 100, Solvesso™ 150, Solvesso™ 200, Solvesso™ 150ND, Solvesso™ 200ND, Aromatic 150, Aromatic 200, Hydrosol A 200, Hydrosol A 230/270, Caromax™ 20, Caromax™ 28, Aromat K 150, Aromat K 200, Shellsol™ A 150, Shellsol™ A 100, Fin FAS-TX 150, Fin FAS-TX 200). In an embodiment, the hydrocarbon is an aromatic hydrocarbon. The composition may comprise further solvents (e.g. the organic solvents listed below) in addition to the hydrocarbon. In various embodiments, the composition can comprise not more than 30% by weight, not more than 10% by weight, or not more than 1 % by weight of the further solvents.
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates. In an embodiment, anionic surfactants include sulfates and sulfonates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Nonionic surfactants can include alkoxylates. Nonionic surfactants such as alkoxylates may also be employed as adjuvants.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds which have negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by
Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol. Suitable antifoam agents are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments which are sparingly soluble in water, and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants).
The composition may comprise at least one anionic surfactant. In various embodiments, the composition comprises not less than 0.5% by weight of anionic surfactants, not less than 2% by weight, or not less than 3% by weight. In other embodiments, the composition can comprise not more than 30% by weight, not more than 15% by weight, or not more than 10% by weight of anionic surfactants.
The composition preferably comprises at least one nonionic surfactant (such as alkoxylates). In various embodiments, the composition can comprise not less than 1 % by weight, not less than 5% by weight, or not less than 10% by weight of nonionic surfactants. In other embodiments, the composition can comprise not more than 65% by weight, not more than 45% by weight, or not more than 35% by weight of nonionic surfactants. Preferably, the composition comprises a nonionic surfactant and an anionic surfactant.
The invention furthermore relates to a process for the preparation of the agrochemical composition according to the invention by mixing the water-insoluble pesticide and submicron hydrophilic- and hydrophobic-coated metal oxide particles. In an embodiment, the water-insoluble pesticide is an isothiazoline insecticide as described herein.
The invention furthermore relates to an emulsion obtainable (preferably obtained) by mixing water, the water-insoluble pesticide, and submicron hydrophilic- and hydrophobic-coated metal oxide particles according to the invention. The emulsion normally arises upon shear mixing. The mixing ratio of water to composition can be in the range of from 1000 to 1 up to 1 to 1 , preferably 200 to 1 up to 3 to 1.
The invention furthermore relates to a method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the agrochemical composition according to the invention is allowed to act on the respective pests, their environment or on the crop plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on the crop plants and/or their environment. In general, the therapeutic treatment of humans and animals is excluded from the method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants.
When employed in crop protection, in certain embodiments, the application rates of the pesticides amount to from 0.001 to 2 kg per ha, from 0.005 to 2 kg per ha, from 0.05 to 0.9 kg per ha, or from 0.1 to 0.75 kg per ha, depending on the nature of the desired effect. In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, from 1 to 100 g, or from 5 to 100 g, per 100 kg of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, or 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizers or micronutrients may be added to the emulsion in the form of a premix or optionally only shortly before use (tank mix). These agents can be admixed to the compositions according to the invention at a weight ratio of from 1 : 100 to 100:1 , or from 1 :10 to 10: 1.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, or 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
Advantages of the present invention are, inter alia, that the composition is highly stable; that the pesticide does not precipitate, cream or crystallize in the composition; that the pesticide does not precipitate, cream or crystallize in the emulsion; that high pesticide concentrations in the composition can be employed; that the composition is capable of being stored over prolonged periods (e.g. 3 months to 3 years; that adjuvants can be included in the composition formulation; that the pesticide in the emulsion is photostable; that the pesticide exhibits a greater effect over time.
The examples which follow illustrate the invention without imposing any limitation.
EXAMPLES
Hydrophilic Particles: Rutile type titanium dioxide particles, post-treated with alumina, primary particle size 30-50 nm, titanium dioxide content 88-94 %, oil absorption 29-38 g/100 g, specific surface area 35-45 m2/g (BET method), commercially available as TT-55B from Ishihara Corp. USA.
Hydrophobic Particles: titanium dioxide dispersion in carrier oil (caprylic/capric triglyceride) with polyhydroxystearic acid as dispersing agent, coated with alumina and stearic acid, commercially available as Solaveil™ AT-300 from Croda USA.
Solvent A: Aromatic hydrocarbon solvent, initial boiling point about 230 °C; aromatic content above
99 %.
Solvent B: Ν,Ν-Dimethyl C8/C10 fatty acid amide, liquid, density about 0.88 g/cm3.
Surfactant A: Ethoxylated castor oil, melting point about 32 °C, HLB 14-15 (Griffin).
Surfactant B: Solution of calcium salt of dodecylbenzenesulfonic acid (60 wt%) in organic solvent, flash point 78 °C.
Isothiazoline: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isothiazol-3-yl]-2-methyl-N-(2- pyridylmethyl)benzamide.
Example 1 : An isothiazoline oil-in-water emulsion B having the following composition was prepared (cf Table 1 ):
Table 1
Figure imgf000036_0001
The pesticidal oil-in-water emulsion was prepared by the following procedure: 1 ) Isothiazoline and Hydrophobic Particles are added to Solvent A, stirred until dissolved / uniform (oil phase). 2) Hydrophilic Particles, Surfactant A, Propylene Glycol, Acticide MBS, Silicon Antifoamer were mixed with D.I. water until uniform (aqueous phase). 3) Poured oil phase into the above aqueous phase with agitation. 4) Homogenized the above mixture for 2 minutes at 7000 rpm using a
Silverson high shear mixer. 5) Checked oil droplet size, and continued shearing until oil droplet size was less than 3 micron. 6) Added biocide and thickeners and mixed until uniform.
A glass plate UV stability tests was used to quantify the UV degradation of the isothiazoline. The detailed test method is described as follows:
Formulations were diluted to the same concentration using D.I. water. 5 drops of 1□ I dilution deposited on glass plate. 2 glass plates per sample per time point. After application, glass plates were put in the UV chamber. 1 and 24 hours after application, glass plates were taken out of UV chamber and washed off with 10 ml water/MEOH at ratio of 50/50. Wash off liquid was analyzed for active ingredient (a.i.) concentration via HLPC/MS/MS. Active ingredient recovery was calculated as a percentage of a.i. applied.
For comparison, a conventional Isothiazoline EC formulation was included in the same tests with following recipe in Table 2:
Table 2: Component Name Amount
(wt/wt%)
Active ingredient Isothiazoline 1.0
Emulsifier Surfactant B 9.38
Emulsifer Surfactant A 6.25
Solvent Solvent B 62.51
Solvent Solvent A To
100%
The pesticidal emulsifiable composition was prepared by the following procedure:
1. Active ingredient was added to Solvent A and Solvent B, stirred until dissolved / uniform (oil phase).
2. Surfactant B and Surfactant A were added to the above mixture and agitated until uniform.
The glass plate testing result is summarized in following Table 3.
Table 3
Figure imgf000037_0001
Photodegradation of the isothiazoline was reduced in emulsion B (cf Table 1 ) when compared to a conventional EC of Table 2.

Claims

We claim:
1 . An agrochemical composition comprising
a) a pesticide,
b) submicron hydrophilic-coated metal oxide particles, and
c) submicron hydrophobic-coated metal oxide particles.
2. The composition according to claim 1 comprising 0.1 to 15 wt% of the submicron hydrophilic- coated metal oxide, and 0.1 to 15 wt% of the submicron hydrophobic-coated metal oxide particles.
3. The composition according to claim 1 or 2, wherein the submicron particles have an average particle size of less than 1000 nm. 4. The composition according to claims 1 to 3, wherein the submicron hydrophilic-coated metal oxide comprises T1O2, and wherein the submicron hydrophobic-coated metal oxide comprises Ti02.
5. The composition according to claims 1 to 4, wherein the metal oxide particles b) and c) are entirely covered by the coating.
6. The composition according to claims 1 to 5, wherein the submicron hydrophilic-coated metal oxide particles are selected from metal oxides coated with inorganic oxides. 7. The composition according to claims 1 to 6, wherein the submicron hydrophobic-coated metal oxide particles are selected from metal oxides coated with a silicon containing polymer, silicon containing polymer and an inorganic oxide, or an inorganic oxide and a fatty acid or salts thereof. 8. The composition according to claim 7, wherein the submicron hydrophobic-coated metal oxide particles are selected from metal oxides coated with an inorganic oxide and a fatty acid or salts thereof.
The composition according to claims 1 to 8, wherein the weight ratio of submicron hydrophilic-
Figure imgf000038_0001
coated metal oxide particles and submicron hydrophobic-coated metal oxide particles is
between 5: 1 and 1 :5.
10. The composition according to claims 1 to 9, wherein the composition is an aqueous emulsion.
1 1 . The composition according to claims 1 to 10, comprising a water-immiscible solvent.
12. The composition according to claim 1 1 , comprising 20 to 60 wt% of the water-immiscible solvent.
13. The composition according to claims 10 or 1 1 , wherein the pesticide is dissolved in the water- immiscible solvent.
14. A process for the preparation of the composition according to claims 1 to 12 by mixing the pesticide, the submicron hydrophilic-coated metal oxide particles, and hydrophobic-coated metal oxide particles.
15. A method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the composition as defined in any of claims 1 to 12 is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
16. Seed containing the agrochemical composition as defined in any of claims 1 to 12.
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US10258047B2 (en) 2016-12-12 2019-04-16 Sumitomo Chemical Company, Limited Agrochemical composite particles and production method thereof

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