WO2014180850A1

WO2014180850A1 - Emulsifiable concentrate comprising pesticide, lactone, and tri-c1-c6-alkyl phosphate

Info

Publication number: WO2014180850A1
Application number: PCT/EP2014/059243
Authority: WO
Inventors: Terrance Cannan
Original assignee: Basf Se
Priority date: 2013-05-10
Filing date: 2014-05-06
Publication date: 2014-11-13
Also published as: JP2016522822A

Abstract

Subject matter of the present invention relates to an emulsifiable concentrate comprising a water-insoluble pesticide, a) a lactone and b) a tri-C₁-C₆-alkyl phosphate as defined herein. The invention further relates to a process for the preparation of said concentrate; an emulsion obtainable by mixing water, a water-insoluble pesticide, the components a) and b); and 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 concentrate or the emulsion 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.

Description

Emulsifiable concentrate comprising pesticide, lactone, and tri-Ci-C₆-alkyl phosphate Description

Subject matter of the present invention relates to an emulsifiable concentrate comprising a water-insoluble pesticide, a) a lactone, and b) a tri-Ci-C6-alkyl phosphate as defined herein. The invention further relates to a process for the preparation of said concentrate; an emulsion obtainable by mixing water, a water-insoluble pesticide, the components a) and b); and 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 concentrate or the emulsion 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 present invention comprises combinations of certain features with other additional features.

Emulsifiable concentrates (also referred to as EC) are widely used formulations in crop protection. The disadvantage of the known emulsion concentrates is the poor cold stability, the pronounced tendency to crystallize and the low pesticide concentration. It was an object of the present invention to provide an emulsifiable concentrate which overcomes these disadvantages.

The object was achieved by an emulsifiable concentrate comprising a water-insoluble pesticide,

a) a lactone, and

b) a tri-CrC₆-alkyl phosphate.

Usually, an emulsifiable concentrate is taken to mean compositions which form 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 arises spontaneously. In various embodiments, the resulting emulsion may have an average droplet size of more than 0.1 μιη, more than 0.5 μιη, more than 0.8 μιη, or more than 1 .1 μιη. The average droplet size may be determined by laser diffraction, e.g. with a Malvern Mastersizer 2000. The concentrate is preferably present as a homogeneous solution. It is usually virtually free from dispersed particles. Lactones can include γ-butyrolactone (gamma-butyrolactone).

In various embodiments, the concentrate can comprise at least 5% by weight, at least 20% by weight, at least 35% by weight, or at least 45% by weight of lactone (such as γ-butyrolactone). In other embodiments, the concentrate can comprise not more than 80% by weight, not more than 70% by weight, or not more than 60% by weight of the lactone.

Th-Ci-C₆-alkyl phosphates can include tributyl phosphate.

In various embodiments, the concentrate can comprise not more than 60% by weight, not more than 45% by weight, or not more than 30% by weight of a tri-Ci-C6-alkyl phosphate. In other embodiments, the concentrate can comprise at least 5% by weight, at least 10% by weight, or at least 15% by weight of a tri-CrC₆-alkyl phosphate. The tri-CrC₆-alkyl phosphate can be tributyl phosphate. The concentrate may further comprise hydrocarbon in addition to the aforementioned solvents a) lactone and b) tri-Ci-C6-alkyl phosphate. In various embodiments, the concentrate can comprise not more than 40% by weight, not more than 20% by weight, or not more than 10% by weight of hydrocarbon. In other embodiments, the concentrate can comprise at least 1 % by weight, at least 20% by weight, or at least 35% by weight of hydrocarbon. 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. In an embodiment, the concentrate can comprise from 5 to 50% by weight of the lactone (e.g. γ-butyrolactone), 10 to 35% by weight the th-Ci-C₆-alkyl phosphate (e.g. tributyl phosphate), and optionally 1 to 40% by weight of the hydrocarbon (e.g. an aromatic hydrocarbon), wherein the amounts of these components adds up to a sum of 40 to 90% by weight.

In another embodiment, the concentrate can comprise from 10 to 35% by weight of the lactone (e.g. γ-butyrolactone), 15 to 25% by weight of the tri-CrC₆-alkyl phosphate (e.g. tributyl phosphate), and optionally 2 to 30% by weight of the hydrocarbon (e.g. an aromatic

hydrocarbon), wherein the amounts of these components adds up to a sum of 45 to 80% by weight.

In yet another embodiment, the concentrate can comprise from 50 to 65% by weight of the lactone (e.g. γ-butyrolactone), 20 to 45% by weight of the tri-Ci-C6-alkyl phosphate (e.g. tributyl phosphate), and optionally 5 to 50% by weight of the hydrocarbon (e.g. an aromatic

hydrocarbon), wherein the amounts of these components adds up to a sum of 50 to 95% by weight.

In most cases, the concentrate is free from water. In another form, the concentrate is essentially free from water. In various embodiments, the concentrate can comprise not more than 3% by weight, not more than 1 % by weight, or not more than 0.5% by weight of water. In another embodiment, the concentrate may comprise not more than 0.3% by weight and in a different embodiment not more than 0.1 % by weight of water.

The concentrate may comprise further solvents (e.g. the organic solvents listed below) in addition to the components a), b), and hydrocarbon. In various embodiments, the concentrate 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.

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 fungicides. 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, fenoxy- strobin/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-di- chlorophenyl)-1 -methyl-allylideneaminooxymethyl)-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-benzodioxol-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-difluoro- quinazolin-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 (DM I 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;3/?)-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;

- Delta 14-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-methyl- piperidin-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-pyhmidines): 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, pyhmorph, 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, propamo- carb-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, t azoxide, 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;

M) 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;

N) 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;

- irnidazolinones: 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, metha- benzthiazuron,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, Drechslera 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.

O) 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, pihmicarb, propoxur, thiodicarb, triazamate;

- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmeth n, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluth n, 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,

pyhprole, 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 carboxamide; N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2- (3-chloro-2-pyndyl)-5-(tnfluoromethyl)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)pyrazo^ 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)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester. The pesticide is 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 linuron. 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 concentrate in dissolved form. Using simple preliminary experiments, the skilled worker can select, from the above pesticide list, a pesticide with a suitable solubility.

In addition to the water-insoluble pesticide, the concentrate can comprise one or more further pesticides. The further pesticide may be water-insoluble. Usually, it is soluble in water to not more than 1 g/l, not more than 200 mg/l, or not more than 50 mg/l at 25°C. Using simple preliminary experiments, the skilled worker can select a pesticide with a suitable water- solubility from the above pesticide list. In an embodiment, the pesticide is dimethenamid-p. In an embodiment, the concentrate comprises the water insoluble pesticide linuron and optionally a further pesticide (e.g. dimethenamid-p). In another embodiment, the concentrate can comprise a third pesticide. In various embodiments, the concentrate may comprise from 0.1 to 60% by weight, from 1 to 25% by weight, or from 5 to 15% by weight, of pesticide, the basis being the total of all the pesticides present in the concentrate.

The emulsifiable concentrate can furthermore comprise auxiliaries conventionally used for crop protection products. Suitable auxiliaries are solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetrants, protective colloids, stickers, thickeners, bactericides, antifreeze agents, antifoam agents, colorants, adhesives and binders.

Suitable solvents and liquid carriers 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.

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 auxilaries. 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 concentrate may comprise at least one anionic surfactant. In various embodiments, the concentrate 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 concentrate preferably comprises at least one nonionic surfactant (such as alkoxylates). In various embodiments, the concentrate 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.

In an embodiment, the concentrate comprises a nonionic surfactant and an anionic surfactant.

The invention furthermore relates to a process for the preparation of the emulsifiable concentrate according to the invention by mixing the water-insoluble pesticide, the lactone, and the tri-CrC₆-alkyl phosphate.

The invention furthermore relates to an emulsion obtainable (preferably obtained) by mixing water, the water-insoluble pesticide, the components a) and b) according to the invention, and optionally hydrocarbon. The emulsion normally arises spontaneously upon mixing. In most cases, the emulsion is an oil-in-water emulsion. The mixing ratio of water to concentrate 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 concentrate according to the invention or the emulsion 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 and further pesticides (for example herbicides, insecticides, fungicides, growth regulators, safeners) 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 concentrate is highly stable to low temperatures (e.g. even below 0 °C); that the pesticide does not precipitate, cream or crystallize in the concentrate at low temperatures (e.g. even below 0 °C); that the pesticide does not precipitate, cream or crystallize in the emulsion obtained from the concentrate, e.g. at low temperatures (e.g. even below 0 °C); that high pesticide concentrations in the concentrate can be employed; that an emulsion forms spontaneously upon dilution of the concentrate with water; that the concentrate is capable of being stored over prolonged periods (e.g. 3 months to 3 years); that the concentrate does not require the presence of water (e.g. because it might freeze below 0 °C or would favor bacterial growth during storage); that the concentrate forms a stable emulsion upon dilution with water; that adjuvants can be included in the concentrate formulations; that the pesticide in the emulsion obtained from the concentrate maintains stability in water with 34 to 342 ppm hardness. The examples which follow illustrate the invention without imposing any limitation.

Examples

Surfactant A: A solid alkylterminated ethylene oxide/propylene oxide block copolymer, HLB about 17, cloud point 70-80 °C.

Hydrocarbon A: A liquid aromatic hydrocarbon solvent, initial boiling point about 225-240 °C.

Example 1 : Preparation of emulsion concentrate (EC)

An emulsifiable concentrate of Linuron, Pendimethalin and Dimethenamid-p (DMTA-p) was prepared by mixing the components with Tributyl Phosphate, γ-butyrolactone, Hydrocarbon A, and the listed surfactants Agnique® MBL 510 H (a hydrophilic emulsifier blend; commercially available from BASF SE) and Agnique® MBL 520 L (a lipophilic emulsifier blend; commercially available from BASF SE). The concentrate mixture is listed in Table 1 as Formulation A. Table 1 : Formulation A

As shown in Table 2, Formulation A showed safe solubility values through storage

temperatures of -7 °C.

Table 2. Solubility Study of Formulation A

Formulation A provided excellent control of annual grass and broadleaf weeds at 4-6 L product/ha as a pre-emergence application in soybean. No phytotoxicity was observed in soybean.

Example 2: Preparation of emulsifiable concentrate (EC)

An emulsifiable concentrate of Linuron, Pendimethalin and Dimethenamid-p (DMTA-p) was prepared by mixing the components with Tributyl Phosphate, γ-butyrolactone, Hydrocarbon A, and the listed surfactants Agnique® MBL 510 H, Agnique® MBL 520 L, and Surfactant A. The concentrate mixture is listed in Table 3 as Formulation B. Formulation B showed improved stability in emulsion with soft water. Table 3. Formulation B

As shown in Table 4, the active ingredients in Formulation B showed good chemical stability over the range of 25 °C through 40 °C for 3 months. A chemical stability shelf life of 3 years expected.

Table 4. Chemical Stability of Formulation B

As shown in Table 5, the emulsion showed good physical stability over the range of 25 °C through 40 °C for varying water hardness conditions and through freeze-thaw from -10 to -20 °C. No crystals were observed using a 200 mesh sieve. Table 5. Physical Stability of Formulation B

As shown in Table 6, Formulation B showed no evidence of crystal growth on 325 mesh screen (44 microns) or when examined under the microscope.

Table 6. Cold Water Application of Formulation B

34 ppm water hardness 24 hours at 5 °C

Dilution Rate Residue - 325 Mesh Screen Visual - Microscope

30X Field Rate None Fine Emulsion - free of crystals

140X Field Rate None Fine Emulsion - free of crystals

300X Field Rate None Fine Emulsion - free of crystals

Claims

I claim:

1 . An emulsifiable concentrate comprising a water-insoluble pesticide,

a) a lactone, and

b) a tri-CrC₆-alkyl phosphate.

2. The concentrate according to claim 1 , comprising at least 5% by weight of the tri-Ci-C6- alkyl phosphate.

3. The concentrate according to claim 1 or 2, comprising at least 5% by weight of the lactone.

4. The concentrate according to claims 1 to 3, comprising a hydrocarbon.

5. The concentrate according to claims 1 to 4, comprising not more than 40% by weight of a hydrocarbon.

6. The concentrate according to claims 1 to 5, comprising from 5 to 50% by weight of the lactone, 10 to 35% by weight of the tri-Ci-C6-alkyl phosphate, and optionally 1 to 40% by weight of the hydrocarbon, wherein the amounts of these components adds up to a sum of

40 to 90% by weight.

7. The concentrate according to claims 1 to 6, wherein the lactone is γ-butyrolactone.

8. The concentrate according to claims 1 to 7, wherein the tri-Ci-C6-alkyl phosphate is tributyl phosphate.

9. The concentrate according to claims 1 to 8, wherein the concentrate is present as a

homogeneous solution.

10. The concentrate according to claims 1 to 9, wherein wherein the concentrate is largely free from water. A process for the preparation of the concentrate according to claims 1 to 10 by mixing the water-insoluble pesticide, the lactone, the tri-Ci-C6-alkyl phosphate, and optionally a hydrocarbon.

An emulsion obtainable by mixing water, a water-insoluble pesticide, a lactone as defined in any of claims 1 to 10, a tri-Ci-C6-alkyl phosphate as defined in any of claims 1 to 10, and optionally a hydrocarbon.

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 concentrate according to any of claims 1 to 10 or the emulsion according to claim 12 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.