EP2557917A1

EP2557917A1 - Uv absorber for reducing the e/z isomerization of pesticides

Info

Publication number: EP2557917A1
Application number: EP11714762A
Authority: EP
Inventors: Michael Ishaque; Vijay Narayanan Swaminathan; Sylke Haremza; Claude Taranta; William Baxter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-04-15
Filing date: 2011-04-14
Publication date: 2013-02-20
Also published as: JP2013523868A; CN102883599B; KR20130051940A; BR112012025827A2; WO2011141264A1; CN102883599A

Abstract

The present invention relates to the use of a UV absorber for reducing the E/Z isomerization of pesticides containing a double bond. The invention further relates to a composition comprising an E isomer and/or a Z isomer of a pesticide containing a double bond, and to a UV absorber.

Description

UV absorber to reduce the E / Z isomerization of pesticides

The present invention is the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond. Furthermore, it relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Combinations of preferred features with other preferred features are encompassed by the present invention. Agrochemical active substances such as pesticides are exposed to sunlight, especially after application in the open field. This results in some agents to reduce their pesticides effectiveness.

For example, it has been found that metaflumizone loses its efficacy upon exposure to light (Takagi et al., Veterinary Parasitology, 2007, 150, 177-181). Metaflumizone can exist as an E and a Z isomer, with the E isomer having up to 10 times higher pesticidal activity than the Z isomer. Light irradiation leads to isomerization of the originally applied E isomer to the Z isomer.

The object of the present invention was to suppress the E / Z isomerization of agrochemical active substances, such as metaflumizone. Another task was to find a cost-effective method for doing so. The object has been achieved by the use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond. E / Z isomerization is usually understood to mean the conversion of a double bond from the E isomer to the Z isomer or from the Z isomer to the E isomer. E / Z isomerization usually occurs in unsymmetrically substituted double bonds, ie in double bonds, which may be present as E-isomer and as Z-isomer. Aromatic double bonds, as present in benzene rings, can not naturally undergo E / Z isomerization. A reduction in E / Z isomerization is usually achieved when the weight ratio of E to Z isomer in a composition changes more slowly compared to the same composition without the UV absorber used in each case. The term pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, pheromones and / or growth regulators. Preferred pesticides are fungicides, insecticides and herbicides. Also, mixtures of pesticides of two or more of the above classes may be used. One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flavinamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates , Oximinoacetamides, peptidyl-pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, P yrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulphamides, sulphamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiocarbons bamate, thiophanate, thiophenecarboxamide, toluenamide, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides of the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio ) benzoates, quinolinecarboxylic acids, semicarbazone, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. Pesticides containing a double bond are usually those pesticides containing a CC double bond and / or a CN double bond. Mostly the double bond is isolated from another multiple bond or conjugated to another multiple bond. Preferred pesticides containing a double bond are abamectin, acetamiprid, acrinathrin, azoxystrobin, bifenthrin, butoxycarboxim, chlorfenvinfos, cyhalothrin, 1, 3 dichloropropene, dicrotophos, dimethomorph, diniconnazol, emamectin, empenthrin, fenpyroximate, flucycloxuron, flumethrin, flumorph, fluoxastrobin, hydroprene, Ki - noprene, kresoxim-methyl, lambda cyhalothrin, metaflumizone, metominostrobin, metoprene, mevinphos, monocrotophos, nitenpyram, oxabetrinil, phosphamidone, picoxystrobin, propetamphos, pyrethrin, pyrifenox, tefluthrin, tetrachlorovinphos, trifloxystrobin, triflumizole, triticonazole, uniconazole, and the pheromones codlemon, dodec-8-enyl acetate, dodec-9-enyl acetate, dodeca-7,9-dienyl acetate, farnesol, nerolidol, gossyplurene, Grandlure II, Grandlure III, hexadec-1 1-enal, hexadec-1 1 -enyl acetate, hexadec-13-en-1 1 -ynylacetate, japoniluronic acid, muscalure, tetradeca-9,12-dienylacetate, tetradeca-11-enylacetate, tetradeca-9-enylacetate, and tridec-4-enylacetate.

Particularly preferred pesticides containing a double bond are abamectin, acetamiprid, azoxystrobin, bifenthrin, cyhalothrin, dimethomorph, diniconnazole, ememectin, flucycloxuron, fluoxastrobin, kresoxim-methyl, lambda cyhalothrin, metaflumizone, picoxystrobin, trifloxystrobin, triflumizole, and triticonazole.

Especially preferred pesticide containing a double bond is metaflumizone. In a further preferred embodiment, pesticides containing a double bond are suitable, wherein the E or the Z isomer of the pesticide has a higher activity than the respective other isomer. The term "higher effectiveness" refers each on a specific biological activity in a particular target organism. These efficiencies of the E and Z isomers of the pesticide are mostly known from the literature. Higher efficacy is considered to be present if one of the isomers has an activity which is at least 1, 1-fold (preferably at least 2-fold, more preferably at least 4-fold) the activity of the other isomer.

The E or Z isomer of the pesticide containing a double bond is preferably at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of E- and Z-isomers of the pesticide. These values refer to the time when the UV absorber is mixed with the pesticide.

The term "UV absorber" refers to all chemical compounds that can absorb UV light. The UV absorber can scatter UV light (such as inorganic UV absorbers) or absorb it. In most cases, the extinction coefficient of the UV absorber of UV light is greater than the extinction coefficient of the pesticide at the same wavelength. The UV absorbers may be oil-soluble or water-soluble. They may also be present in polymers, for example as copolymerized. The UV absorbers may be UV-A absorbers, UV-B absorbers, broadband absorbers (i.e., UV-A and UV-B), or optical brighteners. The UV absorber can be used in pure form, as a technical mixture, or as a mixture of different UV absorbers. Preference is given to UV absorbers having a solubility in water at 20 ° C. of at least 0.01 g / L, preferably at least 0.1 g / L, and particularly preferably at least 1 g / L.

In a preferred embodiment, the UV absorber is water-soluble. In a further preferred embodiment, the composition contains a further UV absorber, wherein the further UV absorber is oil-soluble. In particular, at least one UV absorber is water-soluble and at least one UV absorber is oil-soluble.

In a particularly preferred embodiment, water-soluble UV absorbers are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 10.0 g / l, more preferably at least 50 g / l, and especially at least 100 g / l.

The further oil-soluble UV absorber usually has a solubility in water at 20 ° C. of below 5.0 g / l, preferably below 1.0 g / l, more preferably below 0.5 g / l, and especially below 0.1 g / l. Inorganic UV absorbers are likewise suitable oil-soluble UV absorbers in the context of this application.

Suitable UV absorbers are, for example: A) Benzotriazoles, such as 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Tinuvin® 900, BASF SE), [3- [3- ( 2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1 -oxopropyl] -w- [3- [3- (2-benzotriazol-2-yl) -5- (1, 1-dimethyl-ethyl) -4-hydroxyphenyl] -1-oxopropoxy] poly (oxy-1,2-ethanediyl) (Tinuvin® 1 130, BASF SE), 6-tert-butyl-2- (5-chloro-1-one) 2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® 326, BASF SE), 2,4-di-tert-butyl-6- (5-chloro-2H-benzotnazol-2-yl) -phenol (Tinuvin ® 327, BASF SE), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (Tinuvin® 320, BASF SE), 2- (2H-benzotriazol-2-yl) - 4- (1,1,3,3-tetramethylbutyl) phenol (Tinuvin® 329, BASF SE), 2- (2H-benzotriazol-2-yl) -4-methylphenol (Tinuvin® P, BASF SE), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (Tinuvin® 234, BASF SE), 2,2-methylenebis (6- (benzotriazole-2 -yl) -4-tert-octylphenol, (Tinuvin® 360, BASF SE); 2- (2H-benzotriazol-2-yl) -2- (2-methylpropyl) -phenol-4-sulfonic acid sodium salt (Tinogard H® P, BASF SE), phenol, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl, branched and linear (Tinuvin® 171, BASF SE);

B) cyanoacrylates, such as 2-cyano-3-phenylcinnamate ethyl ester (Uvinul ^® 3035, BASF SE), 2-cyano-3,3-diphenylacrylate 2'-ethylhexyl ester or 2-ethylhexyl-2-cyano-3-phenylcinnamate ( Octocrylene, Uvinul ^® 539 T, Uvinul 3039, BASF SE);

C) Para-aminobenzoic acid (PABA) derivatives, especially esters such as ethyl-PABA, ethoxylated PABA, ethyl-dihydroxypropyl-PABA, glycerol-PABA, 2-ethylhexyl

4- (dimethylamino) benzoate (Uvinul ^® MC 80), 2-octyl 4- (dimethylamino) benzoate, amyl 4- (dimethylamino) benzoate, 4-bis (polyethoxy) 4-amino benzoic acid thoxyethyl polyether ester (Uvinul ^® P 25 , BASF SE);

D) esters of salicylic acid, such as 2-ethylhexyl salicylate, 4-lsopropylbenzyl salicylate, homomenthyl salicylate, TEA salicylate (Neo Heliopan TS ^®, Haarmann and Reimer), Dipropyleneglycol salicylate;

E) esters of cinnamic acids, such as 2-ethylhexyl 4-methoxycinnamate (Uvinul® MC 80), octyl-p-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, conoxates, diisopropyl methyl cinnamate, etocrylene (Uvinul® N 35, BASF SE );

F) Derivatives of benzophenone, such as 2-hydroxy-4-methoxybenzophenone (Uvinul® M 40, BASF SE), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- Hexyl (4-diethylamino-2-hydroxybenzoyl) benzoate (Uvinul® A Plus, BASF SE), 4-n-octyloxy-2-hydroxybenzophenone (Uvinul® 3008, BASF SE), 2-hydroxybenzophenone derivatives such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy-2-hydroxybenzophenones, Sulfonsäurederivative of benzophenones, such as 2-hydroxy-4-methoxybenzo-phenone-5-sulfonic acid (Uvinul ^® MS 40, BASF SE) and its salts, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone-5,5'-sulfonic acid and its salts (disodium salt: Uvinul ^® DS 49, BASF SE); G) 3-Benzylidenecamphor derivatives thereof, such as 3- (4'-methylbenzylidene) c / -1 - camphor, benzylidiene camphor sulfonic acid (Mexoryl SO ^®, Chimex);

H) sulfonic acid Derivative of 3-Benzylidenecamphor, such as 4- (2-oxo-3-bornyl-idenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bionylidenes) - sulfonic acid and its salts;

I) esters of benzalmalonic acid, such as 2-ethylhexyl 4-methoxybenzmalonate;

J) triazine derivatives, such as dioctylbutamidotriazone (Uvasorb® HEB, Sigma), 2,4,6-trinanilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1, 3,5-triazine (Uvinul T 150, BASF SE), 2- [4 - [(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl ) -1, 3,5-triazine (Tinuvin® 405, BASF SE), anisotriazine (Tinosorb® S, BASF

SE), 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine;

K) propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;

L) 2-phenylbenzimidazole-5-sulfonic acid or 2-phenylbenzimidazole-4-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof;

M) Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane or 1-phenyl -3- (4'-isopropylphenyl) propane-1,3-dione;

N) aminohydroxy-substituted derivatives of benzophenones, such as N, N-diethylaminohydroxybenzoyl-n-hexylbenzoate;

O) derivatives of stilbene, for example salts of distyrylbiphenyl disulphonate, such as disodium dististylbiphenyl disulphonate (Uvitex® NFW, BASF SE), 2,2 '- [1,2-ethenediylbis [(3-sulfo-4,1-phenylene) imono [6- (diethylamino) -1, 3,5-triazine-4,2-diyl] imino]] bis-1,4-benzenedisulfonic acid hexasodium salt (Tinopal® SFP, BASF

SE);

P), inorganic UV absorbers, for example those based on ZnO (like Z Cote ^® products, BASF SE), Ti0 ₂ (such as T-Lite ™ productions, BASF SE) or Ce0 _2, as well as the UV absorber as described in WO 2009 / 153231, page 2, line 24 to page 6, line 18 described.

Preferred UV absorbers are those of the group F) (derivatives of benzophenone) and the group O) (derivatives of stilbene), particularly preferably 2-hydroxybenzophenone derivatives, sulfonic acid derivatives of benzophenones and salts of distyrylbiphenyl disulfonate, in particular 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, disodium distyrylbiphenyl disulfonate and 2-hydroxy-4-octoxybenzophenone.

In a further preferred embodiment, at least two UV absorbers are used. Preference is given to using a UV absorber from group A) to N) and a UV absorber from group O). In a particularly preferred embodiment, UV absorbers are used which contain a sulfonic acid group or a polyalkylene oxide group. Preference is given to UV absorbers which contain a sulfonic acid group. UV absorbers containing a sulfonic acid group are well known. Examples are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul ^® MS 40, BASF SE) and its salts (for example, alkali salt such as sodium), 2,2'-dihydroxy-4,4'-dimethoxybenzophenon- 5 , 5'-sulfonic acid and its salts (eg alkali salt, such as sodium). Preference is given to benzophenones which contain a sulfonic acid group (also called sulfonic acid derivative of benzophenones). The sulfonic acid group may be in the acid form or as a salt, with the salt form being preferred.

UV absorbers containing a polyalkylene oxide group are well known. The polyalkylene oxide group preferably contains ethylene oxide in polymerized form. At least 50 mol%, in particular at least 80 mol%, of the alkylene oxide groups are preferably ethylene oxide. Examples are 4-bis (polyethoxy) 4-amino benzoic acid thoxyethyl polyether ester (Uvinul ^® P 25, BASF SE).

The amount of UV absorber is usually 0.5 to 500 wt.% With respect to the amount of pesticide. It is preferably from 1 to 300% by weight, more preferably from 5 to 100% by weight and in particular from 5 to 80% by weight, in each case with respect to the amount of pesticide.

In a preferred embodiment, an antioxidant (also referred to as antioxidant) is used in addition to the UV absorber. Antioxidants having a solubility in water at 20 ° C. of at least 0.01 g / l, preferably at least 0.1 g / l, and particularly preferably at least 1 g / l, are preferred. In a further preferred embodiment, antioxidants are suitable having a solubility in water at 20 ° C. of at least 5.0 g / l, preferably at least 20 g / l, and particularly preferably at least 100 g / l.

Antioxidants are, for example, amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g., urocanic acid), peptides such as e.g. D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg 6. α-carotene, β-carotene, lycopene) and their derivatives,

Lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose,

Propylthiouracil and other thio compounds (e.g., thioglycerol, thiosorbitol,

Thioglycolic acid, thi redoxin, glutathione, cysteine, cystine, cystamine and theirs

Glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof, dilauryl thiodipropionate, Distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages, further

Metal chelators (e.g., α-hydroxy fatty acids, EDTA, EGTA, phytic acid, lactoferrin), α-hydroxy acids (e.g., citric acid, lactic acid, malic acid), humic acids,

Bile acid, bile extracts, gallic acid esters (eg propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and their derivatives, hydroquinone and its derivatives (eg arbutin), ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (eg ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate , Disodium ascorbyl phosphate and sulfate,

Potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and its derivatives, tocopherols and their derivatives (e.g., tocopheryl acetate, linoleate, oleate and succinate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18,

Tocophereth-50, tocopherolan), vitamin A and derivatives (eg, vitamin A palmitate), the benzylic resin coniferyl benzoate, rutin, rutinic acid and derivatives thereof, disodium rubinyldisulfate, cinnamic acid and its derivatives (eg, ferulic acid, ethyl ferulate, Caffeic acid), gallic acid and its esters, for example propyl gallate, kojic acid, chitosan glycolate and salicylate, butylhydroxytoluene, butylhydroxyanisole, tetrakis

[Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (Ir-ganox® 1010, BASF SE), nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and zinc derivatives (eg ZnO, ZnSO 4), selenium and selenium derivatives (eg selenium methionine), stilbenes and stilbene derivatives (eg stilbene oxide, trans-stilbene oxide), salts of monovalent copper, for example copper (l ) chloride, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate

(Tinuvin® 770), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol (Tinuvin® 171), N, N'-bis-formyl-N, N'-bis (2, 2,6,6-tetramethyl-4-piperidinyl) - hexamethylenediamine (Uvinul® 4050 H, BASF SE). Preferred antioxidants are vitamin C and its derivatives, tocopherols and their derivatives, monovalent copper salts, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 770), 2- (2H-benzotriazole) 2-yl) -6-dodecyl-4-methyl-phenol

(Tinuvin® 171), N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine (Uvinul® 4050 H, BASF SE).

The weight ratio of UV absorber to antioxidant is usually in the range of 1/10 to 100/1, preferably in the range of 1/5 to 10/1, more preferably in the range of 1/1 to 5/1. The present invention further relates to a composition comprising an E and / or a Z isomer of a pesticide containing a double bond and a UV absorber. Suitable and preferred pesticides containing a double bond are present standing described. The E-isomer or the Z-isomer of the pesticide is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the pesticide. Preferably, the isomer is present in excess, which has the higher pesticidal activity.

Suitable UV absorbers are as described above. Preferably, the UV absorber is a derivative of benzophenone or a derivative of stilbene. In a further preferred embodiment, at least two UV absorbers are used. Suitable weight ratios of UV absorber to pesticide which is metaflumizone are as described above. In addition to the UV absorber, an antioxidant can be used as described above.

The E isomer of metaflumizone is usually present at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, based on the total amount of the E and Z isomers of the metaflumizone.

The pesticides, such as metaflumizone, are typically present in typical for agrochemical formulations composition types, eg. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The type depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention. Examples of composition types are suspensions (SC, OD, OESC), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, capsules (CS), wettable powders or dusts (WP, SP, SS, WS , DP, DS) or granules (GR, FG, GG, MG), which may be either water-soluble or dispersible, or LLIN (long-lasting insecticidal nets), baits for animals such as ants or rats. The baits may be in various of the aforementioned composition types, preferably as powders, pastes, granules or gels. In general, the composition types (eg SC, EC OD, WG, SG, WP, SP, SS, WS,) are used diluted. Composition types such as DP, DS, GR, FG, GG, MG or bait are generally used undiluted. Preferred types of compositions are suspensions.

In a preferred embodiment, aqueous composition types are suitable, such as aqueous suspension concentrates, or oil-containing suspension concentrates

(DESC). The pH of the aqueous composition types is usually greater than 1.0, more preferably greater than 3.0, and particularly preferably greater than 3.5. The pH is usually below 6.0, preferably below 5.0, and more preferably below 4.5. Suitable ranges for the pH are, for example, 2.5 to 5.5, preferably 3.0 to 5.0.

The UV absorber and / or the antioxidants can already be brought into contact with the pesticide during the preparation of the agrochemical formulation. The agrochemical formulations may furthermore also contain auxiliaries customary for crop protection agents, the choice of auxiliaries being directed to the specific application form or the active substance. Examples of suitable auxiliaries are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment) or customary Aid for bait formulation (eg attractants, feeds, bitter substances).

Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, gycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters, and strong polar solvents, e.g. Amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures and mixtures of the abovementioned solvents and water can also be used.

Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

As surfactants (adjuvants, wetting agents, adhesives, dispersants or emulsifiers) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ^® grades, Borregaard, Norway), phenol, naphthalene (Morwet ^® types, Akzo Nobel, USA) and dibutyl (nekal ^® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and Formaldehyde, polyoxyethylene noctylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite liquors and Proteins, denatured proteins, polysaccharides (eg methylc cellulose), hydrophobic mo- difizierte strengths, polyvinyl alcohol (Mowiol ^® types, Clariant, Switzerland), Polycarboxyla- te (Sokalan ^® types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin ^® - types, BASF, Germany), polyethyleneimine (Lupasol ^® types, BASF, Germany), polyvinylpyrrolidone and their copolymers into consideration.

Examples of thickeners (ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion) are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ^®, CP Kelco, U.S.A.), Rhodopol ^® 23 (Rho dia, France) or Veegum ^® (RT Vanderbilt, USA) or attaclay ^® (Engelhard Corp., NJ, USA).

Bactericides may be added to stabilize the composition. Examples of bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ^® MBS from Thor Chemie)..

Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

Examples of defoamers are silicone emulsions (such as, for example, silicone ^® SRE, Wacker, Germany or Rhodorsil ^®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof. The agrochemical formulations may be used in the form of their compositions, e.g. B. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, misting, dusting, scattering, laying bait, painting, dipping or pouring are applied.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water. The active substances or the compositions containing them may contain oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and / or pesticides, if appropriate also immediately before Application (ie as a tank mix) to be added. These agents can be mixed into the compositions in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. The UV absorber and / or the antioxidants can also be brought into contact with the pesticide only immediately before use (ie as a tank mix).

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg. B. Break Thru S 240®; Alcohol alkoxylates, eg. Atplus® 245, Atplus® MBA 1303, Plurafac® LF 300 and Lutensol® ON 30; EO-PO block polymerizates, eg. Pluronic® RPE 2035 and Genapol® B; Alcohol ethoxylates, eg. Eg Lutensol® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen® RA.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha. In the treatment of plant propagation materials, eg. B. State, are generally used amounts of active ingredient from 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of propagating material or seed. When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.

The present invention has many advantages: the rate of E / Z isomerization is significantly reduced. The applied isomer stays active longer in sunlight. As a result, the rate of application of the active substance, such as metaflumizone, can be reduced. The applied drug has a significantly longer residual effect because the applied active isomer is converted more slowly into the less active isomer. The practice of the invention is readily practicable industrially, as the UV absorber can be easily contacted with the pesticide during preparation of the agrochemical formulation, or immediately before use by the user as a tank mix. The addition of antioxidants can kung of the UV absorber to reduce the E / Z isomerization further increased. Water-soluble UV absorbers are particularly advantageous, since such compositions are very stable on storage, and can also easily be added by the user as a tank mix (since the absorber dissolves easily in the aqueous tank mix and distributes it evenly). Water-soluble UV absorbers are easier to incorporate into the formulation, since they are simply added to the aqueous formulation, while, for example, water-insoluble UV absorbers must be ground separately with the active ingredient. The following examples illustrate the invention without limiting it.

Examples

Metaflumizone SC: aqueous suspension concentrate containing 240 g / l (22.2 wt.%) Of metaflumizone, 2 wt.% Of sodium dioctylsulfosuccinate, 3.5 wt.% Of ethoxylated Cg-

C11 alcohol and 3% by weight polyaryphenol ethoxylate.

UV absorbers used (all commercially available from BASF SE):

Uvitex® NFW: 4,4'-bis (2-sulfostyryl) biphenyl disodium salt

Uvinul® 3050: 2,2 ', 4,4'-tetrahydroxybenzophenone

Uvinul® M40: 2-hydroxy-4-methoxybenzophenone

Uvinul® 4050H: N, N'-bisformyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine

Uvinul® A Plus: 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester

Uvinul® 3008: 2-hydroxy-4-octyloxybenzophenone

Uvinul® MS 40: 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid

Tinuvin® 770: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate

Tinuvin® 171: 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol

Z-Cote®: zinc oxide, micronised

Example 1 - Preparation of mixtures

Metaflumizone SC was mixed with a certain amount (in each case% by weight with respect to metaflumizone) of the UV absorber and / or stabilizer, diluted with water in a weight ratio of 1:18 and stirred for one hour at room temperature.

Example 2 - Irradiation and Analysis of Isomerization

20 mg of the mixture prepared in Example 1 was dropped on a glass plate and allowed to dry at room temperature for one hour. Then, the sample was irradiated with UV light for 0, 30, and 120 minutes, respectively (Sun Test CPS +, Atlas Co., 750 watts, wavelength 300 to 800 nm). The sample was removed from the glass plate after irradiation with 2.0 ml Washed off DMSO and homogenized with stirring and by means of ultrasound (15 s). The sample was fractionated by means of UPLC (Ultra Performance Liquid Chromatography, BEH C18 column, detection at 225 nm) into the E and Z isomers of metaflumizone and quantitated over the peak areas. The proportion of E-isomer is indicated in each case and the proportion of Z-isomer corresponds to 100% less the proportion E-isomer.

Example 3 - Testing of Various UV Absorbers

The mixtures were prepared as in Example 1 and tested as in Example 2 (Table 1). It has been shown that a wide variety of UV absorbers reduce E / Z isomerization compared to a mixture that does not contain a UV absorber.

Table 1: UV absorber

a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers.

Example 4 - Mixture of UV absorbers with antioxidants or with further UV absorbers

The blends were prepared as in Example 1 and tested as in Example 2 (Table 2). It has been shown that mixtures of UV absorbers with antioxidants (such as tocopherol, ascorbic acid, Uvinul 4050H, Tinuvin 770) or with other UV absorbers (such as Z-Cote) reduce E / Z isomerization compared to a mixture containing does not contain a UV absorber.

Table 2: Mixtures

UV absorber Amount ^a > E isomer [%] ^b > E isomer [%]> E isomer [%]>

0 min 30 min 120 min

- - 96 58 43

Uvinul® MS 40 60

100 96 92

a-tocopherol 10

Uvinul® MS 40 60 99 91 80 Ascorbic acid 10

Uvinul® MS 40 60

99 89 93

Uvinul 4050H 10

Uvinul® MS 40 90

97 92 85

Tinuvin 770 10

Uvinul® MS 40 90

98 90 85

Z-Cote® 10

Uvinul® MS 40 30

97 82 78

Z-Cote® 30

Example 5 - Preparation of suspension concentrates

An aqueous suspension concentrate of metaflumizone was prepared by mixing and milling the following components: 180 g / l metaflumizone, 27 g / l sodium diol sulfosuccinate, 54 g / l propylene glycol, 1 g / l xanthan gum, 33 g / l ethoxylated tristy rylphenol. Water-insoluble UV absorbers or stabilizers were added before milling, while water-soluble UV absorbers or stabilizers were added after grinding and dissolved with stirring. The amount of UV absorber or stabilizer was in each case given in% by weight with respect to metaflumizone. The particle size was D90 <2.0

Example 6 - Testing of suspension concentrates

The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 3). The results with formulations prepared according to Example 5 were shown to be as good as the formulations prepared by simple mixing in Example 1.

Table 3: UV absorber

a) amount with respect to metaflumizone; b) Proportion of E isomer to total amount of analyzed E and Z isomers. Example 7 - Testing of Dilute Suspension Concentrates

The suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 4). The 1:18 dilution with water in Example 2 resulted in a formulation in water of 5%. The content was reduced even further here to 1% by more dilution with water. This dilution corresponds to a dilution, which is customary in practice, of a commercial active substance concentrate in order to obtain the spray-ready tank mixture. It has also been shown that the diluted formulations also reduce E / Z isomerization.

Table 4: UV absorber

Example 8 - field trials of white cabbage

An aqueous suspension concentrate "SC-A" of metaflumizone was prepared by mixing and milling the following components: 180 g / l of metaflumizone, 22 g / l of sodium dioctylsulfosuccinate, 35 g / l of ethoxylated Cg-n-alcohol, 30 g / l of polyarylphenolethoxy lat, 1 g / l xanthan gum (thickener), and 50 g / l alkanediol (antifreeze).

An aqueous suspension concentrate "SC-A + UV1" was prepared from SC-A by adding 108 g / L of Uvinul® MS 40.

An aqueous suspension concentrate "SC-A + UV2" was prepared from SC-A by adding 25 g / L of Uvinul® MS 40.

An aqueous suspension concentrate "SC-A + UV3" was prepared from SC-A by adding 50 g / L of Uvinul® MS 40.

An aqueous suspension concentrate "SC-A + UV4" was prepared from SC-A by adding 108 g / l Uvitex® NFW and white cabbage was grown on a field test in the phillipines at a rate of 160 g metaflumizone per ha After 14 days, the cumulative feeding damage was assessed by Crocidolomia binotalis ( belle 5). Due to the addition of UV absorber, the active ingredient had a longer efficacy.

Table 5:

Example 9 - field trials of white cabbage

White cabbage was grown on a test field in California. The field was sprayed at a rate of 160 g metaflumizone per ha with the suspension concentrations according to Example 8. After 14 days, the mortality of the larvae of Lepidoptera was subsequently determined (Table 6). Due to the addition of UV absorber, the active ingredient had a longer efficacy.

Table 6:

Example 10 - Field trials potato

On a test field in North Carolina (USA) potatoes were cultivated (block fields 7 ^* 1 m, three blocks per test point). The field was sprayed at a rate of 60 g metaflumizone per ha with the suspension concentrates according to Example 8. After 19 days, the number of larvae of Leptinotarsa decemlineata (in all larval stages) and their feeding damage was then determined (Table 7). Due to the addition of UV absorber, the active ingredient had a longer efficacy.

Table 7:

Example 1 1 UV chamber lima bean

Lima beans in the growth stage with first leaves were sprayed with 30 g of metaflumizone per ha in a laboratory spray chamber. The plants were then in one Growth chamber with UV and fluorescent light placed with 24h / day irradiation. After 3, 10, 14 and 17 days (DAT), leaves were removed and placed in Petri dishes with a damp filter paper. Per shell 5 Spodoptera eridania (Southern Armyworm, 3rd instar) were added. Four replicas were made per trial. The cumulative feeding damage is summarized in Table 8.

Table 8:

Example 12 - Field trials potato

On a test field in North Carolina (USA) potatoes were grown (block fields 7 ^* 1 m, three blocks per test point). The field was sprayed at a rate of 30 or 60 g metaflumizone per ha with the suspension concentrates according to Example 8. After 19 days, the number of larvae of Leptinotarsa decemlineata (in all larval stages) was then determined (Table 9). Due to the addition of UV absorber, the active ingredient had a longer efficacy.

Table 9: Mean number of larvae per block

30 g metaflumizone / ha 60 g metaflumizone / ha

Without treatment 150 150

SC-A 145 105

SC-A + UV1 37 22

SC-A + UV2 27 12

SC-A + UV4 123 61

Claims

claims

1 . Use of a UV absorber for reducing the E / Z isomerization of pesticides containing a double bond.

2. Use according to claim 1, wherein the double bond is a C-C double bond or a C-N double bond.

Use according to claim 1 or 2, wherein the E or Z isomer of the pesticide is at least 60% by weight, based on the total amount of E and Z isomers of the pesticide.

4. Use according to any one of claims 1 to 3, wherein the UV absorber contains a sulfonic acid group or a polyalkylene oxide group.

5. Use according to any one of claims 1 to 4, wherein the UV absorber contains a sulfonic acid group.

6. Use according to any one of claims 1 to 5, wherein the amount of the UV absorber is 0.5 to 500 wt.% With respect to the amount of the pesticide.

7. Use according to any one of claims 1 to 6, wherein in addition to the UV absorber, an antioxidant is used.

8. Use according to claim 7, wherein the weight ratio of UV absorber to antioxidant in the range of 1/10 to 10/1.

9. Use according to any one of claims 1 to 8, wherein at least two UV absorbers are used.

A composition comprising an E and / or a Z-isomer of a pesticide containing a double bond and a UV absorber, wherein the E-isomer or Z-isomer of the pesticide is at least 60% by weight based on the total amount of the pesticide E and Z isomers of the pesticide, and wherein the UV absorber has a solubility in water at 20 ° C of at least 5.0 g / L.

1 1. A composition according to claim 10, wherein the UV absorber contains a sulfonic acid group or a polyalkylene oxide group.

12. The composition of claim 10 or 11, wherein the UV absorber is a sulfonic acid derivative of benzophenones.

13. The composition according to any one of claims 10 to 12, containing a further UV absorber, wherein the further UV absorber is oil-soluble.

14. A composition according to any one of claims 10 to 13, wherein the pesticide is metaflizizone.

A composition according to claim 14 wherein the E isomer of metaflumizone is present at at least 60% by weight based on the total amount of E and Z isomers of the metaflumizone.

16. A method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to any one of claims 10 to 15 on the respective pests, their Lebens- or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.