KR20130051940A - Uv absorber for reducing the e/z isomerization of pesticides - Google Patents

Abstract

The present invention relates to the use of UV absorbers to reduce the E / Z isomerization of insecticides containing double bonds. The invention also relates to a composition comprising the E isomer and / or Z isomer of a pesticide containing a double bond and a UV absorber.

Description

UV absorbers to reduce the E / I isomerization of insecticides {UV ABSORBER FOR REDUCING THE E / Z ISOMERIZATION OF PESTICIDES}

The present invention provides the use of UV absorbers to reduce the E / Z isomerization of pesticides comprising double bonds. The invention also relates to a composition comprising the UV absorber and the E and / or Z isomers of the pesticide comprising a double bond. Combinations of preferred features with other preferred features are included in the present invention.

Agrochemically active compounds such as insecticides are exposed to sunlight, especially after application outdoors. In the case of some active compounds, this results in a decrease in their pesticidal activity.

As such, for example, metaflumizone has been found to have activity loss after light irradiation (Takagi et al., Veterinary Parasitology, 2007, 150, 177-181). Metaflumizone can exist as E and Z isomers, which have up to 10 times higher pesticidal activity than the Z isomers. By irradiation of light, the phenomenon in which the originally applied E isomer is isomerized to the Z isomer occurs.

Similar E / Z isomerization is known for flumorph (Hu et al., J. Agricul. Food Chem. 2009, 57, 9629-9633).

It was an object of the present invention to inhibit the E / Z isomerization of agrochemically active compounds such as metaflumizone. Another object of the present invention was to find an inexpensive method for this.

The object of the present invention has been achieved by using UV absorbers to reduce the E / Z isomerization of pesticides comprising double bonds.

E / Z isomerization is generally understood to mean that the double bond is converted from the E isomer to the Z isomer or from the Z isomer to the E isomer. E / Z isomerization usually occurs at asymmetrically substituted double bonds, ie double bonds which may exist as either the E isomer or as the Z isomer. E / Z isomerization cannot, of course, occur in aromatic double bonds such as those present in the benzene ring. Typically, reductions in E / Z isomerization are achieved when the weight ratio of E to Z isomers in the composition changes more slowly than in the same composition where no particular UV absorber is used.

Pesticides refer to at least one active compound selected from the group consisting of fungicides, insecticides, nematicides, herbicides, antimitigators, pheromones and / or growth regulators. Preferred insecticides are fungicides, insecticides and herbicides. Pesticide mixtures from two or more of the aforementioned classes may also be used. Those skilled in the art will be familiar with such pesticides, see, eg, Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. Suitable insecticides include carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosine, avermectin, milbamycin, larval hormone analogs, alkyl halides, organotin compounds , Neracetoxin analogues, benzoylurea, diacylhydrazine, insecticides from the class of METI acaricides, and chloropicrin, pymetrozine, phlocarmide, clofentezin, hexthiaxose, ethoxazole, diapentthiuron, Insecticides such as propargite, tetradipon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydrmethylnon, acequinosyl, fluacrypyrim, rotenone or derivatives thereof. Suitable fungicides include dinitroaniline, allylamine, anilinopyrimidine, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamate , Carbamate, carboxamide, carboxylic acid amide, chloronitrile, cyanoacetamide oxime, cyanoimidazole, cyclopropanecarboxamide, dicarboximide, dihydrodioxazine, dinitrophenylcrotonate , Dithiocarbamate, dithiolane, ethylphosphonate, ethylaminothiazolecarboxamide, guanidine, hydroxy- (2-amino) -pyrimidine, hydroxyanilide, imidazole, imidazolinone, inorganic Compound, Isobenzofuranone, methoxyacrylate, methoxycarbamate, morpholine, N-phenylcarbamate, oxazolidinedione, oxyminoacetate, oxyminoacet Mead, peptidylpyrimidine nucleoside, phenylacetamide, phenylamide, phenylpyrrole, phenylurea, phosphonate, phosphorothiolate, phthalamic acid, phthalimide, piperazine, piperidine, propionamide, pyridine Dazinone, pyridine, pyridinylmethylbenzamide, pyrimidinamine, pyrimidine, pyrimidinonehydrazone, pyrroloquinolinone, quinazolinone, quinoline, quinone, sulfamide, sulfamoyltriazole, thiazolecarbox Fungicides of amides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines and triazoles. Suitable herbicides are acetamide, amide, aryloxyphenoxypropionate, benzamide, benzofuran, benzoic acid, benzothiadiazinone, bipyridylium, carbamate, chloroacetamide, chlorocarboxylic acid, cyclohexanedione, Dinitroaniline, dinitrophenol, diphenyl ether, glycine, imidazolinone, isoxazole, isoxazolidinone, nitrile, N-phenylphthalimide, oxadiazole, oxazolidinedione, oxacetamide, phenoxy Cicarboxylic acid, phenylcarbamate, phenylpyrazole, phenylpyrazoline, phenylpyridazine, phosphinic acid, phosphoramidate, phosphorodithioate, phthalamate, pyrazole, pyridazinone, pyridine, pyridine Carboxylic acid, pyridinecarboxamide, pyrimidinedione, pyrimidinyl (thio) benzoate, quinolinecarboxylic acid, semicarbazone, sulfonylaminocarbonyltriazolinone, sulfonylurea, te It is a herbicide of zolinone, thiadiazole, thiocarbamate, triazine, triazinone, triazole, triazolinone, triazolinone, triazolocarboxamide, triazolopyrimidine, triketone, uracil, urea .

Pesticides comprising double bonds are generally pesticides comprising C-C double bonds and / or C-N double bonds. Double bonds are usually separated from another multiple bond or conjugated with another multiple bond.

Preferred pesticides comprising double bonds are abamectin, acetamiprid, acrinatrin, azoxystrobin, bifenthrin, butoxycarboxime, chlorfenbin phos, cyhalothrin, 1,3-dichloropropene, dik Rotoforce, Dimethomorph, Diniconazole, Emamectin, Empentrin, Phenpyroximate, Flucycloxon, Flumethrin, Flumorph, Fluoxastrobin, Hydroprene, Kinoprene, Cresoxime- Methyl, lambda-cyhalothrin, metaflumizone, metominostrobin, methoprene, mevinphos, monoclotophos, nitenpyram, oxavetrinyl, phosphamidone, picoxistrobin, propeptamfos, pyrethrin Pyriphenox, tefluthrin, tetrachlorbinfos, trixystrobin, triflumisol, triticazole, uniconazole, and pheromone cardemon (codlemon), dodes-8-enyl acetate, dodes-9 -Enyl acetate, dodeca-7,9-di Neil acetate, farnesol, nerolidol, gossiflu, grand lure ii, grand lure iii, hexades-11-enal, hexades-11-enyl acetate, hexades-13-en-11-ynyl acetate, japony Luer, muscalluer, tetradeca-9,12-dienyl acetate, tetradeca-11-enyl acetate, tetradeca-9-enyl acetate and trides-4-enyl acetate.

Particularly preferred pesticides comprising a double bond are abamectin, acetamiprid, azoxystrobin, bifenthrin, cyhalothrin, dimethomorph, diconazole, emamectin, fluxycloxone, fluoxastrobin , Cresoxime-methyl, lambda-cyhalothrin, metaflumizone, picoxistrobin, trixystrobin, tripleluminizol and triticonazole.

Metaflumizone is a particularly preferred pesticide comprising double bonds.

In another preferred embodiment, pesticides are suitable which comprise a double bond and whose E or Z isomer has a higher activity than other specific isomers. In each case the expression "higher activity" relates to a specific biological activity for a particular target organism. Such activity of the E and Z isomers of pesticides is generally known in the literature. If any one of the isomers has at least 1.1 times (preferably at least 2 times, particularly preferably at least 4 times) activity than that of the other isomers, there is a higher activity.

The E or Z isomer of the pesticide comprising a double bond is preferably up to at least 60% by weight, preferably at least 75% by weight and particularly preferably at least 90% by weight, based on the total amount of the E and Z isomers of the pesticide. Present in quantities up to These values relate to the values at the point when the UV absorber is mixed with the pesticide.

The expression "UV absorber" refers to all compounds that can absorb UV light. UV absorbers can scatter UV light (as in the case of inorganic UV absorbers) or absorb it. The extinction coefficient of the UV absorber for UV light is usually greater than that of the pesticide at the same wavelength. UV absorbers may be oil-soluble or water soluble. They can also be bonded into the polymer, for example copolymerized. The UV absorber may be a UV-A absorber, a UV-B absorber, a broad absorber (ie, UV-A and UV-B) or an optical brightener. UV absorbers can be used in pure form, as a technical grade mixture, or as a mixture of various UV absorbers. Preferred UV absorbers have a solubility in water at 20 ° C. of at least 0.01 μg / l, preferably at least 0.1 g / l, particularly preferably at least 1 g / l.

In a preferred embodiment, the UV absorbers are water soluble. In another preferred embodiment, the composition comprises an additional UV absorber, wherein the additional 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 having a solubility in water at 20 ° C. of at least 5.0 μg / l, preferably at least 10.0 μg / l, particularly preferably at least 50 μg / l, in particular at least 100 μg / l are suitable. Do.

Further oil-soluble UV absorbers typically have a solubility in 20 ° C. water of less than 5.0 μg / l, preferably less than 1.0 μg / l, particularly preferably less than 0.5 μg / l, especially less than 0.1 μg / l. Inorganic UV absorbers are likewise suitable oil-soluble UV absorbers for this purpose.

Suitable UV absorbers are, for example, the following:

A) benzotriazoles, e.g., 2- (2H- benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN ^(Tinuvin),? 900, BASF BASF SE), [3- [3- (2H-Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropyl] -w -[3- [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropoxy] poly (oxy-1,2 ^? - ethanediyl) (Tinuvin 1130, BASF eseuyi), 6-tert- butyl-2- (5-chloro--2H- benzotriazol-2-yl) -4-methyl phenol (Tinuvin 326, BASF eseuyi ), 2,4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -phenol (tinuvin ^? 327, BASF S), 2- (2H-benzotriazole- 2- yl) -4,6-di -tert- pentyl phenol ^(TINUVIN? 320, BASF eseuyi), 2- (2H- benzotriazol-2-yl) -4- (1,1,3,3- tetramethylbutyl) ^-? phenol (Tinuvin 329, BASF eseuyi), 2- (2H- benzotriazol-2-yl) -4-methylphenol (Tinuvin P, BASF eseuyi), 2- (2H- benzo Triazole-2- Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol ^(TINUVIN? 234, BASF eseuyi), 2,2-methylenebis (6- (benzotriazol-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 eseuyi) phenol, 2- (2H- benzotriazol-2-yl) -6-dodecyl-4-methyl-, branched or linear (Tinuvin 171, BASF ^eseuyi)?;

B) a cyanoacrylate, for example, 2-cyano-3-phenyl cinnamate ester (UB Press ^(Uvinul)? 3035, eseuyi BASF), 2-cyano-3,3-diphenyl acrylate, 2 ' -ethylhexyl ester, or 2-ethylhexyl 2-cyano-3-phenyl cinnamate (loam butylene dimethacrylate, UB 539 T press, UB press 3039, BASF ^eseuyi?);

C) para-aminobenzoic acid (PABA) derivatives, in particular esters such as ethyl PABA, ethoxylated PABA, ethyl dihydroxypropyl-PABA, glycerol-PABA, 2-ethylhexyl 4- (dimethylamino) benzoate ( press ^analogy? MC 80), 2- octyl 4- (dimethylamino) benzoate, amyl 4- (dimethylamino) benzoate, 4-bis (poly-ethoxy) -4-aminobenzoic acid polyethoxy ethyl ester (UB press ^? P 25, eseuyi BASF);

D) a salicylic acid ester, for example, 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, menthyl salicylate Homo salicylate, TEA salicylate (Neo-Helio plate (Neo ^Heliopan)? TS, and-hareuman Haarmann and Reimer), dipropylene glycol salicylate;

E) of cinnamic acid esters such as 2-ethylhexyl 4-methoxycinnamate (UB ^press? MC 80), octyl-p- methoxycinnamate, propyl 4- methoxycinnamate, isoamyl 4- Oxycinnamate, synoxate, diisopropyl methylcinnamate, etocrylene (uvinul ^? N 35, BASF SE);

F) Derivatives of benzophenones such as 2-hydroxy-4-methoxybenzophenone (Uvinul ^? M 40, BASF E), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester ^(? UB pressed A Plus, BASF eseuyi), 4-n- octyl-2-hydroxy-benzophenone (UB press 3008, BASF ^eseuyi?); 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-hydroxybenzophenone; Sulfonic acid derivatives of benzophenones such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (Uvinul ^? MS 40, BASF SE) and salts thereof, 2,2'-dihydroxy-4, 4,4'-dimethoxy benzophenone-5,5'-sulfonic acid and its salts (disodium ^salt: UB press DS 49, eseuyi BASF);

G) 3-benzyl-Li denkam formate and its derivatives, e.g., 3- (4'-methylbenzylidene) d -1- camphor, benzyl Fort Lee denkam acid (MEC talking ^(Mexoryl)? SO, key Mex ( Chimex));

H) sulfonic acid derivatives of 3-benzylidenecamphor, for example 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) Sulfonic acid and salts thereof;

I) esters of benzalmalonic acid, for example 2-ethylhexyl 4-methoxybenzalmalonate;

J) triazine derivatives, such as, dioctyl butanone shown triazol zone (Uva sorbitan probe ^(Uvasorb)? HEB, Sigma (Sigma)), 2,4,6- tree anilino -p- (carbonate-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 eseuyi), no small-triazine (Martino sorbitan ^? probe (Tinosorb) S, eseuyi BASF), 2,4,6-tris (diisobutyl 4'-amino-malonate benzalkonium) -s- triazine;

K) propane-1,3-dione, for example 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;

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

M) derivatives of benzoylmethane, for example 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) amino-hydroxy-substituted derivatives of benzophenone, for example N, N-diethylamino-hydroxybenzoyl-n-hexyl-benzoate;

O) containing the derivatives, examples of the stilbene, as a salt of diseuti rilbi diphenyl sulfonates, e.g., sodium diseuti rilbi phenyl di-sulfonate (UB-Tex ^(Uvitex)? NFW, eseuyi BASF), 2,2 ' -[1,2-ethenediylbis [(3-sulfo-4,1-phenylene) imino- [6- (diethylamino) -1,3,5-triazine-4,2-diyl] no]] bis-1,4-benzene disulfonic acid sodium salt six ^(? Martino arm (Tinopal) SFP, eseuyi BASF);

P) inorganic UV absorbers, for example, ZnO-based UV absorber (for example, Z- Court ^(Z-Cote)? Products, BASF eseuyi), TiO ₂ Based UV absorber (e. G., T- light (T-Lite) ^TM Products, BASF S) or CeO ₂ based UV absorbers, and the UV absorbers described in WO 2009/153231 (p. 24 to p. 6, line 18).

Preferred UV absorbers are those of group F) (derivatives of benzophenone) and group O) (derivatives of steelbene), particularly preferably 2-hydroxybenzophenone derivatives, sulfonic acid derivatives of benzophenone and distyrylbiphenyldisulfo Salts of nates, especially 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, disodium distyrylbiphenyldisulfonate and 2-hydroxy-4-oct Oxybenzophenone.

In another preferred embodiment, at least two UV absorbers are used. In this connection, UV absorbers of groups A) to N) and UV absorbers of group O) are preferably used.

In a particularly preferred embodiment, UV absorbers comprising sulfonic acid groups or polyalkylene oxide groups are used. Preferred are UV absorbers comprising sulfonic acid groups.

UV absorbers comprising sulfonic acid groups are known. Examples are 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (UB ^press? MS 40, BASF eseuyi) and its salts (e.g., alkali metal salts such as sodium salt), 2,2'-dihydroxydiphenyl Hydroxy-4,4'-dimethoxybenzophenone-5,5'-sulfonic acid and salts thereof (eg alkali metal salts such as sodium). Preferred are benzophenones (also called sulfonic acid derivatives of benzophenones) comprising sulfonic acid groups. Sulfonic acid groups can exist in acid form or as salts, with salt forms being preferred.

UV absorbers comprising polyalkylene oxide groups are known. Polyalkylene oxide groups preferably include ethylene oxide in the polymerized form. Preferably at least 50 mol%, in particular at least 80 mol%, of the alkylene oxide groups are ethylene oxides. An example is 4-bis (polyethoxy on) -4-aminobenzoic acid polyethoxy ethyl ester (UB ^press? P 25, BASF eseuyi) on.

The amount of UV absorber is usually from 0.5 to 500% by weight relative to the amount of pesticide. The amount is preferably 1 to 300% by weight, particularly preferably 5 to 100% by weight, more particularly 5 to 80% by weight, in each case relative to the amount of pesticide.

In a preferred embodiment, antioxidants (also called antioxidants) are used in combination with UV absorbers. Preferred antioxidants have a solubility in water at 20 ° C. of at least 0.01 g / l, preferably at least 0.1 g / l, particularly preferably at least 1 g / l. In another preferred embodiment, suitable antioxidants have a solubility in water at 20 ° C. of at least 5.0 μg / l, preferably at least 20 μg / l, particularly preferably at least 100 μg / l.

Antioxidants include, for example, amino acids (eg glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazole and imidazole derivatives (eg urocanoic acid), peptides such as D, L -Carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g., anserine), carotenoids, carotene (e.g., α-carotene, β-carotene, lycopene) and derivatives thereof, liphonic acid and Derivatives thereof (e.g., dihydroliponic acid), orothioglucose, propylthiouracil and other thio compounds (e.g. thioglycerol, thiosorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cis Amine, and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof, dilauryl tea Odypropionate, Distearyl Tee Dipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), as well as very low tolerated doses of sulfoximine compounds (e.g. butionine sulfoximine, Homocysteine sulfoximine, butionine sulfone, penta-, hexa-, heptathione sulfoximine, and also metal chelators (e.g., α-hydroxy-fatty acid, EDTA, EGTA, phytic acid, lactoferrin), α- Hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, gallic acid esters (eg propyl, octyl and dodecyl gallate), flavonoids, catechol, bilirubin, biliberdine and Derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and derivatives thereof, hydroquinones and derivatives thereof (e.g. arbutin), ubiquinones and oils Quinol and its derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphate, sodium and magnesium ascorbate, disodium ascorbyl phosphate and Sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and derivatives thereof, tocopherol and derivatives thereof (e.g. tocopheryl acetate, linoleate, oleate and succinate, tocopheretate -5, tocopheret-10, tocopheret-12, tocopheret-18, tocopheret-50, tocophersollan), vitamin A and derivatives thereof (e.g. vitamin A palmitate), benzoin Coniferylbenzoate, rutin, root acid and derivatives thereof, disodium rutinyl disulfate, cinnamic acid and derivatives thereof (e.g., ferulic acid, ethyl ferulate, Copeic acid), gallic acid and esters thereof such as propyl gallate, kojic acid, chitosan glycolate and salicylate, butylhydroxytoluene, butylhydroxyanisole, tetrakis [methylene (3,5-di-) t-butyl-4-hydroxyhydrocinnamate] -methane (Irganox ^? 1010, BASF SE), nordihydroguaiac resinic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, 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), copper chloride (I) salts of monovalent copper, 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'-bisporyl-N, N'-bis- (2,2,6,6-tetramethyl-4-piperidinyl)- hexa methylene diamine (UB ^press? 4050 H, BASF eseuyi).

Preferred antioxidants include vitamin C and its derivatives, tocopherol and its derivatives, salts of monovalent copper, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (tinuvin ^? 770), 2 -(2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol (tinuvin ^? 171), N, N'-bisporyl-N, N'-bis- (2,2, It is hexamethylene diamine (UB press 4050 H, BASF eseuyi) - ^{6,6-tetramethyl-4-piperidinyl)?}

The weight ratio of UV absorber to oxidant is generally in the range 1/10 to 100/1, preferably in the range 1/5 to 10/1, particularly preferably in the range 1/1 to 5/1.

The invention also relates to a composition comprising the E and / or Z isomers of the pesticide comprising a double bond and the UV absorber. Suitable and preferred pesticides comprising a double bond are as described above. The E isomer or Z isomer of the pesticide is usually present in an amount of up to at least 60% by weight, preferably at least 75% by weight and particularly preferably at least 90% by weight, based on the total amount of the E and Z isomers of the pesticide. . It is preferred that an excess of isomers having higher pesticidal activity is present.

Suitable UV absorbers are as described above. The UV absorber is preferably a derivative of benzophenone or a derivative of stilbene. In another preferred embodiment, at least two UV absorbers are used. Suitable weight ratios of UV absorbers to metaflumizone pesticides are as described above. In addition to the UV absorbers, antioxidants as described above may be used.

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

Insecticides such as metaflumizone are typically present in composition types common to agrochemical formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The type will depend on the intended use and in any case a fine and homogeneous distribution of the compound according to the invention should be ensured. Examples of composition types are soluble or to be soluble in suspensions (SC, OD, OESC), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, capsules (CS), water Animal bites such as wettable powder or dust (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), or LLIN (long-term insecticide net), ant or rat bait). Bites may be present in various forms of the types of compositions described above, preferably in powders, pastes, granules or gels. Generally, the type of composition (eg, SC, EC, OD, WG, SG, WP, SP, SS, WS) is used in diluted form. Composition types such as DP, DS, GR, FG, GG, MG or Bite are generally used undiluted. Preferred composition types are suspensions.

In a preferred embodiment, an aqueous composition type, for example an aqueous suspension concentrate, or an oil-containing suspension concentrate (OESC) is suitable. The pH of the aqueous composition type is typically greater than 1.0, preferably greater than 3.0, particularly preferably greater than 3.5. The pH is usually below 6.0, preferably below 5.0, particularly preferably below 4.5. Suitable pH ranges are, for example, 2.5 to 5.5, preferably 3.0 to 5.0.

UV absorbers and / or antioxidants may be contacted with pesticides in advance in the preparation of agrochemical formulations.

Agrochemical formulations may further include auxiliaries customary in plant protection compositions, which are selected according to the specific use form or active compound. Examples of suitable adjuvants include solvents, solid carrier materials, surface-active substances (eg, additional solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreezes, antifoams, optionally dyes And adjuvants (eg, attractants, food, bitters) that are customary in adhesives (eg for seed treatment) or bite formulations.

Solvents that can be used include water, organic solvents such as medium to high boiling mineral oil fractions, such as kerosene and diesel oils, as well as coal tar oils and oils of plant and animal origin; Aliphatic, cyclic and aromatic hydrocarbons such as paraffin, tetrahydronaphthalene, alkylated naphthalene and derivatives thereof, alkylated benzene and derivatives thereof; Alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as glycol, cyclohexanone, gamma-butyrolactone, dimethyl-fatty acid amides, fatty acids and fatty acid esters, and N-methylpyrrolidone Strong polar solvents such as amines. In principle, not only solvent mixtures but also mixtures of the aforementioned solvents and water can also be used.

Solid carrier materials include inorganic earth powders such as silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, roam, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide Fertilizers such as crushed plastics, ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, and plant products such as flour, bark, wood and nut hulls, cellulose powder or other solid carrier materials.

Surface which can be used - the active substance (adjuvants, wetting agents, adhesives, dispersants or emulsifiers) are the aromatic sulfonic acids, such as, ^lignin-(? Borane Spurs (Borresperse) type, Norway borane the ad (Borregaard)), Phenol, naphthalene - ^(? know wet (Morwet) type, US Akzo Nobel (Akzo Nobel)) and dibutyl-naphthalene-sulfonic acid ^(? nekal (nekal) type, Germany BASF (BASF)), and alkali metal, alkaline earth metal and ammonium salts of fatty acids, Condensation of formaldehyde with alkyl- and alkylarylsulfonates, alkyl, lauryl ethers and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanol, as well as fatty alcohol glycol ethers, sulfonated naphthalenes or derivatives thereof Product, condensation product of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl Tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol-ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate , sorbitol esters, lignin-sulfite waste liquid, and proteins, denatured proteins, polysaccharides (e.g., methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mo wiol (Mowiol) type, Switzerland Cloud Liang ^(Clariant? )), poly-carboxylate (sokalran ^(Sokalan)? type, Germany BASF), poly alkoxylate, polyvinylamine (Lufa District Min ^(Lupamin)? type, Germany BASF), polyethylene imine (Lufa District brush ^(Lupasol)? type , BASF, Germany), polyvinylpyrrolidone and copolymers thereof.

Examples of thickeners (i.e. compounds which impart modified flow properties to the composition, i.e., compounds which give high viscosity in stationary and low viscosity in agitated state) are polysaccharides and organic and inorganic stacked minerals such as xanthan gum ( keljan ^(Kelzan)?, United States kelko CP (CP Kelco)), also Paul ^(Rhodopol)? 23 (Rhodia, France) or Veegum ^? (RT Vanderbilt, USA) or Attaclay ^? (Engelhard Corp., NJ).

A bactericidal agent may be added to stabilize the composition. Examples of live bacterial agents include dichloro-pen and a benzyl alcohol hemi formal, as well as iso-thiazolidine derivative, for example, was the alkyl benzisothiazolinone and benzisothiazolinone the BBIT substrate (actinoids side ^(Acticide)? MBS Thor Chemie).

Examples of suitable cryoprotectants are ethylene glycol, propylene glycol, urea and glycerol.

Examples of anti-foaming agents are silicone emulsions (such as, silicon (Silikon) SRE, Germany wakkeo ^(Wacker);?? Or also room (Rhodorsil), France Rhodia (Rhodia)), salts of long-chain alcohols, fatty acids, fatty acids, organic fluoro Lean compounds and mixtures thereof.

Agrochemical formulations can be sprayed, mistered, sprayed in the form of their compositions, eg, directly in the form of sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dust compositions, spraying compositions or granules ( It can be used by dusting, scattering, biting, brushing, dipping or pouring.

Aqueous use forms can be prepared by adding water to emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions). For the preparation of emulsions, pastes or oil dispersions, the material is homogenized with water, as a solution in oil or solvent, using a wetting agent, an adhesive, a dispersing agent or an emulsifier. However, concentrates comprising wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oils suitable for dilution with water can be prepared from the active substance.

Various oils, wetting agents, adjuvants, herbicides, bactericides, other fungicides and / or pest control agents may be added to the active compounds or compositions comprising them, optionally only immediately before use (ie in a tank mix). have. These agents may be mixed in the composition in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

In addition, UV absorbers and / or antioxidants may be contacted with the pesticide only just prior to use (ie in a tank mix).

Adjuvants which can be used in this regard are, in particular, organic modified polysiloxanes, for example Break Thru S 240 ^? ; Alcohol alkoxylates, such as Atplus ^? 245, Art Plus ^? MBA 1303, Plurafac ^? LF 300 and Lutensol ^? ON 30; EO-PO block polymers such as Pluronic ^? RPE 2035 and Genapol ^? B; Alcohol ethoxylates such as Lutensol ^? XP 80; And sodium dioctyl sulfosuccinate, for example Leophen ^? RA.

The active compound concentration in the ready-to-use formulations can vary in a relatively wide range. In general, the active compound concentration is 0.0001 to 10%, preferably 0.01 to 1%. The amount used for plant protection is from 0.01 to 2.0 kg of active compound per hectare, depending on the nature of the desired effect. In the treatment of plant propagation materials, for example seeds, generally the amount of active compound is used in an amount of 1 to 1000 μg per 100 μg of seed or preferably 5 to 100 g per 100 μg of seed. When used in the protection of materials or stored products, the amount of active compound applied will depend on the nature of the field of use and the desired effect. Amounts conventionally applied for substance protection are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg of active compound per cubic meter of material to be treated.

The invention also relates to a method for controlling phytopathogenic fungi and / or undesirable plant growth and / or invasion of undesirable insects or mites and / or controlling plant growth, the method comprising Action on a particular pest, its habitat, or a plant, soil and / or undesirable plant and / or crop plant and / or its habitat to be protected from a particular pest.

The present invention has a wide variety of advantages: the rate of E / Z isomerization is significantly reduced. The applied isomers remain active for a longer period of time under sunlight. As a result, the application rate of the active compound such as metaflumizone can be reduced. The active compound applied has a fairly long residual activity since the more active isomer applied is converted more slowly to the less active isomer. The present invention can be readily industrially employed because the UV absorber can be easily mixed with the pesticide as a tank mix by the user at the time of preparation of the agrochemical formulation or immediately before use. Antioxidants may be added to further enhance the action of the UV absorber to reduce E / Z isomerization. Water soluble UV absorbers are particularly advantageous because such compositions are also very storage stable and can be easily added as a tank mix by the user (as the absorbent dissolves quickly and is uniformly dispersed in the aqueous tank mix). Water-soluble UV absorbers can easily be incorporated into aqueous formulations and incorporated into them more easily, while, for example, water-insoluble UV absorbers must be further comminuted with the active compound.

The following examples illustrate the invention in more detail rather than limiting it.

<Examples>

Metaflumizone SC: 240 g / l (22.2 wt%) metaflumizone, 2 wt% sodium dioctyl sulfosuccinate, 3.5 wt% ethoxylated C ₉ -C ₁₁ alcohol and 3 wt% polyaryl An aqueous suspension concentrate comprising phenol ethoxylate.

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

Ubitex ^? NFW: 4,4'-bis (2-sulphostyryl) -biphenyl disodium salt

Ubinul ^? 3050: 2,2 ', 4,4'-tetrahydroxybenzophenone

Ubinul ^? M40: 2-hydroxy-4-methoxybenzophenone

Ubinul ^? 4050H: N, N'-bisporyl-N, N'-bis- (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine

Ubinul ^? A plus: 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester

Ubinul ^? 3008: 2-hydroxy-4-octyloxybenzophenone

Ubinul ^? MS 40: 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid

Tinuvin ^{Is your company?} 770: bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate

Tinuvin ^{Is your company?} 171: 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol

Z- ^coat? Zinc oxide, micronized

Example  1-preparation of the mixture

Metaflumizone SC is mixed with a certain amount (in each case wt% of metaflumizone) UV absorbers and / or stabilizers, the mixture is diluted with water in a weight ratio of 1:18 and stirred at room temperature for 1 hour. .

Example  2-investigation and analysis of isomerization

20 mg of the mixture prepared in Example 1 was dropped on a glass plate and allowed to dry for 1 hour at room temperature. Samples were irradiated with UV light (Sun Test CPS +, Atlas Co., 750 watts, wavelength 300-800 nm) for 0, 30 or 120 minutes. After irradiation, the sample was washed with 2.0 ml of DMSO from the glass plate and homogenized with stirring by ultrasonic (15 s) means. Samples were separated into E and Z isomers of metaflumizone by UPLC (ultra high performance liquid chromatography, BEH C18 column, detected at 225 nm) and quantified by peak area. In each case, the content of the E isomer was recorded, and the content of the Z isomer was 100% minus the content of the E isomer.

Example  3-various UV  Test of absorbent

The mixture was prepared as in Example 1 and tested as in Example 2 (Table 1). Most of the various UV absorbers have been found to reduce E / Z isomerization compared to mixtures that do not include UV absorbers.

Example  4 - UV  Absorbents and antioxidants or additional UV  Mixture with Absorbent

The mixture was prepared as in Example 1 and tested as in Example 2 (Table 2). Compared to a mixture without a UV absorber, a mixture of a UV absorber with an antioxidant (e.g., tocopherol, ascorbic acid, uvinul 4050H, tinuvin 770) or an additional UV absorber (e.g. Z-coat) It has been found to reduce / Z isomerization.

Example  5 - Suspension  Preparation of Concentrates

The following components were mixed and triturated to prepare an aqueous suspension concentrate of metaflumizone: 180 g / l metaflumizone, 27 g / l sodium dioctyl sulfosuccinate, 54 g / l propylene glycol, 1.1 g / l xanthan gum, 33 g / l ethoxylated tristyrylphenol. The water insoluble UV absorber or stabilizer was added before grinding, while the water soluble UV absorber or stabilizer was added after grinding and dissolved with stirring. The amount of UV absorber or stabilizer is in each case expressed in weight percent relative to metaflumizone. Particle sizes were D90 μs <2.0 μm and D50 <1.0 μm.

Example  6 - Suspension  Test of Concentrate

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

Example  7-diluted Suspension  Test of Concentrate

Suspension concentrates were prepared as in Example 5 and tested as in Example 2 (Table 4). A 1:18 dilution with water as in Example 2 yielded a formulation with 5% content in water. Here it was further diluted with water, further lowering the content by 1%. This dilution rate corresponds to the usual dilution rates that are used in commercial active compound concentrates to obtain spray tank mixes immediately. It has been found that diluted formulations likewise reduce E / Z isomerization.

Example  8 - On white cabbage  For outdoor test

The following components were mixed and triturated to prepare an aqueous suspension concentrate “SC-A” of metaflumizone: 180 g / l metaflumizone, 22 g / l sodium dioctyl-sulfosuccinate, 35 g / l of ethoxylated C _{9 -11} alcohol, 30 g / l of a poly aryl phenol ethoxylate, xanthan gum (thickener) of 1 g / l, and 50 g / l of alkane diol (cryoprotectant).

108 g / l Ubinul on SC-A ^? MS 40 was added to prepare an aqueous suspension concentrate “SC-A + UV1”.

25 g / l Ubinul on SC-A ^? MS 40 was added to prepare an aqueous suspension concentrate “SC-A + UV2”.

50 g / l Ubinul on SC-A ^? MS 40 was added to prepare an aqueous suspension concentrate “SC-A + UV3”.

108 g / l Ubitex in SC-A ^? NFW was added to prepare an aqueous suspension concentrate "SC-A + UV4".

White cabbage was cultivated on a test plantation in the Philippines. The plantation was sprayed at an application rate of 160 g metaflumizone per ha. Then, 14 days later, Crocidolomia The cumulative feeding damage caused by binotalis ) was evaluated (Table 5). As a result of the addition of the UV absorber, the active ingredient showed higher activity for a longer time.

Cumulative Feeding Damage Rate [%] SC-A 123 SC-A + UV1 98

Example  9 - On white cabbage  For outdoor test

White cabbage was grown on test farms in California. The plantation was sprayed at an application rate of 160 g metaflumizone per ha using the suspension concentrate according to Example 8. Subsequently, after 14 days, the mortality rate of the Lepidoptera larvae was confirmed (Table 6). As a result of the addition of the UV absorber, the active ingredient showed higher activity for a longer time.

Lethality [%] SC-A 41 SC-A + UV1 70

Example  10-outdoor test for potatoes

Potatoes were grown on test plots in North Carolina, USA (plot 7 * 1 m, 3 plots per test point). The plantation was sprayed at an application rate of 60 g metaflumizone per ha using the suspension concentrate according to Example 8. 19 days later, Leptinotarsa decemlineata ) the number of larvae (all larval stages) and their gnawing damage rates were identified (Table 7). As a result of the addition of the UV absorber, the active ingredient showed higher activity for a longer time.

Number of larvae Eating Damage Rate [%] Untreated 150 58 SC-A 105 32 SC-A + UV1 22 15 SC-A + UV2 12 10

Example  11- UV chamber , Lima Bean ( lima bean )

Lima beans in the growth stage with the first lobe were sprayed with 30 g metaflumizone per ha in a laboratory spray chamber. The plants were transferred to a growth chamber with UV light and fluorescent light and irradiated for 24 hours every day. After 3, 10, 14 and 17 days (DAT), the leaves were removed and placed in a Petri dish with the wet piece of filter paper. 5 Spodoptera Eridania on each dish ( Spodoptera Eridania ) (Southern Night Beetle , Larva Phase 3). Four replication tests were conducted for each test. Cumulative eating damage rates are summarized in Table 8.

Eating Damage Rate [%] SC-A 97 SC-A + UV1 58 SC-A + UV2 52 SC-A + UV3 61

Example  12-outdoor test for potatoes

Potatoes were grown on test plots in North Carolina, USA (plot 7 * 1 mm, 3 plots per test point). The plantation was sprayed at a rate of application of 30 or 60 μg of metaflumizone per ha using the suspension concentrate according to Example 8. Subsequently, after 19 days, the number of Leptinotarsa dessimernata larvae (all larval stages) was identified (Table 9). As a result of the addition of the UV absorber, the active ingredient showed higher activity for a longer time.

Average number of larvae per plot 30 g metaflumizone / ha 60 g metaflumizone / ha Untreated 150 150 SC-A 145 105 SC-A + UV1 37 22 SC-A + UV2 27 12 SC-A + UV4 123 61

Claims (16)

Use of a UV absorber for reducing the E / Z isomerization of a pesticide comprising a double bond. The use according to claim 1, wherein the double bond is a C-C double bond or a C-N double bond. The use according to claim 1 or 2, wherein the E or Z isomer of the pesticide is present in an amount up to at least 60% by weight based on the total amount of the E and Z isomers of the pesticide. The use according to any one of claims 1 to 3, wherein the UV absorber comprises a sulfonic acid group or a polyalkylene oxide group. The use according to any one of claims 1 to 4, wherein the UV absorber comprises sulfonic acid groups. The use according to any one of claims 1 to 5, wherein the amount of UV absorber is 0.5 to 500% by weight relative to the amount of pesticide. 7. Use according to any of the preceding claims, wherein an antioxidant is used in addition to the UV absorber. 8. Use according to claim 7, wherein the weight ratio of the UV absorber to the antioxidant is in the range of 1/10 to 10/1. The use according to any one of claims 1 to 8, wherein at least two UV absorbers are used. E and / or Z isomers of the pesticide comprising a double bond and UV absorbers, wherein the E or Z isomer of the pesticide is present in an amount of at least 60% by weight based on the total amount of the E and Z isomers of the pesticide. And the solubility of the UV absorber in water at 20 ° C. is at least 5.0 μg / l. The composition of claim 10 wherein the UV absorber comprises a sulfonic acid group or a polyalkylene oxide group. The composition of claim 10 or 11 wherein the UV absorber is a sulfonic acid derivative of benzophenone. 13. The composition of any one of claims 10-12 comprising an additional UV absorber that is oil-soluble. The composition of claim 10, wherein the pesticide is metaflumizone. The composition of claim 14, wherein the E isomer of metaflumizone is present in an amount up to at least 60% by weight based on the total amount of the E and Z isomers of metaflumizone. A composition according to any of claims 10 to 15 to act on a particular pest, its habitat or a plant, soil and / or undesirable plant and / or crop plant and / or its habitat to be protected from a particular pest. A method of controlling and / or controlling plant growth of phytopathogenic fungi and / or undesirable plant growth and / or undesirable insects or mites, including