A NEW FUNGICIDAL COMPOSITION, PROCESSES FOR ITS PRODUCTION AND ITS USE

Abstract: The invention relates to new fungicidal compositions consisting of one or more fungicidally active ingredients and one or more certain phospholipides in addition to standard vehicles, diluents, solvents and/or other inert auxiliaries, the ratio by weight of fungicidally substances to pure phospholipide or the mixture of pure phospholipides amounting to between 1 : 0.2 and 1 : 20. The invention also relates to processes for controlling fungal diseases using these compositions and to processes for their production.

Description: A new fungicidal composition, processes for its production and its use This invention relates to a new fungicidal tomposition, to processes for its production and to its use. Fungicides' are used primarily for treatinfr crops and also for treating seeds, aetual plants and for decontaminating soil. For controlling fungal diseases, it is now essential to use chemical fungus control agents or fungicides. Numerous chemical substances have been used for controlling fungi. However, fungicides currently in use are still attended by some as yet unsolved problems. Thus, most fungicides are not sufficiently stable. They often have to be used in large quantities and, as a result, can beeome a source of toxic pollution to the environment. The adhesion of the fungicides to the plants or to the seeds or soil is not always satisfactory so that full activity cannot be developend. Accordingly, it would be desirable to have fuiigicides which adhere firmly to the specimens or are &alpha; to be protected, disintegrate readily and are effective even in very los concentrations. Another requirement Is ease of handling both during production and during application of the fungicides. It has now surprisingly been found that the quantity of fungicide per hectare of cultivated area required Tr fungus control can be reduced by up to 40-60% and, in some cases, by up to 80% providing the fungicidally active substance or the mixture of several fungicidally active substances is used in admixture with a phospholipide from the group comprising phosphatidyl choline, hydrogenated phosphatidyl cholines, phosphatidyl erhanolamine, N-acyl phosphatidyl ethanolamines, phosphatidyl inositol, phosphatidyl serine and phosphatidy glycerol or with a mixture of several such phospholipides in a ratio by weight of from 1:0.' to 1:20. In addition, the new mixtures show considerably better adhesion to the produce to be protected, particularly to leaves in the case of plants or, where-they are used for disinfection, to the specimen or area to be disinfected. The improvement in adhesion also provides for uniform distribution of the fungicide over the specimens or area to be protected so that, despite a considerable reduction in the quantity of chemical fungicide used, excellent long-lasting activity is obtained. In addition to an improvement in the economy of the treatment, this also results in less pollution of the environment and in a reduction in the waiting time following a fungicidal treatment. Finally, most of the phospholipides are natural and, in every case, non-toxic products which, by virtue of their nature and their properties, do not themselves cause any pollution of the environment or have any adverse effect upon the waiting time. Some of the phospholipides are of course even used in foods. To produce the new fungicidal composition, the fungicide(s) is/are mixed with the phospholipide or phospholipide mixture in a ratio by weight of from 1:0.2 to 1:20 and preferably in a ratio by weight of from 1:0.5 to l:t0, but more preferably in a ratio by weight of from 1:1 to 1:5. In this connection, the weight of the phospholipide(s) is based on substantially pure phospholipide. Suitable phospholipides are, for example, the commercially available phosphatidyl cholines or phosphatidyl choline mixtures, such as PhospholiponR25 (25% of phosphatidyl choline, 25k of phosphatidyl ethanolamine, 20% of phosphatidyl inositol) PhospholiponR55 (55% of phosphatidyl choline, 25% of phosphatidyl ethanolamine, 2% of phosphatidyl inositol) PhospholiponR80 (80% of phosphatidyl choline, 10% of phosphatidyl ethanolamine) PhospholiponR100 (96% of phosphatidyl choline) PHospholiponR100H (96% of hydrogenated phosphatidyl choline) PhosphoIiponR38 (38 of phosphatidyl choline, 16k of N-acetyl phosphatidyl ethanolamine, 4% of phosphatidyl ethanolamine). It is particularly preferred to use natural phosphatidyl cholines which may be obtained by the processes described in the following Patents: DE-S No. 1,047,579, DE-PS No. 1,053,299, DE-PS No. 1,617,679, DE-PS No. 1,617,680, German Patent Applications Nos. P 30 47 048.5, P 30 47 012.3 and P 30 47 011.2. Suitable N-acyl phosphatidyl ethanolamines are in particular those in which the acyl group emanates from saturated or olefinically unsaturated fatty acids containing from 2 to 20 carbon atoms, particularly from saturated fatty acids containing from 2 to 5 earbon atom or from saturated or mono-olefinieally unsaturated fatty acids containing 14, 16, 18 or 20 earbon atoms. The fungicide used may be virtually any fungicide, such as known fungicides from the following groups; 1. Aromatic nitro compounds corresponding to the following general formula EMI3.1 in which R1 represents C2-C4-alkenyl or branched alkoxy, particularly C1-C 4-alk oxy, R2 represents C2-C6-alkyl. The compounds corresponding to formula I are known compounds. Suitable examples are 2,4-dinitro-6-(2-butyl)-phenyl-3',3'-dimethyl acrylic acid ester (binapacryl), 2,4-dinitro-6-(2-butyl)-phenyl isopropyloxy carboxylic acid ester (dinobuton), 2,4-dinitro-6-(2-octyl)-phenyl crotonic acid ester (dinocap). 2. Chlorobenzenes corresponding to the following general formala EMI4.1 in which R1 represents Cl or H, R2 represents Cl,-OCH3 or H, R3 represents Cl or -ON, R4 represents C1 or H and R5 represents -CN,-OCH3 or -NO2. The compounds corresponding to formula II are known compounds. Suitable examples are hexachlorobenzene, petachloronitrobenzene (quintozen), 1,3-dicyano-2,4,5,6tetrachlorobenzene (chlorthalonil), 1,4-dichloro-2,5- dimethoxybenzene (chloroneb), 2,3,5,6-tetrachloronitrobenzene (teenazen). 3 Phthalic acid derivatives corresponding to the following general formula EMI5.1 in which R represents alkylthio, particularly C1-C4-alkylthio, more particularly methylthio, haloalkyl, particularly C1-C4-haloalkyl, more particularly trichloromethyl ol thionophosphoryl. The compounds corresponding to formula Ill are known compounds. Suitable examples are ditalimphos [N-(diethoxy-thiophosphoryl)-phthalimide], captan [N-(trichloromethylthio)-phthalimide], folpet [N-(trichloromethylthio)-phthalimide], captafol [N-(1,1,2,2-tetrachloroethylthio)-phthalimide], chlorothalonil or nitrothal. 4. A fungicide from the group of thiocarbamates: ferbam, macozeb, maneb = manganese ethylene-1,2-bis-dithiocarbamate, metiram, methyl metiram, propamocarb, propineb = zinc propylene-1,2-bis-dithiocarbamidate, prothiocarb = S-ethyl-N- (3-dimethylaminopropyl )- thiocarbamate hydrochloride, vondozeb, zineb = zinc ethy.lene-1,2-bis-dithiocarbamidate, zinoc = N-methylene-bis-(zinc ethylene-bis-dithiocarb- amidate), ziram = zinc dimethyl dithiocarbamate, thiram = bis-(dimethylthiocarbamoyl)-disulfide. 5. A fungicide from the group of benzimidazoles, such as benomyl = 1-(n-butylcarbamoyl)-2-methoxycarbonylamino)benzimidazole, carbendazin = 2-(methoxycarbonylamino)-benzimidazole, fuberidazol = 2-(2-furyl )-benzimidazole, rabenzazol, thiabendazol = 2-(4-thiazolylr-benzimidazole. - 6. A fungicide from the group of aniline derivatives, for example, benodanil = 2-iodobenzoic acid anilide, carboxin = 2,3-dihydro-2-methyl-1,4-oxathiine-3carboxanilides, chloraniformethan = N-formyl-N'-3,4-dichlorophenyl- trichioroacetaldehyde aminal, dicloran = 2, 6-dichloro-4-nitroaniline, fenfuram, furaloxw methfuroxam, oxycarboxin = 2,3-dihydro-6-methyl-1,4-oxathiine-5carboxylic acid anilide-S-dioxide. 7. Other fungicides which may be used: thiophanat = 1,2-bis-(3-methoxycarbonyl-2-thioureido) benzene, dodemorph = N-cyclododecyl morpholinium acetate, tridemorph = N-tridecyl-2,6-dimethyl morpholine, anilazin = 2,4-dichloro-6-(O-chloroanilino)-S-triazine, bupirimat = 2-ethylamino-4-dimethylamidosulfonate-5butyl-6-methyl pyrimidine, cetactaelat, chinomethionat = 6-methylquinoxaline-2,3-dithiocyclocarbonate, chlormethionat, dichlorfluanid = N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide, dimethirimol = 5n-butyl-2-dimethylamino-4-hydroxy-6 methylpyrimidine, dithianon = 2,3-dicyano-1,4-dithia-anthraquinone, dodin = n-dodecyl guanidine acetate, ethirimol = 2-ethylamino-5n-butyl-4-hydroxy-6- methylpyrimidine, fenaminsulf =- p-dimethylaminobenzene disulfonate-Nasalt, fenarimol = &alpha;-(2-chlorophenyl)-&alpha;-(4-chlorophenyl)-5- pyrimidine methanol, iprodion = 1-isopropylcarbamoyl-3-(3,5-dichlorophenyl)hydantoin, pyrazophos = 0, O-diethyl-O (5-methyl-6-ethyloxycarbon- ylpyrazolo-[1,5-a]-pyrimidin-2-yl)-thiophosphate, tolylfluanid = N,N-dimethyl-N'-(4-methylphenyl)-N'- fluorodichloromethylthiosulfamide, triadimefon = 1-(4-chlorophenoxy)-3,3-dimethyl-1 (1,2,4-triazol-1-yl)-2-butanone, triadimenol, triforin = 1,4-di-(2,2, n t -trichloro-l-formamidoeityl)- piperazine, vinclozolin = 3-(3' ,5'-dichlorophenyl)--5-methyl-5 vinyl-1,3-oxazolidin-2,s-dione. The individual fungicides are used on their own or in combination with other fungicides after the addition of phospholipides. The new fungicidal compositions may be used for controlling a variety of fungal diseases, including for example leaf blight in potatoes and tomatoes (Alternaria solani); grey mold in onions (Botrytis allii); grey rot and botrytis in strawberries and grapes; Dutch elm disease (Ceratocystis ulmi); leaf spot in beet crops (Cercospora beticola); banana spot disease (Cercospora musae); peach scab (Cladosporium carpophilum); cucumber scab (Cladosporium cucumcrinum); brown spot or downy spot in tomatoes (Cladosporium fulvum); shot disease in stone fruit (Clasterosporium carpophilum); ergot in rye (Clavicep purpurea); spray spot disease in cherries (Coccomyces hiemalis); leaf spot in beans (Colletotrichum lindemuthianum); leaf spot in roses (Diplocarpen rosae); black spot in roses (Marssonia rosae); powdery mildew in cucumbers tEryiphe cichoracearum); mildew in cereal crops (Eryspihe graminis); leaf blister in tea (Exobasidium vexans); stem rot (Fusarium culmorum); shrivelling disease in tomatoes (Fusarium oxysporum); Panama disease in bananas, snow rot in cereal crops (Fusarium nivale); cherry scab (Fusicladium cerasi); cluster cup rust in pears (Gymnosporangium sabinae); line disease in barley (Helminthosporium gramineum); coffee rust (Semileia vastatrix); black leaf (Mycena citricolor); blue mold in tobacco (Pernospora tabacina); root rot in beet crops (Phomabetae); rose rust, apple collar rot, blight and rot in potatoes, brown rot in tomatoes (.Phytophthora infestans); Brusone disease in rice (Pyricularia oryzae); leaf drop disease, leather berry disease, apple blight (Podosphaera ieucotricha); hop mildew (Spaerotheca humuli); rose mildew (Spaerotheca pannosa); wart disease in potatoes (Synchytrium endobioticum); bunt, stinking smut in wheat (Tilletia caries); loose smut in oats (Ustilago avenae), barley (Ustilago nuda); and wheat (ustilago triticit; apple scab, pear scab, verticillum wit, wilting diseases in potatoes,' cotton and other cultivated plants. The new fungicidal compositions may be produced in the following manner: The phospholipide(s) is/are dissolved in organic solvents, such as for example toluene, ethyl acetate, xylene, petrols, ethanol or methanol or mixtures of these solvents. The choice of the solvent bill depend upo the solubility of the- particular fungicide used. The fungicide or-the commercially available fungicide preparation is dissolved in the phospholipide solution, optionally by heating. On completion of dissolution, the solvent is removed in vacuo while heating. The product thus obtained is converted into a suitable standard commercial form optionally by the addition of suitable auxiliaries, such as for example fillers, vehicles, diluents, wetting agents, stabilisers, gelating agents, evaporation accelerators and extenders. The new fungicidal compositions may also be prepared by mixing the fungicide or the commercial fungicide product with the phospholipide or the phospholipides and any auxiliaries and fillers required, dissolving or suspending the resulting mixtures in an organic solvent and removing the solvent. The mixture obtained is ready for use. In the case of fungicides which are soluble in water or in water/alcohol mixtures, the fungicide is with advantage first dissolved in water or a water/ alcohol mixture and the phospholipide or phospholipide mixtures are processed to form a solution or emulsion by stirring or by the application of ultrasonic waves. The emulsifiers normally required may be added before or after this stirring operation. The emulsions or solutions thus obtained are freed from the solvent mixture or water in the usual way, for example by distillation, spray-drying or freeze-drying. The resulting product may be used as such or optionally after the addition of suitable auxiliaries. The product may even be re-emulsified or re-dissolved in water and used as a spray. Vehicles are, for example, talcum, kaolin, bentonite, kieselguhr, lime or crsed roc. Other auxiliaries are, or example, suriace-aetive compounds, such as saps (fatty acid salts), fatty alcohol sulfonates or alh¯l sulfonates. Gelatin, casein, albumin, starch or methyl cellulose may be used as stabilisers or protective colloids. The nelf fungicidal compositions may be used in liquid or solid form, for example as dusting powders, granulates, sprays, aerosols, solutions or emulsions, as leaf fungicides, disinfectants or soil fungicides. EXAMPLE 1 Preparation of 1 kg of a spraying powder (20%) containing captan as its active ingredient: 200 g of captan, 200 kg of Phospholipon 55 in 50 ml of ethanol and 10 g of DONSS (dioctyl sodium sulfosuceinate) are dissolved in 3 litres of toluene. 400 ml of the resulting solution are kneaded with 600 g of bentonite and the paste obtained is dried in vacuo. This operation is repeated until the bentonite has absorbed the entire- toluene solution. The end product is ground. 1 kg of this 20% spraying powder in the form of a 0.15% solution in water is as effective against scab in stone fruit as 0.5 kg of an 80% commercial preparat ion. EXAMPLE 2 Preparation of 1 kg of an emulsion concentrate (12.5%) containing bupirimat as its active ingredient: 125 g of bupirimat and 150 g af Phospholipon 55 in 100 ml of ethanol, 50 g of Cellosolve, 2 g of lignin sulfonate and 200 ml of isopropanol are made up to 1 litre with Shellsol and dissolved by stirring. I litre of this 12.5% solution is as effective against blight in apples as 1 litre of a 25% solution of standard commercial preparations. EXAMPLE 3 Preparation of I kg of a spraying powder containing folpet as its active ingredient: H 125 g of- folpet, 200 g of Phospholipon 55 in 50 ml of ethanol and 9 g of DONSS are dissolved in 400 ml of heated toluene, the resulting solution is homogeneously kneaded with 677 g of bentonite (colloidal) and the paste obtained is dried. The product is ground in the presence of 4 g of Aerosil. 1 kg of this spraying powder (12.5%) is as effect ive as a leaf fungicide as 0.5 kg of a standard commercial product containing 50% of folpet. EXAMPLE 4 Preparation of 1 litre of an emulsion concentrate (6 gZl) containing fenarimol as its active ingredient: 60 g of fenarimol, 150 g of Phospholipon 100 in 50 ml of ethanol, 200 ml of xylene and 10 g of Marlowet IIZF are made up to 1 litre with Shellsol N. 1 litre of this formulation is as effective against apple blight as 1 litre of a commercial preparation containing 12 g/l of fenarimol. EXAMPLE 5 Preparation of 1 kg of a spraying powder (12.5%) containing triadimefon as its active ingredient: 125 g of triadimefon, 200 g of Phospholipon 80 in 50 ml of ethanol and 10 g of DONSS are dissolved in 50 ml of toluene. The solution is homogeneously applied to 655 g of bentonite (colloidal), after which the produc is dried, ground and sifted. 1 kg of this formulation is as effective against powdery mildew in cereals as 1 kg of a commercial product containing 25% of triadimefon. EXAMPLE 6 Preparation of 1 kg of an emulsion concentrate (100 g/l) containing triforine as its active ingredient: 100 g of triforine, 100 g of Phospholipon 100 in 100 ml of ethanol, 10 g of Cellosolve, 10 g of Tween SO, 2 g of Span 80, 100 ml of tetrahydrofuran and 100 ml of 1,2-propylene glycol are mixed an made up to l litre by the addition of Shellsol N. 1 kg oL this emulsion concentrale IS as effective against powdery mildew in cucumbers as 1 kg of a commercial product containing 190 g/l of triforine. EXAMPLE 7 Preparation of 1 kg of a spraying powder (20%) containing thiram as its active ingredient: 200 g of thiram, 200 g of Phospholipon 100 in 50 ml of ethanol and 10 g of DONSS are dissolved in hot chloroform. The resulting solution is homogeneously applied to 600 g of bentonite (colloidal) and the mixture obtained is dried and ground. 1 kg of this spraying powder in the form of a 0.2% solution in water is as effective against scab in stone fruit as 0.5 kg of a commercial preparation containing 80% of thiram. EXAMPLE 8 Preparation of 300 g of a spraying powder (40ffi) containing copper oxychloride as its active ingredient: 120 g of copper oxychloride, 120 g of Phospholipon 38, 1.5 g of Marlowet IHF, 52.5 g of dry glucose and 6 g of Bentone EW are stirred into 1080 g of water and homogenised. The suspension concentrate obtained is spray-dried. 1 kg of this spraying powder (40g) is as effective against coffee rust as 1.8 kg of a standard commercial preparation containing 50% of copper oxychloride. EXAMPLE 9 Preparation of 400 g of a spraying powder (40%) containing zineb as its active ingredient: 160 g of zineb, 160 g of Phospholipon 55, 2 g of Marlowet IHF, 8 g of Bentone EW and 20 g of dry glucose are stirred into 1200 g of water and homogenised. The suspension obtained is spray-dried. 1 kg of the spraying powder (40%) obtained is as effective against downy hop mildew in hop fields as 1.5 kg of a standard commercial preparation containing 65% of zineb. EXAMPLE 10 Preparation of 1 kg of an emulsion concentrate (17%) containing propiconazol as its active ingredient: 170 g of propiconazol, 170 g of Phospholipon 38, 140 g of toluec, 120 g of xylene, 160 g of isophorone, 160 g of N-(2-hydroxyethyl)-caproic acid amide and 80 g of Cremophor are mixed together to form a solution. The resulting emulsion concentrate may either be diluted to form the usual spray mixes containing from 0.1 to 0.01% of active substance or alternatively the same quantity of water may be addiI The clear solution thus obtained may be applied by the ULV or LV technique. 1 kg of this emulsion concentrate (17%) is as effective against apple blight as 2.2 kg of a standard commercial product having the same concentration of propiconazol. EXA12LE 11 Preparation of 400 g of a spraying powder (40%) containing benomyl as its active ingredient: 160 g of benomyl, 160 g of Phospholipon 38, 2 g of Marlowet Imp, s g of Bentone EW and 70 g of dry glucose are mixed together in 1000 g of water and homogenised. The suspension obtained is spray-dried to form a spraying powder. As a leaf fungicide in fruit growing, 1 kg of this powder (0.1%) in water is as effective against mildew as 2 kg of a standard commercial preparation containing 50k of benomyl. EXAMPLE 12 Comparison test with triadimefon To control powdery mildew, fields of winter wheat are sprayed with various mixtures and the percentage destruction of the fungus is measured. Test Mixture % Destruction of No. mildew 1 phospholipide 1.6 kg/ha O 2 phospholipide 3.2 kg/ha 0 3 triadimefon (25%) 0.5 kg/ha 80 4 triadimefon (25%) 0.25 kg/ha 50 5 triadimefon (25ffi) 0.25 kg/ha + phospholipide 1.6 kg/ha 90 6 triadimefon (25%) 0.12 kg/ha 10 7 triadimefon (25%) 0.12 kg/ha 50 + phospholipide- 0.8 kg/ha The commercial product containing the active ingredient referred to by its generic name was used as the active ingredient.

Claims: t;LAIMS: 1. A fungicidal composition, characterised in that it consists of a) one or more fungicidally active substances and b) one or more phospholipides from the group comprising phosphatidyl choline, hydrogenated phosphatidyl cholines, phosphatidyl ethanolamine, N-acyl phosphatidyl ethanolaminas, phosphatidyl inositol, phosphatidyl serine, lysolecithin and phosphatidyl glycerol in a ratio by weight of a:b of from 1:0.2 to 1:20 in addition to standard vehicles, diluents, solvents, propellents and/or other inert auxiliarie-s. 2. A fungicidal couposition as claimed in Claim 1, characterised in that constituents a) and b) are present in a ratio by weight of from 1:0.5 to 1:10. 3. A fungicidal composition as claimed in Claim 1 or 2, characterised in that constituents a) and b) are present in a ratio by weight of from 1:1 to 1:5. 4. A fungicidal composition as claimed in one or more of Claims 1 to 3, characterised in that phosphatidyl choline is used as the phospholipide. 5. A fungicidal composition as claimed in one or more of Claims 1 to 4, characterised in that one or more compounds from the following groups is/are used as the fungicidally active substance: 1. aromatic nitro compounds corresponding to the following general formula EMI16.1 in which R1 represents )2-C4-alkenyl or branched alkoxy and R2 represents C2-C6-alykl; 2. chlorobenzenes corresponding to the following general formula EMI16.2 in which R1 represents Cl or H, R2 represents C1, -OCH3 or H, R3 represents Cl or -CN, R4 represents Cl or H and H represents -CN,-OCH3 or -NO2; 3. phthalic acid derivatives corresponding to the following general formula EMI16.3 in which R represents an alkylthio, haloalkyl or thionophosphoryl group; 4. fungicidally active thiocarbamates; 5. fungicidally active benzimidazoles; 6. fungicidally active aniline derivatives; 7. such fungicides as thiophanat; dodemorph, tridemorph, anilazin, bupirimat, cetactaelat, chinomethionat, chlormethionat, dichlorfluanid, dimethirimol, dithianon, dodin, ethirimol, fenaminsulf, fenarimol, iprodion, pyrazophos, tolylfluanid, triadimefon, triadimenol, triflorin, vinclozolin. 6. The use of the fungicidal compositions claimed in one or more of Claims 1 to 5 for controlling flingi. 7. A process for producing the fungicidal compositions claimed in one or more of Claims 1 to 5, characterised in that the phospholipide is dissolved in an organic solvent or in a mixture o e organic solvents and the fungicide is dissolved in the resulting solution, optionally by heating and/or stirring, after which the solvent or solvent mixture is removed in vacuo and the mixture obtained is converted into a standard formulation after the addition of standard fillers and auxiliaries. S. A process for producing te fungicidal compos.. tions claimed in one or more of Claims I to 5, characterised in that the fungicide(s) is/are dissolved or suspended in an organic solvent together with one or more phospholipides and optionally together with standard fillers and auxiliaries, after which the solvent is removed. 9. A process for producing the fungicide? compositions claimed in one or more of Claims 1 to 5, characterised in that one or more water-soluble or alcohol-soluble fungicides is/are dissolved in water or water/alcohol mixtures together with one or more phospholipides by stirring and/or gentle heating and/or by the application of ultrasonic waves, after which the solvent or solvent mixture is removed.

Inventors: ETSCHENBERG, EUGEN, DR., GHYCZY, MIKLOS, DIPL.-CHEM., DR., OSTHOFF, HEINRICH, DR.
Applicants: A. NATTERMANN & CIE. GMBH
Application year: 1982
Main classification: A01N57
IPC codes: A01N57