DE2623847A1 - Oxime ethers of isonitroso-cyanoacetamide - useful as agricultural fungicides having systemic action - Google Patents

Abstract

Oxime ethers for formula (I) (syn or anti) are new. (where R1 = H or CONHR3. R3=H or 1-4C alkyl, R2= phenyl (opt. substd. by >=1 NO2, CF3 or CN and also by a halo), benzyl (opt. ring substd. by >=1 benzoyl (itself opt. substd. by 1 or 2 halo), phenyl, phenoxy or 1-14C alkoxy), di- or tri-phenylmethyl (opt. substd. on the phenyl by a phenyl, CN, CF3, 1-4c alkyl or alkoxy, CH3S or halo), disubstd. methyl in which one substit. is tert. butylcarbonyl and the second opt. substd. phenoxy of biphenyloxy, or R2 is mono- or dicyclohexyl- or mono- or di-phenyl-aminocarbonylmethyl opt. substd. on the methyl by 1 or 2 1-4C alkyl, and on the phenyl by >=1 halo or 1-6C alkyl). (I) are fungicides for curative or preventive use. They are better tolerated by plants than known isonitrosocyanoacetamide derivs. and have a systemic action penetrating deep into the plant. As seed dressings the application is pref. 0.5-5 g/kg and for treating the soil to 10-200 g/cu.m. In an example reaction of isonitrosyanoacetamide and 4-chloromethyldiphenyl gave 2-cyano-2-(4-phenylbenzyl)-oximinoacetamide.

Description

New oxime ethers, processes for their manufacture

The present invention relates to their use as fungicides new oxime ethers of Isonitrosocyanacetamids or its derivatives, a process for their production and their use as fungicides.

As has long been known, are used as fungicides in agriculture and in horticulture in particular zinc-ethylene-1,2-bis-dithiocarbamidate and the N-trichloromethylthiotetrahydrophthalimide is used; possess the compounds mentioned of great importance among commercial products (see R. Wegler, "Chemie der Pflanzenschutz- and Pest Control ", Volume 2, pages 65 and 108, Berlin / Heidelberg / New York (1970)). However, the effect at low application concentrations is not always satisfying.

These fungicides cannot be used curatively either.

The fungicidal effect of some isonitrosocyanacetamide derivatives is also known (see DT-OSS 2 118 317, 2 312 956, 2 350 910, 2 436 654 and 2 436 655 and U.S. Patent 3,919,284). Here, too, the effectiveness is at low application rates not reliable and plant damage is seen at normal concentrations.

It has now been found that the new oxime ethers of isonitrosocyanacetamide or of its derivatives of the general formula in which R¹ stands for hydrogen or the group -CO-NHR³, where R³ can be hydrogen or alkyl with up to 4 carbon atoms and R2 stands for phenyl which is substituted by nitro, trifluoromethyl and / or cyano groups, and furthermore can additionally be halogen-substituted, and furthermore represents benzyl, which is substituted in the aromatic part by benzoyl, mono- or di-halobenzoyl, phenyl and / or alkoxy with 1 to 14 carbon atoms, and furthermore represents diphenylmethyl or triphenylmethyl, said Residues on the phenyl nuclei by phenyl, cyano, trifluoromethyl, alkyl or alkoxy with up to 4 carbon atoms, can be further substituted by the methylthio radical or by halogen, and finally stands for phenylaminocarbonylmethyl, which on the methyl radical has 1 to 2 alkyl groups each with up to 4 carbon atoms and can be further substituted on the phenyl nucleus by halogen and Z or alkyl with up to 6 carbon atoms, strong fung have icidal properties.

The substances according to the invention can be present as oxime derivatives in two different geometric structures: In the following, the spatial structure is not given; For the purposes of the present application, the specified formulas (Ia) should in any case also include the corresponding formula according to the spatial structure (Ib).

It has also been found that compounds of the formula (E) are obtained if isonitrosocyanacetamide derivatives of the formula in which R1 has the abovementioned meaning with a compound of the formula X - R2 (III) in which X is chlorine, bromine or iodine and R2 has the abovementioned meaning, in the presence of an acid binder.

The compounds according to the invention show a good fungicidal action. They can be used protective, curative and even eradicative, and they are systemic and / or locosystemic properties. Surprisingly, they show a better one Plant tolerance than the isonitrosocyanacetamide derivatives known from the prior art. Compared to the dithiocarbamidates and N-trichloromethylthiotetrahydrophthalimide they have the advantage of curative and eradicative effects.

The compounds according to the invention represent because of the many Possibilities of their superior biological application a valuable enrichment of the art. Another essential aspect of this invention is that new active ingredients with properties that are valuable in practice are available at a time be asked, as resistance symptoms of older active ingredients are an addressed There is a need for new fungicides.

If the sodium salt of isonitrosocyanacetamide and 4-chloromethyldiphenyl are used as starting materials, the course of the reaction can be represented by the following equation: The isonitrosocyanacetamide derivatives to be used as starting materials for the process according to the invention are defined by the formula (II). In this formula, R¹ preferably represents hydrogen and the group - CO - NH2, thus preferably isonitrosocyanacetamide and isonitrosocyanacetylurea. These compounds have been known for a long time (cf. Ber. 42, pp. 738, 740, 741 (1909)).

The halogen compounds are also used for the reaction according to the invention of the general formula (III) required.

In this formula, R² preferably represents a by 1 to 3 nitro and / or trifluoromethyl groups substituted phenyl, which is also chlorine-substituted can be; also preferably for one in the aromatic part by phenyl, benzoyl, Monochlorobenzoyl, dichlorobenzoyl or alkoxy substituted with up to 14 carbon atoms Benzyl radical; also preferably for a diphenylmethyl or triphenylmethyl radical, which is optionally attached to a phenyl nucleus, preferably by a phenyl, cyano or Trifluoromethyl group which can be substituted by fluorine or chlorine; in the end preferably for the phenylaminocarbonylmethyl, the 1 - (phenylaminocarbonyl) ethyl and the 2- (phenylaminocarbonyl) isopropyl group, here the three mentioned Groups in the aromatic part preferably up to 2 chlorine atoms and up to 2 alkyl radicals each containing up to 4 carbon atoms.

Using examples of starting materials to be used according to the invention general formula III are to be mentioned: 2-nitrochlorobenzene, 1,2-dichloro-6-nitrobenzene, 2-nitro-1,4-dichlorobenzene, 2,4-dinitrochlorobenzene, 2-nitro-4-trifluoromethylchlorobenzene, 2,6-dinitro-4-cyano-chlorobenzene, 4-trifluoromethyl-chlorobenzene, 1,2-dichloro-4-trifluoromethylbenzene, 2,5-dichloro-3-nitrobenzonitrile, 2-cyano-4-trifluoromethylchlorobenzene, 2-trifluoromethyl-4-cyano-chlorobenzene, 2,4-dinitro-6-trifluoromethylchlorobenzene; 2-phenyl-benzyl chloride, 4-phenyl-benzyl chloride, 4-benzoylbenzyl chloride, 4- (2-, 3- or 4-chlorobenzoyl) -benzyl chloride, 4- (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5 dichlorobenzoyl) benzyl chloride, 2-, 3- or 4-methoxybenzyl bromide, 2-, 3- or 4-ethoxy-benzyl chloride, 4-isopropoxy-benzyl chloride, 2- or 4-butoxy-benzyl chloride, 4-hexyloxybenzyl chloride, 4-octyloxybenzyl chloride, 4-dodecyloxybenzyl chloride, 4-tetradecyloxybenzyl chloride; Triphenylchloromethane, bis-phenyl - [(3-trifluoromethyl-, 3-cyano-, 3-chloro-, 3-fluoro- or 3-bromo) -phenyl -chloromethane, bisphenyl- [(2-chloro-, 2-methoxy- or 2-bromine) -Phenyli -chloromethane, bis-phenyl - [(4-fluoro-, 4-chloro-, 4-bromo-, 4-iodo-, 4-methyl-, 4-tert-butyl-, 4-methylthio- or 4-phenyl) -phenyl] -chloromethane; N- (bromoacetyl) anilide, N- (Chloracety1-2-ethyl-anilide, N- (chloroacetyl) -2-isopropyl-anilide, N- (chloroacetyl) -4-butylanilide, N- (chloroacetyl) -2,6-diethyl anilide, N- (chloroacetyl) -4-chloro-anilide, N- (chloroacetyl) -3-chloro-anilide, N- (chloroacetyl) -2-chloro-anilide, N- (chloroacetyl) -2,4-dichloro-anilide, N- (2-bromopropionyl) -3,4-dichloro-anilide, N- (2-bromo-2-ethyl-butyryl) -3,5-dichloro-anilide, N- (2-chloroisobutyryl) -3,4-dichloro-anilide, N- (2-chloro-isobutyryl) -3t5-dichloro-anilide, N- (2-chloro-isobutyryl) -3-methyl-anilide.

Most of the starting materials of the formula (III) are generally known Links. If they are not yet described, they can in principle well-known and laboratory methods are produced. Find information on this in the production examples.

The preparation of the compounds of the formula (I) according to the invention takes place preferably in the presence of polar solvents such as dimethyl sulfoxide, Dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, methylene chloride, chloroform, Chlorobenzene, toluene, dioxane, tetrahydrofuran, acetonitrile, benzonitrile or ethyl acetate. In some cases, tertiary amines are also suitable as solvents, which then simultaneously are effective as acid binders.

All customary hydrogen halide acceptors can be used as acid binders be used. These include alkali hydroxides, alkali carbonates and other suitable ones Alkali salts.

Examples include sodium carbonate, sodium bicarbonate, borax (disodium tetraborate) and trilithium phosphate. If you work in the presence of water, you can add be neutralized by sodium hydroxide solution, or the salts of the isonitrosocyanoacetic acid derivatives are used a priori a. Organic acid binders can also be used, such as tertiary amines. Mention should be made here of triethylamine, dimethylbenzylamine, dimethylaniline, pyridine, picoline and quinoline.

The reaction temperatures can vary within a wide range will. In general, between about -50 and about + 1200 ° C., preferably between - 5 and + 800C.

The reactions can also take place in mixtures of water and a water-miscible organic solvents or in heterogeneous systems from water and a water-immiscible or only partially miscible solvent; here the temperature range of the reaction is between the freezing point of the Water or the freezing point of the aqueous solution and about 1000C, preferably at -50 to + 800C.

Reaction temperatures and reaction times are determined by the activity the starting products of the formula (IIt determined.

It is advisable to add one to the mixtures before the reaction small amount of an iodide too, if you are not currently using a compound of formula (III) with iodine as a leaving group. This will increase the response speed increases and reduces the risk of the formation of compounds with a nitrone structure (See also Houben-Weyl, "Methods of Organic Chemistry", Volume 10/4, -Stuttgart (1968)).

The active ingredients according to the invention fall depending on the working conditions crystalline or they remain dissolved in the organic solvent and can then by carefully concentrating the solution or by adding less polar organic substances Solvents such as carbon tetrachloride, cyclohexane or dibutyl ether, or optionally separated by adding water.

Some of the compounds according to the invention decompose at higher rates Temperature; in these cases the melting points can only be measured with low accuracy or cannot be determined at all. The presence of certain structural elements can be seen from the NMR spectra. The IR spectra also show characteristic Absorption bands.

The active ingredients according to the invention are highly fungitoxic Effect on. They damage cultivated plants in the areas necessary for combating fungi Concentrations do not.

For these reasons they are suitable for use as pesticides suitable for combating fungi. Fungitoxic agents in crop protection used to combat Plasmodiophoromycetes, Oamycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The active compounds according to the invention can be used against parasitic ones Fungi that attack above-ground parts of plants or attack plants from the ground, as well as against seed-borne pathogens. They can therefore also be used for soil and for Seed treatment can be used.

The active ingredients show in particular a high protective and curative Efficacy against Phycomycetes. In addition, there are good effects against Mycosphaerella and Rhizoctonia species and against rust fungi.

The active ingredients according to the invention not only have the good properties excellent commercial preparations, but also have considerable Advantages.

These lie primarily in the ability of the invention Substances to penetrate the plant.

They can be absorbed from the seed surface, from the roots and also from aboveground plant organs after external application. Also own they have the beneficial ability to have a locosysteisch effect, i.e. a deep effect exercise in plant tissue and thereby eliminate fungal pathogens, which have already penetrated the tissue of the host plant.

The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. In the case of the use of water as an extender, z. B. also organic Solvents can be used as co-solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquids with liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and under normal pressure, e.g. B. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as fixed Carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and powdered synthetic rock, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolysates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

In addition to the above formulation options, it should be noted that that the substances according to the invention together with sucrose, dextrose, dextrins with anhydrous calcium sulfate or calcium sulfate hemihydrate can be formulated.

The active compounds according to the invention can be used in the formulations in Mixtures with other known active ingredients are present, such as fungicides, insecticides, Acaricides, nematicides, herbicides, bird repellants, growth substances, Plant nutrients and soil structure improvers.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, emulsions, suspensions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by watering, squirting, atomizing, Dusting, scattering, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

When used as foliar fungicides, the drug concentrations can be varied in the application forms over a wide range. You are in generally between 0.5 and 0.0005 percent by weight, preferably between 0.2 and 0.001.

In the treatment of seeds, amounts of active ingredient of 0.01 - 50 g per kilogram of seed, preferably 0.5 - 5 g, is required.

For soil treatment, amounts of active ingredients of 1 - 1000 g per cbm of soil are required, preferably from 10 - 200 g, required.

The many possible uses are based on the following Examples: Example A Mycelium growth test Nutrient medium used: 20 parts by weight of agar-agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of disodium phosphate 0.3 parts by weight calcium nitrate Ratio of solvent mixture to nutrient medium: 2 parts by weight solvent mixture 100 parts by weight agar medium composition Solvent mixture: 0.19 part by weight acetone 0.02 part by weight emulsifier alkylaryl polyglycol ether 1.80 parts by weight of water 2 parts by weight of solvent mixture for the desired concentration of active substance in the nutrient medium with the necessary amount of active substance the specified amount of the solvent mixture. The concentrate is mentioned in the The quantity ratio is thoroughly mixed with the liquid nutrient medium, which has been cooled to 420C and poured into petri dishes with a diameter of 9 cm. There are also control panels set up without admixture of preparations.

If the culture medium is cold and solid, the plates are filled with the in inoculated the types of fungi indicated in the table and incubated at about 21 ° C.

The evaluation is carried out after 4 to 10 days, depending on the rate of growth of the fungi. During the evaluation, the radial mycelial growth on the treated culture media is compared with the growth on the control culture media. The rating of the fungal growth is done with the following key figures: 1 no fungal growth up to 3 very strong growth inhibition up to 5 moderate growth inhibition up to 7 weak growth inhibition 9 growth equal to the untreated control active ingredients, active ingredient concentrations and results are shown in the following table: Table AP ilze Mycelium Growth Test Active ingredients concentration ppm 10 # # # # NC-C-CO-NH2 9 9 9 9 " NOH (known) NC-C-CO-NH2 " NO-CH2 - # - # - 5 1 1 C2H5 CN # -NH-CO-CH2-ON = C 5 - 1 - CO-NH2 C2H5 CN # -NH-CO-CH2-ON = C 5 5 - - C2H5 CO-NH2 CN # -CO - # - CH2-ON = C 1 1 1 1 CO-NH2 T able A (continued) Mushrooms Mycelium Growth Test Active ingredients concentration ppm 10 # # # # Cl CN Cl - # - NH-CO-CH2-ON = C - 1 3 5 CO-NH2 Cl CN # -NH-CO-CH2-ON = C - 1 5 - Cl CO-NH2 Table AP ilze Mycelium Growth Test Active ingredients concentration ppm 10 # # # # CN CH3-O - # - CH2-ON = C 2 1 1 1 CO-NH2 CN CH3-O - # - CH2-ON = C - 1 1 - CO-NH-CO-NH2 Example B Phytophthora test (tomato) / Protective solvent 4.7 parts by weight acetone emulsifier 0.3 parts by weight alkylaryl polyglycol ether water 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount Amount of water that contains the additives mentioned.

Young tomato plants are sprayed with the spray liquid 2 to 4 leaves to dripping wet. The plants remain on for 24 hours 200C and a relative humidity of 70% in the greenhouse. Afterward the tomato plants with an aqueous spore suspension of Phytophthora infestans inoculated. The plants are in a humid chamber with a 100% Humidity and a temperature of 18 to 20 ° C.

The attack on the tomato plants is determined after 5 days. The received Rating values are converted to percent infestation.

0% means no infestation, 100% means that the plants are complete are infested.

Active ingredient, active ingredient concentration and results are shown in the table below: Table B Phytophthora test (tomatoes) / Protective Active ingredient infestation in% with an active ingredient concentration of 0.0025% CH -NH-CS-SX I ", zn 41 CH2-NH-CS-S (known) NC-C-CO-NH II NO-CH3 (known) 7 NC-C-CO-NH NO-CH2 <10 / C2H5 CN 4 -NH-CO-CH2-0-N = C.- CO-NH, 19th CN -ON - CO-NH2 7 N02 Cl CH, -NH-C0-C-0-N = C CN Cl, ~ CO-NH2 2 CH3 Cl CN -NH-CO-CH2-0-NC½ Cl CO-NH2 22 Example C Phytophthora test (tomato) / curative solvent 4.7 parts by weight acetone dispersant 0.3 parts by weight alkylaryl polyglycol ether water 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount Amount of water that contains the additives mentioned.

Young tomato plants with 2 to 4 leaves are treated with an aqueous Spore suspension of Phytophthora infestans inoculated. The plants stay for 7 hours stand at 200C and a relative humidity of 100%.

After a short drying time, the plants are treated with the spray liquid, which was prepared in the manner indicated above, sprayed until dripping wet and then placed in a humid chamber with 100% humidity and 18 to 200C temperature.

The attack on the tomato plants is determined after 5 days.

The rating values obtained are converted to percent infestation. 0% means no infestation, 100% means that the plants are completely infested are.

Active ingredients, active ingredient concentrations and results are shown in the following table: Table C Phytophthora test (tomatoes) / curative Active ingredient infestation in% with an active ingredient concentration of 0.025% CH2-NH-CS-S LZn 61 M. CH2-NH-CS-S (known) NC-IC-CO-NH2 II 7 NOH (known) NC-IC-CO-NH2 NO-CH <2 C2H5 NH-CO-CH2-ON = C / CN 6 CO-NH2 H-CO-CHZ-ON = C ~ CN 0 C2Hg C0-NH2 Tab 1 1 e C (continued) Phytophthora test (tomatoes) / curative Active ingredient infestation in% with an active ingredient concentration of 0.025 CN / j-C0- - -CH2-0-N = C0 CO-NH2 CF to-ON = C > CO-NH2 1 N02 cy Cl <-NH-CO-CH2-0-N = CX CN O ¼ CO-NH2 C C1H3 CN Cl ½ffiJ / I £ \ -NH-C0-C-0-N = C. ~ CO-NH2 7 CH3 0 O / / CN 4 ¼ CO-NH Example D Sprout treatment test / grain rust / protective (leaf-destroying mycosis) To produce an appropriate preparation of active ingredient, 0.25 parts by weight of active ingredient in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkylaryl polyglycol ether) are added, and 975 parts by weight of water are added.

The concentrate is diluted with water to the desired final concentration the spray mixture.

To test for protective effectiveness, single-leaved ones are inoculated Young wheat plants of the cultivar "Jubilar" with a uredospore suspension of Puccinia recondita in 0.1% water agar. Sprayed after the spore suspension has dried on the wheat plants are dew-moistened with the preparation of active compound and they are prepared Incubation for 24 hours at around 200C and 100% humidity in a greenhouse.

After the plants have stayed for 10 days at a temperature of 20 ° C and a humidity of 80 to 90% one evaluates the stocking of the plants Rust pustules from. The degree of infestation is expressed as a percentage of the infestation of the untreated Control plants expressed. 0% means no infestation and 100% the same Degree of infestation as in the untreated control. The active ingredient is all the more effective the lower the amount of rust.

Active ingredients, active ingredient concentrations in the spray liquor and degrees of infestation are shown in the table below: Table D Shoot treatment test / grain rust / protective Active ingredients Active ingredient concentration in% of the un- tration in the treated control Spray mixture in% by weight NC-C-CO-NH2 0.025 X 0.025 25 C2H C2H5 CN <3 "-NH-Co-CH2-oN = C-CN CO-NH2 - C2H5 -NH-CO-CH2-ON = CCN C0-NH O C2H5 2 -0-N = C (CH2-0-N = C- "25 2 s CO-NH2 CF3 ~ n -ON = C WCN 1 12.5 CO-NH2 12.5 Cl No2 cl Cl t -NH-CO-CH2-0-N = C wCN "12.5 C CH3 3 -NH-CO-CON = C CN Cl 'C0-NH2 25 CH3 Table D (continued) Active ingredients Active ingredient contamination in% of the un- concentration in the treated concentration Trolle spray mixture in% by weight CN CH3-0-CH2-0-N = Cs 0.025 12.5 CO-NH2 CN CH3-0 - Z- 0.025 25 CO-NH-CO-NH2 0.025 25 -N CN '= C, 0.025 25 t C0-NH Example E Phytotoxicity test solvent 4.7 parts by weight acetone emulsifier 0.3 parts by weight alkylaryl polyglycol ether water 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount of solvent and the concentrate is diluted with the specified amount of water, which contains the contains mentioned additives. Young tomatoes are sprayed with the spray liquid until they are dripping wet. After drying, the plants are placed in a greenhouse at a temperature of + 200 ° C. and about 70% relative humidity.

The plants are repeatedly evaluated for damage. The evaluation takes place according to a rating scheme from 1 to 9.

1 means no damage 9 means that the plants are totally damaged or have died.

The observation period is usually 4 days.

Active ingredients, active ingredient concentration and results are shown in the table below: Table E Phytotoxicity test Active ingredient damage in an active ingredient concentration of 0.2% NC-r-CO-NH2 8th NOH (known) NC-C-CO-NH2 1 STILL C2 H5 U -NH-CO-CH-ON = C-CN ~ -NH-CO-CH2-0-N = C \ CO-NH2¼C0NH2 3 -CO CN 1 ¼ CO-NH2 CF3-Q-ON = C-CN 4 NO CO-NH2 Cl 2 -NH-CO-CON = C 2 0-N = C 2 Cl H3 CO-NH2 3 1 CN W -NH-CO-CH2-0-N = C 1/2 1 ¼ Q CO-NH2 CN to CM CN 3 CO-NH2 Preparation examples Example 1 11.2 g (0.2 mol) of potassium hydroxide, dissolved in 20 ml of water, are added to 22.6 g (0.2 mol) of isonitrosocyanacetamide in 400 ml of dimethyl sulfoxide. 200 g of solvent are distilled off at a pressure of about 0.5 torr.

40.6 g (0.2 mol) of 4-chloromethyldiphenyl, dissolved, are added to the residue in 80 ml of toluene and 100 mg of sodium iodide.

The mixture is then kept at a temperature of 80 ° C. for 8 hours. Most of the solvent is distilled off in vacuo. The residue crystallizes after adding water. The crystals are separated off, washed with water and toluene and recrystallized from 1 liter of toluene after drying in vacuo at 70 to 80.degree. 42.5 g of 2-cyano-2- (4-phenylbenzyl) oximinoacetamide of melting point 172.50 ° C. are obtained.

Spectra: -1 IR (KBr): 3445, 1682, 1653, 1580, 842, 822, 752, 720 cm -1 IR <CHCl3): 3530, 3410, 2240, 1710, 1600, 1578, 1562 cm The as a preliminary product The 4-chloromethyl-diphenyl required with a melting point of 68 ° C. is a compound that has been known for a long time (see.

Beilstein's Handbook of Organic Chemistry, Volume 5, E II, page 505). It can be made from 4-phenylbenzyl alcohol and hydrochloric acid in a sealed glass tube 1000C can be obtained.

The following compounds are obtained in an analogous manner: Example No. Formula Physical properties 2 NH-CO-CH2-ON = CzCN Mp. 184 ° C \ CO -NH, 3 C2Hg 3/2 CN m.p. 201, eo - CO-NH2 C2H5 4 Cl -NH-CO-CH2-ON = Cr'CN m.p. 216.50C - 2 CO-NH2 Cl C1 7r -NH-CO-CHN = CCN 0 5 Cl2 ¼ CONH2 m.p. 230.5 ° C Cl-CH3 6 to NH-Co-coN = c CN, m.p. 236 ° C ¼ C CH3 CO-NH2 7 O -CO- O -CHZ-ON = C, CN m.p. 1620C 8 CH3-O-CH2'0-N = C ;, CN m.p. 1460C C0-NH2 9 O CH3-0-CH-O-N = CN m.p. 150.50C CO-NH-CO-NH2 10 5 9-ON = C CN m.p. 213.50C O CO-NH2 Example No. Formula Physical properties 11 O9 C / m.p. 172 ° C C0-NH2 1) 1 / CN Spectra: 12 5 C-0-N = C IR (CCl4) 3440, - 3410.2230 to C0-NH-CO-NH2 2250.1745.1710- ls t 1720,1650-1675, Rv CF3 795,745,695 cm N02 CN 13 CF30-N = C (m.p. 145.5 C CO-NH2 To illustrate the preliminary products: The preliminary products required for the production of compounds 2 to 5 are known.

That required for the preparation of the compound according to Example 6 C ε -chloro-isobutyric acid-3, 5-dichloroanilide is prepared as follows: 53.3 g -chloro-isobutyric acid chloride are dissolved in 200 ml of chlorobenzene. At a temperature of -350C one leaves one Mixture of 61.5 g of 3,5-dichloroaniline and 46 g of N, N-dimethylaniline in 300 ml of chlorobenzene add dropwise over 35 minutes. The reaction mixture is then at Room temperature first washed with dilute hydrochloric acid and then with water, dried over calcium chloride and concentrated in a water jet pump vacuum. To Addition of about 200 ml petroleum ether occurs. Crystallization occurs. The crystals will be separated, washed three times with 50 ml of petroleum ether and then with one Temperature of 730C and a pressure of 0.1 mm mercury dried. You get 73.2 g of & -chloroisobutyric acid (3,5-dichloroanilide) of m.p. 94.50C.

The starting compounds for the preparation of compounds 7 to 10 and 13 are also known from the literature.

The starting compound for the preparation of compounds 11 and 12 has not yet been described, it takes place as specified below (see German Patent application P 25 53 301.1 dated November 27, 1975 ie A 16 8240): In 570 kg (7308 mol) of benzene are placed in a 1200 ml enamelled kettle and "partially distilled" until the distillate is clear. 90 kg (556 moles) anhydrous Iron (III) chloride are added with stirring. The mixture is left over a feed vessel at an internal temperature of 250 ° to 300 ° C. in the course of 3 hours, 133 kg (506 mol) of m-trifluoromethyl-benzotrichloride flow in. The reaction starts immediately with evolution of hydrogen chloride. It is stirred at 25 to 30 ° C for 5 hours. Then in a 2000 1 capacity enamelled kettle 260 g of ice and 260 kg of concentrated hydrochloric acid submitted. Of the The reaction mixture is pressed into the 2000 l kettle while stirring. For 10 minutes is stirred up, then separated off the lower aqueous phase. The organic phase will separated from residues of the aqueous phase after filtration through a pressure filter and removed twice stirred with 100 kg of concentrated hydrochloric acid for 2 hours. After detaching the aqueous phase is under a pressure of 80 to 100 mm Hg and 700C jacket temperature distilled until no benzene passes over and a final vacuum of approx. 13 mm is reached. 163 kg (93% of theory) iphenyl- (3-trifluoromethyl-phenyl) remain as the distillation residue methylI chloride as a light brown, highly viscous dl. A sample of the chloride is boiling at Kp (0.3 mm Hg) 150 to 1550C.

Claims (6)

Claims 1. Isonitrosocyanacetamide oxime ether of the general formula in which R¹ stands for hydrogen or the group -CO-NHR³, where R3 can be hydrogen or alkyl with up to 4 carbon atoms, and R2 stands for phenyl which is substituted by nitro, trifluoromethyl and / or cyano groups, and can furthermore additionally be halogen-substituted, and furthermore represents benzyl, which is substituted in the aromatic part by benzoyl, mono- or dihalobenzoyl, phenyl and / or alkoxy having 1 to 14 carbon atoms, and furthermore represents diphenylmethyl or triphenylmethyl, the named Residues on the phenyl nuclei can be further substituted by phenyl, cyano, trifluoromethyl, alkyl or alkoxy with up to 4 carbon atoms by the methylthio radical or by halogen, and finally stands for phenylaminocarbonylmethyl, which is represented on the methyl radical by 1 to 2 alkyl groups with each up to 4 carbon atoms and a phenyl nucleus can be further substituted by halogen and / or alkyl having up to 6 carbon atoms. 2. A process for the preparation of oxime ethers of isonitrosocyanacetamide, characterized in that isonitrosocyanacetamide derivatives of the formula in which R1 has the meaning given above, is reacted with a compound of the formula X - R2 in which X is chlorine, bromine or iodine and R2 has the meaning given in claim 1, in the presence of an acid-binding agent. 3. Fungicidal agents, characterized by a content of at least an oxime ether of isonitrosocyanate acetamide according to claim 1. 4. A method of combating fungi, characterized in that one oxime ether of isonitrosocyanacetamide according to claim 1 on mushrooms or their Lets living space act. 5. Use of oxime ethers of Isonitrosocyanacetamids according to claim 1 to control fungi. 6. Process for the production of fungicidal agents, characterized in that that oxime ethers of isonitrosoacetamide according to claim 1 with extenders and / or surfactants mixed.