FR2465715A1 - Fungicide 1-cyano-hydroxy-imino-acetyl-3-cycloalkyl-urea derivs. - prepd. e.g. by reaction of a 1-cyanoacetyl-3-cycloalkyl:urea with alkali nitrite (PT 6.3.81) - Google Patents

Abstract

New 1-(2-cyano-2-hydroxyimino-acetyl)- 3-cycloalkyl-urea derivs. are cpds. of the formula R1-NH-CO-NH-CO-C(CN):N-OR (I) and their salts and complexes (where R is H or Me and R1 is 5-12C cycloalkyl opt. substd. by 1-4C alkyl or 1-4C alkoxy). (I) are pesticides with strong fungitoxic activity against phytopathogenic fungi. In some cases they have curative activity. Rate of application is 0.1-5 kg/ha. In an example, a 0.2% dispersion of (I; R is Me, R1 is cyclohexyl) is sprayed on to vine plants which are kept 10 days, then artificially infected with Plasmopara viticola and kept 11 days under greenhouse conditions, only 15% of leaves show signs of fungal infection whereas in untreated controls the degree of infection is 70%.

Description

 The present invention relates to new derivatives of carbonic acid, to processes for their preparation, to pesticide products containing them and to their use. the new carbonic acid derivatives are active on fungal diseases.

dans laquelle
R représente un atome d'hydrogène ou un groupe méthyle,
et
R1 représente un cycle cyeloallryle contenant de 5 à
12 atomes de carbone, qui peut éventuellement être
substitué par des groupes alkyles ou alcoxy conte
nant de 1 à 4 atomes de carbone.the carbonic acid derivatives according to the invention correspond to the general formula I

in which
R represents a hydrogen atom or a methyl group,
and
R1 represents a cyeloallryl cycle containing from 5 to
12 carbon atoms, which can optionally be
substituted by alkyl or alkoxy groups
from 1 to 4 carbon atoms.

 The compounds of general formula I, because of their biological activity and especially because of their excellent pesticidal, static fungicidal and fungicidal properties, are especially suitable for use in the fight against fungal diseases. They are active for example against Peronospora of the vine, Phytophtora of the tomato, the rust of the beans and similar diseases.

Among the compounds according to the invention, there may be mentioned for example the following N1-r2-cyano-2- (hydroxyimino) l-acetyl ~ N2 -cyclohexyl-
carbamide, N? -L2-cyano-2- (methoyy-imino) l-acetyl-I.J2-cyclo-
hexyl-carbamide, N- [2-cyano-2- (methoxy-imino) 3-acetyl-N-cyclo
pentyl-carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N-cyclo
octyl-carbamide, N-LE-cyano - ;; - (methoxy-imino)] -acetyl-N2-cyclo-
dodecyl-carbamide, as well as the derivatives of these compounds substituted on the cycloalkyl ring by alkyl or alkoxy groups, for example by one or more methyl, ethyl, propyl, isopropyl, butyl, isobutyl groups and / or by ethoxy groups, methoxy, isopropoxy, and for example N- [2-cyano-2- (hydroxy-imino)] - N- (acetyl-N-
cyclohexyl) -carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N- (dimethoxy
cyclohexyl) -carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl, N, (methyl-
cyclohexyl) -carbamide, and the like.

The invention further comprises the salts and complexes of the compounds of general formula I formed by ionic or complex bond with the hydroxy groups of the molecule. Among these compounds, there may be mentioned, for example, the alkali metal, alkaline earth metal and ammonium salts of the molecules containing a free hydroxy group.

dans laquelle R a les significations indiquées cidessus, avec un agent méthylant, ou bien
b) par réaction d'un composé de formule générale VII

avec un isocyanate répondant à la formule générale
VIII
R1 ~ NCO (VIII) ou bien avec le phosgène et une amine de formule générale Ix R1 - 1m2 (Ix) ou bien avec un halogénure d'acide de formule générale X
R1 - NH - COX (X) dans laquelle X represente un halogène, ou bien avec un ester de formule générale XI

ou bien
c) par réaction d'un dérivé de carbamide répondant à la formule générale XII

avec un dérivé d'acide de formule générale XIII

dans laquelle X1 représente un atome d'halogène ou un groupe hydroxy, ou bien
d) par réaction d'un dérivé de l'urée répondant à la formule générale XVI

dans laquelle X représente un halogène, avec des ions cyanures ou bien
e) par réaction d'une amine de formule géné- rale IX
R1 - NH2 (IX) avec un halogénure d' acide de formule XIX

ou avec un ester de formule XX

ou bien
f) par réaction d'un dérivé de l'acide carbo- nique répondant à la formule genérale V

avec un nitrite alcalin, après quoi, le cas échéant, on fait réagir le produit obtenu, de formule générale
V, avec un agent méthylant, et le cas échéant, on convertit les composés obtenus, de formule générale I, en leurs sels ou complexes, ou on les libère de leurs sels ou complexes, ou on convertit un sel ou complexe en un autre sel ou complexe.The invention further relates to processes for preparing the compounds of general formula I as well as their salts and complexes. In accordance with the invention, these compounds are prepared
a) in the case of methoxyimined derivatives general formula I, by reaction of compounds corresponding to general formula VI

in which R has the meanings indicated above, with a methylating agent, or else
b) by reaction of a compound of general formula VII

with an isocyanate corresponding to the general formula
VIII
R1 ~ NCO (VIII) or with phosgene and an amine of general formula Ix R1 - 1m2 (Ix) or with an acid halide of general formula X
R1 - NH - COX (X) in which X represents a halogen, or else with an ester of general formula XI

or
c) by reaction of a carbamide derivative corresponding to the general formula XII

with an acid derivative of general formula XIII

in which X1 represents a halogen atom or a hydroxy group, or else
d) by reaction of a urea derivative corresponding to general formula XVI

in which X represents a halogen, with cyanide ions or else
e) by reaction of an amine of general formula IX
R1 - NH2 (IX) with an acid halide of formula XIX

or with an ester of formula XX

or
f) by reaction of a derivative of carbonic acid corresponding to the general formula V

with an alkaline nitrite, after which, if necessary, the product obtained, of general formula, is reacted
V, with a methylating agent, and where appropriate, the compounds obtained, of general formula I, are converted into their salts or complexes, or they are freed from their salts or complexes, or a salt or complex is converted into another salt or complex.

According to operating variant a), the methoxyimine derivatives of general formula I are prepared by reaction of compounds of general formula VI with methylating agents. Methyl halides, preferably methyl halide, or dimethyl sulfate, or trimethyl phosphate, methyl benzenesulfonate or methyl p-toluene sulfonate, trimethyloxonium fluoborate, can be used as methylating agents. , diazomethane and other common methylating agents. The reaction is preferably carried out in an inert solvent medium, if desired in the presence of an acid neutralizing agent.

 The usual solvents for alkylation reactions can be used as solvents. Among the acid neutralizing agents, alkali hydroxides (for example 11 sodium hydroxide or potassium hydroxide) are preferably used., Alkali carbonates (for example sodium or potassium carbonate), alkaline bicarbonates (for example example sodium or potassium bicarbonate), alkaline earth metal carbonates or tertiary amines.

The reaction is preferably carried out hot, preferably between 20 and 800 C.

 According to operating variant b), the compounds of general formula I are prepared by reaction of compounds of general formula VII with isocyanates of general formula VIII or with phosgene and an amine of general formula IX, or by reaction with halides of acids of general formula X, or active esters of general formula XI. These reactions are advantageously carried out in the presence of an acid neutralizing agent. Among the acid neutralizing agents, alkali carbonates, alkaline bicarbonates, alkaline earth carbonates, tertiary amines, especially triethylamine or, in the case of the use of an amine of general formula IX, are preferred. excess of this amine.

The reaction of the compounds of general formula
XII with an acid derivative of general formula XIII according to the operating variant c) is advantageously carried out in an organic solvent when hot. when, in formula XIII, X1 represents a hydroxy group, the reaction is preferably carried out in the presence of a dehydrating agent. Among the desiccants, acetic anhydride or dicyclohexylcarbodiimide is preferred.

 According to operating variant d), the reaction of the compounds of general formula XVI with the cyanide ions is carried out in an inert solvent, while hot.

Among the products providing cyanide ions, alkaline cyanides are preferred, for example potassium cyanide or sodium cyanide.

The reaction of the amines of general formula
IX with acid halides of general formula
XIX or esters of general formula XX according to operating variant e), is preferably carried out in the presence of an acid neutralizing agent. An excess of the amine can also advantageously serve as an acid neutralizing agent. Usually, the above-mentioned products can be used as acid neutralizing agents.

According to operating variant f), the compounds of general formula are reacted first.
V with alkaline nitrites. Preferably used as alkali nitrite sodium nitrite or potassium nitrite. The reaction is preferably carried out in a hydro-organic solvent mixture, hot, in the presence of mineral or organic acids.

Among the mineral acids which can be used, mention may be made of halogenated hydracids, preferably hydrochloric acid, and among organic acids, acetic acid is preferably used. Among the organic solvents, aliphatic alcohols are preferred. the compounds obtained, corresponding to general formula VI, can optionally be methylated according to operating variant a).

the compounds corresponding to the general formula
V may other prepared by known procedures for analogous compounds, for example by reaction of the corresponding N-cycloalkyl-carbamide with cyanacetic acid (Hungarian patent No. 16?.? 3?).

The synthesis sequence can be carried out by isolating the intermediate products or without isolating them.

 the compounds obtained, corresponding to general formula I, can be converted into the corresponding salts by reaction with bases (for example alkali hydroxides, alkaline earth hydroxides or ammonia).

the compounds corresponding to the general formula
I can be released in a manner known per se from their salts.

the compounds corresponding to the general formula
I can form with metal salts metal complexes which can be prepared in a manner known per se. Among the metal salts which can be used, mention will be made of zinc chloride, zinc bromide, zinc acetate, copper-II chloride, copper-II bromide, copper-II acetate.

 A subject of the invention is also pesticide products which are primarily suitable for use in the fight against fungal plant diseases and which contain, as active materials, one or more compounds of general formula I at a concentration of 0 .0001 to 95% by weight, preferably from 40 to 60% by weight, and from 5 to 99.9999% by weight of vehicles, diluents, fillers, dispersing or emulsifying agents and, where appropriate, other surfactants -active and other fungicidal active ingredients.

products in which the concentration of active substances is at the lower limit (approximately 0.001 to 0.1 ffi by weight) can be applied directly to plants.

 products containing the higher concentration active substance cannot be used directly. These are commercial products that are stored and transported as is, but must be diluted accordingly before application. These products are mixtures containing from about 0.1 to 80% by weight of active substances.

 the products can be used in the form of solutions, powders, suspensions, emulsions, oily dispersions, pastes, dust, etc.

by watering, atomization, dust projection, spraying, etc., depending on the intended application. In all cases, it is necessary to achieve as fine a physical division as possible of the active substance.

For the preparation of spray products, emulsions, oily pastes and dispersions, suitable vehicles and diluents are medium or heavy petroleum fractions, for example diesel or petroleum, vegetable or animal oils, aliphatic and aromatic hydrocarbons and their derivatives, for example benzene, toluene, paraffin oil, methanol, ethanol, butanol, acetone, chloroform, carbon tetrachloride, etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxgde, 1 water, etc.

 The aqueous application forms can be prepared from concentrates or emulsions, pastes, wetting agents, oily dispersions, by adding water. For the preparation of oily emulsions, pastes or dispersions, the active substances are homogenized in water, optionally dissolved in oil or in a solvent, preferably in the presence of an adhesive agent, a dispersing agent and / or an emulsifying agent.

 As surfactants, there may be used lignin-sulfonic acid, naphthalene-sulfonic acid, alkali, alkaline earth and ammonium salts of Venol-sulfonic acids, alkylaryl sulfonates, sulfonates of fatty alcohols, condensation products of formaldehyde and sulfonated derivatives of naphthalene, sulfite detergents, etc.

 The powders, powders or slurries and dust according to the invention can be prepared by mixing and grinding together the active substances according to the invention of general formula I with solid vehicles. Among the solid vehicles, we especially appreciate silica, silica gel, kaolin, talc, lime, limestone, chalk, dolomite, loess, clay, magnesia, calcium sulfate, magnesium sulphate, chemical fertilizers, vegetable products, for example cereal flour, bran and other solid products.

 the products according to the invention may contain, with the active substance of general formula I, other known fungicidal or fungistatic active substances, which make it possible to increase or widen the fungicidal or fungistatic activity of the product. Thus, the products containing one or more active substances of general formula I can be advantageously combined with one or more of the following products: Benomyl, Mancozeb, 2-amino-benzimidazoyl-methylcarbamate, etc.

 the examples which follow illustrate the invention without however limiting its scope; in these examples, the indications of parts and percentages are by weight unless otherwise stated.

EXD: PIE 1
251 g of N- (2-cyano) -acetylN-cyclohexyl-carbamide, 500 ml of water, 500 ml of methanol and 99 g of sodium nitrite are mixed and the mixture is heated to 4000.

 107 g of acetic acid are added dropwise and the reaction mixture is kept at pH 6 to 7 and at a temperature of 40 to 450 C. After 2 hours, it is acidified. to pH 2, the mixture is cooled to OOC and the compound which has precipitated is filtered. 266.5 g of N- [2-cyano-2- (hydoxyimino)] -acetyl -N-cyclohexylcarbamide melting at 210-212 C are obtained.

EXAMPLE 2
238 g of N [2-cyano 2- (hydroxyimino) 7-acetyl-N2-cyclohexyl-carbamide are suspended in 400 ml of water and then 65 ml of an aqueous solution are added dropwise with stirring. sodium hydroxide 50%. The reaction mixture is heated to 40 ° C. and 147 g of dimethyl sulfate are added dropwise over 40 minutes to 40-45 ° C. After 1 hour, the reaction mixture is cooled, filtered, the precipitate is washed first with water and then with water acidified with acetic acid. 214 g of N1 - [2- 2 cyano-2- (methoxy-imino) 3 -acetyl-N2-cyclohexyl-carbamide melting at 143-145 C. are obtained.

Example 2
33.4 g of N-cyclohexylarbamide and 20 g of cyanacetic acid in 30 ml of acetic anhydride are reacted for 3 hours at 70-750C. The excess acetic acid is distilled under vacuum, the residue is redissolved in a mixture of 7Q ml of methanol and 40 ml of water and then 25 g of sodium nitrite in 30 g of water at 40 - 450C are added dropwise. . Stirred for 2 hours at 40-450C, diluted with 30 ml of water and basified to pH 7.5-8 with 18 ml of sodium hydroxide solution at 50 O / Do Add dropwise with stirring and cooling 44.6 g of dimethyl sulfate. A thick crystalline slurry is obtained which is filtered; cover with methanol and dry. 46.3 g of N -L2-cyano-2- (methoxy-imino)] - acetyl-N-cyclohexyl-carbainide are obtained, melting at 143-1450C (after recrystallization from methanol).

EXAMPLE 4
104 g of monochloroacetic acid are introduced into 160 g of water and then, with stirring and while cooling, 200 g of a 25% sodium hydroxide solution are added. To the basic mixture obtained, 62.5 g of sodium cyanide in 125 g of water are added: the temperature rises to 40-50 C. It is then heated to 60-75 C and stirred for 3 hours. After cooling to room temperature, the reaction mixture is acidified with concentrated hydrochloric acid (pH 1.5-2) and then concentrated; the residue is taken up in 120 ml of ethanol and filtered hot. The solution is evaporated. To the residue which contains 90 g of cyanacetic acid, 150 g of cyclohexylcarbamide and of acetic anhydride are added. The process is then terminated as described in Example 3. 194 g of N1-t2-cyano-2- (metho-xy-imino)] - acetyl-N-cyclohexyl-carbamide are obtained, which melts at t142-144 C.

EXAMPLE 5
For the preparation of a wettable powder, the following components are mixed in an air jet mill:
N- [2-cyano-2- (hydroxyimino) 3-acetyl
N-cyclohexyl-carbamide 25% Vanisperse CNH 6%
Wettol NU-1 4%
Evidet 27 1% tylose H 20 1%
Neuburg chalk 38%
EXAMPLE 6
23.8 g of N1-cyano- 2- (hydroxyimino)] - acetyl-N2-cyclohexyl-carbamide are suspended in 100 ml of an 8: 2 mixture of methanol and water and the mixture is cooled. SOC reaction. 100 ml of a solution of diazomethane in ether prepared from 0.1 mol of nitroso-methyl-carbamide are added with stirring while cooling. The reaction mixture is stirred until the evolution of gas (nitrogen ). The thick suspension is filtered and covered with a little methanol. N 2- cyano-2- (methoxy-imino) 3-acetyl-cyclohexyl-carbamide is obtained, melting at 114 C.

EXAMPLE
12.8 g of 2-cyano-2-methoxy-imino-acetamide are introduced into 25 ml of acetone and then a drop of triethylamine and 12.5 g of cyclohexyl-isocyanate are added at room temperature. The mixture is stirred for 6 hours, left to stand overnight, the starting product which has not reacted is filtered off and the mother liquors are evaporated. The residue is recrystallized from methanol. N1 [2-cyano-2- (methoxy-imino) 3-acetyl-N-cyclohexyl-carbamide is obtained, melting at 143-145 C.

EXAMPLE 8
25 g of phosgene is injected into a mixture of 19.8 g of cyclohexylamine and 200 ml of toluene with stirring at OOC. The reaction mixture is stirred for 2 hours and then the unconverted phosgene is removed by vacuum suction. To the toluene suspension obtained, 24 g of 2-cyano-2-acetoxy-imino-acetamide are added while maintaining the pH of the reaction mixture at 7 - 8 by addition of dimethylaniline. The mixture is stirred for 6 hours at room temperature, cooled, the dimethylaniline hydrochloride is removed by washing with water and dried. We obtain the N- [2-cyano-2- (methoxy-imino)] - acetyl-N- N1- [2-cyano-2- (methoxy-imino) -3-acetyl-N2- cyclohexyl-carbamide melting at 145 -145 C.

EXAMPLE 9
21 g of N [2-chloro-2- (methoxyimino)] - acetyl-N-cyclohexyl-carbamide are introduced into 60 ml of ethanol and then an aqueous cyanide solution of cyanide is added with stirring at 35-40 C 25% sodium in an amount corresponding to 7.35 g of sodium cyanide. The mixture is stirred for 5 hours. The thick suspension is filtered, the cyanide ions are removed by washing with a strip and dried.

14.5 g of N-2-cyano-2- (methoxyimino)] 3-acetyl-N-cyclohexyl-carbamide are obtained, which melt at 140 14200.

EX2aISSES 10 to 15
By operating as described in the previous examples but from the amines indicated below, the compounds identified in the third column of the table below are obtained
Ex. N R1-NX2 R1
N - OR
10 Cyclopentyl- rjl-c2-cyano-2- (methoxy-imino) 3-
amine acetyl-cyclopentyl-carbamide;
Il Cyclooctyl- N- [2-cyano-2- (methoxy-imino)] -
amine acetylJ2-cyclooctyl-carbamide;
12 Cyclododecyl- N- [2-cyano-2- (methoxy-imino)] -
amine acetyl-N2-, ycloaoaecyl-carba-
mide;
13 3,4-dimethyl- N- [2-cyano-2- (hydroxyimino)] -
cyclohexyl-acetyl-N- (3,4-dimethyl-cyclo-
carbamide hexyl) -carbamide ;;
14 3,4-dimethoxy- N1 - [2-cyano-2- (methoxy-imino) 3- 2
cyclohexyl-acetyl-N- (3,4-dimethoxy-cyclo-
amine hexyl) -carbamide;
3-methyl- N- [2-cyano-2- (methoxy-imino)] -
cyclohexyl-acetyl-N- (3-methyl-cyclohexyl) -
carbamide amine.

Biological examples
The new compounds which are the subject of the present invention exhibit a very high fungitoxic activity against phytopathogenic fungi. They are in particular suitable for combating Plasmopara viticola of the vine, Plasmopara halstedii of the sunflower,
Peronospora sparsa of the rose, Peronospora tabacina of the tobacco, Peronospora destructor of the onion, Pseudoperonospora humuli of the hops, Pseudoperonospora cubensis of the cucumber, Phytophthora infestans of the tomato,
Phytophthora parasitica of strawberry, Phytophthora cactorum of apple, Sclerospora macrospora of corn and Bremia lactucae of salad. The doses of use of the compounds according to the invention depend of course on the desired effect but are however generally between o, l and 5 kg of active substances per ha. A part of the active substances according to the invention also has curative properties, ie the use of these substances even after declaration of the infection of the plants by the various pathogenic germs still makes it possible to obtain excellent results in the fight against phytopathogenic fungi.

Of course, the compounds of the present invention can also be used in combination with other active substances such as herbicides, insecticides, growth regulators, fungicidal agents or even fertilizers. In many cases the mixture of the compounds according to the invention with other fungicidal agents makes it possible to broaden the spectrum of fungicidal activity of said compounds. Among these fungicidal associations, a synergistic effect is also observed, that is to say that the fungicidal activity of the combination product is greater than the sum of the activities of these various constituents. In practice, an improvement has been observed particularly significant spectrum of activity using the following fungicides
Dithiocarbamate and its derivatives, such as iron dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenbisdithiocarbamate, ethylenediamine-bis-dithiocarbamate of manganese and zinc, ethylenbisdithiocarbamate, zinc ammonium -ethylen-bis-dithiocarbamate) of zinc, and the disulphide of N, N'-polyethylen-bis- (thi-carbamoyl),
Zinc N, N'-propylen-bis-dithiocarbamate, ammonium complex of zinc N, N'-propylen-bis-dithiocarbamate, and N, N'-polypropylen-bis- (thiocarbamoyl) disulfide, N-trichloromethylthio -tetrahydrophthalamide, N-trichloromethylthio-phthalimide, N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide, piperazin-1,4-diyl-bis- (l- (2,2,2-trichloroethyl) - formamide), N- (l-formylamido-2,2,2-trichloroethyl) - morpholine, the diamide of N-dichlorofluoromethylthio-N 'acid, N' dimethyl-N-phenyl-sulfur, N, N-dimethyl-N '- (4-tolyl) -N' - (dichlorofluoromethylthio) - sulfonamide, the di-isopropyl ester of 5-nitro-isophthalic acid, l- (ll, 2 ', 4'-triazolyl- l 4'-chlorophenoxy) 7-3,3- dimethylbutan-2-one, l- (l ', 2', 4'-triazolyl-l ') - [4'-chlorophenoxy) g-3,3- dimethylbutan -2-ol, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo 1,3-oxazolidine, 5-methOxymethyl-5-methyl-3- (3,5 -dichlorophenyl) -2,4- dioxo-1,3-oxazolidine, the acid imide N- (3,5-dichlorophenyl) -1,2-dimethyl- cy clopropan-dicarbonique, la- (3,5-dichlorophenyl) -3- (isopropylcarbamoyl) - imidazolidin-2,5-dione, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine-methylester, copper-containing fungicides such as, for example, copper oxychloride.

Example l Ac ~ ivity ~ c ~ ntre ~ Plasmoeara viticola on the viqne
Potted vine leaves of the "Müller-Thurgau" species are sprayed with aqueous suspensions containing 0.2% by weight of active substance. In order to be able to assess the duration of action of the active substances, the plants are placed after drying of the spray layer for ten days in the vegetation room. The leaves are then infested with a solution of Zoospores de
Plasmopara viticola (Peronospora of the vine) .After that, the vines are first placed for 16 hours in a room saturated with water vapor at 240C and then for two days in a greenhouse of temperature between 20 and 300c. At the end of this time, the plants are again placed for t6 hours in the humid chamber to assess the invasion of the carriers of sporangia. The extent of the fungal invasion is then assessed on the undersides of the leaves.

% attack on leaves
the days after infection
2-Cyano-N- (cyclohexyl-aminocarbonylE-2- (methoxyimino) -acetamide 2-Cyano-N- (ethylamino-carbonyl) -2-. (methoxyimino) -acetamide (known from DE-OS 23 12 956)
Witnesses (untreated) 70
Example 2
Activity against PhytoEhthora infestans on tomatoes
Plant leaves of pots of the "large flesh tomato" species are sprayed with aqueous suspensions containing 0.05, 0.025 and 0.012% by weight of active substance. After drying of the spray layer, the leaves are infested with a solution of Zoospores of fungus Phytophthora infestans. The plants are then placed in a room saturated with water vapor at temperatures between 16 and 18 OC. After five days the disease has developed so much on the untreated but infested control plants that one can assess the fungicidal activity of the substances.

Leaf attack after
spraying a porridge
of active substance to
0.05% 0.025% 0.012 8 2-Cyano-N- (cyclohexyl- O 1 2 aminocarbonyl) -2- (methoxyimino) -acetamide
Witnesses (untreated) 5 O = no attack, gradually up to 5 = total attack.

Claims (10)

- CLAIMS  thyle, and R represents a cycloalkyl ring containing from 5 to R represents a hydrogen atom or a group m  in which

 n - Compounds corresponding to the general formula  containing from 1 to 4 carbon atoms, as well as their salts and complexes.  be substituted by alkyl or alkoxy groups 12 carbon atoms and which can if necessary  2 - Compound according to claim 1, taken from the group formed by the following: N- [2-cyano-2- (hydroxy-imino) 8-acetyl-N-cyclohexyl-  carbamide, its salts and complexes, N -C 2-cyan 0-2- (methoxy-lmino) 1 -ac -cyclohexyl-  carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N-cyclo-  pentyl-carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N-cyclo- octyl-carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N-cyclo-  dodecyl-carbamide, N- [2-cyano-2- (hydroxy-imino)] - acetyl-N- (3,4-  dimethyl-cyclohexyl) -carbamide, its salts and com  plexes, N- [2-cyano-2- (methoxy-imino)] - acetyl-N- (3,4  dimethoxy-cyclohexyl) -carbamide, N- [2-cyano-2- (methoxy-imino)] - acetyl-N- (3-methyl-cyclohexyl) -carbamide. wherein R1 has the meanings given in claim 1, with a methylating agent.

 3 - Process for preparing the compounds according to claim 1 containing a methoxy imino group, characterized in that compounds corresponding to the general formula VI are reacted   wherein R1 has the meanings given in claim 1.

 R1 - im - COX (X) in which X represents a halogen and R1 has the meanings indicated in claim 1, or else with an ester corresponding to the general formula XI R1 - NH2 (IX) in which R has the meanings indicated in claim 1, or else with an acid halide corresponding to the general formula X  R1 - NCO (VIII) in which R has the meanings indicated in claim 1, or else with phosgene and an amine corresponding to the general formula IX  in which R has the meanings indicated in claim 1, with an isocyanate corresponding to the general formula VIII

4 - Process for preparing the compounds according to claim 1, characterized in that a compound of general formula VII is reacted in which X1 represents a halogen atom or a hydroxy group.

 in which R1 has the meanings indicated in claim 1, with an acid derivative corresponding to the general formula XIII

 5 - Process for preparing the compounds according to claim 1, characterized in that a carbamide derivative corresponding to the general formula XII is reacted in which X represents a halogen and R 'has the meanings indicated in claim 1, with cyanide ions.

XVI  6 - Process for preparing the compounds according to late claim 1, characterized in that a urea derivative corresponding to the general formula is reacted

 or with an ester of formula XX

 7 - Process for preparing the compounds according to claim 1, characterized in that an amine of general formula IX is reacted with an acid halide of formula XIX  in which R1 has the meanings indicated in claim 1, with an alkaline nitrite and, where appropriate, the product obtained, of general formula VI, is reacted with a methylating agent.

 8 - Process for the preparation of the compounds according to claim 1, characterized in that a carbonic acid derivative corresponding to the general formula V is reacted 9 - Process according to any one of claims 3 to 8, characterized in that the compounds obtained, of general formula I, are optionally converted into their salts or complexes, or they are freed from their salts or complexes or else, from a salt or complex, another salt or complex is prepared.  10 - Pesticide product characterized in that it contains as active material one or more compounds of general formula I according to claim 1, in the free state or in the state of salt or complex, at a concentration of 0 .0001 to 95% by weight, with 5 to 99.9999% by weight of vehicles, diluents, fillers, dispersing or emulsifying agents and, where appropriate, other surfactants and other fungicidal active ingredients. cyclohexyl) -carbamide. dimethoxy-cyclohexyl) -carbamide, N - [2-cyano-2- (methoxy-imino)] - acetyl-N- (3-methyl- plexes, N- [2-cyano-2- (methoxy-imino)] - acetyl-N- (3,4- dimethyl-cyclohexyl) -carbamide, its salts and com dodecyl-carbamide, N- [2-cyano-2- (hydroxy-imino)] 3-acetyl- - (3,4-  carbamide, N- [2-cyano-2- (methoxy-imino) -acetyl-N-cyclo-  pentyl-carbamide, 2 N1-L2-cyano-2- (methoxy-imino) J-acetyl-l {2-cyclooctyl-  carbamide, its salts and complexes, N- [2-cyano-2- (methoxy-imino)] - acetyl-N-cyclohexyl- carbamide, N- [2-cyano-2- (methoxyimino)] - acetyl-N -cyclo  II - Pesticide product according to claim 10, characterized in that it contains as active material at least one of the following compounds in the free state or in the state of salt or complex N1 - 2-cyan o -2- (hydroxyimino) 3 -aceous tyl-N2-cycl ohexyl- I in which R and R have the meanings indicated in claim 1, or their salts or complexes, according to procedures known per se, where appropriate after addition of vehicles, diluents, fillers, dispersing or emulsifying agents or other substances surfactants and other fungicidal active ingredients, in the form of wettable powders, emulsifiable liquids, solutions, powders, suspensions, emulsions, oily dispersions, pastes, pulverulent products which can be used directly or after further dilution in as phytosanitary products.  12 - Process for the preparation of pesticide products according to claim 10 or 11, characterized in that the compounds of general formula are put