MX2008007942A - Oraganic derivatives, their salts and use for the control of phyto pathogens - Google Patents

Abstract

Organic compounds are described, which are capable of forming quaternary salts, quaternary salts thereof with a structure having general formula (I) and their use for the control of phytopathogen fungi.

Description

ORGANIC DERIVATIVES, THEIR SALTS AND CORRESPONDING USE FOR THE CONTROL OF PHYTOPATHOGENS The present invention relates to organic compounds capable of forming quaternary salts, the corresponding quaternary salts and the corresponding use for the control of phytopathogens. Quaternary salts are compounds known to be soluble in both hydrophilic and lyophilic environments. An example of a quaternary salt is represented by choline, a substance found abundantly in nature, known to be a biostimulant compound for plants as described in TG. Mason, G. Blunden (1989) Bot. Mar. 32 313-316. In addition, choline, inside the plants, is easily oxidized to glycine betaine. In the field of agronomy, being administered to fruit trees for example, glycine betaine contributes in the control of abiotic stress and nutritional development, reducing imperfections in fruit peels and the tendency of the peel to break during ripening, as it is described in EP-A-0806897, by acting as an osmolyte regulator. The Applicant has now discovered, surprisingly, that various organic compounds capable of forming quaternary salts and their quaternary salts have an unexpected activity as fungicidal and bactericidal products in the field of agronomy, obtaining a prolonged protective action on plants against phytopathogenic bacteria and fungi. These compounds are also capable of acting synergistically with numerous other active ingredients known to have a fungicidal activity or, in turn, capable of inducing the natural defenses of plants in the manner of to be able to control both biotic and abiotic stress. An object of the present invention therefore relates to organic compounds of general formula (I), (I) where: - K represents a group CH2OH or COORai - Ra represents a C-C26 linear or branched alkyl group optionally substituted; Ri represents a hydrogen a hydrogen a C1-C26 linear or branched alkyl group optionally substituted; a C 26 linear or branched haloalkyl group optionally substituted; an optionally substituted linear or branched C 26 alkoxy group; an optionally substituted linear or branched C 26 alkylthio group; a C2-C26 linear or branched alkenyl group optionally substituted; a C2-C26 linear or branched alkynyl group optionally substituted; an optionally condensed C3-C30 cycloalkyl group or a C-? 7 fused cycloalkyl group of the optionally substituted steroid type; a C3-C30 cycloalkoxy group optionally condensed and optionally substituted; an optionally substituted heterocyclic group; an optionally substituted aryl group; a heteroaryl group optionally replaced; a linear or cyclic C6-C-? 2 group of the optionally substituted saccharide type; a CrC26 alkylamine group or a C2-C26 dialkylamine group optionally substituted for n other than 0, - R2 and R3, equal or different, represent an optionally substituted C-1-C3 alkyl group, -R4 and R5, equal or different, represent a hydrogen atom, or an optionally substituted straight or branched Ci-Cβ alkyl group; an optionally substituted straight or branched C2-Cβ alkenyl group; an optionally substituted C3-C6 cycloalkyl group; a hydroxyl group; an optionally substituted aryl group; an optionally substituted heteroaryl group; an optionally substituted heterocyclic group, - R4 and R5 can individually form a cycle together with R2, - X represents a nitrogen or sulfur atom, - Z represents a carbon or sulfur atom, - m represents a number comprised between 1 and 5, - n and p represent a number between 0 and 3, - q has the value of 0 for X = sulfur or the value of 0 or 1 for X = nitrogen, - Y, when q has the value of 0 for X = sulfur and when q has the value of 1 for X = nitrogen, represents a halide, such as CI ", Br-, a nitrate anion (N03"), a nitrite anion (N02"); a phosphate anion selected from H2P04", HPO4" 2, PO4"3, a phosphite anion selected from H2P03", HPO3"2, PO3" 3; a carbonate anion (C02-2); a bicarbonate anion (HCO3"), a sulfate anion (SO4 2), a sulphated anion with hydrogen (HS04 ~), or Y represents the salicylate anion, the acetylsalicylate anion, the saccharinate anion, the 3-aminobutanoate anion, the cyclamate anion; the taurinate anion; the ethylphosphonate anion; or Y is absent when q has the value of 0 for X = nitrogen, - s has the value of 1 for Z = carbon or the value of 2 for Z = sulfur. The Applicant has also discovered that the compounds of general formula (I), not only have a direct fungicidal and bactericidal action, but are also capable of stimulating the natural defense systems of plants and inducing resistance in the plants themselves; This method to control diseases is awakening more and more interest since it is based on the amplification of a natural process already present in plants through the application of these compounds. The Applicant has also surprisingly discovered that these compounds of general formula (I) also constitute an optimum medium for the control of phytopathogens in genetically modified plant species to amplify the original natural defenses. Another object of the present invention is therefore the use of compounds of general formula (I): where: K represents a CH2OH or COORa group; - Ra represents a C -? - C 26 linear or branched alkyl optionally substituted group, - Ri represents hydrogen or an optionally substituted straight or branched C-C26 alkyl group; a C 26 linear or branched haloalkyl group optionally substituted; an optionally substituted straight or branched C -? - C 26 alkoxy group; an optionally substituted straight or branched CrC26 alkylthio group; a C2-C26 linear or branched alkenyl group optionally substituted; a C2-C26 linear or branched alkynyl group optionally substituted; an optionally condensed C3-C30 cycloalkyl group or a C group? fused cycloalkyl of the optionally substituted steroid type; a C3-C30 cycloalkoxy group optionally condensed and optionally substituted; an optionally substituted heterocyclic group; an optionally substituted aryl group; an optionally substituted heteroaryl group; a linear or cyclic C6-C? 2 group of the optionally substituted saccharide type; a C C 26 alkylamine group or a C2-C26 dialkylamine group optionally substituted for n other than 0, - R2 and R3, equal or different, represent an optionally substituted C1-C3 alkyl group, - R4 and R5, equal or different, represent a hydrogen atom, or an optionally substituted straight or branched Ci-Cβ alkyl group; an optionally substituted straight or branched C2-C6 alkenyl group; an optionally substituted C3-C6 cycloalkyl group; a hydroxyl group; an optionally substituted aryl group; an heteroa group optionally substituted; an optionally substituted heterocyclic group, - R4 and R5 can individually form a cycle together with R2, - X represents a nitrogen or sulfur atom, - Z represents a carbon or sulfur atom, - m represents a number between 1 and 5, - n and p represents a number between 0 and 3, - q has the value of 0 for X = sulfur or the value of 0 or 1 for X = nitrogen, - Y, when q has the value of 0 for X = sulfur and when q has the value of 1 for X = nitrogen, it represents a halide, such as CI \ Br "; a nitrate anion (NO3"), a nitrite anion (N02 ~); a phosphate anion selected from H2P04", HP04" 2, PO4"3, a phosphite anion selected from H2PO3", HPO3"2, PO3" 3; a carbonate anion (C02 2); a carbonate bianon (HC03"), a sulfate anion (SO4" 2); a hydrogen sulfate anion (HS04); or Y represents the salicylate anion; the acetyl salicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion; or Y is absent when q has the value of 0 for X = nitrogen, - s has the value of 1 for Z = carbon or the value of 2 for Z = sulfur, for the control of phytopathogenic bacteria and fungi. In particular, an object of the present invention relates to the use of compounds with a structure of general formula (I) for the control of phytopathogenic bacteria and fungi by stimulating the natural defense systems of plants and induction of resistance in plants. proper plants. In particular, the use of the compounds of general formula (I) for the control of phytopathogenic fungi is curative and / or preventive. A C -? - C26 alkyl group refers to a linear C26 alkyl C group or branched, optionally substituted by one or more substituents, the same or different. Examples of this group are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, capryl, lauryl, stearyl, eicosyl, hexacosyl. A C 26 haloalkyl group refers to a linear or branched alkyl group, substituted by one or more halogen atoms, the same or different. Examples of this group include: fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3 -pentafluoropropyl, perfluoro-octanyl, perfluorododecyl. A C -? - C 26 alkoxy group refers to a C 26 alkoxyl group, wherein the aliphatic part is a C 1 -C 26 alkyl group, as previously defined. Examples of this group are methoxy, ethoxy, isopropoxy, cyclopropylmethoxy, lauryloxy. A C-C26-thioalkyl group refers to a C -? - C26 thioalkyl group, where the aliphatic part is a C1-C26 alkyl group, as previously defined. Examples of this group are thiomethyl, thioethyl, thiolauryl, thiocapryl. A C2-C26 alkenyl group refers to a C2-C26 alkenyl group, straight or branched group, optionally substituted by one or more substituents, the same or different. Examples of this group are: ethenyl, propenyl, butenyl, 1-decenyl, 8-heptadecenyl, 8,11, 14-heptadecathenyl, 8,11-heptadecadienyl. A C2-C26 alkynyl group refers to a linear or branched C2-C26 alkynyl group, optionally substituted by one or more substituents, the same or different Examples of this group are: ethinyl, propargyl, 1-dodecinyl, 1-octadecinyl. An optionally condensed C3-C30 cycloalkyl group refers to a cycloalkyl group whose ring consists of 3-30 carbon atoms, optionally substituted by one or more substituents, the same or different. Examples of this group are: cyclopropyl, 2,2-dichlorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, decalin, abiethyl. A group C? Condensed cycloalkyl of the steroid type refers to a steroid group consisting of 17 carbon atoms, optionally substituted by one or more substituents, the same or different. Examples of this group are: cholanyl, or chenodeoxycolanyl, or ursodeoxylanyl, or deoxycolanyl, or iodeoxycolanyl, or lithocolanyl. A C3-C30 cycloalkoxy group refers to a C3-C30 cycloalkoxy group where the aliphatic part is a C3-C30 cycloalkyl group as previously defined. Examples of this group are cyclopentoxy, cyclohexyloxy, cholesteryl. A CrC26 alkylamine group or a C2-C26 dialkylamine group refers to an alkylamine or dialkylamine group where the aliphatic part is respectively a CrC26 or two C-1-C13 alkyl group as previously defined. Examples of this group are methylamine, dimethylamine, ethylamine, isopropylamine, dibutyl amine, dioctyl amine, hexadecyloamine, didecyloamine. An "aryl group" refers to an aromatic carbocyclic group optionally substituted by one or more groups, the same or different. Examples of this group are phenyl, naphthyl, phenanthryl.

A "heteroaryl group" refers to a benzocondensate or heterobicyclic heterocyclic aromatic penta- or hexa-atomic group, which contains between 1 and 4 heteroatoms selected from nitrogen, oxygen, sulfur, optionally substituted by one or more groups, the same or different. Examples of heteroaryl groups are: pyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, furan, thiophene, pyrol, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, pyrazole, imidazole, triazole, tetrazole , indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolepyridine, triazolepyrimidine, thiazoletriazole, coumarin. A heterocyclic group refers to a saturated or unsaturated ring with three to twelve terms, containing at least one heteroatom selected from nitrogen, oxygen, sulfur, optionally condensed with another aromatic or non-aromatic ring. Examples of heterocyclic rings are: pyrrolidine, piperidine, dihydropyridine, piperazine, 2,6-diketopiperazine, 2-ketoazetidine, morpholine, thiazine, indoline. A linear or cyclic C6-C12 group of the saccharide type refers to a carbohydrate group in open or closed form. Examples of this group are: gluconyl, glucopyranosyl, β-D-fructofuranosyl-a-D-glucopyranosyl, 4-O-β-D-galactopyranosyl-D-glucosyl. Optionally substituted means, throughout the patent application, one or more substituents, different or different, selected from the following groups: halogen atoms; C-pCβ alkyls, C-pCβ alkoxyls and C-pCβ alkylthio, in turn optionally substituted by halogen atoms; C Cβ alkylcarbonyls and CrC6 alkoxycarbonyl, optionally halogenated; aminocarbonyl, CrC6alkylaminocarbonyl, C2-C? 2 dialkylaminocarbonyl, optionally halogenated; carboxyl; CrC6 optionally halogenated alkylcarbonyloxy; cyano; nitro; formyl; hydroxyl; Not me; aryl and optionally substituted heteroaryl. Examples of compounds of general formula (I), when q has the value of 0 for X = nitrogen, which are interesting for their activity are: N, N-dimethylethanolamine; 3-dimethylamine-1-propanol; N-ethyl, N-methylethanolamine; 2-dimethylaminopropanol; N-lauryl, N-methylethanolamine; N, N-dimethyl-ßalanine methyl ester; N, N-dimethylglycine methyl ester. Examples of compounds of general formula (I) when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, which are interesting for their activity are: Choline phosphite acid; Neutral phosphite hill; Ethylphosphonate choline; Laurylcholine phosphite acid; Laurylcholine neutral phosphite; Cocamidopropylcholine phosphite acid; Cocamidopropylcholine neutral phosphite; Estearilocolina fosfito acid; Neutral stearylcholine phosphite; Colesterilocarboniloamidopropilocolina fosfito acid Colesterilocarboniloamidopropilocolina neutral phosphite; Colanyl amidopropylcholine phosphite acid; Colanyl amidopropylcholine neutral phosphite; Chenodeoxylaniloamidopropylcholine phosphite acid; Chenodeoxylaniloamidopropylcholine neutral phosphite; N, N-dimethyl, N-lauryl amidopropyl [L] valinol phosphite acid; N, N-dimethyl, N-lauryl amidopropyl [L] valinol neutral phosphite; N, N-dimethyl, N-lauryl [L] valinol phosphite acid; N, N-dimethyl, N-lauryl [L] valinol neutral phosphite; N-lauryl, N-methyl [L] 2-pyrrolidinemethanol phosphite acid; N-lauryl, N-methyl [L] 2-pyrrolidinemethanol neutral phosphite; Salicylate hill; Acetylsalicylate Hill; Hill saccharinate; Cyclamate hill; Taurinate Hill; Laurilocolin salicylate; Laurylcholine acetylsalicylate; Laurilocolina saccharinate; Laurylcholine cyclamate; Laurilocolin taurinate; Laurylcholine ethylphosphonate; Cocamidopropylcholine salicylate; Cocamidopropylcholine acetylsalicylate; Cocamidopropylcholine saccharinate; Cocamidopropylcholine cyclamate; Cocamidopropylcholine taurinate; Cocamidopropylcholine ethylphosphonate; Stearylcholine salicylate; Estearilocolina acetylsalicylate; Stearilocolina saccharinate; Stearylocoline cyclamate; Stearilocolina taurinate; Colaniloamidopropylcholine salicylate; Colaniloamidopropylcholine acetylsalicylate; Colaniloamidopropylcholine saccharinate; Colanyl amidopropylcholine cyclamate; Colaniloamidopropylcholine taurinate; Carbonate hill; Bicarbonate hill; Lauryl alcohol carbonate; Laurilocoline bicarbonate; Cocamidopropylcholine carbonate; Cocamidopropylcholine bicarbonate; Stearilocoline carbonate; Stearilocoline bicarbonate; Sulfate Hill; Choline chloride; Lauryl alcohol sulphate; Lauryl alcohol-sulfate; Cocamidopropylcholine sulfate; Cocamidopropylcholine bromide; Stearilocoline sulfate; Stearilokoline chloride; Acid phosphate hill; Neutral phosphate hill; Laurylcholine phosphate acid; Lauryl alcohol-neutral phosphate; Cocamidopropylcholine phosphate acid; Cocamidopropylcholine neutral phosphate; Estearilocolina phosphate acid; Neutral estearilocolina phosphate; Acid Phosphite of cocamidopropyl-betaine methyl ester; Neutral phosphite of cocamidopropyl betaine methyl ester; Acid phosphite of betaine cetyl ester; Neutral phosphite of the betaine cetyl ester; Cocamidopropyl betaine methyl ester salicylate; Cocamidopropyl betaine methyl ester acetylsalicylate; Betaine cetyl ester salicylate; Betaine cetyl ester acetylsalicylate; Cocamidopropylbetaine methyl ester cyclamate; Saccharinate of cocamidopropyl-betaine methyl ester; Betaine cetyl ester cyclamate; Betaine cetyl ester saccharinate; Bicarbonate of cocamidopropyl-betaine methyl ester; Cocamidopropylbetaine methyl ester chloride; Phosphite of colanyl amidopropyl methyl betaine acid; Phosphite of neutral colanyloamidopropyl-betaine methyl ester; Phosphite of the carnitine acid methyl ester; Phosphite of neutral carnitine methyl ester; Salicylate of the carnitine methyl ester; Acetylsalicylate of carnitine methyl ester; Saccharinate of carnitine methyl ester; Carnitine chloride. Particularly preferred are the quaternary salts of the general formula (I) when Y represents the salicylate anion; the acetyl salicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion; or when Y represents a phosphite anion selected from H2P? 3", HP? 3" 2, PO3"3, an anion halide or a carbonate bianon (HC03"). The Applicant has now surprisingly discovered that the quaternary salts of formula (I), when Y represents a phosphite anion selected from H2P03 \ HP03"2, PO3" 3, or the salicylate anion; the acetyl salicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion, have a surprisingly higher activity than what is expected derived from the anion, which is known in the literature for its own biological efficacy, and the corresponding quaternary cation, demonstrating the synergy between the ion pair of compounds of general formula (I ) when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen. An unexpected synergistic effect has therefore been found between the cationic component and the anionic component of quaternary salts of formula (I) when Y represents a phosphite anion selected from H2PO3", HPO3" 2, PO3"3, or the salicylate anion, the acetyl-salicylate anion, the anion saccharinate, the anion 3-aminobutanoate, the cyclamate anion, the taurinate anion and q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen.When they are not commercial products, the compounds of general formula (I), when q has the value of 0 for X = nitrogen, can be easily obtained according to the methods described, for example, in Comprehensive Organic Transformations 1989, R. C. Larock, or in March's Advanced Organic Chemistry 2001 Edition, M. B. Smith, J. March. The compounds of formula (I), when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, can be obtained by different synthetic methods according to the meaning of the anion Y. When Y has the meaning of a CI anion "and Br", and when R1 has the previously defined meanings to the exclusion of a C 26 alkoxy group, or a CrC26 alkylthio group, or a C3-C30 cycloalkoxy group, or a C? -C26 alkylamine group, or a C2-C26 dialkylamine group, the quaternary salts of formula (I) can be easily obtained according to the reaction figure 1 for n other than 0 and according to figure 1 and according to the reaction figure 2 for n = 0: where K, Ri, R2, R3, R4, R5, X, Z, m, p, qys have the meanings already defined and Y represents a leaving group such as a chlorine or bromine atom that also transforms into the counterion of the final product. The quaternary salts of general formula (I), according to the figure of Reaction 1, for X = nitrogen, can be obtained by condensation of the appropriate N ', N'-dialkylamine-N-alkylamine or, for X = sulfur, by condensation of the appropriate α-alkylthioalkylamine with carboxylic acid of a Ri residue, and a condensing agent, optionally in the presence of a base in an organic or aqueous solvent, according to methods well known in the art, for example in Comprehensive Organic Transformations 1989, RC Larock, to form the corresponding amide. The intermediate thus obtained is then subjected to alkylation by reaction with the appropriate halide, in water or in an organic solvent, at temperatures ranging from room temperature to 100 ° C, maintaining the pH at values of about 7.5, by means of the controlled addition of a solution of a strong base. The quaternary salts of the general formula (I), according to the reaction figure 2, for X = nitrogen, can be obtained by alkylation of the appropriate N ', N'-dialkylamine-N-alkylamine or, for X = sulfur, by alkylation of the appropriate α-alkylthioalkylamine with the desired Ri residue having the leaving group Y, in the presence of a base in an organic or aqueous solvent, according to methods well known in the art, for example in Comprehensive Organic Transformations 1989, RC Larock, in order to form the corresponding tertiary amine. The intermediate thus obtained is then re-subjected to alkylation by reaction with the appropriate halide, in water or in an organic solvent, at temperatures ranging from room temperature to 100 ° C, maintaining the pH at values of around 7.5, by the controlled addition of a solution of a strong base. The quaternary salts of formula (I), when Y has the meaning of an anion CI "and Br" and when Ri has the meanings of a C 26 alkoxy group, or a C -? - C 6 alkylthio group, or a C3-C30 cycloalkoxy group, or a C1-C26 alkylamine group, or a C2-C26 dialkylamine group, can be easily obtained according to the reaction figure 3 for n different from 0: where K, Ri, R2, R3, R4, R5, X, Z, m, p, qys have the defined meanings previously and Y represents a leaving group such as a chlorine atom or a bromine atom, which becomes the counter-ion of the final product. The quaternary salts of general formula (I), according to the reaction figure 3, for X = nitrogen, can be obtained by the reaction of the appropriate N ', N'-dialkylamine-N-alkylamine or, for X = sulfur, by reaction of the appropriate α-alkylthioalkylamine with the desired residue R 1 having an alcoholic or thioalkholic, or amino function when R 1 has the meanings of a C-1-C 26 alkoxy group, or a C 3 -C 30 cycloalkoxy group, or a C group C26 alkylthio, or a CrC26 alkylamine group, or a C2-C26 dialkylamine group respectively, in the presence of phosgene or one of its functional substitutes, such as, for example, diphosgene, triphosgene, 1,1'-carbonyldiimidazole, in an organic or aqueous solvent, according to methods well known in the art, for example in Comprehensive Organic Transformations 1989, RC Larock, so as to form the carbamate, thiocarbamate or urea. The intermediate thus obtained is then re-subjected to alkylation by reaction with the appropriate halide, water, or in an organic solvent, at temperatures ranging from room temperature to 100 ° C, maintaining the pH at values of around 7.5, by the controlled addition of a solution of a strong base. When Y has a different meaning to an anion CI "and Br", the quaternary salts of formula (I) can be easily obtained by exchange of the alkali salts, such as for example sodium and potassium, of the appropriate YH acids, the halides of the quaternary cations being synthesized as previously described, according to the figure of reaction 4: where K, Ri, R2) R3, R, R5, X, Z, m, p, qys have the meanings defined above and Y represents the acid residue that acts as counterion to the final product. Alternatively, the quaternary salts of formula (I), for Y other than HCO3", can be easily obtained by the appropriate molar salification of YH acid with the bicarbonates of the corresponding quaternary cations, according to the reaction figure 5: where K , R1 f R2, R3, R4, R5, X, Z, m, p, q and s have the previously defined meanings and Y represents the acid residue that is transformed into the counterion of the final product, the reactions can conveniently be carried out in an inert or aqueous organic solvent, at a temperature between room temperature and the boiling point of the reaction mixture, optionally in the presence of an organic or inorganic base.Preferred examples of solvents for effecting the reaction are ethers (ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc.), esters (ethylacetate, etc.), chlorinated hydrocarbons (methylene chloride, dichloroethane, chloroform, tetrachloride bond, etc.); aromatic hydrocarbons (benzene, toluene, xylene, etc.); aliphatic hydrocarbons (hexane, heptane, cyclohexane, etc.); dipolar aprotic solvents (N-dimethylformamide, dimethisulfoxide, sulfolane, etc.).

Examples of preferred inorganic bases are: hydroxides, alkali metal or alkaline earth metal carbonates (sodium, potassium, calcium, etc.). Examples of preferred organic bases are: pyridine, dimethylaminopyridine, aliphatic amines (triethylamine, etc.), cyclic amines (morpholine, piperidine, etc.). If the substituents R-i, R2, R3, R4, R5 contain optical or geometric isomerism centers, the compounds of general formula (I) may be present in all possible configurational isomeric forms. The scope of the present invention therefore also comprises the use of the compounds of general formula (I) as isomeric mixtures in any proportion, and also the formation and use of the simple isomers for the control of phytopathogenic fungi in the field of agronomy. When derived from natural extracts, the compounds of general formula (I) may also be present in mixtures of their homologous products and the scope of the invention thus also includes the use of the compounds of general formula (I) as mixtures of their homologous products in any proportion, for the control of phytopathogenic bacteria and fungi in the field of agronomy. The compounds of general formula (I) may also be present in hydrated form by the coordination of any number of water molecules, or obtained in aqueous solution and used directly for agronomic purposes. The quaternary salts of the general formula (I) can also contain and possibly coordinate within their structure other metal cations, such as, for example, sodium, potassium, the amount of which can vary in relation to the preparation method used for the synthesis of the compound of general formula (I). The scope of the present invention therefore also comprises the use of said quaternary salt solutions of formula (I), which contain said salts for the control of phytopathogenic bacteria and fungi in the field of agronomy. The scope of the present invention also comprises the use of mixtures of compounds of general formula (I) in any proportion. The Applicant has also discovered, in agronomic practice, that the fungicidal action of the compounds of general formula (I) is particularly effective when combined with that of numerous other fungicidal active ingredients., thus forming an excellent instrument for anti-resistance strategies, allowing the additional reduction of application doses and stimulating the natural defenses of plants. The Applicant, also surprisingly, has discovered that the compounds of general formula (I), when q has the value of 0 for X = nitrogen, are of particular interest since they are capable of exerting considerable synergistic effort if employed in a mixture with Fosetyl-Aluminum (fungicidal active ingredient corresponding to aluminum triethylphosphonate, described in "The Pesticide Manual", 1994, Xa edition, British Crop Protection Council Ed., page 530 and better known by the trade name of Aliette) thus allowing, when applied together, a higher fungicidal activity compared to that of the individual components, as well as the provision of excellent anti-resistance properties. An object of the present invention also relates, therefore, to fungicidal compositions comprising one or more compounds of general formula (I), when q has the value of 0 for X = nitrogen, in mixture with Fosetyl-Aluminum (Fosetyl-AI). Preferred fungicidal compositions are: a). N, N-dimethylethanolamine and Fosetyl-AI; b) 3-dimethylamine-1-propanol and Fosetyl-AI; c). N -ethyl, N-methylethanolamine and Fosetyl-AI; d) .2-dimethylaminopropanol and Fosetyl-AI; e) .N-lauryl, N-methylethanolamine and Fosetyl-AI; F). N-dimethyl-Dalanin methyl ester and Fosetyl-AI; g). N, N-dimethylglycine methyl ester and Fosetyl-AI. Composition a) is particularly preferred for its fungicidal activity. The additional compounds having fungicidal activity and can be used together with the compounds of general formula (I), when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, according to the present invention, they are preferably selected from: (1) IR5885, a dipeptide compound corresponding to diastereomeric mixtures of methyl [S- (R, S)] - [3- (N-isopropoxycarbonyl-valeinyl) -amino] -3- (4-chloro-phenyl) propanoate in any proportion to one of the two diastereomeric forms SR or SS taken individually, (2) IR6141, corresponding to methyl N- (phenylacetyl) -N-2,6-xylyl-R-alaninate (3) Tetraconazole (in its form racemic or as optically active isomer R), (4) Salicylic acid (SA) or its derivatives such as acetylsalicylic acid (ASA), copper salts of salicylic acid (SA2Cu) or (SACu) or acetylsalicylic acid (ASA2CU), (5) A copper (I) or salt of copper (II), such as copper oxychloride, copper hydroxide, Bordeaux mixture, copper sulfate, or a mixture of copper hydroxide and oxychloride (Airone), (6) Benalaxyl corresponding to methyl N- (phenyl acetyl) - N-2,6-xylyl-RS-alaninate, (7) Metalaxyl corresponding to methyl N- (2-methoxyacetyl) -N-2,6-xylyl-10 RS-alaninate, (8) Metalaxyl-M corresponding to methyl N - (2-methoxyacetyl) -N-2,6-xylyl-R-alaninate, (9) Oxadixyl corresponding to 2-methoxy-N- (2-oxo-1,3-oxazolidin-3-yl) aceto-2 ' , 6'-xylidide, -_ 5 (10) Mandipropamid corresponding to 2- (4-chlorophenyl) -N- [2- (3-methoxy-4-prop-2-ynyloxy-phenyl) ethyl] -2-prop -2-inyloxy-acetamide, (11) Iprovalicarb corresponding to 0- (1-methyl-ethyl) -N- [2-methyl-1 - [[[1- (4-methyl-phenyl) -ethyl] amino] carbonyl ] propyl] carbamate, ( 12) Bentiavalicarb-isopropyl corresponding to O-isopropyl [(S) -1-20. { [(1 R) -1- (6-fluoro-1,3-benzo-thiazol-2-yl) ethyl] -carbamoyl-2-methylpropyl] -carbamate, (13) Cymoxanil corresponding to 1- (2-cyano- 2- methoxyimino-acetyl) -3-ethylurea, (14) Azoxystrobin corresponding to methyl (E) -2- [2- [6- (2-cyanophenoxy) - 5-pyrimidin-4-yloxy] phenyl-3-methoxyacrylate, (15) Methominophen corresponding to N-methyl- (E) -methoxyimino- (2-phenoxyphenyl) acetamide, (16) Piraclostrobin corresponding to methyl N- (2- [1- (4-chlorophenyl) pyrazol-3-yloxymethyl] - phenyl) -N-methoxycarbamate, (17) Acibenzolar-S-methyl corresponding to methyl benzo (1,2,3) thiadiazole-7-thiocarboxylate, (18) Famoxadone corresponding to 5-methyl-5- (4-phenoxyphenyl) - 3- (phenyloamino) oxazolidin-2,4-dione, (19) Fenamidone corresponding to 4-methyl-4-phenyl-1- (phenylamino) -2-methylthioimidazolidin-5-one, (20) Cyazofamide, corresponding to 2- cyano-4-chloro-5- (4-methylphenyl) -1- (N, N-dimethylaminosulfamoyl) -imidazole, (21) Fluazinam corresponding to 3-chloro-N- (3-chloro-5-trifluoromethyl-2-pyridyl) ) -aaa-trifluoro-2,6-dinitro-p-toluidine, (22) Dimetomorph corresponding to (E, Z) -4- [3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -acyloyl ] morpholine; or Flumorph (SYP-L190) corresponding to (E, Z) -4- [3- (4-fluorophenol) -3- (3,4-dimethoxyphenyl) -acyloyl] morpholine, (23) Flumetover corresponding to N, N-diethylamide of 4-trifluoromethyl-6-3,4-dimethoxyphenyl) -benzoic acid, (24) Chlorothalonyl corresponding to 1,3-dicyano-2,4,5-tetrachlorobenzene, (25) Mancozeb corresponding to the manganese salt and ethylene bis (dithiocarbamate) zinc (polymer), (26) Tolilofluanide corresponding to N-dichloro-fluoromethylthio-N ', N'-dimethyl-Np-tolylsulfonamide, (27) Folpet corresponding to N- (trichloromethyl-thio) phthalimide, (28) Etridiazole corresponding to ethyl-3-trichloromethyl-1, 2,4-thiadiazolyl ether, (29) Hymexanol corresponding to 5-methylisoxazole-3 ol, (30) Propamocarb corresponding to propyl- (3-dimethylaminopropyl) carbamate, (31) R-3-aminobutanoic acid or RS-3-aminobutanoic acid; (32) Zoxamide, corresponding to 3,5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -p-toluamide, (33) Ethaboxam, corresponding to (RS) - (a -cyano-2-thienyl) -4-ethyl-2 (ethylamino) -5-thiazolecarboxylamide, (34) Fluopicolide, corresponding to 2,6-dichloro-N- [3-chloro-5- (trifluoromethyl) -2 -pyridylmethyl] benzamide, (35) Fosetyl, corresponding to ethyl hydrogen phosphonate, (36) Fosetyl-AI, corresponding to aluminum triethylphosphonate, better known under the trade name Aliette. The compounds (1) are described in the Italian patent application No. MI98A002583. The compound (2) is described in patent application WO 98/26654 A2. The compound (3) is described in "The Pesticide Manual", 1997, XIth edition, British Crop Protection Council Ed., P. 1174. The compounds (4) are commercial products and their copper salts are described in the Italian patent application No. Ml 2001A002430. The compounds (5) are easily obtained in square. The compound (6) is described in "The Pesticide Manual", 1983, Vlla edition, British Crop Protection Council Ed., p. 32. The compound (7) is described in British patent GB 1,500,581. The compound (8) is described in the patent application WO 96/01559 A1. The compound (9) is described in the British patent No. 2,058,059. The compound (10) is described in the patent application WO 01/87822. The compound (11) is described in patent application EP 550,788 and EP 775. 696. Compound (12) is described in patent application EP 775,696. The compound (13) is described in "The Pesticide Manual", 1983, Vllma. edition, British Crop Protection Council Ed., p. 148. Compound (14) is described in European patent application EP 382,375.

The compound (15), corresponding to the experimental abbreviation SSF-126, is described in the patent application US 5,185,242. The compound (16) is described in the patent application WO 96/01258. The compound (17) is described in the patent application US 4,931,581. The compound (18) is described in "Brighton Crop Protection Conference - Pests and Diseases" 1996, Congress Records. The compound (19) is described in the patent application EP 629,616. The compound (20), also called IKF916, is described in the patent application EP 705,823. The compound (21) is described in the patent application EP 31,257. The compounds (22) are respectively described in the EP patent application 219. 756 and in "Brighton Crop Protection Conference - Pests and Diseases" 2000, Congress Records. The compound (23) is described in the patent application EP 360,701 and EP 611, 232. The compound (24) is described in "The Pesticide Manual", 1983, Vllma. edition, British Crop Protection Council Ed., P. 120. Compound (25) is described in "The Pesticide Manual", 1983, Fifth Edition, British Crop Protection Council Ed., P. 339. Compound (26) is described in "The Pesticide Manual", 1983, Vlla. edition, British Crop Protection Council Ed., P. 537. The compound (27) is described in "The Pesticide Manual", 1983, Vlla edition, British Crop Protection Council Ed., P. 599. The compound (28) is described in "The Pesticide Manual", 1983, Vlla edition, British Crop Protection Council Ed., Page 252. Compound (29) is described in "The Pesticide Manual", 1983, Vlla edition, British Crop Protection Council Ed., P. 314. Compound (30) is described in "The Pesticide Manual", 1983, Vlla edition, British Crop Protection Council Ed., P. 471. The compound (31) is described in patent application EP 753,258. The compound (32) is described in "Brighton Crop Protection Conference - Pests and Diseases" 1998, Congress Records. The compound (33) is described in "The Pesticide Manual", 2003, XIIIth edition, British Crop Protection Council Ed. The compound (34) is described in the patent application WO 200111966. The compounds (35) and (36) are described in "The Pesticide Manual", 1994, Xa edition, British Crop Protection Council Ed., P. 530. Another object of the present invention therefore relates to fungicidal compositions comprising one or more quaternary salts of general formula (I), so that it has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, and fungicidal compositions that also contain other active principles. Preferred fungicidal compositions according to the present invention can be selected from: 1. Acid phosphite hill and IR5885 2. Neutral phosphite hill and IR5885 3. Ethylphosphonate hill and IR5885 4. Ethylphosphonate hill and IR6141 10 5. Acid phosphite hill and IR6141 6 Neutral phosphite hill and IR6141 7. Acid phosphite and Bentiavalicarb-isopropyl hill, 8. Neutral phosphite and Bentiavalicarb-isopropyl hill, 9. Acid phosphite hill and ASA2CU, - | _ 5 10. Acid phosphite and SA2Cu hill, 11. Phosphite hill acid and SACu, 12. Neutral phosphite and ASA2Cu hill, 13. Neutral phosphite and SA2Cu hill, 14. Neutral phosphite and SACu hill, 20 15. Laurilocolina fosfito acid and IR5885, 16. Neutrophil phosphite laurilocolina and IR5885, 17. Laurylcholine phosphite acid and IR6141, 18. Laurilocolina neutral phosphite and IR6141, 19. Choline phosphite acid and iprovalicarb, 5 20. Choline phosphite neutral and iprovalicarb, 21. Cocamidopropylcholine phosphite acid and IR5885, 22. Cocamidopropylcholine neutral phosphite and IR5885, 23. Cocamidopropylcholine phosphite acid and IR6141, 24. Cocamidopropylcholine neutral phosphite and IR6141, 25. Cocamidopropylcholine phosphite acid and copper oxychloride, 26. Cocamidopropylcholine neutral phosphite and copper oxychloride, 27. Cocamidopropyl betaine methyl ester of methalester and IR5885, 28. Neutral phosphite of cocamidopropylbetaine methyl ester and IR5885, 29. Phosphite acid methyl ester of cocamidopropylbetaine and IR6141, 30. Phosphite neutral of methyl ester of cocamidopropylbetaine and IR6141, 31. Phosphite acid methyl ester of cocamidopropyl betaine and Airone, 32. Neutral phosphite of cocamidopropylbetaine methyl ester and Airona, 33. Salicylate Hill and IR5885, 34. Acetylsalicylate Hill and IR5885, 35. Saccharinate Hill and IR5885, 36. Bicarbonate Hill and IR5885, 37. Phosphite Choline Acid and Mandipropamid, 38. Phosphite Choline Neutral and Mandipropamid, 39. Phosphite Choline Acid and Oxychloride copper, 40. Phosphite choline neutral and copper oxychloride, 41. Phosphite choline acid and Airona, 42. Phosphite choline neutral and Airona, 43. Phosphite choline acid and Ethaboxam, 44. Phosphite choline neutral and Ethaboxam, 45. Choline bicarbonate and Fosetyl -AI, 46. Choline chloride and Fosetyl-AI, 47. Choline salicylate and Fosetyl-AI, 48. Choline acetylsalicylate and Fosetyl-AI, 49. Cocamidopropylcholine chloride and Fosetyl-AI, 50. Laurilocolin chloride and Fosetyl-AI, 51. Choline bicarbonate and Fosetyl, 52. Chloride and Fosetyl Hill. Particularly preferred are the compositions defined with the following numbers: 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 19., 20., 33., 34., 35., 36., 45., 46., 52. Another object of the present invention therefore relates to the use of fungicidal compositions comprising a compound of general formula ( I), when q has the value of 0 for X = nitrogen, and the fungicide compound (36). Another object of the present invention relates to the use of fungicidal compositions comprising one or more compounds of general formula (I), when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, and one or more fungicidal compounds, in particular one or more fungicidal compounds (1) - (36), even more in particular compounds (1), (2), (4), (5), (35) and (36), for the control of phytopathogenic fungi. An object of the present invention also relates to a method for the control of phytopathogenic fungi in agricultural crops by the application of the compounds of general formula (I) or fungicidal compositions comprising one or more compounds of general formula (I) and one or more fungicidal compounds, in particular one or more fungicidal compounds (1) - (36), even more in particular compounds (1), (2), (4), (5), (35) and (36), for the control of phytopathogenic fungi. The following are examples of bacteria and phytopathogenic fungi controlled by the above-mentioned compounds of general formula (I) and the compositions mentioned above, together with examples of 5 application crops, for purely illustrative and non-limiting purposes: - Helminthosporium spp. in cereals, - Erysife spp. in cereals, - Puccinia spp. in cereals, - Plasmopara viticola in climbers, 1 o - Pithium spp in vegetables, - Phytoñora spp. in vegetables, - Rhynchosporium in cereals, - Septoria spp. in cereals, - Sphaerotheca fuliginaa in cucurbits (for example cucumbers) -j_ 5 - Podosphaera leucotricha in apple trees, - Piricularia oryzae in rice, - Uncinula necator in climbers, - Venturia spp. in fruit trees, - Botrytis cinarea in climbers and vegetables, 20 - Fusarium spp. in cereals, - Alternaria spp. in fruit and vegetables, - Cercospora spp. in sweet potato, - Xantomonas, - Bacillus spp. The compounds of general formula (I) and their mixtures with one or more fungicidal compounds are able to exert a bactericidal / fungicidal action of both curative and preventive nature and have little or no phytotoxicity. Another object of the present invention therefore relates to a method for the control of phytopathogenic bacteria and fungi in agricultural crops by the application of the compounds of general formula (I) having a direct fungicidal and bactericidal activity and a method for the stimulation of the natural defense systems of plants against abiotic stress (temperature, salinity, drought, etc.) and biotic stress and the induction of resistance in the plants themselves through the application of the compounds of general formula (I) - The amount of compound to be applied for obtaining the desired effect may vary in relation to various factors such as, for example, the compound used, the culture to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the method of application and the formulation adopted. Generally, compound doses between 10 g and 5 kg per hectare provide sufficient control. For practical uses in agriculture, it is often convenient to apply fungicidal compositions containing one or more compounds of general formula (I). The application of these compositions can be carried out in all parts of the plant, for example leaves, stems, branches and roots, or in the seeds themselves before planting, or in the soil where the plant grows. The compositions can be used in the form of dry powders, Wettable powders, emulsifying concentrates, microemulsions, pastes, granulates, solutions, suspensions, etc; The choice of the type of formulation will depend on the specific use. The compositions are prepared in known manner, for example by diluting or dissolving the active substance with a solvent medium and / or a solid diluent, possibly in the presence of surface active agents. The solid diluents or supports that can be used are, for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, atapulguite, sepiolite. The liquid diluents which can be used are, for example, in addition to water, aromatic organic solvents (xylols or mixtures of alkylbenzole, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerin, etc.), esters (ethyl acetate, isobutylacetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamidoketone, etc.), amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.). The surface active agents that can be used are the sodium, calcium, triethylamine or triethanolamine salts, alkylsulfonates, alkylaryl sulphonates, polyethoxylated alkylphenols, sorbitol esters, ligninsulfonates, etc. The compositions may also contain special additives for particular purposes, for example adhesion agents such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylates, etc. In the fungicidal compositions object of the present invention, the concentration of active substances varies between 0.1% and 98% by weight, preferably between 0.5 and 90% by weight. If desired, it is also possible to add active ingredients compatible to the compositions object of the present invention, such as, for example, phyto-regulators, antibiotics, herbicides, insecticides, fertilizers. The following examples are provided for further understanding of the invention, for illustrative and non-limiting purposes of the present invention. EXAMPLE 1 Preparation of neutral choline phosphite (compound 1). A solution of 16.10 g of potash in 20 ml of water is added dropwise with cooling to a solution of 10 g of phosphorous acid in 5 ml of water. The mixture is allowed to stir at room temperature and 34.07 g of choline chloride are added in portions. At the end of the addition, the mixture is left stirring for 3 hours and the solution thus obtained is used as such. EXAMPLE 2 Preparation of phosphite choline acid (compound 2). 20.15 g of choline bicarbonate are added in portions, with cooling, to a solution of 10 g of phosphorous acid in 3 ml of water. At the end of the addition, the mixture is left stirring for 4 hours and the solution thus obtained is used as such. EXAMPLE 3 Preparation of cholesterylcarbonylolamido-propyl-dimethylamine. 3.41 g of 3-dimethylamino-1-propylamine are added to a solution of 15 g of cholesterylchloroformate in 70 ml of methylene chloride and 3.49 ml of triethylamine. The mixture is left stirring at room temperature overnight. The product obtained is extracted, washed with water, made anhydrous with Na 2 SO 4, after drying, 15.8 g of the desired compound (yield: 92%). Elemental analysis [% found (theoretical)] = C 77.0 (76.8); H 11.9, (11.2); N 5.1 (5.4). EXAMPLE 4 Preparation of cholesterylcarbonyl amidopropylcholine chloride (compound 3). 12 g of cholesterylcarbonyl amidopropyl dimethylamine in 32 ml of water are charged to a reactor and 1.9 g of 2-chloroethanol are added. The reaction mixture is slowly heated to 98 ° C. After about 5 hours, the starting products have been used up and the solution obtained is used as such. EXAMPLE 5 Preparation of cholesterylcarbonyl amidopropylcholine neutral phosphite (compound 4). A solution of 3.22 g of potash in 4 ml of water is added dropwise with cooling to a solution of 2 g of phosphorous acid in 2 ml of water. The mixture is allowed to stir at room temperature and 28.9 g of cholesterylcarbonyl amidopropylcholine chloride are added in portions. At the end of the addition, the mixture is left stirring for 3 hours and the solution thus obtained is used as such. EXAMPLE 6 Preparation of cholesterylcarbonyl amidopropylcholine phosphite acid (compound 5). A solution of 1.61 g of potash in 2 ml of water is added dropwise with cooling to a solution of 2 g of phosphorous acid in 2 ml of water.

The mixture is allowed to stir at room temperature and 14.45 g of choline chloride are added in portions. At the end of the addition, the mixture is left stirring for 3 hours and the solution thus obtained is used as such. The following compounds were prepared analogously to what is described in the examples: TABLE 1 EXAMPLE 7 Determination of fungicidal activity against grape peronospora. { Plasmopara viticola). Table 2 Vine leaves (cultivar Dolcetto), cultivated in glasses in conditioned environment (20 ± 1 ° C, 70% relative humidity) are treated by spraying both sides of the leaves with compounds 1 and 2, dispersed in a hydroacetone solution at 20% by volume in acetone. After remaining 24 hours in a conditioned environment, the plants were sprayed on both sides of the leaves with an aqueous conidia suspension of Plasmopara viticola (20,000 conidia per cm3). The plants are kept in an environment saturated with humidity at 21 ° C for the incubation period of the fungus. At the end of this period (7 days), the activity of the fungicide is evaluated according to a percentage scale of evaluation from 0 (totally infected plant) to 100 (healthy plant). TABLE 2 7-day preventive activity in Plasmopara viticola of the compounds of general formula (I) * Doses in ppm refer to the amount of equivalent phosphorous acid. EXAMPLE 8 Determination of the fungicidal activity against potato peronospora (Phytophtora infestans). Table 3 Leaves of potato plants, variety First, were infected in vessels in a conditioned environment (20 ± 1 ° C, 70% relative humidity) with an aqueous suspension of spores of Phytophtora infestans (100,000 spores per cm 3). After remaining 24 hours in a conditioned environment, the plants were sprayed on both sides of the leaves with the products under examination dissolved in a solution of hydroacetone at 20% acetone (vol./vol.). After drying, the plants were transferred during the incubation period of the fungi (4 days) in a conditioned environment at 70% relative humidity and 24 ° C. Finally, the intensity of the disease was evaluated according to an evaluation scale of 100 (healthy plant) to 0 (completely infected plant). Table 3 Healing activity of 1 day in Phytophtora infestans of the compounds of general formula (I) * The dose in ppm refers to the amount of choline contained in the compound No. 2 ** Doses in ppm refer to the amount of equivalent phosphorous acid. From the data indicated in Table 3, it is possible to ratify the effect of the ion pair present in Compound No. 2. When in fact the experimentally found fungicidal activity (65) is greater than expected (49), calculated considering the contribution of potassium phosphite and choline chloride and using the Limpel formula ("Pesticide Science" (1987), vol 19, pages 309-315), this activity should be considered as a synergistic effect with a factor of synergy equal to 1.4 (experimental activity / activity calculated according to Limpel). EXAMPLE 9 Determination of the fungicidal activity of fungicidal mixtures against potato peronospora (Phytophtora infestans). Tables 4-6 Leaves of potato plants, Primura variety, were infected, grown in vessels in a conditioned environment (20 ± 1 ° C, 70% relative humidity) with an aqueous suspension of spores of Phytophtora infestans (100,000 spores per cm 3). After remaining 24 hours in a conditioned environment, the plants were sprayed on both sides of the leaves with the products under examination dissolved in a solution of hydroacetone at 20% acetone (vol./vol.). After drying, the plants were transferred during the incubation period of the fungi (4 days) in a conditioned environment at 70% relative humidity and 24 ° C.

Finally, the intensity of the disease was evaluated according to an evaluation scale of 100 (healthy plant) to 0 (completely infected plant). From the data indicated in Tables 4-6, the synergistic effect of the mixtures, consisting of the mixtures under examination, can be confirmed, compared with the expected efficacy using the Limpel formula ("Pesticide Science" (1987), vol. 19, pages 309-315): E = x + y - (xy / 100) where: - E is the expected fungicidal activity, without synergistic effects, of a mixture obtained by mixing gx of compound X with gy of compound Y, - x is the activity of compound X when used alone at a dose of gx, - and it is the activity of compound Y when it is used only at a dose of g.y. When the experimentally found fungicidal activity is greater than the value of E, this activity should be considered a synergistic effect. TABLE 4 Healing activity of 1-day in Phytophtora infestans of fungicide mixtures consisting of Fosetyl-AI which at 1600 ppm * (gx) is 0 (x) with compounds of general formula (I) when q has the value of 0 for X = nitrogen.

* Doses in ppm refer to the amount of equivalent phosphorous acid. TABLE 5 Healing activity of 1-day in Phytophtora infestans of fungicide mixtures consisting of IR5885 which at 150 ppm (gx) is 15 (x) with compounds of general formula (I) when q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen.

* Doses in ppm refer to the amount of equivalent phosphorous acid. TABLE 6 Healing activity of 1-day in Phytophtora infestans of fungicide mixtures consisting of Fosetyl-AI which at 1600 ppm * (gx) is 0 (x) with other compounds of general formula (I) when q has the meaning of 0 for X = sulfur and the value of 1 for X = nitrogen.

* Doses in ppm refer to the amount of equivalent phosphorous acid. EXAMPLE 10 Determination of the fungicidal activity of fungicidal mixtures against peronospora of the vine (Plasmopara viticola). Table 7. Vine leaves (cultivar Dolcetto), grown in vessels in conditioned environment (20 ± 1 ° C, 70% relative humidity) were infected with an aqueous spore suspension of Plasmopara viticola (200,000 conidia per cm3). After remaining 24 hours in a conditioned environment, both sides of the leaves were sprayed with fungicide mixtures under examination, dissolved in a solution of hydroacetone at 20% acetone (vol./vol.). Once dried, the plants were transferred, for the incubation period of the fungi (6 days) to a conditioned environment with 70% relative humidity and 24 ° C. At the end of this period (7 days) the fungicidal activity is evaluated according to a percentage evaluation scale of 0 (completely infected plant) to 100 (healthy plant). From the data indicated in Table 7, it is possible to confirm the synergistic effect of the mixtures examined, in comparison with the expected efficacy using the Limpel formula already described in Example 9. TABLE 7 Healing activity of 1-day in Plasmopara viticola of fungicidal mixtures consisting of Fosetyl-AI which at 1200 ppm * (gx) is 23 (x) with other compounds of general formula (I).

Doses in ppm refer to the amount of equivalent phosphorous acid.

EXAMPLE 11 Determination of the fungicidal activity of fungicidal mixtures against tobacco peronospora (Plasmopara tabacina). Table 8. Tobacco leaves (Barley cultivar), grown in vessels in a conditioned environment (20 ± 1 ° C), 70% relative humidity) were infected with an aqueous spore solution of Plasmopara tabacina (200,000 conidia per cm3). After remaining 24 hours in a conditioned environment, both sides of the leaves were sprayed with fungicide mixtures under examination, dissolved in a solution of hydroacetone at 20% acetone (vol./vol.). Once dried, the plants were transferred, for the incubation period of the fungi (6 days) to a conditioned environment with 70% relative humidity and 24 ° C. At the end of this period (7 days) the fungicidal activity is evaluated according to a percentage evaluation scale of 0 (completely infected plant) to 100 (healthy plant). From the data indicated in table 8, it is possible to confirm the synergistic effect of the mixtures examined, in comparison with the expected efficacy using the formula Limpel already described in Example 9. TABLE 8 Curative activity of 1 day in Plasmopara tabacina of fungicidal mixtures consisting of Fosetyl-AI that at 1200 ppm * (gx) is 15 (x) with other compounds of general formula (I).

Doses in ppm refer to the amount of equivalent phosphorous acid.

Claims (40)

1. CLAIMS 1.- Organic compounds of general formula (I), wherein: - K represents a CH2OH or COORa group, - Ra represents an optionally substituted straight or branched C26 alkyl group, - Ri represents hydrogen or an optionally substituted straight or branched C2- or C2-, alkyl group; an optionally substituted linear or branched C-? - C 26 haloalkyl group; an optionally substituted linear or branched C 26 alkoxy group; an optionally substituted straight or branched CrC26 alkylthio group; a C2-C26 linear or branched alkenyl group optionally substituted; a C2-C26 linear or branched alkynyl group optionally substituted; an optionally condensed C3-C30 cycloalkyl group or a C-? 7 fused cycloalkyl group of the optionally substituted steroid type; a C3-C30 cycloalkoxy group optionally condensed and optionally substituted; an optionally substituted heterocyclic group; an optionally substituted aryl group; an optionally substituted heteroaryl group; a linear or cyclic C6-C-? 2 group of the optionally substituted saccharide type; a CrC26 alkylamine group or a C2-C26 dialkylamine group optionally substituted for n other than 0, - R2 and R3, equal or different, represent an optionally substituted CrC3 alkyl group, - R4 and R5, equal or different, represent a hydrogen atom , or a CrC6 group optionally substituted straight or branched alkyl, an optionally substituted straight or branched C2-C6 alkenyl group, an optionally substituted C3-C6 cycloalkyl group; a hydroxyl group, an optionally substituted aryl group; an optionally substituted heteroaryl group; an optionally substituted heterocyclic group, - P and R can individually form a cycle together with R2, - X represents a nitrogen or sulfur atom, - Z represents a carbon or sulfur atom, - m represents a number comprised between 1 and 5, - n and p represent a number between 0 and 3, - q has the value of 0 for X = sulfur or the value of 0 or 1 for X = nitrogen, - Y, when q has the value of 0 for X = sulfur and when q has the value of 1 for X = nitrogen, represents a halide, such as CI ", Br"; a nitrate anion (N03 ~), a nitrite anion (N02); a phosphate anion selected from H2P04", HPO4" 2, P0"3, a phosphite anion selected from H2P03", HP03 ~ 2, P03"3, a carbonate anion (C02" 2); a carbonate bianon (HC03"), a sulfate anion (SO4" 2); a hydrogen sulfate anion (HS04); or Y represents the salicylate anion; the acetyl salicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion; or Y is absent when q has the value of 0 for X = nitrogen; - s has the value of 1 for Z = carbon or the value of 2 for Z = sulfur
2. 2. Compounds according to claim 1, characterized in that Y represents the salicylate anion; the acetylsalicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion represents a phosphite anion selected from H2P03", HP03" 2, P03"3, an anion halide or a carbonate bianon (HC03"), when q has the value of 0 for X = nitrogen
3. 3.- Compounds in accordance with claim 1, characterized because the C C 26 alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, caprylic, lauryl, stearyl, eicosyl, hexacosyl.
4. 4. Compounds according to claim 1, characterized in that the CrC26 haloalkyl group is selected from fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoro-octanyl, perfluorododecyl.
5. 5. Compounds according to claim 1, characterized in that the C-C26-alkoxy group is selected from methoxy, ethoxy, isopropoxy, cyclopropyl-methoxy, lauroyloxy.
6. 6. Compounds according to claim 1, characterized in that the C C 26 thioalkyl group is selected from thiomethyl, thioethyl, thiolauryl, thiocapryl.
7. 7. Compounds according to claim 1, characterized in that the C2-C2ß alkenyl group is selected from ethenyl, propenyl, butenyl, 1-decenyl, 8-heptadecenyl, 8,11, 14-heptadecatrienyl, 8,11-heptadecadienyl.
8. 8. Compounds according to claim 1, characterized in that the C2-C26 alkynyl group is selected from ethinyl, propargyl, 1-dodecinyl, 1-octadecinyl.
9. 9. Compounds according to claim 1, characterized in that the optionally condensed C3-C30 cycloalkyl group is selected from cyclopropyl, 2,2-dichlorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, decalin, abiethyl.
10. 10. Compounds according to claim 1, characterized in that the C 17 cycloalkyl fused group of the steroid type is selected from colanyl, chenodeoxycolanyl, ursodeoxylanyl, deoxycholanil, iodeoxycolanyl, lithocolanyl.
11. 11. Compounds according to claim 1, characterized in that the group C3-C3o cycloalkoxy is selected from cyclopentoxy, cyclohexyloxy, cholesteryl.
12. 12.- Compounds according to claim 1, wherein the groups C - - C26 alkylamine or dialkylamine C2-C2SS are selected from methylamine, dimethylamine, ethylamine, isopropylamine, dibutylamine, dioctylamine, hexadecylamine, didecylamine.
13. 13. Compounds according to claim 1, characterized in that the aryl group is selected from phenyl, naphthyl, phenanthryl.
14. 14. Compounds according to claim 1, wherein the heteroaryl group is selected from pyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, Urano, thiophene, spiral, oxazole, thiazole, isoxazole, isothiazole , oxadiazole, thiadiazole, pyrazole, imidazole, triazole, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolepiridina, triazolepirimidina, tiazoletriazol, coumarin.
15. 15. Compounds according to claim 1, characterized in that the heterocyclic group is selected from pyrrolidine, piperidine, dihydropyridine, piperazine, 2,6-diketopiperazine, 2-ketoazetidine, morpholine, thiazine, indoline.
16. 16. Compounds according to claim 1, characterized because the linear or cyclic C6-C- group? 2 type saccharide selected from gluconoyl, glucopyranosyl, ß-D-fructofuranosilo-a -D-glucopyranosyl, 4-O-ß-D-galacto-pyranosyl-D-glucosyl.
17. 17. Compounds according to claim 1, characterized in that, when q has the value of 0 for X = nitrogen, they are selected from: • N, N-dimethylethanolamine, • 3-dimethylamino-1-propanol, • N -ethyl, N-methylethanolamine, • 2-dimethylaminopropanol, • N-lauryl.N-methylethanolamine, • N, N-dimethyl-β-alanine methyl ester, • N-dimethylglycine methyl ester. When q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, they are selected from: 'Acid phosphite hill, • Neutral phosphite hill,' Ethylphosphonate hill, • Laurilocolin phosphite acid, • Laurilocolina neutral phosphite, • Cocamidopropylcholine phosphite acid, • Cocamidopropylcholine neutral phosphite, • Stearylcholine phosphite acid, • Neutral stearylcholine phosphite, • Colesterilocarbonyl amidopropylcholine phosphite acid, • Colesterilocarbonylolamidopropylcholine neutral phosphite, • Colanyl amidopropylcholine phosphite acid, • Colanyl amidopropylcholine neutral phosphite, • Chenodeoxylaniloamidopropylcholine phosphite acid, • Quenodeoxicolaniloamidopropilocolina neutral phosphite • NN-dimetil.N-lauriloamidopropilo [L] valinol acid phosphite, • N, N-dimethyl, N-lauriloamidopropilo [L] valinol neutral phosphite, • N, N-dimethyl, N-lauryl [L] valinol phosphite acid, • N, N-dimethyl, N-lauryl [L] valinol, neutral phosphite, • N-lauryl, N-methyl [L] 2-pyrrolidinemethanol, phosphite acid, • N-lauryl, N-methyl [L] 2 -pirrolidinametanol neutral phosphite, "Hill salicylate, 'Colina acetilsalicilato,' Colina saccharinate," Hill cyclamate, 'Colina taurinate, "Laurilocolina salicylate," Laurilocolina acetilsalicilato, • Laurilocolina saccharinate,' Laurilocolina cyclamate, 'Laurilocolina taurinate, "Laurilocolina ethylphosphonate' Cocamidopropylcholine salicylate, • Cocamidopropylcholine acetylsalicylate, • Cocamidopropylcholine saccharinate, • Cocamidopropylcholine cyclamate, • Cocamidopropylcholine taurinate, • Cocamidopropylcholine ethylphosphonate, • Stearylcholine salicylate, • Stearylcholine acetylsalicylate, • Stearylcholine saccharinate, • Stearylcholine cyclamate, • Stearoylcholine taurinate, • Colanyl amidopropylcholine salicylate, • Colaniloamidopropylcholine acetylsalicylate, • Colanyl amidopropylcholine saccharinate, • Colaniloamidopropylcholine cyclamate, • Colanyl amidopropylcholine taurinate, 'Choline carbonate,' Choline bicarbonate, 'Laurilocoline carbonate, • Laurilocoline bicarbonate, • Cocamidopropylcholine carbonate, • Cocamidopropylcholine bicarbonate, • Stearylcholine carbonate, • Stearilocoline bicarbonate, • Sulfate hill, • Choline chloride, • Laurilocoline sulfate, • Laurilocoline hydrogen sulfate, • Cocamidopropylcholine sulfate, • Cocamidopropylcholine bromide, • Stearylcholine sulfate, • Stearylcholine chloride, «Choline phosphate acid, • Choline neutral phosphate, • Laurilocolin phosphate acid, • Neutral lauryl alcohol phosphate, • Cocamidopropylcholine phosphate acid, • Cocamidopropylcholine neutral phosphate, • Stearylcholine phosphate acid, • Neutral stearylcholine phosphate, Cocamidopropyl betaine methyl ester acid phosphite, • Cocamidopropyl betaine methyl ester neutral phosphite, «Betaine cetyl ester acid phosphite,» Neutral phosphite of the betaine cetyl ester, • cocamidopropyl methyl betaine ester salicylate, • cocamidopropyl betaine methyl ester acetylsalicylate, • betaine cetyl ester salicylate, • betaine cetyl ester acetylsalicylate, "cocamidopropyl betaine methyl ester cyclamate, • saccharinate cocamidopropyl betaine methyl ester, betaine cetyl ester cyclamate, betaine cetyl ester saccharinate, cocamidopropyl betaine methyl ester bicarbonate, cocamidopropyl betaine methyl ester chloride, methyl ester methyl ester colaniloamidopropyl-betaine acid, 'Colanyl amidopropyl-betaine neutral methylester phosphite, »Carnitine methyl ester methylester phosphate, • Neutral carnitine methyl ester phosphite, • Carnitine methyl ester salicylate, • Carnitine methyl ester acetylsalicylate, carnitine, • Carnitine chloride.
18. 18. Compounds according to claim 1, characterized in that the substituents R-i, R2, R3, R4, R5 contain optical or geometric isomerism centers, they can be present in all possible configurational isomeric forms.
19. 19. Compounds according to claim 1, characterized in that they consist of homologous mixtures in any proportion, when the compound is derived from natural extracts.
20. 20. Compounds according to claim 1, characterized in that they are present in hydrated form by the coordination of any number of water molecules.
21. 21. Compounds according to claim 1, characterized in that they also contain and possibly coordinate within their structure other metal cations, such as sodium, calcium, potassium, in variable quantity in relation to the preparation method used for the synthesis of the composed of general formula (I).
22. 22. Use of the compounds of general formula (I) where: - K represents a CH2OH or COORa group, - Ra represents an optionally substituted C- or C-C26 alkyl group, - Ri represents hydrogen or an optionally substituted straight or branched C1-C26 alkyl group; a C1-C26 linear or branched haloalkyl group optionally substituted; a C1-C26 linear or branched alkoxy group optionally substituted; an optionally substituted straight or branched CrC26 alkylthio group; a C2-C26 linear or branched alkenyl group optionally substituted; a C2-C26 linear or branched alkynyl group optionally substituted; an optionally condensed C3-C3o cycloalkyl group or a fused cycloalkyl Cu group of the optionally substituted steroid type; a C3-C3o or cycloalkoxy group optionally condensed and optionally substituted; an optionally substituted heterocyclic group; an optionally substituted aryl group; an optionally substituted heteroaryl group; a linear or cyclic Cβ-C? 2 group of the optionally substituted saccharide type; a CrC26 alkylamine group or a C2-C26 dialkylamine group optionally substituted for n other than 0, - R2 and R3, equal or different, represent an optionally substituted CrC3 alkyl group, - R4 and R5, equal or different, represent a hydrogen atom , or an optionally substituted straight or branched Ci-Cβ alkyl group; an optionally substituted straight or branched C2-C6 alkenyl group; an optionally substituted C3-C6 cycloalkyl group; a hydroxyl group; an optionally substituted aryl group; an optionally substituted heteroaryl group; an optionally substituted heterocyclic group, - R4 and R5 can individually form a cycle together with R2, - X represents a nitrogen or sulfur atom, - Z represents a carbon or sulfur atom, - m represents a number comprised between 1 and 5, - n and p represent a number between 0 and 3, - q has the value of 0 for X = sulfur or the value of 0 or 1 for X = nitrogen, - Y, when q has the value of 0 for X = sulfur and when q has the value of 1 for X = nitrogen, represents a halide, such as CI ", Br "; a nitrate anion (N03 ~), a nitrite anion (N02 ~); a phosphate anion selected from H2PO4", HPO4" 2, PO4"3, a phosphite anion selected from H2P03", HP03"2, P03" 3; a carbonate anion (C02 ~ 2); a carbonate bianon (HCO3); a sulfate anion (SO42); a hydrogen sulfate anion (HS0); or Y represents the salicylate anion; the acetyl salicylate anion; the saccharinate anion; the 3-aminobutanoate anion; the cyclamate anion; the taurinate anion; the ethylphosphonate anion; or Y is absent when q has the value of 0 for X = nitrogen, - s has the value of 1 for Z = carbon or the value of 2 for Z = sulfur, for the control of phytopathogenic bacteria and fungi.
23. 23. Use of the compounds according to any of claims 2-21, for the control of phytopathogenic bacteria and fungi.
24. 24. Use of the compounds according to any of claims 1-21, for the control of phytopathogenic bacteria and fungi by stimulating the natural defense systems of plants and the induction of resistance in the plants themselves.
25. 25. Use according to claims 22 or 23 or 24, characterized in that said use is curative and / or preventive.
26. 26. Use according to any of claims 22 to 25, wherein the compound of general formula (I) is used in an amount ranging between 10 g and 5 kg per hectare.
27. 27. Use according to any of claims 22 to 25, of compounds of general formula (I) as simple isomers or as isomeric mixtures in any proportion.
28. 28. - Use according to any of claims 22 to 25, in genetically modified plant species.
29. 29.- Method for the control of phytopathogenic bacteria and fungi in agricultural crops, for the stimulation of the natural defense systems of plants against abiotic stress (temperature, salinity, drought, etc.) and biotic stress and the induction of resistance in the plants themselves by the application of the compounds of general formula (I) according to any of claims 1 to 21.
30. 30.- Fungil composition comprising one or more of the compounds of general formula (I) according to any of claims 1 to 21.
31. 31.- Composition according to claim 30, characterized in that it contains other active ingredients.
32. 32. Composition according to claim 31, characterized in that when in the compound of general formula (I) q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, it contains as active ingredients also at least one of the following products: (1) IR5885, a dipeptide compound corresponding to diastereomeric mixtures of methyl [S- (R, S)] - [3- (N-isopropoxycarbonyl-alkylamino) -amino] -3- (4-chloro-phenyl) propanoate in any ratio to one of the two diastereomeric forms SR or SS taken individually, (2) IR6141, corresponding to methyl N- (phenyl acetyl ) -N-2,6-xylyl-R-alaninate, (4) Salicylic a(SA) or its derivatives such as acetylsalicylic a(ASA), copper salts of salicylic a(SA2Cu) or (SACu) or acetylsalicylic a( ASA2Cu), (5) A copper (I) or copper (II) salt, such as copper oxychloride, copper hydroxide, Bordeaux1 mixture of copper sulfate, or a mixture of copper hydroxide and oxychloride (Airone), (35) Fosetyl, corresponding to ethyl hydrogen phosphonate, (36) Fosetyl-AI, corresponding to aluminum triethylphosphonate, better known under the trade name Aliette.
33. 33.- Composition according to claim 31, characterized in that, when in the compound of general formula (I) q has the value of 0 for X = sulfur and the value of 1 for X = nitrogen, said composition is selected from: (1) Phosphite choline aand IR5885, (2) Phosphite choline neutral and IR5885, (3) Choline ethylphosphonate and IR5885, (4) Choline ethylphosphonate and IR6141, (5) Phosphite choline aand IR6141, (6) Phosphite choline neutral e IR6141, (7) Phosphite choline aand Bentiavalicarb-isopropyl, (8) Phosphite choline neutral and Bentiavalicarb-isopropyl, (9) Phosphite choline aand ASA2Cu, (10) Phosphite choline aand SA2Cu, (11) Phosphite choline aand SACu , (12) Phosphite choline neutral and ASA2Cu, (13) Phosphite choline neutral and SA2Cu;, f19) Phosphite choline aand iprovalicarb, (20) Phosphite choline neutral and iprovalicarb, (33) Choline salicylate and IR5885, (34) Choline acetylsalicylate and IR5885, (35) Choline saccharinate and IR5885, (36) Choline bicarbonate and IR5885, (45) Choline bicarbonate and Fosetyl-AI, (46) Chloride and Fosetyl-AI Hill, (52) Chloride and Fosetyl Hill.
34. 34. Fungil compositions according to claim 31, comprising one or more compounds of general formula (I), when q has the value of 0 for X = nitrogen, in a mixture with Fosetyl-AI as another active principle.
35. 35.- Composition according to claim 34, characterized in that said composition is selected from: a). N, N-dimethylethanolamine and Fosetyl-AI, b). 3-dimethylamino-1-propanol and Fosetyl-AI, c). N-ethyl, N-methylethanolamine and Fosetyl-AI, d). 2-dimethylaminopropanol and Fosetyl-AI, e). N- lauryl, N-methylethanolamine and Fosetyl-AI, f). N, N-dimethyl-ßalanine methyl ester and Fosetyl-AI, g). N, N-dimethylglycine methyl ester and Fosetyl-AI.
36. 36.- Composition according to claim 35, characterized in that said composition is composition a).
37. 37.- Composition according to any of the claims 30 to 36, wherein the concentration of the active principle is between 1% and 90%, preferably between 5 and 50%.
38. 38.- Use of the composition according to any of claims 30 to 37, for the control of phytopathogenic bacteria and fungi.
39. 39.- Use of the composition according to any of claims 30 to 37, for the stimulation of the natural defense systems of plants against abiotic stress and biotic stress and the induction of resistance in the plants themselves.
40. 40.- Use according to claim 38 or 39, wherein the application of the composition is carried out in all parts of the plant, for example leaves, stems, branches and roots, or in the seeds themselves before sowing, or in the soil where the plant grows.