Inorganic copper salts, such as, for example, sul- fates, oxychlorides, hydroxides, carbonates and the well- known Bordeaux mixture, have been widely used in agricul- ture for the control of fungal diseases in preventive ap- plications.

It is also known that copper salts of organic acids such as, for example, copper acetate, copper succinate, copper glutarate, copper adipate, copper citrate, copper tartrate, copper aspartate, copper glutamate, copper phthalates, copper benzoates, can be used for the control of fungal diseases in agricultural crops, optionally mixed with other active principles, as described, for ex- ample, in JP7398021; or in Pesticide (1980), vol. 14 (10), pages 29-30; or in Geobios (1985), vol. 12 (3-4), pages

147-8.

The Applicant has now found that copper salts of some particular organic acids allow a prolonged protec- tive action to be obtained on vegetables, which is higher than that of the copper salts described above and with much lower doses.

The use of these salts in agronomic practice there- fore allows, with respect to the previously known organic or inorganic copper derivatives, a reduction in the cop- per content in the formulates applied with significant beneficial repercussions on the environmental impact.

The Applicant has also found that these salts are an excellent form of controlling phytopathogens also in vegetable varieties genetically modified to amplify the original natural defense mechanism.

Furthermore, the Applicant has found that these salts can also be used for the control of fungal diseases on non-living substrates such as, for example, plastics, metals, textile fibres, glass, wood, paper, foams, bricks, etc. These salts can be applied on the surface of the substrate by methods well-known in the art, such as spraying, painting, immersion, impregnation, etc. at ap- plication doses depending on the nature of the material and conditions to which the substrate is subjected.

Many of these copper salts are new; others are known, but their use has never been described for these particular applications.

An object of the present invention therefore relates to the use of compounds having general formula (I): A#Cu (I)

wherein: - A represents the bibasic ion of an organic acid which can have the meanings (A1) - (A8) ; - Cu represents the copper 2+ ion; - (Al)- (A8) respectively represent the following car- boxylic acids: (A1) : wherein: Ri and R2, the same or different, represent a hydro- gen atom; a Cl-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally substituted; a C2-C6 alkenyl or C2-C6 haloalkenyl group, linear or branched, optionally substituted; a C3-C6 cycloalkyl group, optionally substi- tuted; a Cl-C6 alkoxyl or Cl-C6 haloalkoxyl group, linear or branched, optionally substituted; a C1-C6 alkylthio or

C1-C6 haloalkylthio group, linear or branched, optionally substituted; a C3-C6 cycloalkoxyl group, optionally sub- stituted; an aryl group optionally substituted or a het- eroaryl group optionally substituted; a heterocyclic group optionally substituted; (A2) : Wherein: R2 has the meanings defined above; Q represents a hydrogen atom; a C1-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally sub- stituted; a cyano group; a C1-C6 alkylcarbonyl or C1- C6 haloalkylcarbonyl group, linear or branched, op- tionally substituted; a C1-C6 alkoxycarbonyl group, linear or branched, optionally substituted; an ami- nocarbonyl group; a C1-C6 alkylaminocarbonyl group; a C2-C12 dialkylaminocarbonyl group; X represents a hydrogen atom or a halogen atom; a hydroxyl group; a C1-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally substituted; a Ci-Ce alkoxyl or C1-C6 haloalkoxyl group, linear or

branched, optionally substituted; a cyano group; a nitro group; an amine group; a Cl-C6 alkylamine group; a C2-C12 dialkylamine group; a Ci-Ce linear or branched thioalkyl group, possibly substituted; a C1-C6 linear or branched halothioalkyl group, possi- bly substituted; a C1-C6 linear or branched alkyl- sulfinyl group, possibly substituted; a C1-C6 linear or branched alkylsulfonyl group, possibly substi- tuted; n is a number ranging from 1 to 4; (A3) : (CH2) x-COOH <BR> <BR> Wiz<BR> <BR> <BR> <BR> # (CH2)Y-COOH wherein: W represents an oxygen atom; a C1-C6 alkylimine group, linear or branched, optionally substituted; an arylimine group optionally substituted; a heteroarylimine group optionally substituted; a Cl-C6 alkoxyimine group, linear or branched, optionally substituted; an aryloxy- imine group optionally substituted; - x and y, the same or different, are a number ranging from 0 to 4;

wherein: - R3 represents a C1-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally substituted; a C3-C6 cycloalkyl group, optionally substituted; an aryl group, optionally substituted; a heteroaryl group, optionally substituted; - x and y, the same or different, are a number ranging from 0 to 4; (As) : wherein: - R4 represents a Cl-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally substituted; a C3-C6 cycloalkyl group, optionally substituted; an aryl group, optionally substituted; a heteroaryl group, optionally substituted; (As) :

wherein: - Q, X and n have the same meanings defined above; (A,) : wherein: -R5 and R6, the same or different, represent a hydro- gen atom; a halogen atom; a C1-C6 alkyl or C1-C6 haloalkyl group, linear or branched, optionally substituted; a C2- C6 alkenyl or C2-C6 haloalkenyl group, linear or branched, optionally substituted ; a C2-C6 alkinyl or C2-C6 haloalkinyl group, linear or branched, optionally substi- tuted; a C3-C6 cycloalkyl group, optionally substituted; a C1-C6 alkoxyl or Ci-Cg haloalkoxyl group, linear or branched, optionally substituted; a C1-C6 alkylthio or C1- C6 haloalkylthio group, linear or branched, optionally substituted; a C3-C6 cycloalkoxyl group, optionally sub- stituted; a C1-C6 alkylamine group, linear or branched, optionally substituted ; a C2-C12 dialkylamine group, lin- ear or branched, optionally substituted; a C1-C6 alkyl-

carbonylamine group, linear or branched, optionally sub- stituted; an arylcarbonylamine group, optionally substi- tuted; an aryl group, optionally substituted; a hetero- aryl group, optionally substituted; a heterocyclic group, optionally substituted; - Rs and R6 can jointly form a C1-C6 cycle; - x and y, the same or different, are a number ranging from 0 to 4 excluding cases wherein x and y are a number ranging from 0 to 2 and Rs and R6 are both a hydrogen atom; (A8) : wherein X and n have the same meanings described above ex- cluding salicylic acid; alone or in a mixture, for the control of bacterial and fungal phytopathogens on vegeta- ble or parts thereof.

A Cl-C6 alkyl group refers to a linear or branched C1-C6 alkyl group, optionally substituted by one or more substituents, the same or different.

Examples of this group are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl.

A C1-C6 haloalkyl group refers to a linear or

branched C1-C6 alkyl group, optionally substituted by one or more halogen atoms, the same or different.

Examples of this group are: fluoromethyl, difluoro- methyl, trifluoromethyl, trichloromethyl, 2,2, 2- trifluoroethyl, 2,2, 2-trichloroethyl, 2,2, 3,3-tetra- fluoropropyl, 2,2, 3,3, 3-pentafluoropropyl.

A C2-C6 alkenyl group refers to a linear or branched CZ-C6 alkenyl group, optionally substituted by one or more substituents, the same or different.

Examples of this group are: ethenyl, propenyl, bu- tenyl.

A C2-C6 haloalkenyl group refers to a linear or branched C2-C6 alkenyl group, optionally substituted by one or more halogen atoms, the same or different.

Examples of this group are: 2,2-dichloropropenyl, 1,2, 2-trichloropropenyl.

A C2-C6 alkinyl group refers to a linear or branched Cz-C6 alkinyl group, optionally substituted by one or more substituents, the same or different.

Examples of this group are: ethenyl, propargyl.

A C2-C6 haloalkinyl group refers to a linear or branched C2-C6 alkinyl group, optionally substituted by one or more halogen atoms, the same or different.

Examples of this group are: 3-chloropropinyl.

A C3-C6 cycloalkyl group refers to a cycloalkyl

group whose ring consists of 3-6 carbon atoms, optionally substituted by one or more substituents, the same or dif- ferent.

Examples of this group are: cyclopropyl, 2,2- dichlorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

A Cl-C6 alkoxyl group refers to a Cl-C6 alkoxyl group, wherein the aliphatic portion is a Ci-Cg alkyl group, as described above.

Examples of this group are: methoxyl, ethoxyl, iso- propoxyl, cyclopropyl methoxyl.

A Cl-C6 haloalkoxyl group refers to a Cl-C6 haloalkoxyl group, wherein the aliphatic portion is a Cl- C6 haloalkyl group, as described above.

Examples of this group are: trifluoromethoxyl, 1,1, 2,2-tetrafluoroethoxyl, 1,1, 2,3, 3,3-hexafluoro- propyloxyl.

A Cl-C6 thioalkyl group refers to a Cl-C6 thioalkyl group, wherein the aliphatic portion is a C1-C6 alkyl group, as described above.

Examples of this group are: thiomethyl, thioethyl.

A C1-C6 halothioalkyl group refers to a C1-C6 halothioalkyl group, wherein the aliphatic portion is a Cl-C6 haloalkyl group, as described above.

Examples of this group are: trifluorothiomethoxyl, 1,1, 2,2-tetrafluorothioethoxyl.

A Cl-C6 alkylsulfinyl group refers to a C1-C6 alkyl- sulfinyl group, wherein the aliphatic portion is a Cl-C6 alkyl group, as described above.

Examples of this group are: methylsulfinyl, ethyl- sulfinyl.

A Cl-C6 alkylsulfonyl group refers to a Cl-C6 alkyl- sulfonyl group, wherein the aliphatic portion is a Cl-C6 alkyl group, as described above.

Examples of this group are: methylsulfonyl, ethyl- sulfonyl.

A C3-C6 cycloalkoxyl group refers to a C3-C6 cyclo- alkoxyl group, wherein the aliphatic portion is a C3-C6 cycloalkyl group, as described above.

Examples of this group are: cyclopentoxy, cyclohexyloxy.

A Cl-C6 alkylamine or C2-C12 dialkylamine group re- fers to an alkylamine or dialkylamine group wherein the aliphatic portion is one or two Cl-C6 alkyl groups as de- fined above.

Examples of this group are: methylamino, dimethyl- amino, ethylamino, isopropylamino, dibutylamino.

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.

A heteroaryl group refers to an aromatic penta or

hexatomic heterocyclic group, also benzocondensed or het- erobicyclic, containing from 1 to 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, pyrrol, oxazole, thiazole, isoxazole, isothiazole, oxadi- azole, thiadiazole, pyrazole, imidazole, triazole, tetra- zole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, ben- zopyrazole, benzimidazole, benzotriazole, triazole- pyridine, triazolepyrimidine, thiazoletriazole.

A heterocyclic group refers to a saturated or un- saturated ring with from three to twelve elements, con- taining at least one heteroatom selected from nitrogen, oxygen, sulfur, optionally condensed with another aro- matic or non aromatic ring.

Examples of heterocyclic rings are: pyrrolidine, piperidine, dihydropyridine, piperazine, 2,6-diketo- piperazine, 2-ketoazetidine, morpholines, thiazine, in- doline.

A Ci-Ce alkylimine group refers to an alkylimine group wherein the aliphatic portion is a C1-C6 alkyl group as defined above.

Examples of this group are: ethylimine, isopro- pylimine, benzylimine, 1-phenylethylimine.

An arylimine and heteroarylimine group refers to an arylimine and heteroarylimine group wherein the aromatic and heteroaromatic portion are an aryl group and a het- eroaryl group respectively as defined above.

Examples of this group are: phenylimine, naphthylimine, 2-pyridylimine, 4-pyridylimine, 2- pyrimidylimine, 2-thienylimine, 2-thiazolylimine.

A C1-C6 alkoxyimine group refers to an alkoxyimine group wherein the alkoxyl portion is a C1-C6 alkoxyl group as defined above.

Examples of this group are: methoxylimine, ethoxy- imine, isopropoxylimine, benzyloxylimine.

An aryloxyimine group refers to an aryloxyimine group wherein the aromatic portion is an aryl group as defined above.

Examples of this group are: phenoxyimine, naphthoxy- imine.

A C1-C6 alkycarbonylamine group refers to an alkyl- carbonylamine group wherein the aliphatic portion is a Cl-C6 alkyl group as defined above.

Examples of this group are: acetylamine, propylcar- bonylamine.

An arylcarbonylamine group refers to an arylcarbon-

ylamine group wherein the aromatic portion is an aryl group as defined above.

Examples of this group are: benzoylamine, 4- methylbenzoylamine.

A C1-C6 alkylcarbonyl group refers to an alkylcar- bonyl group wherein the aliphatic portion is a Cl-C6 al- kyl group as defined above.

Examples of this group are: acetyl, ethylcarbonyl, isopropylcarbonyl.

A C1-C6 haloalkylcarbonyl group refers to a haloal- kylcarbonyl group wherein the aliphatic portion is a C1- C6 haloalkylgroup as defined above.

Examples of this group are: 1, 1, 1- trifluoromethylcarbonyl.

A C1-C6 alkoxy carbonyl group refers to an alkoxy- carbonylgroup wherein the aliphatic portion is a Cl-C6 alkoxyl group as defined above.

Examples of this group are: methoxylcarbonyl, eth- oxycarbonyl, isopropoxylcarbonyl, butoxycarbonyl, benzy- loxycarbonyl.

A C1-C6 alkylaminocarbonyl or C2-C12 dialkylaminocar- bonyl group refers to an alkylaminocarbonyl or dial- kylaminocarbonyl group wherein the aliphatic portion is one or two C1-C6 alkyl groups respectively, as defined above.

Examples of this group are: methylaminocarbonyl, di- methylaminocarbonyl, ethylaminocarbonyl, isopropylamino- carbonyl, dibutylaminocarbonyl.

Optionally substituted, in all parts of the patent, refers to one or more substituents, the same or differ- ent, selected from the following groups: halogen atoms; C1-C6 alkyls, Ci-Ce alkoxyls, and C1-C6 alkylthio, C1-C6 alkylsulfinyl and C1-C6 alkylsulfonyl, in turn optionally substituted by halogen atoms; Ci-Ce alkyl carbonyls and C1-C6 alkoxycarbonyls, optionally halogenated; aminocar- bonyls, C1-C6 alkylaminocarbonyls, C2-C12 dialkylaminocar- bonyls, optionally halogenated; carboxyl; C1-C6 alkylcar- bonyloxy optionally halogenated; cyano; nitro; formyl ; hydroxyl; amino; aryl and heteroaryl, optionally substi- tuted.

Examples of compounds having general formula (I) which are interesting for their activity are: copper (II) salt of 4-chlorobenzylidenemalonic acid; copper (II) salt of 4-hydroxy-3-methoxybenzylidene malonic acid; copper (II) salt of 3,4-dimethoxybenzylidenemalonic acid; copper (II) salt of 4-fluorobenzylidenemalonic acid; copper (II) salt of 4- trifluoromethylbenzylidenemalonic acid;

copper (II) salt of 4- dimethylaminobenzylidenemalonic acid; copper (II) salt of 2,4-dichlorobenzylidenemalonic acid; copper (II) salt of 4-bromobenzylidenemalonic acid; copper (II) salt of 4-hydroxy-3-methoxybenzylidene malonic acid monomethyl ester; copper (II) salt of 4-hydroxy-3- methoxybenzylidenemalonic acid monoethyl ester; # copper (II) salt of 2-cyano-3- (4-hydroxy-3- methoxyphenyl) propenoic acid ; # copper (II) salt of 2-acetyl-3- (4-hydroxy-3- methoxyphenyl) propenoic acid ; copper (II) salt of 2-aminocarbonyl-3- (4-hydroxy-3- methoxyphenyl) propenoic acid; # copper (II) salt of 3- (4-hydroxy-3-methoxyphenyl)-2- methoxycarbonyl-2-butenoic acid; # copper (II) salt of 4-hydroxy-3-methoxy cinnamic acid; copper (II) salt of 2-hydroxycinnamic acid; copper (II) salt of 3-hydroxycinnamic acid; copper (II) salt of 4-hydroxycinnamic acid; copper (II) salt of 3-ketoglutaric acid; copper (II) salt of 3-methoxy-2-pentendioic acid; copper (II) salt of 3-amino-2-carboxy-3- (4-chloro-

phenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (2-hydroxy- phenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (4-trifluoro methylphenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (4-hydroxy- 3-methoxyphenyl) propanoic acid; # copper (II) salt of 3-amino-2-carboxy-3- (3, 4- dimethoxyphenyl) propanoic acid; copper (II) salt of 3-amino-3- (2- hydroxyphenyl) propanoic acid; copper (II) salt of 3-amino-3- (4-hydroxy-3- methoxyphenyl) propanoic acid ; # copper (II) salt of 3-amino-2-cyano-3- (4- hydroxyphenyl) propanoic acid; copper (II) salt of 3-amino-2-cyano-3- (4-hydroxy-3- methoxyphenyl) propanoic acid; # copper (II) salt of 2-methoxysuccinic acid; w copper (II) salt of 2-ethoxysuccinic acid ; # copper (II) salt of 3- (2-furyl)-2-carboxypropenoic acid; copper (II) salt of 3- (2-thiazolyl)-2- carboxypropenoic acid; # copper (II) salt of 3-benzylidene-2-carboxypropenoic acid;

copper (II) salt of 1, 1-cyclopropane dicarboxylic acid; copper (II) salt of diallylmalonic acid; copper (II) salt of ethylphenyl malonic acid; copper (II) salt of bis (2-cyano ethyl) malonic acid; copper (II) salt of N-morpholine malonic acid; copper (II) salt of N-benzyloxyimino malonic acid; copper (II) salt of 3-hydroxy benzoic acid; copper (II) salt of 4-hydroxy benzoic acid; copper (II) salt of 5-chloro-2-hydroxy benzoic acid; copper (II) salt of 5-bromo-2-hydroxy benzoic acid; copper (II) salt of 2-hydroxy-3-methoxy benzoic acid ; copper (II) salt of 2-hydroxy-5-methoxy benzoic acid; copper (II) salt of 2-hydroxy-3-methyl benzoic acid; copper (II) salt of 4-hydroxy-3-methoxy benzoic acid; copper (II) salt of 3,5-dimethoxy-4-hydroxy benzoic acid; copper (II) salt of 3,5-dichloro-4-hydroxy benzoic acid; copper (II) salt of 3,5-dibromo-4-hydroxy benzoic acid; copper (II) salt of 3,5-dimethyl-4-hydroxy benzoic

acid; copper (II) salt of 3-chloro-4-hydroxy benzoic acid; copper (II) salt of 2,3-dihydroxy benzoic acid; copper (II) salt of 2,6-dihydroxy benzoic acid; copper (II) salt of 3,4-dihydroxy benzoic acid.

An object of the present invention also relates to the use of the compounds having general formula (I) for the control of fungal phytopathogens on non-living sub- strates such as plastics, metals, textile fibres, glass, wood, paper, foams, bricks.

As specified above, many of the salts of formula (I) are new products.

A further object of the present invention therefore relates to the compounds having general formula (I') : A'cru (I') wherein: - A' represents the bibasic ion of an organic acid which can have the meanings (All)- (A7) ; - Cu represents the copper 2+ ion; - (A'l)-(A',) respectively represent the following car- boxylic acids: wherein: - R'1 represents an aryl group optionally substituted; - R'2 represents a hydrogen atom; (A'2) :

wherein: - X'represents a hydrogen or halogen atom; a hydroxyl group; a Cl-C6 alkoxyl group, linear or branched, option- ally substituted; - n'can have the value of 1 or 2; - R'2 represents a hydrogen atom; - Q'represents a hydrogen atom; a Ci-Ce alkoxycarbonyl group, linear or branched, optionally substituted; an acetyl group; a cyano group; ' (A'3) : wherein: - W'represents an oxygen atom; - x'and y'both have the value of 1;

wherein: - R'3 represents a C1-C3 alkyl group, linear or branched; - x' is equal to 1 and y'is equal to 0 ; # (A'5) : f wherein: - R'4 represents an aryl group, optionally substituted; # (A'6) : wherein: - X'represents a hydrogen or halogen atom; a hydroxyl group; a Cl-C6 alkoxyl group, linear or branched, option- ally substituted;

- n'can have the value of 1 or 2; - Q'represents a hydrogen atom; a C1-C6 alkoxycarbonyl group, linear or branched, optionally substituted; an acetyl group; a cyano group; * (A'7) : wherein: -R's represents a Cl-C6 alkoxyl group, linear or branched; - R'6 represents a hydrogen atom; - x'is equal to 0 and y'is equal to 1.

Examples of products having general formula (I') which have never been described before are: # copper (II) salt of 4-chlorobenzylidenemalonic acid; # copper (II) salt of 4-hydroxy-3-methoxybenzylidene malonic acid; copper (II) salt of 3,4-dimethoxybenzylidene malonic acid; copper (II) salt of 4-fluorobenzylidene malonic acid; o copper (II) salt of 4-trifluoromethylbenzylidene malonic acid; copper (II) salt of 4-dimethylaminobenzylidene malo-

nic acid; copper (II) salt of 2,4-dichlorobenzylidene malonic acid; copper (II) salt of 4-bromobenzylidene malonic acid; copper (II) salt of 4-hydroxy-3-methoxybenzylidene malonic acid monomethyl ester; copper (II) salt of 4-hydroxy-3-methoxybenzylidene malonic acid monoethyl ester; copper (II) salt of 2-cyano-3- (4-hydroxy-3- methoxyphenyl) propenoic acid; # copper (II) salt of 2-acetyl-3- (4-hydroxy-3- methoxyphenyl) propenoic acid; # copper (II) salt of 2-aminocarbonyl-3-(4-hydroxy-3- methoxyphenyl) propenoic acid; copper (II) salt of 3- (4-hydroxy-3-methoxyphenyl)-2- methoxycarbonyl-2-butenoic acid; copper (II) salt of 4-hydroxy-3-methoxy cinnamic acid; copper (II) salt of 2-hydroxycinnamic acid; copper (II) salt of 3-hydroxycinnamic acid; copper (II) salt of 4-hydroxycinnamic acid; # copper (II) salt of 3-ketoglutaric acid; copper (II) salt of 3-methoxy-2-pentendioic acid; copper (II) salt of 3-amino-2-carboxy-3- (4-chloro- phenyl) propanoic acid;

copper (II) salt of 3-amino-2-carboxy-3- (2-hydroxy- phenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (4- trifluoromethylphenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (4-hydroxy- 3-methoxyphenyl) propanoic acid; copper (II) salt of 3-amino-2-carboxy-3- (3, 4- dimethoxyphenyl) propanoic acid; copper (II) salt of 3-amino-3- (2- hydroxyphenyl) propanoic acid; copper (II) salt of 3-amino-3- (4-hydroxy-3- methoxyphenyl) propanoic acid; copper (II) salt of 3-amino-2-cyano-3-(4- hydroxyphenyl) propanoic acid; copper (II) salt of 3-amino-2-cyano-3- (4-hydroxy-3- methoxy phenyl) propanoic acid; * copper (II) salt of 2-methoxysuccinic acid; w copper (II) salt of 2-ethoxysuccinic acid; copper (II) salt of 3- (2-furyl)-2-carboxypropenoic acid; # copper (II) salt of 3- (2-thiazolyl)-2- carboxypropenoic acid; # copper (II) salt of 3-benzylidene-2-carboxypropenoic acid; # copper (II) salt of diallylmalonic acid;

copper (II) salt of ethylphenylmalonic acid; copper (II) salt of bis (2-cyano ethyl) malonic acid; copper (II) salt of N-morpholine malonic acid; copper (II) salt of N-benzyloxyiminomalonic acid; The compounds having formula (I) can be easily ob- tained according to the reaction scheme A: Scheme A 1) Base A 2) cuxz (II) (III) (I) wherein A has the same meanings defined above and z has the value of 1 or 2.

The compounds having general formula (I) can be ob- tained by dissolving the organic carboxylic acid having general formula (II) in water using at least two equiva- lents of an inorganic base such as sodium or potassium bicarbonate, sodium or potassium or calcium hydroxide, and adding an aqueous solution of a copper salt having formula (III) to the resulting mixture, wherein X can be a halogen, such as chlorine or bromine, or a perchlorate, (Z = 2) ; or a sulfate ion, (z = 1) to give a compound having formula (I).

Alternatively, it is possible to use copper hydrox- ide or carbonate (in these cases X represents an OH group or a C03 group respectively and z has the value of 2 or 1

respectively) in the presence of the acid form (II), op- tionally in the presence of an additional base, such as for example, an organic amine such as triethylamine.

Alternatively, the compounds having general formula (I) can be obtained by the saponification of esters cor- responding to the organic carboxylic acids having general formula (II), in water and alcohol according to the tra- ditional synthesis procedures, and subsequent addition to the resulting mixture of an aqueous solution of a copper salt having formula (III) as described above.

The carboxylic acids having general formula (II), when not known in themselves, can be prepared according to methods known in literature, according to what is de- scribed, for example, in: Organic Reactions (1967), vol.

15, page 204; or in Proc. Indian Acad. Sci. (1941), vol.

14A, pages 112-122; or in J. Org. Chem. (1979), vol. 44, page 3136.

If the organic acids corresponding to general for- mula (II) contain optical or geometric isomerism centres, the compounds having general formula (I) can be present in all possible configurational isomeric forms.

The scope of the present invention therefore also includes the use of compounds having general formula (I) as isomeric mixtures in any proportion, as well as the production and use of the single isomers for the control

of phytopathogen fungi in the agronomical field.

The compounds having general formula (I) can also be present in hydrated form by the coordination of a any number of molecules of water.

The compounds having general formula (I) can also coordinate within their structure metallic cations, such as, for example, sodium, calcium, potassium, whose number can vary in relation to the preparation method used for the synthesis of the cupric salt having general formula (I) and they can possibly be present in the hydrated form.

The use of these mixed salts for the control of phy- topathogen fungi in the agronomical field, also falls within the scope of the present invention.

The copper salts of carboxylic acids having general formula (I) are capable of controlling many fungal and bacterial phytopathogens, also with a reduced sensitivity towards other fungicides.

Some examples of phytopathogens controlled by the compounds having general formula (I) alone or in a mix- ture, are listed below for purely illustrative and non- limiting purposes, together with examples of possible ap- plication crops: - Plasmopara viticola on vines; Phytophthora spp. on vegetables;

-Pyricularia oryzae on rice; -Venturia ínaequalis on apples; -Peronospora tabacina on tobacco; -Pseudoperonospora cubensis. on cucurbitaceous pro- ducts; - Bremia on salads, spinach; Alternaria spp. on tomatoes, potatoes.

The cupric salts having general formula (I) are ca- pable of exerting a high fungicidal action of both a curative and preventive nature and they also have a low phyto-toxicity or absence thereof.

A further object of the present invention therefore relates to a method for the control of phytopathogen fungi in agricultural crops by the application of com- pounds having general formula (I).

The quantity of compound to be applied for obtaining the desired effect can vary in relation to several fac- tors, such as, for example, the compound used, the crop to be preserved, the type of pathogen, the degree of in- fection, the climatic conditions, the application method, the formulation adopted.

Dosages of compound ranging from 10 g to 5 kg per hectare, generally provide a sufficient control.

For practical use in agriculture, it is often con- venient to adopt fungicidal compositions containing one

or more of the compounds having general formula (I).

The application of these compositions or compounds having general formula (I) can be effected on any part of the plant, for example on the leaves, stems, branches and roots, or on the seeds before being planted, or on the ground in which the plant grows.

Compositions can be used which are in the form of dry powders, wettable powders, emulsifiable concentrates, micro-emulsions, pastes, granulates, solutions, suspen- sions, etc.: the selection of the type of composition will depend on the specific use.

The compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent and/or solid diluent, possibly in the presence of surfactants.

Silica, kaolin, bentonite, talc, infusorial earth, dolomite, calcium carbonate, magnesia, chalk, clays, syn- thetic silicates, attapulgite, seppiolite, can be used as solid diluents, or carriers.

In addition to water, aromatic organic solvents (xy- lols or mixtures of alkyl benzols, chlorobenzene, etc.), paraffins (oil fractions), alcohols (methanol, propanol, butanol, octanol, glycerin, etc. ), esters (ethyl acetate, isobutyl acetate, etc. ), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc. ), am-

ides (N, N-dimethyl formamide, N-methyl pyrrolidone, etc.), can be used as liquid diluents.

Sodium, calcium, triethyl amine or triethanol amine salts of alkyl sulphonates, alkyl aryl sulphonates, poly- ethoxylated alkyl phenols, polyoxyethylated esters of sorbitol, lignin sulfonates, etc.., can be used as sur- factants.

The compositions can also contain special additives for particular purposes, such as, for example, adhesion agents, such as gum Arabic, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylates.

In the above compositions, the concentration of ac- tive substances ranges from 0.1 to 98%, preferably'from 0.5 to 90%.

Other compatible active principles can be added, if desired, to the compounds having general formula (I), such as, for example, fungicides, phyto-regulators, anti- biotics, herbicides, insecticides, fertilizers.

Examples of other fungicides which can be included in the compositions of the invention are: AC-382042, acibenzolar, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl (in its racemic form or as optically active R isomer), benclothiaz, benomyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, car-

propamid, chinomethionat, chloroneb, chlorothalonil, chlozolinate, cuprocalcic, cyazofamid, cymoxanil, cypro- conazole, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, diclocymet, di- ethofencarb, diphenoconazole, diflumetorim, dimethirimol, dimethomorph, diniconazole, dinocap, a fungicidal dipep- tide, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, eth- aboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbu- conazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluoroim- ide, fluotrimazole, fluoxastrobin, fluquinconazole, flu- silazole, flusulfamide, flutolanil, flutriafol, folpet, fosetylaluminium, fuberidazole, furalaxyl, furconazole, guazatine, hexaconazole, hydroxyquinoline sulfate, hy- mexazol, ICIA0858, imazalil, imibenconazole, iminoc- tadine, ipconazole, iprobenfos, iprodione, iso- prothiolane, iprovalicarb, kasugamycin, kresoxim-methyl, mancopper, mancozeb, maneb, mebenil, mepanipyrim, me- pronil, metalaxyl, metalaxyl-M, metconazole, methfuroxam, metiram, metsulfovax, MON-65500, myclobutanil, natamycin, nicobifen, nitrothal-isopropyl, nuarimol, ofurace, orisastrobin, tetraramic oxychloride, oxadixyl, oxycar-

boxin, pefurazoate, penconazole, pencycuron, pentachloro- phenol and its salts, penthiovalicarb, phthalide, piper- alin, Bordeaux mixture, polyoxins, probenazole, pro- chloraz, procymidone, propamocarb, propiconazole, pro- pineb, proquinazid, prothiocarb, prothioconazole, pycox- ystrobin, pyracar-bolid, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinace- tol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenazole, copper hydroxide, copper oxychloride, copper sulfate, RH-7281, RPA-407213, simeconazole, spiroxamine, spiromesifen, SSF-126, (metominostrobin), streptomycin, SYP-L-190, tebuconazole, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,"ti- oxymid, tolclofos-methyl, tolylfluanid, triadimefon, tri- adimenol, triarimol, triazbutil, triazoxide, tricycla- zole, tridemorf, trifloxystrobin (CGA 279202), triflumizole, triforine, triticonazole, validamycin, vin- clozolin, zineb, ziram, sulfur, zoxamide.

These fungicidal compounds are commercial products or products about to be commercialized. Their description can be easily found in technical literature, for example in"The pesticide manual", 2000, XII Edition, British Crop Protection Council Ed.

Dipeptide with a fungicidal activity refers to one of the compounds among those claimed in patent appli-

cation EP-A-1028125.

It has also been found that the salts of derivatives of carboxylic acids having general formula (I), also ex- ert a synergic action with many of the active principles listed above, thus representing an excellent instrument for anti-resistance strategies and allowing a further lowering in the applicative dosages.

The following examples are provided for illustrative purposes, for a better understanding of the invention, and should in no way be considered as limiting the scope of the present invention.

EXAMPLE 1 in Preparation of the copper salt of 4-chlorobenzylidene malonic acid (Compound Nr. 1) 8 g of 4-chlorobenzylidenemalonic acid are added to a solution of 5.95 g of sodium bicarbonate in 140 cm3 of water. After the complete dissolution of the acid, a so- lution of 8.74 g of copper sulfate in 20 cm3 of water, are added to the reaction mixture. The mixture is kept under stirring at room temperature for a night. The solid precipitated is filtered and washed with water, obtain- ing, after drying in the air, 8.85 g of compound Nr. 1 (yield: 88%).

Elemental analysis [% found (theoretical) ] = C 41.1 (41.7) ; H 1.9 (1.7) ; Cl 12.3 (12.7) ; Cu 21.9

(22.1).

EXAMPLE 2 Preparation of the copper salt of 4-hydroxy-3- methoxybenzylidene malonic acid monomethyl ester (Com- pound Nr. 50).

17.8 cm3 of a 3.1 N solution of NaOH are slowly added dropwise on an ice bath to a suspension of 7.4 g of 4-hydroxy-3-methoxybenzylidene malonic acid dimethyl es- ter in 8 cm3 of methanol. The resulting solution is left under stirring for 24 hours at room temperature; a solu- tion of copper sulfate (6.95 g in 16 cm3 of H20) is then added and the mixture is kept under stirring for a fur- ther 24 hours. The solid precipitated is filtered and washed with water, obtaining, after drying in the air, 7.0 g of compound Nr. 47 (yield: 81%).

Elemental analysis [% found (theoretical) ] = C 45.2 (45.9) ; H 3.1 (3.2) ; Cu 20.4 (20.2).

Example 3 Preparation of the copper salt of 3-ketoglutaric acid (Compound Nr. 132).

11.5 g of sodium bicarbonate are added in portions, on an ice bath, to a suspension of 10 g of 3-ketoglutaric acid in 45 cm3 of Ho. 9. 1 g of copper (II) chloride are then added, again on an ice bath. The reaction mixture is left under stirring for 24 hours at room temperature. The

solid precipitated is filtered and washed with water, ob- taining, after drying in the air, 12.0 g of compound Nr.

129 (yield 83%).

Elemental analysis [% found (theoretical)] = C 28.2 (28.9) ; H 2.0 (1.9) ; Cu 30.7 (30.6).

Example 4 Preparation of the copper salt of 2-methoxysuccinic acid (Compound Nr. 239).

10 g of dimethyl maleate are added under stirring to 25 cm3 of a 3 M methanol solution of MeONa. After an hour, 10 cm3 of a 7 N solution of NaOH are added dropwise and after another hour a solution of copper sulfate (17.2 g in 45 cm3 of H2O) is added. The reaction mixture is kept under stirring for a further 24 hours. The solid precipitated is filtered and washed with water, obtain- ing, after drying in the air, 11.2 g of compound Nr. 235 (yield 80%).

Elemental analysis [% found (theoretical) ] = C 28.3 (28.6) ; H 2.7 (2.9) ; Cu 29.9 (30.3).

Example 5 Preparation of the copper salt of 5-chlorosalicylic acid (Compound Nr. 275).

10 cm3 of a 5.8 N solution of NaOH are added to a suspension of 5 g of 5-chlorosalicylic acid in 10 cm3 of H20. After the complete dissolution of the acid, a solu-

tion of copper chloride (3.9 g in 40 cm3 of HzO) is added. The reaction mixture is kept under stirring for 24 hours. The solid precipitated is filtered and washed with water, obtaining, after drying in the air, 6.3 g of com- pound Nr. 269 (yield 93%).

Elemental analysis [% found (theoretical) ] = C 35. 4 (35. 9); H 1. 25 (1.3) ; Cl 15.1 (14.9) ; Cu 26. 9 (27.1).

Analogously to what is described in the examples, the following compounds were prepared: Table 1 Derivatives of general formula (I) wherein A has the meaning of (Ai) : Compound Nr. R, R2 2 4-OH-3-OCH3-phenyl H 3 3, 4-di-OCH3-phenyl H 4 4-F-phenyl H 5 4-CF3-phenyl H 6 4-CH3-phenyl H 7 4-OCH3-phenyl H

2, SBr-phenyl H 10 11 H 4-OH-phenyl H 13 H 14 H 15 4-OH-3-OCH3-phenyl CH3 16 3, 4-diOCH3-phenyl 17 18 4-CF3-phenyl 19 4-OH-3-OCH3-phenyl phenyl 20 3, 4-diOCH3-phenyl phenyl 21 4-Ci-phenyl phenyl 22 4-OH-3-OCH3-phenyl cyclopentyl 23 3, 4-diOCH3-phenyl 24 4-OCF3-phenyl 25 1-naphthyl H 26 4-N (CH3) 2 phenyl 27 Cyclopentyl H 28 Cyclohexyl H 29 3, 4-methylenedioxyphenyl H 30 CH3 CH3 31 Isopropyl H 32 Benzyl H 33 CF3 34 Isobutyl CH3 35 2-(phenyl) 36 1-(phenyl)

37 2-furyl H 38 2-thiazolyl 39 2-furyl CH3 40 2-thiazolyl CH3 41 2-pyridyl 42 2-pyridyl CH3 43 4-pyridyl CH3 44 4-pyridyl 45 2-pyrimidyl H 46 benzylidene 47 2-CI-phenyl 48 ethoxyl H 49 phenyl Table 2 Derivatives of general formula (I) wherein A has the meaning of (A2) : Comp. Nr. OH pos. X n R2 Q 51 4 3-OCH3 1 H CN 52 4 3-OCH3 1 H H 53 4 3-OCH3 1 H COCH3

Comp. Nr. OH Q 54 4 3-OCH3 H CONH2 55 4 3-OCH3 1 CH3 COOCH3 56 4 3-OCH3 1 H COOCH2CH3 57 4 3-OCH3 1 H COOCH (CH3) 58 4 3-OCH3 1 H CONHCH3 59 4 3-OCH3 1 H CON 60 4 3-OCH3 1 H CH2CH3 61 4 3-OCH3 1 H CH3 62 4 3-OCH3 1 H CF3 63 4 3-OCH3 1 H COOCH2Ph 64 4 3-OCH3 1 H COCF3 65 4 3-OCH3 1 Ph COCF3 66 4 3, 5-diOCH3 2 H COOCH3 67 4 3, 5-diOCH3 2 H H 68 4 3, 5-diOCH3 2 H COCH3 69 4 3, 5-diOCH3 2 H CONH2 70 4 3, 5-diOCH3 2 H CN 71 4 3, 5-diCI 2 H COOCH3 72 4 3, 5-diCl 2 H H 73 4 3, 5-diCl 2 H COCH3 74 4 3, 5-diCl 2 H CONH2 75 4 3, 5-diCl 2 H CN 76 4 3, 5-diBr 2 H COOCH3 77 4 3, 5-diBr 2 H H 78 4 3, 5-diBr 2 H COCH3 79 4 3, 5-diBr 2 H CONH2 80 4 3, 5-diBr 2 H CN 81 2 5-CI 1 H COOCH3

Comp. Nr. OH 82 2 5-CI 1 H CN 83 2 5-CI 1 H H 84 2 5-CI 1 H COCH3 85 2 5-CI 1 H CONH2 86 2 5-CI 1 H COOCH2CH3 87 2 5-CI 1 H CONHCH3 88 2 5-CI H CON (CH3) 2 89 2 5-CI 1 H CH2CH3 90 2 5-CI 1 H CH3 91 3-CH3 1 H COOCH3 92 2 3-CH3 1 CH3 COOCH3 93 2 3-CH3 1 Ph COOCH3 94 2 3-CH3 1 H COOCH2CH3 95 2 3-CH3 1 H COCF3 96 3-CH3 1 H CONHCH3 97 3-CH3 1 CH3 COOCH2Ph 98 2 3-CH3 1 H COOCH2Ph 99 2 5-Br 1 H COCF3 100 2 5-Br 1 H CON (CH3) 101 2 5-Br 1 H H 102 2 H 1 H COOCH3 103 2 H 1 H CN 104 2 H 1 CH3 CN 105 2 H 1 H COCH3 106 2 H 1 H CONH2 107 2 H 1 H H 108 2 H 1 H COCF3 109 2 H 1 H CONHCH3 110 2 H H COOCH2Ph 111 2 H H COOCH (CH3) 2 112 3 H 1 H H

Comp. Nr. OH 113 3 H 1 H COOCH3 114 3 H 1 H CN 115 3 H 1 H COCH3 116 3 H 1 H CONHz 117 4 H 1 H H 118 4 H 1 H COOCH3 119 4 H 1 H CN 120 4 H 1 H COCH3 121 4 H 1 H CONH2 122 4 H 1 H 123 4 H 4-OHPh COOCH2CH3 124 4 H H 125 4 H CON (CH3) z 126 4 H H 127 4 H 1 H 128 4 H 1 H CF3 129 4 1 130 4 H 1 131 4 H 1 CN Table 3 Derivatives of general formula (I) wherein A has the meaning of (A3) :

Comp. Nr. W 133 O 0 0 134 CH30N 135 CH30N 0 136 CH3N 0 137 CH3N 138 O 1 0 139 CH3N 140 EtN 141 PhCH2N 142 PhN 143 4-CIPhN 144 PhN 0 145 2-pyridyl 146 4-pyridylN 147 PhON 148 PhON 0 149 BzON 0 150 CH3N 1 151 PhON 1 152 CH30N 1 153 4-CIPhON 154 4-OCH3PhON 155 4-OCH3PhN 1 156 4-CH3PhN Table 4 Derivatives of general formula (I) wherein A has the meaning of (A) :

Comp. Nr. R3 x y 157 CH3 1 0 158 CH3 1 1 159 Ethyl 1 1 160 Benzyl 1 1 161 CH3 162 i-propyl 1 0 163 Benzyl 2 1 164 CH3 0 0 165 Ethyl 0 0 Table 5 Derivatives of general formula (I) wherein A has the meaning of (A5) : Compound Nr. R4 166 4-CI-phenyl 167 4-OH-3-OCH3-phenyl 168 3, 4-diOCH3-phenyl 169 4-CF3-phenyl 170 4-CH3-phenyl

Compound Nr. R4 171 4-OCH3-phenyl 172 2, 4-diCl-phenyl 173 4-Br-phenyl 174 2-OH-phenyl 175 2, 6-diCl-phenyl 176 4-OCF3-phenyl 177 2-CF3-phenyl 178 2-pyridyl 179 4-pyridyl 180 2-furyl 181 2-thiazolyl 182 2-pyrimidyl 183 isopropyl 184 isobutyl 185 CF3 186 Cyclopentyl 187 Cyclopropyl 188 Cyclohexyl 189 CHs 190 Benzyl 191 2-(phenyl) ethyl 192 1-(phenyl) ethyl 193 t-butyl 194 4-F-phenyl Table 6 Derivatives of general formula (I) wherein A has the meaning of (A6) :

Comp. Nr. OH pos. n Q 195 4 3-OCH3 1 CN 196 4 3, 5-diOCH3 2 CN 197 4 3-OCH3 1 H 198 4 3, 5-diOCH3 2 H 199 4 3-OCH3 1 COCH3 200 4 3-OCH3 1 COCF3 201 4 3-OCH3 1 CONH2 202 4 3-OCH3 1 COOCH2CH3 203 4 3-OCH3 1 COOCH (CH3) 2 204 4 3-OCH3 1 CONHCH3 205 4 3-OCH3 1 CON (CH3) 2 206 4 3-OCH3 1 CH2CH3 207 4 3-OCH3 1 CH3 208 4 3-OCH3 1 CF3 209 4 3-OCH3 1 COOCH2Ph 210 4 H 1 CN 211 4 H 1 COOCH2CH3 212 4 H 1 COOCH (CH3) 2 213 4 H 1 CONHCH3 214 4 H 1 CON (CH3) 2 215 4 H 1 CH2CH3 216 4 H 1 CH3

Comp. Nr. OH Q 217 218 4 1 COOCH2Ph 219 4 1 220 2 5-CI 221 4 3, 5-CI 222 2 5-CI 1 H 223 3, 224 2 5-CI 1 COCH3 225 2 5-CI 1 CONH2 226 2 5-CI 1 COCF3 227 2 5-CI 1 228 5-CI COOCH (CH3) 2 229 5-CI 230 5-CI CON (CH3) 2 231 5-CI 232 2 5-CI CH3 233 5-CI 234 2 3-CH3 1 CN 235 2 236 2 CON (CH3) 2 237 2 5-Br 1 238 2 H H Table 7 Derivatives of general formula (I) wherein A has the meaning of (A7) :

Comp. Nr. Rs 240 241 IPrO 242 Allyl 0 0 243 0 0 244 N-morpholine 245 0 246 0 0 247 0 0 248 0 249 H 0 0 250 Cyclopentyl H 0 0 251 4-OH-propyl 4-OH-propyl 0 0 252 0 0 253 0 0 254 H 0 255 H 0 256 257 0 258 H 0 259 H 0 260 H 0 261 H 0 262 H 0 263 N, N-dibutyl H 0 0 264 1 2 265 1 2 266 N. N-diethyl H 0 3 267 268 CH3CONH H 0 0 269 4-CH3PhCO H 0 0 270 2, 6-dimethylmorpholine 0 271 0 0 272 (CH3) 2N 273-CH2CH2-0 0 274-CH2 0 Table 8 Derivatives of general formula (I) wherein A has the meaning of (A8) :

Comp. Nr. OH pos. X n 276 3 H 1 277 4 H 1 278 2 3-OH 1 279 2 6-OH 1 280 3 4-OH 1 281 2 3-OCH3 1 282 2 5-OCH3 1 283 2 5-Br 284 2 3-CH3 1 285 2 5-F 1 286 2 5-CN 1 287 2 5-CF3 288 2 3-NH2 1 289 2 3-N (CH3) 2 1 290 4 3, 5-diCl 2 291 4 3, 5-diBr 2 292 4 3, 5-diOCH3 2 293 4 3, 5-diCH3 2 294 4 3-OCH3 1 295 4 3-Cl 1 296 4 3-NO2 1 Example 6 Determination of the fungicidal activity against perono- spora in vines (Plasmopara viticola).

Vine plant leaves (cultivar Dolcetto) grown in vases in a conditioned environment (201°C, 70% relative humid- ity) are treated by spraying both sides of the leaf with compounds 1,2 and 3, dispersed in a hydro-acetone solu- tion at 20% by volume in acetone.

After remaining 24 hours in a conditioned atmos- phere, the plants are sprayed on both sides of the leaf with an aqueous suspension of conidia of Plasmopara viti- cola (20000 conidia per cm3).

The plants are kept in a humidity saturated environ- ment at 21°C for the incubation period of the fungus.

At the end of said period (7 days), the fungicidal activity is evaluated according to a percentage evalua- tion scale from 0 (completely infected plant) to 100 (healthy plant).

All the compounds tested showed a fungus control higher than 90 at a concentration of 1000 ppm.