IT202000007234A1 - Compounds with fungicidal activity, relative agronomic compositions and use for the control of phytopathogenic fungi - Google Patents

Description

? Activity compounds? fungicide, related agronomic compositions and use for the control of phytopathogenic fungi?

The present invention relates to high activity aminoesters? fungicide; in particular it concerns suitably substituted compounds endowed with high activity? fungicide and their use for the control of phytopathogenic fungi of important agricultural crops.

Activity aminoesters fungicides have been described in the literature and are described in particular in patent applications WO99 / 27783, WO01 / 14339, WO01 / 12587 and WO01 / 05769.

The products described in these documents result in? often unsatisfactory in terms of efficacy against various phytopathogenic fungi of interest in important agricultural crops.

The Applicant has now surprisingly discovered that the combination of specific substituents in such compounds allows to broaden the spectrum of action already? previously known on similar compounds, without demonstrating symptoms of phytotoxicity? in agricultural crops of interest.

Therefore, new compounds of general formula (I) are the object of the present invention:

in which:

- X represents a hydrogen atom or a C (O) R <5> group;

- Y represents a hydrogen atom or a C (O) R <5> group or a Q group:

- Z <1> and Z <2>, equal or different from each other, can represent a nitrogen atom, a N? O group, or a CRc group;

- Rc represents a hydrogen atom, a halogen atom selected from fluorine, chlorine, bromine or iodine, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a nitro group, an amino group, a formylamine group; - M represents a halogen atom selected from fluorine, chlorine, bromine or iodine or a W <2> -R <6> group;

- W <1> and W <2>, equal or different from each other, represent an oxygen atom or a sulfur atom;

- R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>; a CH (CH3) COOR <7> group;

- R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- Rd represents a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12cycloalkyl-C1-C12-alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxy group, a C3-C12 cycloalkoxyl group, an aryl group, a phenoxy group, a benzyloxy group, an aryl group -C1-C12-alkyl, or a heterocyclyl-C1-C12-alkyl group wherein the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>;

- n represents a number between 0 and 2;

- m represents a number between 1 and 2;

- p represents a number between 1 and 4;

- R <5> represents a C1-C12 alkoxy group, a benzyloxy group or a fluorenylmethoxy group;

- R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group;

- or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring;

- R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic group, penta or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulphone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups;

- or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups;

- R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a penta-or hexa-atomic, aromatic or non-aromatic heterocyclic group, whether or not benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above, said groups being optionally replaced with one or more? Rd groups, or R <4> represents a T group:

T =

in which:

- Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups;

- Rg represents a hydrogen atom, a hydroxyl, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a C1-C12 alkyl group, a C1C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C1-C12 alkoxy group;

provided that:

- when Z <1> assumes the value of CH, Z <2> represents a CRc group where Rc takes on the meaning of a formylamino group or a nitro group, W <1> and W <2> are both oxygen, R < 6>? a hydrogen atom, n takes the value 0, m takes the value 1 or 2 and Ra and Rb both represent a hydrogen atom and, if R <1> takes the meaning of methyl, 4-methoxybenzyl or 4-methoxyphenyl carbonyl and R <4> takes on the meaning of hydrogen, R <2> and R <3>, different from each other, cannot take on the meanings of hydrogen, ethyl, heptyl and isobutyl;

- when Z <1> takes the value of N, Z <2> represents a CRc group where Rc takes on the meaning of hydrogen, W <1> and W <2> are both oxygen, R <6>? a hydrogen atom, n takes the value 0, m takes the value 1 and Ra and Rb both represent a hydrogen atom, if R <1> takes the meaning of methyl, 2-naphthylmethyl, 4-pyridylmethyl or 2-pyridylmethyl, R <2>, R <3>, R <4> cannot assume the meaning of hydrogen and, if R <1> takes the meaning of 2-pyridylmethyl, R <2> and R <3> take the meaning of hydrogen , R <4> can not? take on the meaning of octyl.

New compounds of general formula (I?) Constitute a further object of the present invention, for X which takes on the meaning of hydrogen and Y which takes on the meaning of Q

in which

- G represents a hydrogen atom or an atom of an alkali metal such as for example lithium, sodium, potassium or a group NR <8> R <9>, - R <8>, R <9>, Q, n, m , R <1>, Ra and Rb take on the meanings described above;

provided that:

- when Z <1> takes the value of N, Z <2> represents a CRc group, Rc takes on the meaning of hydrogen, W <1> and W <2> are both oxygen, R <6> takes the meaning of hydrogen , n takes on the value 0, m takes on the value of 1 or 2, Ra and Rb take on the meaning of hydrogen

- when R <1> takes on the meaning of hydrogen, methyl, 4-pyridylimethyl, 2-pyridylmethyl, G does not take on the meaning of hydrogen.

Preferably the compounds of general formula (I) are the compounds in which:

- X represents a hydrogen atom and Y represents a Q group;

- Z <1> and Z <2>, equal or different from each other, represent a nitrogen atom or a CRc group;

- Rc represents a hydrogen atom, a halogen atom, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a formylamine group;

- M represents a group W <2> -R <6>;

- W <1> and W <2>, equal or different from each other, represent an oxygen atom; - Rd represents a hydrogen atom, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkyl group C1-C12-alkyl, C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a C3 group -C12 cycloalkoxy, an aryl group, a phenoxy group, a benzyloxy group, an aryl-C1-C12-alkyl group, a penta- or hexaatomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>;

- n represents a number between 0 and 2;

- m represents a number between 1 and 2;

- p represents a number between 1 and 2;

- R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>, a group CH (CH3) COOR <7>;

- R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group , an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group;

- or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring;

- R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups; - R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups, or R <4> represents a T group:

T =

in which:

- Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups;

- Rg represents a hydrogen atom, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 alkoxy group;

- or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups.

In the present description, when a numerical interval is indicated, the extremes are also intended to be included therein.

Examples of C1-C12 alkyls which may be linear or branched are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl.

Examples of C1-C12 haloalkyls are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 4,4,4-trichloro-butyl, 4 , 4-difluoropentyl, 5,5-difluorohexyl.

Examples of C2-C12 alkenyls, which can be linear or branched, are vinyl, allyl, 3-butenyl, 4-pentyl.

Examples of haloalkenyls are C2-C12 are 1- (1,1,2-trifluoro) -butenyl, 1- (2,2-difluoro) -butenyl.

Examples of C3-C12 cycloalkyls are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

Examples of C3-C12 cycloalkenyls are cyclopropenyl, cyclopentenyl, cyclohexenyl. Examples of C3-C12 haloalkyls are 2,2-dichloro-cyclopropyl, 2,2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl, 3,3-difluorocyclopentyl, 2-fluorocyclohexyl.

Examples of C3-C12cycloalkyl-C1-C12-alkyl are cyclopropylmethyl, 2-cyclopentylethyl, 2-cyclohexylpropyl.

Examples of C1-C12 alkoxy are methoxy, ethoxy, iso-propoxy, tert-butoxy. Examples of C1-C12 thioalkoxyls are thiomethoxy, thioethoxy, iso-thiopropoxy. Examples of C3-C12 cycloalkoxyls are cyclopropoxy, cyclopentoxyl.

Examples of phenoxy groups are 4-chloro-phenoxy, 2,4-difluoro-phenoxy, 3-methyl-phenoxy.

Examples of aryls, for which aromatic systems formed by carbon atoms only, are phenyl, naphthyl.

Examples of heterocyclic rings, for which we mean cyclic systems with 5 or 6 terms, aromatic or non-aromatic, possibly benzocondensed containing from 1 to 3 heteroatoms selected from O, N, S, are: thiazole, 1,3,4 thiadiazole, pyrrolidine, piperidine, morpholine, pyrazole etc.

Examples of aryl-C1-C12-alkyl are benzyl, phenylethyl, 2-phenyl-propyl, 3- (2-fluoro) -phenyl-butyl.

Examples of heterocyclyl-C1-C12-alkyl are 2- (1,3,4-thiadiazolyl) -methyl, 4-pyrazolyl-methyl, 2- [3- (N-methyl) -pyrrolidinyl] -propyl.

It is also intended to fall within the spirit of the present invention:

a) all the possible geometric isomers of the compounds of general formula (I) and (I?) and all the stereoisomers determined by the chiral centers present in the molecules of general formula (I) and (I?);

b) the salts of the compounds of formula (I) and (I?) obtained by addition of inorganic or organic acids;

c) any hydrated forms of the compounds of formula (I) and (I?);

d) any oxidized forms on the sulfur and nitrogen atoms of the compounds of general formula (I) and (I?).

Examples of compounds of general formula (I) with X assuming the meaning of hydrogen and Y representing a group C (O) R <5> (compounds of general formula (Ia)), are the compounds in which m, n, Ra, Rb, R <1>, R <2>, R <3>, R <4> and R <5> take on the meanings shown in Table 1:

Table 1

Examples of compounds of general formula (I) with X and Y representing a hydrogen atom (compounds of general formula (Ib)), are the compounds in which, Ra, Rb, n, m, R <1>, R < 2>, R <3> and R <4> take on the meanings shown in Table 2:

Table 2

For compounds of general formula (I) in which Y takes on the meaning of Q as described above, said group can? assume the following meanings Q1-Q4, as reported in tables 3-6.

Q1: Z <1> = CH, Z <2> = CRc

Table 3

Q2: Z <1> = N, Z <2> = CRc

Table 4

Q3: Z <1> = CRc, Z <2> = N

Table 5

Q4: Z <1> = Z <2> = N

Table 6

Examples of compounds of general formula (I) in which X represents a hydrogen atom and Y takes on the meaning of Q selected from the groups from Q1 to Q4 (compounds of general formula (Ic)) are reported in Table 7.

Table 7

Particularly preferred are the compounds of general formula (Ic) in which X represents a hydrogen atom and Q, Ra, Rb, n, m, R <1>, R <2>, R <3> and R <4> assume the meanings reported in Table 8.

Table 8

Even more? preferred are the compounds of general formula (Ic) in which X represents a hydrogen atom and Q, Ra, Rb, n, m, R <1>, R <2>, R <3> and R <4> assume the meanings reported in Table 9.

Table 9

Examples of compounds of general formula (I?) With X representing a hydrogen atom and Y assuming the meaning of Q, chosen from the groups Q1 to Q4, are the compounds in which Q m, n, Ra, Rb, R <1>, and G take on the meanings shown in Table 10:

Table 10

723 Q1.48 H H 0 1 CH3 Li

724 Q1.48 H H 0 1 CH3 Na

725 Q1.48 H H 0 1 CH3 K

726 Q1.48 H H 0 1 CH3 NH4

727 Q1.48 H H 0 1 CH3 N (Et) 3

A further object of the present invention? the use of the above compounds of formula (I?) as intermediates in the preparation of compounds of general formula (Ic).

Compounds of general formula (I) where X assumes the value of hydrogen and Y represents a group Q, (compounds of general formula (Ic)) can be obtained using various synthetic methods; for example, by way of example but not exhaustive, they can be prepared from the compounds of general formula (II) by reaction with a suitable amine of general formula (Ib) according to reaction scheme 1.

Scheme 1

(II) (Ib) (Ic)

The reaction is carried out by activating the acid by forming the corresponding chloride, for example with thionyl chloride in dichloromethane or chloroform at a temperature between -10 ° C and the reflux temperature of the solvent used, or by using a condensing agent such as N, N? -Dicyclohexylcarbodimide or N- (3-dimethylaminopropyl) -N? -Ethylcarbodimide in tetrahydrofuran or ethyl acetate, or using 1,1-carbonyldimidazole in tetrahydrofuran or methylene chloride or PyBOP [(1-Benzotriazolaphylloxy) triphoniophonate (1- [Bis (dimethylamino) methylene] -1H-1,2,3-triazole [4,5-b] pyridinium-3-oxide

hexafluorophosphate) at a temperature between 0 ° C and the reflux temperature of the solvent used, as widely described in R. C. Larock? Comprehensive Organic Transformations ?.

The activated form of the acid, in the presence of the amine of formula (Ib), reacts in a suitable solvent such as methylene chloride, or dichloroethane, or chloroform at a temperature between 0 ° C and the reflux temperature of the solvent in the presence or in the absence of a base such as triethylamine or 4-dimethylaminopyridine or diisopropylethylamine to give the compounds of general formula (I), according to what is known in the literature in R. C. Larock? Comprehensive Organic Transformations ?.

Alternatively the compounds of general formula (I) where X takes on the value of hydrogen and Y the value of Q (compounds of general formula (Ic)) can be obtained according to reaction scheme 2.

Scheme 2

The activated form of the acidic acid of general formula (II) obtained according to what previously said in the reaction scheme 1, reacts in the presence of the amine of general formula (Ib), to give the compound of general formula (Ic) where R? , in both cases, it assumes the meaning of C1-C4 alkyl. The latter is subjected to acid or basic hydrolysis to give compound (I?) Which is condensed with a suitable alcohol of general formula (III) in a suitable solvent such as methylene chloride, or dichloroethane, or chloroform, in the presence of a condensing agent such as N, N? -dicyclohexylcarbodimide or N- (3-dimethylaminopropyl) -N? -ethylcarbodimide in tetrahydrofuran or ethyl acetate, or using 1,1-carbonyldimidazole in tetrahydrofuran or methylene chloride at a temperature between 0? C is the reflux temperature of the solvent in the presence or absence of a base such as triethylamine or 4-dimethylaminopyridine or diisopropylethylamine according to what is known in the literature in R. C. Larock? Comprehensive Organic Transformations ?.

Alternatively, the compounds of general formula (Ic) when Z <1> assumes the meaning of group CH and Z <2> of group CRc, with Rc representing the NHCHO group, can be obtained by condensation of the appropriate 3-nitrosalicylic acid of formula (IIa) with the aminoester of general formula (Ib) to give the compound of formula (Ic?). By subsequent reaction of reduction of the nitro group, the compound of formula (Ic ??) is obtained which can? be subjected to a formylation reaction to give the compound of general formula (Ic), according to reaction scheme 4:

Scheme 4

The same sequence of reactions can? be applied also in reaction schemes 2 and 3 when Z <1> assumes the meaning of CH group and Z <2> represents the CRc group, with Rc representing the NHCHO group.

The modalities? to carry out the condensation reaction between the compounds of general formula (IIa) and (Ib) are the same as described in the previous paragraphs.

The reduction reaction of the nitro group present in the compounds of general formula (Ic?) Pu? be carried out according to the usual methods well known in the art and described extensively in R. C. Larock? Comprehensive Organic Transformations?, such as for example the catalytic hydrogenation in the presence of catalysts such as for example Pd on coal at 5% or Pd on coal at 10% in a solvent such as methanol, ethanol or tetrahydrofuran, at atmospheric pressure or under pressure and at a temperature between ambient values and 80 ° C, or using ammonium formate in methanol at atmospheric pressure and ambient temperature or metallic iron and acetic acid in a hydroalcoholic mixture at temperatures between ambient and reflux values of the reaction mixture, or tin chloride in ethyl acetate at the reflux temperature of the solvent.

The formylation reaction of the amino group cos? obtained, can? be carried out according to the usual methods well known in the art such as, for example, using a mixed anhydride between formic acid and acetic anhydride in a solvent such as tetrahydrofuran or dioxane as described in Krishnamurthy S.? Tetrahedron Letters ?, 1982, vol. 23, p. 3315-3318, or in formamide at 150? C as described in John Janetzko, Robert A. Batey,? Journal of Organic Chemistry ?, 2014, vol. 79, pages 7415-7424 or with zinc oxide and formic acid as described in Hosseini-Sarvari Mona, Sharghi Hashem,? Journal of Organic Chemistry ?, 2006, vol. 71 (17), p. 6652-6654 or cerium oxide and formic acid in the presence of ultrasound as described in Sajadi S. Mohammad et al.,? Letters in Organic Chemistry ?, 2014, vol. 11, pages 49-54.

Alternatively, the compounds of general formula (Ic) when Z <1> assumes the meaning of group CH and Z <2> of group CRc, with Rc representing an NHCHO group, can be obtained according to the procedure described in scheme 2, i.e. by condensation of the appropriate compound of general formula (IIb), where PG represents a protective group, such as for example a benzyl group or a p-methoxybenzyl or pchlorobenzyl group with an amine of general formula (Ib) to give the compound of formula ( Ic <???>), where R? in both cases it assumes the meaning of C1-C4 alkyl. The latter is subjected to acid or basic hydrolysis to give compound (I? A) which is condensed with a suitable alcohol of general formula (III) to give the compound of general formula (Ic <????>).

The subsequent reaction of reduction of the nitro group also involves the removal of the protective group PG to give the compound of formula (Ic ??) which can? be subjected to a formylation reaction to give the compound of general formula (Ic) using the procedures described above and according to reaction scheme 5:

Scheme 5

The compounds of general formula (Ic) for W <1> which assumes the meaning of sulfur atom, can be easily obtained from the corresponding compounds with W <1> which represents an oxygen atom, by sulfonation of amides by reaction with P4S10 or with Lawesson's reagent, according to what is known in the literature and described, for example, in R. Larock? Comprehensive Organic Transformations? and according to reaction scheme 6:

Scheme 6

Compounds with general formula (Ic) in which R <6> takes on the meaning of benzyl group or COR group <7>, or of CH2OCOR group <7>, or of CH2OR group <7>, or of CH2SR group <7 > can be obtained by benzylation or acylation or alkylation reaction of the corresponding compounds of general formula (Ic), in which M represents a group W <2> H, using a compound of general formula L-R <6>, with R <6> other than a hydrogen atom and with L representing a leaving group such as a halogen atom, selected from chlorine, bromine or iodine, or a mesylate group or a triflate group, in a suitable solvent such as ethyl acetate or N, N-dimethylformamide o acetone at a temperature between -15 ° C and 70 ° C, in the presence of an organic or inorganic base such as potassium carbonate, or sodium carbonate, or triethylamine or pyridine or sodium hydride and in the presence or absence of a catalyst such as sodium iodide, potassium iodide and a corona ether such as 1 5-crown-5 or 18-crown-6, according to methods well known in literature and described, for example, in WO2016 / 109257 and represented in reaction scheme 7.

Scheme 7

The compounds of formula (Ib), when they are not commercial and for X and Y which take the meaning of hydrogen, can be prepared as described, for example, in EP652229.

The alcohols of general formula (III), when they are not commercial, can be easily obtained by reducing the corresponding ketones by means of hydrides such as sodium borohydride, lithium aluminum hydride in suitable solvents such as tetrahydrofuran or dioxane at a temperature between 0 ° C and the boiling temperature of the solvent according to methods known in literature as described in E. Tadashi, U. Norichika, Y. Masataka, et al. ? Tetrahedron ?, 2009, vol. 65, p. 9583? 9591, or in WO2016 / 109257.

Q1-Q4 groups, when non-commercial, can be obtained using the procedures outlined in R. E. Buntrock? Review of Heterocyclic Chemistry ?, 5? Edition, 2012 Copyright? 2012 The American Chemical Society and Division of Chemical Education, Inc.

The compounds of general formula (Ic), for n which takes the value of 1 or 2, can be obtained by oxidation reactions of the compounds of formula (Id), in which PG? represents a COR5 protective group, such as for example a tbutoxycarbonyl (BOC) or fluorenylmethoxycarbonyl (FMOC) group, to give the compound of formula (Ie), according to methods known in the literature as described for example in Loginova, Rubtsova, Kuchin? Chemistry of Natural Compounds, 2008, vol 44, p. 752-754 or in WO2014 / 9759, WO2015 / 8019 or in M. Matteucci, G. Bhalay, M. Bradley? Org. Lett. 2003, 5, 3, p. 235-237 ?. The compounds of general formula (Ie), cos? obtained, can they be subjected to an esterfication reaction with a suitable alcohol of formula (III) and then to a subsequent reaction to remove the protective group PG? obtaining the compounds of formula (Ib). The amino ester cos? obtained is reacted with the acids of formula (II) to give the compound of general formula (Ic), according to the reaction scheme 8.

Scheme 8

Alternatively the compounds of general formula (Ic), for n which takes the value of 1 or 2, can be obtained by oxidation reaction of the corresponding thioethers of general formula (Ic), in which n takes the value 0, according to methods known in literature and described above, according to reaction scheme 9:

Scheme 9

AND? a further object of the present invention is the use of compounds of general formula (I):

in which:

- X represents a hydrogen atom or a C (O) R <5> group;

- Y represents a hydrogen atom or a C (O) R <5> group or a Q group:

- Z <1> and Z <2>, equal or different from each other, can represent a nitrogen atom, a N? O group, or a CRc group;

- Rc represents a hydrogen atom, a halogen atom selected from fluorine, chlorine, bromine or iodine, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a nitro group, an amino group, a formylamine group; - M represents a halogen atom selected from fluorine, chlorine, bromine or iodine or a W <2> -R <6> group;

- W <1> and W <2>, equal or different from each other, represent an oxygen atom or a sulfur atom;

- R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>; a CH (CH3) COOR <7> group;

- R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- Rd represents a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12cycloalkyl-C1-C12-alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxy group, a C3-C12 cycloalkoxyl group, an aryl group, a phenoxy group, a benzyloxy group, an aryl group -C1-C12-alkyl, or a heterocyclyl-C1-C12-alkyl group wherein the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>;

- n represents a number between 0 and 2;

- m represents a number between 1 and 2;

- p represents a number between 1 and 4;

- R <5> represents a C1-C12 alkoxy group, a benzyloxy group or a fluorenylmethoxy group;

- R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other;

- Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group;

- or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring;

- R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic group, penta or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulphone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups;

- or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups;

- R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, whether or not benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above, said groups being optionally replaced with one or more? Rd groups, or R <4> represents a T group:

T =

in which:

- Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups;

- Rg represents a hydrogen atom, a hydroxyl, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a C1-C12 alkyl group, a C1C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C1-C12 alkoxy group;

provided that:

- when Z <1> assumes the value of CH, Z <2> represents a CRc group where Rc takes on the meaning of a formylamino group or a nitro group, W <1> and W <2> are both oxygen, R < 6>? a hydrogen atom, n takes the value 0, m takes the value 1 or 2 and Ra and Rb both represent a hydrogen atom and, if R <1> takes the meaning of methyl, 4-methoxybenzyl or 4-methoxyphenyl carbonyl and R <4> takes on the meaning of hydrogen, R <2> and R <3>, different from each other, cannot take on the meanings of hydrogen, ethyl, heptyl and isobutyl;

for the control of phytopathogenic fungi of agricultural crops.

The compounds of general formula (I) are in fact endowed with an activity? very high fungicide that is expressed against numerous phytopathogenic fungi that attack important agricultural crops.

Examples of phytopathogenic fungi that can be effectively treated and combated with the compounds of general formula (I) are those belonging to the classes of Basidiomycetes, Ascomycetes, Deuteromycetes or imperfect fungi, Oomycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Eryiphe spp., Sphaerotheca spp., Podosphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotoria spp., (Mycosphaerella spp.), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colletotrichum spp., Pyricularia oryzae, Sclerotium spp., Phytophtora spp., Plythopasmium sppicola. , Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.

The main crops that can be protected with the compounds according to the present invention include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple, pear, plum, peach, almond, cherry, banana , grapevine, strawberry, raspberry, blackberry, etc.), citrus fruits (orange, lemon, mandarin, grapefruit, etc.), legumes (bean, pea, lentil, soy, etc.), vegetables (spinach, lettuce, asparagus, cabbage , carrot, onion, tomato, potato, eggplant, pepper, etc.), cucurbits (pumpkin, courgette, cucumber, melon, watermelon, etc.), oil plants (sunflower, rapeseed, peanut, castor, coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton.

In particular, the compounds of formula (I) have proved remarkably effective in the control of Plasmopara viticola on grapevine, Phytophtora infestans and Botrytis cinerea on tomato, Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum, Septoria tritici and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soybeans, in the control of Uromyces appendiculatus on beans, in the control of Venturia inaequalis on apple trees, in the control of Sphaerotheca fuliginea on cucumber.

Furthermore, the compounds of general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as for example Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the tobacco mosaic virus.

The compounds of formula (I) are capable of carrying out a fungicidal action of both curative and preventive character and exhibit phytotoxicity. very little or no on treated crops.

For practical uses in agriculture? it is often preferable to use fungicidal compositions containing suitably formulated compounds according to the present invention.

A further object of the present invention are fungicidal compositions comprising one or more? compounds of formula (I), a solid or liquid solvent and / or diluent, optionally a surfactant.

The aforementioned fungicidal compositions can be in the form of dry powders, wettable powders, emulsifiable concentrates, emulsions, microemulsions, pastes, granules, water-dispersible granules, solutions, suspensions, etc .: the choice of the type of composition will depend on the product. from specific use.

The fungicidal compositions are prepared in a known manner, for example by diluting or dissolving the active substance with a solvent medium and / or a solid or liquid diluent, optionally in the presence of surfactants.

As solid diluents or supports, for example, silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, seppiolite can be used.

As liquid solvents or diluents, in addition to water, for example, aromatic organic solvents (xylols or mixtures of alkylbenzols, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerin) can be used. , etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, alkyl esters of adipic acid, alkyl esters of glutaric acid, alkyl esters of succinic acid, alkyl esters of lactic acid, etc.), oils vegetables (rapeseed oil, sunflower oil, soybean oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone, etc.), amides ( N, N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides and sulfones (dimethylsulfoxide, dimethylsulfone, etc.), and their mixtures.

Propellant gases such as butane, propane, halogenated hydrocarbons, nitrogen or carbon dioxide can be used as liquefied diluents or liquefied substances that gasify at ambient temperature and pressure.

As surfactants, sodium, calcium, potassium, triethylamine or triethanolamine salts of alkylnaphthalenesulphonates, poly-naphthalenesulphonates, alkylsulfonates, arylsulfonates, alkylaryl sulphonates, polycarboxylates, sulphosuccinates, alkylsulfosulfonates, lymphosulfonates can be used; and polyethoxylated fatty alcohols, polyethoxylated alkylphenols, polyethoxylated arylphenols or polypropoxy-polyethoxylates or polyethoxylated, polypropoxy-polyethoxylated sorbitol esters (block polymers) can also be used.

The fungicidal compositions can also contain special additives for particular purposes, for example antifreeze such as propylene glycol, or adhesive agents such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, dispersants, for example lignin and its salts, cellulose or alginate derivatives, or stabilizers, for example for example antioxidants or ultraviolet absorbers.

The concentration of active compound of formula (I) in the above compositions can? vary over a wide range and depends on several factors. It varies according to the active compound of formula (I), the applications to which said compositions are intended, the environmental conditions and the type of formulation adopted. In general, the concentration of active compound of formula (I) ranges from 0.1 to 90% by weight with respect to the total weight of the composition, preferably from 0.5 to 90% by weight.

If desired,? It is possible to add to the fungicidal compositions containing the compounds of general formula (I), other active ingredients compatible with them, such as for example fungicides other than those of general formula (I), plant growth regulators, antibiotics, herbicides, insecticides, fertilizers, biostimulants and / or their blends.

Examples of fungicides other than those of general formula (I) that can be included in the fungicidal compositions object of the present invention are: acibenzolar, aldimorph, ametoctradin, aminopyrifen, amisulbrom, ampropylfos, anilazine, azaconazole, azithiram, azoxystrobin, benalaxyl, benalax , benodanil, benomyl, benodanil, benquinox, benthiavalicarb, benzamacril, benzamorf, benzovindiflupyr, binapacryl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captanimamidia, carenthamorazole, carenthamorazole, captan-phorph , chlorfenazole, chloroneb, chlorothalonil, chlorquinox, chlozolinate, cufraneb, coumoxystrobin, cyazofamid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazometoline, debloracarbent, dicafluxone, dichutlocol , diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethom orph, dimoxystrobin, diniconazole, dinobuton, dinocap, dipymethitrone, dinocton, dinopenton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, enoxastrobin, epoxiconazole, etaconazole, ethoxquinamamidy, ethboximidone, ethboxirone, fam fenaminstrobin, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, florylpicoufxamid, flicolapenam, flicolap fluopyram, fluopimomide, fluotrimazole, fluoxapiprolin, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetylaluminium, fuberidazole, furalpacratine, furvinhanate, fuberidazole, furalpacratine, furvinconate, fuberidazole, furisacratine, fur hexaconazole, hexylthiofos, hymexazol, hydroxyquinoline sulfate, Imazalil, imibenconazole, iminoctadine, inpyrfluxam, ipconazole, ipfentrifluconazole, ipflufenoquin, iprobenfos, iprodione, isoprothiolane, iprovalicarb, isofetamid, isoflucypram, isopyrazam, isotianil, khugas-methyl, manbyl-methyl, manbyl-methyl, manbylamamid, kamilco-zestrus, mandilco-zestro mecarbinzid, mefentrifluconazole, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metam metconazole, methasulfocarb, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, metyltetrautprole, myzylclobin, myzylclobin, myzylcloban, myzylcloban, myzyl-metil, nitrile, myzylcloban, myzil , ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, penthiopyrad, picarbutrazox, picoxystrobin, piperalin, polyoxorim, prochloraz, propamarbole, prochloraz, propamarbidone, , pyrametostrobin, pyraoxystrobin, pyrapropoyne , pyraziflumid, pyrazophos, pyribencarb, pyridachlometyl, pydiflumetofen, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoflumetofen, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoflumetofen, quinofenamamine, silicofumelin, quinthoin , tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl, tolprocarb, tolzoxide-methyl , tridemorf, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, valifenalate, vinclozolin, zineb, ziram, zoxamide.

Therefore, a further object of the present invention are fungicidal compositions comprising at least one compound of general formula (I) and at least one other fungicide different from the compounds of formula (I).

Fungicidal compositions containing at least one compound of formula (I) and one or more? known fungicides, particularly preferred for their particularly broad spectrum of action and a marked synergistic effect, are those in which one or more? compounds of general formula (I) are combined with one or more? known fungicides belonging to the following classes:

a) azoli scelti tra azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, simeconazole , tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, triflumizole, triticonazole;

b) amines inhibiting ergosterol biosynthesis selected from aldimorph, dodemorph, fenpropimorph, fenpropidin, spiroxamine, tridemorph;

c) succinatodehydrogenase inhibitors (SDHI) chosen from benzovindiflupyr, bixafen, boscalid, carboxin, fluindapyr, fluopyram, flutolanil, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, oxycarboxin, penflufen, sedifluzamide, thaxiopyr.

d) strobilurins selected from azoxystrobin, coumoxystrobin, dimoxystrobin, enoxastrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxostrobin, trifloxystrobin; e) specific antioids selected from cyflufenamid, flutianil, metrafenone, proquinazid, pyriofenone, quinoxyfen;

f) anilinopyrimidines selected from pyrimethanil, mepanipyrim, cyprodinil; g) benzimidazoles and analogues selected from carbendazim, benomyl, thiabendazole, thiophanate-methyl;

h) dicarboximides selected from iprodione, procymidone;

i) phthalimides selected from captafol, captan, folpet;

l) inducers of SAR (acquired systemic resistance) selected from acibenzolar, probenazole, isothianil, thiadinil;

m) phenylpyrroles selected from phenpiclonyl, fludioxonil;

n) acylalanines selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M;

o) other specific antiperonosporics chosen from among ametoctradin, amisulbrom, benthiavalicarb, cyazofamid, cymoxanil, dimethomorph, ethaboxam, famoxadone, fenamidone, flumetover, flumorph, fluopicolide, iprovalicarb, mandipropamid, oxathiaxalamide, valamide.

p) dithiocarbamates selected from maneb, mancozeb, propineb, zineb, metiram; q) phosphorous acid and its inorganic or organic salts, fosetyl-aluminum; r) cupric compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulphate, copper salicylate;

s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, silthiofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine, tolclofos-methyl.

Fungicidal compounds are indicated in this description with their international ISO name; the chemical structures and their CAS and IUPAC names are listed in Alan Wood? s Website (www.alanwood.net), Compendium of Pesticide Common Names; the chemical-physical data and the biological characteristics of most of these compounds are reported in the? Pesticide Manual ?, C.D.S. Tomlin, 15th Edition, 2009, British Crop Production Council.

Preferred compositions containing at least one compound of formula (I) (component A) and at least one other known fungicide are those consisting of:

C1: compound 433 tetraconazole;

C2: compound 433 tebuconazole;

C3: compound 433 epoxyconazole;

C4: compound 433 prothioconazole;

C5: compound 433 diphenoconazole;

C6: compound 433 penconazole;

C7: compound 433 prochloraz;

C8: compound 433 fenpropimorph;

C9: compound 433 spiroxamine;

C10: compound 433 bixafen;

C11: compound 433 boscalid;

C12: composed 433 carboxin;

C13: compound 433 fluopyram;

C14: compound 433 fluxapyroxad;

C15: compound 433 isopyrazam;

C16: compound 433 penthiopyrad;

C17: compound 433 sedaxane;

C18: compound 433 azoxystrobin;

C19: compound 433 dimoxystrobin;

C20: compound 433 fluoxastrobin;

C21: compound 433 kresoxim-methyl; C22 compound 433 picoxystrobin;

C23: compound 433 pyraclostrobin;

C24: compound 433 trifloxystrobin;

C25: compound 433 metrafenone;

C26: compound 433 proquinazid;

C27: compound 433 mepanipyrim;

C28: compound 433 cyprodinil;

C29: compound 433 iprodione;

C30: compound 433 procymidone;

C31: compound 433 carbendazim;

C32: compound 433 thiophanate-methyl; C33: compound 433 fluindapyr;

C34: compound 433 benalaxyl-M;

C35: compound 433 fenpyrazamine;

C36: compound 433 fluazinam;

C37: compound 433 tolclofos-methyl; C38: compound 433 mandipropamid; C39: compound 433 copper oxychloride; C40: compound 433 copper salicylate; C41: compound 433 chlorothalonyl;

C42: compound 433 cimoxanil;

C43: compound 433 dimetomorph;

C44: compound 433 oxathiopiproline; C45: compound 426 fluopicolide;

C46: compound 426 tetraconazole;

C47: compound 426 tebuconazole;

C48: compound 426 epoxyconazole;

C49: compound 426 prothioconazole;

C50: compound 426 diphenoconazole;

C51: compound 426 penconazole;

C52: compound 426 prochloraz;

C53: compound 426 fenpropimorph;

C54: compound 426 spiroxamine;

C55: compound 426 bixafen;

C56: compound 426 boscalid;

C57: composed 426 carboxin;

C58: compound 426 fluopyram;

C59: compound 426 fluxapyroxad;

C60: compound 426 isopyrazam;

C61: compound 426 penthiopyrad;

C62: compound 426 sedaxane;

C63: compound 426 azoxystrobin;

C64: compound 426 dimoxystrobin;

C65: compound 426 fluoxastrobin;

C66: compound 426 kresoxim-methyl; C67: compound 426 picoxystrobin;

C68: compound 426 pyraclostrobin;

C69: compound 426 trifloxystrobin; C70: compound 426 metrafenone;

C71: compound 426 proquinazid;

C72: compound 426 mepanipyrim;

C73: compound 426 cyprodinil;

C74: compound 426 iprodione;

C75: compound 426 procymidone;

C76: compound 426 carbendazim;

C77: compound 426 thiophanate-methyl; C78: compound 426 fluindapyr;

C79: compound 426 benalaxyl-M;

C80: compound 426 fenpyrazamine;

C81: compound 426 fluazinam;

C82: compound 426 tolclofos-methyl;

C83: compound 426 mandipropamid;

C84: compound 426 copper oxychloride; C85: compound 426 copper salicylate; C86: compound 426 chlorothalonyl;

C87: compound 426 cimoxanil;

C88: compound 426 dimetomorph;

C89: compound 426+ oxathiopiproline;

C90: compound 426 fluopicolide;

C91: compound 330 tetraconazole;

C92: compound 330 tebuconazole;

C93: compound 330 epoxyconazole;

C94: compound 330 prothioconazole;

C95: compound 330 diphenoconazole;

C96: compound 330 penconazole;

C97: compound 330 prochloraz;

C98: compound 330 fenpropimorph;

C99: compound 330 spiroxamine;

C100: compound 330 bixafen; C101: compound 330 boscalid;

C102: composed of 330 carboxins;

C103: compound 330 fluopyram;

C104: compound 330 fluxapyroxad;

C105: compound 330 isopyrazam;

C106: compound 330 penthiopyrad;

C107: compound 330+ sedaxane;

C108: compound 330 azoxystrobin;

C109: compound 330 dimoxystrobin;

C110: compound 330 fluoxastrobin;

C111: compound 330 kresoxim-methyl; C112: compound 330 picoxystrobin;

C113: compound 330 pyraclostrobin;

C114: compound 330 trifloxystrobin;

C115: compound 330 metrafenone;

C116: compound 330 proquinazid;

C117: compound 330 mepanipyrim;

C118: compound 330 cyprodinil;

C119: compound 330 iprodione;

C120: compound 330 procymidone;

C121: compound 330 carbendazim;

C122: compound 330 thiophanate-methyl; C123: compound 330 fluindapyr;

C124: compound 330 benalaxyl-M;

C125: compound 330 fenpyrazamine;

C125: compound 330 fluazinam;

C126: compound 330 tolclofos-methyl;

C127: compound 330 mandipropamid;

C128: compound 330 copper oxychloride; C129: compound 330 copper salicylate;

C130: compound 330 chlorothalonyl; C131: compound 330 cymoxanil;

C132: compound 330 dimetomorph;

C133: compound 330 oxathiapiproline;

C134: compound 330 fluopicolide;

C135: compound 330 pyrachlostrobin;

C136: compound 330 zoxamide;

C137: compound 330 ametoctradin;

C138: compound 330 metiram;

C139: compound 330 potassium phosphite;

C140: compound 433+ tetraconazole azoxystrobin,

C141: compound 433 pyraclostrobin tetraconazole;

C142: compound 433 epoxyconazole azoxystrobin;

C143: compound 433 pyraclostrobin epoxyconazole;

C144: compound 433 azoxystrobin fluindapyr;

C145: compound 433 pyraclostrobin fluindapyr;

C146: compound 433 fosetyl-aluminum copper oxychloride;

C147: compound 433 fosetyl-aluminum copper salicylate;

C148: compound 433 fluindapyr + tetraconazole;

C149: compound 330 tetraconazole azoxystrobin;

C150: compound 330 pyraclostrobin tetraconazole;

C151: compound 330 azoxystrobin fluindapyr;

C152: compound 330 fluindapyr tetraconazole

The component A, that is? the compounds of general formula (I), of the previous compositions C1-C152 are described and exemplified in Table 1 and precisely they are the following compounds of general formula (I) in which the substituents have the meanings reported below:

The synergistic effect of compositions containing a compound of general formula (I) (component A) and a known fungicide (component B), can be evaluated by applying Colby's formula (? Weeds, 1967, 15, pp. 20-22):

Et = EA + EB? (EA x EB): 100

in which Age? the expected efficacy percentage for the composition containing compounds A and B at doses dA + dB, EA? the observed efficacy rate for component A at dose dA, EB? the observed efficacy percentage for component B at dose dB.

When is the observed efficacy for composition A B (EA + B)? higher than the expected efficacy according to the Colby formula (EA + B / Et> 1), yes? in the presence of a synergistic effect.

In the case of ternary combinations, the Colby formula takes the form:

Et = EA + EB1 + EB2? (EAxEB1 + EAxEB2 + EB1xEB2) / 100

in which Age? the expected efficacy percentage for the composition containing compounds A, B1 and B2 at doses dA + dB1 + dB2, EA? the observed efficacy rate for component A at dose dA, EB1? the observed efficacy percentage for component B1 at dose dB1, EB2? the percentage of efficacy observed for component B2 at the dB2 dose.

When is the observed efficacy for composition A B1 B2 (EA + B1 + B2)? higher than the expected efficacy according to the Colby formula (EA + B1 + B2 / Et> 1), yes? in the presence of a synergistic effect.

AND? therefore a further object of the present invention is the use of compositions comprising at least one compound of general formula (I) for the control of phytopathogenic fungi in agricultural crops.

The main crops that can be protected with compositions comprising at least one compound of formula (I), alone or in combination with at least another known active ingredient, include cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple, pear, plum, peach, almond, cherry, banana, vine, strawberry, raspberry, blackberry, etc.), citrus fruits (orange, lemon, mandarin, grapefruit, etc.), legumes (bean, pea , lentil, soy, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, eggplant, pepper, etc.), cucurbits (pumpkin, courgette, cucumber, melon, watermelon, etc.) , oil plants (sunflower, rapeseed, peanut, castor, coconut, etc.), tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton, nuts.

In particular, the compositions of the present invention have proved remarkably effective in the control of Plasmopara viticola on grapevine, Phytophtora infestans and Botrytis cinerea on tomato, Phytophtora infestans on potato, Puccinia recondita, Erysiphe graminis, Helminthosporium teres, Septoria spp and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soybeans, in the control of Uromyces appendiculatus on beans, in the control of Venturia inaequalis on apple trees, in the control of Sphaerotheca fuliginea on cucumber.

Furthermore, the compositions of the present invention are also effective in the control of soil fungi, such as for example Rhizoctonia solani, Sclerotinia spp, Pythium ultimum on horticultural crops.

Furthermore, the compositions of the present invention are effective in the control of phytopathogenic bacteria and viruses, such as for example Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the tobacco mosaic virus.

The compositions object of the present invention are capable of carrying out a fungicidal action which can? be curative, preventive or eradicating, and, in general, exhibit a phytotoxicity? very little or no on treated crops. In the case in which the compositions comprise a compound of general formula (Ic) and at least one known active principle, the weight ratios in the aforementioned compositions vary according to the selected compounds and can normally be between 1: 100 and 100: 1, preferably between 1:10 to 10: 1.

The total concentration of the active components in the above compositions can? vary over a wide range; in general it ranges from 1% to 99% by weight with respect to the total weight of the composition, preferably from 5 to 90% by weight with respect to the total weight of the composition.

The application of these compositions can? take place on every part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the ground where the plant grows.

Further object of the present invention? therefore a method for the control of phytopathogenic fungi in agricultural crops, which consists in applying on any part of the plants to be protected or on the soil effective and non-phytotoxic doses of compositions comprising at least one compound of general formula (I) and, optionally, one or more? active ingredients known to be compatible with it.

The concentration of the amide compounds of general formula (I) in the above compositions can? vary over a wide range; in general it? between 1% and 90% by weight with respect to the total weight of the composition, preferably between 5 and 50% by weight with respect to the total weight of the composition.

The application of these compositions can? take place on every part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sowing, or on the ground where the plant grows.

Further object of the present invention? therefore a method for the control of phytopathogenic fungi in agricultural crops, which consists in the application of effective doses of the compounds of formula (I), used as such or formulated in fungicidal compositions as described above.

The quantity of compound to be applied to obtain the desired effect can? vary according to various factors such as, for example, the compound used, the crop to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the method of application, the formulation adopted.

Compost doses ranging from 10g to 5kg per hectare of agricultural crop generally provide sufficient control.

In order to better illustrate the invention, the following examples are now provided which are to be considered illustrative and not limitative thereof.

EXAMPLE 1

Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethanol (compound No. 426) a) Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate (compound No. 477)

To a solution of 5.3 g of the methyl ester of S-methyl-L-cysteine hydrochloride (29 mmol), 11.2 g (87 mmol) of diisopropylethylamine and 15.08 g (29 mmol) of PyBOP [(1 -Benzotriazolyloxy) tripyrrolidinophosphonium hexafluorophosphate] in 90 ml of CH2Cl2 was added to 0? C 5.0 g (29 mmol) of 3-hydroxy-4-methoxypyridine-2-carboxylic acid. The reaction mixture? it was kept under stirring at this temperature for 2 hours, then allowed to rise to ambient values and under stirring for a further 8 hours. After checking the reaction mixture with LC-MS? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml) and with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. 18 g of a crude were obtained which? been washed with ethyl ether and filtered to eliminate the by-products of the condensing agent. The ethereal phase? it was then concentrated in the rotavapor and purified by chromatography on silica gel using an automatic Biotage separator. 6.2 g of the desired product were obtained. Yield 72%

LC-MS: M <+> = 300

b) Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropanoic acid (compound No. 518)

60 ml of trifluoroacetic acid was added to a solution of 6.2 g (20.7 mmol) of methyl (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate in 60 ml of CH2Cl2 and yes ? left to shake overnight. After checking the reaction mixture in LC-MS? was concentrated in the rotavapor until dryness. Quantitative yield

LC-MS: M <-> = 286

c) Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl

To a 5.9 g (20.7 mmol) solution of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropanoic acid in 230 ml of CH2Cl2 were added under stirring on an ice bath 6.16 g (24.8 mmol) of 2,2-bis (4-fluorophenyl) -1-methylethanol and then 7.9 g (41.4 mmol) of EDCI [N- (3-dimethylaminopropyl) -N ? -ethylcarbodiimide hydrochloride] and 3.03 g (24.8 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 3 hours. After checking with TLC (eluent hexane / ethyl acetate 6/4) the reaction mixture? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml), then with a 1M solution of HCl and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of an automatic Biotage separator, 10.0 g of the desired product were obtained. Yield 94%

LC-MS: M <+> = 516

EXAMPLE 2

Preparation of (2R) -2- (3-isoproxycarboxycarbetoxymethoxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl (compound n? 433)

To a 5.0 g (9.7 mmol) solution of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2.2-bis (4-fluorophenyl) - 1-methylethyl in 100 ml of acetone 2.7 g (19.4 mmol) of potassium carbonate and 3.55 g (14.5 mmol) of iodomethyl-isopropyl carbonate were added under stirring and the reaction mixture? been heated at 55 ° C for 2 hours. After checking in LC-MS yes? concentrated the reaction mixture to the rotavapor and yes? purified by chromatography on silica gel using Biotage automatic separator. 4.35 g of desired product were obtained. Yield 71%

LC-MS: M <+> = 632

EXAMPLE 3

Preparation of (2R) -2- (4-formylaminosalicylamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl (compound n? 425)

a) Preparation of methyl (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionate (compound no? 481)

3.4 g (18.3 mmol) of the S-methyl-L-methyl ester was added to a solution of 5.0 g (18.3 mmol) of O-benzyl-nitrosalicylic acid in 50 ml of CH2Cl2. cysteine hydrochloride, yes? the reaction mixture was cooled to 0 ° C and 3.64 g of HOBT (N-hydroxybenzotriazole) (23.8 mmol) was added. By dripping? the solution obtained by dissolving 4.56 g (23.8 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 4.82 g (47.6 mmol) of triethylamine in 100 ml of CH2Cl2, the temperature? been left to go back to environmental values and yes? kept under agitation for 24 hours. After checking the reaction mixture with LC-MS? been washed with water and the phases are separated. The aqueous phase is extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml) and with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. 7 g of crude were obtained which? was purified by chromatography on silica gel using an automatic Biotage separator. 5.54 g of the desired product were obtained. Yield 75%

LC-MS: M <+> = 404

b) Preparation of (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionic acid (compound n? 530)

55 ml of trifluoroacetic acid were added to a solution of 5.54 g (13.7 mmol) of methyl (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionate in 60 ml of CH2Cl2. yes ? left to shake overnight. After checking the reaction mixture in LC-MS? was concentrated in the rotavapor until dryness. Quantative yield

LC-MS: M <-> = 390

c) Preparation of (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl

To a solution of 5.34 g (13.7 mmol) of (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionic acid in 200 ml of CH2Cl2 were added under stirring on an ice bath 3.4 g (13.7 mmol) of 2,2-bis (4-fluorophenyl) -1-methylethanol and then 5.25 g (27.4 mmol) of EDCI [N- (3-dimethylaminopropyl) -N ? -ethylcarbodiimide hydrochloride] and 2.0 g (16.44 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 3 hours. After checking with TLC (eluent hexane / ethyl acetate 6/4) the reaction mixture? washed with water and the phases separated, the aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml), then with a 1M solution of HCl and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of an automatic Biotage separator, 7.6 g of the desired product were obtained. Yield 89%

LC-MS: M <+> = 620

d) Preparation of (2R) -2- (4-aminosalicylamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl

A 0.05 M solution in methanol of 7.6 g of the product obtained in the previous step? flowed into the H-Cube Thalesnano <? > through a 10% Pd / C cartridge with 15 bar of H2 at 60 ° C. The collection solution? was then concentrated to give the desired product. Quantitative yield

LC-MS: M <-> = 500

e) Preparation (2R) -2- (4-formylaminosalicylamido) -3-methylthio propanoate of (1S) -2,2-bis (4-fluorophenyl) -1-methylethyl

A suspension of 6.1 g (12.2 mmol) (2R) -2- (4-aminosalicylamido) -3-methylthiopropionate of (1S) -2.2-bis (4-fluorophenyl) -1-methylethyl in 25 ml of THF? 3.54 ml (94 mmol) of formic acid and 0.49 g (6.1 mmol) of zinc oxide was added and kept under stirring at a temperature of 70 ° C for 1 hour. After checking the reaction mixture in LC-MS? filtered to remove the metal and evaporated to dryness, azeotroping the excess formic acid with hexane. The raw co? obtained ? was purified by chromatography on silica gel by means of an automatic Biotage separator and 4.5 g of the desired product were obtained. Yield 70%

LC-MS: M <-> = 528

EXAMPLE 4

Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluoro-2-methylphenyl) -1-methylethyl (compound No. 438)

a) (2R) -2-tert-butoxycarbonylamino-3-methylthiopropionate of (1S) -2,2-bis (4-fluoro-2-methylphenyl) -1-methylethyl (compound No. 164)

5.88 g of (1S) -2 were added under stirring on an ice bath to a solution of 5.0 g (21.3 mmol) of t-butoxycarbonylamino-S-methyl-L-cysteine in 50 ml of CH2Cl2. , 2-bis (4-fluoro-2-methylphenyl) -1-methylethanol and then 8.16 g (21.3 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -Ethylcarbodiimide hydrochloride] (42, 6 mmol) and 2.6 g (21.3 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 8 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? washed with water and the phases separated, the aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30ml), and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of Biotage automatic separator, 8.6 g of desired product were obtained. Yield 82%

GC-MS: M <+> = 493

b) Preparation of (2R) -2-amino-3-methylthiopropionate of (1S) -2,2-bis (4-fluoro-2-methylphenyl) -1-methylethyl hydrochloride (compound n? 300)

To a solution of 8.6 g (17.4 mmol) of (2R) -2-tert-butoxycarbonylamino-3-methylthiopropionate of 2,2-bis (4-fluoro-2-methylphenyl) -1-methylethanol in 100 ml of CH2Cl2 were added under stirring at room temperature 21.7 ml (87 mmol) of a 4 N solution of HCl in dioxane. After 4 hours, the solvent? been evaporated and the acidity? residual? removed by stripping 3 times with ethyl ether. 6.5 g of the desired product were obtained.

Yield 95%

GC-MS: M <+> = 393

c) Preparation of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluoro-2-methylphenyl) -1-methylethyl (compound n? 436)

To a solution of 6.5 g (16.5 mmol) of (2R) -2-amino-3-methylthiopropionate hydrochloride of (1S) -2.2-bis (4-fluoro-2-methylphenyl) -1- methylethyl were added at 0 ° C and in sequence 6.39 g (49.6 mmol) of diisopropylethylamine and 8.58 g (16.5 mmol) of PyBOP [(1-Benzotriazolyloxy) -tripyrrolidinophosphonium hexafluorophosphate] in 150 ml of CH2Cl2 and finally 2.79 g (16.5 mmol) of 3-hydroxy-4-methoxypyridine-2-carboxylic acid. The reaction mixture? it was kept under stirring at this temperature for 2 hours, then allowed to rise to ambient values and under stirring for another 24 hours. After checking the reaction mixture with LC-MS? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml) and with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. 18 g of a crude were obtained which? been washed with ethyl ether and filtered to eliminate the by-products of the condensing agent. The ethereal phase? it was then concentrated in the rotavapor and purified by chromatography on silica gel using an automatic Biotage separator. 6.1 g of the desired product were obtained.

Yield 68%

LC-MS: M <+> = 544

EXAMPLE 5

Preparation of (2R) -2- (3-isobutyryloxymethoxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2,2-bis (4-fluoro-2-methylphenyl) -1-methylethyl (compound n? 439)

To a solution of 3.0 g (5.5 mmol) of (2R) -2- (3-hydroxy-4-methoxycolinamido) -3-methylthiopropionate of (1S) -2.2-bis (4-fluoro-2 -methylphenyl) -1-methylethyl in 60 ml of acetone were added under stirring 1.52 g (11.0 mmol) of potassium carbonate and 1.88 g (8.25 mmol) of iodomethyl isobutyrate and the reaction mixture? been heated at 55 ° C for 2 hours. After checking in LC-MS yes? concentrated the reaction mixture to the rotavapor and yes? purified by chromatography on silica gel using Biotage automatic separator. 2.48 g of desired product were obtained.

Yield 70%

LC-MS: M <+> = 644

EXAMPLE 6

Preparation of (2R) -2- (4-formylaminosalicylamido) -3-methylthiopropanoate of 6-methyl-2-heptyl (compound No. 330)

a) Preparation of (2R) -2 - [(9H-fluoren-9-yl) methoxy] carbonylamino-3-methylthiopropionate of 6-methyl-2-heptyl (compound No. 25)

To a solution of 5.0 g (14.0 mmol) of (R) -2 - [(9H- fluoren-9-yl) methoxy] carbonylamino-3-methylthiopropionic acid in 50 ml of CH2Cl2 were added under stirring on ice bath 1.8 g (14.0 mmol) of 6-methyl-2-heptanol alcohol and then 5.4 g (28 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 0.17 g (1.4 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 3 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? washed with water and the phases separated, the aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml), then with a 1M solution of HCl and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of Biotage automatic separator, 5.9 g of desired product were obtained. Yield 90%

GC-MS: M <+> = 469

b) Preparation of (2R) -2-amino-3-methylthiopropionate of 6-methyl-2-heptyl (compound No. 187)

To a solution of 5.9 g (12.5 mmol) of (2R) -2 - [(9H-fluoren-9-yl) methoxy] carbonylamino-3-methylthiopropionate of 6-methyl-2-heptyl in 126 ml of DMF 9.2 g of triethylamine (10 equiv) was added and the whole? was left under stirring for 2 hours. After checking in GC-MS yes? concentrated the reaction mixture under high vacuum to remove the pi? can the solvent and yes? quickly purified on a silica foot to eliminate the dibenzofulvene by-product. The product obtained? was used as it is for the subsequent reaction.

GC-MS: M <+> = 261

c) Preparation of (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropionate of 6-methyl-2-heptyl

To a solution of 3.8 g (14 mmol) of O-benzyl-nitrosalicylic acid in 50 ml of CH2Cl2? the aminoester obtained in the previous step was added, yes? the reaction mixture was cooled to 0 ° C and 3.2 g (21 mmol) of HOBT (N-hydroxybenzotriazole) was added. By dripping? The solution obtained by dissolving 4.03 g (21 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 2.13 g (21 mmol) of triethylamine in 100 ml of CH2Cl2 was then added. ? let the temperature rise to environmental values and yes? kept under agitation for 24 hours. After checking the reaction mixture with LC-MS? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml) and with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. 8 g of crude was obtained which? was purified by chromatography on silica gel using an automatic Biotage separator. 4.57 g of the desired product were obtained.

Yield 65%

LC-MS: M <+> = 502

d) Preparation of (2R) -2- (4-aminosalicylamido) -3-methylthiopropionate of 6-methyl-2-heptyl

A 0.05 M solution in methanol of 4.57 g (19.1 mmol) (2R) -2- (3-benzyloxy-4-nitrobenzamido) -3-methylthiopropanoate of 6-methyl-2-heptyl? flowed into the H-Cube Thalesnano <? > through a 10% Pd / C cartridge with 15 bar of H2 at 60 ° C. The collection solution? was then concentrated to give the desired product.

Quantitative yield

LC-MS: M <-> = 382

e) Preparation of (2R) -2- (4-formylaminosalicylamido) -3-methylthiopropionate of 6-methyl-2-heptyl

A suspension of 3.48 g (9.1 mmol) (2R) -2- (4-aminosalicylamido) -3-methylthiopropanoate of 6-methyl-2-heptyl in 15 ml of THF? 2.64 ml (70 mmol) of formic acid and 0.37 g (4.55 mmol) of zinc oxide were added and kept under stirring at a temperature of 70 ° C for 1 hour. After checking the reaction mixture in LC-MS? filtered to remove the metal and evaporated to dryness, azeotroping the excess formic acid with hexane. After purification by chromatography on silica gel by means of Biotage automatic separator 2.72 g of the desired product were obtained.

Yield 73%

LC-MS: M <-> = 410

EXAMPLE 7

Preparation of 6-methyl-2-heptyl (2R) -2-amino-3-benzylthio-propionate hydrochloride (compound No. 206)

a) Preparation of (2R) -2-t-butoxycarbonylamino-3-benzylthio propionate of 6-methyl-2-heptyl (compound No. 61)

To a solution of 5.9 g (19.0 mmol) of t-butoxycarbonyl-S-benzyl-L-cysteine in 50 ml of CH2Cl2 was added under stirring on an ice bath 2.46 g (19.0 mmol) of 6-methyl-2-heptanol and subsequently 7.2 g (38 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 0.23 g (1.9 mmol) of DMAP ( dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 3 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? washed with water and the phases separated, the aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml), then with a 1M solution of HCl and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of Biotage automatic separator, 8.1 g of desired product were obtained.

Quantitative yield

GC-MS: M <+> = 423

b) Preparation of 6-methyl-2-heptyl (2R) -2-amino-3-benzylthio-propionate

A solution of 8.5 g (19.0 mmol) of (2R) -2-t-butoxycarbonylamino-3-benzylthiopropionate of 6-methyl-2-heptyl in 100 ml of CH2Cl2 was added under stirring at room temperature 23 ml (95 mmol) of a 4 N solution of HCl in dioxane. After 4 hours, yes? controlled the reaction in LC-MS, the solvent? been evaporated and the acidity? residual? removed by stripping 3 times with ethyl ether. 6.5 g of the desired product were obtained.

Yield 95%

GC-MS: M <+> = 459

EXAMPLE 8

Preparation of (R) -2 - [(9H-fluoren-9-yl) methoxy] carbonylamino-3-methylthiopropionate of (S) -2-nonyl (compound No. 24)

To a solution of 5.0 g (14.0 mmol) of (R) -2 - [(9H- fluoren-9-yl) methoxy] carbonylamino-3-methylthiopropionic acid in 50 ml of CH2Cl2 were added under stirring on ice bath 2.02 g (14.0 mmol) of alcohol (S) -2nonanol and then 5.4 g (28 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 0 , 17 g (1.4 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 16 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30 ml), then with a 1M solution of HCl and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of an automatic Biotage separator, 6.5 g of the desired product were obtained. Yield 96%

GC-MS: M <+> = 483

EXAMPLE 9

a) Preparation of (2R) -2-t-butoxycarbonylamino-3-t-butylthio propionate of 2,2-bis (3-fluoro-4-methylphenyl) -1-methylethyl (compound No. 169)

4.98 g of 2.2 were added under stirring on an ice bath to a solution of 5.0 g (18 mmol) of N- (t-butoxycarbonylamino) -S-t-butyl-L-cysteine in 50 ml of CH2Cl2. -bis (3-fluoro-4-methylphenyl) -1-methylethanol (18 mmol) and then 6.9 g (36 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 2, 2 g (18 mmol) of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 8 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? washed with water and the phases separated, the aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30ml), and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of Biotage automatic separator, 8.2 g of desired product were obtained. Yield 85%

GC-MS: M <+> = 535

EXAMPLE 10

Preparation of (2R) -2-t-butoxycarbonylamino-4-methylthiobutyrate of 2,2-bis (4-fluorophenyl) -1-methylethyl (compound n? 160)

4.98 g (20 mmol) of 2.2 were added under stirring on an ice bath to a solution of 5.0 g (20 mmol) of N- (t-butoxycarbonylamino) -L-methionine in 50 ml of CH2Cl2. -bis (4-fluorophenyl) -1-methylethanol and subsequently 6.7 g (40 mmol) of EDCI [N- (3-dimethylaminopropyl) -N? -ethylcarbodiimide hydrochloride] and 2.44 g (20 mmol). of DMAP (dimethylaminopyridine). The solution cos? obtained? was stirred for 1 hour at about 0 ° C and at room temperature for 8 hours. After checking with TLC (eluent hexane / ethyl acetate 7/3) the reaction mixture? was washed with water and the phases were separated. The aqueous phase? was extracted with CH2Cl2 (3 x 15 ml) and the combined organic phases were washed with water (1 x 30ml), and finally with a saturated solution of NaCl (1 x 30 ml). These were then dried on Na2SO4, filtered and concentrated. After purification by chromatography on silica gel by means of Biotage automatic separator, 7.7 g of desired product were obtained.

Yield 81%

GC-MS: M <+> = 479

Operating similarly to what reported in the previous examples, the compounds 317, 330, 331, 339, 340, 345, 348, 350, 353, 355, 357, 359, 361, 412, 413, 414, 415, 427, were obtained. 428, 429, 430, 431, 432, 434, 435, 436, 437, 440, 441, 442, 443, 446, 447, 448, 449, 450, 451, 452, 453, 454, 455, 456, 457, 458, 459, 460 of general formula (Ic) shown in Table 11.

Table 11

Table 12 shows the results of the GC-MS analyzes conducted on compounds 317, 330, 331, 339, 340, 345, 348, 350, 353, 355, 357, 359, 361, 412, 413, 414, 415, 427, 428, 429, 430, 431, 432, 434, 435, 436, 437, 440, 441, 442, 443, 446, 447, 448, 449, 450, 451, 452, 453, 454, 455, 456, 457, 458, 459, 460 of general formula (Ic).

Table 12

EXAMPLE 11

Determination of the activity? fungicide of the compounds of Formula (I) against Zymoseptoria tritici on detached wheat leaf

The central part of the first true leaf of the wheat plants of the variety? Bologna at the phenological phase BBCH12? was peeled off and placed in Petri dishes with a sheet of bibulous paper soaked in 2ml of 5% kinetin. The molecules to be tested were homogeneously distributed on the leaf surface through a Potter tower (Burkard Manufacturing Co Ltd). The leaf surface? was infected using an inoculum prepared with two strains of Z. tritici grown in liquid at a conidia concentration equal to 3 * 10 <6> CFU / ml. The inoculum? was evenly distributed using the Potter tower. The Petri dishes were placed to incubate with light temperature cycles: 20 ° C / 16 hours of light and 14 ° C / 8 hours of dark. Estimating wheat septoria symptoms? was performed 21 days after the start of the test using an infection scale based on the leaf surface covered by pycnidia reported in the literature (Eyal et al., 1987; ISBN 968-612 7-06-2). AND? Finally, the simple efficacy was calculated according to the Abbott formula.

All compounds N? 426, 429, 433, 430 have highlighted activities? greater than 80% at the dose of 125mg / l.

Table 13 shows the results obtained with compounds N? 426, 429, 433 and 430.

Table 13

EXAMPLE 12

Determination of the activity? fungicide of the compounds of Formula (I) against Phakopsora pachyrhizi on detached soybean leaf

The ex vivo tests against Asian soybean rust (ASR) were carried out by taking from soybean plants of the variety? Zora to the phenological phase BBCH12 the first trifoliate and placing it in Petri dishes containing cotton soaked in 5% kinetin. Experimental products (IR) were applied to the leaf using a Potter tower. The leaf surface? was infected 24 hours after treatment using an inoculum consisting of P. pachyrhiz uredospores suspended in water at a concentration of 3 x 10 <5> spores / ml using DeVilbiss jet nebulizer. The Petri dishes were placed to incubate with light temperature cycles: 26 ° C / 16 hours of light and 23 ° C / 8 hours of dark. Estimating Soy ASR Symptoms? was performed 12 days after the start of the test using an infection scale based on the leaf surface covered by lesions reported in the literature (Godoy et al., 2006; Fitopatologia Brasileira, 31 (1), 63-68). ? Finally, the simple efficacy was calculated according to the Abbott formula.

All compounds N? 428, 425, 427, 426, 431, 430, 317 have highlighted activities? greater than? 80% at a dose of 30mg / l

Table 14 shows the results obtained by carrying out the test described with compounds N? 428, 425, 427, 426, 431, 430 and 317.

Table 14

EXAMPLE 13

Determination of the activity? preventive fungicide (3 days) of the compounds of Formula (I) against Phytophthora infestans on tomato.

Variety tomato plant leaves Marmande, grown in pots in a conditioned environment at 20? C and 70% of R.H. (Relative humidity), were treated by spraying both pages with the compound under examination dispersed in a hydroacetonic solution at 20% by volume of acetone.

After 1 day in a conditioned environment, the plants were sprayed on both leaves with an aqueous suspension of Phytophthora infestans conidia (50,000 spores per 1 ml of suspension for infection).

After spraying, the plants were kept in an environment saturated with humidity. and at 15? C for the mushroom incubation period (7 days).

After this period of time, the external symptoms of the pathogen appeared and? was therefore possible to proceed with the visual assessment of the intensity? of the infection.

The activity fungicide? was expressed as a percentage of reduction, compared to untreated seedlings (witness), of the leaf area affected by the disease (100 = complete efficacy; 0 = null efficacy).

All compounds N? 425, 330, 317 of general formula (I) have shown activity? greater than? 80% at the dose of 125 ppm.

Table 15 shows the results obtained by carrying out the test described with compounds N? 425, 330, 317 in comparison with the compound CR1 described in WO2016109257 (N? 145)

CR1: Florypicoxamid

Table 15

EXAMPLE 14

Determination of the activity? in vitro antifungal of the compounds of Formula (I) The molecules of general formula (I) have been tested to evaluate their activity? in vitro antifungal against the following fungi and straminipila: Alternaria alternata, Botrytis cinerea, Cercospora beticola, Colletotrichum lindemuthianum, Drechslera graminea, Fusarium graminearum, Magnaporthe oryzae, Monilia fructigena, Parastagonospora nodorum, Solimumytophiorum, Scythimum sc Ustilago maydis, Venturia inaequalis and Zymoseptoria tritici.

The pure culture isolates were maintained and stored at 4 ° C in a refrigerator on agar nutrient substrates suitable for each of them. For the execution of the activity tests? yes ? prepared the inoculum which, depending on the species of the pathogen, could be a suspension of conidia or a mycelial homogenate. For strains not readily sporulating in vitro, six to eight patches of mycelium were transferred to a grinding egg containing 6 ml of 2x Potato Dextrose Broth (PDB) and some metal balls. The suspension ? was homogenized with a Pulverisette 23 mini-mill (Fritsch GmbH).

For all in vitro sporulating strains the conidic suspension? was prepared starting from a culture grown on a suitable agar medium and in suitable conditions to stimulate sporulation. The conidia were collected in 1 ml of PDB2x and counted under the microscope with a counting chamber in order to obtain a final inoculum of 2 x 10 <4> conidia / ml.

The concentrations tested for each active molecule were 0.001, 0.01, 0.1, 1, 5 and 10 mg / l. For each molecule to be tested,? was prepared a stock solution in dimethyl sulfoxide (DMSO) at 80000 mg / l which? It was then serially diluted in sterile demineralized water to obtain the solutions to be tested at twice the concentrations of the final doses. Inhibition assays were performed in 96-well plates: 50µl of inoculum is mixed with 50µl of active molecule solution in each well using the Eppendorf Multipette serial dispenser. System E3. Four wells were used as replicates for each concentration of active ingredient. All strains of the pathogens were grown in untreated control wells containing 50 µl of fungal suspension and 50 µl of sterile demineralized water. The inoculated multiwell plates are incubated at 20 ° C for 72 hours (96 or 120 if necessary).

The sensitivity? to the molecules? was evaluated as growth inhibition of the fungus and measured in terms of absorbance just before and after the incubation period. The absorbance? been measured for each well by the Infinite spectrophotometer? F50 Absorbance Reader (Tecan Group Ltd) at 405 nm (for mycelial inocula) and at 492 nm (for conidial inocula).

For each strain, the percentage of growth inhibition (GIP) caused by each of the concentrations of the active ingredient? was calculated using the following formula:

where At72-120 and At0 are respectively the absorbances of the treated well and the untreated control measured at the end and at the beginning of the incubation period. GIP data were used to calculate EC50 which are, respectively, the actual concentrations (mg / l) of the active molecule that reduce mycelial growth by 50% compared to the untreated control.

In particular, all the compounds tested showed an EC50 lower than 2mg / l on Zymoseptoria tritici and Parastagonospora nodorum.

Table 16 shows the results obtained by carrying out the test described with compounds N? 428, 425, 427, 426, 331, 330, 340, 431, 339, 429, 430, 433 and 317. Table 16

All the products tested showed a high level of activity. antifungal against the majority of phytopathogenic fungal strains. As can be seen from Table 16, from an efficacy point of view, i.e. lower effective dose than 50% (EC50), many molecules tested reported effective doses lower than 1 mg / l.

The compounds pi? active, on at least one phytopathogenic fungus, were: N? 428, 425, 426, 427, 331, 330, 340, 431, 339 and 433.

In particular, relatively more fungal strains? sensitive to the compounds tested were M. oryzae, P. nodorum, Z. tritici.

In addition B. cinerea, B. sorokiniana, C. beticola, C. lindemuthianum and S. sclerotiorum were found to be fungal pathogens with low EC50 values for compounds N? 425, 426, 431, 429.

Taking into consideration the spectrum of action, the compounds N? 428, 425, 330, 317 reported a broad spectrum including not only fungal phytopathogens but also agents afferent to the Straminipila kingdom such as P. infestans and P. ultimum.

Claims (14)

Claims 1. Compounds of general formula (I): in which: - X represents a hydrogen atom or a C (O) R <5> group; - Y represents a hydrogen atom or a C (O) R <5> group or a Q group: - Z <1> and Z <2>, equal or different from each other, can represent a nitrogen atom, a N? O group, or a CRc group; - Rc represents a hydrogen atom, a halogen atom selected from fluorine, chlorine, bromine or iodine, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a nitro group, an amino group, a formylamine group; - M represents a halogen atom selected from fluorine, chlorine, bromine or iodine or a W <2> -R <6> group; - W <1> and W <2>, equal or different from each other, represent an oxygen atom or a sulfur atom; - R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>; a CH (CH3) COOR <7> group; - R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - Rd represents a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12cycloalkyl-C1-C12-alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxy group, a C3-C12 cycloalkoxyl group, an aryl group, a phenoxy group, a benzyloxy group, an aryl group -C1-C12-alkyl, or a heterocyclyl-C1-C12-alkyl group wherein the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>; - n represents a number between 0 and 2; - m represents a number between 1 and 2; - p represents a number between 1 and 4; - R <5> represents a C1-C12 alkoxy group, a benzyloxy group or a fluorenylmethoxy group; - R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group; - or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring; - R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic group, penta or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulphone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups; - or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups; - R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, whether or not benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above, said groups being optionally replaced with one or more? Rd groups, or R <4> represents a T group: T = in which: - Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups; - Rg represents a hydrogen atom, a hydroxyl, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2- group C12 haloalkenyl, a C3-C12 cycloalkyl group, a C1-C12 alkoxy group; provided that: - when Z <1> assumes the value of CH, Z <2> represents a CRc group where Rc takes on the meaning of a formylamino group or a nitro group, W <1> and W <2> are both oxygen, R < 6>? a hydrogen atom, n takes the value 0, m takes the value 1 or 2 and Ra and Rb both represent a hydrogen atom and, if R <1> takes the meaning of methyl, 4-methoxybenzyl or 4-methoxyphenyl carbonyl and R <4> takes on the meaning of hydrogen, R <2> and R <3>, different from each other, cannot take on the meanings of hydrogen, ethyl, heptyl and isobutyl; - when Z <1> takes the value of N, Z <2> represents a CRc group where Rc takes on the meaning of hydrogen, W <1> and W <2> are both oxygen, R <6>? a hydrogen atom, n takes the value 0, m takes the value 1 and Ra and Rb both represent a hydrogen atom and, if R <1> takes the meaning of methyl, 2-naphthylmethyl, 4-pyridylmethyl or 2-pyridylmethyl , R <2>, R <3>, R <4> cannot take on the meaning of hydrogen; and if R <1> takes on the meaning of 2-pyridylmethyl, R <2> and R <3> take on the meaning of hydrogen, R <4> cannot? take on the meaning of octyl. 2. Compounds according to claim 1, where: - X represents a hydrogen atom and Y represents a Q group; - Z <1> and Z <2>, equal or different from each other, represent a nitrogen atom or a CRc group; - Rc represents a hydrogen atom, a halogen atom, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a formylamine group; - M represents a group W <2> -R <6>; - W <1> and W <2>, equal or different from each other, represent an oxygen atom; - Rd represents a hydrogen atom, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkyl group C1-C12-alkyl, C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a C3 group -C12 cycloalkoxy, an aryl group, a phenoxy group, a benzyloxy group, an aryl-C1-C12-alkyl group, a penta- or hexaatomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>; - n represents a number between 0 and 2; - m represents a number between 1 and 2; - p represents a number between 1 and 2; - R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>, a group CH (CH3) COOR <7>; - R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group , an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group; - or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring; - R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups; - R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups, or R <4> represents a T group: in which: - Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups; - Rg represents a hydrogen atom, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 alkoxy group; - or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups. 3. Compounds according to any one of the preceding claims, where X represents a hydrogen atom and Y takes the meaning of Q, having general formula (Ic) (Ic) where Q, Ra, Rb, n, m, R <1>, R <2>, R <3> and R <4> take on the meanings reported below 4. Compounds according to claim 3, selected from the compounds of general formula (Ic) in which X represents a hydrogen atom and Q, Ra, Rb, n, m, R <1>, R <2>, R <3 > and R <4> take on the meanings reported below 5. Compounds of general formula (I?) in which - G represents a hydrogen atom or an atom of an alkali metal such as for example lithium, sodium, potassium or a group NR <8> R <9>, - R <8>, R <9>, Q, n, m , R <1>, Ra and Rb take on the meanings according to claim 1; provided that: - when Z <1> takes the value of N, Z <2> represents a CRc group, Rc takes on the meaning of hydrogen, W <1> and W <2> are both oxygen, R <6> takes the meaning of hydrogen , n takes on the value 0, m takes on the value of 1 or 2, Ra and Rb take on the meaning of hydrogen - when R <1> takes on the meaning of hydrogen, methyl, 4-pyridylimethyl, 2-pyridylmethyl, G does not take on the meaning of hydrogen. 6. Use of the compounds of formula (I?) According to claim 5, as intermediates in the preparation of the compounds of general formula (Ic). 7. Use of compounds of general formula (I): in which: - X represents a hydrogen atom or a C (O) R <5> group; - Y represents a hydrogen atom or a C (O) R <5> group or a Q group: - - Z <1> and Z <2>, equal or different from each other, can represent a nitrogen atom, a N? O group, or a CRc group; - Rc represents a hydrogen atom, a halogen atom selected from fluorine, chlorine, bromine or iodine, a C1-C12 alkoxy group, a C1-C12 thioalkoxyl group, a nitro group, an amino group, a formylamine group; - M represents a halogen atom selected from fluorine, chlorine, bromine or iodine or a W <2> -R <6> group; - W <1> and W <2>, equal or different from each other, represent an oxygen atom or a sulfur atom; - R <6> represents a hydrogen atom, a benzyl group also optionally substituted on the phenyl ring, a COR <7> group, a CH2OCOR <7> group, a CH (CH3) OCOR <7> group, a ( CH2) pOR <7>, a group (CH2) pSR <7>, a group CH2COOR <7>; a CH (CH3) COOR <7> group; - R <7> represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C1-C12 haloalkyl group, a C1-C12 alkoxy group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - Rd represents a nitro group, a cyano group, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C3-C12cycloalkyl-C1-C12-alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkenyl group, a C1-C12 alkoxy group, a C1-C12 thioalkoxy group, a C3-C12 cycloalkoxyl group, an aryl group, a phenoxy group, a benzyloxy group, an aryl group -C1-C12-alkyl, or a heterocyclyl-C1-C12-alkyl group wherein the heterocyclic group? as defined above; a group C (= W <1>) R <8>, a group C (= O) OR <8>, a group C (= O) NR <8> R <9>, a group S (= O) nR <8>, a group S (= O) 2NR <8> R <9>; - n represents a number between 0 and 2; - m represents a number between 1 and 2; - p represents a number between 1 and 4; - R <5> represents a C1-C12 alkoxy group, a benzyloxy group or a fluorenylmethoxy group; - R <8> and R <9>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group , a C3-C12 cycloalkyl group, a C3-C12 haloalkyl group, an aryl group, an aryl-C1-C12-alkyl group, said groups being optionally substituted with one or more? Rd groups equal or different from each other; - Ra and Rb equal or different from each other, represent a hydrogen atom, a C1-C12 alkyl group; - or Ra and Rb together with the carbon atom to which they are bonded form a C3-C12 cycloalkyl ring; - R <1>, R <2> and R <3>, the same or different from each other, represent a hydrogen atom, a C1-C12 alkyl group, a C1-C6 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a heterocyclic group, penta or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulphone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above; said groups being optionally replaced with one or more? Rd groups; - or R <2> and R <3> together with the carbon atom to which they are bound form a C3-C12 cycloalkyl group or a C3-C12 cycloalkenyl group, or a heterocyclic, penta- or hexa-atomic group, containing at least a heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide, said groups being optionally replaced with one or more? Rd groups; - R <4> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, a C3- C12 cycloalkenyl, a C3-C12 cycloalkyl-C1-C12-alkyl group, an aryl group, an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, whether or not benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group in which the heterocyclic group? as defined above, said groups being optionally replaced with one or more? Rd groups, or R <4> represents a T group: in which: - Re, Rf, the same or different, represent a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2-C12 haloalkenyl group, a C3-C12 cycloalkyl group, an aryl group , an aryl-C1-C12-alkyl group, a penta- or hexa-atomic, aromatic or non-aromatic heterocyclic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, optionally oxidized to sulfoxide or sulfone, nitrogen, optionally oxidized to N-oxide or a heterocyclyl-C1-C12-alkyl group, said groups being optionally substituted by one or more? Rd groups; - Rg represents a hydrogen atom, a hydroxyl, a halogen atom chosen from fluorine, chlorine, bromine or iodine, a C1-C12 alkyl group, a C1-C12 haloalkyl group, a C2-C12 alkenyl group, a C2- group C12 haloalkenyl, a C3-C12 cycloalkyl group, a C1-C12 alkoxy group; provided that: - when Z <1> assumes the value of CH, Z <2> represents a CRc group where Rc takes on the meaning of a formylamino group or a nitro group, W <1> and W <2> are both oxygen, R < 6>? a hydrogen atom, n takes the value 0, m takes the value 1 or 2 and Ra and Rb both represent a hydrogen atom and, if R <1> takes the meaning of methyl, 4-methoxybenzyl or 4-methoxyphenyl carbonyl and R <4> takes on the meaning of hydrogen, R <2> and R <3>, different from each other, cannot take on the meanings of hydrogen, ethyl, heptyl and isobutyl; for the control of fungi, bacteria and phytopathogenic viruses of agricultural crops, preferably for the control of fungi, more? preferably for the control of Plasmopara viticola on grapevine, Phytophtora infestans and Botrytis cinerea on tomato, Puccinia recondita, Erisiphae graminis, Helminthosporium teres, Septoria nodorum, Septoria tritici and Fusarium spp. on cereals, of Phakopsora pachyrhizi on soybeans, of Uromyces appendiculatus on bean, of Venturia inaequalis on apple tree, of Sphaerotheca fuliginea on cucumber, of Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, on tobacco. 8. Fungicidal compositions comprising one or more? compounds of formula (I) according to any one of claims 1 to 4, a solid or liquid solvent and / or diluent, optionally a surfactant. 9. Fungicidal compositions according to claim 8, comprising at least one compound of general formula (I) and at least one other fungicide other than those of general formula (I), plant growth regulators, antibiotics, herbicides, insecticides, fertilizers, biostimulants and / or their mixtures . 10. Fungicidal compositions according to claim 9, comprising at least one compound of general formula (I) and at least one other fungicide other than compounds of formula (I). 11. Fungicidal compositions according to claim 10, where one or more? compounds of formula (I) are combined with one or more? known fungicides belonging to the following classes: a) azoli scelti tra azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, simeconazole , tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, triflumizole, triticonazole; b) amines inhibiting ergosterol biosynthesis selected from aldimorph, dodemorph, fenpropimorph, fenpropidin, spiroxamine, tridemorph; c) succinatodehydrogenase inhibitors (SDHI) chosen from benzovindiflupyr, bixafen, boscalid, carboxin, fluindapyr, fluopyram, flutolanil, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, oxycarboxin, penflufen, sedifluzamide, thaxiopyr. d) strobilurins selected from azoxystrobin, coumoxystrobin, dimoxystrobin, enoxastrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxostrobin, trifloxystrobin; e) specific antioids selected from cyflufenamid, flutianil, metrafenone, proquinazid, pyriofenone, quinoxyfen; f) anilinopyrimidines selected from pyrimethanil, mepanipyrim, cyprodinil; g) benzimidazoles and analogues selected from carbendazim, benomyl, thiabendazole, thiophanate-methyl; h) dicarboximides selected from iprodione, procymidone; i) phthalimides selected from captafol, captan, folpet; l) inducers of SAR (acquired systemic resistance) selected from acibenzolar, probenazole, isothianil, thiadinil; m) phenylpyrroles selected from phenpiclonyl, fludioxonil; n) acylalanines selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M; o) other specific antiperonosporics chosen from among ametoctradin, amisulbrom, benthiavalicarb, cyazofamid, cymoxanil, dimethomorph, ethaboxam, famoxadone, fenamidone, flumetover, flumorph, fluopicolide, iprovalicarb, mandipropamid, oxathiaxalamide, valamide. p) dithiocarbamates selected from maneb, mancozeb, propineb, zineb, metiram; q) phosphorous acid and its inorganic or organic salts, fosetyl-aluminum; r) cupric compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulphate, copper salicylate; s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, silthiofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine, tolclofos-methyl. 12. Fungicidal compositions according to any one of claims 8-11, where the compound of formula (I)? compound 330, 426 or 433, said compositions being chosen from: C1: compound 433 tetraconazole; C2: compound 433 tebuconazole; C3: compound 433 epoxyconazole; C4: compound 433 prothioconazole; C5: compound 433 diphenoconazole; C6: compound 433 penconazole; C7: compound 433 prochloraz; C8: compound 433 fenpropimorph; C9: compound 433 spiroxamine; C10: compound 433 bixafen; C11: compound 433 boscalid; C12: composed 433 carboxin; C13: compound 433 fluopyram; C14: compound 433 fluxapyroxad; C15: compound 433 isopyrazam; C16: compound 433 penthiopyrad; C17: compound 433 sedaxane; C18: compound 433 azoxystrobin; C19: compound 433 dimoxystrobin; C20: compound 433 fluoxastrobin; C21: compound 433 kresoxim-methyl; C22 compound 433 picoxystrobin; C23: compound 433 pyraclostrobin; C24: compound 433 trifloxystrobin; C25: compound 433 metrafenone; C26: compound 433 proquinazid; C27: compound 433 mepanipyrim; C28: compound 433 cyprodinil; C29: compound 433 iprodione; C30: compound 433 procymidone; C31: compound 433 carbendazim; C32: compound 433 thiophanate-methyl; C33: compound 433 fluindapyr; C34: compound 433 benalaxyl-M; C35: compound 433 fenpyrazamine; C36: compound 433 fluazinam; C37: compound 433 tolclofos-methyl; C38: compound 433 mandipropamid; C39: compound 433 copper oxychloride; C40: compound 433 copper salicylate; C41: compound 433 chlorothalonyl; C42: compound 433 cimoxanil; C43: compound 433 dimetomorph; C44: compound 433 oxathiopiproline; C45: compound 426 fluopicolide; C46: compound 426 tetraconazole; C47: compound 426 tebuconazole; C48: compound 426 epoxyconazole; C49: compound 426 prothioconazole; C50: compound 426 diphenoconazole; C51: compound 426 penconazole; C52: compound 426 prochloraz; C53: compound 426 fenpropimorph; C54: compound 426 spiroxamine; C55: compound 426 bixafen; C56: compound 426 boscalid; C57: composed 426 carboxin; C58: compound 426 fluopyram; C59: compound 426 fluxapyroxad; C60: compound 426 isopyrazam; C61: compound 426 penthiopyrad; C62: compound 426 sedaxane; C63: compound 426 azoxystrobin; C64: compound 426 dimoxystrobin; C65: compound 426 fluoxastrobin; C66: compound 426 kresoxim-methyl; C67: compound 426 picoxystrobin; C68: compound 426 pyraclostrobin; C69: compound 426 trifloxystrobin; C70: compound 426 metrafenone; C71: compound 426 proquinazid; C72: compound 426 mepanipyrim; C73: compound 426 cyprodinil; C74: compound 426 iprodione; C75: compound 426 procymidone; C76: compound 426 carbendazim; C77: compound 426 thiophanate-methyl; C78: compound 426 fluindapyr; C79: compound 426 benalaxyl-M; C80: compound 426 fenpyrazamine; C81: compound 426 fluazinam; C82: compound 426 tolclofos-methyl; C83: compound 426 mandipropamid; C84: compound 426 copper oxychloride; C85: compound 426 copper salicylate; C86: compound 426 chlorothalonyl; C87: compound 426 cimoxanil; C88: compound 426 dimetomorph; C89: compound 426+ oxathiopiproline; C90: compound 426 fluopicolide; C91: compound 330 tetraconazole; C92: compound 330 tebuconazole; C93: compound 330 epoxyconazole; C94: compound 330 prothioconazole; C95: compound 330 diphenoconazole; C96: compound 330 penconazole; C97: compound 330 prochloraz; C98: compound 330 fenpropimorph; C99: compound 330 spiroxamine; C100: compound 330 bixafen; C101: compound 330 boscalid; C102: composed of 330 carboxins; C103: compound 330 fluopyram; C104: compound 330 fluxapyroxad; C105: compound 330 isopyrazam; C106: compound 330 penthiopyrad; C107: compound 330+ sedaxane; C108: compound 330 azoxystrobin; C109: compound 330 dimoxystrobin; C110: compound 330 fluoxastrobin; C111: compound 330 kresoxim-methyl; C112: compound 330 picoxystrobin; C113: compound 330 pyraclostrobin; C114: compound 330 trifloxystrobin; C115: compound 330 metrafenone; C116: compound 330 proquinazid; C117: compound 330 mepanipyrim; C118: compound 330 cyprodinil; C119: compound 330 iprodione; C120: compound 330 procymidone; C121: compound 330 carbendazim; C122: compound 330 thiophanate-methyl; C123: compound 330 fluindapyr; C124: compound 330 benalaxyl-M; C125: compound 330 fenpyrazamine; C125: compound 330 fluazinam; C126: compound 330 tolclofos-methyl; C127: compound 330 mandipropamid; C128: compound 330 copper oxychloride; C129: compound 330 copper salicylate; C130: compound 330 chlorothalonyl; C131: compound 330 cymoxanil; C132: compound 330 dimetomorph; C133: compound 330 oxathiapiproline; C134: compound 330 fluopicolide; C135: compound 330 pyrachlostrobin; C136: compound 330 zoxamide; C137: compound 330 ametoctradin; C138: compound 330 metiram; C139: compound 330 potassium phosphite; C140: compound 433+ tetraconazole azoxystrobin, C141: compound 433 pyraclostrobin tetraconazole; C142: compound 433 epoxyconazole azoxystrobin; C143: compound 433 pyraclostrobin epoxyconazole; C144: compound 433 azoxystrobin fluindapyr; C145: compound 433 pyraclostrobin fluindapyr; C146: compound 433 fosetyl-aluminum copper oxychloride; C147: compound 433 fosetyl-aluminum copper salicylate; C148: compound 433 fluindapyr + tetraconazole; C149: compound 330 tetraconazole azoxystrobin; C150: compound 330 pyraclostrobin tetraconazole; C151: compound 330 azoxystrobin fluindapyr; C152: compound 330 fluindapyr tetraconazole 13. Use of the fungicidal compositions according to any one of claims 8 to 12, for the control of phytopathogenic fungi of agricultural crops. 14. Method for the control of phytopathogenic fungi in agricultural crops, which consists in applying on any part of the plants to be protected or on the soil effective and non-phytotoxic doses of compounds of formula (I) according to any one of claims 1 to 6 , or of fungicidal compositions according to any one of claims 8 to 12.