IT201800009385A1 - Caffeine derivatives with nematicide activity, their agronomic compositions and relative use - Google Patents

Description

DESCRIPTION

attached to a patent application for an INDUSTRIAL INVENTION PATENT entitled:

"Caffeine derivatives with nematicide activity, their agronomic compositions and relative use"

The present invention relates to caffeine derivatives of general formula (I)

The present invention also relates to agronomic compositions containing said compounds of formula (I) and their use for the control of nematodes in agricultural crops.

STATE OF THE ART

Plant parasitic nematodes pose a serious threat to horticultural crops. In fact, nematodes, small worm-like organisms present in the soil, are able to settle in the roots of plants and live at their expense, thus slowing down their development and growth due to insufficient supply of nutrients.

Various techniques are currently used in the fight against nematodes, among which we can mention soil solarization, treatment with biological and / or chemical products or the use of nematode-resistant cultivars.

As for the chemical fight, the compounds belonging to the class of carbamates and organophosphorus, mostly used as chemical nematicides, are lately limited or even abandoned due to problems of toxicity or environmental impact.

The need is therefore felt to identify new molecules with reduced environmental impact capable of effectively containing the attack of nematodes on crops.

The Italian patent IT1368843 reports that caffeine, a molecule of natural origin, can be validly used against some species of nematodes that affect horticultural crops. However, the Applicant has verified that this compound is unsatisfactory in terms of nematicide activity, as it is unable to effectively contain the attack of the parasite and reduce the formation of galls on the root system of the plant.

Furthermore, caffeine is phytotoxic towards important agricultural crops, showing a significant necrosis of the leaves and the stem, at the doses that allow to obtain a good nematicide activity.

To the knowledge of the Applicant, caffeine derivatives substituted in position 8 with nematicide activity are not known in the literature.

DESCRIPTION

The Applicant has now surprisingly found that, by introducing suitable substituents in position 8 of the caffeine ring, products with considerable nematicidal activity against numerous plant parasitic nematodes are obtained.

At the same time, these products exhibit, at effective doses, a low or zero phytotoxicity for crops of agricultural interest and can therefore be used as nematocides.

A first object of the present invention therefore constitutes a compound of formula (I):

in which:

- n represents an integer between 0 and 3;

- A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, -C (= Y) -NR1-, - C (= Y) -NR1-S (O) 2-;

- Y represents an oxygen or sulfur atom;

- R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a group C (= Y) R2, a group C (= O) OR2, a group C (= O) NR2R3, a group S (= O) rR2, a group S (= O) 2NR2R3;

- R2 and R3, the same or different from each other, represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group cycloalkyl, a C3-C8 haloalkyl group, an aryl group, a benzyl group;

- r represents an integer between 0 and 2;

- E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group -cycloalkyl, a C3-C8 haloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic, penta or hexaatomic, aromatic or non-aromatic group, including benzocondensed or etherobycyclic , containing at least one heteroatom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above;

- m represents an integer between 1 and 6;

- X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylene, heterocyclic or heterocyclylalkylene group can optionally be replaced by one or more Q groups selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C4-C9 -cycloalkylalkyl, C3-C6- haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxyl, C1-C6-thioalkoxyl, C1-C6-thioaloalkoxyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfonyl, , C3-C6-cycloalkoxycarbonyl, amino, N-C1-C6-alkylamino, N, N-C2-C12-dialkylamino, N-C1-C6-alkoxycarbonylamino N-C3-C6-cycloalkylamino, N, N-C6-C12- dicycloalkylamino, N-C3-C6-cycloalkoxycarbonylamino, C1-C6-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, C1-C6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta or hexatomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur , nitrogen, optionally oxidized to N-oxide, an optionally substituted (C1-C6) -alkyl-heterocyclic group, penta- or hexa-atomic also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen, possibly oxidized to N-oxide,

provided that when A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, then E represents the group - (CH2 ) m-CX = CF2; And

with the exception of compounds of general formula (I) in which:

- n = 0, A = -CO-NH-, E = 3-chloro phenyl;

- n = 1, A = -CO-N (Et) -, E = Et;

- n = 1, A = -CO-NH-, E = benzyl;

- n = 1, A = -CO-NH-, E represents a group of formula (W)

in which

each R4 independently represents halogen, a hydroxyl group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C2-C6 alkenoxyl group, a C1-C6 group haloalkyl, a -N (R6) 2 group, a -CON (R6) 2 group, a -CO2H group, a cyano group or a nitro group;

p represents an integer between 0 and 3;

R5 represents a halogen, a hydroxyl group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C2-C6 alkenoxyl group, a C1-C6 haloalkyl group , a -N (R6) 2 group, a -CON (R6) 2 group, a -CO2H group, a cyano group or a nitro group, or is absent; And

R6 independently represents H or a C1-C4 alkyl group.

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

Examples of halogen are: fluorine, chlorine, bromine, iodine.

Examples of C1-C6 alkyl, 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-C6 haloalkyl 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 linear or branched C2-C6 alkenyl are vinyl, allyl, 3-butenyl, 4-pentyl.

Examples of C2-C6 haloalkenyl are 1- (1,1,2-trifluoro) -butenyl, 1- (2,2-difluoro) -butenyl.

Examples of linear or branched C1-C6 alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 3-methylbutoxy, hexyloxy, 3,3- dimethylbutoxy.

Examples of C1-C6 haloalkoxy are fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetra-fluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy , 4,4,4-trichlorobutoxy, 4,4-difluoropentoxy, 5,5-difluorohexyloxy.

Examples of C3-C8 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

Examples of C3-C8 haloalkyl are 2,2-dichloro-cyclopropyl, 2,2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl, 3,3-difluorocyclopentyl, 2-fluorocyclohexyl.

Examples of C4-C9 cycloalkylalkyls are cyclopropylmethyl, 2-cyclopentylethyl, 2-cyclohexylpropyl.

Examples of aryl are phenyl, 2-chloro-5-methoxy-phenyl, 2-chloro-6-fluoro-phenyl, 2-chloro-phenyl, 2,4,6-trifluoro-phenyl.

Examples of C7-C14 arylalkylene are phenylethylene, benzyl, 3-chloro-1-benzyl.

Examples of heterocycles, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic are: pyridine, pyridine N-oxide, pyrimidine, pyridazine, pyrazine, furan, thiophene, pyrrole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole , thiadiazole, pyrazole, imidazole, triazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyridine, triazolopyrazole, [triazolopyridine, [triazolopyrazole], [triazolopyrazole], [triazolopyrazole], [triazolazole, [triazolopyridine] 3,2-b] - thiazole, morpholine.

Examples of heterocyclylalkylene are: 2- (2-pyridyl) -1-ethylene, 2- [3-chloro-5- (trifluoromethyl) -2-pyridyl] -1-ethylene, 2-pyridyl-methylene, 3-pyridyl-methylene .

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

a) any geometric isomers of the compounds of general formula (I)

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

c) any hydrated, solvated and polymorphic forms of the compounds of formula (I);

d) all possible optical isomers and their mixtures, including racemic mixtures of the compounds of formula (I). Preferred compounds of formula (I-A) are the compounds of general formula (I) in which:

- n is an integer between 0 and 2;

- R1 represents a hydrogen atom or a C1-C6 alkyl group;

- E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C3-C8-cycloalkyl group, an aryl group, a C7-C14 arylalkylene group, a naphthyl group or a heterocyclic group , penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined herein;

- m represents an integer between 1 and 5,

under the conditions and with the exceptions indicated for the general formula (I).

Preferred compounds of formula (I-B) are the compounds of general formula (I) in which:

- n is an integer chosen between 0 and 1;

- A represents a group chosen from: - (SO) -, -S (O) 2-, -C (= O) -O-, -C (= O) -NR1-, -C (= O) -NR1 -S (O) 2-;

- R1 represents a hydrogen atom or a C1-C6 alkyl group;

- E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C3-C8-cycloalkyl group, an aryl group, a C7-C14 arylalkylene group, a naphthyl group or a heterocyclic group , penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined herein; And

- m represents an integer between 1 and 5,

under the conditions and with the exceptions indicated for the general formula (I).

Preferred compounds of formula (I-C) are the compounds of general formula (I) in which:

- n is an integer between 0 and 1;

- A represents a group selected from: -S (O) -, -S (O) 2-, -C (= O) -O-;

- R1 represents a hydrogen atom or a C1-C6 alkyl group;

- E represents a group - (CH2) m-CX = CF2; And

- m represents an integer between 1 and 5.

Preferred compounds of formula (I-D) are the compounds of general formula (I) in which:

- E represents a group - (CH2) m-CX = CF2; And

- n is chosen between 0 and 1.

Preferred compounds of formula (I-E) are the compounds of general formula (I) in which:

- E represents a group selected from an aryl group, a naphthyl group, a C7-C14 arylalkylene group or a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen , sulfur and nitrogen, or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above;

- n is chosen between 0 and 1,

under the conditions and with the exceptions indicated for the general formula (I).

Preferred compounds of formula (I-F) are the compounds of general formula (I) in which:

- A represents a group selected from: -C (= Y) -NR1- and -C (= Y) -NR1-S (O) 2-;

- E represents a group selected from an aryl group, a naphthyl group, or a C7-C14 arylalkylene group;

- n is chosen between 0 and 1,

under the conditions and with the exceptions indicated for the general formula (I).

Preferred compounds of formula (I-G) are the compounds of general formula (I) in which:

- A represents a group selected from: -C (= Y) -NR1- and -C (= Y) -NR1-S (O) 2-;

- E represents a group selected from a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen, or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above;

- n is chosen between 0 and 1,

under the conditions and with the exceptions indicated for the general formula (I).

Preferred compounds of formula (I-H) are the compounds of general formula (I) in which:

- E represents a group selected from an aryl group, a naphthyl group, a C7-C14 arylalkylene group or a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen , sulfur, nitrogen, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above; And

wherein said aryl, naphthyl, arylalkylene, heterocyclic or heterocyclylalkylene group as defined herein, is replaced by one or more Q groups selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-haloalkyl, C1-C6 -alkoxy, C1-C6-haloalkoxyl, C1-C6-thioalkoxyl or C1-C6-thioaloalkoxyl.

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

- E represents a group selected from an aryl group, a naphthyl group, a C7-C14 arylalkylene group or a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen , sulfur, nitrogen, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above; And

wherein said aryl, naphthyl, arylalkylene, heterocyclic or heterocyclylalkylene group as defined above, is replaced by one or more Q groups selected from fluorine, chlorine, bromine, C1-C3-fluoro-, chloro- or bromoalkyl, C3-C6- fluoro-, chloro- or bromo-cycloalkyl, C1-C3-alkoxy, C1-C3-fluoro-, chloro- or bromoalkoxyl.

Specific examples of compounds of general formula (I), interesting for their nematicide activity, are the compounds in which n, A and E have the meanings shown in table 1:

Table 1

Particularly preferred are the compounds of general formula (I) in which n, A and E take on the meanings shown in table 2:

Table 2

Even more preferred are the compounds of general formula (I) in which n, A and E take on the meanings shown in table 3:

Table 3

The compounds of general formula (I) can be prepared according to the procedures illustrated herein. A = -S (O) -, -S (O) 2-In particular, compounds of general formula (I), with A representing a -S (O) - group (compound of general formula (Ia)) or a -S (O) 2- group (compound of general formula (Ib)) can be prepared from the respective thioethers of general formula (Ic) by oxidation reactions as indicated in scheme 1.

Scheme 1

The reaction conditions, as reported in WO 02/062770 and WO 2017/002100, provide for the use of an oxidizing agent in a suitable solvent. Oxidizing agents that can be used are perbenzoic acids such as 4-chloroperbenzoic acid, peracetic acid or inorganic peroxides, such as hydrogen peroxide, hydrogen peroxide adduct-urea and other oxidizing agents such as potassium permanganate, sodium or potassium periodate peroxymonosulfate. The solvents used are preferably halogenated hydrocarbons, such as dichloromethane, chloroform or dichloroethane, ethers such as dioxane or tetrahydrofuran, amides such as N, N-dimethylformamide or N-methylpyrrolidone, alcohols such as methanol, ethanol, propanol, isopropanol, ketones such as for example acetone 2 -butanone, organic acids such as acetic acid and water or mixtures of these.

The reaction is carried out at a temperature between 0 ° C and the boiling temperature of the solvent, for a time between 1 and 72 hours.

A = -S-According to a first embodiment, the compounds of general formula (I), in which A represents a sulfur atom (compound of formula (Ic)), can be prepared according to scheme 2, by reaction of the derivative thiol of formula (II) and the compounds of formula (III), as reported in WO 03/037878 and WO 2017/002100.

Scheme 2

The reaction provides for a substitution between the compound of formula (II) and the compound of formula (III), where T represents a leaving group, such as for example a halogen atom selected from Cl, Br or I, or a p-toluenesulfonate group , trifluoromethanesulfonate or methanesulfonate, in the presence of an organic or inorganic base such as, for example, triethylamine, pyridine, diiopropylethylamine, dimethylaminopyridine, sodium acetate, potassium or sodium bicarbonate, potassium or sodium carbonate, sodium or potassium or lithium hydroxide , in a suitable solvent such as, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform or amides such as N, N-dimethylformamide or N-methylpyrrolidone, ethers such as dioxane or tetrahydrofuran, nitriles such as acetonitrile, ketones such as acetone or 2-butanone .

This reaction is carried out at a temperature ranging from 0 ° C to the boiling temperature of the solvent, for a time ranging from 1 to 96 hours.

The compounds of formula (II), for n equal to zero, can be obtained as reported in Yan et al., Chemical Communications 2017 vol. 53 (26) p.3637 - 3640.

For n assuming non-zero values, the compounds of formula (II) can be obtained according to scheme 3.

Screen 3

The alcoholic intermediate (IV) can be transformed into the compound of structure (V) bearing a leaving group T, such as for example a halogen atom selected from Cl, Br or I, or a p-toluenesulfonate, trifluoromethanesulfonate or methanesulfonate group, according to well-known methods in organic chemistry, as reported in Theodora W. Green, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS”, Third Edition.

The compound of general formula (V) can in turn be transformed directly into the intermediate (II) by reaction with alkali metal hydrosulfide such as sodium, potassium or lithium, by means of bases such as potassium or sodium carbonate, in solvents such as N , N-dimethylformamide or N-methylpyrrolidone, dioxane or tetrahydrofuran, acetonitrile, at a temperature between 0 ° C and the respective boiling temperatures.

Alternatively, the compounds of formula (II) can be obtained by reaction of compounds of formula (V) with thiourea to give the respective thiouronium salt of formula (VI), in solvents such as alcohols, such as for example ethanol, methanol, isopropanol, propanol, or water or mixtures thereof, at a temperature between 0 ° C and the boiling temperature of the solvent. The subsequent in situ hydrolysis is carried out in solvents such as alcohols, water or their mixtures, tetrahydrofuran, dioxane, toluene, in the presence or absence of inorganic bases such as sodium or potassium carbonate and bicarbonate, sodium or potassium or lithium hydroxide, at room temperature.

According to a further synthesis method, the compounds of formula (II) can be prepared by reaction between the compounds of formula (V) and the sodium or potassium salts of thioacetic acid, to obtain the respective thioesters of formula (VII), in solvents such as N, N-dimethylformamide or N-methylpyrrolidone, dioxane or tetrahydrofuran, acetonitrile, at a temperature between 0 ° C and the respective boiling temperatures. The subsequent hydrolysis is carried out in solvents such as alcohols, water or their mixtures, tetrahydrofuran, dioxane, toluene, in the presence or absence of inorganic bases such as sodium or potassium carbonate and bicarbonate, sodium or potassium or lithium hydroxide, at room temperature.

The above compounds of formula (II) can also be obtained starting from the corresponding thioesters of formula (VII) by transacetylation reaction with reagents such as sodium or potassium methylate or ethylate, in solvents such as methanol or ethanol, at room temperature.

The compounds of formula (IV) can in turn be prepared according to procedures described in Yang, Shyh-Ming et al., Journal of Medicinal Chemistry, 2015, vol. 58 (15), p.5967 - 5978 and in Mueller et al. ., Archiv der Pharmazie 1997 vol. 330 (6) p.181 - 189.

The compounds of formula (III), when T represents a halogen atom, are commercially available. Alternatively, when T represents a p-toluenesulfonate, trifluoromethanesulfonate or methanesulfonate group, said compounds can be obtained starting from the respective alcohols, as described in Theodora W. Green, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS”, Third Edition.

According to a further embodiment, the compounds of formula (Ic) can be prepared by treating the compounds of formula (V) with compounds of formula (VIII), as indicated in scheme 4. Scheme 4

The reaction involves the use of an organic or inorganic base such as, for example, triethylamine, pyridine, diisopropylethylamine, dimethylaminopyridine, sodium acetate, potassium or sodium bicarbonate, potassium or sodium carbonate, sodium or potassium or lithium hydroxide, in a suitable solvent such as, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform or amides such as N, N-dimethylformamide or N-methylpyrrolidone, ethers such as dioxane or tetrahydrofuran, nitriles such as acetonitrile, ketones such as acetone or 2-butanone, at a temperature between 0 ° C and the boiling temperature of the solvent, for a time between 1 and 96 hours.

A = -C (O) O-According to one embodiment, compounds of general formula (I), wherein A represents a -C (O) O- group (compound of general formula (Id)), can be prepared from the corresponding acid of general formula (IX) by esterification reaction with a suitable alcohol of general formula (X) as reported in the reaction scheme 5, according to well-known methods in organic chemistry.

Sc hema 5

The reaction conditions provide for the use of a condenser such as N, N-dicyclohexylcarbodimide, in the presence or absence of an amine such as N, N-dimethylaminopyridine, in an appropriate solvent such as dichloromethane, chloroform, tetrahydrofuran or dioxane at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours. Alternatively, the compounds of formula (Id) can be obtained by reaction of the acid of formula (IX) with the alcohol of formula (X) in the presence of an acid catalysis using for example hydrochloric acid or sulfuric acid as described in R.C. Larock “Comprehensive Organic Transformations” or for example in F. T. Schevenels, M. Shen. A. Scott “J. American Chemical Society ", 2017, vol. 139 pages 6329-6337. According to a further embodiment, the above compounds of formula (Id) can be obtained by Mitsunobu reaction between the acid of formula (IX) and the alcohol of general formula (X) in the presence of triphenylphosphine and diethylazodicarboxylate in a solvent such as for example tetrahydrofuran, diethyl ether or dioxane at a temperature comprised between room temperature and the reflux temperature of the solvent, as described for example in US 7601849.

According to another embodiment, the compounds of formula (Id) can be obtained by activating the carboxylic acid of formula (IX) or via acyl chloride or via mixed anhydride to give the compound of formula (XI) in which V represents a atom of chlorine or an OCORW residue, with RW assuming the meaning of C1-C4 alkyl, and subsequent addition of the appropriate alcohol of general formula (X), according to reaction scheme 6.

Screen 6

The reaction is carried out by reacting a compound of formula (XI) obtained from the compound of general formula (IX) by methods known in literature with an alcohol of general formula (X) in the presence of a base such as triethylamine, N-methyl-morpholine or pyridine in a suitable solvent such as methylene chloride, chloroform or tetrahydrofuran at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours as widely described in R.C. Larock “Comprehensive Organic Transformations” or for example in US 2003/109563 or in US 2004/198702.

According to a further embodiment, the compounds of general formula (Id) can be obtained from a suitable salt of formula (XII) of the carboxylic acid of general formula (IX) of an alkali metal, such as sodium, lithium or potassium, or ammonium, such as trimethylammonium or triethylammonium, in the presence of a derivative of formula (III) where T represents a leaving group such as a halogen atom, selected from chlorine, bromine or iodine or a trifluoromethanesulfonate or p-toluenesulfonate group, or methanesulfonate according to reaction scheme 7.

Scheme 7

The reaction involves salification of the carboxylic acid with a base such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride or potassium t-butylate, triethylamine, diisopropylamine, in a solvent such as tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, toluene or acetone, acetonitrile and subsequent addition of a compound of formula (III) at a temperature between room temperature and the reflux temperature of the chosen solvent , as for example described in US 5519015.

The compounds of formula (IX) can be synthesized by hydrolysis of the respective esters of formula (XIII) with Rw taking on the meanings seen above, in solvents such as water or tetrahydrofuran, dioxane or mixtures thereof, in the presence or absence of inorganic bases such as sodium or potassium carbonate and bicarbonate, sodium, potassium or lithium hydroxide, at room temperature, according to scheme 8.

Scheme 8

The esters having formula (XIII) can be prepared according to procedures reported in Ryu et al., Angewandte Chemie - International Edition, 2012, vol. 51 (15), p. 3677 - 3681 or in Zilber et al., Tetrahedron, 1989, vol. 45 (3), p.721 - 732.

A = -C (O) -NH-S (O) 2-I compounds of general formula (I), with A representing the -C (Y) -NR1-S (O) 2- group, in which Y which represents an oxygen atom and R1 an H atom (compounds of general formula (Ie)), can be prepared by reaction of the respective carboxylic acids of formula (IX) with sulfonamides of formula (XIV), as illustrated in diagram 9.

Scheme 9

The reaction conditions provide for the use of a condensing agent, in the presence or absence of an amine such as N, N-dimethylaminopyridine in solvents such as alcohols, ethers, esters, amides or halogenated hydrocarbons or mixtures thereof.

Condensing agents are for example 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide or its salts, N, N-dicyclohexylcarbodimide, N, N-diisopropylcarbodimide or 1,1'-carbonyldiimidazole.

The reaction is carried out at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours.

The compounds of formula (Ie) can also be prepared by activating carboxylic acid, via acyl chloride or via mixed anhydride, as illustrated in diagram 10.

Scheme 10

The reaction is carried out by reacting a compound of formula (XI), where V represents a chlorine atom or a residue -OC (O) Rw, with Rw taking on the meaning of C1-C4 alkyl, obtained from the compound of general formula ( IX) by methods known in literature, with the sulfonamide of formula (XIV) in the presence of a base such as triethylamine, N-methyl-morpholine or pyridine in a suitable solvent such as methylene chloride, chloroform or tetrahydrofuran at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours as widely described in R.C. Larock “Comprehensive Organic Transformations” or for example in Pan et al., European Journal of Medicinal Chemistry, 2012, vol. 50, p.18 or in WO2010 / 129500.

A = -C (O) -NR1-S (O) 2-I compounds of general formula (I), with A representing the group -C (Y) -NR1-S (O) 2-, where Y represents an oxygen atom and R1 representing a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group (compounds of general formula (If) ) can be prepared by reaction between compounds of general formula (Ie) and appropriate halides, in the presence or absence of an organic or inorganic base, such as for example potassium or sodium carbonate, potassium or sodium bicarbonate, potassium or sodium hydroxide, potassium or sodium hydride, triethylamine, in solvents such as ethers or amides, such as for example tetrahydrofuran, dioxane or N, N-dimethylformamide (Scheme 11).

The halides used can be chlorides, iodides or bromides, commercial or obtainable from the respective alcohols by well-known organic chemistry techniques.

Scheme 11

Alternatively, said compounds of general formula (If) can be prepared by reaction between the compounds of formula (XI) and sulfonamides of formula (XV), as illustrated in scheme 12.

Scheme 12

The reaction can be carried out in the presence or absence of a base such as triethylamine, N-methylmorpholine or pyridine in a suitable solvent such as methylene chloride, chloroform or tetrahydrofuran at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours, as extensively described in R.C. Larock “Comprehensive Organic Transformations” or for example in US2014 / 163024 or in WO2010 / 129500.

The sulfonamides having general formula (XIV) and (XV) are structures known in literature and they can be commercially available or can be prepared according to well known methods in organic chemistry or according to what is reported in WO2010 / 129500.

Compounds of formula (If), when R1 represents a -C (Y) R2 group, a -C (O) OR2 group, a -C (O) NR2R3 group, a -S (O) rR2 group, a - S (O) 2NR2R3, can be synthesized by reaction of compounds of general formula (Ie) with acyl, sulfonyl or sulfinyl chlorides, for example ClC (Y) R2, ClC (O) OR2, ClC (O) NR2R3, ClS (O ) rR2, ClS (O) 2NR2R3, by acylation, sulfonylation or sulfinylation methods well known in the literature.

A = -C (S) -NR1-S (O) 2-I compounds of general formula (I), with A representing the group -C (Y) -NR1-S (O) 2-, where Y represents a sulfur atom and R1 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group (compounds of general formula (Ig)) they can be prepared starting from the compounds of general formula (If) by reaction with phosphorus pentasulfide or with Lawesson's reagent, as shown in scheme 13, according to well-known procedures in organic synthesis.

Scheme 13

Compounds of general formula (I), with A representing the -C (Y) -NR1- group, in which Y represents an oxygen atom and R1 an H atom (compounds of general formula (Ih)), can be prepared by reaction of the respective carboxylic acids of formula (IX) with amines or their salts of formula (XVI), as illustrated in scheme 14.

Scheme 14

The reaction conditions provide for the use of a condensing agent, in the presence or absence of an amine such as N, N-dimethylaminopyridine in solvents such as alcohols, ethers, esters, amides or halogenated hydrocarbons or mixtures thereof. Condensing agents are for example 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide or its salts, N, N-dicyclohexylcarbodimide, N, N-diisopropylcarbodimide or 1,1'-carbonyldiimidazole. The reaction is carried out at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours.

The compounds of formula (Ih) can also be prepared by activating carboxylic acid or via acyl chloride or via mixed anhydride, as illustrated in diagram 15.

Scheme but 15

The reaction is carried out by reacting a compound of formula (XI), where V represents a chlorine atom or a -OCORW residue, with RW taking on the meaning of C1-C4 alkyl, obtained from the compound of general formula (IX) by methods known in literature, with amino compounds of formula (XVI) in the presence of a base such as triethylamine or N-methyl-morpholine or pyridine in a suitable solvent such as methylene chloride or chloroform or tetrahydrofuran at a temperature between 0 ° C and the temperature boiling of the solvent for a time between 1 and 72 hours as widely described in R.C. Larock “Comprehensive Organic Transformations” or in WO2010 / 129500 (2010).

A = -C (O) -NR1-I compounds of general formula I, with A representing the -C (Y) -NR1- group, in which Y represents an oxygen atom and R1 a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group (compounds of general formula (Ii)) can be prepared by reaction between the compounds of formula Ih and appropriate C1 halides -C6 alkyls, C1-C6 haloalkyls, C2-C6 alkenyls, C2-C6 haloalkenyls, C3-C8 cycloalkyls, in the presence or absence of an organic or inorganic base, such as for example potassium or sodium carbonate, potassium or sodium bicarbonate, potassium or sodium hydroxide, potassium or sodium hydride, triethylamine, in solvents such as ethers or amides, such as for example tetrahydrofuran, dioxane or N, N-dimethylformamide (Scheme 16). The halides used can be chlorides, iodides or bromides, commercial or obtainable from the respective alcohols by well-known organic chemistry techniques.

Scheme 1 6

Compounds of formula (Ii), in which R1 represents a C (Y) R2 group, a C (O) OR2 group, a C (O) NR2R3 group, an S (O) rR2 group, an S (O) group 2NR2R3, can be synthesized by reaction of the compounds of formula (Ii) with acyl, sulfonyl or sulfinyl chlorides, for example ClC (Y) R2, ClC (O) OR2, ClC (O) NR2R3, ClS (O) rR2, ClS ( O) 2NR2R3, by acylation, sulfonylation or sulfinylation methods well known in the literature.

Alternatively, the compounds of formula (Ii), where R1 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group can be prepared by reaction between the compounds of formula (XI) and substituted amines of formula (XVII), as illustrated in scheme 17.

Schem at 17

XVII

The reaction can be carried out in the presence or absence of a base such as triethylamine or N-methylmorpholine or pyridine in a suitable solvent such as methylene chloride or chloroform or tetrahydrofuran at a temperature between 0 ° C and the boiling temperature of the solvent for a time between 1 and 72 hours, as extensively described in R.C. Larock “Comprehensive Organic Transformations” and in WO2010 / 129500 (2010).

The amines having general formula (XVI) and (XVII) are structures known in the literature or they can be commercially available or can be prepared according to well-known methods in organic chemistry or as reported in R.C. Larock "Comprehensive Organic Transformations". A = -C (S) -NR1-I compounds of general formula (I), with A representing the -C (Y) -NR1- group, in which Y represents a sulfur atom and R1 represents a C1-C6 group alkyl, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group (compounds of general formula (Ij)) can be prepared starting from the compounds of general formula (Ii ) by reaction with phosphorus pentasulfide or with Lawesson's reagent, as shown in scheme 18, according to well-known procedures in organic synthesis.

Scheme 1 8

The compounds having general formula (I), for particular meanings of A or E, can be obtained in racemic form or as optically active isomers.

It therefore falls within the spirit of the present invention to consider both the compounds having general formula (I) isomerically pure, and mixtures thereof, possibly obtained during the preparation of the compounds having general formula (I) or derived from an incomplete separation of the isomers themselves, in any proportion.

As mentioned, the compounds of general formula (I) are endowed with a high nematicide activity and at effective doses they do not manifest phytotoxicity towards the application crops, making them suitable for use in the agricultural field in defense against nematodes.

In particular, the compounds object of the present invention are effective in the control of numerous nematodes such as: Pratylenchus spp, Globodera spp, Heterodera spp, Meloidogyne spp, Aphelenchoides spp, Radopholus Similis, Ditylenchus Dipsaci, Tylenchulus Semipenetrans, Longidorus spp, Xiphinepp Trichodorus spp, Bursaphelenchus spp ,. Belonolaimus spp. and similar.

A second object of the present invention is a method for controlling nematodes in cultivated areas by applying to the plant and / or the soil of at least one compound of general formula (XVIII):

in which:

- n represents an integer between 0 and 3;

- A represents a group chosen from: -S-, -S (O) -, -S (O) 2-, -C (= Y) -O-, -C (= Y) -NR1-, -C ( = Y) -NR1-S (O) 2-;

- Y represents an oxygen or sulfur atom;

- R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a group C (= Y) R2, a group C (= O) OR2, a group C (= O) NR2R3, a group S (= O) rR2, a group S (= O) 2NR2R3;

- R2 and R3, the same or different from each other, represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group cycloalkyl, a C3-C8 haloalkyl group, an aryl group, a benzyl group;

- r represents an integer between 0 and 2;

- E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group -cycloalkyl, a C3-C8 haloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic, penta or hexaatomic, aromatic or non-aromatic group, including benzocondensed or etherobycyclic , containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above;

- m represents an integer between 1 and 6;

- X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylene, heterocyclic or heterocyclylalkylene group can optionally be replaced by one or more Q groups selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C4-C9 -cycloalkylalkyl, C3-C6- haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxyl, C1-C6-thioalkoxyl, C1-C6-thioaloalkoxyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfonyl, , C3-C6-cycloalkoxycarbonyl, amino, N-C1-C6-alkylamino, N, N-C2-C12-dialkylamino, N-C1-C6-alkoxycarbonylamino N-C3-C6-cycloalkylamino, N, N-C6-C12- dicycloalkylamino, N-C3-C6-cycloalkoxycarbonylamino, C1-C6-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, C1-C6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta or hexatomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur , nitrogen, optionally oxidized to N-oxide, an optionally substituted (C1-C6) -alkyl-heterocyclic group, penta- or hexa-atomic also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, possibly oxidized to N-oxide,

provided that when A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, then E represents the group - (CH2 ) m-CX = CF2.

The general formula (XVIII) corresponds to the general formula (I) but without the exceptions indicated for the general formula (I).

Preferably, in the present method at least one compound of general formula (I), more preferably of formula (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), ( I-H) or (I-I) as defined above but without the exceptions possibly indicated therein, even more preferably at least one of the compounds listed in Table 1 or in Table 2, even more preferably at least one of the compounds listed in Table 3.

In particular, this method allows the prevention and treatment of phytoparasites caused by nematodes.

In the present method, compounds of general formula (XVIII) may be effective in several stages of parasite development such as reducing egg hatching, killing larvae, inhibiting population growth rate or eliminating the adults.

The compounds of general formula (XVIII) can be applied at different moments of the vegetative development of the plant, for example before transplanting / sowing or during growth, by foliar application, or to the soil by fertigation, or incorporation into the soil, or by tanning. of the seed. The amount of compound to be applied to obtain the desired effect may vary depending on various factors such as, for example, the compound used, the crop to be protected, the degree of infestation, the climatic conditions, the characteristics of the soil, the method of application, etc. Compost doses between 100g and 10000g per hectare generally provide sufficient control.

Preferred doses are those between 500g and 5000g per hectare.

For uses in agriculture it is often advantageous to use compositions with nematicide activity containing, as active substance, one or more compounds having general formula (XVIII) or (I), possibly also as a mixture of isomers.

Depending on the stage of development of the parasite and the quantity applied, the compounds of formula (XVIII) or (I) can act as nematostatic and / or nematocide.

A third object of the present invention is therefore the use of a compound of formula (XVIII) as a nematostatic and / or nematicide.

A fourth object of the present invention is an agronomic composition for the treatment and prevention of plant parasites caused by nematodes comprising at least one compound of general formula (XVIII) and possibly at least one carrier and / or at least one excipient suitable for application to plants and / or to the ground.

Preferably, the agronomic composition comprises at least one compound of general formula (I), more preferably of formula (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H ) or (I-I) as defined above, even more preferably at least one of the compounds listed in Table 1 or Table 2, even more preferably at least one of the compounds listed in Table 3.

The term carrier means a generally inert compound whose main function is to dissolve, dilute or disperse the active compound. The term excipient means a compound which, in addition to possibly dissolving, diluting or dispersing the active compound, can also modify one or more properties of the composition, contributing to obtaining a certain technical effect such as for example a higher stability of the composition, a better applicability of the same to plants or soil and the like.

You can use compositions that come in the form of dry powders, wettable powders, emulsifiable concentrates, microemulsions, pastes, granulates, solutions, suspensions, fumigants, etc .: the choice of the type of composition will depend on the specific use.

At least one carrier can be present in the present composition, i.e. at least one solvent or at least one diluent or mixtures thereof. The diluent can be solid or liquid. The compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent medium and / or solid diluent, optionally in the presence of surfactants.

Kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonite, diatomaceous earth, cellulose, starch, etc. can be used as solid inert diluents or supports.

Water or organic solvents such as aromatic hydrocarbons (xylols, mixtures of alkylbenzols, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated aromatic hydrocarbons (chlorobenzol, etc.), alcohols (methanol) can be used as liquid inert diluents , propanol, butanol, octanol, etc.), esters (isobutyl acetate, etc.), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethylamyl ketone, etc.), or vegetable or mineral oils or their mixtures, etc.

One or more excipients may be present in the present composition.

Non-ionic wetting and emulsifying agents can be used as surfactants (polyethoxylated alkylphenols, polyethoxylated fatty alcohols, etc.), anionic (alkylbenzenesulfonates, alkylsulfonates, etc.), cationic (quaternary alkylammonium salts, etc.).

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

Furthermore, dispersants (for example lignin and its salts, cellulose derivatives, alginates, etc.), stabilizers (for example antioxidants, absorbers of ultraviolet rays, etc.) can also be added.

The compounds of the present invention, as such or formulated, can be used in admixture with other active ingredients such as, for example, herbicides, fungicides, bactericides, insecticides, acaricides, nematocides, fertilizers, biostimulants, etc. to broaden its spectrum or prevent resistance.

In some cases, this results in a synergistic effect between the components that leads the mixture, for example, to perform a higher activity than that of the individual elements that compose it. Examples of fungicides that can be added to compositions containing one or more compounds of general formula (I) are the following:

acibenzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benomyl, benthiavalicarb, bitertanol, bixafen, blasticidimatein-S, boscalid, bromuconazole, capbirolate, cartanazole, capbiral quinomethionat, chloroneb, chlorothalonil, chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, diclocymet, diethofencole, diphicon, diphicon, diphicon, diphicon, dinethymyrazole, diphicon ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, phenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenxilan, fenentin, fenamidone, fenamidone ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumetover, flumorph, fluopicolide , fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetylaluminium, fuberidazole, furalaxyl, furamoleetpyr, furconazoline, furconazoline, hydrolazole, furconazole, hyacolazole, furconazoline, hydrolazole, furcon imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, iprovalicarb, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, meprothiolane-methyl, methylap-methyl, meponty-yrimala metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, natamycin, nicobifen, nitrothal-isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, penconazole, salts, pflencyoferal, pentholachin , Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propic onazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxy oxide, quincidoolfur, quinonazide copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methymylid, tetraconazole, tebufloquin , triadimefon, triadimenol, triarimol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziramamide.

Examples of herbicides which can be added to compositions containing one or more compounds of general formula (I) are the following:

acetochlor, acifluorfen, aclonifen, AKH-7088, alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryne, BAY MKH 6561, benflubide, bulfamidin, benflubide, bulfuronal, benflubidin bentazone, benzfendizone, benzobicyclon, benzofenap, benzthiazuron, bifenox, bilanafos, bispyribac-sodium, bromacil, bromobutide, bromophenoxim, bromoxynil, butachlor, butafenacil, butamifos, butenachlor, butralin, butrofenyentramide, ethofenylomethyl, butrofenyentrone chloramben, chlorbromuron, chlorbufam, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chlorotoluron, chloroxuron, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon ethyl, cinmethylin, cinosulfuron, chloroxuron ), cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, d esmetryn, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethatyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenebamid, dinebamid, dinosoterate, dinosymetry , dithiopyr, 1-diuron, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethidimuron, ethiozin (SMY 1500), ethofumesate, ethoxyfen-ethyl (HC-252), ethoxysulfuron, etobenzanid (HW 52), fenoxaprop-P, fentrazamide, fenuron, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate (JV 485), flucarbazone-sodium, fluchloralin, flufenacet, flufenpyrum ethyl, flumetsulam, flumazropy , fluometuron, fluoroglycofen, fluoronitrofen, flupoxam, flupropanate, flupyrsulfuron, flurenol, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacetmethyl, fomesafen, foramsulfuron, fosamine, furyloxyinate, glufosinate glyphosate, halosulfuronmethyl, haloxyfop, haloxyfop-P-methyl, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, iodosulfoxapy, ioxynole, isopachonPyron, isfloxifoxrifox, isfloxyropon, isfloxropon, isfloxypole, isop 421, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mesosulfuron, mesotrione, metamitron, metazachlor, methabenzthiazuron, methazole, methoprolymuronryon, methazole, methoprolymolon, meth metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monolinuron, naproanilide, napropamide, naptalam, NC-330, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oryzalin, oxzonide, ozonate, oxorphonylady pebulate, pendimethalin, penoxsulam, pentanochlor, pentoxazone, pethoxamid, phenmedipham, picloram, picolinafen, piperophos, pretilachlor, primisulfuron, prodiamine, prof luazol, proglinazine, prometon, prometryne, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrazogyl (HSA-961), pyrazolynurate, pyrosimulida, pyrosimeno , pyridate, pyriftalid, pyriminobacmethyl, pyrithiobac-sodium, pyroxasulfone quinclorac, quinmerac, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfuronyl, sulfentrazone, 2,3 TCA-sodium, tebutam, tebuthiuron, tepraloxydim, terbacil, terbumeton, terbuthyl-azine, terbutryn, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thifensulfuron-methyl, thiobencarb, tiocarbias, trazilzuron-methyl, thiobencarb, tiocarbias, trazilzuron, tioclim triclopyr, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron, UBI-C4874, vernolate.

Examples of bactericides that can be added to compositions containing one or more compounds of general formula (I) are the following:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furanecarboxylic acid, probenazole, streptomycin, teclophthalam, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, copper salicylate.

Examples of insecticides, acaricides, nematocides that can be added to compositions containing one or more compounds of general formula (I) are the following

abamectin, acetamiprid, acrinathrin, alphacypermethrin, alphamethrin, azadirachtin, Bacillus subtilis, Bacillus thuringiensis, Beauveria bassiana, betacyfluthrin, bifenazate, bifenthrin, buprofezin, chlorpyperrifos, chlorotrinpyrifos, chlorxylothrin, chlorxian deltamethrin, diflubenzuron, dimethoat, dazonet, sulfuryl difluoride, dimethyldisulfide, emamectin, esfenvalerate, ethoprophos, etofenprox, etoxazole, fenamiphos, fenazaquin, fenoxycarb, fenpyroximate, fipronil, fluazole, viruses hexythiazox, imidaclopridae, indoxacarb, lambdacyhalothrin, lufenuron malathion, metaldehyde, methamidophos, Metharhizium spp, methiocarb, methomyl, methoxyfenozide, milbemectin, metaflumizone, metam sodium, metamosemetos, pyrosimarbons, pyrosimetals, pyrosimarbons, pyrosimmetrum, pyrosimmetals pyriproxyfen, piperonyl butoxide, s pinosad, spironesifen, spirotetramat, spinetoran, spirodiclofen, tau-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, thiacloprid, triflumuron, zeta-cypermethrin, (lR-cis) - [5- (furmethyl-3-) 3 - [(dihydro-2-oxo-3 (2H) -furanylidene) methyl] -2,2-dimethylcyclopropanecarboxylate, (3-phenoxyphenyl) -methyl-2,2,3,3-tetramethyl-cyclopropanecarboxylate, 1 - [( 2-chloro-5-thiazolyl) methyl] -5-triazine 2- (1H) -imine, 2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4 , 5-dihydro-oxazole, 2- (acetlyoxy) -3-dodecyl-1,4-naphthalenedione, 2-chloro-N - [[[4- (l-phenylethoxy) -phenyl] -amino] -carbonyl] -benzamide , 2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide, 3-methylphenyl-propylcarbamate, 4- [4- (4 -ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxybenzene, 4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6dimethyl-4-phenoxyphenoxy) ethyl] thio] -3- (2H) -pyridazinone, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) (2-chloro-2-methylpropyl ) -5 - [(6-iodo-3-pyridinyl) -methoxy] -3- (2H) pyridazinone, 4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4 -dichlorophenyl) -3 (2H) pyridazinone, Bacillus thuringiensis strain EG-2348, [2-benzoyl-1- (1,1-dimethylethyl) -hydrazinobenzoic acid, 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] -dec-3-en-4-yl butanoate, [3 - [(6-chloro-3-pyridinyl) -methyl] -2-thiazolidinyli-dene] -cyanamide, dihydro -2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde, ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] -carbamate, N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine, N- (4-chlorophenyl) -3- [4- (difluoromethoxy) -phenyl] -4,5 -dihydro-4-phenyl-1H-pyrazole-1-carboxamide, N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine, N-methyl-N '- ( 1-methyl-2-propenyl) -1,2-hydrazinedi-carbothioamide, N-methyl-N'-2-propenyl-1,2-hydrazinedicarbothioamide, O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethyl-phosphoroamidothioate. Examples of fertilizers and biostimulants that can be added to compositions containing one or more compounds of general formula (I) are the following: mixtures of amino acids and / or oligopeptides of animal and / or vegetable origin, 4-thiazolidinedecarboxylic acid, 4-acetylthiazolidin -carboxylic, ectoin, phytosterols.

The concentration of active substance in the above compositions can vary within a wide range, depending on the active compound, the applications for which they are intended, the environmental conditions and the type of formulation adopted. In general, the concentration of active substance is between 0.1 and 99%, preferred is that between 0.5 and 90% by weight.

Some examples are now provided which are intended as descriptive and not limitative of the present invention.

EXAMPLE 1

Preparation of 1,3,7-trimethyl-8- (3,4,4-trifluorobut-3-enylthio) -1H-purine-2,6 (3H, 7H) -dione (compound 1.5)

To a solution of 8-mercapto-1,3,7-trimethyl-1H-purin-2,6 (3H, 7H) -dione (380 mg, 1.67 mmol) in DMF (5 mL), 440 mg of carbonate is added of anhydrous potassium (3.2 mmol) and 0.36 mL of 4-bromo-1,1,2-trifluoro-1-butene (3.2 mmol). The reaction mixture is placed in an inert atmosphere under stirring, at room temperature. After 12 hours, the reaction mixture is poured into a H2O / EtOAc mixture, the phases are separated; the organic phase is washed with water and brine, subsequently anhydrified, filtered and evaporated. 440 mg of a white solid are obtained, with a yield of 82%.

LC-MS [M + H <+>] = 335.

EXAMPLE 2

Preparation of 1,3,7-trimethyl-8- (3,4,4-trifluorobut-3-enylsulfinyl) -1H-purine-2,6 (3H, 7H) -dione (compound 1.9)

To a solution of 1,3,7-trimethyl-8- (3,4,4-trifluorobut-3-enylthio) -1H-purine-2,6 (3H, 7H) -dione (220 mg, 0.66 mmol) in chloroform (6 mL), 160 mg (720 mmol) of mchloroperbenzoic acid are added at 0 ° C. It is allowed to slowly rise to room temperature, and the reaction is stirred at room temperature for 12 hours. At the end of the reaction, the reaction solution is poured into a 5% aqueous solution of sodium metabisulphite, the mixture is left under vigorous stirring for 15 minutes. The phases are separated, the organic phase is washed twice with a saturated solution of sodium bicarbonate, then with water and finally with brine. The organic phase is anhydrified, filters and evaporates. The crude compound is purified by silica chromatography (eluent: heptane / EtOAc 1: 1). Compound 1.9 (100 mg, 43% yield) is obtained as a white solid.

LC-MS [M + H <+>]: 351.

EXAMPLE 3

Preparation of 1,3,7-trimethyl-8- (3,4,4-trifluorobut-3-enylsulfonyl) -1H-purine-2,6 (3H, 7H) -dione (compound 1.13)

A solution of 870 mg of 1,3,7-trimethyl-8- (3,4,4-trifluorobut-3-enylthio) -1H-purine-2,6 (3H, 7H) -dione (compound 1.5) is prepared in 20 mL of chloroform, under a nitrogen atmosphere. The solution is cooled to 0 ° C and 1.74 g (7.8 mmol) of m-chloroperbenzoic acid are added. After 1 h 314 mg (1.8 mmol) of m-chloroperbenzoic acid are added again, and the reaction is left under stirring at room temperature. After 10 hours, the reaction solution is poured into a 5% aqueous solution of sodium metabisulphite, the mixture is left under vigorous stirring for 15 minutes. The phases are separated and the organic phase is washed twice with a saturated solution of sodium bicarbonate. The aqueous phases are extracted with dichloromethane, and the combined organic phases are washed with water and finally with brine. The organic phase is anhydrified, filters and evaporates. The crude compound is purified by trituration with heptane. 550 mg (58% yield) of the compound 1.13 are obtained as a white solid.

LC-MS [M + H <+>]: 367.

EXAMPLE 4

Preparation of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxylate of 3,4,4-trifluoro-3-butenyl (compound 1.1)

To a solution of 150 mg (0.63 mmol) of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxylic acid in 1 mL of acetonitrile, they add 240 mg (1.26 mmol) of 4-bromo-1,1,2-trifluoro-1-butene and 0.18 mL (1.26 mmol) of triethylamine. The reaction is heated under reflux for 9 h and after 36 hours at room temperature, it is recovered by evaporation of the solvent. The residue is redissolved in dichloromethane and washed with cold water; the aqueous phase is extracted twice with dichloromethane, the combined organic phases are washed with brine, anhydrified with sodium sulphate, filtered and evaporated. The crude obtained in this way is purified by chromatography on silica, by means of a heptane / EtOAc gradient. Product 1.1 is obtained as a white solid (70 mg, yield 32%).

LC-MS [M + H <+>]: 347.2.

EXAMPLE 5

Preparation of N - [(2-chloro-5-methoxyphenyl) sulfonyl] -1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxamide (compound 2.3)

In a nitrogen atmosphere, a solution of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxylic acid (426 mg, 1.79 mmol) is prepared, N, N-dimethylaminopyridine (656 mg, 5.37 mmol) and EDC hydrochloride (694 mg, 4.48 mmol) in a mixture of tert-butanol (9 mL) and dichloromethane (9 mL). The solution is stirred at room temperature for 15 minutes, then 374 mg (1.68 mmol) of 2-chloro-5-methoxy-benzenesulfonamide are added and the mixture is left under stirring at room temperature. After 72 hours, the reaction solution is acidified by adding 1 M HCl, then it is extracted with dichloromethane (2x). The organic phase is washed with water, brine, then anhydrified, filtered and evaporated. The crude is purified by silica chromatography, with a dichloromethane / methanol gradient. 513 mg of a white solid are obtained.

LC-MS [M + H <+>]: 456.8.

EXAMPLE 6

Preparation of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-8-yl-acetate of 3,4,4-trifluoro-3-butenyl (compound 1.21 )

In a nitrogen atmosphere, a solution of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-8-yl acetic acid (550 mg, 2.18 mmol) is prepared in dichloromethane; the solution is brought to 0 ° C and EDC hydrochloride (676 mg, 4.36 mmol) and DMAP (800 mg, 6.54 mmol) are added in sequence and left under stirring at 0 ° C for 10 minutes. Then 550 mg of 3,4,4-trifluorobuten-1-ol (4.36 mmol) are added and the mixture is left under stirring at room temperature for 24 h. The reaction is then acidified with 1M HCl, the phases are separated; the organic phase is washed with water, brine, then dried, filtered and evaporated. The residue is purified by silica chromatography, using a heptane / EtOAc gradient. 670 mg of a white solid are obtained (yield 85%).

LC-MS [M + H <+>]: 361.1.

EXAMPLE 7

Preparation of N - [(2-bromophenyl) sulfonyl] -1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxamide (compound 2.253)

1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxylic acid (630 mg, 2.65 mmol), is dissolved in a mixture of tert- butanol (13 mL) and dichloromethane (13 mL). N, N-dimethylaminopyridine (970 mg, 7.95 mmol) and EDC hydrochloride (820 mg, 5.3 mmol) are added to this solution and stirred at room temperature. The solution is stirred at room temperature for 15 minutes, then 625 mg (2.65 mmol) of 2-bromobenzenesulphonamide are added. After 72 hours of reaction at room temperature, the reaction solution is acidified by adding 1 M HCl, then it is extracted with dichloromethane (2x). The organic phase is washed with water, brine, anhydrifies, filters and evaporates. The crude is purified by silica chromatography, with a dichloromethane / methanol gradient. 880 mg of a white solid are obtained (yield 73%). LC-MS [M + H <+>] = 456.3, 458.3

EXAMPLE 8

Preparation of N - [(3,4,4-trifluoro-3-buten-1-yl] -1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin -8-carboxamide (compound 3.1)

Step A: preparation of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-8-carbonyl chloride Under nitrogen atmosphere, 700 mg (2.94 mmol) are diluted of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxylic acid in 3 mL of dichloromethane; subsequently a catalytic quantity of DMF and 0.24 mL of SOCl2 are added; it leads to reflux. After 5 hours the reaction is recovered by evaporation of the solvent. The crude thus obtained is used directly for step B. Step B: preparation of N - [(3,4,4-trifluoro-3-buten-1-yl] -1,3,7-trimethyl-2,6- dioxo-2,3,6,7-tetrahydro-1H-purine-8-carboxamide.

The crude obtained in step A (1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carbonyl chloride) dissolves in 6 mL of dichloromethane; the solution is brought to 0 ° C and 0.53 mL of triethylamine and 0.44 g of 3,4,4-trifluorobut-3-enylamine are added in sequence. The reaction is left under stirring at room temperature. After 12 hours, the reaction is terminated by adding water; the phases are separated and the aqueous phase extracted with dichloromethane. The organic phases are combined and washed with a saturated solution of bicarbonate and subsequently with brine. It is dried, filtered and evaporated. Compound 3.1 is obtained as a white solid (910 mg, yield 90% on two steps).

LC-MS [M + H <+>]: 346.2.

EXAMPLE 9

Preparation of N - [(3,4,4-trifluoro-3-buten-1-yl] -1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin -8-yl-acetamide (compound 3.47)

1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purin-8-yl acetic acid (1.1 g, 4.37 mmol) in dichloromethane (20 mL); the solution is brought to 0 ° C and EDC hydrochloride (1.7 g, 10.93 mmol) and DMAP (1.6 g, 13.11 mmol) are added in sequence and left under stirring at 0 ° C for 10 minutes. Then 546 mg of 3,4,4-trifluorobut-3-enylamine (4.37 mmol) are added and the mixture is left under stirring at room temperature for 24 h. The reaction is then acidified with 1M HCl, the phases are separated; the organic phase is washed with water, brine, then dried, filtered and evaporated. The residue is purified by silica chromatography, using a heptane / EtOAc gradient. 1.3 g of a white solid are obtained (yield 83%).

LC-MS [M + H <+>]: 360.2.

EXAMPLE 10

Preparation of N- [2- [3-chloro-5- (trifluoromethyl) -2-pyridyl] -1-ethyl] -1,3,7-trimethyl-2,6-dioxo-2,3,6,7- tetrahydro-1H-purine-8-carboxamide (compound 3.3)

1 g (3.9 mmol) of 1,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1H-purine-8-carbonyl chloride (Step A, example 8) are dissolved in 8 mL of dichloromethane; after cooling the reaction solution to 0 ° C, 0.7 mL of triethylamine (5.07 mmol) and 1.05 g of 2- [3-chloro-5- (trifluoromethyl) -2-pyridyl] -1-ethanamine are added in sequence. After 12 hours of stirring at room temperature, the reaction is terminated by adding water; the phases are separated and the aqueous phase extracted with dichloromethane. The organic phases are combined and washed with a saturated solution of bicarbonate and subsequently with brine. It is dried, filtered and evaporated. Compound 3.3 is obtained as a white solid (1.4 g, yield 81% on two steps).

LC-MS [M + H <+>]: 445.7.

Operating analogously to the previous Examples, the compounds reported in Table 4 were prepared.

Table 4

Table 5 shows the results of the LC-MS analyzes conducted on Compounds 1.2, 1.10, 1.14, 1.22, 1.29, 1.33, 2.1, 2.2, 2.5, 2.9, 2.14, 2.25, 2.43, 2.44, 2.85, 2.86, 2.127, 2.254, 3.2, 3.4, 3.5, 3.6, 3.7, 3.48, 3.49, 3.50, 3.51, 3.53, 3.93, 3.94, 3.95, 3.96, 3.97, 3.99.

Table 5

EXAMPLE 11

Determination of nematicide activity against Meloidogyne sp.

Tests aimed at testing the nematocidal activity of the product in question are carried out using inocula taken from a farm of Meloidogyne sp. kept on tomato and cucumber plants in pots and grown in greenhouses.

To carry out the experiments, portions of roots are taken from the infested vessels which have a good number of galls and soil, in which larvae are present starting from the second stage of age. New pots with a diameter of 15 cm are half filled with sterile earth. The portions of infested roots, previously cleaned, are placed on it in order to correctly assess the degree of infestation and ensure that each pot contains the same nematic charge. Then 200-300 g of infested soil are added, which are covered with a thin layer of sterile earth.

The treatment is carried out by pouring on the surface of the soil 100 ml of aqueous solution containing 10% of acetone in which the product to be tested has been dissolved at a concentration between 70 and 100 ppm.

In the pots thus prepared, one or seven days after application, tomato or cucumber seedlings are transplanted at the stage of two or three true leaves. Different tomato cultivars (Microtom, Marmande) or cucumber (Lungo from China) are used, having different sensitivity to the parasite and different growth times. In particular, to estimate the final production, a variety of ornamental tomato (CV Microtom) is used, whose seedlings are small and able to reach fruit maturity in pots and greenhouse conditions in about two months. .

The parasite's containment capacity is detected, 30 and 60 days after transplantation, considering the development of the plant (of which the fresh weight is detected), and the presence of galls on the roots. This is estimated both using the infestation scale proposed by Bridge-Page (Tropical Pest Management 26 (3): 296-298, September 1980), according to which the zero value corresponds to 0% of the root affected and to the value 10 corresponds the 100% infested root, both considering the percentage of root mass affected.

Furthermore, the product was evaluated considering any phytotoxic effects that can compromise the development of the plant (a scale from zero to ten was used in which: zero = no symptoms, 10 = plant destroyed).

Table 6 shows the results relating to the efficacy of Compounds N ° 1.9, 1.13, 1.1, and of caffeine, on tomato, cv Marmande, at a dose of 4000 g / hectare, carrying out the survey 30 days after transplanting.

Table 6

As highlighted by the data shown in Table 6, the compounds according to the invention show a root-knot index and a percentage of infested root that are decidedly lower than those of both infested and untreated plants (infested witness), and those treated with caffeine. The reduction of parasitosis at the root level found for the compounds of the invention is reflected in the improved well-being of the plants, whose weight appears to be markedly higher. Furthermore, the compounds of the invention, unlike caffeine, do not show phytotoxicity at effective doses.

Finally, it can be seen from the data tabulated here that caffeine is even worse as a nematicide, with an increase in the root-root index and the percentage of infested roots, compared to infested and untreated plants (infested witness).

Claims (12)

CLAIMS 1. A compound of formula (I): in which: - n represents an integer between 0 and 3; - A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, -C (= Y) -NR1-, - C (= Y) -NR1-S (O) 2-; - Y represents an oxygen or sulfur atom; - R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a group C (= Y) R2, a group C (= O) OR2, a group C (= O) NR2R3, a group S (= O) rR2, a group S (= O) 2NR2R3; - R2 and R3, the same or different from each other, represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group cycloalkyl, a C3-C8 haloalkyl group, an aryl group, a benzyl group; - r represents an integer between 0 and 2; - E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group -cycloalkyl, a C3-C8 haloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic, penta or hexaatomic, aromatic or non-aromatic group, also benzocondensed or etherobycyclic , containing at least one heteroatom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above; - m represents an integer between 1 and 6; - X represents a hydrogen or fluorine atom; wherein said aryl, naphthyl, benzyl, arylalkylene, heterocyclic or heterocyclylalkylene group can optionally be replaced by one or more Q groups selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C4-C9 -cycloalkylalkyl, C3-C6- haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxyl, C1-C6-thioalkoxyl, C1-C6-thioaloalkoxyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfonyl, , C3-C6-cycloalkoxycarbonyl, amino, N-C1-C6-alkylamino, N, N-C2-C12-dialkylamino, N-C1-C6-alkoxycarbonylamino N-C3-C6-cycloalkylamino, N, N-C6-C12- dicycloalkylamino, N-C3-C6-cycloalkoxycarbonylamino, C1-C6-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, C1-C6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta or hexaatomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur , nitrogen, optionally oxidized to N-oxide, an optionally substituted (C1-C6) -alkyl-heterocyclic group, penta- or hexa-atomic also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen, possibly oxidized to N-oxide, provided that when A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, then E represents the group - (CH2 ) m-CX = CF2; And with the exception of compounds of general formula (I) in which: - n = 0, A = -CO-NH-, E = 3-chloro phenyl; - n = 1, A = -CO-N (Et) -, E = Et; - n = 1, A = -CO-NH-, E = benzyl; - n = 1, A = -CO-NH-, E represents a group of formula (W) in which - each R4 independently represents halogen, a hydroxyl group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C2-C6 alkenoxyl group, a C1- C6 haloalkyl, a -N (R6) 2 group, a -CON (R6) 2 group, a -CO2H group, a cyano group or a nitro group; - p represents an integer between 0 and 3; - R5 represents a halogen, a hydroxyl group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C2-C6 alkenoxyl group, a C1-C6 group haloalkyl, a -N (R6) 2 group, a -CON (R6) 2 group, a -CO2H group, a cyano group or a nitro group, or is absent; And - R6 independently represents H or a C1-C4 alkyl group. 2. The compound according to claim 1 of formula (I-A) wherein: - n is an integer between 0 and 2; - R1 represents a hydrogen atom or a C1-C6 alkyl group; - E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C3-C8-cycloalkyl group, an aryl group, a C7-C14 arylalkylene group, a naphthyl group or a heterocyclic group , penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined herein; And - m represents an integer between 1 and 5. 3. The compound according to claim 1 of formula (I-B) wherein: - n is an integer chosen between 0 and 1; - A represents a group chosen from: -S (= O) -, -S (= O) 2-, -C (= O) -O-, -C (= O) -NR1-, -C (= O ) -NR1-S (= O) 2-; - R1 represents a hydrogen atom or a C1-C6 alkyl group; - E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C3-C8-cycloalkyl group, an aryl group, a C7-C14 arylalkylene group, a naphthyl group or a heterocyclic group , penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined herein; And - m represents an integer between 1 and 5. 4. The compound according to claim 1 of formula (I-C) wherein: - n is an integer between 0 and 1; - A represents a group selected from: -S (= O) -, -S (O) 2-, -C (= O) -O-; - R1 represents a hydrogen atom or a C1-C6 alkyl group; - E represents a group - (CH2) m-CX = CF2; And - m represents an integer between 1 and 5. 5. The compound according to claim 1 of formula (I-D) wherein: - E represents a group - (CH2) m-CX = CF2; And - n is chosen between 0 and 1. The compound according to claim 1 wherein: - A represents a group selected from: -C (= Y) -NR1- and -C (= Y) -NR1-S (O) 2-; - n is chosen between 0 and 1; and - E represents a group selected from an aryl group, a naphthyl group, or a C7-C14 arylalkylene group (formula I-F); or - E represents a group selected from a heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic group, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen, or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above (formula I-G). 7. The compound according to claim 1 of general formula (I) in which n, A and E have the following meanings: 8. A method for controlling nematodes in cultivated areas by applying to the plant and / or the soil of at least one compound of general formula (XVIII): in which: - n represents an integer between 0 and 3; - A represents a group chosen from: -S-, -S (O) -, -S (O) 2-, -C (= Y) -O-, -C (= Y) -NR1-, -C ( = Y) -NR1-S (O) 2-; - Y represents an oxygen or sulfur atom; - R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a group C (= Y) R2, a group C (= O) OR2, a group C (= O) NR2R3, a group S (= O) rR2, a group S (= O) 2NR2R3; - R2 and R3, the same or different from each other, represent a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group cycloalkyl, a C3-C8 haloalkyl group, an aryl group, a benzyl group; - r represents an integer between 0 and 2; - E represents a group selected from - (CH2) m-CX = CF2, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 group -cycloalkyl, a C3-C8 haloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic, penta or hexaatomic, aromatic or non-aromatic group, also benzocondensed or etherobycyclic , containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide or a C3-C9 heterocyclylalkylene group in which the heterocyclic group is as defined above; - m represents an integer between 1 and 6; - X represents a hydrogen or fluorine atom; wherein said aryl, naphthyl, benzyl, arylalkylene, heterocyclic or heterocyclylalkylene group can optionally be replaced by one or more Q groups selected from halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C4-C9 -cycloalkylalkyl, C3-C6- haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxyl, C1-C6-thioalkoxyl, C1-C6-thioaloalkoxyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfonyl, , C3-C6-cycloalkoxycarbonyl, amino, N-C1-C6-alkylamino, N, N-C2-C12-dialkylamino, N-C1-C6-alkoxycarbonylamino N-C3-C6-cycloalkylamino, N, N-C6-C12- dicycloalkylamino, N-C3-C6-cycloalkoxycarbonylamino, C1-C6-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, C1-C6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta or hexaatomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur , nitrogen, optionally oxidized to N-oxide, an optionally substituted (C1-C6) -alkyl-heterocyclic group, penta- or hexa-atomic also benzocondensed or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, possibly oxidized to N-oxide, provided that when A represents a group chosen from: -S-, -S (= O) -, -S (= O) 2-, -C (= Y) -O-, then E represents the group - (CH2) m-CX = CF2, or of a compound of formula (I) according to any one of claims 1 to 7. 9. The method according to claim 8 wherein said nematodes are selected from Pratylenchus spp, Globodera spp, Heterodera spp, Meloidogyne spp, Aphelenchoides spp, Radopholus Similis, Ditylenchus Dipsaci, Tylenchulus Semipenetrans, Longidorus spp, Xiphurshelma spp, Trichlorus spp . and Belonolaimus spp. Use of a compound of formula (XVIII) according to claim 8 or of a compound of formula (I) according to any one of claims 1 to 7 as nematostatic or nematicide. 11. An agronomic composition for the treatment and prevention of nematode phytoparasitises comprising at least one compound of formula (XVIII) according to claim 8 or a compound of formula (I) according to any one of claims 1 to 7 and at least one carrier and / or at least one excipient suitable for application to plants and / or soil. The composition according to claim 11 further comprising at least one second active compound selected from herbicides, fungicides, bactericides, insecticides, acaricides, nematocides, fertilizers and biostimulants.