WO2020075107A1 - Caffeine derivatives with nematocidal activity, agronomic compositions thereof and use thereof - Google Patents

Abstract

The present invention relates to caffeine derivatives of general formula (I) agronomic compositions which contain said compounds of formula (I) and analogous compounds of formula (XVIII) and their use for the control of nematodes in agricultural crops. Advantageously, these compounds prove at the same time effective against parasites and without phytotoxicity.

Description

"CAFFEINE DERIVATIVES WITH NEMATOCIDAL ACTIVITY, AGRONOMIC COMPOSITIONS THEREOF AND USE THEREOF"

DESCRIPTION

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

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

PRIOR ART

Plant parasitic nematodes pose a serious threat to vegetable crops. In fact, nematodes, small wormlike organisms present in the soil, are able to settle in the roots of plants and to live at the expense of the same, thus slowing their development and growth due to insufficient intake of nutrients.

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

As far as chemical control is concerned, the compounds belonging to the class of carbamates and organophosphorus compounds, mostly used as chemical nematicides, are recently limited or even abandoned due to toxicity or environmental impact issues.

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

Italian patent IT 1368843 reports that caffeine, a molecule of natural origin, can be validly used against some species of nematodes that affect vegetable crops. However, the Applicant has verified that this compound is not very satisfactory from the point of view of the nematocidal activity, since it is not able to effectively contain the attack of the parasite and reduce the formation of galls on the plant's root system.

Furthermore, caffeine is phytotoxic to important agricultural crops, showing significant necrosis of the leaves and stem, at doses that allow good nematocidal activity to be obtained.

To the knowledge of the Applicant, caffeine derivatives substituted in position 8 for nematocidal 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 are obtained which have remarkable nematocidal activity against numerous phytoparasitic nematodes.

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 nematicides.

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

wherein:

- n represents an integer of between 0 and 3;

- A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, -C(=Y)-NRi-, -C(=Y)- NRI-S(0)₂-;

- Y represents an oxygen or sulfur atom;

- Ri 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 C(=Y)R2 group, a C(=0)0R2 group, a C(=0)NR2R3 group, an S(=0)_rR2 group, an S(=0)₂NR₂R3 group; - R2 and R3, equal to or different from each other, represent a hydrogen atom, a Ci-Ce alkyl group, a Ci-Ce haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, an aryl group, a benzyl group;

- r represents an integer of between 0 and 2;

- E represents a group selected from -(CH2)m-CX=CF2, a Ci-Ce alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic group, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above;

m represents an integer of between 1 and 6;

- X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylenic, heterocyclic or heterocyclylalkylene group may optionally be substituted by one or more Q groups selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C6-cycloalkyl, C4-C9-cycloalkylalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxyl, Ci-Ce-haloalkoxyl, Ci-Ce- thioalkoxyl, Ci-Ce-thiohaloalkoxyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-alkoxycarbonyl, C3- Ce-cycloalkoxycarbonyl, amino, N-Ci-C6-alkylamino, N,N-C2-Ci2-dialkylamino, N-Ci-Ce- alkoxycarbonylamino N-C3-C6-cycloalkylamino, N,N-C6-Ci2-cycloalkylamino, N-C3-C6- cycloalkoxycarbonylamino, Ci-Ce-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, d -c6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, a (Ci-C6)-alkyl-heterocyclic optionally substituted group, penta- or hexa-atomic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide,

with the proviso that when A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, then E represents the group -(CH2)m-CX=CF2; and

with the exception of compounds of general formula (I), in which: - n = 0, A = -C0-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)

wherein

each R₄ independently represents halogen, a hydroxyl group, a Ci-Ce alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a Ci-Ce alkoxyl group, a C2-C6 alkenyloxyl group, a Ci-Ce haloalkyl group, a -N(R6)2 group, a -CON(R6)2 group, a -CO2H group, a cyano group or a nitro group;

p represents an integer of between 0 and 3;

R5 represents a halogen, a hydroxyl group, a Ci-Ce alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxyl group, a C2-C6 alkenyloxyl 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 range is indicated, the extremes are understood to be included in the same.

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

Examples of linear or branched Ci-Ce alkyl 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-difl uoropentyl , 5, 5-difl uorohexyl .

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)-butyl. Examples of linear or branched Ci-Ce alkoxyl are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 3-methyl butoxy, hexyloxy, 3,3-dimethylbutoxy.

Examples of Ci-Ce haloalkoxy are fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, 2, 2, 2-trifl uoroethoxy, 1 ,1 ,2,2-tetra-fluoroethoxy, 1,1, 2, 3, 3, 3 -exafluoropropoxy, 4,4,4-trichlorobutoxy, 4,4-difluoropentoxy, 5, 5-difl uoro hexyloxy.

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

Examples of C3-C8 halocycloalkyl are 2,2-dichloro-cyclopropyl, 2,2-difluorocyclopropyl, 2, 2,3,3- tetrafluorocyclobutyl, 3,3-difluorocyclopentyl, 2-fl uorocyclo hexyl .

Examples of C4-C9 cycloalkyl alkyls 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 heterocyclic, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensed or heterobicyclic compounds are: pyridine, pyridine N-oxide, pyrimidine, pyridazine, pyrazine, furan, thiophene, pyrrole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole , tiadiazole, pyrazole, imidazole, triazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyridine, triazolopyrimidine, tiazolopyrimidine, [1,2,4]-triazole-[3,2-b]-thiazole, morpholine.

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

The following are also intended to be included in the scope of the present invention:

a) all the 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) any optical isomers and mixtures thereof, including racemic mixtures of the compounds of formula (I).

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

- n is an integer of between 0 and 2;

- R1 represents a hydrogen atom or a Ci-Ce alkyl group; - E represents a group selected from -(CH2)m-CX=CF2, a Ci-Ce 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 benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group, wherein the heterocyclic group is as defined herein;

- m represents an integer of between 1 and 5,

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

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

- n is an integer selected from 0 and 1 ;

- A represents a group selected from: -(SO)-, -S(0)2-, -C(=0)-0-, -C(=0)-NRi-, -C(=0)-NRi-

S(0)2-;

- R1 represents a hydrogen atom or a Ci-Ce alkyl group;

- E represents a group selected from -(CH2)m-CX=CF2, a Ci-Ce 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 benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group, wherein the heterocyclic group is as defined herein; and

- m represents an integer of between 1 and 5,

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

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

- n is an integer of between 0 and 1 ;

- A represents a group selected from: -S(0)-, -S(0)2-, -C(=0)-0-;

- R1 represents a hydrogen atom or a Ci-Ce alkyl group;

- E represents a -(CFl2)m-CX=CF2 group; and

- m represents an integer of between 1 and 5.

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

- E represents a -(CFl2)m-CX=CF2 group; and

- n is selected from 0 and 1.

Preferred compounds of formula (l-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 hexahomic group, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, or a C3-C9 heterocyclyl al kyle ne group, wherein the heterocyclic group is as defined above;

- n is selected from 0 and 1,

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

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

- A represents a group selected from: -C(=Y)-NRi- and -C(=Y)-NRI-S(0)2-;

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

- n is selected from 0 and 1,

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

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

- A represents a group selected from: -C(=Y)-NRi- and -C(=Y)-NRI-S(0)2-;

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

- n is selected from 0 and 1 ,

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

Preferred compounds of formula (l-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 hexahomic group, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom 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 heterocyclylenic group as defined herein is substituted by one or more Q groups selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C6- halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-thioalkoxy or Ci-C6-thiohaloalkoxy.

Preferred compounds of formula (l-l) 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 hexahomic group, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur, nitrogen, or a C3-C9 heterocyclyl al kyle ne group, wherein the heterocyclic group is as defined above; and

wherein said aryl, naphthyl, arylalkylene, heterocyclic or heterocyclylenic group as defined above, is substituted by one or more Q groups selected from fluorine, chlorine, bromine, Ci-C3-fluoro-, chloro- or bromo-alkyl, C3-C6-fluoro-, chloro- or bromo-cycloalkyl, Ci-C3-alkoxy, Ci-C3-fluoro-, chloro- or bromo-alkoxy.

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

Table 1

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

Table 2

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

Table 3

The compounds of general formula (I) can be prepared according to the processes illustrated herein. A = -S(O)-, -SfOh-

In particular, the compounds of general formula (I), with A representing a group -S(O)- (compound of general formula (la)) or a group -S(0)2- (compound of general formula (lb )) can be prepared from the respective thioethers of general formula (lc) 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 which can be used are perbenzoic acids such as 4-chloroperbenzoic acid, peracetic acid or inorganic peroxides, such as for example hydrogen peroxide, hydrogen-urea peroxide adduct and other oxidizing agents such as potassium permanganate, sodium or potassium periodate peroxymonosulphate. 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 acetone, 2-butanone, organic acids such as acetic acid and water or mixtures thereof.

The 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 72 hours.

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

Scheme 2

The reaction involves 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.

Such a 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), with n equal to zero, can be obtained as reported in Yan et al., Chemical Communications 2017 vol. 53 (26) p. 3637-3640.

For n which takes values other than zero, the compounds of formula (II) can be obtained according to the scheme 3.

Scheme 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 methods well known 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 directly transformed into the intermediate (II) by reaction with alkali metal hydrosulphide such as sodium, potassium or lithium, by means of bases such as potassium carbonate or sodium, in solvents such as N,N-dimethylformamide or N- methylpyrrolidone, dioxane or tetrahydrofuran, acetonitrile, at a temperature ranging from 0 °C to 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 like alcohols, such as ethanol, methanol, isopropanol, propanol, or water or mixtures thereof, at a temperature ranging from 0 °C to the boiling temperature of the solvent. The subsequent hydrolysis in situ is carried out in solvents such as alcohols, water or mixtures thereof, 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 ranging from 0 °C to the respective boiling temperatures. The subsequent hydrolysis is carried out in solvents such as alcohols, water or mixtures thereof, 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 furthermore 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 the 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 (lc) 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 ranging from 1 to 96 hours.

A = -CfOIO-

According to an embodiment, the compounds of general formula (I), wherein A represents a -C(0)0- 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 methods well known in organic chemistry.

Scheme 5

The reaction conditions involve the use of a condenser such as for example 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 p. 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 between room temperature and that of solvent reflux, 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 chlorine atom or an OCORw residue, with Rw taking the meaning of C1-C4 alkyl, and subsequent addition of the appropriate alcohol of general formula (X), according to the reaction scheme 6.

Scheme 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 ranging from 0 °C to the boiling temperature of the solvent for a time ranging from 1 to 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 alkaline metal, such as sodium, lithium or potassium, or of ammonium, such as trimethylammonium or triethylammonium, in the presence of a derivative of formula (III) wherein T represents a leaving group such as a halogen atom, selected from chlorine, bromine or iodine or a trifluoromethanesulfonate or methanesulfonate group according to the reaction scheme 7.

Scheme 7

The reaction involves the salification of the carboxylic acid with a base such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium 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 ranging from room temperature to that of reflux of the selected 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 R_w which takes 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(0)-NH-S(0)2-

The compounds of general formula (I), with A representing the group -C(Y)-NRI-S(0)2-, wherein Y representing an oxygen atom and R 1 an H atom (compounds having general formula (le)), can be prepared by reaction of the respective carboxylic acids of formula (IX) with sulfonamides of formula (XIV), as shown in scheme 9.

Scheme

The reaction conditions involve 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 salts thereof, N, N-dicyclohexylcarbodimide, N, N-diisopropylcarbodimide or 1 , 1 '-carbonyldiimidazole.

The 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 72 hours.

The compounds of formula (le) can also be prepared by activation of the carboxylic acid, via acyl chloride or via mixed anhydride, as illustrated in scheme 10.

Scheme 10

The reaction is carried out by reacting a compound of formula (XI) where V represents a chlorine atom or a residue -0C(0)R_w, with R_w taking 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 ranging from 0 °C to the boiling temperature of the solvent for a time ranging from 1 to 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(0)-NRI-S(Q)2-

The compounds of general formula (I), with A representing the group -C(Y)-NRI-S(0)2-, wherein Y represents an oxygen atom and Ri 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 the compounds of general formula (le) 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 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

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

Scheme 12

The reaction can be carried out in the presence or absence 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 ranging from 0 °C to the boiling temperature of the solvent for a time ranging from 1 to 72 hours as widely 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 the literature and they can be commercially available or can be prepared according to methods well known in organic chemistry or according to what reported in WO2010/129500.

The compounds of formula (If), when Ri represents a group -C(Y)R2, a group -C(0)0R2, a group - C(0)NR2R3, a group -S(0)_rR2, a group -S(0)2NR2R3, can be synthesized by reaction of the compounds of general formula (le) with acyl, sulfonyl or sulfinyl chlorides, for example CIC(Y)R2, CIC(0)0R2, CIC(0)NR2R3, CIS(0)rR₂, CIS(0)2NR2R3, by acylation, sulfonylation or sulfinylation methods well known in the literature.

A = -C(S)-NRI-S(0)2- The compounds of general formula (I), with A representing the group -C(Y)-NRI-S(0)2-, wherein Y represents a sulfur atom and Ri 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 (lg)) can be prepared starting from the compounds of general formula (If) by reaction with phosphorus pentasulfide or with Lawesson reagent, as shown in scheme 13, according to procedures well known in organic synthesis.

Scheme 13

The compounds of general formula (I), with A representing the group -C(Y)-NRi-, wherein Y represents an oxygen atom and R 1 an H atom (compounds having general formula (lh)), can be prepared by reaction of the respective carboxylic acids of formula (IX) with amines or salts thereof of formula (XVI), as shown in scheme 14.

Scheme 1 ^*

The reaction conditions involve 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 salts thereof, N, N-dicyclohexylcarbodimide, N,N- diisopropylcarbodimide or 1 , 1 '-carbonyldiimidazole. The 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 72 hours.

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

Scheme

The reaction is carried out by reacting a compound of formula (XI) where V represents a chlorine atom or a residue -OCORw, with R_w taking the meaning of C1-C4 alkyl, obtained from the compound of general formula (IX) by methods known in literature with amine 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 ranging from 0 °C to the boiling temperature of the solvent for a time ranging from 1 to 72 hours as widely described in R.C. Larock“Comprehensive Organic Transformations” or in WO2010/129500 (2010).

A = -CfOTNRi-

The compounds of general formula I, with A representing the group -C(Y)-NRi-, wherein Y represents an oxygen atom and R1 a Ci-Ce alkyl group, a Ci-Ce haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group or a C3-C8 cycloalkyl group (compounds of general formula (li)) can be prepared by reaction between the compounds of formula Ih and appropriate Ci-Ce alkyl halides, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, 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 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

The compounds of formula (li), when Ri represents a group -C(Y)R2, a group -C(0)0R2, a group - C(0)NR2R3, a group -S(0)_rR2, a group S(0)2NR2R3, can be synthesized by reaction of the compounds of formula (li) with acyl, sulfonyl or sulfinyl chlorides, for example CIC(Y)R2, CIC(0)0R2, CIC(0)NR2R3, CIS(0)rR2, CIS(0)2NR2R3, by acylation, sulfonylation or sulfinylation methods well known in the literature.

Alternatively, the compounds of formula (II), wherein Ri represents a Ci-Ce alkyl group, a Ci-Ce 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.

Scheme 17

XVII

The reaction can be carried out in the presence or absence 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 ranging from 0 °C to the boiling temperature of the solvent for a time ranging from 1 to 72 hours as widely 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 methods well known in organic chemistry or according to what reported in R.C. Larock“Comprehensive Organic Transformations”.

A = -C(S)-NRi- The compounds of general formula (I), with A representing the group -C(Y)-NR, wherein Y represents a sulfur atom and Ri 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 (Ij)) can be prepared starting from the compounds of general formula (li) by reaction with phosphorus pentasulfide or with Lawesson reagent, as shown in scheme 18, according to procedures well known in organic synthesis.

Scheme 18

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 scope of the present invention to consider both the isomerically pure compounds having the general formula (I) and mixtures thereof, optionally 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 said, the compounds of general formula (I) are provided with a high nematocidal activity and at the effective doses do not show phytotoxicity with respect to the application cultures, making them suitable for use in the agrarian field against nematodes.

In particular, the compounds 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, Xiphinema spp, Trichodorus spp, Bursaphelenchus spp., Belonolaimus spp. and the like.

A second object of the present invention is method for controlling nematodes in cultivated areas by soil of at least one compound of

(XVIII)

wherein:

- n represents an integer of between 0 and 3;

- A represents a group selected from: -S-, -S(O)-, -S(0)2-, -C(=Y)-0-, -C(=Y)-NRi-, -C(=Y)-NRi- S(0)2-;

- Y represents an oxygen or sulfur atom;

- Ri represents a hydrogen atom, a Ci-Ce alkyl group, a Ci-Ce haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a

C(=Y)R₂ group, a C(=0)0R2 group, a C(=0)NR2R3 group, an S(=0)_rR2 group, an S(=0)₂NR₂R3 group;

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

- r represents an integer of 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 cycloalkyl group, a C3-C8 halocycloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic group, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above;

- m represents an integer of between 1 and 6;

- X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylenic, heterocyclic or heterocyclylalkylene group may optionally be substituted by one or more Q groups selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C6-cycloalkyl, C4-C9-cycloalkylalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxyl, Ci-Ce-haloalkoxyl, Ci-Ce- thioalkoxyl, Ci-Ce-thiohaloalkoxyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-alkoxycarbonyl, C3- C6-cycloalkoxycarbonyl, amino, N-Ci-C6-alkylamino, N,N-C2-Ci2-dialkylamino, N-Ci-Ce- alkoxycarbonylamino N-C3-C6-cycloalkylamino, N,N-C6-Ci2-cycloalkylamino, N-C3-C6- cycloalkoxycarbonylamino, Ci-C6-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, d -c6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, a (Ci-C6)-alkyl-heterocyclic optionally substituted group, penta- or hexa-atomic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide,

with the proviso that when A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, 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 (l-A), (l-B), (l-C), (l-D), (l-E), (l-F), (l-G), (l-H) or (l-l) as defined above but without any exceptions indicated therein, 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.

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

In the present method, the compounds of general formula (XVIII) can be effective in several stages of the development of the parasite, for example in reducing the hatching of the eggs, in killing the larvae, in inhibiting the growth rate of the population or in eliminating the adults.

The compounds of general formula (XVIII) can be applied at different times of the vegetative development of the plant, for example before transplanting/sowing or during growth, via leaves, or on the ground by fertigation, or incorporation into the ground, or by tanning of the seed. The amount of compound to be applied to obtain the desired effect can 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.

Compound doses between 10Og and 10OOOg 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 nematocidal activity containing, as an active substance, one or more compounds having general formula (XVIII) or (I), possibly also as a mixture of isomers.

Depending on the development phase of the parasite and of the applied quantity, the compounds of formula (XVIII) or (I) can act as nematostatics and/or nematocides.

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

A fourth object of the present invention is an agronomic composition for the treatment and prevention of phytoparasitosis from 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 soil.

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

The term carrier refers to a generally inert compound whose main function is to dissolve, dilute or disperse the active compound. By the term excipient it is meant 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 better stability of the composition, a better applicability thereof to plants or soil and similar.

It is possible to use compositions which are 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.

In the present composition at least one carrier may be present, 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. As inert solvent diluents or media, kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonite, diatomaceous earth, cellulose, starch, etc. can be used.

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

In the present composition one or more excipients may be present.

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

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.

Dispersants can also be added (for example lignin and salts thereof, cellulose derivatives, alginates, etc.), stabilizers (for example antioxidants, ultraviolet ray absorbers, etc.).

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, nematicides, fertilizers, biostimulants, etc. to broaden the 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 the 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, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid chinomethionat, chloroneb, chlorothalonil, chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, dichlomethyl, dichloran, diclocymet, diflumetorim, dimenirazol, dimethomor, dinocap, dinyrazone, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, famoxadone, fenamidone, phenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumetover, flumorph, fluopicolide , fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, furconazole, furconazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, iprovalicarb, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, metalaxyl, metalaxyl-M, metconazole, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, natamycin, nicobifen, nitrothal-isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, and salts thereof, penthiopyrad, phthalide , piperalin, Bordeaux mixture, polyoxins, probenazole, prochloraz, procymidone, propamocarb, propi conazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyphen, quintozene, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolylfluanid , triadimefon, triadimenol, triarimol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziram, sulfur, zoxamide.

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

acetochlor, acifluorfen, aclonifen, AKH-7088, alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, amitrole, anilophos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryne, BAY MKH 6561 , beflubutamid, benazolin, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzfendizone, benzobicyclon, benzofenap, benzthiazuron, bifenox, bilanafos, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chlorbufam, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chlorotoluron, chloroxuron, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, clomazone, clomeprop, clopyralid, chlorylulon (JC - 940), cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethatyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoseb, dinoseb, dinoterb, diphenamid, dipropetryn, diquat , dithiopyr, 1 -diuron, eglinazine, endothal, EPTC, exprocarb, ethalfluralin, ethametsulfuron-methyl, ethidimuron, ethiozin (SMY 1500), ethofumesate, ethoxyfen-ethyl (HC-252), ethoxysulfuron, etobenzanid (HW 52), fenoxaprop, fenoxaprop-P, fentrazamide, fenuron, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate (JV 485), flucarbazone-sodium, fluchloralin, flufenacet, flufenpyr ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, flumipropin , fluometuron, fluoroglycofen, fluoronitrofen, flupoxam, flupropanate, flupyrsulfuron, flurenol, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinat and, glyphosate, halosulfuron-methyl, haloxyfop, haloxyfop-P-methyl, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, iodosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, KPP-421 , lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mesosulfuron, mesotrione, metamitron, metazachlor, methabenzthiazuron, methazole, metobenzuron, metobromuron, metolachlor, S- metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monolinuron, naproanilide, napropamide, naptalam, NC-330, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pebulate, pendimethalin, penoxsulam, pentanochlor, pentoxazone, pethoxamid, phenmedipham, picloram, picolinafen, piperophos, pretilachlor, primisulfuron, prodiamine, p rofluazol, proglinazine, prometon, prometryne, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrazogyl (HSA-961 ), pyrazoxyphenate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyridafol , pyridate, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, pyroxasulfone quinclorac, quinmerac, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron, 2,3,6- TBA, TCA-sodium, tebutam, tebuthiuron, tepraloxydim, terbacil, terbumeton, terbuthyl-azine, terbutryn, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thifensulfuron-methyl, thiobencarb, tiocarbazil, thioclorim, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron, triclopyr, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron, UBI-C4874, vernolate.

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

bronopol, dichlorophen, nitrapyrina, nickel dimethyl dithiocarbamate, kasugamycin, octhylinone, furancarboxylic acid, probenazole, streptomycin, tecloftalam, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, copper salicylate.

Examples of insecticides, acaricides, nematocides that can be added to the 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, chlorpyrifos, chlorpyrifos M, clofentezine, cyhalothrin, chloropicrin, chlorantranilipid, chloropicrin, deltamethrin, diflubenzuron, dimethoat, dazonet, sulfuryl difluoride, dimethyldisulfide, emamectin, esfenvalerate, ethoprophos, etofenprox, etoxazole, fenamiphos, fenazaquin, fenoxycarb, fenpyroximate, fipronil, fluazinam, flufenoxuron, fluvalinate, fosthiazate, formentanate, flonicamid, formet, viruses, hexythiazox, imidacloprid, indoxacarb, lambda-cyhalothrin, lufenuron malathion, metaldehyde, methamidophos, Metharhizium spp, methiocarb, methomyl, methoxyfenozide, milbemectin, metaflumizone, metam sodium, metam potassium, oxamyl, Paecilomyces fumosoroseus, phosmet, pirimicarb, pirimiphos M, pyrethrum, pyridaben, pyriproxyfen, piperonyl butoxide, spinosad, spironesifen, spirotetramat, spinetoran, spirodiclofen, tau-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, thiacloprid, triflumuron, zeta-cypermethrin, (IR- cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)methyl]-2,2- dimethylcyclopropanecarboxylate, (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethyl-cyclopropane- carboxylate, 1 -[(2-chloro-5-thiazolyl)methyl]-5-triazine 2-(1 H)-imine, 2-(2-chloro-6-fluorophenyl)-4-[4- (l, 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-(2,6- dimethyl-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-d i hydro-6-oxo- 1 -(p henyl methyl)-4-py ri dazi nyl]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, 0,0-diethyl[2-(dipropylamino)-2-oxoethyl]-ethyl-phosphoroamidothioate. Examples of fertilizers and biostimulants which can be added to the 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-thiazolidincarboxylic acid, 4-acetylthiazolidine-carboxylic acid, ectoin, phytosterols.

The concentration of active substance in the aforesaid 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 comprised between 0.5 and 90% by weight.

Some examples are now given which are to be intended as descriptive and non-limiting of the present invention.

EXAMPLE 1

Preparation of 1 ,3,7-trimethyl-8-(3,4,4-trifluorobut-3-enylthio)-1 H-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) are added 440 mg of anhydrous potassium carbonate (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 mixture of h O/EtOAc, the phases are separated; the organic phase is washed with water and brine, subsequently dried, 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)-1 H-purine-2,6(3H,7H)-dione (compound 1.9)

To a solution of 1 ,3,7-trimethyl-8-(3,4,4-trifluorobut-3-enylthio)-1 H-purine-2,6 (3H,7H)-dione (220 mg, 0.66 mmol) in chloroform (6 mL) are added 160 mg (720 mmol) of m-chloroperbenzoic acid at 0 °C. It is left to slowly recover to room temperature, and the reaction is placed under stirring at room temperature for 12 hours. At the end of the reaction, the reaction solution is poured into a 5% aqueous solution of sodium metabisulfite, 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 anhydrated, filtered and evaporated. The crude compound is purified by chromatography on silica (eluent: heptane/EtOAc 1 :1 ). Compound 1.9 (100 mg, yield 43%) 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-enylsulfunyl)-1 H-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)-1 H-purine-2,6(3H,7H)-dion (compound 1.5) is prepared in 20 mL of chloroform, under a nitrogen atmosphere. The solution is cooled to 0 °C and added with 1.74 g (7.8 mmol) of m-chloroperbenzoic acid. 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 metabisulfite, 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 anhydrated, filtered and evaporated. The crude compound is purified by trituration with heptane. 550 mg (58% yield) of compound 1.13 are obtained as a white solid.

LC-MS [M+H⁺]: 367.

EXAMPLE 4

Preparation of 1 , 3, 7-tri methyl-2, 6-dioxo-2, 3, 6, 7-tetrahyd ro- 1 H-p u ri ne-8-carboxy late 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-1 H-purine-8- carboxylic acid in 1 mL of acetonitrile are added 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 to reflux for 9 h and after 36 hours at room temperature is recovered by evaporating the solvent. The residue is redissolved in dichloromethane and washed with cold water; the aqueous phase is re-extracted twice with dichloromethane, the combined organic phases are washed with brine, dried with sodium sulfate, filtered and evaporated. The crude thus obtained is purified by chromatography on silica, using a heptane/EtOAc gradient. The product 1.1 is obtained as a white solid (70 mg, 32% yield).

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- 1 H-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-1 H-purine-8- carboxylic acid (426 mg, 1.79 mmol), 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) is prepared. The solution is stirred at room temperature for 15 minutes, then 374 mg (1.68 mmol) of 2- chloro-5-methoxy-benzene sulfonamide are added and the mixture is left under stirring at room temperature. After 72 hours, the reaction solution is acidified by adding 1 M HCI, then it is extracted with dichloromethane (2x). The organic phase is washed with water, brine, then dried, filtered and evaporated. The crude is purified by chromatography on silica, 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-1 H-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-1 H-purin-8-yl acetic acid is prepared (550 mg, 2.18 mmol) 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 the mixture is 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 HCI 1 M, the phases are separated; the organic phase is washed with water, brine, then dried, filtered and evaporated. The residue is purified by chromatography on silica, 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-tri methyl-2, 6-di oxo 2, 253, 6, 7-tetrahyd ro- 1 H-purine- 8-carboxamide (compound 2.3)

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

EXAMPLE 8

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

Step A: preparation of 1 ,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1 H-purin-8-carbonyl chloride Under nitrogen atmosphere, 700 mg (2.94 mmol) of 1 ,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1 H- purin-8-carboxylic acid are diluted in 3 mL of dichloromethane; then a catalytic amount of DMF and 0.24 mL of SOCI2 is added; it is brought 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-1 H- purin-8-carboxamide.

The crude obtained in step A (1 ,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1 H-purin-8-carbonyl chloride) is dissolved 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 are washed with a saturated bicarbonate solution and then with brine. It is anhydrated, filtered and evaporated. The compound 3.1 is obtained as a white solid (910 mg, 90% yield on two steps).

LC-MS [M+H⁺]: 346.2.

EXAMPLE 9

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

1 ,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1 H-purin-8-yl acetic acid is prepared (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, 13.1 1 mmol) are added in sequence and the mixture is 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 HCI 1 M, the phases are separated; the organic phase is washed with water, brine, then dried, filtered and evaporated. The residue is purified by chromatography on silica, 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-1 H-purin-8-carboxamide (compound 3.3)

1 g (3.9 mmol) of 1 ,3,7-trimethyl-2,6-dioxo-2,3,6,7-tetrahydro-1 H-purin-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 are washed with a saturated bicarbonate solution and then with brine. It is anhydrated, filtered and evaporated. The compound 3.3 is obtained as a white solid (1.4 g, 81 % yield on two steps).

LC-MS [M+H⁺]: 445.7.

Operating similarly to the preceding examples, the compounds shown in Table 4 were prepared.

Table 4

Table 5 shows the results of the LC-MS analyses 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 1 1

Determination of nematocidal activity against Meloidoqyne sp.

Tests aimed at testing the nematocidal activity of the product under examination are carried out using inocula taken from a Meloidogyne sp. maintained on tomato and cucumber plants in pots and bred in greenhouses.

To carry out the experiments, from the infested pots portions of roots are taken that have a good number of galls and soil, in which there are larvae starting from the second stage of age.

New pots with a diameter of 15 cm are half filled with sterile soil. On it are placed the portions of infested roots, previously cleaned, in order to correctly assess the degree of infestation and ensure that each pot contains the same nematic load. Then 200-300 g of infested soil are added, which are covered with a thin layer of sterile soil.

The treatment is carried out by pouring 100 ml of aqueous solution containing 10% of acetone into which the product to be tested was dissolved at a concentration between 70 and 100 ppm.

In the so prepared pots, after one or seven days from the application, tomato or cucumber seedlings are transplanted to the stage of two or three true leaves. Different tomato cultivars (Microtom, Marmande) or cucumber (Lungo della Cina) are used, with different sensitivity to the parasite and different growth times. In particular, for the estimation of the final production, a variety of ornamental tomato (cv Microtom) is used, whose plants are small and able to reach the ripeness of the fruit in about two months in pots and in greenhouse conditions.

The containment capacity of the parasite is detected, 30 and 60 days after transplanting, considering the development of the plant (whose fresh weight is detected), and the presence of galls on the roots. This is estimated either by 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 the 0% of root hit and to the value 10 corresponds the 100% of infested root, both considering the percentage of affected root mass. ln addition, the product was evaluated considering the possible phytotoxic effects that could 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 related to the effectiveness 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 test at 30 days from transplantation.

Table 6

As evidenced by the data reported in Table 6, the compounds according to the invention show a gall- index and a percentage of infested root decidedly lower than those of both the infested and untreated plants (infested sample), and those treated with caffeine. The reduction of the 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 exhibit phytotoxicity at effective doses.

Finally, it can be observed from the data reported herein that caffeine turns out to be even pejorative as a nematicide, with an increase in the gall-index and the percentage of infested root, compared to infested and untreated plants (infested sample).

Claims

1. A compound of formula (I):

- n represents an integer of between 0 and 3;

- A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, -C(=Y)-NRi-, -C(=Y)- NRI-S(0)₂-;

- Y represents an oxygen or sulfur atom;

- Ri represents a hydrogen atom, a Ci-Ce alkyl group, a Ci-Ce haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C4-C9 cycloalkylalkyl group, a C(=Y)R₂ group, a C(=0)0R2 group, a C(=0)NR2R3 group, an S(=0)_rR2 group, an S(=0)₂NR₂R3 group;

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

- r represents an integer of 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 cycloalkyl group, a C3-C8 halocycloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic group, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above;

m represents an integer of between 1 and 6; - X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylenic, heterocyclic or heterocyclylalkylene group may optionally be substituted by one or more Q groups selected from halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C3-C6-cycloalkyl, C4-C9-cycloalkylalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxyl, Ci-Ce- haloalkoxyl, Ci-Ce-thioalkoxyl, Ci-Ce-thiohaloalkoxyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce- alkoxycarbonyl, C3-C6-cycloalkoxycarbonyl, amino, N-Ci-C6-alkylamino, N,N-C2-Ci2-dialkylamino, N- Ci-C6-alkoxycarbonylamino N-C3-C6-cycloalkylamino, N,N-C6-Ci2-cycloalkylamino, N-C3-C6- cycloalkoxycarbonylamino, Ci-Ce-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a

NR2R3CONR2- group; formyl, d -c6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, a (Ci-C6)-alkyl-heterocyclic optionally substituted group, penta- or hexa-atomic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, optionally oxidized to N-oxide,

with the proviso that when A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, 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)

wherein

- each R₄ independently represents halogen, a hydroxyl group, a Ci-Ce alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a Ci-Ce alkoxyl group, a C2-C6 alkenyloxyl 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;

- p represents an integer of between 0 and 3;

- R5 represents a halogen, a hydroxyl group, a Ci-Ce alkyl group, a C2-C6 alkenyl group, a C2- C6 alkynyl group, a C1-C6 alkoxyl group, a C2-C6 alkenyloxyl 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.

2. The compound according to claim 1 of formula (l-A), wherein:

- n is an integer of 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 Ci-Ce alkyl group, a C3-C8- cycloalkyl group, an aryl group, a C7-C14 arylalkylene group, a naphthyl group or a heterocyclic, penta- or hexa- atomic, aromatic or non-aromatic group, also benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group, wherein the heterocyclic group is as defined herein; and - m represents an integer of between 1 and 5.

3. The compound according to claim 1 of formula (l-B), wherein:

- n is an integer selected from 0 and 1 ;

- A represents a group selected from: -S(=0)-, -S(=0)2-, -C(=0)-0-, -C(=0)-NRi-, -C(=0)-NRi- S(=0)2-;

- R1 represents a hydrogen atom or a Ci-Ce 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 benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur and nitrogen or a C3-C9 heterocyclylalkylene group, wherein the heterocyclic group is as defined herein; and

- m represents an integer of between 1 and 5.

4. The compound according to claim 1 of formula (l-C), wherein:

- n is an integer of between 0 and 1 ;

- A represents a group selected from: -S(=0)-, -S(0)2-, -C(=0)-0-;

- R1 represents a hydrogen atom or a Ci-Ce alkyl group;

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

- m represents an integer of between 1 and 5.

5. The compound according to claim 1 of formula (l-D), wherein:

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

- n is selected from 0 and 1.

6. A compound according to claim 1 , wherein:

- A represents a group selected from: -C(=Y)-NRi- and -C(=Y)-NRI-S(0)2-;

- n is selected from 0 and 1 ; and

- E represents a group selected from an aryl group, a naphthyl group, or a C7-C14 arylalkylene group (formula l-F);

or

- E represents a group selected from a heterocyclic group, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur and nitrogen, or a C3-C9 heterocyclylalkylene group, wherein the heterocyclic group is as defined above (formula l-G).

7. The compound according to claim 1 of general formula (I), wherein n, A and E take the following meanings:

8. A method for controlling nematodes in cultivated areas by applying to the plant and/or soil of at least one compound of general formula (XVIII):

(XVIII)

wherein:

- n represents an integer of between 0 and 3;

- A represents a group selected from: -S-, -S(O)-, -S(0)2-, -C(=Y)-0-, -C(=Y)-NRi-, -C(=Y)-NRi- S(0)2-;

- Y represents an oxygen or sulfur atom;

- Ri 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 C(=Y)R₂ group, a C(=0)0R2 group, a C(=0)NR2R3 group, an S(=0)_rR2 group, an S(=0)₂NR₂R3 group; - R2 and R3, equal to or different from each other, represent a hydrogen atom, a Ci-Ce alkyl group, a Ci-Ce haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, an aryl group, a benzyl group;

- r represents an integer of between 0 and 2;

- E represents a group selected from -(CH2)m-CX=CF2, a Ci-Ce alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C3-C8 cycloalkyl group, a C3-C8 halocycloalkyl group, a C4-C9 cycloalkylalkyl group, an aryl group, a naphthyl group, a C7-C14 arylalkylene group, a heterocyclic group, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, or a C3-C9 heterocyclylalkylene group wherein the heterocyclic group is as defined above;

- m represents an integer of between 1 and 6;

- X represents a hydrogen or fluorine atom;

wherein said aryl, naphthyl, benzyl, arylalkylenic, heterocyclic or heterocyclylalkylene group may optionally be substituted by one or more Q groups selected from halogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C3-C6-cycloalkyl, C4-C9-cycloalkylalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxyl, Ci-Ce-haloalkoxyl, Ci-Ce- thioalkoxyl, Ci-Ce-thiohaloalkoxyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-alkoxycarbonyl, C3- Ce-cycloalkoxycarbonyl, amino, N-Ci-C6-alkylamino, N,N-C2-Ci2-dialkylamino, N-Ci-Ce- alkoxycarbonylamino N-C3-C6-cycloalkylamino, N,N-C6-Ci2-cycloalkylamino, N-C3-C6- cycloalkoxycarbonylamino, Ci-Ce-alkylaminocarbonyl, C3-C6-cycloalkylaminocarbonyl, a NR2R3CONR2- group; formyl, d -c6-alkylcarbonyl, carboxyl, cyano, an optionally substituted aryl, a benzyl, a heterocyclic, optionally substituted, penta- or hexa-atomic, aromatic or non-aromatic, also benzocondensate or heterobicyclic, containing at least one heteroatom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, a (Ci-C6)-alkyl-heterocyclic optionally substituted group, penta- or hexa-atomic, also benzocondensate or heterobicyclic, containing at least one hetero atom selected from oxygen, sulfur, nitrogen, optionally oxidized to N-oxide, with the proviso that when A represents a group selected from: -S-, -S(=0)-, -S(=0)2-, -C(=Y)-0-, 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, Xiphinema spp, Trichodorus spp, Bursaphelenchus spp. and Belonolaimus spp.

10. 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 phytoparasitosis from nematodes 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.

12. The composition according to claim 11, further comprising at least one second active compound selected from herbicides, fungicides, bactericides, insecticides, acaricides, nematicides, fertilizers and biostimulants.