FR2722499A1 - NEW DERIVATIVES OF 2-IMIDAZOLINE-5-ONES FUNGICIDES - Google Patents

Abstract

2-imidazoline-5-one derivatives of general formula (I), wherein R<1> is H, vinyl, allyl, C1-3 alkyl or C1-3 haloalkyl; R<2> is a mono- or bicyclic aromatic heterocyclic radical having 5-10 atoms of which 2-4 are heteroatoms selected from O, S or N, and being joined to the imidazolinone nucleus via a carbon or nitrogen atom, and further being optionally substituted; R<3> is a hydrogen atom when n = 0, or a C1-3 alkyl or haloalkyl group or a cyclopropyl group; R<4> is an aromatic heterocyclic or aryl radical; R<5> is H, C1-3 alkyl or C1-3 haloalkyl; n is 0 or 1; Y is an oxygen or sulphur atom; and W is O, S or SO. The preparation of said derivatives and their use as broad-spectrum fungicides are also disclosed.

Description

I

New derivatives of 2-imidazoline-5-ones fungicides.

The present invention relates to novel compounds with a 2imidazolin-5-one group for phtosanitary use. It also relates to the processes for the preparation of said compounds and the products which may be used as intermediates in the preparation prcédés. Finally, it relates to the fungicidal compositions based on these compounds and the processes for combating fungal attacks on crops using these compounds. 2ihT: dazcline-5-ones for phytosanitary use are known from European patent applications EP 551048 and EP 599749 and from applications

international WO 93 24467 and WO 94 01410.

An aim of the present invention is to provide new compounds comprising a '-imidazolin-5-one group exhibiting improved properties.

in the treatment of fungal attacks on crops.

Another aim of the present invention is to provide compounds exhibiting a spectrum of use which is also improved in the field of fungal attacks. especially for the treatment of fungal attacks in rice

and for the treatment of brown rust of wheat.

It has now been found that these goals can be achieved, by

in whole or in part. by means of the products of the invention. described below.

A subject of the invention is firstly compounds which are derivatives of 2-imidazolne-5-ones of general formula (I): R / N '=, / :) n- R R

- T R4

RD in which: - R1 represents a hydrogen atom, or a vinyl or allyl group, or an alkyl or haloalkyl radical with 1 to 4 carbon atoms - R2 represents an aromatic heterocyclic radical, mono or bicyclic, having from 5 to 10 atoms in the ring (s), among which 2 to 4 are heteroatoms chosen from O, S, or N, which radical being linked to the imidazolinone ring by a carbon or nitrogen atom, and being optionally substituted by 1 to 5 groups , preferably by 1 to 3 groups. chosen from the meanings of R6, each sulfur or nitrogen atom linked to a cycle of said radical optionally carrying a positive charge and linked to an oxygen located outside the cycle and carrying a negative charge - or else R1 represents a divalent ethylene, trimethylene or tetramethylene radical whose second valence is connected to the atom of R2 adjacent to the atom through which R2 is connected to the imidazolinone ring - R3 represents - the hydrogen atom when n = 0 , or - an alkyl or haloalkyl group of 1 to 3 carbon atoms or the cyclopropyl group - R4 represents an aryl or aromatic heterocyclic radical chosen from phenyl and naphryl. pyridyl. pyrimidinyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl. thiazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, isothiazolyl. oxadiazolyl, thiadiazolyl, or methylene dioxyphenyl. each of these radicals being optionally substituted by 1 to 7 groups. preferably from 1 to 3 groups, chosen from the radicals having the same meanings as R6 - R5 represents a hydrogen atom. an alkyl or haloalkyl radical of 1 to 3 carbon atoms. an acyl radical of 2 to 6 carbon atoms, an alkoxycarbonyl radical of 2 to 6 carbon atoms. or a formyl, aroyl or cyclopropyl radical. arloxycarbony the. alkylsulfonyl, arylsulfonyl, alkvloxalyl or alkoxyoxalvle -n = O or 1; Y represents the oxygen atom or the sulfur atom - W represents O, S or SO; - R6 represents: - a halogen atom or the hydroxy, mercapto, nitro or cyano group. thiocvanato or azido: or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio radical. alkylsulfinyl. alkylsulfonyl, haloalkylsulfinyl or haloalkylsulfonyl, each of 1 to 6 carbon atoms; or - a cycloalkyl or halocycloalkyl radical of 3 to 6 carbon atoms - an alc.nyloxy, alkynyloxy, alcer.ylio, alkynylthio radical, each of 2 to 6 carbon atoms: or - an amino radical. optionally mono or disubstituted with an alkyl radical of 1 to 6 carbon atoms or an acyl radical of 2 to 6 carbon atoms; or - an alkenyl group. alkynyl, alkoxycarbonyl, cyanoalkoxy, cyanoalkylthio, cyanoalkyl, N-alkylcarbamoyl of 2 to 7 carbon atoms or - an NN-dialkylcarbamoyl group of 3 to 13 carbon atoms or - a radical of formula -X-R7 in which - X represents a sequence of general formula (R) j- (A) k- (R ') m in which - j. k. m identical or different, are equal to O or 1: - R and R '. identical or different, represent a hydrocarbon chain. saturated or unsaturated. which contains 1 to 6 carbon atoms. possibly substituted by 1 to 12 groups. preferably with 1 to 3 groups, chosen from R8, and in which one or more of the carbon atoms can be replaced by O, S, N (R9) - A represents a divalent, mono or polyatomic group comprising O, S. N (R9), SO, SO2, CO, CS, Si (RlO) (R'10), N2, C (R ") (R" l), or

R9-N -N R9-N

C- or I / C- or S-

R12 or Ri2

RI1 \ R'II RI R'11

or -C - C or -CC- or> 7 <z in which Z represents 0, S. C (R13) (R'13) R7 represents a mono or bicyclic system of 5 to 10 atoms, aromatic, saturated or unsaturated , and which is either a carbocyclic system or a heterocyclic system comprising from 1 to 4 heteroatoms chosen from O, S, or N. and which comprises the phenyl, naphthyl, dihydronaphthyl, tetrahydronaphthyl, thienyl and furyl radicals. pyrrolyl, pyridyl, benzothienyl, benzofuryl. indanyl, indolyl, quinolinyl, isoquinolinyl, methylenedioxyphenyl. pyrazolyl. imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl. thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyrimidinyl. pyrazinyl. pyridazinyl, triazinyl, tetrazinyl, each of these radicals being optionally substituted by 1 to 7 groups, preferably by 1 to 3 groups. chosen from the radicals having the same meanings as R'4 - R8 represents a halogen atom, a cyano, thiocyanato or oxo group. thioxo. carboxy ,. amino. hydroxyl, thiol, acyloxy, alkyl, aroyloxy, heteroaroyloxy, arvlacyloxy, cycloalkylcarbonyloxy, acylthio, aroylthio, heteroaroylthio, arvlacylthio. cycloalkylcarbonylthio, carbamoyloxy,

carbamovlthio. thiocarbamoviox, dithiocarbamoyl, acylamino.

cycloalkylcarbonylamino, aroylamino, ureido, thioureido, alkoxycarbonylaniino, aryloxycarbonylamino, alkylsulfonylamino, arylsulfonylamino, aminosulfonylamino - R9 represents - a hydrogen atom or a cyano, hydroxy, amino, formyl group. morpholino. piperidino, piperazino, or - an alkyl radical. haloalkyl, alkoxy, haloalkoxy, alkylsulfonyl, haloalkylsulfonyl, each of 1 to 6 carbon atoms, or - a cyanoalkyl, cyanoalkoxy, cyanoalkylsulfonyl radical, each comprising from 2 to 6 carbon atoms, or - an amino radical, optionally mono or disubstituted by an aryl radical or an alkyl radical of 1 to 6 carbon atoms, or - a cycloalkyl radical. halocycloalkyl of 3 to 6 carbon atoms, or - an alkenyl radical. alkynyl, alkenyloxy, alkynyloxy, acyl or alkoxycarbonyl of 2 to 6 carbon atoms; or - a carbamoyl radical of 2 to 7 carbon atoms or a sulfamoyl radical of 1 to 6 carbon atoms; or - an aroyl or arylsulfonyl radical; or - an alkyloxalyl or alkoxyoxalyl radical of 3 to 8 carbon atoms: or - an oxamyl radical of 2 to 8 carbon atoms -R10 and R'10, identical or different, represent - an alkyl radical of 1 to 6 carbon atoms ; or - a cycloalkyl radical of 3 to 7 carbon atoms; or - an alkenyl or alkynyl radical of 2 to 6 carbon atoms; or - an arylalkyl radical, preferably benzyl, or an aryl radical, preferably phenyl optionally substituted with 1 to 5 groups, preferably with 1 to 3 groups. chosen from the meanings of R14 - Rll and R'1l which are identical or different, represent the hydrogen atom or an alkoxy radical or have one of the meanings of R8; - Rt 'represents - the hydrogen atom, or a morpholino, piperidino, pyrrolidino or piperazino group; or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or haloalkylthio radical, each of 1 to 6 carbon atoms; or - a cyanoalkyl, cyanoalkoxy or cyanoalkylthio radical, each of 2 to 7 carbon atoms; or a dialkylamino radical - R13 and R'13, which are identical or different, represent the hydrogen atom or a halogen or an alkyl group of 1 to 3 carbon atoms - R'4 represents: - a halogen atom or the hydroxy, mercapto, nitro, cyano, thiocyanato or azido group; or an alkyl radical. haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkvlsulfinyl. alkylsulfonyl, haloalkylsulfminyl, haloalkylsulfonyl, each of 1 to 6 carbon atoms; or - a cyanoalkyl, cyanoalkoxy or cyanoalkcylthio radical, each of 2 to 7 carbon atoms; or - a cycloalkyl or halocycloalkyl radical of 3 to 6 carbon atoms; or - an alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical. each of 2 to 6 carbon atoms; or - an amino radical, optionally mono or disubstituted by an alkyl radical of 1 to 6 carbon atoms or by an acyl or alkoxycarbonyl radical of 2 to 6 carbon atoms; or - an alkoxycarbonyl group of 2 to 7 carbon atoms; or - an N-alkylcarbamoyl group of 2 to 7 carbon atoms; or

- an N.N-dialkylcarbamoyl group of 3 to 13 carbon atoms.

A subject of the invention is also the salified forms, the tautomeric forms, as well as the stereoisomers and diastereomers of the compounds of

formula (I).

It relates in particular to the optical isomers resulting from the presence of one or more asymmetric carbons, and most particularly, the

optical isomers arising from the presence of the asymmetric carbon of the 2- nucleus

imidazolin-5-one carrying R 1 and R 2. These optical isomers are compounds that are optically pure or highly enriched in one enantiomer. In what follows, the term “optically active compound highly enriched in a given enantiomer” is understood to mean a compound containing at least 80%, preferably at least 90% of this enantiomer. All these compounds are considered as included in formula (I) defined above. When the compound of formula (I) is such that R2 represents a mono or bicyclic aromatic heterocyclic radical as defined above and / or that R4 represents an aromatic heterocyclic radical, and when at least one of these radicals is substituted by an OH, SH, NH group, this compound is capable of admitting a tautomeric form in chemical equilibrium, resulting from the displacement of the proton of said OH, SH, NH group. Tautomeric forms of such compounds are included in the invention. More generally, the tautomeric forms of the compounds of formula (T) in which R2 represents a mono or bicyclic arcmatic heterocyclic radical as defined above are also included in the invention and / or R4 represents an aromatic heterocyclic radical. Such tautomeric forms are in particular defined in the work "The tautomerism of heterocycles, Advances in

Heterocyclic Chemistry ,, Supplement 1 "by J. Elguero, C. Martin, A.R.

Katritzkv, P. Linda. edited by Academic Press, New York, 1976, pages 1-4.

Moreover, the term “haloalkyl radical” is understood to mean within the meaning of the present

description an alkyl radical substituted by one or more halogen atoms.

Among the compounds of general formula (I), preference is given to those in the formula of which R2 is chosen from a derivative radical, by elimination of a hydrogen atom. of one of the following rings - a 5-link ring described by the formula (i) QA- A4 (i) in which each of the groups in the list A1, A2, A3, A4, is chosen from the CNO S atoms of such that said list comprises from 0 to 2 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 oxygen atom and from 1 to 4 nitrogen atoms: or else - a 6-link ring described by formula (ii) B'OB2 (ii) in which each of the groups of list B1, B2, B3, B4, B5, is chosen from atoms C or N such that said list comprises from 1 to 3 atoms of carbon and from 2 to 4 nitrogen atoms; or - two merged cycles with 6 links each, described by formula (iii):

EJ E6

EA E 7

(iii) in which each of the groups of the list E1, E2, E3, E4, E5, E6, E7, E8 is chosen from C or N atoms such that said list comprises 4 to 6 carbon atoms and 2 to 4 nitrogen atoms; or else a cycle with 6 links and a cycle with 5 fused links described by formula (iv) GL, - LlJ G4 (iv) in which: - each of the groups of the list G1, G2, G3, G4, G5, G6 is chosen from C, N atoms such that said list comprises from 0 to 6 carbon atoms. and from 0 to 3 nitrogen atoms; and - each of the letters of the list L1, L2, L3 is chosen from C, NO or S atoms such that said list comprises from O to 3 carbon atoms, from O to 1 sulfur atom, from O to i oxygen atom and from 0 to 3 nitrogen atoms: or - two fused rings with 5 links each described by the formula (. -)

Q3 T3

Q I - .. / .- Ti (v) in which: - each of the groups of the list Q1, Q2, Q3, represents the atoms C, N. O, S such that said list comprises from 0 to 3 atoms carbon, from 0 to 1 atom of sulfur, from 0 to 1 atom of oxygen and from 0 to 3 atoms of nitrogen; - each of the groups of the list TI, T2, T3 represent the atoms C, N, O. S such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 atom of oxygen and from 0 to 3 nitrogen atoms —Z represents the C or N atoms. It is understood that in formulas (i). (ii), (iii), (iv), (v) indicated above. the groups which represent a carbon or nitrogen atom either carry the free valence which connects R2 to the imidazolinone nucleus of formula (I). or carrying the number of hydrogen atoms required for checking the valence rules well known to those skilled in the art. Among the more especially preferred values of R2 defined above, the following heterocyclic rings are still preferred - pTazoly le; imidazolle: oxazolvle; isoxazolyl; thiazolyl

isothiazolyl 1.2.3-oxadiazolyl 1.2.4-oxadiazolyl; 1,2,5-

oxadiazolyl 1.3.4-oxadiazolyl 1,2.3-thiadiazolyl; 1,2,4-

thiadiazolvyl 1.2.5-thiadiazolyl; 1,3,4-thiadiazolyl; 1,2,3-

triazolvle; 1.2.4-triazolyl: tetrazolyl

- p yrimidinyle pyTazinyle pyridazinyle; 1.2,3-triazinyl; 1,2,4-

triazinyl 1.3.5-triazinyl; 1.2.3,4-tetrazinyl 1,2.3,5-tetrazinyl 1. 2.4 ._- tetrazinvle - indazolle benzimidazolvle; benzotriazolyl; benzoxazolyl

I.2-Benzisoxazol-le: 2.I-benzisoxazolyl benzothiazolvle; 1,2-

benzisothiazolyl: 2.1-benzisothiazolyl: 1.2.3-benzoxadiazolyl;

1,2,5-benzoxadiazolyl; 1,2,3-benzothiadiazolyl; 1,2,5-

benzothiadiazolyl; - quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl; benzotriazinyl; - 1,5-naphthvridinyl; 1,6-naphthyridinyl; 1,7-naphthyridinyl; 1,8-naphthvridinyl; imidazo ['. 1-b] thiazolyl; thieno [3,4-b] pyridyl; purine

pyrolo [1.2-b] thiazolyl.

Advantageously. more preferred are the compounds of formula (I) in which at least one of the following characteristics is verified - R2 is chosen from one of the following heterocycles - pTyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazole isothiazoivle; 1,2.5-oxadiazolyl; 1,3,4-oxadiazolyl;

1,2 4-thiadiazolyvle; 1,25-thiadiazolyl; 1.3,4-thiadiazolyl; 1,2,4-

triazolyl - pyrimidinyl; pyrazinyl; pyridazinyl; 1,3,5-triazinyl; benzimidazolyl; indazolyl; benzotriazolyl benzoxazolyl: 1.2benzisoxazolyl; 2,1-benzisoxazolyl; benzothiazolyl: 1.2-benzisothiazolyl; 2,1-benzisothiazolyl; - quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl; and / or - R4 is chosen from a phenyl, pyridyl, benzothiazolyl group, and / or - R5 is a hydrogen atom, and / or

- W is an oxygen atom.

A very particularly preferred group of compounds of formula (I) is obtained by combining one of the preceding characteristics with one of the following meanings of R2 - pyTazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl isothiazolyvle 1. 2.4-thiadiazolyl; 1,2,5-thiadiazolyl; 1.3.4-thiadiazolvil - pyrimidinyl - benzoxazolyl; benzothiazolyl;

- quinazolinyl.

The compounds of formula (I) are prepared according to at least one of the two preparation methods explained below. When certain reagents and certain operating conditions described in the following are not compatible with certain functional groups of the groups of formula (1), those skilled in the art advantageously have recourse to well-known techniques of protection and / or deprotection necessary for the preparation of the desired compounds of formula (I), in particular using the techniques described in the book “Protective groups in organic synthesis” by Theodora W. Greene and Peter GM Wuts, edited by John

Wiley & Sons, Inc .. 2nd edition.

All the groups appearing in the chemical formulas which follow, and already defined in the general formula (I). keep the same meaning, for

as far as it is not specified otherwise.

The structures of all the products which illustrate these processes have been established by at least one of the following spectral techniques: nuclear magnetic resonance spectrometry (RIMN) of protun, RIMN spectrometry of carbon 13,

Infra-Red spectrometry and mass spectrometry.

In the table which brings together these products, the ethyl and phenyl radicals are

respectively represented by Et and Ph, and PF means melting point.

First method of preparation A first method of preparing the compounds of

formula (I). according to the particular meaning of the group (Y) n.

Process A detailed below describes a method of preparing the compounds of formula (I) in which n equals 1 and Y represents S. Process A: The compounds of formula (I) in which n equals 1 and Y represents S and W represents O. or the compounds of formula (II), are prepared by hydrolysis of -imino-imidazoline of formula (III) according to the reaction scheme Ri N Sc. R1 N S-R3 2 N R4 aNRsolvent R2t R4 NN PIN o50 15

R R

III II

As acidic, a mineral or organic acid is used. The reaction is carried out in an organic solvent. in water or in a water / organic solvent mixture, comprising one or two liquid phases. As organic solvent, cyclic or acyclic ethers, esters, chlorinated solvents, alcohols, aromatic solvents, acetonitrile, acetone and organic acids can be used. The reaction is carried out at a temperature between 5 and C. The following example illustrates the preparation of the compounds of formula (II) by this

process.

Example CF1 (4-R, S) -4-methyl-2-methylthio-i-phenylamino-4- (2-phenyl-

thiazol-4-vl) -imidazolin-5-one (compound 9), of formula

H-C N- 'S-CH3

Phu \ Il é N "Ph H

A solution of 15 g (39 mrnol) of (4-R.S) -5-imino4-methyl-2-methylthio1-

phenylamino-4- (2-phenyl-thiazol-4-yl) -2-imidazoline in 100 ml of dichloromethane is a2itée with 100 ml of dilute aqueous hydrochloric acid solution for 1 h at room temperature. The reaction medium is then neutralized; the organic phase is separated from the aqueous phase, dried, filtered and evaporated. After recrystallization, 2.9 g of solid are obtained (mp =

233 C, yield 55%). which is (4-R, S) 4-methyl-2-methylthio-1-

phenylamino-4- (2-phenyl-thiazol-4-yl) -imidazolin-5-one. The compounds of formula (III) are prepared according to the reaction scheme R 'NiX

R 'N = C = S HN-NR4'R5 R N ,,

-s

R2> N

R CN solvent L (R5

(V) (IV)

R [N ... S

r "s-3 R2 N NR base R

P- 2 N, N

R3 - L N

END HI

(IV) (III)

in which: - L represents a leaving group chosen from the atom of chlorine, bromine, iodine, or the sulfate group. or an alkylsulfonyloxy or arylsulfonyloxy group: - the base is chosen from an alkaline or alkaline-earth alcoholate, from

preferably potassium tert-butoxide, an alkali or alkaline hydroxide

earth, an alkali or alkaline earth carbonate or a tertiary amine the solvent is chosen from ethers, cyclic ethers, acetonitrile,

alcohols, chlorinated solvents. aromatic solvents.

The reaction is carried out at a temperature between -5 C and +80 C.

The following example illustrates this process for the preparation of the compounds of

formula (III).

Example CIl: (4-R.S) -5-imino-4-methyl-2-methylthio-1 -phenylamino4- (2-

phenyl-thiazol-4-yl) -2-imidazoline, of formula

H-C N S-CH3

N \ ..- N .. "Ph N H

A 17.3 g (64 mmol) of (2-R.S) -2-isothiocyanato-2- (2-phenyl-thiazol-4-yl) -

propionitrile in 150 ml of THF are added 4.3 ml (64 mmol) of phenylhydrazine. After 30 rmn. the reaction medium is cooled to 0 ° C. and 7.9 g (70 mmol) of potassium tert-butoxide are added. After allowing to react min, 4.5 ml (70 mmol) of methyl iodide are added and the mixture is stirred at room temperature for 30 min. 200 ml of ether and 200 ml of water are added. The organic phase is separated and then dried, filtered and evaporated. The residual solid is crystallized with diisopropyl ether, filtered and dried. We

obtains 15.5 g of brown solid (mp = 123 C. Yield 64%), which is (4-

R. S) -5-imino-4-methyl-2-methylthio- 1-phenylamino-4- (2-phenyl-thiazol-4yl) -2-

imidazoline. The compounds of formula (V) are prepared according to the reaction scheme r

RI NH4C1 / MCN R1 \ 2 C2C = S R1 N = C = S

R-) solvent I | R2 soa 2> <-

CN CN

(VII) (VI) (V)

in which: - MNI represents Na. K. or (CH3) 3Si - the solvent 1 is chosen from an alcohol, a cyclic or non-cyclic ether, acetonitrile - the solvent 2 is chosen from an aromatic or aliphatic hydrocarbon. The isothiocyanates of formula V) derived from aminonitriles are prepared from the corresponding aminonitriles of formula (VI) according to one of the processes cited in Sulfur Reports (1989) Volume 8 (5) pages 327-375. One can also use one of the methods described in Advanced Organic

Chemistry ', J March, 3rd Edition, (1985) pages 370, 803.

The aminonitriles of formula (VI) are obtained from the corresponding ketones of formula (VII) by a Strecker reaction as described in Advanced Organic Chemistrv, J March, 3rd edition, (1985) page 855. The reaction is optionally carried out in the presence of ammonia. A variant of this process consists in carrying out the reaction under ultrasound in the presence of alumina as described by T. HANAFUSA, J. ICHIHARA, T.

ASHIDA, Chem. Lett., (1987), pp. 687 to 690.

The following example illustrates the preparation of a compound of formula (V).

Example CI2. (2-R.S) -2-phenyl4- (2-isothiocyanate-prop-2-yl-nitrile) thiazole, fo, -mule (V)

HC N = C-S

Ph N, 4 g (0.42 mol) of sodium cyanide and 22.3 g (0.42 mol) of ammonium chloride are dissolved in 25 ml (0.42 mol) of concentrated ammonia and ml of water. 42 g (0.21 mol) of 2-phenyl-4-acetyl thiazole in 100 ml of ethanol are added and the mixture is heated to 60 ° C. After 2 h, the mixture is cooled to room temperature. 300 ml of toluene and 200 ml of water are added and the mixture of the 2 liquid phases is filtered. The organic phase is dried, filtered and concentrated to reduce the volume to 200 ml. This aminonitrile solution is mixed with 84 g (0.84 mol) of calcium carbonate and 32 ml (0.42 mol) of thiophosgene. The mixture is heated at reflux for 2 h,

filtered and evaporated. We obtain 17.3 g of brown liquid which is (2-R, S) 2-phenyl-

4- (2-isothiocyanate-prop-2-yl-nitrile) thiazole.

The compounds of formula (VII) are obtained by different methods and combinations of methods described in the literature such as those cited in Heterocyclic Chemistry, T.L. Gilchrist, second edition, (Longman Scientific and Tehnical 1992); Comprehensive heterocyclic chemistry, the structure, reactions synthesis and uses of heterocyclic compounds, A.R. Katritzky, C.W. Rees, Volumes 3, 5 and 6; or the series The chemistrv of Heterocyclic compounds, A series of monographs. A. Weissberger; E.C. Taylor, dealing with heterocycles such as

described above.

It is also possible to use methods such as those described: ar 10 T. Coronna, G.P. Gardini. F. Minisci, J. Chem Soc, Chem Commun, page 201 (1969) G.P. Gardini, F. Minisci. J. Chem Soc C, page 929 (1970) F. Fontana. F. MIinisci: MNI.C. Nogueira Barbosa, E. Vismara, J. Org. Chem., Vol 56. page 2866 (1991); V.N. Kalinin, Synthesis. page 413 (1992) N.K. Ralhan. G. S. Sandhu, H. S. Sachdev, K. S. Narang; J. Indian Chem. Soc., Vol 37, page 773 (1960)

M. Ryozo, O. Eiichi. F. Toshihiro, H. Katsurmi; Chem. Pharm. Bull.

page 3424, Vol 31, 1983; H. Erlenmeyer. H. Ueberwasser. Helv. Chim. Acta, page 197, Vol. 23, F.A.J. Kerdeskv, A. Basha. Tet. Letters, Vol 32, page 2003 (1991)

Y. Yamamoto, A. Yanagi, Heterocycles, Vol 19, page 41 (1982).

For the preparation of the compounds of formula (I) in which n equals 1 and Y represents S. a person skilled in the art can also refer to the preparation methods described in European patent application EP 551048, in particular for the preparation of compounds of formula (I) in which W represents S or SO. Method B detailed now describes a mode of preparation of the compounds of formula (I) in which n equals 1 and Y represents O. Method BR The compounds of formula (I) in which n equals 1 and Y represents O, that is to say the compounds of formula (VIII) are obtained by reacting the compounds of formula (IX) in which the radical R'3, identical or different from R3, has any one of the meanings of R3, with an alcohol R3OH according to the scheme

R1 -. S - R R 'N O-R

R'OH y 2AI, R4 Rbase R3NN

R- R

lx VIII in which: - the base is a strong base, and preferably a strong organic base, or an alkali or alkaline earth carbonate or a compound of formula R "30-M + in which: - M is an alkali or alkaline metal - earthy, - R "3, identical or different from R3, has any one of the meanings of R3, and also represents hydrogen

the reaction being carried out at a temperature between 20 and 80 C.

It is preferred to carry out the reaction using the alcohol R3OH as solvent, and the corresponding alkali alkali metal R30-Na + or R30-K + as a base. According to a variant of the method. the reaction is carried out in the presence of an amount between 0.001 and 1 molar equivalent of a Lewis acid derived from a transition metal. preferably chosen from ferric chloride or titanium isopropoxide, and optionally in the presence of periodate

sodium or potassium. or else chloroacetic acid.

The following example illustrates the preparation of a compound of formula (VIII), according to method B.

Example CF: (4-R. S) - 1 -pheny lamino-2 -methoxy-4-methyl-4 (benzothiazol-2-

yl) -imidazolin-5-one (compound n 3), of formula

H. C N O-CH3

s 4 = tN. / Ph

(\,/ // NOT

Dû'NO iH To a solution of 0.25 g (10 mmol) of sodium in 50 ml of methanol, are added 0.5 g (5.4 mmol) of monochloroacetic acid, 50 mg of ferric chloride

and 2 g (5.4 mmol) of (4-R.S) - 1-phenylamino-2-methylthio-4-methyl-4- (benzothiazol-2-yl) -imidazolin-5-one. The mixture is heated to reflux

for h, cooled, poured into 100 ml of acidified water. The precipitate is extracted with dichloromethane; the organic solution is dried and evaporated. The residue is purified by chromatography on silica. 1.1 g of white solid are obtained (PF =

192 C, Yield 45%), which is (4-R, S) -1-phenylamnino-2-methoxy-4-

methyl-4- (benzothiazol-2-yl) -imidazolin-5-one.

For the preparation of the compounds of formula (I) in which n equals 1 and Y represents O, a person skilled in the art can also refer to the methods of

preparation described in European patent application EP 599749.

The compounds of formula (I) in which n equals 0 are prepared according to one of

processes described in international patent application WO 94/01410.

Second method of preparation: We now describe a second method of preparation of the compounds of formula

(I) usable whatever the particular meaning of the group (Y) n.

Process C: This process is particularly advantageous in that it makes it possible to prepare

all of the compounds of formula (I).

The compounds of formula (I) are prepared by reaction in a solvent of the imidazolines of formula (X) with a compound of formula R2L in which L represents a halogen, the sulfate group. cyano, trialkylamino or nitro, or an alklsulfonyloxy arylsulfonyloxy, alkylsulfonyl, arylsulfonyl, alkoxy, haloalkoxy group, in the presence of a base and optionally of a promoter, according to the reaction scheme R 'x MNn-R' R1 N / (Y) n-R3 HN low R2NN, R4 base N | sovant 1

(X) (I) R

in which: the base is an alkaline or alkaline-earth alcoholate (preferably potassium tert-butoxide). an alkali or alkaline earth hydroxide, an alkali or alkaline earth carbonate or a tertiary amine, a lithium amide (preferably lithium diisopropyl amide), an alkyllithium or aryllithium (preferably n-butyllithium or phenyl lithium) , a hydride (preferably sodium or potassium hydride) - the solvent is an ether, a cyclic ether, a chlorinated solvent, an aromatic solvent, dimethylforrnamide, dimethylsulfoxide the promoter, optionally usable. being a compound selected from a crown ether, a cryptand. or a silver salt such as AgNO3, Ag2O, Ag2CO3 the reaction being carried out at a temperature between -80 C and

+ 80 C.

By cryptand and crown ether is meant a chemical compound as defined

in Advanced Organic Chemistry. J. March, 3rd edition, (1985) page 14.

According to another mode of the process. the reaction is carried out in a mixture of 2

phases using a phase transfer catalyst.

For the determination of the reaction conditions best suited to particular compounds of formula (X) and of formula R2L, those skilled in the art may refer to one of the following references: Salfou, A .; Johnson, fM. E .; 5Nagarathnam, D. Svnth. Comm. 1993, pages 23, 2435; Nagarathnam, D .; Johnson, M. E. Svnth. COMM. 1993, vol. 23, page 2011; Zindel, J .; Zeeck, A .; Konig, W. A .; De Meijere, A. Tetrahedron Let. 1993, vol. 34, page 1917; Bey, P .; Veverr, J.P. Tetrahedron Lert. 1977, vol. 17, page 1455; Wender, P. A .; Filosa, M. P. J. Org. Chem. 1976, vol. 41, page 3491; Kotha, S .; Kuki, A. Tetrahedron Lett. 1992, vol. 33, page 1565; O'Donnell, M. J .; Bennett, W. D., Wu, S. J. Am. Chem. SOC. 1989, vol. 111, page 2353; Shvedov, V. I .; Vasil'eva, V.K .; Trofimki ;, Y. I .; Grinev, A. N. Chem. Heterocycl. Compd. 1973, vol. 9, page 1473; Chem. Absrr. 1974, vol. 80, abstract 82744j, Vegh, D .; Dandarova, M. Coil. C: echoslovak Chem. Common. 1983, vol. 48,

pc, e 1885.

The addition of a catalyst can facilitate the reaction described. For this, reference may be made in particular to one of the methods cited in the following publication.

V.N. Kalinin, Svnthesis, page 413 (1992).

The 2 examples below illustrate the preparation of 2 compounds of formula (I) according to method C. respectively without and with the promoter defined above.

Example CF3: (4-R. S) - 1 -phenylamino-2-methylthio-4-methyl-4 (benzothiazol-

2-yl) -2-imidazolin-5-one (compound ns 12), of formula Hi C N S-CH3 N. ,, NPh

N0 N

H

Has a solution of 11 g (47 mmol) of (4-R, S) -1-phenylamino-2-methylthio-4-

methyl-2-imidazolin-5-one and 7.9 g (47 mmol) of 2-chlorobenzothiazole in 50 ml of N., N-dimethylformamide are added 5.7 g (51 mmol) of potassium tert-butanolate. After 30 min, the mixture is poured into 200 ml of water and extracted with ethyl acetate. The organic phase is washed with saturated sodium chloride solution. dried and evaporated. The residue is purified by chromatography on silica. The product is crystallized from diisopropyl ether, filtered and dried. 7.9 g of yellow solid are obtained (mp = 164 C,

Yield 46%), which is (4-R.S) -1-phenylamino-2-methylthio4-methyl-4-

(benzothiazol-2-yl) -2-imidazolin-5-one.

Example CE4 (4-R, S) -l1-phenvlamino-2-methylthio4-methyl-4- (6-chloro-

benzothiazol-2-yl) -2-imidazolin-5-one (compound 6), of the formula:

H3C N- --S-CH3

s W Ph s N H Cl

Has a mixture of 2 g (8.51 mmol) of 1-phenylamino-2-methylthio-4-methyl-2-

imidazolin-5-one, 1.74 g (8.51 mmol) of 2,6-dichlorobenzothiazole and 1.12 g (4.26 mmol) of crown ether consisting of 6 units (-O-CH2-CH2), said 18-C-6, in 20 ml of tetrahydrofuran (THF) under an argon atmosphere at 0 C are

gradually adding 0.95 g (8.51 mmol) of potassium tert -in-butnolate.

The mixture is neutralized and extracted with ethyl acetate. The organic phase is dried and evaporated. The product is crystallized from diisopropyl ether, filtered and dried. 2.32 g of beige solid are obtained (mp = 159 C, yield 68%), which

is (4-R, S) - 1 -phenylamino-2-methylthio-4-methyl-4- (6-chlorobenzothiazol-2-

yl) -2-imidazolin-5-one. The products of structure (X) can be prepared according to one of the methods described in European patent applications EP 551048 and EP 599749, and

in international applications WO 93/24467 and WO 94/01410.

The following process describes a mode of preparation of the compounds of formula (I), in which R2 comprises at least one substituent of formula -X-R7 such that

previously defined. These compounds have the formula (Ia).

Process D: The compounds of general formula (Ia). in which R'2 has the same meaning as R2. are obtained by reacting an imidazolinone of formula çXI) in which Hal represents a halogen atom, preferably chlorine or bromine. with a compound of formula (XII). according to a process similar to that described in Comprehensive heterocyclic chemistry, AR Katritzky, Volume2, Part2A, Page 359, in other words according to the diagram: RX N7 R [N3 .- (Y) n R3 Ha <R'l NN R4 R0 INRW ( XII) a) RR (Ia) The reaction is carried out under the conditions usually carried out in

aromatic substitution reactions.

According to a preferred variant. the reaction is carried out in the presence of a catalyst. In this case, a person skilled in the art can refer to one of the methods cited in the following publications V.N. Kalinin, Synthesis, page 413 (1992); L. Gundersen, Tetrahedron Letters, vol 35, page 3155 (1994); A. Ohsawa. Y. Abe, H. Igeta. Chem Pharm. Bull, Vol 26, page 2550 (1978), H. Yamanaka, K. Edo. F. Shoii. S. Konno. T. Sakamoto, M. Mizugaki, Chem

Pharm. Bull, Vol 26, page 2160 (1978).

The compound of formula (XI) is obtained according to one of the processes A, B or C described above. The following process E describes another mode of preparation of the compounds of

formula (la) defined above.

Process E: The compounds of general formula (Ia) are obtained by condensation of an organometallic derivative of an imidazolinone of formula (XIm) in which R'2 has the same meaning as R2 and MI represents a metal chosen from lithium, sodium, magnesium. zinc, titanium, tin, copper, boron or silicon. and is preferably lithium, with a compound of formula R7-XL in which L represents a leaving group such as the chlorine, bromine, fluorine or iodine atom, or the sulfate group, or an alkylsulfonyloxy or arylsulfonyloxy group , according to the reaction scheme R1 NR (Y) nIN N

RXV R7X

_R S ,,, R-4 X "R) N \ R4

-V W lo

N N

w K

R 'Re

(XIII) (Ia) The compounds of formula (XIII) in which M represents lithium are obtained from the halogenated derivatives (XI) defined above, by reacting the latter with n-butyl lithium in tetrahydrofuran (THF) at by means of a halogenated metal exchange reaction as described by RG JONES and H. GILMvIAN, Organic Réaccions, vol. 6, page 339, according to the diagram RI N (y)) n-R3 RI N .. (Y) n-R3 Hal - R R4 nBuLi N R

Hal --- R N ,, M - -

W jbN ... VR R

THF N

JRR (xI) (XIII) The compounds of formula (XIII) in which M represents lithium can also be obtained from the derivatives of formula (XIa), in which R'2 has the same meaning as R2, by a reaction of lithiation as described by HW Gschwend, HR Rodriguez. Organic Reactions, vol. 26, page 1, according to the diagram RI N - / (Y) nR Rl N-- (Y) n-R3 nBuLi R,

H-MR, NIR4

N., RTHF

R: RI

(XIa ') (XIII) The compounds of formula (XIII) in which M represents a metal chosen from sodium, magnesium, zinc, titanium, tin, copper, boron or silicon, are obtained from starting from the compounds of formula (XII) in which M represents lithium by transmetallation reaction as described in Advanced organic chemistry, J. MNarch, (1985), page 557, 3rd Edition. The addition of a catalyst can facilitate the reaction described. For this, one can use in particular one of the methods cited in the following publication

V.N. Kali-in, Synthesis, 413 (1992).

The optical isomeric compounds included in formula (I) and resulting from the asymmetric nature of the carbon of the 2-imidazolin-5-one ring carrying Rlet R2, are obtained from the corresponding racemic compounds. by high performance liquid chromatography on chiral stationary phase. Preferred is a chiral stationary phase comprising D phenyl glycine molecules covalently attached to silica gel. The table below collates the compounds of formula (I) which were prepared according to one of the processes described above. These compounds have the formula CH N (Y) n-CH3

R N "\

0 H

the meaning of the generic substituents being explained in the table below.

after compound R2 Y n PF C Process n 1 4- (2-Ph) -quinazolinyl S 1 102 C 2 2-Benzoxazolyl S 1 207 C 3 2-Benzothiazolyl O 1 192 C 4 2- (6-EtO-7-Cl ) -Benzothiazolyl S 1 210 C 2- (6-EtO.7-CI) -Benzothiazolyl O 1 240 B 6 2- (5-CI-Benzothiazolvle) S 1 159 C 7 2- (5-CI-Benzothiazolvle) O 1 109 B 8 2- (6-CI-Benzothiazolyl) S 1 128 C 9 2- (4- Ph) -Thiazolyl S 1 233 A 2- (4- [2,4- diCl] -Ph) -Thiazolyl S 1 267 C 11 2- (4-Ph) - Thiazolyle O 1 honey B 12 2- benzothiazolvle S 1 164 C 13 4- (2- Ph) -thiazolyle S 1 230 A 14 2- benrizoxazolvle O 1 158 B The present invention has for subject some of the new compounds described above as intermediates. namely the compounds of formula mII in which the substituents have the meaning defined above. As the compounds defined by general formula (I) of the invention. these compounds can exist under one or

several isomeric forms depending on the number of asymmetric centers in the molecule.

The invention therefore relates both to all the optical isomers of the compounds which can be used as intermediates and to their racemic mixtures and the corresponding diastereoisomers, separated or as a mixture. and in particular the enantiomers of the compounds

comprising the asymmetric carbon of the 5-imino-2-imidazoline ring carrying R1 and R2.

The separation of optical isomers and / or diastereomers from mixtures

racemic can be carried out according to methods known per se.

The invention also relates to a process for the treatment of cultivated plants affected or liable to be affected by fungal diseases, characterized in that an effective dose of a compound according to formula (I) is applied to the aerial parts of these plants. ). The term “effective dose” is understood to mean an amount sufficient to allow the control and destruction of the fungi present on these cultivated plants. The doses of use can however vary within wide limits according to the fungus to be controlled, the type of crop, the climatic conditions, and according to the compound used. In practice, the compounds are advantageously applied at doses of 0.002 to 5

kg / ha, and preferably 0.005 to 1 kg! ha.

By fungal diseases. we mean diseases caused by phytopathogenic fungi, in particular those of the daughter of oomycetes, ascomycetes and

basidiomycetes.

Among the crops which may be the subject of a fungicidal treatment using a compound according to the invention, mention may be made of rice, cereals, in particular wheat and barley, as well as vegetable plants. Rice is a preferred crop for treatments

fungicides using a compound according to the invention.

The following examples illustrate the good fungicidal activity of

compounds according to the invention.

Example B1: In vivo test on Pyricularia oryzae responsible for piriculariasis of rice: A suspension of 60 mg of the active material to be tested is prepared in a liquid mixture consisting of 0.3 ml of a surfactant (oleate of a polyoxyethylene derivative of

sorbitan) diluted to 10% in water, 5 ml of acetone, and 60 ml of water.

This suspension is then diluted with water to obtain the concentration

desired in active matter.

Rice, sown in pots in a 50/50 mixture of enriched peat and pozzolan, is processed at the about 10 cm high stage (which corresponds to the 2-3 leaf stage) by

spraying the above aqueous suspension.

After 24 hours. an aqueous suspension of Pvricularia ornzae spores is applied to the leaves. obtained from a culture of 15 days, then suspended

at the rate of 100,000 units per cm.

The rice plants are incubated for 24 hours (25 ° C., 100% relative humidity), then placed in an observation cell, under the same conditions, for days.

The reading is taken 6 days after contamination.

* Under these conditions, we observe. at a dose of 1 gIl, good protection (at least

%) or total with the following compounds: 2, 3, 6, 7, 9 to 11.

Example B2: In vivo test on Puccinia recondita responsible for the brown rust o0 of wheat: A suspension of 60 mg of the active material to be tested is prepared in a liquid mixture consisting of 0.3 ml of a surfactant (oleate of a polyoxyethylene derivative of

sorbitan) diluted to 10% in water. of 5 ml of acetone, and of 60 ml of water.

This aqueous suspension is then diluted with water to obtain the

desired concentration of active ingredient.

Wheat sown on a 50/50 peat and pozzolan mixture in a cup and not kept at 12 C. is treated at the 10 cm height stage by spraying the suspension

aqueous above.

After 24 hours. an aqueous suspension of spores (100,000 sp / cm3) is sprayed onto the wheat: this suspension was obtained from contaminated plants. The wheat is then placed for 24 hours in an incubation cell at about 20 C and 100%

relative humidity, then for 7-14 days at 60% relative humidity.

The condition of the plants is checked between the 8th and 15th day after

contamination, by comparison with an untreated control.

Under these conditions, we observe. at a dose of 1 g / l, good protection (at

minus 75%) or total with the following compounds: 6, 7, 12.

Example B3: In vivo test on Septoria tritici responsible for septoria in wheat: A suspension of 60 mg of the active material to be tested is prepared in a liquid mixture consisting of 0.3 ml of a surfactant (oleate of a polyoxyethylene derivative of

sorbitan) diluted to 10% o in water. of 5 ml of acetone, and of 60 ml of water.

This aqueous suspension is then diluted with water to obtain the

desired concentration of active ingredient.

Wheat plants (variety Darius), sown on a 50/50 peat peat substrate and grown in a greenhouse at 10-1'2 C. are treated at the 1 leaf stage (size 10 cm

envi-on) by spraying the suspension of acti material, .- described above.

Plants, used as controls, are sprayed with a solution

aqueous not containing the active ingredient.

24 hours after treatment. plants are contaminated by spraying with

aqueous suspension of spores (500,000 sp / ml) harvested from a 7-day-old culture.

After contamination. the plants are placed at 18 ° C. in a humid atmosphere. Scoring is carried out 20 days after contamination in comparison with the control plants. Under these conditions, at a dose of 1 gl'1, good protection is observed (at least

%) or total with the compounds: 1. 3, 6.

A subject of the present invention is also compositions, which can be used as fungicidal agents, containing as active material (s) one (or more) compound according to formula (I) as described above, as a mixture with the solid or liquid supports. acceptable in agriculture and the surfactants also acceptable in agriculture. In particular, the inert and customary supports and the customary surfactants can be used. These compositions cover not only the compositions ready to be applied to the crop to be treated by means of a suitable device, such as a spray device, but also the concentrated compositions.

commercial products which must be diluted before application to the crop.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids. adhesives, thickeners, thixotropic agents, penetrating agents. stabilizers, sequestering agents, etc. More generally, the compounds used in the invention can be combined with all the solid or liquid additives corresponding to the usual techniques for setting

formulation.

In general, the compositions according to the invention usually contain from 0.05 to 95% approximately (by weight) of a compound according to the invention (hereinafter called active material), one or more solid or liquid supports. and,

optionally, one or more surfactants.

By the term “support”, in the present description, is meant an organic or inorganic material, natural or synthetic, with which the compound is combined to facilitate its application to the plant, to seeds or to the soil. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol, etc.). The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example: of salts of pc!: Crylic acids, salts of lgnosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with acids fatty or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols , esters of fatty acids and of polyols, derivatives containing a function of sulfates, sulfonates and phosphates of the above compounds. The presence of at least one surfactant is generally essential when the compound and / or the inert support are not soluble in water and the agent

application vector is water.

Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 0.05% to 95% (by weight). Their surfactant content is advantageously between 5% and

% c by weight.

These compositions according to the invention are themselves in fairly

various, solid or liquid.

As forms of solid compositions, mention may be made of powders for dusting (with a compound content of up to 100%) and granules, in particular those obtained by extrusion. by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound in these granules being between 0.5

and 80% for the latter cases). effervescent tablets or tablets.

The compounds of formula (I) can also be used in the form of powders for dusting; it is also possible to use a composition comprising 50 g of active material and 950 g of talc; it is also possible to use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by powdering. As forms of compositions which are liquid or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates. emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or spray powder),

pasta, gels.

The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, as for

they, 0.001 to 20% dc = active ingredient.

In addition to the solvent. emulsifiable concentrates can contain, when necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetrators, corrosion inhibitors, dyes or adhesives

previously cited.

From these concentrates. emulsions of any desired concentration can be obtained by dilution with water. which are particularly suitable for the application

on cultures.

For exemple. here is the composition of some emulsifiable concentrates

Example CE 1

- active ingredient 400 g / 1 - alkaline dodecylbenzene sulfonate 24 g / l oxvethylated nonylphenol with 10 molecules of ethylene oxide 16 g / l cyclohexanone 200 g / l - aromatic solvent qsp1 liter According to another emulsifiable concentrate formula, we uses

Example E2

- active ingredient 250 g - epoxidized vegetable oil 25 g - mixture of alkylaryl sulphonate and polyglycol ether and fatty alcohols 100 g dimethylformamide 50 g - xylene 575 g The suspension concentrates, also applicable as a spray, are prepared from so as to obtain a stable fluid product which does not settle and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 10% suitable additives such as defoamers, corrosion inhibitors, stabilizers, penetrators and adhesives and. such as carrier, water or an organic liquid in which the active ingredient is poorly or not soluble: some organic solids or inorganic salts may be dissolved in the carrier to help prevent

sedimentation or as antifreeze for water.

As an example, here is a concentrated suspension composition

Example SC 1:

- active ingredient 500 g - polyethoxylated tristyrylphenol phosphate 50 g polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g polysaccharide 1.5 g - water 316.5 g Wettable powders ( or spray powder) are usually prepared so that they contain 20 to 95% active ingredient, and they usually contain. in addition to the solid support, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent. and, when necessary, from 0.1 to 10 a of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or

anti-caking agents, coloring agents, etc ...

To obtain spray powders or wettable powders, the active ingredients are intimately mixed in the appropriate mixers with the additional substances and are ground with mills or other suitable grinders. In this way, spraying powders are obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously in particular for the application

on the leaves of plants.

Instead of wettable powders, you can make pastes. The conditions and methods of making and using these pastes are similar to those of powders

wettable or spray powders.

By way of example, here are various compositions of wettable powders (or spray powders):

PMI example I

- active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert support) 42.5%

PMN 2 example:

- active ingredient 10% - synthetic oxo alcohol of branched type, C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% neutral calcium lignosulfonate (dispersing agent) 12% - calcium carbonate (inert filler) qsp 100%

PNM Y example:

This wettable powder contains the same ingredients as in the previous example. in the following proportions - active ingredient 75% - wetting agent 1.50% - dispersing agent 8% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 4

- active ingredient 90% - ethoxylated fatty alcohol (wetting agent) 4% phenylethylphenol, hoxyvl (dispersing agent) 6%

PMN example 5

- active material 50% - mixture of anionic surfactants and hrn Iniques (wetting agent) 2.5% - sodium lignosulphonate (dispersing agent) 5% kaolin clay (inert support) 42.5% Aqueous dispersions and emulsions, for example example the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a

consistency thick like that of a "mayonnaise".

The compounds according to the invention can be formulated in the form of granules.

dispersible in water also included within the scope of the invention.

These dispersible granules. of bulk density generally between about 0.3 and 0.6 have a particle size generally between about

and 2000 and preferably between 300 and 1500 microns. The active material content of these granules is generally understood

Between

about 1% and 90% 7c. and preferably between 25% and 90%.

The remainder of the granule is essentially composed of a solid filler and optionally of surface-active adjuvants which give the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the charge retained is soluble or not in water. When the filler is water soluble. it can be mineral or. preferably. organic. Excellent results have been obtained with urea. In the case of an insoluble filler, the latter is preferably mineral, such as, for example, kaolin or bentonite. It is then advantageously accompanied by surfactants (in an amount of 2 to 20% by weight of the granule) of which more than half is, for example, constituted by at least one dispersing agent, essentially anionic, such as a polynaphthalene. alkali or alkaline earth sulfonate or an alkali or alkaline earth lignosulfohate, the remainder consisting of nonionic or anionic wetting agents such as an alkali alkali naphthalene sulfonate

or alkaline earth.

By the way, although this is not essential. we can add others

adjuvants such as defoamers.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). This generally ends with crushing followed by sieving to the particle size chosen within the limits mentioned above. We still use aianuilé obtained as before and then impregnated with a

composition containing the active ingredient.

Preferably, it is obtained by extrusion, by operating as indicated in the

examples below.

Example GD-I: Dispersible granules In a mixer. 90% by weight of active material and 10% of pearl urea are mixed. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules of one dimension

between 150 and 2000 microns.

Example GD2: Dispersible granules In a mixer, the following constituents are mixed - active ingredient 75% - wetting agent (sodium alkylnaphthalenesulphonate) 2% - dispersing agent (sodium polynaphthalenesulphonate) 8% - inert filler insoluble in water ( kaolin) 15% This mixture is granulated in a fluid bed. in the presence of water, then dried. crushed and

sieved so as to obtain granules of size between 0.15 and 0.80 mm.

These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active ingredients, in particular fungicides, the latter being

in the form of wettable powders, or aqueous granules or suspensions.

As regards the compositions suitable for storage and transport, they

more preferably contain from 0.5 to 95% (by weight) of active substance.

Claims (15)

1. Derivatives of 2-imidazoline-5-ones of general formula (I) RI N - (Y) nR NIR> (I) in which: - RI represents a hydrogen atom, or a vinyl or allyl group, or a alkyl or haloalkyl radical with 1 to 4 carbon atoms - R2 represents an aromatic heterocyclic radical, mono or bicyclic, having 5 to 10 atoms in the ring (s), among which 2 to 4 are heteroatoms chosen from O, S. or N, which radical being linked to the imidazolinone ring via a carbon or nitrogen atom, and being optionally substituted with 1 to 5 groups, preferably by 1 to 3 groups, chosen from the meanings of R6. each sulfur or nitrogen atom linked to a cycle of said radical optionally carrying a positive charge and linked to an oxygen located outside the cycle and carrying a negative charge: - or RI represents a divalent ethylene radical , trimethylene, or tetramethylene, the second valence of which is linked to the R2 atom adjacent to the atom via which R2 is linked to the imidazolinone nucleus: - R3 represents - the hydrogen atom when n = 0. or - an alkyl or haloalkyl group of 1 to 3 carbon atoms or the cyclopropyl group - R4 represents an aryl or heterocyclic aromatic radical chosen from phenyl, naphthyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, thiazolyl, benzothiazolyl, quinolinyl, quinolinyl, quinolinyl , isoquinolinyl, isothiazolyl, oxadiazolyl, thiadiazolyl, or methylene dioxyphenyl, each of: the radicals being optionally substituted by 1 to ', groups, preferably from 1 to 3 groups, chosen from the radicals having the same meanings as R6 - R5 represents a hydrogen atom, an alkyl or haloalkyl radical of 1 to 3 carbon atoms, an acyl raucal of 2 to 6 carbon atoms, an alkoxycarbonyl radical of 2 to 6 carbon atoms, or a formyl, aroyl, cyclopropyl, aryloxycarbonyl radical , alkylsulfonyl, arylsulfonyl, alkyloxalyl or alkoxyoxalyl - n = or i Y represents the oxygen atom or the sulfur atom - W represents O, S or SO; - R6 represents: - a halogen atom or the hydroxy, mercapto, nitro or cyano group. thiocyanato or azido; or - an alkyl radical. haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkvlsulfinyl. alkylsulfonyl, haloalkylsulfminyl or haloalkvylsulfonyl, each of 1 to 6 carbon atoms; or - a cycloalkl or halocycloalkyl radical of 3 to 6 carbon atoms - an alkenyloxv radical. alkynyloxy, alkenylthio, alkynylthio, each of 2 to 6 carbon atoms: or - an amino radical, optionally mono or disubstituted by an alkyl radical of 1 to 6 carbon atoms or an acyl radical of 2 to 6 carbon atoms: or - an alkenyl group. alkynyl. alkoxycarbonyl, cyanoalkoxy. cyanoalkylthio, cyanoalkyl. N-alk'lcarbamoyl of 2 to 7 carbon atoms or - an N, N-dialkylcarbamoyl group of 3 to 13 carbon atoms or - a radical of formula -X-R7 in which - X represents a sequence of general formula (R ) j- (A) k- (R ') m in which: - j, k. m identical or 5 different, are equal to O or 1: - R and R '. identical or different, represent a hydrocarbon chain. saturated or unsaturated, which contains from 1 to 6 carbon atoms, optionally substituted by 1 to 12 groups, preferably by 1 to 3 groups, chosen from Re, and in which one or more of the carbon atoms can be replaced by O, S, N (R9) - A represents a divalent, mono or polyatomic group comprising: O, S. N (R9), SO, SO2, CO, CS, Si (RI) (R'10), N2, C (R1l ) (R'l1), or R9-N -N R9-N / C-- or R12 / - or S- R12 / RII \ R'1l R1I or -CC-- or -C = C- or> '<o in which Z represents OS C (R13) (R'13) - R7 represents a mono or bicyclic system from 5 to 10 atoms. aromatic, saturated or unsaturated. and which is either a carbocyclic system or a heterocyclic system comprising from 1 to 4 heteroatoms chosen from O, S. or N. and which comprises the phenyl radicals. naphthyl, dihydronaphthyl, tetrahydronaphthyl. thienyl. furyl. pyrrolyl, pyridyl, benzothienyl, benzofuryl, indanyl, indolyl, quinolinyl, isoquinolinyl, methylenedioxyphenyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyrraziniazolyl, pyraziniazolyl, pyraziniazolyl, isothiazolyl, pyraziniazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyraziniazolyl, isothiazolyl, pyraziniazolyl, isothiazolyl, pyrraziniazolyl, isothiazolyl, pyraziniazolyl, isothiazolyl, pyraziniazolyl triazinyl, tetrazinyl, each of these raaicals being optionally substituted with 1 to 7 groups, preferably by 1 to 3 groups, chosen from the radicals having the same meanings as RI4 - R8 - represents a halogen atom, a cyano or thiocyanato group , oxo, thioxo, carboxy, amino. hydroxyl, thiol, acyloxy, alkyl, aroyloxy, heteroaroyloxy. arylacyloxy. cycloalkylcarbonyloxy, acylthio, aroylthio, heteroaroylthio, arylacylthio, cycloalkylcarbonylthio, carbamoyloxy carbamoylthio, thiocarbamoylox, dithiocarbamoyl, acylamino, ycloalkylcarbonylamnino, aroylcarbonylthio. ureïdo, Libout iido, alkoxycarbonylamino, aryloxycarbonylamino, alky'lsulfonylamino, arylsulfonylamino, aminosulfonylamino - R9 represents - a hydroene atom or a cyano, hydroxy, amino, formyl, morpholino, piperidino, piperazino radical, or - an alkali radical. haloalkyl, alkoxy, haloalkoxy, alkylsulfonyl, haloalkylsulfonyl. each of 1 to 6 carbon atoms, or - a cyanoalkyl radical. cyanoalkoxy, cyanoalkylsulfonyl, each comprising from 2 to 6 carbon atoms, or - an amino radical. optionally mono or disubstituted with an aryl radical or an alkyl radical of 1 to 6 carbon atoms, or - a cycloalkyl radical. halocycloalkyl of 3 to 6 carbon atoms, or - an alkenyl radical. alkynyl. alkenyloxy, alkynyloxy, acyl or alkoxycarbonyl of 2 to 6 carbon atoms; or - a carbamoyl radical with 2 to 7 carbon atoms or a sulfamoyl radical with 1 to 6 carbon atoms; or - an aroyl or arylsulfonyl radical; or - an alkvloxalyl or alkoxyoxalyl radical of 3 to 8 carbon atoms or - an oxamyl radical of 2 to 8 carbon atoms -R10 and R '10, which are identical or different, represent - an alkyl radical of 1 to 6 carbon atoms; or - a cycloalkyl radical of 3 to 7 carbon atoms; or an alkenyl or alkynyl radical of 2 to 6 carbon atoms; or - an arylalkyl radical, preferably benzyl, or an aryl radical, preferably phenyl optionally substituted by 1 to 5 groups, preferably by 1 to 3 groups chosen from the meanings of R14 RI1 and R '11, which are identical or different, represent the hydrogen atom or an alkoxy radical or have one of the meanings of R8; - R12 represents - the hydrogen atom. or a morpholino, piperidino, pyrrolidino, piperazino group; or - an alkyl radical. haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, each of 1 to 6 carbon atoms; or - a cyanoalktle radical. cyanoalkoxy, cyanoalkylthio, each of 2 to 7 carbon atoms; or a dialkylamino radical - R13 and R'13, which are identical or different, represent the hydrogen atom or a halogen or an alkyl group of 1 to 3 carbon atoms; - R14 represents: - a halogen atom or the hydroxy, mercapto, nitro, cyano, thiocyanato or azido group: or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfinyl radical. alkylsulfonyl, haloalkcylsulfminyl, haloalkylsulfonyl. each of 1 to 6 carbon atoms; or - a cyanoalkyl radical. cyanoalkoxy, cyanoalkylthio, each of 2 to 7 carbon atoms; or - a cycloalkyl or halocycloalkyl radical with 3 to 6 carbon atoms: or - an alkenyl radical. alkynyl, alkenyloxy. alkynyloxy, alkenylthio, alkynylthio. each of 2 to 6 carbon atoms; or - an amino radical. optionally mono or disubstituted with an alkyl radical of 1 to 6 carbon atoms or with an acyl or alkoxycarbonyl radical of 2 to 6 carbon atoms, or an alkoxycarbonyl group of 2 to 7 carbon atoms; or -an N-alkylcarbamoyl group of 2 to 7 carbon atoms; or -an N, N-dialkylcarbamoyl group of 3 to 13 carbon atoms. as well as the salified forms, the tautomeric forms, the stereoisomers and diastereomers of these compounds, preferably the optical isomers resulting from the presence of the asymmetric carbon of the novau 2-imidazolin-5-one carrying R1 and R2. 2. Derivatives of 2-imidazoline-5-ones according to claim 1, characterized in that R2 is chosen from a radical derived, by elimination of a hydrogen atom, from one of the following cycles - a 5-ring cycle. links described by formula (i) QA- A4 (i) in which each of the groups of the list A1, A2, A3, A4, is chosen from the atoms C, N, O. S such that said list comprises of 0 to 2 carbon atoms, 0 to 1 sulfur atom, 0 to 1 oxygen atom and 1 to 4 nitrogen atoms; or - a 6-link cycle described by formula (ii) B -. B3 BK (ii) in which each of the groups of list B1, B2, B3, B4, B5, is chosen from C or N atoms such that said list comprises from 1 to 3 carbon atoms and from 2 to 4 atoms nitrogen; or two cycles merged with 6 links each. described by the formula (iii 'to E3- E E6 E 8 E6 (iii) in which each of the groups of the list E1, E2, E3, E4, E5, E6, E7, E8 is chosen from C or N atoms such that said list comprises 4 to 6 carbon atoms and 2 to 4 nitrogen atoms; or a 6-link cycle and a 5-link fused link cycle described by formula (iv) G LI 6O ', 1 L (iv) in which - each of the groups of the list G1, G2, G3, G4, G5, G6 is chosen from the atoms C, N such that said list comprises from 0 to 6 carbon atoms, and from O to 3 nitrogen atoms; and - each of the letters of the list L1, L2, L3 is chosen from C, N, O. or S atoms such that said list comprises from 0 to 3 carbon atoms. from 0 to 1 sulfur atom, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms; or - two merged rings with 5 links each described by the formula (v) Q Ti Q <\ 0 I O T2 Q IZ-Til (v) in which - each of the groups of the list QI, Q2, Q3, represents the atoms C, N. O, S such that said list comprises from O to 3 carbon atoms, from O to 1 atom of sulfur. from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms; - each of the groups in the TI list. T2, T3 represent the CN O, S atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms - Z represents C or N atoms. 3. Derivatives of 2-imidazoline-5-ones according to one of claims 1 or 2, characterized in that R2 represents one of the following heterocycles pyrazolvle; imidazolyl: oxazolyl; isoxazolyl; thiazolyl 1.2.3-oxadiazolyl isothiazolyl; 1,2,4-oxadiazolyl; 1,2,5- oxadiazolyl; 1,3,4-oxadiazolvle; 1,2,3-thiadiazolyl; 1 7.4- thiadiazolyl 1.2.5-thiadiazolyl; 1,3,4-thiadiazolyl; 1,2,3- triazolyl 1.2.4-triazolyl; tetrazolyl - pyrimidinyl; pyrazinyl; pyridazinyl; 1,2,3-triazinyl; 1,2,4- triazinyl; 1.3,5-triazinyl 1.2.3,4-tetrazinyl; 1,2,3,5-tetrazinyl: I.2,4.5-tetrazinylc: - benzimidazolyl indazolyl; benzotriazolyl; benzoxazolyl 1.2-benzisoxazolvle; 2.1-benzisoxazolyl; benzothiazolyl; 1,2- benzisothiazolyl; 2.1-benzisothiazolyl; 1,2,3-benzoxadiazolyl; 1,2,5-benzoxadiazolvle; 1,2,3-benzothiadiazolyl; 1,2,5- benzothiadiazolyl; - quinoxazolinvle: quinazolinyl; cinnolyl or phthalazyl; pteridinvle; benzotriazinvle - 1,5-naphthvridinvle; 1.6-naphthyridinyl; 1,7-naphthyridinyl; 1,8-naphthyridinyl; imidazo [2, 1-b] thiazolyl: thieno [3,4-b] pyridyl; purine pyrolo [1.2-b] thiazolyl. 4. Derivatives of 2-imidazoline-5-ones according to one of claims 1 to 3, characterized in that they have at least one of the following characteristics: - R2 is chosen from one of the following pvrazolyl heterocycles; imidazolyl; oxazolyl; isoxazolyl; thiazolvle isothiazoivie To 1.2.5-oxadiazolvle; 1,3,4-oxadiazolyl 1.2.4-thiadiazolyl 1.2.5-thiadiazolyl; 1,3.4-thiadiazolyl; 1.2.4- triazolvle -pyrimidin le: pyrazinyl: pvridazinvle; 1.3.5-triazinyl; benzimidazolyl; indazolyl; benzotriazolyl; benzoxazolyl; 1,2benzisoxazolyl; 2,1-benzisoxazolyl; benzothiazolyl; 1.2benzisothiazolyl; 2,1-benzisothiazolyl; - quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl; and / or - R4 is chosen from a phenyl, pyridyl, benzothiazolyl group, and / or - R5 is a hydrogen atom, and / or - W is an oxygen atom. 5. Derivatives of 2-imidazoline-5-ones according to one of claims 1 to 4, characterized in that R2 has one of the following meanings: p \ Tazolyl: imidazoly! l; oxazolyl; iscxazolyl thiazolyl; isothiazolyl: 1.,. 4-thiadiazolyl 1,2,5-thiadiazolyl; 1.3, 4-thiadiazolyl pyrimidinyl - benzoxazolyl benzothiazolyl; - quinazolinyl. 6. Process for preparing the compounds of formula (I), according to one of claims 1 to 5 in which n equals 1 and Y represents S and W represents O, or compounds of formula (II), characterized in that they are prepared by hydrolysis of 5-imrnino-imidazoline of formula (HI) according to the reaction scheme Ri LES-R- Y - Rt RI N__ S R R4 solvate R2 - R acid R N NR4 III II in which: - the acid is an inorganic or organic acid - the solvent is an organic solvent, water or a water / organic solvent mixture, comprising one or two liquid phases at a temperature between 5 and 80 C. 7. Preparation process according to claim 6, characterized in that the organic solvent used is chosen from cyclic or acyclic ethers, esters, chlorinated solvents. alcohols, solvents Aromatics, acetonitrile, acetone, organic acids. 8. Process for preparing the compounds of formula (I), according to one of claims 1 to 5, wherein n equals 1 and Y represents O, either compounds of formula (VIII), characterized in that one reacts the compounds of formula (IX) in which the radical R'3, identical or different from R3, has any one of the meanings of R3. with an alcohol R3OH according to the diagram R1 N./S-R H R1 N-. _GOLD- NOT R 'R30H WR R5 lX VIII in which: - the base is a strong base, and preferably a strong organic base, or an alkali or alkaline earth carbonate or a compound of formula R "30-M + in which: - MNI is an alkali or alkaline metal -terreux, - R "3. identical or different from R3, has any of the meanings of R3. and also represents a hydrogen at a temperature between 20 and 80 C. 9. Preparation process according to claim 8, characterized in that the reaction is carried out using the alcohol R3OH as solvent, and the corresponding alkali alcoholate R30-Na + or R30-K + as the base. 10. Process for preparing the compounds of formula (1), according to one of claims 1 to 5, characterized in that one reacts in a solvent of imidazolines of formula (X) with a compound of formula R2L in which L represents halogen. the sulfate, cyano, trialkylamino or nitro group, or an alkylsulfonyloxy arylsulfonyloxy, alkylsulfonyl, arylsulfonyl, alkoxy, haloalkoxy group, in the presence of a base and optionally of a promoter, according to the reaction scheme R1 N X-- <Y) n -Ré R1 Ns / (Y) n --R3 H'N R4 2.R4 NâN >>, base (X,) / 7 solvent (X) (') R in which: - the base is an alkaline or alkaline-earth alcoholate (preferably potassium tert-butoxide), an alkaline or alkaline-earth hydroxide, an alkaline or alkaline-earth carbonate or a tertiary amine, a lithium amide (preferably lithium diisopropylamide), an alkyllithium or aryllithium (preferably n-butyl lithium or phenyl lithium), a hydride (preferably sodium or potassium hydride); - the solvent is an ether, a cyclic ether, a chlorinated solvent, an aromatic solvent, dimethylformamide, dimethylsulfoxide - the promoter, which may be used, is a compound chosen from a crown ether. a crvptand, or a silver salt such as AgNO3, Ag20O, Ag2CO3 at a temperature between -80 C and +80 C. 11. Compounds which can be used in particular as intermediates in the preparation derivatives of 2-irnidazoline-5-ones according to one of claims 1 to 5, characterized in that they correspond to the formula R1 N S-R3 Re N N R3 III 12. Compositions, usable as fungicidal agents, containing as active material (s) one (or more) compound according to one of claims 1 to , mixed with solid or liquid supports, acceptable in agriculture and surfactants also acceptable in agriculture. 13. Process for the treatment of cultivated plants affected or liable to be affected by fungal diseases, characterized in that it is applied to the aerial parts of these plants an effective dose of a compound according to one of claims 1 to 5. 14. A method of treating cultivated plants according to claim 13, characterized in that the effective dose is between 0.002 and 5 kg / ha, preferably between 0.005 and 1 kg / ha.