AU674150B2 - Fungicidal 2-imidazoline-5-one and 2-imidazoline-5-thione derivatives - Google Patents

Description

OPI DATE 31,/01/94 APPLN. ID 45045/93 AOJP DATE 28/04/94 PCT NUMBER PGT/FR93/00647 AU9345045 DEMANDE INTERNATIONALE PUBLIEE EN VERTU DU TRAITE DE COOPERATION EN MATIERE DE BREVETS (PCT) (21) Numno de la demnande iiiternationale: PCT/FR93/00647 (74) Mandataire: CHRETIEN, Frangois; Rh6ne Poulenc Agrochimie DPI, 14-20, rue Pierre-Baizet, BP 9163, F-69009 (22) Date de d~p6t international: 29juin 1993 (29.06.93) Lyon C~dex 09 (FR).

Donn~es relatives i la priorit&: (81) Etats d~sign~s: AU, BG, BR, CA, CZ, Fl, HU, JP, KR, 92/08405 2juillet 1992 (02.07.92) FR NZ, PL, RO, RU, SD, SK, UA, US, brevet europ~en (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE).

(71) D~posant (pour tous les Elats dksign~s sauf US): RHONE POULENC AGROCHIMIE [FR/FR]; 14-20, rue Pierre-Baizet, F-69009 Lyon PublUie Ai'ec rapport de rech erche internationale.

(72) Inventeurs; et Inventeurs/D~posants (US seulement) BASCOU, Jean-Philippe [FR/FR]; 3, rue Gabriel-Chevallier, F-69009 Lyon LACROIX, Guy [FR/FR]; 332 F, rue du Doyen- Chapas, F-69009 Lyon PEREZ, Joseph [FR/FR]; 19 All6e D, rue Ernest- Fabr~gue, F-69009 Lyon (FR).

SCHMITZ, Christian [FR/FR]; Chemin de St-Trys, Pommiers, F-69480 Anse (FR).

674150 (54) Title: FUNGICIDAL 2-IMIDAZOLINE-5-ONE AND 2-IMIDAZOLIN E-5-THIONE DERIVATIVES (54) Titre: DERIVES DE 2-IMIDAZOLINE-5-ONES ET 2-IMIDAZOLINE-5-THIONES FONGICI DES

R_

W (57) Abstract or 2-imidazoline-5-thione derivatives have general formula in which W is the sulphur or oxygen atom, or the group S 0, n is 0 or 1, A is N(R5) or 0 or S or C(R5)(R6) or S02 or C 0, RI to R4 are hydrogen or a hydrocarbon radical, optionally substituted by halogen atoms in particular. Used as fungicides in agriculture.

(57) Abr~lg6 D~riv~s de 2-imidazoline-5-ones ou de 2-imidazoline-5-thiones; ils sont de formule g~n~rale dans laquelle W est l'atome de soufre ou d'oxyg~ne ou le groupe S 0; n 0 ou I, A repr~sente N(R5) ou 0 ou S ou C(R5)(R6) ou S02 ou C 0, R I a R4 repr~sentent l'atome d'hydrog~ne ou un radical hydrocarbon6, 6ventuellement substitu6 notamnment par des Itomes d'halog~ne, utilisation comme fongicides en agriculture.

W094/01410 PCT/FR93/00647 Fungicidal 2-imidazolin-5-one and derivatives The present invention relates to new imidazolinone or imidazolinethione compounds for use in plant protection. It also relates to the processes for the preparation of the said compounds and to the products which can optionally be used as intermediates in the preparation processes. It then relates to the use of these compounds as fungicides, to the fungicidal compositions based on these compounds and to the processes for combating fungal diseases of crops using these compounds.

One object of the present invention is to provide compounds which have improved properties in the treatment of fungal diseases.

Another object of the present invention is to provide compounds which have a use spectrum, in the field of fungal diseases, which is also improved.

It has now been found that these objects can be achieved by virtue of the products of the invention, which are 2-imidazolin-5-one or derivatives of general formula (I)

R

N R4( W (A)n in which: W is a sulphur or oxygen atom or an S=O group n 0 or 1 A represents N(R5) or 0 or S or C(R5)(R6) or S02 or C=0.

R1 and R2, which are identical or different, represent: H, provided that one of the 2 groups is different from H, or an alkyl or haloalkyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or R1 and R2 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally 3 substituted by 1 to 3 groups chosen from R7; R3 represents: a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 atoms; R4 represents: a hydrogen atom when n is equal to 1 or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms or an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, bsnzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or an amino group disubstituted by 2 identical or different groups chosen from: an alkyl radical containing 1 to 6 carbon atoms an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms a cycloalkyl radical containing 3 to 7 carbon atoms an arylalkyl, such as defined above, phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 or a thienylmethyl or furfuryl radical a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; R5 represents: H, except when R4 is H, or an alkyl, haloalkyl, alkylsulphonyl or haloalkylsulphonyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioakyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or cyanoalkylsulphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical containing 3 to 6 carbon atoms or a formyl radical or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical containing 3 to 6 carbon atoms or a cycloalkylcarbonyl radical containing 4 to 8 carbon atoms or a phenyl; arylalkylcarbonyl, especially phenylacetyl and phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydrofurfuryloxycarbonyl; thienylmethoxycarbonyl; pyridylmethoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 group from R7; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or a carbamoyl radical, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 group; a sulphamoyl group, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 groups; an alkylthioalkylsulphonyl group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; R6 represents: a hydrogen atom or a cyano group or an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or a benzoyl group, optionally substituted by one 1 to 3 R7 groups; R7 represents: a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical containing 1 to 6 carbon atoms or a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or a nitro or cyano group or an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical containing 1 to 6 carbon atoms or an alkoxycarbonyl radical containing 2 to 6 carbon atoms a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted; their salts and the optically active isomers, with the proviso that when n 0, R4 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid.

Certain compounds belonging to the family of the 2-imidazolin-5-ones of general formulae: R N R\ l R2

R

2 B ad W B and W B are known for their herbicidal properties by the documents of European Patents 41,623, 41,624, 215,738, 226,947, 261,705, 303,863, 433,655 and 436,483 and Patents US 4,925,944, DE 3,913,757, GB 2,167,062, GB 2,192,877 and JP 3,196,570.

The imidazolinones of formula:

R

3 R1 R2 N X

CH

2 R N Aryl NC'

ZN

O

B

and Aryl

N

Aryl

N

0 B have been described for their pharmaceutical properties by Applications WO 91 14679, JP 8,055,467 and DE 1,176,660 and 1,258,412 respectively.

No agricultural fungicidal activity has been described for compounds of formula I.

The compounds of formula Ia are novel: N\

R

SR

A) The compounds of formula Ib (n 0) can be prepared according to standard processes described in the literature: (Ib) By cyclisation of an a-amino acid amide:

-NH-R

4

(II)

with a carboxylic acid orthoester:

R

3 -C(OR')3 in which R' represents a linear or branched alkyl radical having 1 to 4 carbon atoms.

This process has been described, for example, by J. Brunken and G. Bach in Chem. Ber., 89, pp 1363-1373 (1956) or S. Ginsburg in J. Org. Chem., 27, pp 4062-4064 (1962).

The amino acid amides cf the formula II can be prepared conventionally by reacting an amine of formula R4NH2 with an amino acid ester of formula III:

R

2 0 RI C OR NH2

(I)

The reaction can then be carried out according to the conditions described by J. Brunken and G. Bach in Chem. Ber., 89, pp 1363-1373 (1956).

By reaction of an amine R4NH2 with an iminoester of formula IV: R1 ROCO -C-N-

OR'

R

2

(V)

This process has been described in J. Chem.

Soc., 1959, p 1648 by G. Shaw et al.

The iminoesters IV can be obtained by reaction of an amino acid ester III with an imidate of formula:

NH

R

3

OR

as described in Ber. dt. Chem. Ges., 47, p 2545 (1914).

The compounds of formula Ib in which R3 is a hydrogen atom can be obtained by cyclisation of an isonitrile derived from amides of formula V in the presence of base.

R N=C R N

R

N

R NH-R 4 O

R

(Ib) This process has been described by Belgian Patent Application No. 862,194 of 22 December 1977.

The compounds of formula Ib can be obtained by alkylation of compounds Ib', in which R2 is hydrogen, by a compound R2X in basic medium according to the method described in the abovementioned Belgian Patent Application: R 3 C N R3 R4 N R3 (Ib) By reaction of an amine R4NH2 with an azalactone VI of formula: R2 0 0

(VI)

This reaction can be carried out by acid catalysis (acetic acid for example) or by basic catalysis. An example of the latter case can be found in the article by Ito et al., Yakugaku Zasshi, 1975, 95(1), 28-32.

B) The compounds of formula Ia can be obtained by analogy with one of the abovementioned processes by reacting hydrazine derivatives of formula R4NR5NH2 in place of the amine derivatives R4NH2.

They can also be prepared according to a process which forms part of the invention, by hot cyclisation of a hydrazide of formula VII: R1

R

R

3 -C -NH C-NH-N-R 4 II I II O R 2

O

2 0

(VII)

The reaction is catalysed by acids. Inorganic acids, alkylsulphonic acids, arylsulphonic acids, acidic resins or carboxylic acids can be used as acid.

The reaction can be carried out in aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters or alcohols.

It is carried out at a temperature between and 150°C. The reaction is generally carried out at the reflux temperature of the solvent, the water being distilled off as it is formed.

The hydrazides of formula VII can be prepared according to one of the processes described in the literature, for example: 1) By reaction of certain hydrazines R4NR5NH2 with certain methyl, ethyl, propyl or butyl amino acid esters of formula:

R

1

R

3 -C--NH-C C-OR II II 0

R

2 0 as described by German Patent Application 1,089,390 of 22 September 1960 (Chem. Ab., 1962, 56, pp 4860-4862).

2) By condensation of an N-acylated amino 14 acid with a hydrazine in the presence of papain extracts in buffered aqueous solution according to the article by Niemann and Nichols in J. Biol. Chem., 143, 1942, pp 191-201.

3) By reaction of a hydrazine R4NR5NH2 with an azalactone of formula VI according to the reference by J.P. Branquet et al. in Bull. Soc. Chim. de France, 1965, pp 2942-2954.

The azalactones of formula VI are themselves described in the abovementioned article.

4) A preferred general access route analogous to Point 2 above consists in activating the acid in the imidazolide (Reaction a) or mixed anhydride (Reaction b) form in order to condense it with a hydrazine: a)

R

1

R

3 -C-NH-C

C-OH

II 1 II

CO

II /N R3- -NHO

R

4 N- -N O 2 0 R4NR5NH2 b)

R

1

R

3 -C-NH -C C--OH II t 1 O 2 0 t C1CO 2 R +TEA

R

1 R3-C--NH--C- C--O-C-OR tSI SI I II II O R 2 O 0 R 4

NR

5

NH

2 The condensation is carried out under the usual conditions for this type of reaction, as is illustrated in Examples 1 and 2.

C) Another preferred route for preparing the compounds of formula Ia consists in reacting a hydrazine R4NR5NH2 with an azalactone VI under certain conditions: By heating the reactants in an inert solvent in the presence of an acid in order to catalyse the reaction. Halogenated hydrocarbons, esters, aromatic solvents or alcohols can be used as solvent.

Inorganic acids, alkylsulphonic acids, arylsulphonic acids, acidic resins or carboxylic acids can be used to catalyse the reaction. The reaction is carried out at a temperature from 50 to 150 0

C.

This process is illustrated in Example 4.

By heating the mixture of the reactants in acetic acid at reflux in the presence of sodium acetate in order to catalyse the reaction.

These conditions are illustrated in Example D) The compounds of formula in which is other than a hydrogen atom, are also possible starting from compounds Ia' which can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulphamoylated by R5X in the presence of base and solvent: R1 N R N R 3 2 R4 2 N\

R

4 N W N H (Ia) here represents an alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, carbamoyl or sulphamoyl group, as defined above.

X represents a halogen, a sulphate or optionally substituted phenoxy group, or an alkylsulphonyloxy or arylsulphonyloxy group, or a group R50, when R5 is acyl.

Alkali metal hydrides, alkoxides or a tertiary amine can be used as base. The reaction can be carried out at a temperature between -30°C and +50 0

C.

Ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents, for example, can be used as solvent.

The carbamoylation or the thiocarbamoylation of the compounds can be carried out by reaction with isocyanates or isothiocyanates according to the scheme: R1 N R 3 N R3 N\ N R4 2 N R 4 W N W N H R 5 -N C=Y y NHR The reaction is carried out under the same conditions as those described above, it beinj possible, however, for the base to be used in a catalytic amount.

E) The compounds of formula Ia in which the group R3 is a hydrogen atom can be obtained by reaction of dimethylformamide dimethyl acetal (DMFDMA) with an aminohydrazide of formula VIII according to the scheme: R N

R

4

R

2

N

HNH-N

2N 0Y R (CH 3 NCH OCH 2 R4| 2 0 R R 4 VIII Ia The reaction is carried out at a temperature between 10 and 1000C in DMFDMA used in excess.

The intermediate aminohydrazides of formula VIII can be obtained according to a new process by reacting the hydrochloride of the acid chloride of the corresponding a-amino acid in the presence of a base according to the scheme: R R 'R4 i1 Cl R 1 NH-N/ C, H 3

H

2 N-N 4

H

2

R

0 R R2 O R 5 R2 O

VIII

The reaction is carried out at a temperature between -20 0 C and 40 0 C in cyclic or noncyclic ethers.

Nitrogenous organic bases such as triethylamine or pyridine can be optionally used as base. The intermediate acid chlorides can be obtained by the method described by S. Levine in J. Am. Chem. Soc. of 1953, Volume 76, page 1392. They are then obtained by reacting phosphorus pentachloride with the a-amino acid according to the scheme below: 1 OH 1 Cl R R 0 R2 2 The compounds which are preferred for their better fungicidal activity and/or for their ease of synthesis are: 1) the compounds of formula la, 2) the compounds of formula I, in particular la, in which R5 is a hydrogen atom, 3) the compounds in which R1 and R2 are other than H, 4) the compounds in which R2 represents an alkyl group containing 1 to 3 carbon atoms, preferably methyl, the compounds in which R1 represents the phenyl ring, optionally substituted by R7, 6) the compounds in which R3 represents a hydrogen atom or an alkyl group containing 1 to 3 carbon atoms, optionally substituted by one or more halogens, methoxy or methylthio, 7) the compounds in which R4 represents the phenyl ring, optionally substituted by R7, 8) the compounds of formula I in which W represents an oxygen atom.

The examples below are given by way of illustration of the compounds according to the invention, of the processes for their preparation and of their antifungal properties.

The structures of all the products were established by at least 1 of the following spectral techniques: proton NMR spectrometry, carbon-13 NMR spectrometry, infrared spectrometry or mass spectrometry.

In the tables below, the methyl, ethyl, propyl, butyl and phenyl radicals are represented respectively by Me, Et, Pr, Bu and Ph, and M.p. means melting point: Example 1: This example illustrates the preparation of a hydrazide (VII) according to Process B 4a): preparation of 2-propionylamino-2-phenyl- 2'-phenylpropionohydrazide (compound 102): 4.51 g (0.0278 mol) of N,N'-carbonyldiimidazole are added to a solution, stirred under an inert atmosphere, of 5.6 g (0.0253 mol) of N-propionyl- 2-methyl-2-phenylglycine in 150 ml of anhydrous dichloromethane and the mixture is allowed to react until gas evolution has ceased. 3.28 g (0.0304 mol) of phenylhydrazine are then added and the mixture is allowed to react for 12 hours. The reaction mixture is then concentrated under reduced pressure and the residue obtained is chromatographed on 400 g of Si02, the eluent being an ethyl acetate/heptane (65 %/35 mixture. The advantageous fractions are then concentrated under reduced pressure. 4.80 g (0.0154 mol) of 2-propionylamino-2-phenyl- 2'-phenylpropionohydrazide, melting at 144°C, are thus recovered with a yield of 61 By carrying out the reaction according to the same procedure, Compounds 101 to 109 and 112, collated in the following table, are obtained, which are intermediates of Compounds 1 to 9 and 12:

R

i

R

3 -C -NH C N--NH-NH-R 4 0

C

3 0 No. R1 R3 R4 Yd M.p.

101 Ph Me Ph 53 150 0

C

102 Ph Et Ph 61 1440C 103 Ph CF3 Ph 50 161 0

C

104 Ph CC13 Ph 49 187 0

C

105 Ph nPr Ph 55 1020C 106 Ph iPr Ph 45 1300C 107 Ph tBu Ph 77 134°C 108 4-Cl-Ph Me Ph 71 1800C 109 4-Cl-Ph Me 2-Me-Ph 64 1520C 112 Ph CICH2 Ph 55 1460C Example 2: Preparation of a hydrazide (VII) according to Process B 4b): phenylhydrazide of N-trifluoroacetyl-2-(4-methylphenyl)glycine: 1.38 g (5 mmol) of N-trifluoroacetyl- 2-(4-methylphenyl)glycine, 25 ml of anhydrous toluene and then 0.75 ml (5.5 mmol) of anhydrous triethylamine are introduced into a 100 ml round-bottomed flask. The reaction mixture is cooled to -15 0 C and then 0.475 ml (5 mmol) of ethyl chloroformate is run in dropwise. A white precipitate is then formed and stirring is continued at -10 0 C for 30 minutes.

g (4.5 mmol) of phenylhydrazine and 25 ml of anhydrous toluene are introduced into a vacuum flask and the mixture is cooled to -15 0

C.

The content- of the first round-bottomed flask are rapidly filtered through sintered glass into the Erlenmeyer flask containing the phenylhydrazine.

The reaction mixture is allowed to return to room temperature, washed with dilute sodium hydroxide solution and water, and then dried over MgS04 before filtering and evaporating. 1.4 g (78 yield) are thus obtained of a white solid with a melting point equal to 162 0 C of formula:

CH

3 F3C-C -NH-C- C-NH--NH- O H O Example 3: This example illustrates the preparation of the compounds of formula Ia according to Process B, by cyclisation of compounds of formula VII: preparation of 2,4-dimethyl-4-phenyl-l-phenylamino- 2-imidazolin-5-one (compound No. 1).

A stirred solution of 1.5 g (0.005 mol) of 2-acetylamino-2-phenyl-2'-phenylpropionohydrazide and of 0.17 g (0.001 mol) of paratoluenesulphonic acid in ml of toluene is held at reflux for 7 hours, the water being removed as it is formed. The reaction mixture is then concentrated under reduced pressure and the residue obtained is chromatographed on 200 g of Si02, the eluent being an ethyl acetate/heptane %/50 mixture. A thick oil is isolated which crystallises by triturating with diisopropyl ether.

After filtration, 0.5 g (0.0018 mol) of 2,4-dimethyl- 4-phenyl-l-phenylamino-2-imidazolin-5-one (compound 23 No. 1) is recovered with a yield of 36 in the form of a white powder melting at 135 0

C.

Compounds 1 to 9 and 12 of formula,

R

1 N R3

C

3 N\

R

4 0 N 4

H

recorded in the following table, are prepared according to the same procedure with the appropriate reactants.

No. RI R3 R4 Yd M.P.

1 Ph Me Ph 36 135 0

C

2 Ph Et Ph 86 honey 3 Ph CF3 Ph 66 104 0

C

4 Ph CC13 Ph 14 68 0

C

Ph nPr Ph 84 honey 6 Ph iPr Ph 69 122 0

C

7 Ph tBu Ph 11 87 0

C

8 4-aI-Ph .Me Ph 54 140 0

C

9 4-Cl-Ph Me 2-Me-Ph 65 142C 12 Ph C1CH2 Ph 79 76C 14 Ph 'Et Ph 53 780C Ph Et 2-Me-Ph 68 107 0

C

16 Ph Me 2-Me-Ph 53 180 0

C

18 Ph MeOCH2 Ph 8 95 0

C

19 Ph MeOCH2 3-Cl-Ph 20 125 0

C

26 4-Me-Ph Me Ph 41 142 0

C

29 Ph MeOCH2 2-Me-Ph 54 122 0

C

S33 4MePh ICF3 Ph 35 166 0

C

Ph _MeOCH2 12,3-diMe-Ph 55 912'C Example 4: Preparation of a compound of formula Ia according to Process C 10), 2,4-dimethyl- 4-phenyl-1-phenylamino-2-imidazolin-5-one (compound No.

1).

A solution containing 0.9 g (4 inmol) of 2, 4-dimethyl-4-phenyl-2-oxazolin-5-one, 0.43 g (4 mmol) of phenyihydrazine and 0.1 g of paratoluenesulphonic acid in 30 ml of toluene is heated at ref lux for one hour. The water formed is removed by azeotropic entrainment and the mixture is concentrated under reduced pressure. The crude product is then purified by chromatography on silica gel.

Compound 1 is thus obtained with a yield of According to the same procedure, 2,4-dimethyl-4-(4-chlorophenyl)-1-(2,3-dimethyl- (Compound 10) is obtained with a yield of 18 164 0

C).

Example 5: Preparation of a compound of formula Ia according to Process C 20): 2,4-dimethyl- 4-(4-chlorophenyl)-l-(2-chlorophenylamino)- (compound No. 11).

A solution containing 1.5 g (6.7 mmol) of 2,4-dimethyl-4-(4-chlorophenyl)-2-oxazolin-5-one, 0.93 g (6.7 mmol) of 2-chlorophenylhydrazine and 0.25 g of sodium acetate in 20 ml of acetic acid is heated at reflux for 2 hours. The mixture is concentrated under reduced pressure and the residues dissolved in 150 ml of methylene chloride. The methylene chloride solution is washed with an aqueous bicarbonate solution and then with pure water. The solution is concentrated and the product purified by chromatography on silica gel, the eluent being an ethyl acetate/heptane (30 %/70 mixture.

Compound No. 11 is thus obtained with a yield of 43 Compound 13 is obtained according to the same procedure with a yield of 33.5 The compounds of formula: I

CH

3 \-N O N R4 0 N

H

are obtained according to the same procedure, which compounds are collated in the following table: No. R1 R3 R4 Yd M.p.

13 4-Br-Ph Me Ph 34 147 0

C

17 4-Cl-Ph Ph 3-Cl-Ph 31 120 0

C

Ph Me 3-Cl-Ph 43 163°C 21 4-Cl-Ph EC Ph 27 144 0

C

22 4-Br-Ph Me 2-Me-Ph 38 144 0

C

23 4-Br-Ph Me 2-Cl-Ph 41 145°C 24 4-Br-Ph Et Ph 20 110°C 4-Cl-Ph Me iPr 53 honey 4-F-Ph Me Ph 150 0

C

31 PhCH2 Me Ph 192 0

C

32 PhCH2 Et Ph 167 0

C

34 Ph Me 4-iPr-Ph 20 162 0

C

Ph Me 2,3-diMe-Ph 16 64 0

C

36 Ph Me 2,3-diCl-Ph 33 165°C 37 Ph Me 2,4-diMe-Ph 43 100 0

C

38 Ph Me 3,4-diMe-Ph 30 135 0

C

39 Ph Me 4-Cl-Ph 56 69 0

C

Ph Me 2-Cl-Ph 50 196 0

C

41 Ph Me 4-MePh 34 142°C 42 Ph Me 2-MePh 45 129 0

C

43 Ph Et 3-Cl-Ph 26 82 0

C

44 Ph Et 2,3-diCl-Ph 41 60 0

C

No. R1 R3 R4 Yd M.p.

46 Ph Et 3,4-diMe-Ph 32 94°C 47 Ph Et 2,3-diMe-Ph 27 109 0

C

48 Ph Et 2,4-diMe-Ph 50 450C 49 Ph Et 4-Cl-Ph 48 73°C Ph Et 4-iPr-Ph 16 73°C 51 Ph Et 2-Cl-Ph 56 84°C 52 Ph Et 3-Me-Ph 14 85 0

C

53 4-PhO-Ph Me Ph 54 134 0

C

56 4-PhO-Ph Et Ph 58 honey 59 3-Cl-Ph Et Ph 49 117 0

C

Likewise, the spiro compounds 27 (yield 56 203 0 C) and 28 (yield 56 153°C) of formulae:

-CH

3 -R4

CH

3 ,R4 are obtained.

Example No. 6: Preparation according to Process E of compounds of formula Ia, in which R3 is a hydrogen atom, and of their intermediates of formula

VIII:

a) 4.58 g (0.0208 mol) of methylphenylglycine acid chloride hydrochloride are added, in a single step, to a solution of 2.25 g (0.0208 mol) of phenylhydrazine in 50 ml of diethyl ether and the suspension thus formed is left stirring for 18 hours.

The suspension is filtered and the solid sucked dry and then redissolved in distilled water. The solution obtained is slowly basified to pH 7-8 using a saturated sodium hydrogencarbonate solution. The precipitate thus formed is filtered and washed with distilled water and then recrystallised from isopropanol. After filtering the crystals and drying under reduced pressure at 50°C, 2 g (0.0078 mol) of 2-(R,S)-2-amino-2-phenyl-2'-phenylpropionohydrazide (Compound 155), melting at 154°C, are recovered, i.e.

with a yield of 38 The phenylpropionohydrazides of formula: R

R

4 R1 NH-N/

H

2

R

R

2

VIII

were obtained according to the same procedure, which compounds are recorded in the following table: No. R1 R2 R4 R5 Yd.% M.p.

155 Ph Me Ph H 38% 154 0

C

157 Ph Me 2-Me-Ph H 32% 1150C 158 Ph Me 3-Cl-Ph H 20% 164°C 160 Ph Me 2-Cl-Ph H 68% 112C 161 Ph Me 4-Cl-Ph H 48% 177°C 163 Ph Me 2-F-Ph H 43% 112 0

C

164 Ph Me 4-F-Ph H 40% 142°C 165 Ph Me 3-Me-Ph H 45% 110°C 166 Ph Me 4-Me-Ph H 26% 168 0

C

167 Ph Me 3-F-Ph H 33% 161 0

C

Likewise, the spiro compound 162 (R1 C6H4, R2 (CH2)2, R3 H, R4 Ph; yield 7 171 0

C)

is obtained.

b) 4-(R,S)-4-(4-fluorophenyl)-4-methyl- 1-phenylamino-2-imidazolin-5-one (Compound 54).

A solution of 2.73 g (0.01 mql) of 2-(R,S)-2-amino-2-(4-fluorophenyl)- 2'-phenylpropionohydrazide in 16 ml of N,N-dimethylformamide dimethyl acetal is stirred for 48 hours. The reaction mixture is concentrated under reduced pressure. The residue obtained is then chromatographed on silica, the eluent being an n-heptane/ethyl acetate mixture in the proportion: 50/50. The fractions containing the pure product No. 54 are concentrated together under reduced pressure. 1.5 g (0.0053 mol) of 4-(R,S)-4-(4-fluorophenyl)-4-methylmelting at 140°C on a Kofler-type bench, are thus recovered, i.e. a yield of 53 The compounds of formula Ia, in which R3 is a hydrogen atom, that is to say:

R

2 0 were obtained according to this procedure, which compounds are collated in the following table: No. R1 R2 R4 Y.d. M.p.

54 4-F-Ph Me Ph 53% 140 0

C

Ph Me Ph 38% 129°C 57 Ph Me 2-Me-Ph 72% 175 0

C

58 Ph Me 3-C1-Ph 46% 177 0

C

Ph Me 2-Cl-Ph 79% 176 0

C

61 Ph Me 4-Cl-Ph 33% 153 0

C

*62 C6H4 (CH2)2 Ph 64% 202 0

C

63 Ph Me 2-F-Ph 86% 151"C 64 Ph Me 4-F-Ph 40% 124"C Ph Me 3-Me-Ph 50% 109 0

C

66 Ph Me 4-Me-Ph 41% 127 0

C

67 Ph Me 3-F-Ph 20% 137"C spiro compound Example 7: In vivo test on Plasmopara viticola (grape downy mildew): An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition: active material: 60 mg 31 Tween 80 surface-active agent (oleate of polycondensate of ethylene oxide with sorbitan) diluted to 10 in water: 0.3 ml volume made up to 60 ml with water.

This aqueous suspension is then diluted with water to produce the desired concentration of active material.

Vine cuttings (Vitis vinifera), Chardonnay variety, are grown in pots. When these seedlings are 2 months old (8 to 10-leaf stage, height of 10 to 15 cm), they are treated by spraying with the above aqueous suspension.

Seedlings used as controls are treated with an aqueous solution which does not contain the active material.

After drying for 24 hours, each seedling is infected, by spraying, with an aqueous suspension of spores of Plasmopara viticola obtained from a 4-5 day culture, and then suspended at a concentration of 100,000 units per cm 3 The infected seedlings are then incubated for two days at approximately 18 0 C in an atmosphere saturated with moisture and then for 5 days at approximately 20-22°C under 90-100 relative humidity.

Reading is carried out 7 days after infecting, by comparison with the control seedlings.

Under these conditions, a good (at least or complete protection is observed, at a dose of 32 1 g/l, with the following compounds: 1, 2, 3, 13, 15 to 18, 20 to 22, 24, 26 to 30,, 35, 37 to 57, 59 to 62, 64 to 67.

Example 8: In vivo test on Puccinia recondita (brown rust of wheat): An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition: active material: 60 mg Tween 80 surface-active agent (oleate of polycondensate of ethylene oxide with sorbitan) diluted to 10 in water: 0.3 ml volume made up to 60 ml with water.

This aqueous suspension is then diluted with water to produce the desired concentration of active material.

Wheat, in pots, sown on a 50/50 peat/pozzolana earth substrate, is treated at the 10 cm high stage by spraying the above aqueous suspension.

After 24 hours, an aqueous suspension of spores (100,000 sp/cm 3 is sprayed on the wheat; this suspension was obtained from infected seedlings. The wheat is then placed for 24 hours in an incubation cell at approximately 20°C and at 100 relative humidity, and then for 7 to 14 days at 60 relative humidity.

Monitoring of the condition of the seedlings is carried out between the 8th and 15th day after infection, by comparison with an untreated control.

Under these conditions, a good (at least or complete protection is observed, at a dose of 1 g/l, with the following compounds: 1, 2, 3, 8, 12, 17, 21, 22, 24, 28, 30, 35, 53, 54, 56, 59.

Example 9: In vivo test on Phytophthora infestans (tomato late blight): An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition: active material: 60 mg Tween 80 surface-active agent (oleate of polycondensate of ethylene oxide with sorbitan) diluted to 10 in water: 0.3 ml volume made up to 60 ml with water.

This aqueous suspension is then diluted with water to produce the desired concentration of active material.

Tomato seedlings (Marmande variety) are grown in pots. When these seedlings are one month old (5 to 6-leaf stage, 12 to 15 cm high), they are treated by spraying the above aqueous suspension at various concentrations of the compound to be tested.

After 24 hours, each seedling is infected by spraying with an aqueous suspension of spores (30,000 sp/cm') of Phytophthora infestans.

After this infecting, the tomato seedlings are incubated for 7 days at approximately 20°C in an atmosphere saturated with moisture.

34 Seven days after infecting, the results obtained in the case of the seedlings treated with the active material to be tested are compared with those obtained in the case of the seedlings used as controls.

Under these conditions, a good (at least 75 or complete protection is observed, at a dose of 1 g/l, with the following compounds: 1, 2, 13, 18, 21, 24, 49, 54.

These results clearly show tke good fungicidal properties of the derivatives according to the invention against funga,. diseases of plants due to fungi belonging to the most diverse families, such as the Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or Fungi Imperfecti, in particular grape downy mildew, tomato late blight and brown rust of wheat.

For their practical use, the compounds according to the invention are rarely used on their own. Most often these compounds form part of compositions. These compositions, which can be used as fungicidal agents, contain, as active material, a compound (or compounds) according to the invention as described above as a mixture with solid or liquid vehicles which are acceptable in agriculture, and surface-active agents which are also acceptable in agriculture. In particular, the customary inert vehicles and the customary surface-active agents can be used. These compositions also form part of the I invention.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickening agents, thixotropic agents, penetration agents, stabilising agents, sequestering agents and the like. More generally, the compounds used in the invention can be used in combination with any of the solid or liquid additives which correspond to the usual formulating techniques.

Generally, the compositions according to the invention usually contain approximately 0.05 to 95 by weight of a compound (or compounds) according to the invention (subsequently called active material), one or more solid or liquid vehicles and, optionally, one or more surface-active agents.

The term "vehicle", in the present account, means a natural or synthetic, organic or inorganic material with which the compound is combined in order to facilitate its application to the plant, to seeds or to the soil. This vehicle is therefore generally inert and it has to be acceptable in agriculture, especially to the treated plant. The vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, and the like) or liquid (water, alcohols, especially butanol, and the like).

The surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surface-active 36 agents. There may be cited, for example, salts of poly(acrylic acids), salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, derivatives of taurine (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of fatty acids and of polyols, and the derivatives of the above compounds having sulphate, sulphonate or phosphate functional groups. The presence of at least one surface-active agent is generally indispensable where the compound and/or the inert vehicle are not soluble in water ard where the vector agent of the application 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 surface-active agent content is advantageously between and 40 by weight.

These compositions according to the invention are themselves in fairly diverse, solid or liquid forms.

There may be mentioned, as solid composition forms, powders for dusting (containing the compound at a content of up to 100 and granules, especially those obtained by extrusion, by compacting, by impregnation of a granulated vehicle, or by granulation from a powder (the content of the compound in these granules being between 0.5 and 80 for the latter cases), tablets or effervescent tablets.

The compounds of formula 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 milled and the mixture is applied by dusting.

As composition forms which are liquid or intended to constitute liquid compositions during application, there may be mentioned solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or sprayable powder), pastes or gels.

The emulsifiable or soluble concentrates most often comprise 10 to 80 of active material, while the ready-to-apply solutions or emulsions contain 0.001 to of active material.

In addition to the solvent, the emulsifiable concentrates can contain, when this is necessary, 2 to of suitable additives such as the stabilising agents, surface-active agents, penetration agents, 38 corrosion inhibitors, dyes or adhesives mentioned above.

It is possible, by diluting these concentrates with water, to obtain emulsions of any desired concentration which are particularly suitable for application to crops.

By way of example, the composition of several emulsifiable concentrates will now be given: EC Example 1 active material 400 g/l alkaline dodecylbenzenesulphonate 24 g/l nonylphenol oxyethylated with 10 molecules of ethylene oxide 16 g/l cyclohexanone 200 g/l aromatic solvent qs 1 litre According to another emulsifiable concentrate formula, there are used: EC Example 2 active material 250 g epoxidised vegetable oil 25 g mixture of alkylarylsulphonate and of ether of polyglycol and fatty alcohols 100 g dimethylformamide 50 g xylene 575 g The suspension concentrates, which can also !e applied by spraying, are prepared so as to produce a stable fluid product which does not settle out and they generally contain from 10 to 75 of active material, from 0.5 to 15 of surface-active agents, from 0.1 to of thixotropic agents, from 0 to 10 of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilising agents, penetration agents and adhesives and, as vehicle, water or an organic .'qut.

in which the active material has little or no solubility: certain solid organic materials or inorganic salts can be dissolved in the vehicle to help in preventing sedimentation or as antifreeze for the water.

By way of example, the composition of a suspension concentrate will now be given: SC Example 1 active material 500 g polyethoxylated tristyrylphenyl 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 The wettable powders (or sprayable powders) are generally prepared so that they contain 20 to 95 of active material, and they generally contain, in addition to the solid vehicle, from 0 to 30 of a wetting agent, from 3 to 20 of a dispersing agent and, when necessary, from 0.1 to 10 of one or more stabilising agents and/or other additives, such as penetration agents, adhesives, or anticaking agents, dyes, and the like.

In order to obtain the sprayable powders or wettable powders, the active materials are intimately mixed in suitable mixers with the additional substances and the mixture is milled in mills or other suitable grinders. Sprayable powders are thereby obtained whose wettability and suspensibility are advantageous; they can be suspended in water at any desired concentration and these suspensions can be used very advantageously in particular for application to plant leaves.

Instead of wettable powders, it is possible to produce pastes. The conditions and methods for producing and using these pastes are similar to those for the wettable powders or sprayable powders.

By way of example, various wettable powder (or sprayable powder) compositions will now be given: WP Example 1 active material 50 ethoxylated fatty alcohol (wetting agent) 2.5 ethoxylated phenylethylphenol (dispersing agent) 5 chalk (inert vehicle) 42.5 WP Example 2 active material 10 C13 branched-type synthetic oxo alcohol ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75 neutral calcium lignosulphonate (dispersing agent) 12 calcium carbonate (inert filler) qs 100 WP Example 3: This wettable powder contains the same ingredients as in the above example, in the proportions below: active material 75 wetting agent 1.50 dispersing agent 8 calcium carbonate (inert filler) qs 100 WP Example 4: active material 90 ethoxylated fatty alcohol (wetting agent) 4 ethoxylated phenylethylphenol (dispersing agent) 6 WP Example active material 50 mixture of anionic and nonionic surface-active agents (wetting agent) 2.5 sodium lignosulphonate (dispersing agent) 5 kaolin clay (inert vehicle) 42.5 The aqueous dispersions and emulsions, for example the compositions obtained by di 3 uting a wettable powder or an emulsifiable concentrate according to the invention using water, are included within the general scope of the present invention. The emulsions can be of water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

The compounds according to the invention can be formulated in the form of water-dispersible granules also included in the scope of the invention.

These dispersible granules, with an apparent density generally between approximately 0.3 and 0.6, have a particle size generally between approximately 150 and 2,000 and preferably between 300 and 1,500 microns.

The active material content of these granules is generally between approximately 1 and 90 and preferably between 25 and 90 The remainder of the granule is essentially composed of a solid filler and optionally of 43 surface-active adjuvants which confer waterdispersibility properties on the granule. These granules can be essentially of two distinct types depending upon whether the filler used is soluble or insoluble in water. When the filler is water-soluble, it can be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, the latter is preferably inorganic, such as, for example, kaolin or bentonite. It is then advantageously accompanied by surface-active agents (at an amount of 2 to 20 by weight of the granule) of which more than half consists, for example, of at least one essentially anionic dispersing agent such as an alkali metal or alkaline-earth metal polynaphthalene sulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anioric wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalene sulphonate.

Moreover, although this is not indispensable, it is possible to add other adjuvants such as antifoaming agents.

The granule according to the invention can be prepared by mixing the required ingredients and then granulating according to several techniques known per se (pelletiser, fluid bed, atomiser, extrusion, and the like). Generally, the preparation is completed by crushing followed by sieving to the particle size chosen within the abovementioned limits.

Preferably, it is obtained by extrusion, the preparation being carried out as shown in the examples below.

DG Example I: Dispersible granules 90 by weight of active material and 10 of urea in the pearl form are mixed in a mixer. The mixture is then milled in a pin mill. A powder is obtained which is moistened with approximately 8 by weight of water. The damp powder is extruded in a perforated-cylinder extruder. A granule is obtained which is dried and then crushed and sieved so as to retain only the granules with a size between 150 and 2,000 microns respectively.

DG Example 2: Dispersible granules The following constituents are mixed in a mixer: active material 75 wetting agent (sodium alkylnaphthalene sulphonate) 2 dispersing agent (sodium polynaphthalene sulphonate) 8 water-insoluble inert filler (kaolin) 15 This mixture is granulated in a fluid bed, in the presence of water, and is then dried, crushed and sieved so as to produce granules of between 0.15 and 0.80 mm in size.

These granules can be used alone or in solution or dispersion in water so as to produce the l:\OIIER\MIN504J-93.Sl'n 18/9/96 required dose. They can also be used to prepare combinations with other active materials, especially fungicides, the latter being in the form of wettable powders or of granules or aqueous suspensions.

As regards the compositions which are suitable for storing and transporting, they more advantageously contain from 0.05 to 95 (by weight) of active substance.

A subject of the invention is also the use of the compounds according to the invention for combating fungal diseases of plants by preventative or curative *treatment of the latter or of their growth site.

They are advantageously applied at doses of °'0.005 to 5 kg/ha, and more specifically of 0.01 to 15 1 kg/ha.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

Claims (30)

1. A compound containing an imidazolinone or imidazolinethione group, characterised in that it corresponds to the general formula (la): N R3 r r r cr r o o o r o a r in which: W is a sulphur or oxygen atom R1 and R2, which are identical or different, represent: H, provided that one of the 2 groups is different from H, or an alkyl or haloalkyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical, each containing 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl radical, each containing 3 to 7 carbon atoms or an aryl radical comprising phenyl, naphthyl, thienyl, furyl pyridyl, benzothienyl, benzofuryl, 1;- 'I optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or R1 and R2 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R7; R3 represents: a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonyl- alkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 atoms; R4 represents: a hydrogen atom whe-n n is qual te-1 or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms or an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or an amino group disubstituted by 2 identical or different groups chosen from: an alkyl radical containing 1 to 6 carbon atoms an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms a cycloalkyl radical containing 3 to 7 carbon atoms an arylalkyl, such as defined above, phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 or a thienylmethyl or furfuryl radical a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; R5 represents: H, except when R4 is H, or an alkyl, haloalkyl, alkylsulphonyl or haloalkylsulphonyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioakyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or cyanoalkylsulphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical containing 3 to 6 carbon atoms or a formyl radical or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical containing 3 to 6 carbon atoms or a cycloalkylcarbonyl radical containing 4 to 8 carbon atoms or a phenyl; arylalkylcarbonyl, especially phenyl- acetyl and phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro- furfuryloxycarbonyl; thienylmethoxycarbonyl; pyridyl- methoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 group from R7; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)- carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or a carbamoyl radical, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 group; a sulphamoyl group, optionally mono- or disubstituted by an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 group; an alkylthioalkylsulphonyl group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; R6 represents: a hydrogen atom or a cyano group or an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or a benzoyl group, optionally substituted by one 1 to 3 R7 groups; R7 represents: a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical containing 1 to 6 carbon atoms or a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or a nitro or cyano group or an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical containing 1 to 6 carbon atoms or an alkoxycarbonyl radical containing 2 to 6 carbon atoms a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted; their salts and the optically active isomers, with the proviso that when n 0, R4 is other than an optically active residue, deriving from an optically active primary amine or from an optically OPER\RMH'4545-93.PE 1919/96 -52- to 6 carbon atoms or an alkoxycarbonyl radical containing 2 to 6 c atoms a phenyl, phenoxy or pyridyloxy radical; their salts and the optically active isomers, with the proviso that: when n 0, R4 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid; when n equals 1, A-R 4 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid; when n equals 1 and A is SO 2 one of the 2 radicals R, or R 2 has to be 10 anaryl; when and R 2 simultaneously represent a phenyl, n equals 1; when R, and R 2 simultaneously represent a paramethoxyphenyl, n equals 1.

2. A compound according to Claim 1, characterised in that R5 is a hydrogen atom.

3. A compound according to either Claim 1 or Claim 2, characterised in that R1 and R2 are other than a hydrogen atom. 20

4. A compound according to one of Claims 1 to 3, characterised in that R2 is an alkyl group containing 1 to 3 carbon atoms.

A compound according to Claim 4, characterised in that R2 is a methyl group.

6. A compound according to one of Claims 1 to 5, characterised in that R1 is a phenyl, optionally substituted by a R7 group.

7. A compound according to one of Claims 1 to 6, characterised in that R3 is an alkyl group containing 1 to 3 carbon atoms, optionally substituted by one or more halogens, 30 mL'thxy or methylthio. 'Y~3 b J&3W P:\OPlERMIM46jS-93SPU3 -1919196 -53

8. A compound according to one of Claims 1 to 6, characterised in that R3 is a hydrogen atom.

9. A compound according to one of Claims 1 to 8 characterised in that R4 is a phenyl, optionally substituted by a R7 group. A compound according to one of Claims 1 to 9, characterised in that W is an oxygen atom.

10

11. A fungicidal composition comprising, in combination with one or more solid or liquid vehicles which are agriculturally acceptable and/or surface-active agents which are also agriculturally acceptable, and(or more) active material which is a compound of formula (Ia): R N R 3 SN\ R 4 W N (la) C *o *0 C *0 0 C a *s C in which: W is a sulphur or oxygen atom or an S =0 group. R1 and R2, which are identical or different, represent: H, provided that one of the 2 groups is different from H, or h- C' an alkyl or haloalkyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonyl- alkyl, monoalkylaminoalkyl, alkenyl or alkynyl radical containing 2 to 6 carbon atoms or a dialkylaminoalkyl or cycloalkyl radical containing 3 to 7 carbon atoms or an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyi radical, the terms aryl and alkyl having the definitions given above or R1 and R2 can form, with the carbon to which they are bonded on the ring, a carbocycle or a heterocycle having from 5 to 7 atoms, it being possible for these rings to be fused to a phenyl, optionally substituted by 1 to 3 groups chosen from R7; R3 represents: a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, alkylsulphonyl- alkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 atoms; R4 represents: a hydrogen atom when n in equal to 1 or an alkyl group containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group containing 2 to 6 carbon atoms or a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group containing 3 to 6 carbon atoms or an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms or an aryl radical, comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups chosen from R7 or an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or an amino group disubstituted by 2 identical or different groups chosen from: an alkyl radical containing 1 to 6 carbon atoms an alkoxyalkyl, alkenyl or alkynyl radical containing 3 to 6 carbon atoms a cycloalkyl radical containing 3 to 7 carbon atoms an arylalkyl, such as defined above, phenyl or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 or a thienylmethyl or furfuryl radical a pyrrolidino, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; R5 represents: H, except when R4 is H, or an alkyl, haloalkyl, alkylsulphonyl or haloalkylsulphonyl radical containing 1 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or cyanoalkylsulphonyl radical containing 2 to 6 carbon atoms or an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical containing 3 to 6 carbon atoms or a formyl radical or a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical containing 3 to 6 carbon atoms or a cycloalkylcarbonyl radical containing 4.to 8 I-- carbon atoms or a phenyl; arylalkylcarbonyl, especially phenyl- acetyl and phenylpropionyl; arylcarbonyl, especially benzoyl, optionally substituted by 1 to 3 groups from R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro- furfuryloxycarbonyl; thienylmethoxycarbonyl; pyridyl- methoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 group from R7; (alkylthio)carbonyl; (haloalkylthio)carbonyl; (alkoxyalkylthio)carbonyl; (cyanoalkylthio)carbonyl; (benzylthio)carbonyl; (furfurylthio)carbonyl; (tetrahydrofurfurylthio)carbonyl; (thienylmethylthio)- carbonyl; (pyridylmethylthio)carbonyl; or arylsulphonyl radical or a carbamoyl radical, optionally mono- or disubstituted by an alkyl or haloalkyl group containing i to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 group; a sulphamoyl group, optionally mono- or disubstituted by 58' an alkyl or haloalkyl group containing 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group containing 3 to 6 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group containing 2 to 6 carbon atoms or a phenyl, optionally substituted by 1 to 3 R7 group; an alkylthioalkylsulphony. group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; R6 represents: a hydrogen atom or a cyano group or an alkyl group containing 1 to 6 carbon atoms or a cycloalkyl group containing 3 to 7 carbon atoms or an acyl or alkoxycarbonyl group containing 2 to 6 carbon atoms or a benzoyl group, optionally substituted by one 1 to 3 R7 groups; R7 represents: a halogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical containing 1 to 6 carbon atoms or a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or P:\OPER\RMI 145043-93.SP1- 19/9196 -59- a nitro or cyano group or an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical containing 1 to 6 carbon atoms or an alkoxycarbonyl radical containing 2 to 6 carbon atoms a phenyl, phenoxy or pyridyloxy radical; their salts and the optically active isomers.

12. A fungicidal composition according to Claim 11, characterised in that they contain from 0.05% to 95% by weight of a compound according to any one of Claims 1 to

13. A process for the treatment of crops affected or capable of being affected by fungal diseases, characterised in that there is preventively or curatively applied an effective quantity of a compound according to any one of Claims 1 to 11 or of a composition according to either Claim 11 or Claim 12.

14. A treatment process according to Claim 13, characterised in that the effective dose is between 0.005 and 5 kg/ha.

A treatment process according to Claim 14, characterised in that the effective dose is 20 between 0.01 and 1 kg/ha.

16. A process for the preparation of a compound of formula Ia, as claimed in Claim 1: N ,R 3 R R W N R4 (Ia) R P:\OPERMRM445l93.SP. I18/9J96 characterised in that the compound of formula VII: RI R3-C -NH -C- I I 0 p. C--NH-N-R 4 (VII) o f ft o o ft ft oo II o o o Q• ft ft ft... 6 f ft ft *ft...f ft. Oft 0 9 is cyclised in a hot solvent by acid catalysis.

17. A process according to Claim 16, characterised in that the acid is chosen from the 10 group comprising inorganic acids, alkylsulphonic acids, arylsulphonic acids, acidic resins or carboxylic acids.

18. A process according to Claim 16, characterised in that the solvent is chosen from the group comprising aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters 15 or alcohols.

19. A process according to Claim 16, characterised in that the temperature is between and 150°C.

20. A process for the preparation of a compound of formula Ia, as claimed in claim 1: ,N "K R W (Ia) /h AQ, y ~D C).'i i':\OITMO\RMSiPA5O493,SPII. -10196 -61- characterised in that a hydrazine of formula R4NR5NH2 is reacted while hot with an azalactone of formula VI: R R 3 R 2 (VI) in an inert solvent in the presence of an acid to catalyse the reaction. S S S S. S *o S a S Sa

21. A process according to Claim 20, characterised in that the solvent is chosen from the group comprising aromatic solvents, halogenated hydrocarbons, esters or alcohols.

22. A process according to Claim 20, characterised in that the acid is chosen from the group comprising inorganic acids, alkylsulphonic acids, arylsulphonic acids, acidic resins or carboxylic acids.

23. A process according to Claim 20, characterised in that the temperature is between and 150"C.

24. A process according to Claim 20, characterised in that the hydrazine of formula R4NR5NH2 and the azalactone of formula VI are heated at reflux in acetic acid in the presence of sodium acetate to catalyse the reaction.

A process for the preparation of the compounds of formula la, as claimed in claim 1, in which the group R3 is a hydrogen atom, by reaction of dimethylformamide dimethyl acetal with an aminohydrazide of formula VIII according to the scheme: R 4 R R RNH-4-N R4 H2N 1 R 5 (CH) 2NCH(OCH3) 2 R2 R 4 R2 NR1/R R.3 0 R VIII T- 30 P:\OPER\RMH\45045-93.SPE 1919196 -62-

26. A process according to Claim 25, characterised in that the reaction is carried out at a temperature between 10 and 100°C.

27. A process according to either Claim 25 or Claim 26 wherein the amount of dimethylformamide dimethyl acetyl is in excess.

28. A compound of formula as claimed in Claim 1, substantially as hereinbefore described with reference to the Examples. 10

29. A fungicidal composition, as claimed in Claim 11, substantially as hereinbefore So" described with reference to the Examples.

30. A process for the preparation of a compound of formula as claimed in Claim 1, substantially as hereinbefore described with reference to the Examples. S DATED this NINETEENTH day of SEPTEMBER, 1996 Rhone-Poulenc Agrochimie oo by DAVIES COLLISON CAVE 20 Patent Attorneys for the Applicants '4 INTERNAAOINAL SE~ARCH REPORT Internatonl application No. .PCIVFR 93/00647 A. CLASSMFCA7ION OF SUBJECT MATIER C07D233/70; A01N43/50 According to International Patent Classification (IPC).or to both national classification and IPC B. FIELDS SEARCHED Myinimum documentation searched (classification system followed by classification symbols) Int..L C07D Documentation searched other than minimum documentation to the extent that such documecnts arm included in the fields searched Electronic data bute consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIIEREID TO BE RELEVANT Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. X DEA,2 658 941 (BASF) 1, 3-U1 6 July 1978 see examples X EP,A,0 303 863 (A4EUICAN CYANAMJ COMtPANY) 146 22 February 1989 .81 ciLted 3-n the applicaticon see claim 1; example 7; tables I,11 X DE,B,l 176 660 BEIERSDCOF Ca.) 1, 4,7-U1 27 Augjust 1964 cited in the application see the whole -document X DEB, 1 25ni 412 (E]XRSDOR A~KIEN~GESELSCHAFT) 1,4,7-U- U Januiirr 2968 cited in tche application see the whole document Further documents are listed in the continuation of Box C. See patent family annex. Special categories of cited documents: later document published after the international filing date orpriority document defining the gentall state of tlieartwhlch is no osdrd data &ad not in conflict with the application but cited to wrnderstand to be of particular relevance the principle or theory underlying the Invention eartier document but pnblished on or after the international filing date document of particular relevance. the claimed Invention annot he "LV documient which may throw doubts on priority claim~s rw~hI conaldezed sovel or cannot be considered to Involve an Inventive cited to eatablish the publication date of another citation of stpothtedouetertke tn special reason (a speciied) document of particular relevance; the claimed invention cannot tbe document referring to as, oral disclosure, use, exibition or other considered to involve an Inventive stopi when the document Is meanUs tanitined withoneor momn otheraucha documents, such oombination document pzblished prior to the international Mlig data but later than being obvious to a pumao skilled In the art the priority date claimed document member of the same patent [&aily Date of the actual completion of the international search Date of mailing of the international search report 01 Septembte~r 1993 (01.09.93) 09 Septembter 1993 (09.09.93) Name and mailing address of the ISAJ Authorized officer European Patent Officy' Facsi mile No. Telephone No. Form PCT(/ISA/210 (second sheet) (July 1992) INTERATIONAL SEARCH REPORT Intematioatl application No. PCT/yFR 93/00647 C (Continuaion) DOCUMENTS CONS IDERED TO BE RELEVANT category- Cibedo of documet, withi Indication, whem approdnute, of the imIevant passages Rejevnt to claimi No. A EP, A,0 283 245 (E.IL, DU POW~ DE ND"=UR AND COM4PANY) 1,12 .21 Septetuber-1988 Form PCr/ISA/210 (continuation of second sheet) (July IM9) INTERNATIONAL SEARCH REPORT International application No. PCT/FR 93/00647 Box I Observatlons where certain claims were found unsearchable (Continuation of Item 1 of first sheet) This international search report has notbeen established in respect of certain claims underArticle 17(2)(a) for the followingreasons: 1. MO Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: For reasons of economy, claims 1, 3-11 have not been searched exhaustively since the search revealed too many relevent documents and compounds. Several examples of those documents have been cited (Guidelines B 1II.2). 2. Claims Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3. Claims Nos.: Sbecause they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a). Box II 'Observations where unity of invention Is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inwv,:ions in this international application, as follows: 1. F As all required additional search fees were timely paid by the applicant, this international search report covers all searchable c'ins. 2. [E As all searcbable claims couldbesearch-dwithout effort justifying an additional fee, this Authority didnotinvitepayment of any additional fee. 3. l As only some of the required additional search fees were timely paid by the applicant, this interational search report covers only those claims for which fees were paid, specifically claims Nos.: 4. No required additional search fees were timely paid by the applicant. Consequently, this international search report is J restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest SI The additional search fees were accompanied by the applicant's protest. No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (continuation of first sheet (July 1992) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. FR 9300647 SA 75837 Th1b -M imt the patent family members relatian to the ptnt jamacens cited In the aboveusdw kmonational search repomt The mueabem we as contained in the European Patent Onkie EDiP fle an The European Patent Office is in at way liable for tha partivigars which ame merey give for the purp.m of informma.. 01/09/93 Patent doument I Publicato Ffits family~atai cited im inarch report I da IMelaer(s) a 1 DE-A-265894 1 06-07-78 CA-A- 1100974 CA-A- 1110271 CH-A- 643545 FR-A,B 2375218 GB-A- 1593560 JP-A- 53079866 JP-B- 61031102 NL-A- 7714199 US-A- 42110008 12-05-81 06-10-81 15-06-84 21-07-78 15-07-81 14-07-78 17-07-86 27-06-78 21-07-81 EP-A-0303863 22-02-89 AU-B- 607250 28-02-9 1 AU-A- 2107388 23-02-89 AU-A- 6463190 14-03-91 .JP-A- 1068350 14-03-89 US-A- 4883914 28-11-89 US-A- 4992094 12-02-91 US-A- 5120854 09-06-92 DE-B-1176660 None DE-9-1258412 None EP-A-0283245 21-09-88 AU-A- 1543488 10-10-88 EP-A,B 0349580 10-01-90 JP-T- 2502721 30-08-90 WO-A- 8807040 22-09-88 US-A- 5041458 20-08-91 SFor mome detill uabout this annx se Offcal Jouraml of the European Patect Office, No. 12182