NZ253727A - 1-aminoimidazolin-5-one derivatives and fungicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 253727 New Zealand No. 253727 International No. PCT/FR93/00647 Priority Date(s): Compete Specification Fifed: Class: ©.

* - I Publication Dfto: P.O. Journal No: ... i.^.9.5.

NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Fungicidal 2-imidazoline-5-one and 2-imidazoline-5-thione derivatives Name, address and nationality of applicant(s) as in international application form: RHONE-POULENC AGROCHIMIE, a Pierre-Baizet, F-69009, Lyon, France French body corporate of 14-20 rue 3 7 27 l Fungicidal 2-imidazolin-5-one and 2-imidazoline-5-thione 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 go some way towards providing compounds which have improved properties in the treatment of fungal diseases, and/or to go some way towards providing compounds which have a use spectrum, in the field of fungal diseases, which is also improved, or at least to provide the public with a useful choice.

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 2-iinidazoline-5-thione derivatives of general formula (la) N^Z. PATE KM or r 1 9 AUG 1996 Ny/F n, w \ N R/i da) R5 3 7 2 in which: - W is a sulphur or oxygen atom or an S=0 group - Rx 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, 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 R, or - an arylalkyl, aryloxyalkyl, aryl thioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or - Rx 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; N.Z. PATENT CrriCE 1 9 AUG 1996 RECDVf/n ^ —„——„ I 3 3 727 - 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 carbon atoms; - R4 represents: - a hydrogen atom or - an alkyl group containing 1 to 6 caxbon 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 n.z, patent office 1 9 AUG 1996 253727 4 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, 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 N.Z. PATENT cm 1 9 AUG 1996 253727 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; (alkyIthio)carbony1; (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 3 727 - 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 t - a phenyl, optionally substituted by 1 to 3 R7 groups; - 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 alkyl thioalkylsulphonyl group containing 3 to 8 carbon atoms or a cycloalkylsulphonyl group containing 3 to 7 carbon atoms; n.z, patent office 1 9 AUG 1996 Received" 3 727 7 - R7 represents: - a halogen atom or an alkyl/ haloalkyl# alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulphonyl radical 5 containing 1 to 6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or disubstituted by an alkyl or acyl radical containing 1 to S carbon atoms or an alkoxycarbonyl radical containing 2 to 6 carbon atoms - a phenyl, phenoxy or pyridyloxy radical/ these 15 radicals optionally being substituted; their salts and the optically active isomers, with the proviso that N(R5)R4 is other than an optically active residue deriving from an optically active primary amine or from an optically active amino acid. - a nitro or cyano group or - an amino radical, optionally mono- or Certain compounds belonging to the family of the 2-imidazolin-5-ones of general formulae: Y X W B and W B are known for their herbicidal properties by N.Z. patent office 1 9 AUG 1996 253727 8 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. 5 The imidazolinones of formula: and have been described for their pharmaceutical properties by Applications WO 9,114,679, JP 8,055,467 10 and DE 1,176,660 and 1,258,412 respectively.

The compounds o£ formula la are novel: n.z. pai cmt office 1 9 AUG 1996 rccxived V 253727 W N (la) R5 A) The compounds of formula lb can be prepared according to standard processes described in the literature: Ob) 1°) By cyclisation of an o-amino acid amide: r2 0 II -c -nh r a NHi cd) with a carboxylic acid orthoesteri R3-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 6. Bach in Chem. Ber., 89, pp 1363-1373 (1956) or S. Ginsburg in J. Org. Chem., 27, n.z. pat!." nt on :ci 1 9 AUG 1996 received 253727 1363-1373 (1956) or S. Ginsburg in J. Org. Chem., 27, pp 4062-4064 (1962)- The amino acid amides of the formula II can be prepared conventionally by reacting an amine of 5 formula R4NH2 with an amino acid ester of formula Ills l2 O •or fh- m 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). 2 ° ) By reaction of an amine R4NH2 with an 10 iminoester of formula IV: *1 r3 roco c—n=^ | or' R2 (TV) 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 15 formula: 253727 11 NH OR as described in Ber. dt. Chem. Ges., 47, p 2545 (1914). 3°) The compounds of formula lb in which R3 is a hydrogen atom can be obtained by cyclisation of an isonitrile derived from eutiides of formula V in the presence of base.

This process has been described by Belgian Patent Application No. 862,194 of 22 December 1977. 4°) The compounds of formula lb can be obtained by alkylation of compounds lb', in which R2 is hydrogen, by a compound R2X in basic medium according to the method described in the abovementioned Belgian Patent Application: 0 (V) Ob) 253727 12 50) By reaction of an amine R4NH2 with an azalactone VI of formula: (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 la 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: 253727 13 T1 ?5 r->—c —nh—c—c nh—n r4 O Rj O I II (ve) 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 5 solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters or alcohols.

It is carried out at a temperature between 50 and 150°C. The reaction is generally carried out at the reflux temperature of the solvent, the water being 10 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 15 with certain methyl, ethyl, propyl or butyl amino acid esters of formula: t1 r-i—c nh—c — c or J! J 11 0 i2 o 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 253727 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, (10), 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 rt—c nh—c — c- O J 11 fL o oh N V n- co R^—C /=n -nh- II O -c — C~—N \ I II ^ Ro 0 > VIL r4nr5nh2 253727 b) ?1 R-i—C nh —c — c oh II O J 11 fL o f C1C02R + TEA R-a—C NH— c— G O C OR ** VlT II I || || JUU O R2 O O R4NR2NH2 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 5 compounds of formula la consists in reacting a hydrazine R4NR5NH2 with an azalactonfi VI under certain condi.tions: 1°) By heating the reactants in an inert solvent in the presence of an acid in order to catalyse 10 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 15 temperature from 50 to 150°C.

This process is illustrated in Example 4. 2°) By heating the mixture of the reactants in acetic acid at reflux in the presence of sodium acetate in order to catalyse the reaction. 16 These conditions are illustrated in Example 5.

D) The compounds of formula (la), in which R5 is other than a hydrogen atom, are also possible starting from compounds la' which can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulphamoylated by R5X in the presence of base and solvent: R5 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°C. Ethers, cyclic ethers, dimethylformamide, dimethyl sulphoxide or aromatic solvents, for example, can be used as solvent.

(Ia) *5 The carbamoylation or the thiocarbamoylation 17 of the compounds (la') can be carried out by reaction with isocyanates or isothiocyanates according to the scheme: + r5 n—c= y nhr5 The reaction is carried out under the same 5 conditions as those described above, it being possible, however, for the base to be used in a catalytic amount.

E) The compounds of formula la in which the group R3 is a hydrogen atom can be obtained by reaction of dimethylformamide dimethyl acetal (DMFDMA) with an 10 aminohydrazide of formula VIII according to the scheme: ?1 NH—4 R2 H2NH—< V+ -«X3) 2*01(0013)2 ^ X 4 1^° 5 "i^V4 0 Re VIII Ia 5 The reaction is carried out at a temperature between 10 and 100°C in DMFDMA used in excess.

The intermediate aminohydrazides of formula VIII can be obtained according to a new process by 15 reacting the hydrochloride of the acid chloride of the corresponding a-amino acid in the presence of a base according to the scheme: 3 727 18 reacting the hydrochloride of the acid chloride of the corresponding a-amino acid in the presence of a base according to the scheme: - + 1 CI ci h3n ^ + h2n-n^ 4 h2n- < nh—n ✓ r4 rc viii The reaction is carried out at a temperature between -20°C and 40°C in cyclic or noncyclic ethers. Nitrogenous organic bases such a3 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 cc-amino acid according to the scheme below: R\ u n ■ ■ -tS 4* I /0H H2N—T—^ + PCir I O el h3it 1 ci -X o The compounds which are preferred for their better fungicidal activity and/or for their ease of 15 synthesis are: 1) the compounds of formula la, 2) the compounds of formula la, in which Rs is a hydrogen atom, N.Z. PATENT OFFICE 1 9 AUG 1998 RECEIVED 3) the compounds in which Ra and R2 are other 3 727 19 than H, 4) the compounds in which R2 represents an alkyl group containing 1 to 3 carbon atoms, preferably methyl, 5) the compounds in which Rj 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 lay R7, 8) the compounds of formula la 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 20 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, 25 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 N.Z. patent office 1 9 AUG 1996 received 2537 *7 diimidazole 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 5 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, 10 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 15 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: T1 ro—c — nh— c— c nh nh r4 11 ch ii O 3 o 21" No.

R1 R3 R4 Yd M.p. 101 Ph Me Ph 53 % 150°C 102 Ph Et Ph 61 % 144°C 103 Ph CF3 Ph 50 % 161°C 104 Ph CC13 Ph 49 % 187°C 105 Ph nPr Ph 55 % 102*C 106 Ph iPr Ph 45 % 130°C 107 Ph tBu Ph 77 % 134°C 108 4-Cl-Ph Me Ph 71 % 180°C 109 4-Cl-Ph Me 2-Me-Ph 64 % 152°C 112 Ph C1CH2 Ph 55 % 146°C Example 2: Preparation of a hydrazide (VII) according to Process B 4b): phenylhydrazide of N-trifluoroacetyl-2-(4-methylphenyl)glycine: 15 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°C and then 0.475 ml 1(0 (5 mmol) of ethyl chloroformate is run in dropwise. A white precipitate is then formed and stirring is continued at -10°C for 30 minutes. 0.5 g (4.5 mmol) of phenylhydrazine and 25 ml of anhydrous toluene are introduced into a vacuum flask 25 and the mixture is cooled to -15°C.

The contents 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 22 25372? 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 5 162°C of formula: preparation of the compounds of formula la according to Process B, by cyclisation of compounds of formula VII: preparation of 2,4-dimethyl-4-phenyl-l-phenylamino-10 2-imidazolin-5-one (compound No. 1). 2-acetylamino-2-phenyl-2'-phenylpropionohydrazide and of 0.17 g (0.001 mol) of paratoluenesulphonic acid in 25 ml of toluene is held at reflux for 7 hours, the 15 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 %/50 %) mixture. A thick oil is isolated which 20 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 Example 3: This example illustrates the A stirred solution of 1.5 g (0.005 mol) of 2537 23 No. 1) is recovered with a yield of 36 % in the form of a white powder melting at 135°C.

Compounds 1 to 9 and 12 of formula, Ri yy>5 O N CH K recorded in the following table, are prepared according to the same procedure with the appropriate reactants. 253727 24 No.

R1 R3 R4 Yd % M.p. 1 Ph Me Ph 36 135°C 2 Ph Et Ph 86 hoaey 3 Ph CF3 Ph 66 104°C 4 Ph CC13 Ph 14 68°C Ph nPr Ph 84 honey 6 Ph iPr Ph 69 122°C 7 Ph tBu Ph 11 87°C 8 4-Cl-Ph • Me Ph 54 140°C 9 4-Cl-Ph Me 2-Me-Ph 65 142°C 12 Ph C1CH2 Ph 79 76°C 14 Ph Et Ph 53 78°C Ph Et 2-Me-Ph 68 107°C 16 Ph Me 2-Mc-Ph 53 180°C 18 Ph MeOCH2 Ph 8 95°C 19 Ph MeOCH2 3-Cl-Ph 125°C 26 4-Me-Ph Me Ph 41 142°C 29 Ph MeOCH2 2-Me-Ph 54 122°C 33 4-Me-Ph CF3 Ph 166°C 45 Ph MeOCH2 2.3-diMe-Ph 55 91 °C Example 4: Preparation of a compound of formula la according to Process C 1°), 2,4-dimethyl-4-phenyl-l-phenylamino-2-imidazolin-5-one (compound No. 1).

A solution containing 0.9 g (4 mmol) of 2,4-dimethyl-4-phenyl-2-oxazolin-5-one, 0.43 g (4 mmol) of phenylhydrazine and 0.1 g of paratoluenesulphonic acid in 30 ml of toluene is heated at reflux for one hour. The water formed is removed by azeotropic 10 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-phenylamino)-2-imidazolin-5-one (Compound 10) is obtained with a yield of .18 % (M.p.: 164°C).

Example 5; Preparation of a compound of formula la according to Process C 2°): 2,4-dimethyl 10 4- (4-chlorophenyl) -1- (2-cb.lorophenylamino) -2-imidazolin-5-one (compound No. 11). 2,4-dimethy1-4-(4-chloropheny1)-2-oxazolin-5-one, 0.93 g (6.7 mmol) of 2-chlorophenylhydrazine and 0.25 g 15 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 20 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.

A solution containing 1.5 g (6.7 mmol) of 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: 253727 are obtained according to the same procedure, which compounds are collated in the following table: No.

Rl R3 R4 Yd % M.p. 13 4-Br-Ph Me Ph 34 147*0 17 4-Cl-Ph Ph 3-Cl-Ph 31 120°C Ph Me 3-Cl-Ph 43 163°C 21 4-Cl-Ph Et Ph 27 144°C 22 4-Br~Ph Me 2-Me-Ph 38 144°C 23 4-Br-Ph Me 2-Cl-Ph 41 145°C 24 4-Br-Ph Et Ph 110°C 4-Cl-Ph Me iPr 53 honey 4-F-Ph Me Ph - 150*0 31 PhCH2 Me Ph - 192°C 32 PhCH2 Et Ph - 167°C 34 Ph Me 4-iPr-Ph % 162°C Ph Me 2,3-diMe-Ph 16 % 64°C 36 Ph Me 2,3-diCl-Ph 33 % 165°C 37 Ph Me 2,4-diMe-Ph 43 % 100°C 38 Ph Me 3,4-diMe-Ph % 135°C 39 Ph Me 4-Cl-Ph 56 % 69°C 40 Ph Me 2-Cl-Ph 50 % 196°C 41 Ph Me 4-MePh 34 % 142°C 42 Ph Me 2-MePh 45 % 129°C 43 Ph Et 3-Cl-Ph 26 % 82 °C 44 Ph Et 2,3-diCl-Ph 41 % 60°C 25372 27 No.

R1 R3 R4 Yd % M.p. 46 Ph Et 3,4-diMe-Ph 32 % a o o\ 47 Ph Et 2,3-diMe-Ph 27 % 109*C 48 Ph Et 2,4-diMe-Ph 50 % 45°C 49 Ph Et 4-Cl-Ph 48 % 73 °C 50 Ph Et 4-iPr-Ph 16 % 73°C 51 Ph Et 2-Cl-Ph 56 % U © *1" 00 52 Ph Et 3-Me-Ph 14 % 85°C 53 4-PhO-Ph Me Ph 54 % 134°C 56 4-PhO-Ph Et Ph 58 % honey 59 3-Cl-Ph Et Ph 49 % 117 °C Likewise, the spiro compounds 27 (yield 56 %, M.p.: 203°C) and 28 (yield 56 %, M.p.: 153°C) of formulae: 27 28 are obtained.

Example No. 6: Preparation according to Process E of compounds of formula la. in which R3 is a hydrogen atom, and of their intermediates of formula VIII: a) 4.58 g (0.0208 mol) of methylphenylglycine 20 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 25372 28 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 5 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 10 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, h2n- r <-4 1 nh—nv —i R5 0 R2 VIII were obtained according to the same procedure, which compounds are recorded in the following table: 25372 29 No.

Rl R2 R4 R5 Yd.% M.p. 155 Ph Me Ph H 38% 154°C 157 Ph Me 2-Me-Ph H 32% 115°C 158 Ph Me 3-Q-Ph H % 164°C 160 Ph Me 2-Q-Ph H 68% 112°C 161 Ph Me 4-Q-Ph H 48% 177°C 163 Ph Me 2-F-Ph H 43% 112°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°C 167 Ph Me 3-F-Ph H 33% 161°C Likewise, the spiro compound 162 (Rl = C6H4, R2 = (CH2)2, R3 = H, R4 = Ph; yield 7 %, M.p.s 171°C) is obtained. b) 4-(R.S)-4-(4-fluorophenvl)-4-methvl-5 l-phenvlamino-2-imidazolin-5-one (Compound 54}.

A solution of 2.73 g (0.01 mol) of 2-(R,S)-2-amino-2-(4-fluorophenyl)-2'-phenylpropionohydrazide in 16 ml of N,N-dimethylfonnamide dimethyl acetal is stirred for 48 10 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 proportions 50/50. The fractions containing the pure product No. 54 15 are concentrated together under reduced pressure. 1.5 g (0.0053 mol) of 4-(R,S)-4-(4-fluorophenyl)-4-methyl-l-phenylamino-2-imidazolin-5-one, melting at 140°C on a Kofler-type bench, are thus recovered, i.e. a yield of 53 %.

The compounds of formula la, in which R3 is a hydrogen atom, that is to say: were obtained according to this procedure, which compounds are collated in the following table: No.

Rl R2 R4 Y.d.

M.p. 54 4-F-Ph Me Ph 53% 140°C 55 Ph Me Ph 38% 129°C 57 Ph Me 2-Me-Ph 72% 175°C 58 Ph Me 3-Cl-Ph 46% 177°C 60 Ph Me 2-Cl-Ph 79% 176°C 61 Ph Me 4-Cl-Ph 33% 153°C *62 C6H4 (CH2)2 Ph 64% 202°C 63 Ph Me 2-F-Ph 86% 151°C 64 Ph Me 4-F-Ph 40% 124°C 65 Ph Me 3-Me-Ph 50% 109°C 66 Ph Me 4-Me-Ph 41% 127°C 67 Ph Me 3-F-Ph % 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 2537 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 10 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 15 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 20 100,000 units per cm3.

The infected seedlings are then incubated for two days at approximately 18°C in an atmosphere saturated with moisture and then for 5 days at approximately 20-22°C under 90-100 % relative humidity. 25 Reading is carried out 7 days after infecting, by comparison with the control seedlings.

Under these conditions, a good (at least 75 %) or complete protection is observed, at a dose of a** on* 253727 32 1 g/1, 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 Puccinxa 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/cm3) 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. 25372 33 Under these conditions, a good (at least 75 %) or complete protection is observed, at a dose of 1 g/1, 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 T-/ith 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/cm3) of Phytophthora infestans.

After this infecting, the tomato seedlings are incubated for 7 days at approximately 20°C in an atmosphere saturated with moisture. 2537 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 those conditions, a good (at least 75 %) or complete protection is observed, at a dose of 1 g/1, with the following compounds: 1, 2, 13, 18, 21, 24, 49, 54. fungicidal properties of the derivatives according to the invention against fungal 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 15 downy mildew, tomato late blight and brown rust of wheat. according to the invention are rarely used on their own. Most often these compounds form part of 20 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 25 surface-active agents which are also acceptable in agriculture. In particular, the customary inert vehicles and the customary surfafje-active agents can be used. These compositions also form part of the These results clearly show the good For their practical use, the compounds 2537 invention.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickening agents, thixotropic 5 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. 10 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 15 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 20 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, 25 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 25372? 36 6=3 * 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 5 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 10 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 15 in water and 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 20 limits, ranging from 0.05 % to 95 % (by weight). Their surface-active agent content is advantageously between 5 % and 40 % by weight.

These compositions according to the invention are themselves in fairly diverse, solid or liquid 25 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 253727 37 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 5 granules being between 0.5 and 80 % for the latter cases), tablets or effervescent tablets.

The compounds of formula (la) 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 10 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, 20 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 25 20 % f>f active material.

In addition to the solvent, the emulsifiable concentrates can contain, when this is necessary, 2 £oN.? 20 % of suitable additives such as the stabilising offic 1 9 AUG 1996 Received V ;/ 38 corrosion inhibitors, dyes or adhesives mentioned above.

It is possible, by diluting these concentrates with water, to obtain emulsions of any 5 desired concentration which are particularly suitable for application to crops.

By way of example, the composition of sev&ral emulsifiable concentrates will now be given: EC Example 1 - active material 400 g/1 - alkaline dodecylbenzenesulphonate 24 g/1 - nonylphenol oxyethylated with 10 molecules of ethylene oxide 16 g/1 - cyclohexanone 200 g/1 15 - aromatic solvent qs 1 litre According to another emulsifiable concentrate formula, there are used: EC Example 2 - active material 250 g 20 - epoxidised vegetable oil 25 g - mixture of alkylarylsulphonate and of ether of polyglycol and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g 25 The suspension concentrates, which can also be 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, "7 "*? / i f 39 from 0.5 to 15 % of surface-active agents, from 0.1 to 10 % of thixotropic agents, from 0 to 10 % of suitable additives, such as antifoam.ing agents, corrosion inhibitors, stabilising agents, penetration agents and 5 adhesives and, as vehicle, water or an organic liquid 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 10 water.

By way of example, the composition of a suspension concentrate will now be given: SC Example 1 - active material 500 g 15 - polyethoxylated tristyrylphenyl phosphate 50 g - polyethoxylated alkylphenol 50 ' g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g 20 - 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 25 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 40 25572" 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 5 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 10 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 15 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 % 20 - ethoxylated fatty alcohol (wetting agent) 2.5 % - ethoxylated phenylethylphenol (dispersing agent) 5 % - chalk (inert vehicle) 42.5 % 53 72 r 41 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 % 15 - 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 % 42 WP Example 5: - active material 50 % - mixture of anionic and nonionic surface-active agents (wetting agent) 5 - sodium lignosulphonate (dispersing agent) - kaolin clay (inert vehicle) 42.5 % 2.5 % % The aqueous dispersions and emulsions, for example the compositions obtained by diluting a 10 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 15 "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 20 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 25 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 25372 43 surface-active adjuvants which confer water-dispersibility properties on the granule. These granules can be essentially of two distinct types depending upon whether the filler used is soluble or 5 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 10 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 15 sulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalene sulphonate.

Moreover, although this is not indispensable, 20 it is possible to add other adjuvants such as anti-foaming agents.

The granule according to the invention can be prepared by mixing the required ingredients and then granulating according to several techniques known 25 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. 2537 44 Preferably, it is obtained by extrusion, the preparation being carried out as shown in the examples below.

DG Example 1: Disperaible granules 5 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 10 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 15 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 25 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

Claims (30)

2537 45 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 1 kg/ha. 46 253727 Claims

1. Compounds containing an imidazolinone or imidazolinethione group, characterised in that they correspond to the general formula (la): in which: - W is a sulphur or oxygen atom - Rl 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, alkylsulphonyl-alkyl, 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 thienyl, furyl, pyridyl, benzothienyl, benzofuryl, an aryl radical comprising phenyl, naphthyl, IPEA/EP MODIFIED SHEET n.z. patent c 1 9 AUG 1996 RECElVL'j 25 3 72 7 47 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 - Rl 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 or haloalkyl group, each containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalky1, alkylsulphonyl-alkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group, each containing 2 to 6 carbon atoms or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group, each containing 3 to 6 carbon atoms or - an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms; - R4 represents: - a hydrogen atom or - an alkyl group containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalky1, haloalkyl, IPEA/EP MODIFIED SHEET n.z. patent office 19 AUG 1996 RECEIVED 25 3 72 7 48 cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group, each containing 2 to 6 carbon atoms or - a dialkylaminoalkyl/ alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group, each containing 3 to 6 5 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, 10 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 15 having the definitions given above or - an amino group disubstituted by 2 identical or different groups chosen from: - an alkyl radical cor Gaining 1 to 6 carbon atoms 20 - an alkoxyalkyl, alkenyl or alkynyl radical/ each containing 3 to 6 carbon atoms - a cycloalkyl radical containing 3 to 7 carbon atoms - an arylalkyl, as defined above, phenyl 25 or naphthyl radical, optionally substituted by 1 to 3 groups chosen from R7 or - a thienylmethyl or furfuryl radical IPEA/EP MODIFIED SHEET n.z. patent office 1 9 AUG 199E RECEIVED 23172 7 49 - a pyrrolidine, piperidino, morpholino or piperazino group, optionally substituted by alkyl containing 1 to 3 carbon atoms; - R5 represents: 5 - H, except when R4 is B, or - an alkyl, haloalkyl, alkylsulphonyl or • haloalkylsulphonyl radical, each containing 1 to 6 carbon atoms or - an alkoxyalkyl, alkylthioakyl, acyl, alkenyl, 10 alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulphonyl or cyanoalkylsulphonyl radical, each containing 2 to 6 carbon atoms or - an alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl or cyanoalkoxycarbonyl radical, each containing 3 to 6 15 carbon atoms or - a formyl radical or - a cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl or alkynylcarbonyl radical, each containing 3 to 6 carbon atoms or 20 - a cycloalkylcarbonyl radical, each containing 4 to 8 carbon atoms or - a phenyl; arylalkylcarbonyl, arylcarbonyl, optionally substituted by 1 to 3 groups from 25 R7; thienylcarbonyl; furylcarbonyl; pyridylcarbonyl; benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro-furfuryloxycarbonyl; thienylmethoxycarbonyl; pyridyl- IPEA/EP MODIFIED SHEET n.z. patent office 1 9 AUG 1996 RECEIVED 2 50 ' 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, each containing 1 to 6 carbon atoms or - a cycloalkyl, alkenyl or alkynyl group, each containing 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group, each 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, each containing 3 to 6 carbon atoms or - an alkoxyalkyl, alkylthioalkyl or IPEA/EP MODIFIED SHEET 253727 51 cyanoalkyl group, each 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; 10 15 - R7 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, 20 alkylthio, haloalkylthio or alkylsulphonyl radical, each containing 1 to 6 carbon atoms or - a cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio radical, each containing 3 to 6 carbon atoms or 25 - a nitro or cyano group or - an amino radical, optionally mono- or disubstituted by an alkyl or acyl radical containing 1 IPEA/EP MODIFIED SHEET n.z. patent office 1 9 AUG 1996 RECEIVED 25 3 72 7 52 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 N(R5>R4 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid. 10 15 20 IPEA/EP MODIFIED SHEET N.Z. patent orncf 1 9 AUG 1996 • • 253727

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

3. Compounds according to Claim 1 10 or 2, characterised in that Rx and R2 are other than a hydrogen atom.

4. Compounds .according to any one of Claims 1 to 3, characterised in that Ra is an alkyl group containing 1 to 3 carbon atoms. 15

5. Compounds according to Claim 4, characterised in that Ra is a methyl group.

6. Compounds according to any one of Claims 1 to 5, characterised in that Rj is a phenyl, optionally substituted by a R7 group. 20

7. Compounds according to one of Claims 1 to 6, characterised in that R3 is an alkyl group containing 1 to 3 carbon atoms, optionally substituted IPEA/EP MODIFIED SHEET "N.Z. patent ornoe 1 9 AUG 1996 RECEIVED 54 253727 by one or more halogens, methoxy or methylthio.

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

9. Compounds according to any one of Claims 1 to 8, characterised in that R4 is a phenyl, optionally substituted by a R7 group.

10. Compounds according to one of Claims 1 to 9, characterised in that W is an oxygen atom.

11. Fungicidal compositions 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, at least one compound of formula la: da) *5 in which s - W is a sulphur or oxygen atom or an S=0 group - Rx and R2, which are identical or different, represent: - H, provided that one of the 2 groups is different from H, or ...... - an alley 1 or haloalkyl radical containing 1 to 6 N.Z. patent office 1 9 AUG 1996 received 55 25 3 72 7 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 R, or - an arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulphonylalkyl radical, the terms aryl and alkyl having the definitions given above or - Ra 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 n.z. pait-.r.7 i. atoms or 56 253727 - an N,N-dialkylcarbamoylalkyl group containing 4 to 8 carbon atoms; - R4 represents: - a hydrogen atom 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, guinolyl, 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: I - an alkyl radical containing 1 to 6 carbon atoms - an alkoxyalkyl, alkenyl or alkynyl radical N.Z. PATE.r, i • 1 9 AUG 1996 RECEIVED \ 57 containing 3 to 6 carbon atoms - a cycloalkyl radical containing 3 to 7 carbon atoms - an arylalkyl, 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 R« 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, haloalkoxycarbony1, 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 25 3 72 7 N.Z. patent 0! 1 9 AUG 1996 RECEIVED \ 25 3 72 7; - a phenyl; arylalkylcarbonyl, arylcarbonyl, optionally substituted by 1 to 3 groups from R7; thienylcarbonyl? furylcarbonyl; pyridylcarbonyl; t benzyloxycarbonyl; furfuryloxycarbonyl; tetrahydro-furfuryloxycarbonyl; thienylmethoxycarbony1; pyridyl-methoxycarbonyl; phenoxycarbonyl or (phenylthio)carbonyl, the phenyl being itself optionally substituted by 1 to 3 groups 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 grtpups; - a sulphamoyl group, optionally mono- or disubstituted by - an alkyl or haloalkyl group containing 1 to i — ' n-z- pafent office 1 1 9 AUG 1998 J — [ received 10 15 20 25 25 3 727 59 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; - R, 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, aikynyloxy, alkenylthio or alkynylthio radical containing 3 to 6 carbon atoms or - a nitro or cyano group or N.Z. patent office 1 9 AUG 1996 RECEIVED 60 - 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 5 - a phenyl, phenoxy or pyridyloxy radical, these radicals optionally being substituted; their salts and the optically active isomers, with the proviso that N(Rs)R4 is other than an optically active residue, deriving from an optically active primary amine or from an optically active amino acid.

12. Fungicidal compositions according to Claim li, characterised in that they contain from 10 0.05 % to 95 % by weight of compounds according to one of Claims 1 to 10.

13. Process for the treatment of crops affected or capable of being affected by fungal diseases, characterised in that there is preventively 15 or curatively applied an effective quantity of a compound according to one of Claims 1 to 10 or of a composition according to Claim 11 or 12.

14. Treatment process according to Claim 13, characterised in that the effective dose is between 20 0.005 and 5 kg/ha.

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

16. Process for the preparation of the 25 compounds of formula la: 25 3 72 7 n.Z. patent office 1 9 AUG 1996 RECEIVED 61 253727 wherein Rj to R5 and W are as defined in claim 1, characterised in that the compound of formula VII *1 f Ra—C —NH—C— C—NH—N R4 II I II 0 R2 0 (VID is cyclised in a hot solvent by acid catalysis. 5

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

18. Process according to Claim 16, 10 characterised in that the solvent is chosen from the group comprising aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters or alcohols.

19. Process according to Claim 16, 15 characterised in that the temperature is between 50 and 150®C.

20. Process for the preparation of the N.Z. patent c)-r'r.r 1 9 AUG 1996 25 3 72 7 (la) wherein Rj to R5 and W are as defined in claim 1, characterised in that a hydrazine of formula R4NR5NH2 is reacted while hot with an azalactone of formula VI: in an inert solvent in the presence of an acid to catalyse the reaction.

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

22. 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. Process according to Claim 20, characterised in that the temperature is between 50 and 1 n.?. patent office 150°C. j— I 1 9 AUG 1996 j RECEIVED 63 253727

24. Process according to Claim 20, characterised in that the hydrazine of formula R4KR5NH2 and the azalactone of formula VI are heated at reflux in acetic acid in the presence of sodium acetate to catalyse the reaction.

25. Process for the preparation of the compounds of formula la, 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: ,nh-N' 4 R2v "i'VX*4 0 X. R= wherein, in formulae VIII and la, Rj to R5 and W are as defined in claim 1.

26. Process according to Claim 25, characterised in that the reaction is carried out at a temperature between 10 and 100°C, preferably in excess dimethylformamide dimethyl acetal.

27. A compound as claimed in claim 1 substantially as hereirr'described with reference to any example thereof.

28. A composition as claimed in claim 11 substantially as herein described with reference to any example thereof.

29. A process for the treatment of crops as claimed in claim 13 substantially as herein described with reference to any example thereof • p.—,. , „ | n f-'atent office * — 1 9 AUG 1996 FflXSIVLQ 25 3 727 64

30. A process for the preparation of the compounds of formula la as claimed in claim 16 substantially as herein described with reference to any example thereof. n.z. patent u- hce 1 9 AUG 1996 RECEIVED