SI9300360A - 2-imydazoline-5-ones and 2-imidazoline-5-thiones derivates and their use as fungicides - Google Patents

Abstract

2-imidazoline-5-one or 2-imidazoline-5-thione derivatives have general formula (I) in which W is the sulphur or oxygen atom, or the group S=O, n is 0 or 1, A is N(R5) or O or S or C(R5)(R6) or SO2 or C=O, R1 to R4 are hydrogen or a hydrocarbon radical, optionally substituted by halogen atoms in particular. Used as fungicides in agriculture.

Description

(57) 1) Derivatives of 2-imidazolin-5-ones or 2-imidazolin5-thione; 2) They have the general formula:

W in which - W is a sulfur or oxygen atom or a group S = O, -n = 0 or 1 - A represents N (R5) or O or S or C (R5) (R6) or SO2 or C = O, - R1 to R4 represent a hydrogen atom or a hydrocarbon radical optionally substituted, in particular by halogen atoms; 3) Use as agricultural fungicides.

Sl 9300360 A

RHONE-POULENC AGROCHIMIE

Fungicidal derivatives of 2-imidazolin-5-ones and 2-imidazolin-5-thione

The present invention relates to novel imidazolinone or imidazolinethionine compounds for phytosanitary use. It also relates to processes for the preparation of these compounds and to products which are useful as intermediates in the preparation processes as appropriate. It further relates to the use of these compounds as fungicides, to fungicidal compositions based on these compounds, and to methods of controlling fungal diseases of cultures using these compounds.

It is an object of the present invention to provide compounds having improved properties in the treatment of fungal diseases.

Another object of the present invention is to propose compounds that also have an improved spectrum of use in the field of fungal diseases.

We have now found that these objectives can be achieved by the products of the invention which are derivatives of 2-imidazolin-5-ones or 2-imidazolin-5-thione of the general formula (I)

G) (A) n in which

- W is a sulfur or oxygen atom or an S = O group,

- n = 0 or 1

- A represents N (R5) or O or S or C (R5) (R6) or SO2 or C = O,

- R1 and R2, which are the same or different, represent:

- H, provided that one of the 2 groups is other than H, or

an alkyl or haloalkyl radical having 1 to 6 carbon atoms, or

- alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or

a dialkylaminoalkyl or cycloalkyl residue having 3 to 7 carbon atoms, or

- an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups selected from R7, or

- arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals having the terms aryl and alkyl having the above definitions, or

- R1 and R2 may form a ring-attached carbon, carbocyclic or heterocycle of 5 to 7 atoms, these rings may be fused to phenyl optionally substituted by 1 to 3 groups selected from R7;

- R3 represents:

a hydrogen atom or an alkyl group of 1 to 6 carbon atoms or

- alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or

- a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or

- a Ν, dial-dialkylcarbamoylalkyl group of 4 to 8 atoms;

- R4 represents:

a hydrogen atom when n is 1, or

an alkyl group of 1 to 6 carbon atoms, or

- alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or

- a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or

- a Ν, dial-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or

- an aryl residue comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted, doodenyl, in one case selected from R7, or

- arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl having the above definitions, or

- an amino group disubstituted by 2 groups, which are the same or different and are selected from residues such as:

- an alkyl residue having 1 to 6 carbon atoms

- alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms

- a cycloalkyl residue having 3 to 7 carbon atoms

- an arylalkyl radical as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R7, or

- thienylmethyl or furfuryl residue

- a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl of 1 to 3 carbon atoms;

- R5 represents:

- H, except where the residue R4 is H, or

- an alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl residue having 1 to 6 carbon atoms, or

- alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl residue having 2 to 6 carbon atoms, or

- alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl residue having 3 to 6 carbon atoms, or

- formyl residue or

- cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radicals having 3 to 6 carbon atoms, or

- a cycloalkylcarbonyl residue having 4 to 8 carbon atoms, or

- a phenyl residue; arylalkylcarbonyl, in particular phenylacetyl and phenylpropionyl radicals; arylcarbonyl, in particular a benzoyl radical, optionally substituted by 1 to 3 groups of R7; a thienylcarbonyl residue; furylcarbonyl residue; a pyridylcarbonyl residue; benzyloxycarbonyl residue; furfuryloxycarbonyl residue; tetrahydrofurfuryloxycarbonyl residue; thienylmethoxycarbonyl residue; pyridylmethoxycarbonyl residue; a phenoxycarbonyl or phenylthiocarbonyl residue, wherein the phenyl itself is optionally substituted by 1 to 3 groups of R7; an alkylthiocarbonyl residue; a haloalkylthiocarbonyl residue; alkoxyalkylthiocarbonyl residue; a cyanoalkylthiocarbonyl residue; benzylthiocarbonyl residue; furfurylthiolcarbonyl residue; tetrahydrofurfurylthiolcarbonyl residue; thienylmethylthiolcarbonyl residue; pyridylmethylthiolcarbonyl residue; or an arylsulfonyl radical or

- a carbamoyl residue, optionally mono- or disubstituted by

an alkyl or haloalkyl group having 1 to 6 carbon atoms or

a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or

an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or

- a phenyl group optionally substituted by 1 to 3 R7 groups;

- a sulfamoyl group, optionally mono- or disubstituted by

an alkyl or haloalkyl group having 1 to 6 carbon atoms or

a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or

an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or

- a phenyl group optionally substituted by 1 to 3 R7 groups;

- an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms;

- R6 represents:

- hydrogen atom ah

- cyano group or

- an alkyl group of 1 to 6 carbon atoms or a cycloalkyl group of 3 to 7 carbon atoms, or

an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or

- a benzoyl group optionally substituted by 1 to 3 R7 groups;

- R7 represents:

- a halogen atom or

- an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or

- cycloalkyl, halocycloalkyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio 5 thin with 3 to 6 carbon atoms, or

- a nitro or cyano group, or

- an amino residue, optionally mono or substituted by an alkyl or acyl radical of 1 to 6 carbon atoms or an alkoxycarbonyl residue of 2 to 6 carbon atoms

- a phenyl, phenoxy or pyridyloxy residue, these residues being optionally substituted;

- their salt forms and their optically active isomers, provided that if n is 0, R4 is different from the optically active residue derived from the optically active primary amine or optically active amino acid.

Certain compounds belonging to the family of 2-imidazolin-5-ones of the general formulas

are known for their herbicide properties from EP-PS 41623, 41624, 215738, 226947, 261705,303863,433655 and 436483 and US-PS 4925944, DE 3913757, GB 2167062, GB 2192877 and JP 3196570.

Imidazolinones of formula

R \ ff

x

aryl

and their pharmaceutical properties are described in WO 9114679, JP 8055467 and DE 1176660 respectively. 1258412.

No agricul- tural fungicidal activity was described for the compounds of formula I.

The compounds of formula la are novel

yes) ^R 5

A) Compounds of formula Ib (n = 0) can be prepared according to the usual procedures described in the literature:

1 °) by cyclization of the α 2 -amino acid amide ^R 2 O

C -NH-R ₄ nh ₂ (Π) with a carboxylic acid orthoester

R3-C (OR ') ₃ wherein R' represents a straight or branched alkyl radical of 1 to 4 carbon atoms.

This process is described e.g. in J. Brunken et G. Bach in Chem. Ber. 89, p. 1363-1373 (1956), or S. Ginsburg in J.Org.chem, 27 p. 4062-4064 (1962).

Amides of amino acids of formula II can be prepared by reacting an amine of formula R ₄ NH ₂ with an ester of an amino acid of formula III:

^R 2 O

II

--C - OR nh ₂ (none)

Therefore, we can work under the conditions described in J. Brunken and G. Bach in Chem. Ber. 89, p. 1363-1373 (1956).

2 °) By reaction of an amine R ₄ NH ₂ with an iminoester of formula IV

This process is described in J.Chem.Soc., 1959, p. 1648, G.Shaw et al.

Iminoesters IV can be obtained by reacting an amino acid ester III with an imidate of the formula

NH

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

3 °) Compounds of formula Ib in which R 3 is a hydrogen atom can be obtained by cyclization of an isonitrile amide derivative of formula V in the presence of a base.

This process is described in Belgian patent application no. 862 194, Dec 22 1977.

(4 °) Compounds of formula Ib can be obtained by alkylating compounds Ib 'in which R2 is hydrogen, with compound R ₂ X in a basic medium according to the procedure described in the aforementioned Belgian patent application:

5 °) by reaction of amine R ₄ NH ₂ with azalactone VI of the formula

This reaction can be carried out by acid catalysis (eg acetic acid) or basic catalysis. An example of the latter can be found in the article by Ito et al., Yakugaku Zasshi, 1975.95 (1), 28-32.

B) Compounds of formula Ia can be prepared analogously to one of the above processes by allowing the reaction of hydrazine derivatives of formula R ₄ NR ₅ NH _{2 to be} substituted instead of the amine derivatives R ₄ NH ₂ .

They can also be prepared by the process forming part of the invention by cyclization in hot hydrazide of formula VII

Ri ^ 5

I I

R3-C - NH - C-C-NH-NR ₄

The reaction is catalyzed by acids. Mineral acids, alkylsulfonic acids, arylsulfonic acids, acidic resins, carboxylic acids can be used as acids.

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

It is carried out at a temperature between 50 and 150 ° C. Generally, we work on the reflux of a solvent while distilling water as it is produced.

Hydrazides of formula VII can be prepared by one of the processes described in the literature, for example:

1) By reaction of certain hydrazines R ₄ NR ₅ NH ₂ on certain methyl, ethyl, propyl or butyl esters of amino acids of the formula

Ri

R ₃ - C - NH - C - C

OR r ₂ o as described in German patent application 1089390, 22 September. 1960 (Chem.Ab., 1962, 56, pp. 4860-4862).

2) Condensation of the N-acylated amino acid with hydrazine in the presence of papain extracts in a purified aqueous solution according to the article by Niemann et Nichols in J. Biol.Chem., 143,1942, p. 191-201.

3) By reaction of hydrazine R ₄ NR ₅ NH ₂ on azalactone of formula VI according to the reference of JPBranquet et al. in Bula. Soc. Chim. de France, 1965, (10), p. 2942-2954.

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

4) A general preferred approach, analogous to item 2 above, consists of the activation of an acid in the form of imidazolid (reaction a) or mixed anhydride (reaction b) to condense it with hydrazine:

a)

Ro — C

II o

T ¹

-NH-C - C-OH r ₂ o

N · ^J 2

CO., LTD

-> vil r ₄ nr ₅ nh ₂

b)

T ¹

R? -C-NH-C-C-OH

II II ⁰ Ro o

-a>

t C1CO ₂ R + TEA

-ΤΪII r II ||

O O θ R4NR5NH2

Condensation is carried out under conditions customary to this type of reaction, as shown in Examples 1 and 2.

C) Another preferred method of preparing compounds of formula Ia is by allowing hydrazine R ₄ NR ₅ NH ₂ to be reacted with azalactone VI under certain conditions:

1 °) When the reactants are heated in an inert solvent, the presence of acid to catalyze the reaction. Halogenated hydrocarbons, esters, aromatic solvents, alcohols can be used as solvent. Mineral acids, alkylsulfonic acids, arylsulfonic acids, acidic resins, carboxylic acids can be used to catalyze the reaction. The reaction is carried out at a temperature of from 50 to 150 ° C.

This procedure illustrates Example 4.

2 °) Upon heating the mixture of reactants in acetic acid at reflux in the presence of sodium acetate to catalyze the reaction.

These conditions are illustrated by Example 5.

D) Compounds of formula (Ia) in which R 5 is other than a hydrogen atom are also possible starting from compounds 1a 'which can be alkylated, acylated, alkoxycarbonylated, carbamoylated or sulfamoylated with R5X in the presence of a base and solvent:

da ') ^H (1a) ^R 5

R5 represents an alkyl, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl or sulfamoyl group as defined above.

X represents a halogen, sulfate or phenoxy group, optionally substituted, or an alkylsulfonyloxy or arylsulfonyloxy group or R ₅ O when R ₅ is acyl.

Alkali hydrides, alcoholates or tertiary amines can be used as the base. The reaction can be carried out at a temperature between -30 ° C and + 50 ° C. As a solvent, e.g. ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide, aromatic solvents.

Carbamoylation or thiocarbamoylation of compounds (la ') can be carried out by reaction with isocyanates or isothiocyanates according to the scheme

The reaction is carried out under the same conditions as those described above, but the base can be used in a catalytic amount.

E) Compounds of formula Ia in which the group R 3 is a hydrogen atom can be obtained by the reaction of dimethylacetal dimethylformamide (DMFDMA) with an aminohydrazide of formula VIII according to the scheme .NH-N.

with ^R 4 h ₂ nRVIII

»V

Rc

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 by a novel process by allowing the hydrochloride of the corresponding α-amino acid to react in the presence of a base according to the scheme:

+ cxh ₃ n1 C1 < ⁺ h ₂ n ~ n _x

R,

R / i

R / 4

NH — N _X

Rc ^H 2 ^N '

RVIII

The reaction is carried out at or between -20 ° C and 40 ° C in cyclic ethers. Alternatively, it can be used as a nitrogen organic base, such as triethylamine or pyridine. Intermediate acid chlorides can be obtained by the procedure described in S.LEVINE in J. Am. Chem. Soc. 1953, Volume: 76, p. 1392. They are thus obtained by allowing the phosphorus pentachloride to react with the α-amino acid according to the scheme below:

h ₂ n1 OH ⁺ O

PCI +

ci, h ₃ tt ^R 1 C1

Compounds preferred for their better fungicidal activity and / or for their ease of synthesis are:

1) compounds of formula Ia,

2) compounds of formula I, in particular 1a, wherein R5 is a hydrogen atom,

3) compounds in which R1 and R2 are other than H,

4) compounds in which R2 represents an alkyl group of 1 to 3 carbon atoms, preferably a methyl group,

5) compounds in which R1 represents a phenyl core optionally substituted by R7,

6) compounds in which R3 represents a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, optionally substituted by one or more halogens, methoxy or methylthio,

7) compounds in which R4 represents a phenyl core optionally substituted by R7,

8) compounds of formula I in which W represents an oxygen atom.

The examples below are given to illustrate the compounds of the invention, the processes for their preparation and their antifungal properties.

The structures of all products was determined by at least one of the following spectral techniques such as proton NMR spectroscopy, ¹³ C -NMR spectroscopy, IR spectroscopy or mass spectrometry.

In the tables below, methyl, ethyl, propyl, butyl and phenyl residues are represented by Me, Et, Pr, Bu and Ph and PF indicates the melting point.

IS

EXAMPLE 1

This example illustrates the preparation of hydrazide (VII) according to method B 4a): preparation of 2-propionylamino-2-phenyl-2′-phenyl propionohydrazide (compound 102).

To a solution of 5.6 g (0.0253 mol) of N-propionyl-2-methyl-2-phenyl glycine in 150 ml of anhydrous dichloromethane stirred under an inert atmosphere, 4.51 g (0.0278 mol) of N, N'carbonyldiimidazole were added and allowed to react to the end of gas development. Then 3.28g (0.0304 moles) of phenylhydrazine are added and allowed to react for 12 hours. The reaction medium was then concentrated under reduced pressure and the residue obtained was chromatographed on 400 g SiO ₂ eluting with ethyl acetate-heptane (65% -35%). The essential fractions were then concentrated under reduced pressure. Thus, 4.80 g (0.0154 mol) of 2-propionylamine-2-phenyl-2'-phenyl propionic hydrazide are recovered from the m.p. 144 ° C in 61% yield.

Working in the same way, compounds 101 to 109 and 112 are summarized in the following table, which are intermediates of compounds 1 to 9 and 12:

RO-C-NH C-C-NH-NH-R ₄

Oh

N ” R1 R3 R4 Profit PF 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 hydrazide (VII) according to method B 4b): N-trifluoroacetyl-2- (4-methyl phenyl) glycinphenyl hydrazide

38 g (5 mmol) of N-trifluoroacetyl-2- (4-methyl phenyl) glycine, 25 ml of anhydrous toluene are then introduced into the 100 ml flask, then 0.75 ml (5.5 mmol) of anhydrous triethylamine. The reaction mixture was cooled to -15 ° C, then 0.475ml (5 mmol) of ethyl chloroformate was poured dropwise. Then a white precipitate formed and continued stirring at -10 ° C for 30 minutes.

Introduce 0.5 g (4.5 mmol) of phenylhydrazine and 25 ml of anhydrous toluene into the empty vial and cool the mixture to -15 ° C.

The contents of the first pumpkin were quickly filtered on a glass fryer into a flask containing phenylhydrazine. Allow the reaction mixture to come back to room temperature, wash with dilute soda, water, then dry to MgSO ₄ before filtration and evaporation. This gives 1, 4g (78% yield) of white solids from the ground. 162 ° C with the formula:

EXAMPLE 3

This example illustrates the preparation of compounds of formula Ia according to process B by cyclization of compounds of formula VII: preparation of 2,4-dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound No. 1).

A mixed solution of 1.5 g (0.005 mol) of 2-acetylamino-2-phenyl-2'-phenyl propionic hydrazide and 0.17 g (0.001 mol) of paratoluenesulfonic acid in 25 ml of toluene was refluxed for 7 hours while removing the resulting water. The reaction medium was then concentrated under reduced pressure and the resulting residue chromatographed on 200g SiO ₂ eluting with ethyl acetate-heptane (50% -50%). A dense oil is isolated which crystallizes by trituration in diisopropyloxide. After filtration, we recover

0.5g (0.0018 mol) of 2,4-dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound No. 1) as a white powder from the ground. 135 ° C in 36% yield.

Compounds 1 to 9 and 12 of the formula

The H listed in the following table are prepared in the same manner with the appropriate reactants.

N ° R1 R3 R4 Profit. % PF 1 Ph Me Ph 36 135 ° C 2 Ph Et Ph 86 miel 3 Ph CF3 Ph 66 104 ° C 4 Ph CC13 Ph 14 68 ° C 5 Ph nPr Ph 84 miel 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 15 Ph Et 2-Me-Ph 68 107 ° C 16 Ph Me 2-Me-Ph 53 180 ° C 18 Ph MeOCH2 Ph 8 95 ° C 19 Ph MeOCH2 3-Cl-Ph 20 125 ° 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 35 166 ° C 45 Ph MeOCH2 2,3-diMe-Ph 55 91 ° C

EXAMPLE 4

Preparation of a compound of formula Ia by the ClO process), 2,4-dimethyl-4-phenyl-1-phenylamino-2-imidazolin-5-one (compound no. 1)

An hourly solution containing 0.9g (4 mmol) of 2,4-dimethyl-4-phenyl-2-oxazolin-5-one, 0.43g (4 mmol) of phenylhydrazine and 0, 1g of paratoluenesulfonic acid in 30ml of toluene is heated at reflux. Remove the azeotropic distillation water and concentrate the medium under reduced pressure. The crude product is then purified by chromatography on silica gel.

Compound 1 is thus obtained in 25% yield.

In the same manner, 2,4-dimethyl-4- (4-chlorophenyl) -1- (2,3-dimethylphenylamino) -2-imidazolin-5-one (compound 10) is obtained in a yield of 18% (mp 164 ° C).

EXAMPLE 5

Preparation of the compound of formula Ia by the C2 ° process): 2,4-dimethyl-4- (4-chlorophenyl) -1- (2-chlorophenylamino) -2-imidazolin-5-one (compounds No. 11)

A reflux solution was heated for 2 hours containing a solution of 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 0.25g sodium acetate in 20ml acetic acid. The medium was concentrated under reduced pressure and the residue was dissolved in 150 ml of methylene chloride. The chloromethylene solution was washed with water containing bicarbonate and then with pure water. Concentrate the solution and purify the product by chromatography on silica gel eluting with ethyl acetateheptane (30% -70%).

Thus, compound No. 11 with a gain of 43%.

In the same way, compound 13 was obtained in a yield of 33.5%.

The compounds of the formula are obtained in the same manner

which are summarized in the following table

N ° R1 R3 R4 Yield% PF 13 4-Br-Ph Me Ph 34 147 ° C 17 4-Cl-Ph Ph 3-Cl-Ph 31 120 ° C 20 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 20 110 ° C 25 4-Cl-Ph Me iPr 53 miel 30 4-F-Ph Me Ph 150 ° C 31 PhCH2 Me Ph • 192 ° C 32 PhCH2 Et Ph 167 ° C 34 Ph Me 4-iPr-Ph 20% 162 ° C 35 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 30% 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 46 Ph Et 3,4-diMe-Ph 32% 94 ° C 47 Ph Et 2,3-diMe-Ph 27% 109 ° C 48 Ph Et 2,4-diMe-Ph 50% 41 ° 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% 84 ° C 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% miel 59 3-Cl-Ph Et Ph 49% 117 ° C

Spiro compounds 27 (yield 56%, mp 203 ° C) and 28 (yield 56%, mp 153 ° C) are also obtained by the formulas

EXAMPLE 6

Preparation according to method E of compounds of formula Ia, wherein R3 is a hydrogen atom, as well as their intermediates of formula VIII

a) To a solution of 2.25g (0.0208 moles) of phenylhydrazine in 50ml of diethyl ether, 4.58g (0.0208 moles) of methylphenylglycine acid chloride hydrochloride were added at once and the suspension thus formed was stirred for 18 hours. The suspension is filtered and the solid is dried and then dissolved again in distilled water. The resulting solution was slowly basified to pH 7 to 8 using saturated sodium bicarbonate solution. The precipitate thus formed is filtered and washed with distilled water and then recrystallized in isopropanol. After filtering the crystals and drying under reduced pressure at 50 ° C, recover 2g (0.0078 mol) of 2- (R, S) 2-amino 2-phenyl 2′-phenyl propionohydrazide (compound 155) from the melt. 154 ° C, i.e. with a yield of 38%.

In the same manner, phenylpropionohydrazides of the formula h ₂ nz with ^R 4 1 NH-N _with ^ZR 5 are obtained

VIII listed in the following table:

N ° Rl R2 R4 R5 Profit-% PF 155 Ph Me Ph H 38% 154 ° C 157 Ph Me 2-Me-Ph H 32% 115 ° C 158 Ph Me 3-Cl-Ph H 20% 164 ° C 160 Ph Me 2-Cl-Ph H 68% 112 ° C 161 Ph Me 4-Cl-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 Mb 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

Spiro compound 162 is also obtained (R1 = C6H4, R2 = (CH2) 2, R3 = H, R4 = Ph; 7% yield, mp 171 ° C) b: 4- (R, S) 4- (4- fluorophenyl) 4-methyl-1-phenylamino 2-imidazolin 5-one (compound 54) was stirred for 2 hours with a solution of 2.73g (0.01 mol) 2- (R, S) 2-amino-2- (4-fluorophenyl) 2 'phenylpropionohydrazide in 16ml Ν, Ν-dimethylformamide-dimethylacetal. The reaction medium is concentrated under reduced pressure. Chromatograph the resulting residue on silica eluting with a 50/50 n-heptane / ethyl acetate mixture. Concentrate the collected fractions containing pure product no. 54, under reduced pressure. Thus, 1.5 g (0.0053 mol) of 4- (R, S) 4- (4-fluorophenyl) -4-methyl-phenylamino-2-imidazolin-5-one are recovered. 140 ° C at Koflei's table, i.e. with a gain of 53%.

In this way, compounds of formula Ia are obtained, Iger is R 3 a hydrogen atom, i.e.

collected in the following table

N ° Rl R2 R4 profit PF 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-a-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 20% 137 ° C

* spiro compound

EXAMPLE 7

In vivo test on Plasmopara viticola (vines)

By fine grinding, prepare an aqueous suspension of the active substance for testing with the following composition:

- Active substance: 60 mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% with water: 0,3ml

- Make up to 60ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active substance.

Vine (Vitis vinifera) seedlings, Chardonnay version, are cultivated in pots. When these plants are 2 months old (stage 8 to 10 leaves, height 10 to 15 cm), they are sprayed with the upper aqueous suspension.

The plants used as controls were treated with an aqueous solution containing no active substance.

After drying for 24 hours, infect each plant by spraying an aqueous suspension of Plasmopara viticol spores obtained from the culture for 4 to 5 days, then embedded in the suspension at a concentration of 100,000 units per cm ³ .

The infected plants are then incubated for 2 days at about 18 ° C in a saturated humidity atmosphere, then for 5 days at about 20 to 22 ° C at a relative humidity of 90 to 100%.

We evaluate 7 days after infection compared to control plants.

Under these conditions, a good protection (at least 75%) or complete protection with the following compounds is found at a dose of lg / 1: 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 (wheat rust)

By fine grinding, prepare an aqueous suspension of the active substance for testing with the following composition:

- active substance: 60mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% with water: 0,3ml

- Make up to 60ml with water

This aqueous suspension is then diluted with water to obtain the desired concentration of the active substance.

The wheat in the pots, sown on a 50/50 peatland soil substrate, is treated at a lOcm height by spraying the upper aqueous suspension.

After 24 hours, an aqueous spore suspension (100,000 spores / cm ³ ) was sprayed onto the wheat; this suspension was obtained from infected plants. The wheat is then incubated for 24 hours in an incubation cell at about 20 ° C and 100% relative humidity, then for 7 to 14 days at 60% relative humidity.

Plant condition control was performed between 8 and 15 days after infection by comparison with the untreated control.

Under these conditions, a good protection (at least 75%) or complete protection with the following compounds is found at a dose of lg / 1: 1, 2, 3, 8,12,17, 21, 22,24, 28, 30, 35, 53, 54 , 56, 59.

EXAMPLE 9

Phytophthora infestans in vivo test (tomato mold)

By fine grinding, prepare an aqueous suspension of the active substance for testing with the following composition:

- active substance: 60mg

- Tween 80 surfactant (oleate polyoxyethylated sorbitan derivative) diluted to 10% with water: 0,3ml

- Make up to 60ml with water.

This aqueous suspension is then diluted with water to obtain the desired concentration of the active substance.

Tomato plants (version of Marmanda) are grown in pots. When these plants are 1 month old (stage 5 to 6 leaves, height 12 to 15 cm), they are treated by spraying the upper aqueous suspension and at different concentrations of the test compound.

After 24 hours, infect each plant by spraying it with an aqueous suspension of the spores (30,000 spores / cm ³ ) of Phytphthora infestans.

Following this infection, the tomato plants are incubated for 7 days at about 20 ° C under saturated humidity.

Seven days after infection, the results obtained in the case of plants treated with the active substance for testing are compared with those obtained in the case of plants used as controls. Under these conditions, a good protection (at least 75%) or complete protection with the following compounds is found at a dose of lg / l: 1, 2,13,18, 21,24,49, 54.

These results clearly demonstrate the good fungicidal properties of the derivatives of the invention against fungal diseases of plants due to fungi belonging to a variety of families, such as Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or fungi imperfecti, in particular grapevine, tomato and wheat mold.

For their practical use, the compounds of the invention are rarely used alone. Most often, these compounds are part of the compositions. These compositions, useful as fungicidal agents, comprise, as active substance, one (or more) compound of the invention as previously described, in admixture with solid or liquid carriers acceptable in agriculture, and surfactants also acceptable in agriculture. Particularly useful are inert carriers and conventional surfactants. These compositions are also part of the invention.

These compositions may also contain any type of other ingredients, such as e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc. More generally, the compounds used in the invention can be combined with any solid or liquid additives that conform to conventional formulation techniques.

Generally, the compositions of the invention typically contain about 0.05 to 95% by weight of one (or more) compounds of the invention (hereinafter referred to as the active substance), one or more solid or liquid carriers, and optionally one or more surfactants funds.

The term carrier in the present report designates an organic or mineral substance, natural or synthetic, to combine a compound to facilitate its application to a plant, seed or soil. This carrier, however, is generally inert and must be acceptable in agriculture, especially on the treated plant. The carrier may be solid (clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water; alcohols, in particular butanol, etc.).

The surfactant may be an emulsifying, dispersing agent or wetting agent of the ionic or non-ionic type, or a mixture of such surfactants. We can cite e.g. salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty amines, substituted phenols (especially alkylphenols or aryphenols), salts of esters of sulfoacetic acids, derivatives of alkali thiourethanes, or derivatives of alkali phosphoric acids phenols, fatty acid esters and polyols, derivatives having the sulfate, sulfonate and phosphate function of the precursors. The presence of at least one surfactant is generally indispensable because the compound and / or inert carrier is insoluble in water and because the solvent for application is water.

Thus, compositions for agricultural use according to the invention may contain the active substances of the invention within very wide limits, from 0.05% to 25% (w / w). Their surfactant content is preferably between 5 and 40% by weight.

These compositions of the invention are themselves in very different forms, solid or liquid.

Dust powders (containing up to 100% compound) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granular carrier, by granulation from powders (the content of the compound in these granules is between 0.085% for these latter cases), compress or effervescent tablets.

The compounds of formula (I) may also be used in powder form; we can also use a composition containing 50g of active ingredients and 950g of talc; a composition containing 20g of active ingredient, 10g of finely divided quartz and 970g of talc may also be used; mix and grind these ingredients and apply the mixture by dusting.

Forms of liquid compositions or intended to form liquid compositions upon application may include solutions, in particular water soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wetting powders (or spray powders), pastes, gels.

Emulsifiable or soluble concentrates usually contain 10 to 80% of the active ingredient, and emulsions or solutions ready for administration contain 0.001 to 20% of the active substance.

In addition to the solvent, the emulsifiable concentrates may contain, where necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, colorants or adhesives, as previously mentioned.

From these concentrates can be obtained by diluting with water emulsions of any desired concentration, which are particularly suitable for application to cultures.

For example, the composition of some emulsifiable concentrates is as follows:

EXAMPLE CE1:

- active substance

- Alkaline dodecylbenzenesulfonate

- nonylphenol, oxetylated with 10 ethylene oxide molecules

- cyclohexanone

- aromatic solvent

400g / l

24g / l

16g / l

200g / l q.s.do 11

Following the second recipe for emulsifiable concentrate, use:

CE 2 EXAMPLE:

- active substance 250g

- epoxidized vegetable oil mixture of alkylarylsulfonate and polyglycol ether and fatty alcohols lOOg

- dimethylformamide 50g

- xylene 575g

Concentrated suspensions, also useful for spraying, are prepared to give a liquid, stable, non-settling product and typically contain from 10 to 75% of the active ingredient, from 0.5 to 15% of surfactants, from 0, 1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as antifoam, squeeze inhibitors, stabilizers, penetrating agents and adhesives, and as a carrier water or organic liquid in which the active substance is slightly soluble or insoluble:

some solids or minerals may be dissolved in the carrier to help prevent sedimentation, or as water antibodies.

As an example, the composition of a concentrated suspension is as follows:

EXAMPLE SCI:

- active substance 500g

- polyethoxylated tristylylphenolphosphate 50g

- polyethoxylated alkylphenol 50g

- sodium polycarboxylate 20g

- ethylene glycol 50g

- organopolysiloxane oil (antifoam) lg

- polysaccharide 1, 5g

-water 316,5g

Wetting powders (or spray powder) are usually prepared to contain 20 to 95% of the active substance and typically contain, in addition to a solid carrier, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent and, if necessary, from 0.1 to 10 % of one or more stabilizers and / or other additives such as penetrating agents, adhesives or anti - caking agents, colorants, etc.

To obtain spray powders or wettable powders, thoroughly mix the active ingredients in suitable mixers with additional substances and grind with mills or other suitable milling devices. Spray powders are thus obtained whose wettability and suspending ability are preferred; they can be suspended with water at any desired concentration and these suspensions are particularly useful for application to plant leaves.

We can make pastes instead of wettable powders. The conditions and methods of making and using these traps are similar to those for wettable powders or spray powders.

For example, the various compositions of wettable powders (or spray powders) are as follows:

EXAMPLE PM1

- active substance 50% - ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersant) 5% - chalk (inert carrier) 42,5%

EXAMPLE PM 2

- active substance 10%

- branched-type synthetic oxoalcohol, ethoxylated at 8 to 10 ethylene oxides (wetting agent) at 0.75%

- calcium calcium lignosulfonate (dispersant) 12%

- calcium carbonate (inert filler) q.s. up to 100%

EXAMPLE PM 3:

This wettable powder contains the same ingredients as in the previous example with the ratios below:

- active substance

- wetting agent

- dispersing agent

- calcium carbonate (inert filler)

75%

1.50%

8%

q.s.to 100%

EXAMPLE PM 4:

- active substance 90%

- ethoxylated fatty alcohol (wetting agent) 4%

- ethoxylated phenylethylphenol (dispersing agent) 6%

EXAMPLE PM 5:

- active substance 50%

- mixture of anionic and nonionic surfactants (wetting agent) 2.5%

- Sodium lignosulfonate (dispersing agent) 5%

- kaolin clay (inert carrier) 42.5%

Aqueous dispersions and emulsions, e.g. compositions obtained by diluting a wettable powder or emulsifiable concentrate of the invention with water are within the general scope of the present invention. Emulsions can be water-in-oil or oil-in-water and may have a thick consistency, such as mayonnaise consistency.

The compounds of the invention may be formulated in the form of water-dispersible granules and are also within the scope of the invention.

These dispersible granules having a apparent density generally of between about 0.3 and 0.6 have a particle size generally of between about 150 and 2000 and preferably between 300 and 1500μιη.

The active ingredient content of these granules is generally between about 1% and 90%, preferably between 25% and 90%.

The granule residue consists essentially of a solid support and, optionally, of surfactant adjuvants which confer granularity on the granularity of the dispersibility in water. These granules can be essentially of two different types, whether or not the filler is water soluble. If the filler is soluble in water, it may be mineral or preferably organic. Excellent results were achieved with urea. In the case of insoluble filling, the year is preferably mineral, such as e.g. kaolin or bentonite. It is advantageously accompanied by surfactants (in the amount of 2 to 20% by weight of the granule), of which more than half e.g. it consists of at least one dispersing agent, substantially anionic, such as alkali or alkaline earth polynaphthalenesulfonate or alkali or alkaline earth alkaline sulfonate, and the remainder consists of non-ionic or anionic wetting agents, such as alkali or alkaline earth alkylnaphthalen sulfonate.

Otherwise, while not absolutely necessary, other adjuvants may be added as antifoaming agents.

The granules of the invention can be prepared by mixing the necessary ingredients, then granulating according to various techniques known per se (irritation, liquid cushion, atomization, extrusion, etc.). Generally, we end with crushing followed by sieving to the particle dimension selected within the limits mentioned above.

It is preferably obtained by extrusion, doing as indicated in the following examples.

EXAMPLE WHERE:

Dispersible granules

In the mixer, 90% by weight of the active ingredient and 10% of the urea in the beads are mixed. The mixture is then ground in a thorn mill. A powder is obtained which is moistened with about 8% by weight of water. The wet powder is extruded in an extruder with a perforated cylinder. A granule is obtained which is dry, then crushed and sieved to obtain granules having a dimension between 150 and 2000μπι.

EXAMPLE GD2:

Dispersible granules

The following ingredients are mixed in the blender:

- active ingredient 75%

- wetting agent (sodium alkylnaphthalenesulfonate) 2%

- dispersant (sodium polynaphthalenesulfonate) 8%

- inert filler insoluble in water (kaolin) 15%

This mixture is granulated in a liquid cushion in the presence of water, then dried, crushed and sieved to obtain granules having a dimension between 0.15 and 80mm.

These granules can be used alone, in solution or dispersion in water, to obtain the desired dose. They can also be used to prepare combinations with other active substances, in particular fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions.

For compositions adapted for storage and transport, they preferably contain from 0.05 to 95% (w / w) of the active substance.

The subject of the invention is also the use of the compounds of the invention for the control of fungal diseases of plants by preventive or curative treatment of them or the place where they grow.

They are advantageously applied in doses from 0.005 to 5kg / ha, more specifically from 0.01 to 1kg / ha.

For

RHONE-POULENC AGROCHIMIE:

PATENT OFFICE

LOVE 9 / r

PATENT APPLICATIONS

Claims (21)

1) Compounds having an imidazolinone or imidazolynthionine group, characterized in that they conform to general formula (I) R- (D in which - W is a sulfur or oxygen atom or an S = O group, - n = 0 or 1 - A represents N (R5) or O or S or C (R5) (R6) or SO2 or C = O, - R1 and R2, which are the same or different, represent: - H, provided that one of the 2 groups is other than H, or an alkyl or haloalkyl radical having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or a dialkylaminoalkyl or cycloalkyl residue having 3 to 7 carbon atoms, or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups selected from R7, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals having the terms aryl and alkyl having the above definitions, or - R1 and R2 may form a ring-attached carbon, carbocyclic or heterocycle of 5 to 7 atoms, these rings may be fused to phenyl optionally substituted by 1 to 3 groups selected from R7; - R3 represents: a hydrogen atom or an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group of 4 to 8 atoms; - R4 represents: a hydrogen atom when n is 1, or an alkyl group of 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups selected from R7, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl having the above definitions, or - an amino group disubstituted by 2 groups, which are the same or different and are selected from residues such as: - an alkyl residue having 1 to 6 carbon atoms - alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms - a cycloalkyl residue having 3 to 7 carbon atoms - an arylalkyl radical as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R7, or - thienylmethyl or furfuryl residue - a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl of 1 to 3 carbon atoms; - R5 represents: - H, except where the residue R4 is H, or - an alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl residue having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl residue having 2 to 6 carbon atoms, or - alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl residue having 3 to 6 carbon atoms, or - formyl residue or - cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radicals having 3 to 6 carbon atoms, or - a cycloalkylcarbonyl residue having 4 to 8 carbon atoms, or - a phenyl residue; arylalkylcarbonyl, in particular phenylacetyl and phenylpropionyl radicals; arylcarbonyl, in particular a benzoyl radical, optionally substituted by 1 to 3 groups of R7; a thienylcarbonyl residue; furylcarbonyl residue; a pyridylcarbonyl residue; benzyloxycarbonyl residue; furfuryloxycarbonyl residue; tetrahydrofurfuryloxycarbonyl residue; thienylmethoxycarbonyl residue; pyridylmethoxycarbonyl residue; a phenoxycarbonyl or phenylthiocarbonyl residue, wherein the phenyl itself is optionally substituted by 1 to 3 groups of R7; an alkylthiocarbonyl residue; a haloalkylthiocarbonyl residue; alkoxyalkylthiocarbonyl residue; a cyanoalkylthiocarbonyl residue; benzylthiocarbonyl residue; furfurylthiolcarbonyl residue; tetrahydrofurfurylthiolcarbonyl residue; thienylmethylthiolcarbonyl residue; pyridylmethylthiolcarbonyl residue; or an arylsulfonyl radical or - a carbamoyl residue, optionally mono- or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - a phenyl group optionally substituted by 1 to 3 R7 groups; - a sulfamoyl group, optionally mono- or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - a phenyl group optionally substituted by 1 to 3 R7 groups; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms; - R6 represents: - a hydrogen atom or - cyano group or - an alkyl group of 1 to 6 carbon atoms or a cycloalkyl group of 3 to 7 carbon atoms, or an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or - a benzoyl group optionally substituted by 1 to 3 R7 groups; - R7 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio moiety having 3 to 6 carbon atoms, or - a nitro or cyano group, or - an amino residue, optionally mono or substituted by an alkyl or acyl radical of 1 to 6 carbon atoms or an alkoxycarbonyl residue of 2 to 6 carbon atoms - a phenyl, phenoxy or pyridyloxy residue, these residues being optionally substituted; - their salt forms and their optically active isomers, provided that if n is 0, R4 is different from the optically active residue derived from the optically active primary amine or optically active amino acid. 2) Compounds according to claim 1, characterized in that they correspond to formula Ia wherein R1 to R5 and W have the same meaning as in claim 1. 3) Compounds according to claim 1 or 2, characterized in that R5 is a hydrogen atom. 4) Compounds according to one of claims 1 to 3, characterized in that R1 and R2 are different from the hydrogen atom. 5) Compounds according to one of claims 1 to 4, characterized in that R2 is an alkyl group of 1 to 3 carbon atoms. 6) Compounds according to claim 5, characterized in that R2 is a methyl group. Compounds according to any one of claims 1 to 6, characterized in that R 1 is phenyl optionally substituted by a group R 7. Compounds according to one of claims 1 to 7, characterized in that R 3 is an alkyl group of 1 to 3 carbon atoms, optionally substituted by one or more halogens, methoxy or methylthio. Compounds according to one of claims 1 to 7, characterized in that R 3 is a hydrogen atom. Compounds according to one of claims 1 to 9, characterized in that R4 is phenyl optionally substituted by the group R7. Compounds according to one of claims 1 to 10, characterized in that W is an oxygen atom. 12) Fungicidal compositions, characterized in that they comprise, together with one or more solid or liquid, agriculturally acceptable carriers and / or also agriculturally acceptable surfactants, one or more active substances which is a compound of formula I Ε- ν which is - W is a sulfur or oxygen atom or an S = O group, - n = 0 or 1 - A represents N (R5) or O or S or C (R5) (R6) or SO2 or C = O, - R1 and R2, which are the same or different, represent: - H, provided that one of the 2 groups is other than H, or an alkyl or haloalkyl radical having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, monoalkylaminoalkyl, alkenyl or alkynyl radicals having 2 to 6 carbon atoms, or a dialkylaminoalkyl or cycloalkyl residue having 3 to 7 carbon atoms, or - an aryl radical comprising phenyl, naphthyl, thienyl, furyl, pyridyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted by 1 to 3 groups selected from R7, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals having the terms aryl and alkyl having the above definitions, or - R 1 and R 2 may form, with the ring-attached carbon, a carbocyclic or heterocycle of 5 to 7 atoms, whereby these rings may be fused with phenyl optionally substituted by 1 to 3 groups selected from R 7; - R3 represents: a hydrogen atom or an alkyl group of 1 to 6 carbon atoms or - alkoxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, oxoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group of 4 to 8 atoms; - R4 represents: a hydrogen atom when n is 1, or an alkyl group of 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, haloalkyl, cyanoalkyl, thiocyanatoalkyl, alkenyl or alkynyl group having 2 to 6 carbon atoms, or - a dialkylaminoalkyl, alkoxycarbonylalkyl or N-alkylcarbamoylalkyl group having 3 to 6 carbon atoms, or - a Ν, dial-dialkylcarbamoylalkyl group having 4 to 8 carbon atoms or - an aryl residue comprising phenyl, naphthyl, thienyl, furyl, pyridyl, imidazolyl, pyrazolyl, pyrrolyl, triazolyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuryl, quinolinyl, isoquinolinyl or methylenedioxyphenyl, optionally substituted, doodenyl, in one case selected from R7, or - arylalkyl, aryloxyalkyl, arylthioalkyl or arylsulfonylalkyl radicals, the terms aryl and alkyl having the above definitions, or - an amino group disubstituted by 2 groups, which are the same or different and are selected from residues such as: - an alkyl residue having 1 to 6 carbon atoms - alkoxyalkyl, alkenyl or alkynyl radicals having 3 to 6 carbon atoms - a cycloalkyl residue having 3 to 7 carbon atoms - an arylalkyl radical as defined above, phenyl or naphthyl optionally substituted by 1 to 3 groups selected from R7, or - thienylmethyl or furfuryl residue - a pyrrolidino, piperidino, morpholino or piperazino group optionally substituted by alkyl of 1 to 3 carbon atoms; - R5 represents: - H, except where the residue R4 is H, or - an alkyl, haloalkyl, alkylsulfonyl, haloalkylsulfonyl residue having 1 to 6 carbon atoms, or - alkoxyalkyl, alkylthioalkyl, acyl, alkenyl, alkynyl, haloacyl, alkoxycarbonyl, haloalkoxycarbonyl, alkoxyalkylsulfonyl, cyanoalkylsulfonyl residue having 2 to 6 carbon atoms, or - alkoxyalkoxycarbonyl, alkylthioalkoxycarbonyl, cyanoalkoxycarbonyl residue having 3 to 6 carbon atoms, or - formyl residue or - cycloalkyl, alkoxyacyl, alkylthioacyl, cyanoacyl, alkenylcarbonyl, alkynylcarbonyl radicals having 3 to 6 carbon atoms, or - a cycloalkylcarbonyl residue having 4 to 8 carbon atoms, or - a phenyl residue; arylalkylcarbonyl, in particular phenylacetyl and phenylpropionyl radicals; arylcarbonyl, in particular a benzoyl radical, optionally substituted by 1 to 3 groups of R7; a thienylcarbonyl residue; furylcarbonyl residue; a pyridylcarbonyl residue; benzyloxycarbonyl residue; furfuryloxycarbonyl residue; tetrahydrofurfuryloxycarbonyl residue; thienylmethoxycarbonyl residue; pyridylmethoxycarbonyl residue; a phenoxycarbonyl or phenylthiocarbonyl residue, wherein the phenyl itself is optionally substituted by 1 to 3 groups of R7; an alkylthiocarbonyl residue; a haloalkylthiocarbonyl residue; alkoxyalkylthiocarbonyl residue; a cyanoalkylthiocarbonyl residue; benzylthiocarbonyl residue; furfurylthiolcarbonyl residue; tetrahydrofurfurylthiolcarbonyl residue; thienylmethylthiolcarbonyl residue; pyridylmethylthiolcarbonyl residue; or an arylsulfonyl radical or - a carbamoyl residue, optionally mono- or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - a phenyl group optionally substituted by 1 to 3 R7 groups; - a sulfamoyl group, optionally mono- or disubstituted by an alkyl or haloalkyl group having 1 to 6 carbon atoms or a cycloalkyl, alkenyl or alkynyl group having 3 to 6 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl group having 2 to 6 carbon atoms, or - a phenyl group optionally substituted by 1 to 3 R7 groups; - an alkylthioalkylsulfonyl group of 3 to 8 carbon atoms or a cycloalkylsulfonyl group of 3 to 7 carbon atoms; - R6 represents: - a hydrogen atom or - cyano group or - an alkyl group of 1 to 6 carbon atoms or a cycloalkyl group of 3 to 7 carbon atoms, or an acyl or alkoxycarbonyl group having 2 to 6 carbon atoms, or - a benzoyl group optionally substituted by 1 to 3 R7 groups; - R7 represents: - a halogen atom or - an alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio or alkylsulfonyl radical having 1 to 6 carbon atoms, or - cycloalkyl, halocycloalkyl, alkenyloxy, alkinyloxy, alkenylthio, alkynylthio moiety having 3 to 6 carbon atoms, or - a nitro or cyano group, or - an amino residue, optionally mono or substituted by an alkyl or acyl radical of 1 to 6 carbon atoms or an alkoxycarbonyl residue of 2 to 6 carbon atoms - a phenyl, phenoxy or pyridyloxy residue, these residues being optionally substituted; - their salt forms and their optically active isomers. 13. Fungicidal compositions according to claim 12, characterized in that they contain from 0.05 to 95% by weight of the compounds according to any one of claims 1 to 11. A method for treating cultures with fungal diseases or susceptible to fungal diseases, characterized in that an effective amount of a compound according to one of claims 1 to 11 or a composition of claims 12 or 13 is applied preventively or curatively. The method of treatment according to claim 14, wherein the effective dose is between 0.005 and 5kg / ha. The method of treatment according to claim 15, wherein the effective dose is between 0.001 and 1kg / ha. 17) A process for the preparation of compounds of formula la (la) ^R 5 characterized in that in a solvent in hot acid acid catalysis cyclize a compound of formula VII R < Oh -NH-C-C-NH-Nr ₄ R ₂ O (VII) Process according to claim 17, characterized in that the acid is selected from the group consisting of mineral acids, alkylsulfonic acids, arylsulfonic acids, acidic resins, carboxylic acids. A process according to claim 17, characterized in that the solvent is selected from the group consisting of aromatic solvents, halogenated hydrocarbons, ethers, cyclic ethers, esters, alcohols. 20) The process according to claim 17, characterized in that the temperature is between 50 and 150 ° C. 21) A process for the preparation of compounds of formula Ia ^Rl V _r ^R3 -R, N (1a) ^R 5 characterized in that it is allowed to react in hot hydrazine of formula R ₄ NR ₅ NH ₂ with azalactone of formula VI