HU184777B - Fungicide compositions containing 3-/n-acyl-n-arylamino/- and 3-/n-thionoacyl-n-arylamino/-gamma-butyrolactones and -gamma-thiobutyrolactones - Google Patents

Abstract

3-(N-acyl-N-arylamino) and 3-(N-thionoacyl-N-aryl-amino)-gamma-butyrolaceones and thiobutyrolactones have fungicidal activity.

Description

FIELD OF THE INVENTION The present invention relates to fungicidal compositions containing 3- (N-acyl-N-arylamino) and 3- (Ntionoacyl-N-arylamino) -gamma-butyrolactones and gamma-thiobutyrolactones.

U.S. Patent Nos. 3,933,860, 4,012,519, 4,107,322, 4,141,989, and U.S. Pat.

3- (N-acyl-N-arylamino) lactones and 3- (N-acyl-N-arylamino) lactams are described as fungicidal compounds.

U.S. Patent Nos. 4,034,108 and 4,015,648 disclose that N- (methoxycarbonylethyl) -N-haloacetylanilines are preventive and curative fungicidal compounds.

According to German Patent Laid-Open Nos. 2,643,403 and 2,643,445, N- (alkylthiocarbonylethyl) acetanilides are used as fungicides, in particular against fungi of the Phycomycetes class.

Dutch Patent Publication No. 152,849 describes the use of N (alkoxymethyl) acetanilides as fungicides.

Belgian Patent No. 867,556 discloses 3- (N-cyclopropylcarbonyl-N-arylamino) gamma-butyrolactones.

Belgian Patent No. 863,615 discloses the fungicidal action of 3-N-acyl-N-arylamino) -gamma-butyrolactones.

We have found that 3- (N-acyl-N-arylamino) - and 3- (Ntionoacyl-N-arylamino) -gamma-butyrolactones and butyrothiolactones are effective fungicides, in particular against fungal infections caused by peronosporacea in the Peronosporaceae family. potato and fungal infections caused by Phytophthora infestans. In particular, we have found fungicidal compounds in which the N-acyl group is alkenylcarbonyl, alkenyloxycarbonyl, and cycloalkylcarbonyl. We have also found new thionoacil derivatives having fungicidal activity. According to the invention, certain compounds are also protective fungicides and curative fungicides, that is, they prevent or protect against fungal infections and at the same time eliminate and cure existing infections. The compositions of the present invention are particularly effective against grape powdery mildew.

The active compounds of the present invention are compounds of formula I wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R ¹ is C 2-6 alkenyl, C 2-6 alkenyl oxide, C 3-6 cycloalkyl, R ² is hydrogen, Y is oxygen or sulfur, or NR, ahor R is C 1 -C 4 alkyl, W is oxygen or sulfur, X is oxygen or sulfur, provided that when W is sulfur, AK ¹ R ¹ is in addition to the above groups, hydroxymethyls, provided that when Ar is substituted phenyl, W is oxygen and R ¹ is cyclopropyl, then Y cannot be oxygen.

In the context of price, substituted phenyl groups preferably include the following groups:

2.3.6-trimethylphenyl, 2,3,5,6-tetramethylphenyl. When Ar is substituted phenyl, it is preferred that the phenyl may be substituted with 1 to 2 identical or different substituents having from 1 to 4 carbon atoms. The most preferred substituted phenyl group for Ar is the 2,6-dialkylphenyl, especially the

2.6-dimethylphenyl.

Preferred groups for Ar-substituted naphthyl are:

1-methyl-2-naphthyl, 4-methyl-2-naphthyl, 4-methyl-1-naphthyl, 2,4-dimethyl-1-naphthyl or 2,7-dimethyl-1-naphthyl. When Ar is substituted naphthyl, Ar is particularly preferred

2-alkyl-1-naphthyl, especially 2-methyl-1-naphthyl.

In the meaning of R ¹ , cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and

4-methylcyclohexyl.

Preferred groups for R ¹ alkoxyalkyl are methoxymethyl, ethoxymethyl, isopropoxymethyl and n-pentoxymethyl. Preferably R ^{1 for} alkoxyalkyl is methoxymethyl.

Examples of R ¹ alkylthioalkyl include methylthiomethyl, n-propylthiomethyl and n-pentylthiomethyl.

If ^R1 is an alkenyl group, the preferred groups are:

vinyl, 2-methylvinyl, 2,2-dimethylvinyl, 1-methylvinyl, allyl, isopropenyl, butenyl, 3-methoxyprop-1-en-1-yl,

3-chloroprop-1-en-1-yl. Preferred alkenyl groups are vinyl, 2-methylvinyl and 2,2-dimethylvinyl.

Examples of R ^{1 for} alkenyloxide include oxiranyl, 1-methyloxiran-1-yl, 2,2-dimethyloxiran-1-yl and 2-methyloxiram-1-yl.

Preferably Ar is phenyl substituted with 1 to 2 same or different substituents, C 1 -C 2 alkyl, or 2-alkyl-1-naphthyl. Most preferred ar is 2,6-dimethylphenyl or 2-methyl-1-naphthyl.

R ^{1 is} preferably vinyl, 2-methylvinyl, 2,2-dimethylvinyl,

C 1-6 alkoxymethyl. ^R1 may in particular vinyl, allyl, 2-methylvinyl, 1,2-epoxipropil-, methoxymethyl group.

When R "is C 3-6 cycloalkyl, then R ¹ in case of Y = S and Y is cyclopropyl - O event cyclopentyl.

W and X preferably is oxygen when W is sulfur, R ¹ is preferably a methoxymethyl group. R ^{2 is} hydrogen.

A preferred group of N-substituted phenylaminolactones are those compounds represented by Formula II wherein R * is

C 2 -C 6 alkenyl or C 2 -C 6 alkenyloxide, R ² is hydrogen and R ⁴ and R ⁵ are each independently methyl or ethyl and Y is oxygen or sulfur. Particularly preferred are compounds of Formula II, wherein ^R1 is vinyl, 2-methylvinyl, 1,2- or 2,2-epoxipropil- dimetilvinilcsoport, R ² is hydrogen and R ⁴ and R ⁵ are methyl.

3- (N-Thionoacyl-N-arylamino) -lactones and thiolactones are represented by Formula III, wherein Ar is phenyl or naphthyl substituted by the substituents indicated above, and R ¹ , X Y and R ² are as defined above. THE

A preferred group of 3- (N-thionoacyl-N-arylamino) -actones is represented by formula IV wherein R ¹ is C 2 -C 6 alkoxyalkyl, R ² is hydrogen, and R ⁴ and R ⁵ are each independently methyl or ethyl. Preferred compounds of formula IV are those wherein R ^{1 is} methoxymethyl, R ^{2 is} hydrogen and R ⁴ and R ^{5 are} methyl.

Preferred compounds of formula I are the following:

3- (N-acryloyl-N-2,6-dimetilfeniIamino) -gamma-butyrolactone,

3- (N-3-metilkrotonil-N-2,6-dimethylphenylamino) -gamma-butyrolactone,

3- (N-crotonyl-N-2,6-dimethylphenylamino) -gamma-butyrolactone,

3- (N-acryloyl-N-2,6-dimethylphenylamino) -gamma-tiobutirolakton,

3- (N-2-metilakriloil-N-2-methyl-6-etilfenilamino) -gamma-butyrolactone,

3- (N-3-methyl-2,3-epoxy-butanoyl-N-2,6-dimethylphenylamino) -gamma-butyrolactone,

3- (N-2-methyl-2-3-epoxy-N-propanoyl-2,6-dimethyl-phenylamino) -gamma-butyrolactone,

3- (Nmetoxitionoacetil-N-2,6-dimethylphenylamino) -gamma-butyrolactone,

3- (N-metoxitionoacetil-N-2,6-dimethylphenylamino) -gamma-biobutirolakton.

The N-cycloalkylcarbonyl fenilaminotiolaktonok preferred group represented by the formula V, wherein R 'is a C3-6 cycloalkyl group, R ² is hydrogen and R ⁴ and R ₅ are independently methyl or ethyl. Particularly preferred compounds are compounds of formula V is a compound wherein A in formula ^I R is cyclopropyl, R ² is hydrogen and R ⁴ and R ⁵ is methyl.

The N-cycloalkylcarbonylphenylaminolactones can be represented by the general formula VI wherein Ar is substituted phenyl, R ² is as defined above and R 'is C 3-6 cycloalkyl.

A preferred group of N-phenylamino and N-substituted phenylaminolactones is represented by Formula VII, wherein R ^{1 is C} 4 -C 6 cycloalkyl, R ^{2 is} hydrogen, and R ⁴ and R ⁵ are each independently methyl or ethyl.

A preferred group of compounds of formula VII are those wherein R ¹ is cyclopentyl, R ² is hydrogen and R ⁴ and R ^{5 are} methyl.

The N-cycloalkylcarbonylphenylaminolactones and thiolactones can be represented by the general formula VIII wherein Ar is a substituted naphthyl group and R ', R ² and Y are as defined above. Compounds which form a preferred group of N-naphthylaminolactones and thiolactones are represented by the general formula IX wherein R ¹ is C 3 -C 6 cycloalkyl, R ³ is hydrogen and Y is oxygen or sulfur. Particularly preferred compounds of formula IX are those wherein R ¹ is cyclopropyl, R ³ is methyl, and Y is oxygen.

Examples of compounds of formula I include:

3- (N-cyclopropylcarbonyl-N-2,6-dimethylphenylamino) -5-methyl-gamma-butyrothiolactone,

3- (N-cyclopentylcarbonyl-N-2,6-dimethylphenylamino) -gamma-butyrothiolactone,

3- (N-cyclopropylcarbonyl-N-3,4-dimethylphenylamino) -gamma-butyrothiolactone,

3- (N-cyclohexylcarbonyl-N-2-methylnaphthalene-l-ylamino) -5-phenyl-gamma-butyrothiolactone,

3- (N-cyclobutylcarbonyl-N-2-methylnaphthalene-l-ylamino) -gamma-butyrothiolactone,

3- (N- (2 * metilciklopropilkarbonil) -N-2-methylnaphthalene-l-ylamino) -gamma-butyrolactone.

3- (N-cyclopropylcarbonyl-N-2,6-dimethylphenylamino) -gamma-butyrothiolactone.

According to the invention, lactones and thiolactones can be prepared as described in our pending US Patent Application No. 13,856, filed February 22, 1979. The aniline NH ₂ (X) is alkylated by alpha-halo-gamma-butyrolactone XI or alpha-halo-gamma-thiobutyrolactone and the alpha- (N-arylamino)-gamma-butyrolactone XII or thiobutyroolactone XIII is acyl halide, to give 3- (N-acyl-N-arylamino) -gamma-butyrolactone or thiobutyrolactone (VIII) according to Scheme 1. In the reaction scheme, Ar, R ¹ , R ² and Y are as defined above and X is a chloro-desired bromine.

The alkylation reaction 1 is carried out in the presence of a base such as inorganic alkali metal carbonates, e.g. sodium carbonate, potassium carbonate or organic amines, e.g. trialkylamines, preferably triethylamine or pyridine compounds, preferably pyridine or 2,6-dimethylpyridine are used. The reagents NH ₂ and XI are generally used in equimolar amounts with the base. In one embodiment of the reaction, an aniline reagent of formula X is used in a molar excess as the base and no additional base is required. The reaction is carried out in an inert organic solvent, e.g. in a nonpolar diprotic solvent, e.g. dimethylformamide and acetonitrile; and aromatic hydrocarbons, e.g. in benzene and toluene at a reaction temperature of from 25 to 150 ° C, preferably from 50 to 150 ° C. Water may also be used as an additional solvent. The reaction pressure is usually atmospheric pressure, but lower or higher pressures may be employed. The reaction is usually carried out at atmospheric pressure. The reaction time, of course, also depends on the reagents and reaction temperature. The reaction time may vary from 1/4 hour to 24 hours. The product of Formula XII is generally prepared by conventional methods, e.g. extraction, distillation, or crystallization prior to acylation reaction # 2. The acylation preferred reaction conditions can be more fully described in U.S. Patent No. 847,503. The acylation reaction is usually carried out in the usual manner. The reagents XII and XIII are generally contacted in equimolar amounts in an inert organic solvent at a temperature of 0 to 100 ° C. As the inert organic solvent, ethyl acetate, methylene chloride, dimethoxyethane or benzene may be used. The product can be obtained by conventional techniques such as extraction, distillation, chromatography, crystallization, and the like. isolated and purified.

When the butyrolactone of formula I wherein W, X and Y are oxygen is prepared, the acid acceptor is an organic amine, e.g. trialkylamine or pyridine may be used. However, when the butyrothiolactone containing W and X is oxygen and Y is sulfur, the organic amine is preferably not used.

The conditions for the acylation reaction are described in more detail in U.S. Patent No. 847,504.

Compounds of formula VIII containing alkeniloxidot represented by R ^1, R ¹ is an alkenyl group containing an oxidizing agent suitable compounds, e. Oxidation of 3-chloroper3 with benzoyl acid can give an inorganic base, e.g. in the presence of potassium acid phosphate.

The 3- (N-thionoacyl-N-arylamino) -butyrolactones and thiobutyrolactones can be prepared from the 3- (N-acyl-Narylamino) -butyrolactones II and thiobutyrolactones II according to Scheme 4.

Reaction 5, illustrated in Scheme 4, is preferably carried out at the reflux temperature of the solvent and the molar ratio of HA to phosphorus pentasulfide is about 4: 1 and the reaction is carried out with a small amount of base, e.g. in the presence of pyridine. The product of Formula XIV can be isolated by conventional chromatography.

Thiolactones are prepared by cleavage of the corresponding lactones of formula I with an alkyl mercaptyl salt followed by formation of the thiolactone. For the latter, a halogenating agent, e.g. phosphorus trichloride, phosphorus pentachloride, thionyl chloride or oxalyl chloride are used according to Scheme 5. In the reaction scheme, R ¹ , R ² , and Ar are as defined above.

The compounds of the present invention are useful as fungicides, especially for plant fungal infections. Some of the fungicidal compositions of the present invention are more potent fungicides than other compositions of the invention in certain fungi. so e.g. a preferred class of compounds of the present invention has a particular activity against certain fungal diseases, e.g. apron spores, e.g. grape downy mildew (Plasmopara viticola) and downy mildew of cabbage and American kale (Peronospora parasitica); tomato and potato plague (Phytophthora infestans) and white flake root mold, as well as seedling fungus disease, e.g. Phytophthora.

The compounds of the present invention are particularly useful fungicides because they cure pre-existing fungal infections. Accordingly, the fungicidal compositions of the present invention are economically useful because the plant need only be treated with the fungicidal composition once a fungal infection has occurred. Preventive application of fungicides against potential fungal infections is not required.

When using the fungicides, the compound of the invention is applied in an effective amount to the fungi and / or their environment, e.g. vegetative hosts or non-vegetative hosts e.g. animal products. The amount used will, of course, depend on several factors, such as the host, the species of fungus, and the type of compound used in the present invention. Like most pesticides, fungicides are generally used in conjunction with conventional biologically inert carriers, which ease the dispersion of the fungicidal active ingredient and thus demonstrate that the formulation and application can greatly affect the action of the fungicide. After formulation, the fungicides of the invention may be used in the form of granules, powders, wettable powders, emulsifiable concentrates, solutions or any other formulated formulation known in the art, depending on the intended use.

Wettable powders are readily dispersed in water or other decorative dispersants in the form of finely divided particles. These preparations are usually

5 to 80% fungicide and the remainder inert, e.g. containing dispersants, emulsifiers and wetting agents. The powder, in the form of a dry powder, is preferably applied to the soil in the form of an aqueous suspension. Typical carriers include e.g. earwax, kaolin material, silica or other highly adsorbent wettable inorganic diluent. As a wetting dispersant or emulsifier, e.g. the following compounds are contemplated:

aryl and alkylaryl sulfonates and sodium salts, alkyl amides sulfonates including fatty methyl esters, alkylaryl polyether alcohols, sulfated high alcohols, polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, ethylene and fatty oils, sulfonated petroleum oils, ethylene oxide addition products. Many other useful surfactants are commercially available. When used as a surfactant, its proportion will vary from 1 to 15% by weight of the fungicidal composition.

The powders are free-flowing mixtures of the active ingredient which are dispersed in a finely divided solid, e.g. formulated with talc, natural material, silicic acid, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, kennel, lime, flour and other organic or inorganic solids which act as dispersants and carriers. The finely divided solid particles have an average particle size of less than 50 microns. A typical powder formulation contains 75% silica and 25% toxic agent.

Liquid concentrates include an emulsifiable concentrate, which is a homogeneous liquid or paste preparation which is readily dispersible in water or other decorative dispersant and which, in addition to the fungicide, is a liquid or solid emulsifier or liquid carrier, e.g. may contain xylene, heavy aromatic naphtha, isoform or other non-volatile organic solvents. In the mode of application, these concentrates may be dispersed in water or other liquid carriers and sprayed onto the area to be treated.

Other formulated fungicidal formulations include simple solutions of the active ingredient with a dispersant in which the fungicidal active ingredient is completely soluble in the desired concentration, e.g. acetone, alkylated naphthalenes, xylene or other organic solvents. In granular formulations, the fungicidal agent is carried by relatively coarse particles and is very useful in airborne applications or for penetration of closed foliage forest consisting of soil protection plants. Pressurized sprays or aerosols may be used, in which the active ingredient is dispersed in a finely divided form in a low boiling point dispersing solvent carrier, e. as a result of evaporation of freons. Formulation technology and methods of application of fungicides are known in the literature. The weight% of the fungicides depends on the application of the composition and the type of formulation and generally ranges from 0.5 to 95% by weight of the fungicidal composition. The fungicidal compositions may contain other active ingredients, i.e. other fungicides, insecticides, nematocides, bactericides, growth regulators, fertilizers. etc

The compositions of the present invention and their fungicidal activity are illustrated by the following examples:

Example 1

3- (N-methoxyacetyl-N-2,6-dimethylphenylamino) -gamma-tiobutirolakton

A solution of methoxyacetyl chloride (1.46 g, 0.0135 mole) in dichloromethane (10 ml) was added dropwise to a solution of 3- (N-2,6-dimethylphenylamino) gamma-thiobutyrolactone (3 g, 0.0135 mole) in toluene (200 ml). The reaction mixture was heated at reflux for 3 hours and evaporated to give a solid which was recrystallized from ether: benzene: hexane (10: 1: 10) to give 1.8 g of the title product as a tan product. 86-87 ° C. The infrared spectrum of the product shows two strong carbonyl absorption bands at 5.85 and 6.03 microns.

Example 2

Preparation of 3- (N-acetoxyacetyl-N-, 2,6-dimethylphenylamino) gamma-butyrolactone (not required)

13.7 g (0.1 mol) of acetoxyacetyl chloride are added dropwise to a solution of 20.5 g (0.1 mol) of N-2,6-dimethylphenylamino-gamma-butyrolactone and 7.9 g (0.1 mol) of pyridine in 150 ml of benzene. . After the addition was complete, the reaction mixture was stirred for ca. After stirring at 25 ° C for 4 hours, it was washed with water, dried over magnesium sulfate and concentrated under reduced pressure to give an oily residue. The residue was recrystallized from ethyl ether-hexane to give 27.3 g of product, m.p. 90-91 ° C.

In an analogous manner, 3- (N-cyclopropylcarbonyl-N-2,6-dimethylphenylamino)-gamma-butyrolactone can be prepared from cyclopropylcarbonyl chloride and N-2,6-dimethylphenylamino-gamma-butyrolactone as starting materials.

Example 3

Preparation of N-hydroxyacetyl-N-2,6-dimethylphenylamino-gamma-butyrolactone (not required) g (0.18 mol) of 3- (N-chloroacetyl-N-2,6-dimethylphenylamino)-gamma-butyrolactone, 14.5 A solution of sodium hydroxide (g, 0.36 mol) in water (50 ml) and dimethoxyethane (450 ml) was stirred at 25 ° C for 16 hours. The resulting mixture was filtered and diluted with 500 mL of dichloromethane. Hydrogen chloride gas was bubbled into the reaction mixture for 1 hour. The mixture was filtered, dried over magnesium sulfate and concentrated under reduced pressure. The residue was washed with a mixture of 10% ethyl ether and 90% hexane, filtered and air dried. 36.5 g of the expected product are obtained in the form of white crystals. Mp 173-174 ° C.

Example 4

Preparation of N-ethoxyacetyl-N-2,6-dimethylphenylamino-gamma-butyrolactone (not claimed).

Ethoxyacetyl chloride (6.2 g, 0.05 mol) was added dropwise to a solution of 3- (N-2,6-dimethylphenylamino) gamma-butyrolactone (10.3 g, 0.05 mol) in toluene (150 ml) under reflux. The reaction mixture was then heated under reflux for 2 hours. After cooling, the mixture was washed with water, saturated sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated.

11.2 g of 3- (netoxyacetyl-N-2,6-dimethylphenylamino) gamma-butyrolactone are obtained. M.p. 73-75 ° C.

Example 5

Preparation of N-Methylthioacetyl-N-2,6-dimethylphenylamino)-gamma-butyrolactone g (0.3 mol) of sodium methylmercaptide in small portions 25.3 g (0.08 mol) of N-bromoacetyl-N-2,6-dimethylphenylamino) - of gamma-butyrolactone (m.p. 116-117 ° C) in 200 ml of dimethylsulfoxide. The reaction is slightly exothermic. The mixture was stirred at 25 ° C for 16 hours. The reaction mixture was heated to 150 ° C under reduced pressure with a water jet pump to remove some of the dimethyl sulfoxide solvent. The residue was diluted with water and the aqueous layer was separated. The organic layer was dissolved in dichloromethane (350 mL), washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give an oily product. The oil was chromatographed on a silica gel column eluting with 20% acetone and 80% petroleum ether. 11 g of product are obtained which is recrystallized from ethyl ether / acetone. The product melts at 77-78 ° C.

Example 6

Preparation of 3- (N-methoxyacetyl-N-2-methylnaphth-1-ylamino) -gammabutyrolactone (not required)

Methoxyacetyl chloride (2.4 g, 0.022 mol) was added dropwise to 3- (N-2-methylnaphthyl-1-ylamino) gamma-butyrolactone (5.5 g, 0.022 mol) and pyridine (1.7 g, 0.022 mol) in dichloromethane (100 ml). added. After stirring for 1 hour at 25 ° C, the reaction mixture was heated at reflux for 6 hours, cooled overnight, and washed with water, saturated sodium bicarbonate and water again, dried over magnesium sulfate and concentrated under reduced pressure. The residue was chromatographed on silica gel columns. The eluent was a mixture of 25% acetone and 75% petroleum ether. 4.3 g of the expected product are obtained, m.p. 42-46 ° C.

Example 7

Preparation of 3- (N-methoxy-thionoacetyl-N-2,6-dimethylphenylamino) -gamothiobutyrolactone g phosphorus pentasulfide g was heated under Dean Stark water separator (300 mL xylene) to azeotropically remove any water present. After cooling to 100 ° C, the solution was treated with 2 ml of pyridine, followed by the addition of 33.3 g of 3- (N-methoxyacetyl-3-N-2,6-dimethylphenylamino)-gamma-butyrolactone. The stirred suspension was heated to 150 ° C. After about 40 minutes, the phosphorus pentasulfide is dissolved and the mixture is maintained at 150 'C at the end of the week. The mixture was diluted with an equal volume of methylene chloride and washed with saturated sodium bicarbonate (200 mL), water (200 mL) and dried over magnesium sulfate. The solution was filtered and the filtrate was evaporated in vacuo to give a dark oil which was chromatographed on a 300 g silica gel column. Light petroleum, then. Ethyl ether containing 80% petroleum ether and ethyl ether containing 70% petroleum ether, ethyl ether containing 60% petroleum ether and ethyl ether containing 40% petroleum ether and ethyl ether containing 25% petroleum ether were used.

The oil isolated from the petroleum ether and ethyl ether solutions was dissolved in methylene chloride and treated with activated carbon and magnesium sulfate, filtered, distilled to give the title product as an oil (1.8 g). The product is compound 10 of Table B.

Example 8

Preparation of 3- (N-crotonyl-N-2,6-dimethylphenylamino)-gamma-butyrolactone g of crotonic acid and 12 g of thionyl chloride were refluxed for 1 hour and excess thionyl chloride was removed in vacuo. 14 g of 3- (N-2,6-dimethylphenylamino) gamma-butyrolactone are added together with 150 ml of toluene and refluxed for 2 hours. The mixture was washed with water-saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered and the solvent was distilled off. The product was chromatographed on a silica gel column (260 g) and eluted with acetone: ether: petroleum ether. 3.1 g of the expected product are obtained, m.p. 122-123 ° C. The product is compound 3 of Table A.

Example 9

Preparation of 3- (N-3-methyl-2,3-epoxybutanoyl-N-2,6-dimethylphenylamino) gamma-butyrolactone.

3- (N-3-Methyl-crotonyl-N-2,6-dimethyl-phenylamino)-gamma-butyrolactone (A) was prepared as described in Example 8 from the starting material of 3-methyl-crotonic acid. 9 g of the product is heated to reflux for 6 hours in 6 g of 3-chloroperbenzoic acid and 4.7 g of potassium dihydrogen phosphate in 75 ml of dichloromethane. The mixture was washed with water, dried over magnesium sulfate and distilled. The residue was crystallized from ether / hexane to give 5.4 g of the title compound, m.p. 100-104 ° C. The product is compound 7 in Table A.

Example 10

Mycelium inhibition

Compound # 2 of the present invention was evaluated for fungicidal activity by the mycelial inhibition test. The assay is used to measure the fungitoxic effect of fungicidal compounds on the degree of inhibition of mycelial growth. No. 2 Compound II was dissolved in acetone to give a solution of 500 ppm. Paper strips were inoculated with mycelial growth of Pythium Ultiumum by covering the paper with mycelial suspension of potato dextrose. The inoculated papers were then placed on potato dextrose agar plates and sprayed with a fungicide solution using a microplate. Treated strips of paper were incubated at 25 ° C and data recorded after 24 hours. Fungicidal activity is measured by measuring the inhibited zone of mycelial growth from the center of the paper strip. No. 2 Compound was found to be 100% effective, expressed as% inhibition relative to Difolatan.

Example 11

Emergency tomatoes

The compounds of the present invention were tested for prevention of tomato disease (Phytophthora infestans). Tomato seedlings were used for 5 or 6 weeks (Bonny Best sore). The tomato plants are sprayed with a 250 ppm suspension of the test compound in acetone, water and a small amount of nonionic emulsifier. The sprayed plants are then inoculated one day later with the organism placed in the chamber and incubated at 19-20 ° C and 100% relative humidity for at least 16 hours. After incubation, the plants were kept in a greenhouse at a relative humidity of 60-80% for approx. 7 days. The fungicidal activity of the test compound was determined relative to the control of untreated plants. The results are shown in Tables 1 and 2. The concentration of the test compound is 250 ppm unless otherwise indicated in parentheses.

Example 12

Zeller Emergency

Celery tests were performed on 11-week-old celery plants (Utah). The celiac disease causing organism is Septo6 ria apii. Celery plants were sprayed with a solution of the test compound in acetone, water and a nonionic emulsifier. The plants were then inoculated with the organism and placed in a chamber at 19-20 ° C and 100% relative humidity for approx. Incubate for 48 hours. After incubation, the plants are allowed to dry and, at a relative humidity of 60 to 80, for approx. Allow to stand for 14 days.

The antifungal activity was evaluated against untreated control plants. The results are shown in Tables 1 and 2.

Example 13

Grape powdery mildew

The compounds of the present invention were tested against plasmopara viticola grape mite organism. We used 7 weeks old Vitis vinifera Emperor vine leaves with a diameter of 70 to 85 mm. The leaves were sprayed with a solution of the test compound in acetone. The sprayed leaves were dried and inoculated with a spore suspension of the organism, then placed in a humid chamber and incubated at 18-22 ° C and 100% relative humidity. Seven to nine days after vaccination, the spheroidal kill was determined. The fungicidal activity was evaluated as% of untreated control plants. The results are shown in Tables 1 and 2.

Example 14

Tomato alternaria

The compounds of the invention were tested on tomato altemaria. Alternaria solani conidia was used as the test organism. We used 6-7 weeks Bonny Best tomato seedlings. The tomato plants were sprayed with a 250 ppm solution of the test compound in acetone and water containing a small amount of non-ionic emulsifier. After one day, the sprayed plants are inoculated with the organism, dried and maintained at 12 nJ at 60-80% RH. The% fungicidal activity is evaluated as a percentage of the disease observed on untreated control plants. The compounds tested and the results are shown in Tables 1 and 2.

Example 15

powdery mildew

The powdery mildew test was carried out on Bountiful seedlings with well-developed cotyledons. The pathogen was Erysiphe polygoni. The bean seedlings were sprayed with acetone and aqueous 250 ppm solution containing the test compound and nonionic emulsifier. The treated plants are inoculated with the pathogen one day after spraying. The plants were then stored at 60-80% relative humidity and at 19-20 ° C in a greenhouse. The degree of leaf infestation was evaluated after 10 days. The fungicidal activity of the test compound was expressed as a percentage of the activity observed on untreated control plants. The results are shown in Table 2.

Example 16

leaf rust

The leaf rust was examined on a nipple. Uronyces phaseoli tipica served as a pathogenic organism. The bean plants were sprayed with a 250 ppm aqueous solution of the test compound in acetone aqueous nonionic emulsifier. The treated plants were then inoculated with the pathogen and placed in a chamber for approx. Incubate for 20 hours at 100% relative humidity and 20-21 ° C. The plants were then removed from the chamber, allowed to dry, and stored in a greenhouse at 60-80% RH. The degree of leaf infestation was evaluated after 14 days. The fungicidal activity of the test compound was expressed as a percentage of that of untreated control plants. The results are shown in Table 2.

Example 17

Preparation of 3- (N-cyclopentylcarbonyl-N-2,6-dimethylphenylamino) -15-gamma-butyrolactone

Cyclopentylcarbonyl chloride (5.7 g, 0.043 mol) was added dropwise to a solution of 8.8 g (0.043 mol) of N-2,6-dimethylphenylaminogammbutyrolactone in 100 ml of toluene.

After the addition was complete, the solution was heated to reflux overnight, washed with water, saturated sodium carbonate solution, then water, dried over magnesium sulfate and concentrated under reduced pressure. This gives an oily residue which is crystallized from ethyl ether. 6.1 g of the title compound are obtained, m.p. 109-113 ° C. The product is listed in Table C as Cl.

Example 18

Preparation of 2- (N-cyclopropylcarbonyl-2,6-dimethylanilino) -4- (t-butylthio) butanoic acid.

To a solution of 4.2 g of tert-butyl mercaptan in 100 ml of 1,2-dimethoxyethane is added 2.5 g of sodium methoxide with stirring. 3- (Cyclopropylcarbonyl-2,6-dimethylanilino) butyrolactone (11.6 g) prepared in Example 1 was added and stirred at room temperature overnight and then poured into ice water. The mixture was washed with toluene (2 x 100 mL) and the toluene was washed with water. The aqueous phase was acidified to pH = 1 with 12N hydrochloric acid and extracted twice with methylene chloride. The methylene chloride extracts were washed with water, dried over magnesium sulfate, filtered and distilled to give the title compound (10.6 g) as an oil.

Example 19

Preparation of 3- (N-cyclopropylcarbonyl-2,6-dimethylanilino) butyrolactone

The acid obtained in Example 18 (10.6 g) was dissolved in methylene chloride (200 ml), cooled to -20 ° C in a condensed flask, and 6 g of phosphorus trichloride were added dropwise. The exotherm causes the mixture to warm to 36 ° C. Additional methylene chloride was added and the mixture was allowed to stand at room temperature overnight, resulting in two phases. The methylene chloride layer was collected, dried, magnesium sulfate and silica gel, filtered and distilled. The resulting oil was crystallized from petroleum ether to give the title compound, m.p. 145-147 ° C. The compounds listed in Table C are shown in Table 17-19. Prepared in the same manner as described in Examples. The structure of the individual compounds is summarized in the table and confirmed by nuclear magnetic resonance spectra and / or infrared spectral analysis.

The table is a compound of formula IA

Example number Price Y _R , m.p. C Analysis H N calculation to Found calculation to Found calculation to Found 1 2,6- (OH ₃ ) ₂ O 0 CH = CH ₂ 142-3 69.48 68.7 6.61 6.77 5.40 5.42 2 2,6- (OH ₃ ) ₂ O 0 CH = C (CH ₃ ) ₂ 86-7 71.06 71.39 7.37 7.67 4.88 4.96 3 2,6- (OH ₃ ) ₂ O 0 CH = CHCH ₃ 122-3 70.31 69.38 7.01 6.99 5.12 5.16 4 2,6- (OH _{3) 3} 0 s CH = CH ₂ 101-2 65.43 62.56 6.22 6.23 5.09 4.93 5 2,6- (OH ₃ ) ₂ O 0 C (CH ₃ ) = CH ₂ 115-23 70.31 68.5 7.01 6.99 5.12 5.17 6 2,6- (OH ₃ ) ₂ O S CH = C (CH ₃ ) ₂ 123-4 67.29 68.25 6.98 7.2 4.62 4.86 7 2,6- (OH ₃ ) ₂ O 0 (1) 100-04 67.31 67.44 6.98 7.36 4.62 4.66 8 2,6- (OH ₃ ) 10 0 (2) 109-10 66.42 68.3 6.62 7.05 4.84 5.02 11 2,6- (OH ₃ ) ₂ O 0 (3) 117-18 66.42 66.15 6.62 6.72 4.84 4.76 12 2,6- (OH ₃ ) ₂ O S CH = CHCH ₃ 117-122 66.4 68.17 6.62 6.98 4.84 5.0 13 2,6- (OH ₃ ) ₂ O S CH ₂ CH = CH ₂ 67-69 66.4 67.0 6.62 7.08 4.84 4.89 14 2,6- (OH ₃ ) ₂ O 0 CH ₂ CH = CH ₂ 84-87 70.31 70.65 7.01 7.42 5.13 5.26 15 2-methyl- 0 CH = CHCH ₃ 73.77 72.13 4.53 naphthalen-l-yl (rotamer A) ¹⁶⁶ „ ¹⁷² 6.19 6.36 4.45 16 2-methyl- 0 CH = CHCH ₃ ,,, 73.77 74.53 6.19 6.65 4.53 4.92 naphthalen-l-yl , "Nx 104-111 (rotamer B) 17 2-methyl- naphthalen-l-yl 0 CH = CH ₂ 158-176 73.2 73.35 5.80 5.79 4.74 4.43 (rotamer A) 18 2-methyl- naphthalen-l-yl 0 CH = CH ₂ 177-178 73.2 71.32 5.80 5.92 4.74 4.53

(rotamer B)

Table B

Compounds of formula IB

Example Price γ R ¹ op C Analysis H number C Sarni- _{Talahh did} Numerically, _{he did} calculation to

9 2,6- (CH ₃ ) ₂ 0 0 ch ₂ and ₃ 85.6 61.41 66.17 6.53 6.82 4.77 5.35 10 2,6- (CH ₃ ) ₂ 0 S CH ₂ OCH ₃ oil 58.22 57.35; 6.19 6.11 4.53 4.55

Table 1 Control% Table 2 Fungicidal effect Song Grapes apron- tomatoes csom- Celery- Tomato alternaria Song GDM TLB CLB YOU B BR BPM dust _z emergency buy cl C2 - 81 50 19 19 0 0 0 0 10 0 - 1 89 0 65 7 C3 - 0 7 0 0 4 2 54 0 23 0 C4 98 71 19 0 29 4 3 100 100 33 29 C5A 99 6 44 21 0 0 4 110 57 94 '29 C5b 99 13 44 56 0 23 5 18 23 23 18 C6 13 11 0 0 0 98 6 54 13 57 8 7 - 14 11 11 8 - 0 50 11 9 100 98 37 0 10 100 99 50 - 11 100 71 23 0 12 100 84 36 0 13 100 96 44 0 14 100 96 44 0 15 100 89 11 0 16 100 84 37 0 17 100 37 - 0 18 83 0 - 0

Table C

Compounds of formula IC

number

Is R * Y

op C Analysis H N C ^Sami - Found _Calculators Numeric, Found to to to

cl

C2

C3

C4

C5A *

C5b *

C6

2,6- (CH ₃ ) ₂ O

2,6- (CH ₃ ) ₂ O

2,6- (CH ₃ ) ₂ O

2,6- (CH ₃ ) ₂ 0 (4) (5)

2,6- (CH ₃ ) ₂ 0 cyclopentyl cyclobutyl cyclohexyl cyclopropyl cyclopropyl cyclopropyl cyclopropyl

S nch ₃

109-113 71.73 72.78 7.69 7.94 4.65 4.67 119-120 71.06 70.87 7.37 7.54 4.88 4.75 162-163 72.35 73.37 7.98 8.36 4.44 4.48 145-147 66.40 66.97 6.62 6.75 4.84 5.4 186-190 73.77 73.79 6.19 6.43 4.53 4.47 139-142 73.77 74.35 6.19 6.29 4.53 4.49 113-114 71.30 70.35 7.74 7.74 9.78 9.69

'Rotators A and B

11-16. Examples 1 to 5 use a 1% stock solution in acetone of the active ingredient, i.e. 100 ml stock solution containing 1 g of the active ingredient. About 2-3 drops of nonionic Ortho X-77 Spreader Emulsifier are added to 10 mL stock slurry (manufactured by Ortho Division of Chevron Chemical Company of San Francisco, USA). The actual concentration used for the bioassay is determined by diluting the stock solution with deionized water. For example, a formulation containing 250 ppm of test compound is prepared by diluting 25 ml stock solution with 975 ml deionized water.

EXAMPLE 20 An emulsion concentrate containing 3% by weight of 3- (N-crotonyl-N-2,6-dimethylphenylamino)-gamma-butyrolactone was prepared by mixing 10.2 g of a 99% pure lactone with 949.8 g of xylene, 40 g. emulsifier (a mixture of calcium alkylbenzenesulfonate and octylphenol ethoxylated, i.e. 20 g Atlox 3403F and 20 g Atlox 3404F, ICI, USA).

Example 21 An emulsion concentrate containing 3-% (N-crotonyl-N-2,6-dimethylphenylamino) gamma-butyrolactone by weight was prepared. 51 g of 99% pure above mixture with 884 g of xylene. 25 g of cyclohexanone and 40 g of the emulsifier of Example 20 are mixed.

Example 22

A smooth aqueous liquid composition containing 35.5% by weight of 3- (N-crotonyl-N-2,6-dimethylphenylamino) gamma-butyrolactone was prepared by preparing 375.2 g of the above. 95% pure lactone with 490.7 g water. 19.6 g polyvinyl alcohol, 14.3 g silicone antifoam agent! (Antifoam C, Dow Corning Company of Midland. United States of America). 98 g of propylene glycol. 2 g sodium citrate, 2 g butylated hydroxytoluene and butylated hydroxy amisole antioxidant mixture (Tenox 6, Eastman Chemicals Co. of Kingsport, Tennessee, USA) and 2 g xanthan gum and 18 g octylphenol ethoxylate.

EXAMPLE 23 A wettable powder containing the active ingredient of the preceding Example was prepared by weight. 808 g of the above lactone (99% purity) are mixed with 142 g of attapulgite and 50 g of a dispersant mixture of lignosulfate and tauride, sulfosuccinate (Drysperse by Witco Chemical Company of Housten, Texas, USA).

Example 24 A wettable powder containing the above active ingredient was prepared by mixing 657 g of a 99% pure lactone lactone with 293 g of attapulgite and 50 g of the dispersant of the previous example.

Example 25 A wettable powder containing by weight of the above active compound was prepared by mixing 521 g of the above active compound (96% purity) with 379 g of talc, 50 g of synthetic silica and 50 g of the above dispersant.

Example 26 To obtain a wettable powder containing the above active ingredient, 206 g (97% purity) of lactone were mixed with 734 g of powdered calcium carbonate and 50 g of the above dispersant.

Example 27 To obtain a wettable powder containing the above active ingredient, 103 g of lactone are mixed with 847 g of kaolin and 50 g of the above dispersant.

Example 28 To obtain a powder containing the above active ingredient, 909 g of a 99% pure lactone were mixed with 91 g of finely divided kaolin.

Example 29 A powder containing the above active ingredient was prepared by weight. to mix 253 g of lactone with 749 g of finely divided kaolin.

Example 30

To produce an aerosol, 40.8 g of the above-mentioned active ingredient of 99% purity are mixed with 969.7 g of finely divided kaolin. It is then mixed with 2000 g of a propellant containing 30% by weight of propane and 70% by weight of isobutane under pressure and filled into spray bottles under pressure. On release, an aerosol powder containing 4% by weight of lactone is released. Together with the buoyant gas, the composition contains 1.3% of the above lactone.

EXAMPLE 31 Granules containing the above active ingredient were prepared by weight. 204 g of lactone are mixed with 786 g of granulated natural pine resin and 10 g of butylated hydroxytoluene antioxidant.

Example 32 To obtain a granular formulation containing by weight of the above active compound, 102 g of 98% pure lactone were mixed with 738 g of diatomaceous earth particles and 160 g of N-methylpyrrolidone.

EXAMPLE 33 To obtain a granular formulation containing by weight of the above active compound, 102 g of the above lactone (98% purity) are mixed with 718 g of diatomaceous earth particles and 160 g of dimethylformamide.

Example 34 Granules containing by weight of the above active ingredient were prepared by mixing 50.5 g of 99% pure lactone with 949.5 g of diatomaceous earth granules.

The active ingredients listed in Tables A, B, C and Tables are formulated similarly.

Most preferred are wettable powders containing a mineral carrier such as kaolin and the anionic surfactant.

Claims (11)

PATENT CLAIMS 1. A fungicidal composition comprising, as active ingredient 0.1 to 95% by weight of Compound I of the formula: - wherein ₅ Ar is C 1 -C 4 alkyl-substituted phenyl or naphthyl, R ¹ is C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxide. R ² is hydrogen; Y is oxygen, sulfur or NR, wherein R is C 1-4 alkyl, W is oxygen or sulfur, X is oxygen or sulfur, with the proviso that when W is sulfur, R * may be, in addition to the above 15 groups, hydroxylmethyl or C 2-6 alkoxyalkyl or C 2-6 alkylthioalkyl - and a biologically inert solid or a liquid carrier, preferably a mineral solid, optionally anionic or nonionic surfactant, and optionally other excipients, preferably an antifoaming agent and antioxidant. (Priority: June 1, 1979) An embodiment of the composition of claim 1, wherein the active ingredient is a compound of the formula: wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R ¹ is hydroxymethyl, C 2-6, θ mos alkoxyalkyl, C2-6 alkylthioalkyl, R ² is hydrogen, Y is oxygen, sulfur or NR, wherein R is C1-4 alkyl, X is oxygen or sulfur. (Priority: June 1, 1978) 35 3. The composition of claim 1 wherein the active ingredient is a compound of formula VIII wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R ¹ is C 3-6 cycloalkyl, R ² is hydrogen, Y is oxygen, sulfur or NR, wherein R is C 1-4 alkyl, with the proviso that when Ar is substituted phenyl and R 'is cyclopropyl, then Y is not oxygen. . (Priority: December 12, 1979) An embodiment of the composition of claim 1, wherein the active ingredient is a compound of Formula I, wherein Ar is phenyl substituted with C 1-4 alkyl, and R ¹ and R ² are as defined in claim 3. specified. (Priority: December 12, 1979) 55 5. The method of claim 1. A composition, wherein the active ingredient is a V comprises a compound of formula - is R ¹ C 3-6 cycloalkyl, R ² is hydrogen and R ⁴ θθ ^and R is methyl or ethyl. (Priority: December 12, 1979) 6. An embodiment of the composition of claim 1 wherein the active ingredient is a needle compound of formula VI wherein Ar, R ¹ and R ² are as defined in claim 3. (Priority: December 12, 1979) 7. The composition of claim 1 wherein the active ingredient is a compound of formula VII wherein R ¹ is C 4 -C 6 cycloalkyl, R ² is hydrogen, and R ⁴ and R ⁵ are methyl or ethyl. (Priority: December 12, 1979 8. The composition of claim 1 wherein the active ingredient is a compound of formula VIII wherein Ar is C 1-4 alkyl-substituted naphthyl and R ¹ , R ² and Y are as defined in claim 3. (Priority: December 12, 1979) 9. The composition of claim 1 wherein the active ingredient is a compound of formula IX wherein R ¹ is as defined in claim 3 and R ³ is hydrogen and Y is oxygen or sulfur. (Priority: December 12, 1979) 10. A process for the preparation of gamma-butyrolactones of formula I and gamma-butyrothiolactones, wherein the substituents are as defined in claim 3, characterized in that: (a) Compounds of general formula (III) which are narrower compounds of formula I wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R ¹ is C 3-6 cycloalkyl, R ² is hydrogen, Y is oxygen or sulfur or NR wherein R is a C 1 -C 4 alkyl group and X is oxygen or sulfur, a compound of formula R'COZ, wherein Z is chlorine, fluorine or bromine, with a compound of formula XII, wherein Ar, X , Y, R ¹ and R ² are as defined in the subgroup, and the resulting compound of formula VIII is reacted with phosphorus pentasulfide, wherein Ar, R 1, X, Y, and R ² are as defined herein, b) Compounds of general formula VIII, which are more narrow compounds of formula I, wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R ¹ is C 3-6 cycloalkyl and R ² is hydrogen, Y is oxygen or sulfur. or NR-, wherein R is C1-C4 alkyl, provided that when Ar is substituted phenyl and R * is cyclopropyl, then Y is other than oxygen, a compound of formula R'COZ wherein Z is chloro or a bromine atom with a compound of formula XII wherein Ar, X. Y, R ¹ and R ² are as defined in sub-paragraph b), c) for the preparation of a compound of the general formula Id, which is a narrower group of compounds of formula I, wherein Ar is phenyl substituted with C 1-4 alkyl, R ¹ is C 3-6 cycloalkyl, and R ² is hydrogen or bromine; COZ, wherein Z is chlorine or bromine-101, a compound of formula XII, wherein Ar, and R ² are as defined in (c) and Y is sulfur; d) for the preparation of a compound of Formula V, wherein R ¹ g is C 2 -C 6 cycloalkyl, R ² is hydrogen, and R ⁴ and R ⁵ are methyl or ethyl, a compound of formula I - in which Z = chlorine or bromine with a compound of the formula XIIa where R ⁴ , R ⁵ and R ² are as defined in (d) - e) VI being a narrower group of the compounds of Formula I. The compounds of the formula: - wherein Ar is a C1-4 alkyl group substituted jg phenyl and R 'is C3-6 cycloalkyl and ^R2 is hydrogen - for the preparation of a R'COZ compound - wherein Z is chlorine or bromine, a compound of formula XII, - in which Ar, R 20 ² are as defined in altárgyikör e) and Y is an oxygen atom - is reacted, t) for the preparation of a compound of formula VII, which is a narrower group of compounds of formula I, wherein R ¹ is C 4 -C 6 cycloalkyl, R ^{2 is} hydrogen and R ⁴ is methyl or ethyl, a compound of formula R'COZ - wherein Z is Cl or Br - XHB a compound of the formula: - wherein R ^{4 and} R 30 is methyl or ethyl and ^R2 is hydrogen - is reacted, g) for the preparation of compounds of the general formula VIII wherein Ar is C 1-4 alkyl substituted naphthyl, R ¹ is C 3-6 cycloalkyl and R ² is hydrogen, a compound of formula VIII wherein R'COZ reacting a compound of Formula (II) wherein it is chlorine or bromine with a compound of Formula (XII) wherein Ar, Y and R ² have subgroups g); h) IX: Among the compounds of the formula I compounds of the formula: - wherein R * is C 3-6 cycloalkyl, R ³ is hydrogen or C1-3 alkyl, and Y is O or S - by reacting an R ¹ COZ general wherein Z is chlorine or bromine, with a compound of formula XIIc wherein R ³ , R ² and Y are alpha (h). Priority: December 12, 1979 11. A process for the preparation of gamma-butyrolactones and gamma-butyrothiolactones of formula I, characterized in that: a) a compound of formula I wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R * is C 2-6 alkenyl or C 2-6 alkenyloxide, R ² is hydrogen, Y is oxygen or sulfur or NR-, wherein R is C 1 -C 4 alkyl, W is oxygen and X is oxygen or sulfur, a compound of formula R'COZ wherein Z is chlorine or bromine is a compound of formula XII with a compound of the formula wherein Ar, X. Y, R * and R ² are as defined in sub-a), b) a compound of formula I wherein Ar is phenyl or naphthyl substituted with C 1-4 alkyl, R 'is C 2-6 alkenyl, C 2-6 alkenyloxide and R ² is hydrogen, Y is oxygen or sulfur, or NR - in which R is a C 1-4 alkyl group, W is a sulfur atom and X is an oxygen or sulfur atom - a compound of the formula R'COZ, where Z is a chlorine or bromine atom - with a compound of the formula XII - in which Ar , X, Y, R ¹ and R ^{2 are} reacted with the phosphorus pentasulfide of sub-point b) and the resulting compound of formula VIII wherein Ar, R 1, X, Y and R ² are as defined in b).