GB2039487A

GB2039487A - New fungicidal derivatives of N- phenyl-N-(alkoxycarbonylalkyl) -acetamide phosphorodithioates

Info

Publication number: GB2039487A
Application number: GB7942238A
Authority: GB
Original assignee: Philagro SA
Current assignee: Bayer CropScience SA
Priority date: 1978-12-14
Filing date: 1979-12-07
Publication date: 1980-08-13
Also published as: ES486793A0; IL58927A0; ES493387A0; ES8106537A1; ES8107242A1; DD149455A5; JPS5583793A; ZA796654B; EP0012703A1; DE2961280D1; PT70589A; DK530879A; FR2444044A1; BR7908188A; EP0012703B1; GR73912B

Description

SPECIFICATION New derivatives of N- phenyl -N- (alkoxycarbonyl alkyl) - acetamide phosphates This invention relates to new/V- (substituted phenyl) -N - (alkoxycarbonylalkyl) - acetamide phosphates, processes for their preparation, and compositions containing them which can be used for protecting plants against fungi. N - Phenyl -N- (alkoxycarbonylalkyl) - acetamide dithiophosphates have already been described in United States Patent No. 3517089, but the compounds therein disclosed are compounds having insecticidal properties and are not substituted on the phenyl nucleus. The present invention relates to a new class of compounds of this type having particular substituents on the phenyl nucleus and having original biological properties, namely a remarkable fungicidal action which surprisingly may also be expressed systemically through plants. The N - (substituted phenyl) -N- (alkoxycarbonyl alkyl) - acetamide phosphate derivatives of the present invention are those compounds of the general formula:

wherein X represents a halogen atom (preferably chlorine) or an alkyl radical containing 1 to 4 carbon atoms (preferably methyl), n represents zero or 1, or 3, Y represents the methylene (i.e. -CH2-) or ethylidene [i.e. -CH(CH3)-] radical, R1 and R2 have the same or different significances and each represents a halogen atom (preferably chlorine), an alkyl radical containing 1 to 4 carbon atoms (preferably methyl) or an alkoxy radical containing 1 to 4 carbon atoms, R3 represents an alkyl radical containing 1 to 4 carbon atoms (preferably methyl), and R4 and R5 have the same (preferably) or different significances and each represents an alkyl radical containing 1 to 18 carbon atoms optionally carrying one or more substituents selected from halogen atoms (preferably chlorine) and alkoxy radicals containing 1 to 4 carbon atoms (preferably methoxy).When n represents 2 or 3 the substituents represented by symbol X may be the same or different. Preferred compounds of the invention are those of the general formula:

wherein R1, and R2, have the same or different significances and each represents a halogen atom (preferably chlorine) orthe methyl radical, R3 is as hereinbefore defined, and R4, and R5, have the same or different significances and each represents an alkyl radical containing 1 to 18 carbon atoms, the carbon atoms of which are primary, secondary or tertiary, optionally substituted by an alkoxy radical containing 1 to 4 carbon atoms (preferably methoxy). Of such compounds of general formula (II) those in which R1' and R2, both represent the methyl radical, R3 represents the methyl radical, and R4. and R5. have the same or different significances and each represents an alkyl radical containing 2 to 12 carbon atoms optionally substituted by an alkoxy radical containing 1 to 4 carbon atoms (e.g. 2-methoxyethyl) are of outstanding interest. The compounds of general formula (I) can be prepared by the application of known procedures. According to a feature of the invention, they are prepared by reacting an aniline derivative of the general formula:

(wherein the various symbols are as hereinbefore defined) with a phosphorus compound of the general formula:

[wherein A represents a halogen atom (preferably chlorine) orthe hydroxy radical, and R4 and R5 are as hereinbefore defined] with the concomitant formation of an acid or water HA. The reaction can be carried out in the absence or presence of an inert organic solvent such as, in particular, aliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylenes and petroleum ether, halogenohydrocarbons, e.g. chlorobenzene, methylene chloride, ethylene chloride and chloroform, ethers, e.g. diethyl ether, dioxan and tetrahydrofuran, nitriles, e.g. acetonitrile, amides, e.g. dimethylformamide and dimethylacetamide, dimethylsulphoxide, ketones, e.g. methyl ethyl ketone, and mixtures of such solvents with one another. The reaction is advantageously carried out at temperatures between 0[deg] and 180[deg]C and preferably between 20[deg] and 120[deg]C. In many cases, acid-binding agents or condensation agents are advantageously used. Tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, such as alkali metal and alkaline earth metal oxides, hydroxides, bicarbonates and carbonates, and also sodium acetate, are envisaged for this purpose. An excess of the particular aniline derivative of general formula (III) can also be used as the acid-binding agent. The aforedescribed process can also be carried out without an acid-binding agent as, in certain instances, it is advisable to pass a stream of nitrogen through the reaction mixture in orderto displace the hydrogen halide formed when symbol A in general formula (IV) represents a halogen atom. In other cases, the addition of dimethylformamide as a reaction catalyst is very advantageous. Details concerning the preparation of starting materials of general formula (III) can be obtained from publications which give particulars of general methods for the preparation of esters of anilino alkane - carboxylic acids, for example J. Org. Chem., 30, page 4101 (1965) and Tetrahedron, 1967, pages 487 and 493. The derivatives of dithiophosphonylacetic acid (or dialkoxyphosphinothioylmercaptoacetic acids) of general formula (IV) can be obtained in manner known perse by reacting an alkali metal salt of a dithiophosphate with a monohalogenated acid in accordance with, for example, the reaction scheme:-

(wherein R4 and R5 are as hereinbefore defined), the acid obtained then being converted, if necessary, into a halide such as the acid chloride. According to a further feature of the present inven tion, the compounds of general formula \1) are prepared by reacting an N - (substituted phenyl) - N (alkoxycarbonylalkyl) - chloroacetamide of the general formula:

(wherein the various symbols are as hereinbefore defined) with an alkali metal salt or ammonium salt of a dithiophosphoric acid of the general formula:

(wherein Me represents an alkali metal atom or the ammonium group, and R4 and R5 are as hereinbefore defined) with the concomitant formation of an alkali metal chloride or ammonium chloride MeCI. The reaction can be carried out in an inert organic solvent, such as acetone, methyl ethyl ketone, benzene, dimethylformamide or carbon tetrachloride. The reaction can be catalysed, in particular, by sodium iodide. The compounds of general formula (VII) can themselves be obtained by forming the monochloroacetyl derivative of compounds of general formula (III). The following Example illustrates the preparation of a compound of general formula (I) by the first process hereinbefore described. EXAMPLE 1

- dimethylaniline (6.2 g; 0.03 mol) in toluene (100 ml) is heated under reflux, for 1 hour, with S - (0, 0 - di - n - propyl - phosphonothioyl) mercaptoacetyl chloride (8.7 g; 0.03 mol). The hydrogen chloride formed is liberated. After cooling, the organic phase is washed successively with water (100 ml), 5% aqueous sodium bicarbonate solution (100 ml) and water (2 x 100 ml). After drying the solution with anhydrous sodium sulphate, the toluene is removed under reduced pressure. The volatile impurities are removed by molecular distillation at 90[deg]C under a pressure of 10- mm Hg. N - [1 - (Methoxycarbonyl) ethyl] - N - [S - (0, 0 - di - n - propylphosphonothioyl) mercaptoacetyl] - 2,6 - dimethylaniline (hereinafter identified as Compound 1) (11 g) is thus obtained (yield 79.5%). By following the procedure of the foregoing Example but employing appropriate starting materials of general formulae (III) and (IV), the following products of general formula (I) are also obtained.

Compound No.

diethyl - phosphonothioyl) mercaptoacetyl] - 2, 6 dimethylaniline

di - isopropyl - phosphonothioyl) mercaptoacetyl] 2, 6 - dimethylaniline

di - n - butyl - phosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline

di - sec - butyl - phosphonothioyl) mercaptoacetyl] 2, 6- dimethylaniline (6) /V-[1 - (methoxycarbonyl) ethyl] - N-[S - (0, 0di - isobutyl - phosphonothioyl) mercaptoacetyl] - 2, 6-dimethylaniline (7) /V-[1 - (methoxycarbonyl) ethyl] -N-[S- (0, 0di - 2 - methoxyethyl - phosphonothioyl) mercaptoacetyl] - 2,6 - dimethylaniline

di - 2 - chloroethyl - phosphonothioyl) mercaptoacetyl] - 2,6 - dimethylaniline (9) /V-[1 - (methoxycarbonyl) ethyl] N-[5 - (0, 0di - isobutyl - phosphonothioyl) mercaptoacetyl] - 2 chloro - 6 - methylaniline

di - n - propyl - phosphonothioyl)mercaptoacetyl] - 2 - chloro - 6 - methylaniline

diethyl - phosphonothioyl) mercaptoacetyl] - 2, 4, 6 trimethylaniline (12) /V-[1 -(methoxycarbonyl) ethyl] -N-[S- (0, 0diethyl - phosphonothioyl) mercaptoacetyl] - 3 chloro - 2, 4, 6 - trimethylaniline

diethyl - phosphonothioyl) mercaptoacetyl] - 2, 6 dimethylaniline

di - n - pentyl - phosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline (15) /V-[1 - (methoxycarbonyl) ethyl] - N-[S - (0, 0di - isopentyl - phosphonothioyl) mercaptoacetyl] - 2, 6-dimethylaniline

di - n - dodecyl - phosphonothioyl) mercaptoacetyl] 2, 6- dimethylaniline (17) N -[1 -(methoxycarbonyl) ethyl] N - [S - (0, 0di - neopentyl - phosphonothioyl) mercaptoacetyl] 2, 6- dimethylaniline It will be appreciated that all the aforementioned products are compounds of general formula (1)wherein R3 is the methyl radical, and Y is the ethylidene radical with the exception of Compound 13 wherein Y is the methylene radical. The yield of product and physical characteristics thereof are given in following Tables 1, 2 and 3. In the Tables the abbreviation m.p. denotes the melting point; nD20 denotes the refractive index measured at 20.C forthe sodium D-line.

TABLE E

TABLE 2

TABLE 3

The fungicidal properties of the compounds according to the invention are illustrated by results obtained in Tests 1 to 5 described hereafter; none of the compounds tested exhibited phytotoxicity. Test 1: In vivo test using Plasmopara viticola on vine plants (preventive treatment). Vine plants (Gamay variety), cultivated in pots, are treated by spraying the underside of the leaves, using a gun, with an acetone solution of the active ingredient or with an aqueous suspension of a wettable powder having the following composition by weight:

at the desired dilution, containing the relevant dose of the active ingredientto be tested; each test is repeated three times. After 48 hours, contamination of the plants with Plasmopara viticola is carried out by spraying the underside of the leaves with an aqueous suspension of fungus spores (about 80,000 units/cc). The pots are then placed for 48 hours in an incubation cell at 100% relative humidity and at 20[deg]C. The plants are checked 9 days after infestation. Underthese conditions, it is observed that, at a dose of 0.25 g/litre, compounds 1 to 7, 10, and 14 to 16 effect a total protection (> 95%), compounds 9 and 13 effect a good protection (from 75 to 95%) and compounds 11 and 12 effect a moderate protection (from 50 to 60%) against the fungus. Several of these compounds also exert a good action against mildew at doses well below 0.25 g/litre (e.g. compounds 1, 2, 3, 5, 6, 7, 9 and 16 also effect a total protection at a dose of 63 mg/litre). Furthermore, in all these experiments, no phytotoxicity phenomenon on the plants was observed. Test 1b: In vivo systemic test using vine mildew by absorption through the roots Several vine cuttings (Gamay variety) are placed in flasks containing a nutrient solution. These young vine plants are watered with an aqueous solution (100 cc) containing the ingredientto be tested (0.5 g/litre). After 5 days, the vine is contaminated with an aqueous suspension ofPlasmopara viticola (100,000 spores/cc). Incubation is allowed to proceed for 48 hours in a chamber at 20[deg]C and at 100% relative humidity. The degree of infestation is observed after about 9 days and compared with an infested control plant which has been watered with distilled water (40 cc). Under these conditions, it is observed that compound 2, absorbed by the roots, effects a total protection of the vine leaves against mildew, which clearly shows the systemic character of this compound. Test 2: In vivo survival test using phytophtora infestans on tomato leaves Tomato plants (Marmande variety), which have been cultivated in a greenhouse and are 60 to 75 days old, are treated by spraying them with a suspension containing 2 g/litre of the active product to be tested. After 48 hours, the leaves are cut off and each placed in a Petri dish (diameter 11 cm), the bottom of which has been covered with a moist filter paper beforehand (5 folioles/dish: 2 dishes/product/dose). The inoculum is then applied by depositing plugs of filter paper (diameter: 9 mm) soaked with a suspension of spores (3 plugs/foliole). The suspension of spores (zoo sporanges) is obtained from a 20 day old Phytophtora infestans culture on a medium based on chick-pea flour. The experiment is kept at 16[deg]C for 8 days. Observations are made by evaluating the surface area of the leaves infested by the fungus. Under these conditions, it is observed that compound 2 effects a total protection of the tomato leaves. Test 3: In vivo test using Peronospora tabacina on tobacco Tobacco plants (PBD6 variety), which have been cultivated in a greenhouse and are one month old, are preventively treated on the underside of the leaves using an aqueous suspension of a wettable powder having the same composition as that described in Test 1. After 48 hours, contamination is carried out by spraying the underside of the leaves with an aqueous suspension ofPeronospora tabacina spores (100,000 spores/ml). The tobacco plants are then placed for48 hours in an enclosure at 100% relative humidity and at a temperature of 20[deg] to 25[deg]C. Observation is carried out in a plastic cloth cell which ensures a relative humidity of 80 to 100%. Observations are made 6 day after contamination. Under these conditions, it is observed that, at a dose of 250 ppm, compound 2 effects a total protection of the tobacco plants, combined with complete absence of phytotoxicity. Test 4: In vivo test using Erysiphe graminis on barley Barley, in pots, which has been sown in loam, is treated at the 10 cm high stage by spraying it with a wettable powder having the same composition as that described in Test 1. The experiment is repeated twice per dose. After48 hours, the barley plants are sprinkled with spores ofErysiphegraminis from diseased plants. Observations are made 12 days after contamination. Under these conditions, it is observed that compounds 1, 2, 4, 5, 7, 9 and 10 effect a fairly good protection (from 50 to 75%) of the barley plants. Test 5: In vivo test using Uromices phaseoli, which is responsible for bean rust Bean plants are cultivated in pots of diameter 8 cm. At the two cotyledon leaf stage, the plants are treated by spraying them with the products to be studied, at the desired dose. After 48 hours, the beans are contaminated with a suspension of spores of Uromices phaseoli (50,000 spores/cc), obtained from contaminated plants. The beans are then placed in a climatic cell controlled in the following manner:

for 48 hours, and the humidity is then reduced to 80%. The plants are checked 15 days after contamination by comparison with an untreated control plant. Under these conditions, it is observed that compounds 1,4,6,9 and 16 effect a good protection (from 60 to 95%) of the bean plants against rust. Compound 5 effects a moderate protection (50%). The results obtained in the aforedescribed Tests clearly illustrate the remarkable fungicidal properties of the compounds according to the invention against very diverse species of fungi, whether this be phycomycetes (mildew), ascomycetes (oidium) or basidiomycetes (rust), and also their lack of phytotoxicity. These compounds can therefore be used for combating fungal diseases, in both a preventive and a curative capacity, and especially for combating those diseases due to the above fungi, in plants in general and, in particular, in vine, tobacco, hop and tomato plants, cereals and cucurbitaceae.The use doses can vary within wide limits, depending on the virulence of the fungus and the climatic conditions. In general, compositions containing from 0.001 to 5 g/l of active ingredient are very suitable. For use in practice, the compounds of general formula (I) are rarely employed alone. Mostfrequently, they form part of compositions which generally comprise, in addition to the active compound(s) according to the invention, a carrier and/or a surface-active agent compatible with the compound(s) and suitable for use in agricultural compositions. The term "carrier" in the sense of the present description denotes an organic or inorganic, natural or synthetic material with which the active ingredient is associated in order to facilitate its application to plants, to seeds orto the soil, or in orderto facilitate its transportation or handling. This carrier should therefore be inert and acceptable in agriculture, in particularto the plant concerned. The carrier can be solid (e.g. clays, natural or synthetic silicates, resins, waxes and solid fertilisers) or liquid (e.g. water, alcohols, ketones, petroleum fractions, chlorohydrocarbons or liquefied gases). The surface-active agent can be an emulsifying, dispersing or wetting agent, and each of these can be ionic or non-ionic. Examples which may be mentioned are salts of polyacrylic acids or of ligninsulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, products resulting from the polycondensation of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates) and phosphoric acid esters of alcohols or of polyoxyethyleneated phenols. The presence of at least one surface-active agent is essential if the inert carrier is a liquid. The compositions according to the invention can be prepared in the form of wettable powders, soluble powders, dusting powders, granules, solutions, in particular aqueous solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. They generally contain between 0.0001 and 95% (by weight) of active ingredient. The wettable powders are usually prepared so that they contain from 20 to 95% by weight of active ingredient, and they usually contain, in addition to the solid carrier, from 0 to 5% by weight of a wetting agent, from 3 to 10% by weight of a dispersing agent and, where necessary, up to 10% by weight of one or more stabilisers and/or other additives such as penetrating agents, adhesives or anti-caking agents and dyestuffs. By way of example, the composition of a wettable powder is given in Example 2 wherein the expressed percentages are by weight. EXAMPLE 2

Granules, which are intended to be disposed on the soil, are usually prepared so that they have dimensions of between 0.1 and 2 mm; they can be manufactured by agglomeration or impregnation. In general, the granules contain from 0.5 to 25% of active ingredient, and from 0 to 10% by weight of additives such as stabilisers, slow-release modifiers, binders and solvents. Emulsifiable concentrates which can be applied by spraying, after dilution with water, usually contain in addition to the solvent 10 to 50% by weight/volume of active ingredient, from 2 to 20% by weight/volume of an emulsifying agent and, where necessary, from 2 to 20% by weight/volume of suitable additives such as stabilisers, penetrating agents, corrosion inhibitors, dyestuffs and adhesives. By way of example, the composition of an emulsifiable concentrate is given in Example 3, the amounts being expressed in g/litre. EXAMPLE3 active ingredient (compound 7) 400 g/litre alkali metal dodecylbenzenesulphonate 24 g/litre oxyethyleneated nonylphenol containing 10 molecules of ethylene oxide 16 g/litre cyclohexanone 200 g/litre aromatic solvent q.s.p. 1 litre Suspension concentrates, which can also be applied by spraying, are prepared in such a way that a stable fluid product which does not settle out is obtained, and they usually contain from 10 to 75% by weight of active ingredient, from 0.5 to 15% by weight of surface-active agents, from 0.1 to 10% by weight of thixotropic agents, from 0 to 10% by weight of suitable additives such as anti-foam agents, corrosion inhibitors, stabilisers, penetrating agents and adhesives, and, as the carrier, water or an organic liquid in which the active ingredient is substantially insoluble;certain solid organic materials or inorganic salts can be dissolved in the carrier to assist in preventing sedimentation or to act as anti-freeze agents when water is the carrier. Aqueous dispersions and aqueous emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, fall within the general scope of the present invention. The emulsions can be of the water-in-oil type or of the oil-in-water type and they can have a thick consistency such as that of a "mayonnaise". The compositions according to the invention can contain other ingredients, for example protective colloids, adhesives or thickeners, thixotropic agents, stabilisers or sequestering agents, as well as other known substances having pesticidal properties, in particular insecticidal or fungicidal properties. The present invention also includes within its scope a method for preventing ortreating fungal diseases in plants which comprises applying to the plant or to its environment a composition comprising at least one compound of general formula (I) and a carrier therefor and/or at least one surface-active agent as hereinbefore described.

Claims

bonylalkyl) - acetamide phosphate derivatives of the general formula:

wherein X represents a halogen atom or an alkyl radical containing 1 to 4 carbon atoms,/? represents zero or 1, 2 or 3, Y represents the methylene or ethylidene radical, R, and R2 have the same or different significances and each represents a halogen atom, an alkyl radical containing 1 to 4 carbon atoms or an alkoxy radical containing 1 to 4 carbon atoms, R3 represents an alkyl radical containing 1 to 4 carbon atoms, and R4 and R5 have the same or different significances and each represents an alkyl radical containing 1 to 18 carbon atoms optionally carrying one or more substituents selected from halogen atoms and alkoxy radicals containing 1 to 4 carbon atoms. 2. Compounds according to claim 1 of the general formula:

wherein R1' and R2. have the same or different significances and each represents a halogen atom or the methyl radical, R3 is as defined in claim 1, and R4. and R5' have the same or different significances and each represents an alkyl radical containing 1 to 18 carbon atoms, the carbon atoms of which are primary, secondary or tertiary, optionally substituted by an alkoxy radical containing 1 to 4 carbon atoms.

3. Compounds according to claim 1 or 2 wherein R3 represents the methyl radical.

4. Compounds according to claim 1 or 3 wherein R, and R2 both represents the methyl radical.

5. Compounds according to claim 2 or 3 wherein R1' and R2, both represent the methyl radical.

6. Compounds according to claim 1 or 3 wherein X represents a chlorine atom and n represents 1, 2 or 3. 7. Compounds according to claim 2 or 3 wherein R,. and/or R2' when a halogen atom represents chlorine.

8. Compounds according to claim 2 wherein R1, and R2. both represent the methyl radical, R3 represents the methyl radical, and R4, and R5. have the same or different significances and each represents an alkyl radical containing 2 to 12 carbon atoms optionally substituted by an alkoxy radical containing 1 to 4 carbon atoms.

9. Compounds according to claim 1,3,4, or 6 wherein R4 and R5 in general formula (I) both represent the same radical.

10. Compounds according to claim 2, 3, 5, 7 or wherein R4, and R5, in general formula. (II) both represent the same radical.

- di - n - propylphosphonothioyl) mercaptoacetyl] - 2, 6- dimethylaniline.

12. /V-[1 - (Methoxycarbonyl) ethyl] -N-[S- (0, 0 - diethylphosphonothioyl) mercaptoacetyl] - 2, 6dimethylaniline. 13. N-[1- -(Methoxycarbonyl) ethyl] - N - [S - (0, 0 - di - isopropylphosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline.

14. /V-[1 - -(Methoxycarbonyl) ethyl] -/V-[S- (0, 0 - di - n - butylphosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline.

15. /V-[1 - (Methoxycarbonyl) ethyl] -N-[S- (0, 0 - di - sec- butylphosphonothioyl) mercaptoacetyl] 2,6-dimethylaniline.

- di - isobutylphosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline.

- di - 2 - methoxyethyl - phosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline. 18. N - [1 - -(Methoxycarbonyl) ethyl] - N-[S- (0, 0 - di - 2 - chloroethyl - phosphonothioyl) mercaptoacetyl] - 2,6 - dimethylaniline.

- di - isobutylphosphonothioyl) mercaptoacetyl] - 2 chloro - 6 - methylaniline.

- di - n - propylphosphonothioyl) mercaptoacetyl] - 2 - chloro - 6 - methylaniline.

21. N- [1 - -(Methoxycarbonyl) ethyl] N-[S-(0,0 - diethylphosphonothioyl) mercaptoacetyl] - 2,4,6 trimethylaniline.

22. /V-[1 -(Methoxycarbonyl) ethyl] -N-[S- (0,0 - diethylphosphonothioyl) mercaptoacetyl] - 3 chloro - 2, 4, 6 - trimethylaniline.

diethylphosphonothioyl) mercaptoacetyl] - 2,6 dimethylaniline.

24. /V-[1 - -(Methoxycarbonyl) ethyl] -N-[S- (0, 0 - di - n - pentylphosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline. 25. N-[1- (Methoxycarbonyl) ethyl] -N-[S- (0, 0 - di - isopentylphosphonothioyl) mercaptoacetyl] - 2, 6 - dimethylaniline.

26. /V-[1 - (Methoxycarbonyl) ethyl] -N-[S- (0, 0 - di - n - dodecylphosphonothioyl) mercaptoacetyl] 2, 6-dimethylaniline.

27. /V-[1 - (Methoxycarbonyl) ethyl] - N - [S - (0, 0 - di - neopentylphosphonothioyl) mercaptoacetyl] 2, 6- dimethylaniline.

28. A process forthe preparation of a compound as claimed in claim 1 which comprises reacting an aniline derivative of the general formula:

(wherein the various symbols are as defined in claim 1) with a phosphorus compound of the general formula:

wherein A represents a halogen atom or the hydroxy radical, and R4 and R5 are as defined in claim 1.

29. Process according to claim 28 wherein A represents a chlorine atom. 30. Process forthe preparation of a compound as claimed in claim 1 which comprises reacting an N(substituted phenyl) -N- (alkoxycarbonylalkyl) chloroacetamide of the general formula:

(wherein the various symbols are as defined in claim 1) with an alkali metal salt or ammonium salt of a dithiophosphoric acid derivative of the general formula:

wherein Me represents an alkali metal atom or the ammonium group, and R4 and R5 are as hereinbefore defined.

31. Process for the preparation of an N - (substituted phenyl) -N - (alkoxycarbonylalkyl) - acetamide phosphate as claimed in claim 1 substantially as hereinbefore described with especial reference to Example 1.

- alkyl) - acetamide phosphates of the general formula specified in claim 1 when prepared by a process claimed in any one of claims 28 to 31. 33. A fungicidal composition which comprises, as active ingredient, at least one compound as claimed in any one of claims 1 to 27 in association with at least one carrier and/or surface-active agent compatible with the said compound(s) and suitable for use in agricultural fungicidal compositions.

34. A fungicidal composition according to claim 33 in which the carrier is water and, in addition, the composition contains a surface-active agent.

35. A fungicidal composition according to claim 33 in which the carrier is an organic solvent and, in addition, the composition contains a surface-active agent.

36. Afungicidal composition according to claim 33 which comprises a said active compound, an organic solvent therefor, water and a surface-active agent. 37. Afungicidal composition according to any one of claims 33 to 36 in which the quantity of active compound is from 0.0001% to 95% by weight of the composition.

38. Afungicidal composition according to claim 33 in which the carrier is a solid.

39. A fungicidal composition according to claim 33 in the form of a wettable powder which comprises 20 to 95% of said active compound, a solid carrier therefor, from 0 to 5% of a wetting agent and from 3 to 10% of a dispersing agent, the said percentages being by weight.

40. Afungicidal composition according to claim 33 in the form of granules which comprise 0.5 to 25% of said active compound, a solid carrier therefor and from 0 to 10% of suitable additives, the said percentages being by weight. 41. A fungicidal composition according to claim 33 in the form of an emulsifiable concentrate which comprises a said active compound, an organic solvent therefor and an emulsifying agent, the percentage (weight/volume) of the active compound in the composition being from 10 to 50%, and the percen- tage (weight/volume) of the emulsifying agent in the composition being from 2 to 20%.

42. A fungicidal composition according to claim 33 in the form of a suspension concentrate which comprises 10 to 75% by weight of said active compound, a liquid carriertherefor, from 0.5 to 15% by weight of a surface-active agent and from 0.1 to 10% by weight of a thixotropic agent.

43. A fungicidal composition according to any one of claims 33 to 42 in which the surface-active agent is a non-ionic compound. 44. A fungicidal composition according to any one of claims 32 to 43 which includes another pesticide compatible with the active compound and with the carrier and/or surface-active agent.

45. A fungicidal composition according to claim 33 substantially as hereinbefore described with especial reference to Example 2 or 3.

46. A method of preventing or treating fungal diseases in plants which comprises applying to a plant or its environment a compound as claimed in any one of claims 1 to 27 or a fungicidal composition comprising the said compound as claimed in any one of claims 33 to 45.

47. A method according to claim 46 in which a liquid composition is applied to the plant, the composition containing from 0.001 to 5 g of active compound per litre of liquid diluent.