GB2092585A - Fungicidal oxazolidinyl-2-one derivatives - Google Patents

Abstract

Novel compounds of the formula <IMAGE> wherein R1 is <IMAGE> R7 and R8 are alkyl, halogen or alkoxy, R9 is hydrogen, alkyl or halogen, R2 is Co &cirf& CH2 &cirf& A &cirf& R10, A is O or S, R3, R4, R5 and R6 are each hydrogen or alkyl, R10 is H, -COR11, COOR11, CONR11R12, -SO2R11, SO2NR11R12, CSR11, CSNR11R12 or CSOR11 R11 and R12 are substituents, possess fungicidal activity.

Description

SPECIFICATION Fungicides The present invention provides compounds useful in the combatting of phytopathogenic fungi.

More specifically the present invention provides compounds of formula I,

wherein R, is

wherein R7 and R8, independently, are C1-4 alkyl, halogen or C1-4 alkoxy, and R9 is hydrogen, C1-4 alkyl or halogen.

R2 is CO-CH2-A-R10 wherein A is O or S, and R10 is hydrogen, -COR11, COOR11, CONR11R12, -SO2R11, SO2NR11R12, CSR11,CSNR11R12 or CSOR11, R11 is C1-6 alkyl, C2-6alkenyl, C2-4alkinyl, C2-6cycloalkyl, unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, alkoxy, alkylthio, CN or SCN; or phenyl unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, alkyl, alkoxy or NO2, R,2 is hydrogen or has a R11 significance, R3, R4, R5 and R6 are independently hydrogen or C1-4 alkyl.

When any of R3, R4, R5, Re, R, R8, R9, R11 or R,2 is or includes an alkyl group (e.g. alkoxy), this is preferably C1-3alkyl, i.e. methyl, ethyl, n-propyl or i-propyl.

When either of R7 or Re is halogen, this is F, Cl, Br or I, preferably F, Cl or Br, more preferably Cl or Br, particularly Cl.

When any of R9, R, or R,2 is or includes halogen this is F, Br or I, preferably F, Cl or Br, particularly Cl or Br.

R7 and R8 are preferably in the 2- and the 6-position of the phenyl group to which they are bound.

They are preferably identical.

When one of R3 and R4 is C,~4alkyl, the other is preferably hydrogen.

When one of R5 and R8 is C1-4alkyl, the other is preferably hydrogen.

When R,2 is other than H, it is preferably identical to R".

When R11 and/or R12 are C1-6alkyl, C2-6alkenyl, C2-6alkinyl, C3-6cycloalkyl, substitutes by one or more substituents selected from the group consisting of halogen, alkoxy, alkylthio, CN or SCN they are preferably mono-substituted.

Peferred C2-6 alkenyl or C2-6alkinyl significances of R11 and/or R12 are C2-4 alkenyl or C2-4alkinyl.

When R11 and/or R,2 are phenyl substituted by one or more substituents selected from the group consisting of halogen, alkyl, alkoxy or NO2 they are preferably mono- or di-substituted.

A is preferably 0.

R10 is preferably COR11, SO2R11, SO2NR11R12 or H.

Thus, a preferred group of compounds are the compounds of formula la,

wherein R2' is -COCH2OH,-COCH2COCH3, -COCH2OSO2CH3,-COCH2OSO2N(CH3)2 R7' and R8, independently are CH3, Cl or Br and R9' is H, Cl, Br or methyl.

R7, and R8, are preferably identical.

The invention also provides processes for the production of the compounds of formula I comprising a) obtaining compounds of formula Ib

wherein R'10 has the significance of R,,, defined above, except that R'10 is not H, and R1R3,R4, R5 and R6 are as defined above, by subjecting compounds of formula II

wherein R1, R3, R4, R5, Re and A are as defined above, R1,0 is as defined above and Y is halogen to an intramolecular condensation or b) obtaining compounds of formula Ib as defined above by reacting a compound of the formula Ill

wherein R1,R3,R4,R5 and Re have the same meaning as defined above, and W is a leaving group with a compound of formula IV B-A-R10, IV wherein B is H or a metal equivalent and A and R,O' are as defined above, c) obtaining compounds of formula Ic

wherein R1,R3,R4, R5 and Re and A are as defined above by alcoholysis of corresponding compounds of formula Id

wherein R"10 is COR or SO2R, R" being as defined above and R1, R3, R4, R5, Re and A are as defined above.

The above intramolecular condensation according to process a) can be carried out in a conventional manner. The reaction is exothermic. It can e.g. be carried out in a water-free medium using as solvent an ether such as dimethoxyethane, an hydrocarbon such as toluene or another solvent which is inert under the reaction conditions. The reaction temperature is not critical and can lie between about 0 and 1 000C. Since the reaction is exothermic one starts the reaction conveniently at room temperature and allows the reaction temperature to rise gradually.

Y is preferably chlorine or bromine, particularly chlorine.

The reaction is conveniently carried out in the presence of an acid binding agent such as sodium hydride, sodium amide or a sodium alcoholate e.g. sodium ethylate.

The intramolecular condensation can also be carried out in an aqueous/organic two-phase system in the presence of an anorganic base e.g. sodium hydroxide and optionally a catalytic amount of a phase transfer catalyst.

The organic phase may comprise any appropriate inert water immiscible solvent such as hydrocarbons or halogenated carbons, e.g. xylene, toluene, o-dichlorobenzene or dichloromethane.

Appropriate phase transfer catalysts are quaternary ammonium compounds such as benyltrimethyl ammonium bromide, quaternary phosphonium compounds such as benzyltriphenyl phosphonium chloride and crown ethers such as 1 8-crown-6.

In process b) W is preferably halogen, or the sulphonyloxy moiety of an organic sulphonic acid e.g.

an C15alkyI-SO2-O group such as mesyloxy or a phenyl-S020 group wherein the phenyl is optionally substituted e.g. by C,~5alkyl, NO2, CN or halogen, such as p-tosyloxy.

The reaction is conveniently carried out in an organic solvent which is inert under the reaction condition, such as e.g. alcohols, hydrocarbons, halogenated hydrocarbons, nitriles such as acetonitrile, or amides such as dimethylformamide.

The reaction temperature is not critical, and may be between room temperature and the boiling point of the solvent used. The exact reaction conditions vary with the choice of Wand R0-A-B, as is known to the art. B is preferably a metal equivalent e.g. Na, K or 2Ca.

The compounds of formula Ic are suitably obtained by base catalysed alcoholysis of the corresponding compounds of formula Id. Such an alcoholysis is conveniently carried out under mild conditions, e.g. at ambient temperature, preferably in a large excess of an alcohol e.g. methanol and in the presence of a catalytic amount of a sodium alcoholate, e.g. sodium methanolate.

As will be appreciated, interconversion of one compound of formula I to another compound of formula I may be carried out in conventional manner.

The compounds of formula I, wherein R10 is other than H may for example also be prepared by acylating the corresponding compounds of formula I wherein R10 is H with an acylating agent e.g. with the acid halide (preferably acid chloride or acid bromide) or acid anhydride of R10, (R1O' being as defined above) or with R11NCO in conventional manner.

The compounds of formula II are novel. They may be obtained by acylation of compounds of formula V

wherein R1, R3, R4, R5, Re and Y are as defined above, with a compound of formula VI

wherein R'10 and A are as defined above, and Z is halogen, particularly CI, or O-COCH2AR110 wherein A and R1'0 are as defined above.

Suitable solvents for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is conveniently effected at a temperature of from about 200 to about 1 200C, e.g. 800 C.

The compounds of formula V may be obtained by reacting compounds of formula VII R1-NH-NH2 VII wherein R, is as defined above with a compound of formula VIII

wherein R3,R4,R, Re and Y are as defined above, and X is halogen, particularly Cl.

This conversion may be effected at a temperature of from about 0 to about 100C in water or in an organic solvent which is inert under the reaction conditions, conveniently in the presence of a base e.g. an organic amine or sodium hydrogen carbonate.

The compounds of formula III can be obtained by intramolecular condensation analogous to process a).

The starting materials and reagents employed in the processes described above are either known or, insofar as they are not known, they may be produced in analogous manner to the processes dcscribed herein or to known processes.

The compounds of formula I have useful fungicidal activity, particularly against phytopathogenic fungi, especially against fungi of the class Oomycetes as indicated by a significant effect in the following tests.

TEST A: Fungicidal effect against Phytophthora infestans Young potted potato plants (3-5 leaf stage) are sprayed with an aqueous spray suspension containing 0.003% (weight/volume) of a compound of formula I, e.g. 2-methylsulphonyloxy-N-(2,6 dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)acetamide (formulated in accordance with Formulation Example I). Two hours later, the treated plants are inoculated with a spore suspension of Phytophthora infestans and the plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperature of 1 60C and a day length of 1 6 hours. Disease control is evaluated 4-5 days later by comparing the treated plants with untreated, similarly inoculated plants.With the above test compound, substantial control of the fungal infestation is observed without any sign of phytotoxicity on the host plants.

TEST B: Fungicidal effect against Plasmopara viticola Young potted plants of grape vine (3-6 leaf stage) are sprayed with an aqueous spray suspension containing 0.0008% (weight/volume) of a compound of formula I, e.g. 2-methylsulphonyloxy-N-(2,6dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example I). Two hours later, the treated plants are inoculated with a spore suspension of Plasmopara viticola and the plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperature of 1 5-220C (fluctuating over a 24 hr-period) and a day length of 1 6 hours.

Disease control is evaluated 6 days after inoculation by comparing the treated plants with untreated, similarly inoculated plants. With the test compound, substantial control of the fungal infection is observed without significant sign of phytotoxicity on the host plants.

TEST C: Curative fungicidal effect against Plasmopara viticola Young potted plants of grape vine (3-6 leaf stage) are inoculated in the same way as determined in Test B, but the application of the compound, e.g. 2-methylsulphonyloxy-N-(2,6-dimethylphenyl)-N-(2oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example I), follows only after 3 days after inoculation: the incubation conditions are the same as described in Test B. Disease control is evaluated as stated in Test B. With the test compound, substantial control of the fungal infection is observed.

TEST D: Eradicative fungicidal effect against Plasmopara viticola The procedcure to evaluate this kind of activity is evaluated as described in Test C, with the exception that the treatment is carried out only 6 days after inoculation, when sporulation on the lower leaf surface is already evident. Disease control evaluated 7 days after application of, e.g., 0.012% of the compound 2-methylsulphonyloxy-N-(2,6-dimethylphenyl)-N-(2-oXo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example 1), reveals a stopping effect on already sporulating zones.

TEST E: Translation in treated leaves of grape vines Excised leaves of grape vine are treated with an aqueous spray suspension containing 0.012% of a compound of formula I, e.g. 2-methylsulphonyloxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)- acetamide (formulated in accordance with Formulation Example I), in that only the lower half of such leaves is treated. Two hours after treatment, the whole leaf is inoculated witha spore suspension of Plasmopara viticola after which the leaves are incubated in a tent providing 100% atmospheric humidity at conditions as described in Test B. Although only the lower half of the leaves was treated as stated above, with the test compound substantial disease control on the entire leaf inoculated was observed. The same effect was also observed, when only the upper half of the leaves was treated.This Test thus shows, that the 2-methylsulphonyloxy-N-(2,6-di methylphenyl)-N-(2-oxo-3-oxazolidinyl)- acetamide (formulated in accordance with Formulation Example I), is distributed within a leaf both acropetally and basipetally.

TEST F: Soil Treatment In vivo, employing Pythium aphanidermatum. The fungus is cultivated in a sterile mixture of same and forn meal (97:3 v/v); cultivation lasts for 4 days at 250C. The fungus is then mixed into a semi sterile mixture of peat and sand which then is treated with a suspension containing the formulated active ingredient to give concentration of 10 to 1 60 ppm (e.g. 1 0, 40 and 1 60 ppm) calculated per volume substrate). The substrate is transferred to pots of 5 cm diameter which are seeded with cucumber seeds. The planted pots are incubated at 240C and 6070% relative humidity in an incubation chamber for 7 days, after which disease attack is determined by comparing the number of healthy emerged plants with that in untreated, similarly inoculated check pots.The compound of Example 1, hereinafter, used in the wettable powder formulation given above provides significant disease control.

Tests analogous to Test F give similar results with peas and sugar beets.

Each of the compounds listed below in the following Examples is found to possess fungicidal properties indicating their usefulness cs fungicides.

Particuiarly effective fungicidal activity is found in the above tests with the compound of formula la wherein R,' and Re' are CH3; R9, is H; and R2, is COCH2OH or-COCH20S02CH3.

The invention therefore also provides a method of combatting phytopathogenic fungi, especially of the class Oomycetes, in plants, seeds or soil, which process comprises treating the plants, seeds or soil with a fungicidally effective amount of a compound of formula I.

Fungi of the class Oomycetes, against which the method of the invention is particularly effective, are those of the genus Phytophthora in plants such as potatoes, tomatoes, tobacco, citrus, cacao, rubber, apples, strawberries, vegetables and ornamentals, e.g. Phytophthora infestans in potatoes and tomatoes; of the genus Plasmopara viticola in grape vines; of the genus Peronospora in plants such as tobacco, e.g. Peronospora tabacina in tobacco; of the genus Pseudoperonospora in plants such as hops and cucumber, e.g. Pseudoperonospora humuli in hops; of the genus Bremia in plants such as lettuce, e.g.Bremia lactucae in lettuce; of the genus Pythium causing damping-off and root rots in a great number of plants, such as vegetables, sugar beets, ornamentals and conifers, e.g. Pythlum aphanidermatum in sugar beets; of the genus Sclerospora in plants such as sorghum and corn, e.g.

Sclerospora sorghis in sorghum.

For use in the method of the invention, the amount of the preparation to be employed will vary depending on such factors as the species of fungi to be combated, the time and nature of application and the amount and nature of the compound of formula I employed in the preparation.

However, in general, satisfactory results are obtained when applied to a locus, e.g. on crops or to soil with a dosage rate in the range of from 0.05 to 5 kg, preferably from 0.1 to 3 kg of a compound of formula I/ha treated locus, the application being repeated as required. When employed as a seed dressing, satisfactory results are obtained when applied at a rate of from about 0.05 to 0.5, preferably about 0.1 to 0.3 g compound of formula l/kg seed.

Depending on the circumstances, the compounds of formula I may be used in association with other pesticides e.g. fungicides, bactericides, insecticides, acaricides, herbicides or plant growth regulating agents in order to enhance their activity or to widen their spectrum of activity.

A particularly preferred method of the invention comprises applying to the locus to be treated fungicidally effective aggregate amounts of a compound a) comprising a compound of formula I and of one or more compounds selected from a copper fungicide, captan, folpet, mancozeb or maneb.

Examples of copper fungicides suitable for use in association with a compound of formula I are e.g.

copper (II) carbonate, copper (II) calcium sulphate, copper (II) calcium oxychloride, tetracupric oxychloride, Bordeaux mixture, Burgundy mixture, cuprous oxide, cupric hydroxide, copper (II) oxychloride or also copper complexes such as copper triethanolamine hydroxide of the formula [CuN(CH2CH20H)3]-(0H)2, commercially available under the Trademark K-Lox, or bis(ethylenediamine)-copper (II) sulphate of the formula [Cu(H2NCH2CH 2NH2)2]S04, commercially available under the Trademark Komeen, and mixtures thereof, particularly cuprous oxide, copper (II) oxychloride, cupric hydroxide and a mixture of copper (II) calcium sulphate and copper (II) oxychloride.

Captain, Folpet, Manoczeb and Maneb are the common names for protective fungicides effective against foliage diseases (Pesticide Manual, 5th Ed., by H. Martin and C. R. Worthing, page 76,281,328 and 329 resp.).

The The compounds of formula I are conveniently employed as fungicidal compositions in association with ågriculturally acceptable carriers or diluents. Such compositions also form part of the present invention. They may contain, aside from a compound of formula I as active agent, other active agents, such as fungicides. They may; be employed in either solid or liquid application forms e.g..in the form of a wettable powder, an emulsion concentrate, a water dispersible suspension concentrate ("flowable"), a dusting powder, a granulate; a delayed release form, incorporating conventional carriers, diluents and/or adjuvants. -Such compositions may be produced in conventional manner, e.g. by mixing the active ingredient with a carrier and other formulating ingredients.

Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol.

In general, the formulations include from 0.01 to 90% by weight of active agent, said active agent consisting either of at least one compound of formula I or mixtures thereof with other active agents, such as fungicides. Concentrate forms of compositions generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.

The invention is illustrated by the following Examples wherein parts and percentages are by weight and temperatures are in OC.

FORMULATION EXAMPLE I: Wettable powder 50 Parts of 2-methylsulphonyloxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide are ground with 2 parts of lauryl sulphate, 3 parts sodium lignin sulphonate and 45 parts of finely divided kaolinite until the mean particle size is below 5 microns. The resulting wettable powder so obtained is diluted with water before use to a concentration of between 0.01% to 5% active agent.

The resulting spray liquor may be applied by foliar spray as well as by root drench application.

FORMULATION EXAMPLE 2: Granulate Onto 94.5 parts by weight of quartz sand in a tumbler mixer is sprayed 0.5 parts by weight of a binder (non-ionic tenside) and the whole thoroughly mixed. 5 Parts by weight of powdered 2 methylsulphonyloxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide are then added and thoroughly mixing continued to obtain a granulate formulation with a particle size in the range of from 0.3 to 0.7 mm. The granulate may be applied by incorporation into the soil adjacent the plants to be treated.

FORMULATION EXAMPLE 3: Emulsion Concentrate 25 Parts of a compound of formula I, e.g. the compound of Example 8.1, hereinafter given, 65 parts of xylene, 10 parts of the mixed reaction product of an alkylphenol with xyleneoxide and calciumdodecylbenzene sulphonate are thoroughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.

EXAMPLE 1 2-4-Meihylphen yll-sulphonyloxy]-N-(2, 8-dime thylphenyl)-N-(2-oxo-3-oxazolidinylj-ace tamide A slurry of 95.5 g (0.21 mol) 2-chloroethyl 2-(4-methylphenylsulphonyloxyacetyl)-2-(2,6dimethylphenyl)-hydrazine carboxylate in 500 ml dry methanol are slowly added with stirring to a solution of 12.4 g (0.23 mol) sodium methanolate in 200 ml dry methanol. After the exothermic reaction is completed, the mixture is stirred for two hours at room temperature, then freed of the solvent in vacuo. The residue is dissolved in dichloromethane, washed twice with water, dried over MgSO4 and evaporated.

The residue was chromatographed on silica gel using toluene/ethylacetate as eluant, yielding the title compound as a yellow oil, which solidifed upon treatment with toluene to give a colourless solid, m.p. 1225C.

EXAMPLE 2 Following the procedure of Example 1 but employing the appropriate starting material of formula II the following compounds of formula I are obtained (Table A: R3, R4, R5 and R6 being H).

TABLE A

x. R7R8R9. A-R10 2-1 2-CH3 6-CH3 3-C1 OS02 OSO2CH3 2-2 2-CH3 6-CH3 3-Br 2 z : 2-3 2-CH3 6-CH3 3-CH3 2 CH3 EXAMPLE 3 2-A cetoxy-N42, 6-dimethylphenyl)-N-(2-oxo-3-oxazolldinyl)-ace tamide A mixture of 70.6 g (0.25 mol) 2-chloro-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)- acetamide and 49.2 g (0.6 mol) dry sodium acetate are heated with stirring in 500 ml dry dimethylformamide at 11 OOC for three hours. The cooled mixture is filtered with suction, the residue washed thoroughly with dimethylformamide, and the combined filtrates concentrated in vacuo.The residue is dissolved in dichloromethane, washed with water, dried and freed of the solvent and yield after crystallization from ethanol the title compound as colourless crystals, m.p. 1 02-60C.

EXAMPLE 4 Following the procedure of Example 3, but employing the appropriate starting material of formula III, wherein W is Cl or p-tosyl, and of formula IV wherein B is Na, the following compounds of formula I are obtained (Table B: R3, R4, R5 and R6 being H).

TABLE B

Vex. R8* j R9 A-R10 Characteriza tion 0 1 4-1 CH3 Cl H -OC-CH3 122-5 0 4-2 CH3 CH3 ~ H -OC-CH20CH3 oil 0 4-3 CH3 C1 H -ac-cH2ocH3 oil 0 4-4 CH3 CH3 H -SC-CH3 0 4-5 CH3 CH3 3-C1 -OC-CH3 0 4-6 CH3 CH3 3-Br -OCO'-CH3 115-7e ~ -- 'S 4-7 CH3 CH3 H -SCN(CH3)2 173-5 S'.

4-8 CH3 CH3 H -SCOCH3 -scocH, t CH3 CH3 H -OC < * R7 and R8 being in 2- and 6-position respectively.

EXAMPLE 5 2-Hydroxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide A solution of 24.8 g (0.46 mol) sodium methanolate in 200 ml dry methanol is slowly added to a slurry of 258 g (0.843 mol) 2 acetoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide, prepared as in Example 3, in 2.5 1 dry methanol with stirring. The mixture, which becomes a clear solution after 30 minutes, is stirred for a total of two hours at room temperature, then freed of the solvent in vacuo. The resulting oil is poured into water and the pH adjusted to pH=2 with 2N aqueous HCI. The product is extracted with three portions of chloroform, the combined organic layers washed with water and dried over MgSO4, and the solvent evaporated in vacuo to yield a colourless solid.The title compound is obtained as colourless crystals from ethanol, m.p. 138-9 , EXAMPLE 6 Following the procedure of Example 5, but alcoholizing the appropriate starting materials of formula I, wherein R2 is COCH2OCOCH3, the following compounds of formula I, wherein R2 is COCH2OH are obtained (Table C: R3, R4, R5 and Re being H).

TABLE C

Ex. R7 R8 R9 A-R10 Characterization 6-1 2-CH3 6-Cl H OH 169-71 6-2 2-CH3 6-CH3 3-CI OH 6-3 2-CH3 6-CH3 3-CH3 OH 6-4 2-CH3 6-CH3 3-Br OH 139;;41' EXAMPLE 7 2-(Dimethylaminosulphonyloxy)-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide 13.2 g (0.05 mol) 2-hydroxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide is added in portions to a slurry of 2.2 g (appr. 0.05 mol) sodium hydride (as 5560% dispersion in oil) in 100 ml dry dimethoxyethane with stirring at 10-1 5 C under a blanket of nitrogen. The mixture is stirred at room temperature for half an hour, and then are added 7.9 g (0.055 mol) dimethylsulphamic acid chloride. The mixture is heated to 500 and stirred overnight at this temperature. The mixture is filtered, after cooling, the filtrate concentrated in vacuo, the resulting oil dissolved in chloroform and washed thoroughly with water, dried over MgSO4 and freed of the solvent in vacuo.

The title compound is obtained as a yellow, sticky oil after chromatography on silica gel, using a 1:1 mixture of toluene/ethyl acetate as eluent.

EXAMPLE 8 Following the procedure of Example 7, but employing the appropriate compounds of formula Ic and acid chlorides RtoCI, the following compounds of formula I are obtained (Table D: R3, R4, R5 and Re being H).

TABLE D

Ex. R7* R8* Rg A-R10 Characteriza tion 8-1 CH3 CH3 H -OS02CH3 142-5" 0 8-2 CH3 CH3 H -OCOCH3 133-8 1 0 8-3 CH3 CH3 H -OCNHCH3 174-70 0 8-4 CH3 CH3 H -OCNH C1 115-20 8-5 CH3 CH3 3-C1 -OS02CH3 8-6 CH3 CH3 3-Br -OS02CH 168-72 0 8-7 CH3 CH3 3-C1 -OCNHCH3 .

* R7 and R8 being in the 2- and 6-position respectively.

Ex. R7* Raw R9 A-R10 Characterization 0 ii OH3 CH3 CH, H OCN(CH3)2 157-61" 0 II 8-9 CH3 CH3 H OCSCH2CH3 oil * R7 and R8 being in the 2- and 6-position respectively.

STARTING MATERIALS The starting materials used in Example 1 can be prepared as follows: EXAMPLE A: 2-Chloroethyl 2-(4-methylphenylsulphonyloxyacetyl)-2-(2,6-dimethylphenyl)-hydrazine carboxylate A solution of 112 g (0.45 mol) 2-(4-methylphenylsulphonyloxy)-acetyl chloride in 100 ml toluene is slowly added with stirring at room temperature to a slurry of 2-chloroethyl 2-(2,6-dimethylphenyl)hydrazine carboxylate in 500 ml toluene, and the mixture stirred at room temperature for 4 hours. The reaction mixture is then subsequently washed with water, an aqueous NaHCO3 solution and water, dried over MgSO4 and evaporated in vacuo to yield a yellowish solid, which upon recrystallization from ethanol gives the title compound as colourless crystals, m.p. 1 2570.

EXAMPLE B 2-Chioroethyl 2-(2, 6-dimethylphenyl)-hydrazine carboxylate A mixture of 17.7 g (0.1 mol) 2,6-dimethylphenyl hydrazine hydrochloride and 21.2 (0.2 mol) sodium carbonate in 50 ml water/50 ml xylene are stirred for 30 minutes at room temperature, then cooled to 5 C. 14.3 g (0.1 mol) chloroformic acid 2-chloroethylester is then added over a period of 1 hour, the temperature being maintained at 50C with external cooling. The mixture is stirred at 50C for another hour, at the end of which 100 ml water are added, the precipitate thus formed filtered off, washed with water and dried, to yield the title compound as a slightly coloured solid, m.p. 6970 .

Recrystallization from diethyl ether/light petroleum raises the m.p. to 74--5 0.

EXAMPLE C Following the procedure of Example 1, but employing starting materials analogous to compounds of formula H, wherein AR10 is, however, Cl or Br, the following compounds of formula Ill are obtained (Table E: R3, R4, R5 and Re being H), TABLE E

Ex. R, R8 Rg W Characterization m.p.

C-i 2-CH3 6-CH3 H Cl 134-6 0-2 2-CH3 6-CH3 3-CI Cl 154-7 C-3 2-CH3 6-CH3 H Br 148-4

Claims (4)

1. A compound of formula I

wherein R, is

wherein R7 and R8, independently, are C1-4 alkyl, halogen or C1-4 alkoxy, and R9 is hydrogen, C1-4 alkyl or halogen, R2 is CO-CH2-A-R10 wherein A is O or S, and R10 is hydrogen, -COR11, COOR11, CONR11R12, -SO2R11, SO2NR11R12, CSR11, CSNR11R12 or CSOR11, R11 is C1-6 alkyl, C2-6 alkenyl, C2-6 alkinyl, C3~6cycloalkyl, unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, alkoxy, alkylthio, CN or SCN: or phenyl unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, alkyl, alkoxy or NO2, R,2 is hydrogen or has a 11 significance, Rs, R4, R5 a and Re are independently hydrogen or C1-4 alkyl.

2. A method of combatting phytopathogenic fungi in plants, seeds or soil, which comprises applying to the plants, seeds or soil a fungicidally effective amount of a compound of Claim 1.

3. A fungicidally composition comprising a compound of Claim 1 in association with an agriculturally acceptable carrier or diluent.

4. A process for the production of a compound of Claim 1, characterized by a) obtaining compounds of formula Ib

wherein R10 has the significance of R1O, defined in Claim 1, except that R'10 is not H, and R1,R3,R4,R5 and Re are as defined in Claim 1 by subjecting compounds of formula II

wherein R,, R3, R4, R5, Re and A are as defined in Claim 1, R'10 is as defined in this Claim, and Y is halogen, to an intramolecular condensation or b)obtaining compounds of formula ib as defined in Claim 1, by reacting a compound of the formula III

wherein R1, R3, R4, R5 and Re have the same meaning as defined in Claim 1, and W is a leaving group with a compound of formula IV B-A-R10, IV wherein B is H or a metal equivalent and A and R10' are as defined in Claims 1 and 4 resp., c) obtaining compounds of formula Ic

wherein R1, R3, R4, R5, R6 and A are as defined in Claim 1, by alcoholysis of corresponding compounds of formula Id

wherein R'' 10 is COR11 or SO2R11, R11 being as defined in Claim 1, and R1, R3, R4, R5, R6 and A are as defined in Claim 1.