GB2058059A

GB2058059A - Novel N-acylamino-2-oxo-3- oxazolidine derivatives and their use as fungicides

Info

Publication number: GB2058059A
Application number: GB8026318A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-08-16
Filing date: 1980-08-13
Publication date: 1981-04-08
Also published as: GB2058059B; CY1247A

Abstract

Novel N-acylamino-2-oxo-3- oxazolidine derivatives of formula I, <IMAGE> wherein R1 is <IMAGE> 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-R10, wherein R10 is C1-4 alkoxy-C1-4 alkyl, C1-4 alkylthio-C1-4 alkyl, 2-furyl, 2- tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1- imidazolylmethyl, 1-pyrazolylmethyl, 2- tetrahydrofuryloxymethyl, 2- tetrahydropyranyloxymethyl, or C1-4 halogenalkyl, and R3, R4, R5 and R6 are independently hydrogen or C1-4 alkyl, as useful as fungicides.

Description

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

More specifically the present invention provides compounds of formula I, wherein R1 is

wherein R7 and R8, independently, are C1-4alkyl, halogen or C1-4 alkoxy, and Rg is hydrogen, C1-4 alkyl or halogen, R2 is CO-R10, wherein R10 is C1-4 alkoxy-C14 alkyl, C1-4 alkylthio-C1-4alkyl, 2-furyl, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1-imidazolylmethyl, 1-pyrrazolylmethyl, 2-tetrahydrofu ryloxymethyl, 2tetrahydropyranyloxymethyl, or C1.4halogenalkyl, and R3, R4, R5 and R6 are independently hydrogen or C1.4alkyl.

When any of R3, R4, Re, Re, R7, R8 or R9 is or includes an alkyl group (e.g. alkoxy), this is preferably C1-3 alkyl, i.e. methyl, ethyl, n-propyl or i-propyl.

When either of R7 or R8 is halogen, this is F, Cl, Br of I, preferably F, Cl or Br, more preferably Cl or Br, particularly Cl.

When any of Rg or R10 is or includes halogen this is F, Cl, Br or I, preferably F, Cl or Br, particularly Cl or Br.

Preferred halogenated 2-furyl significances of R1O are monohalogenated 2-furyl, e.g. 5-chloro-2-furyl and 5-bromo-2-furyl.

Preferred C, 4 halogenalkyl significances of R10 are C1.4chloroalkyl, or C1-4bromoalkyl, e.g. chloromethyl, bromomethyl and C2He CHBr-; Preferred halogenated 2-tetrahydrofuryl significances of R10 are monohalogenated 2-tetrahydrofury, particularly monochlorinated or monobrominated 2-tetrahydrofury! e.g. 5-chloro-2-tetrahydrofuryl.

Preferred C1.4alkoxy-C1.4alkyl significances of R10 are C1.3alkoxymethyl, particularly CH3OCH2- and C2H5OCH2-.

Preferred C1.4alkylthio-C1.4alkyl significances of R10 are C1.3alkylthiomethyl, e.g. CH3SCH2-; R lo is preferably C1.4alkoxy-C1.4a 4alkyl, 2-furyl or 5-halo-2-furyl.

When one of R3 and R4 is C1.4alkyl, the other is preferably hydrogen.

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

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

wherein R2' is -COCH2OCH3, -COCH2OC2H5, -CO-(2-furyl) or-CO-(5-halo-2-furyl), R7 and R8' independently are CH3, Cl or Br and R9 ' is H, Cl, Br or methyl whereby R7' and R8' are preferably identical.

According to a further aspect of the present invention, the compounds of formula I are produced by intramolecular condensation of a compound of formula 11

wherein R1, R3, R4, , R5, R6 and R10 are as defined above and Y is halogen.

Y is preferably chlorine or bromine, particularly chlorine.

The above intramolecular condensation 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 an other solvent which is inert under the reaction conditions. The reaction temperature is not critical and can lie between about 0 and 1 00 C. Since the reaction is exothermic one starts the reaction conveniently at room temperature and allows the reaction temperature to rise gradually.

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-dichloro benzene or dichioromethane.

Appropriate phase transfer catalysts are quaternary ammonium compounds such as benzyltrimethyl ammonium bromide, quaternary phosphonium compounds such as benzyltriphenyl phosphonium chloride and crown ethers such as 18-crown-S.

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

wherein R1, R, R4, R5, R6 and Y are as defined above, with a compound of formula IV, 0 R10 -C- Z IV wherein Rao is as defined above, and Z is halogen, particularly Cl, or O-CORlo, wherein Rro is 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 500 to about 120do, e.g. 80 C.

The compounds of formula Ill may be obtained by conversion of compounds of formula V, R1 -NH-NH2 V wherein R1 is as defined above, with a compound of formula VI

wherein R3, R4, R5, R6 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 10-C 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 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 described herein orto 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.

TestA : 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-methoxy-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 6zC and a day length of 16 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 phytotoxivity on the host plants.

TestB : FungicidaleffectagainstPlasmopara viticola Young potted plants of grape vine (3-6 leaf stage) are sprayed with an aqueous spray suspension containing 0.0008% (weightvolume) of a compound offormula I, e.g. 2-methoxy-N-(2,6-dimethylphenyl)-N (2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example 1). 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 15 - 22"C (fluctuating over a 24hr-period) and a day length of 16 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 any 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-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)acetamide (formulated in accordance with Example Il, 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 procedure to evaluate this kind of activity is evaluated as described in Test C, with the exception that the treatment is carred out only 6 days after inoculation, when sporulation on the lower leaf surface is alreay evident. Disease control evaluated 7 days after application of, e.g., 0.012% of compound 2-methoxy-N-(2,6dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide (formulated in accordance with Formulation Example 1), reveals a stopping effect on already sporulating zones, in that sporulation ceases completely.

Test E : Translocation in treated leaves of grape vines Excised leaves of grape vine are treated with an aqueous spray suspension containing 0.012% of compound of formula I, e.g. 2-methoxy-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 with a 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 observed, when only the upper half of the leaves was treated. This Test thus shows, that the 2-methoxy-N-(2,6dimethylphenyl)-N-(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 vico, employing Pythium aphanidermatum. The fungus is cultivated in a sterile mixture of sand and corn meal (97:3 v v) to which water is added in a ratio of about 1:4 (v v); cultivation lasts for 4 days at 25JC. 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 160 ppm (e.g. 10,40 and 160 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 60 - 70% 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 full 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 as fungicides.

Particularly effective fungicidal activity is found in the above test with the compounds of formula la wherein R2, is COCH2OC2Hs, R7' and R8' are CH3 and Rg' is H, wherein R2' is CO-(2-furyl), R7' and R8, are CH3 and Rg'is H, wherein R2, is CO-(5-bromo-24uryl), R7' and R8, are CH3 and Rg' is H, wherein R2' is COCH2OCH3, R7, R8, are Cl and Rg' is H, wherein R2, is COCH2OCH3, R7, and R8, are CH3 and Rg' is 3-Br and especially with the compound of formula la, wherein R2, is COCH2OCH3, R7, and R8' are CH3 and Rg' is H.

The invention therefore also provides a method of combating 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. Pseydoperonospora 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. Pythium 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 orto 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 05, preferably about 0.1 to 0.3 g compound of formula l/kg seed.

According to a preferred method of the invention the compounds of formula I are used in association with otherfungicideswhich are effective against phytopathogenic fungi. Such combinations having an enhanced or broadened fungicidal activity.

A particularly preferred method of the invention comprises applying to the locus to be treated fungicidally effective amounts of a component a) comprising a compound of formula I and of a component b) selected from a component b1) a copper fungicide or a component b2) captan orfolpetor a component b3) mancozeb or maneb.

Examples of copper fungicides suitable for use as component b1) are copper (li) carbonate, copper (II) calcium sulphate, copper (II) carbon 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 [Cu N(CH2CH2OH)3 ]-(OH)2, commercially available under the Trademark K-Lox, or bis(ethylenediamine)-copper (II) sulphate of the formula [Cu(H2NCH2CH2NH2)2]SO4, 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.

Captan, Folpet, Mancozeb 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 method of this invention wherein component a) and component b) are used, is effective against a wide range of phytopathogenic fungi.

Preferably component a) is applied at a rate of 100-400 g/ha and component b) at a rate of 200-2000 g/ha.

Preferably the weight ratio of component a) : component b) is in the range of 1:1 to 1:10, more preferably of 1:2to1:10,particularlyof1:2to1:7.

The method of the invention wherein component a) and component b) are used is particularly effective against phytopathogenic fungi in plants such as potato, tomato and other Solanaceae tobacco, citrus, cacao, rubber, apple, strawberry, vegetables and ornamentals, e.g. against fungi of the genus Plasmopara, e.g.

Plasmopara viticola in grape vine, of the genus Guignardia, e.g. Guignaridia bidwelllin grape vine of the genus Phoma in grape vine, of the genus Pseudopeziza, e.g. Pseudopeziza tracheiphila in grape vine, of the genus Gloeosporium, e.g. Gloeosporium ampelophagum in grape vine of the genus Botrytis in grape vine and lettuce, e.g. Botrytis cinerea in grape vine, of the genus Phytophthora, Phytophthora infestans in potato, tomato or other Solanaceae, Phytophthora parasitica in tomato or other Solanacease, Phytophthora cryptogaea in tomato and other Solanaceae, Phytophthora mexicana in tomato and other Solanaceae, Phytophthora nicotianae in tobacco and Phytophthora palmivora in rubber or cacao, of the genus Peronospora, e.g. Peronospora tabacina in tobacco, of the genus Pseudoperonospora, e.g.Pseudoperonospora tumuli in hop, of the genus Bremia in plants such as lettuce, e.g. Bremia lactucae, of the genus Pythium, e.g. Pythium aphanidermatum in sugar beet, of the genus Alternaria, e.g. Alternaria solani in potato, tomato and other Solanaceae, Alternaria tenuis in tobacco, of the genus Spondylocladium, e.g.

Spondylocladium atrovirens in potato, of the genus Rhizoctonia, e.g. Rhizoctonia solani in potato, tomato and other Solanaceae, of the genus Cladosporium, e.g. Cladosporium fulvum in tomato or other Solanaceae, of the genus Colletotrichum in plants such as cacao or tomato, e.g. Colletotrichum atramentarium in tomato or other Solanaceae, of the genus Glomeralla, e.g. Glomerella lycopersici in tomato and other Solanaceae, of Corticium spp in tomato and other Solanaceae, of the genus Botryodiplodia, e.g. Botryodiplodia theobromae in cacao. This method of the invention allows the control of a significantly wider range offungal diseases than by treatment with only one of the components.

In general, a greater than additive effect of the components is observed, especially after treatment with concentrations of component a) and component b) allowing a practically complete, more specifically more than 80%, control of the fungi, particularly when copper (II) oxychloride, cuprous oxide, captan, mancozeb or maneb is used as component b), and especially when used against phytopathogenic fungi of the class Oomycetes, especially against Oomycetes of the genus Phytophthora, e.g. Phytophthora infestans, of the genus Plasmopora, e.g. Plasmopora viticola, of the genus Peronospora, e.g. Peronospora tabaccina, of the genus Pseudoperonospora, e.g. Pseudoperonospora humuli, of the genus Bremia, e.g. Bremia lactucae, and of the genus Pyth/um, e.g. Pythium aphanidermatum.

The method of the invention wherein the components a) and b) are used, is especially indicated for combating or preventing fungi in grape vines, tomato and other Solanaceae and in cacao when a component b1) is used, in grape vines when a component b2) is used and in grape vines, potato, tomato and other Solanaceae, tobacco and hop when a component b3) is used.

The components a) and b) may be employed in formulation form and applied e.g. as a tank mix or separately. They are, however, preferably applied in admixture in the form of an aqueous spray or oil based concentrate.

The useful fungicidal activity obtained after treatment with a component a) and b) is illustrated by the following tests.

Test G : Fungicidal effect against Phytophthora infestans The test is carried out as described in Test A, whereby the plants are treated with a tank mix of an aqueous spray suspension containing component a) and component b) in concentrations indicated in Tables A1 to A6 below. The disease control is evaluated 4-5 days later by comparing the resuls with the effect that would be obtained if only an additive effect would arise. A more than additive effect is indicated, as illustrated in the following Tables A1 to A6.

TABLE A1 TABLE A2

Component a) of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 , 0 2 8 32 c 0 0 30 70 90 0 O 0 40 80 100 0 O 40 80 100 '9 2 0 50 100 100 2 (30) (80) (100) z (40) (80) (100) ~ x o 20 20 60 90 100 r 8 30 80 100 100 8 8 (45) (90) (90) c (60) (85) (100) 0 0 60 60 80 100 100 m 32 75 90 100 100 3 32 (70) (90) (95) 3 (85) (95) (100) 0 calculated additive effect (1) in commercially available Copper-Sandoz form (2) in commercially available Kocide 101 form TABLE A3 TABLE A4

Component a) of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 0 2 8 32 0 0 30 80 100 0 0 40 80 100 2 2 20 50 100 100 c 2 30 70 90 100 Cam (45) (85) (100) QQ (40) (80) (100) n 8 8 40 80 100 100 ~ 8 20 90 100 100 (60) (90) (100) < (50) (85) (100) 32 70 90 100 100 < 32 80 100 100 100 (80) (95) (100) (90) (95) (100) calculated additive effect.

TABLE A5 TABLE A6

Component a) of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 0 2 8 32 0 0 20 80 95 0 0 30 70 95 2 2 20 80 100 100 2 30 70 90 100 (35) (85) (95) E (50) (80) (100) n 8 8 40 90 100 100 ' 8 40 85 100 100 (50) (90) (100) S (60) (80) (100) C C Co Co 32 75 95 100 100 E 32 85 100 100 100 (80) (95) (100) (90) (95) (100) calculated additive effect.

Test H : Fungicidal effect against Plasmopara viticola The Test is carried out as described in Test B, whereby the plants are treated with a tank mix of an aqueous spray suspension containing component a) and component b) in concentrations indicated in Tables B1 to B6 below. The observed effect is given by the following Tables B1 to B6.

TABLE B1 TABLE B2

Component a) of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 Q 0 2 8 32 C Q 0 0 30 70 100 0 40 70 100 a) 2 2 10 30 70 100 Vx 2 20 40 70 100 (35) (35) (75) (100) 2 (45) (75) (100) a) V V 8 8 50 60 100 100 -' 8 40 60 100 100 0 Co Co (65) (85) (100) O (60) (80) (100) 0 o Q Q 32 80 85 100 100 ' 32 70 80 100 100 (85) (95) (100) (80) (90) (100) calculated additive effect (1) in commercially available Copper-Sandoz form (2) in commercially available Kocide 101 form TABLE B3 TABLE B4

Component at of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 0 2 8 32 0 0 40 80 100 0 0 40 70 100 2 40 60 100 100 c 2 0 40 80 100 (65) (90) (100) QQ (40) (70) (100) Q C CQ 8 70 80 100 100 z 8 70 95 100 100 (80) (95) (100) < (80) (90) (100) H flu a 'L 32 100 100 100 100 8 32 100 100 100 100 LL (100) (100) (100) (100) (100) (100) calculated additive effect.

TABLE B5 TABLE B6

Component a) of Component a) of Example 1 hereinafter Example 1 hereinafter (in ppm) (in ppm) 0 2 8 32 0 2 8 32 0 0 35 80 100 0 0 40 80 100 2 20 50 90 100 2 2 20 60 100 100 (50) (85) (100) m (50) (85) (100) 0 a 0 m 8 60 90 100 100 8 70 95 100 100 C (75) (90) (100) (80) (95) (100) oa) 0 C 32 95 100 100 100 go 32 90 100 100 100 :E (100) (100) (100) (95) (100) (100) calculated additive effect.

The compounds of formula I are conveniently employed as fungicidal compositions in association with agriculturally 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, particularly a fungicide selected from the group comprised by component b) as defined hereinbefore. 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.

The compositions of the invention comprising both components a) and b) may for example be obtained by mixing said components a) and b), optionally 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 alkylarylsuiphonate, 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 e.g. a component b) as defined hereinbefore. Concentrate forms of composition generally contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent. Liquid application forms of formulation may 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 "C.

Formulation Example I: Wettable Powder 50 parts of 2-methoxy-N-(2,6-dimethylphenyl )-N-(2-oxo-3-oxazol idinyl)-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-methoxy-N-(2,6dimethylphenyl)-N-(2-oxo-3-oxazolidinyll-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 Examples 3 to 6 (wettable powders) % by weight Example 3 4 5 6 Component a)'1' 12.65 6.25 12.5 6.25 copper (II) oxychloride (-569/0 Cu) 47 47 cuprous oxide (~88% Cu) 29 29 Na laurylsulphate 1 1 1 1 ligninsulphonate 10 10 10 10 Kaolin 29.5 35.75 39.5 45.75 (1) e.g. 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolidinyl)-acetamide.

All the components of the formulation are mixed, milled and mixed again in conventional manner.

Formulation Examples 7to 9 (wettable powders) % by weight Example 7 8 9 Component a)(1) 25 12.5 6.25 Component b2(2) 50 50 50 Na oleoylmethyltauride 2 2 2 Condensation product of Na alkyl naphthalene sulphonate and formal dehyde 5 5 5 silica gel 5 5 5 Kaolin 13 25.5 31.75 (1).e.d. 2-methoxv-N-(2.6-dimethvlohenvl)-N-(2-oxo-3-oxazolidinv)-acetamide (2) e.g. Folpet All the components of the formulation are mixed, milled and mixed again in conventional manner.

Formulation Examples 10 to 12 (wettable powders) % by weight Example 10 11 12 Component a)(1) 25 12.5 6.25 Component b3)(2) 50 50 50 Na laurylsulphate 1 1 1 lignisulphonate 4 4 4 Silica gel 5 5 5 Kaolin 15 27.5 33.75 (1) e.g. 2-metoxy-N-(2,6-dimethylphenyl)-N-(2-oxo-3-oxazolindinyl)-acetamide (2) e.g. mancozeb The formulation is obtained by mixing the components, subsequently milling the mixture and repeated mixing in conventional manner.

Example 1 : 2 -Methoxy-N-(2,6-dimethylphenyl)-N~(2-oxo-3-oxazolidinyl)-acetamide 11.8 g (0.0375 mol) 2-Chloroethyl 2-(methoxy-acetyl)-2-(2,6-dimethylphenyl)-hydrazinecarboxylate are added portion-wise to a suspension of 2.0 g sodium hydride (in form of about 55% by weight in mineral oil) in 100 ml absolute toluene at room temperature under a blanket of nitrogen.The reaction temperature rises gradually during this addition up to 40 . After the addition is complete the mixture is stirred during 30 minutes without cooling and afterwards cooled to 10 . The unreacted sodium hydride is then destroyed with ethanol, the obtained solution washed with water dried with MgS04 and the solvent removed in vacuo to give the end title compound which is recrystallised from ethanol to yield the title compound as colourless crystals. m.p. 103-1040.

Example la : 2-Chloroethyl-2-(methoxyacetyl)-2-(2,6-dimethylhenyl)-hydrazinecarboxylate The starting material used in Example 1 is obtained as follows: A mixture of 14.7 g (0.06 mol) 2-chloroethyl 2-(2,6-dimethylphenyl)-hydrazinecarboxylate and 16.2 g (0.1 mol) methoxy acetic acid anhydride [(CH3OCH2CO)20] are stirred in 100 ml dry toluene during 1 hour at 80 .

After cooling, the solution is washed with water, then with a 5% NaHCO3 aqueous solution and then again with water.

The solution is dried with MgS04 and the solvent removed in vacuo to give the title compound of Example la.

Example : 2-Chloroethyl 2-(2, 6-dimethy/phen yl)-hydrazinecarboxylate To a mixture of 127g (0.935 mol) 2,6-dimethyl. phenylhydrazine, 102.5 g (1.3 mol) pyridine and 400 ml water is added, at 0-5,, 133.5 g (0.935 mol) chloroformic acid ss-chloroethyl ester. After the addition is complete, the mixture is stirred for 2 hours at room temperature, the formed precipitate filtered off, washed with water and dried. The so obtained title compound is recrystallised from toluene to yield colourless crystals, m.p. 74-75 .

According to a preferred alternative procedure of Example 1, 1 a and 1 b, one proceeds as follows: Example 2 : 2-Methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo3-oxazolidinyl)-acetamide 236.1 g (0.75 mol) 2-Oh loroethyl 2-(methoxyacetyl )-2-( 2,6-d i m ethyl phenyl)-hyd razi neca rboxylate, 375 ml xylene and 187 ml water are stirred with external cooling, while 82.5 ml (0.82 mol) of an aqueous solution of sodium hydroxide (containing -0.4 g NaOH per ml) are added at a rate to maintain the internal temperature at approx. 200. The mixture is stirred after completion of the addition for 1 hour at 20 , and for 2 hours at 00.

The solid is filtered off, washed with 150 ml water and dried to yield the title compound as a slightly coloured solid, m.p. 102-13 .

Example 2a : 2-Chloroethyl 2-(methoxyacetyl-)-2-(2, 6-dimethylphenyl)-hydrazinecarboxylate 200 g (0.825 mol) 2-Chloroethyl 2-(2,6-dimethylphenyl)-hydrazinecarboxylate in 500 ml xylene are warmed to 80 , and added to warm (80 ) solution of 2-methoxy-acetylchloride in 250 ml xylene, prepared in situ by treating 73.5 g (0.826 mol) 2-methoxyacetic acid in 250 ml xylene with 107.1 g (0.9 mol) thionyl chloride at 800 for 2 hours. The mixture is heated for 30 minutes at 80 , then worked up as described in Example 1 a.

Example 2b : 2-Chloroethyl 2-62,6-dimethylphenylJ-hydrazinecarboxylate A mixture of 17.7 g (0.1 mol) 2,6-dimethylphenylhydrazine hydrochloride, 21.2 g (0.2 mol) sodium carbonate in 50 ml water and 50 ml xylene are stirred for 30 minutes at room temperature, then cooled to 5 .

14.3 g (0.1 mol) chloroformic acid 2-chloroethylester is then added over a period of 1 hour, the temperature being maintained at 5 . The mixture is stirred at 5 for another hour, at the end of which 100 ml water are added, the precipitate thus formed filtered off, washed with water and dried. Further work-up as in Example 1b.

In analogous manner to that described in the preceding Examples 1 and 2 the following compounds of formula I are produced

Ex. R3 R R R R b(.p. No. R4 R5 6 7 8 9 10 (0c) 3 H H H H CH3 CH3 H CH20C2H5 62-4 4 H H H H CH3 C1 H CH20CH3 99-100 5 H H H H CH3 CH3 H 8 190-1 6 H H H H CH3 CH3 4-C1 CH20CH3 107-9 7 H CH3 CH3 H CH3 CH3 H CH20CH3 8 H H H H CH3 CH3 H CF.2SCH3 113-5 9 H H H H CH3 CH3 H CH2C1 134-6 10 H H H H CH3 C1 H CH2C1 135-6 11 H H H H CH3 CH3 H CH20CH(CH3)2 12 H H H H CH3 C1 H CH20CH(CH3)2 13 H H H H CH3 C1 H 166-7 14 H H H H CH3 CH3 H CH25C4H9 (n) oil 15 H H H H CH3 C1 H CH2SC4H9(n) oil 16 H H H H H3 CH3 H C1E-C2E5 123-4 Br 17 H H H - H CH3 CH3 H CH-CH3 147-8 C1 18 H H H H H3 CH3 H CH2Br 143-4 19 H H H 4 H3 CH3 H t 119-20 20 H H H 4 Cl C1 H CH20CH3 107-9 21 H H H H Cl Cl H CH2C1 142-4

Ex. R B R B P B H.p. No. I B4 B5 6 7 8 '9 9 10 ("C) 22 H H H H C1 C1 H ILOl 173-4 23 H H H H CH3 CH3 H CH2N 139-41 24 H H H H CH3 CH3 4-CH3 CH20CH3 oil 25 H H H H CH3 C2E5 H CH2C1 oil 26 H H H H CH3 CH3 3-C1 CH20CH3 90-2 27 H H H H CH3 CH3 3-Br CH20CH3 96-7 28 H H H H CH3 CH3 3-Br CH2C1 182-3 29 H H H H CH3 CH3 3-Br t 145-8 30 H H H H CH3 Br 4-CH3 CH20CH3 125-6 31 H H H H CH3 Br 4-CH3 CH2C1 124-6 32 H H H H CH3 Br 4-CH3 t 193-4 33 H H H H CH3 CH3 H CHOCH3 90-4 CH3 34 H H H H CH3 CH3 H t 149-52 35 H H H H CH3 CH3 4-C1 CH2C1 gum 36 H H H H CH3 CH3 4-C1 n 164-5 37 H H H H C 2E5 C2H5 H CH20CH3 109-12 38 H H H H CE3 CH.3 H CH2oC3H7(n) oil

Ex. R3 3 R4 Rg W 99 R R M.p. No. 4 .5 for10 (0C) 39 H H H H CH3 CH3 H CH20C4H9(n) 40 H H H H CH3 CH3 H CH20CH-C2H5 CH3 41 H H H H CH3 CH3 H ECH2CH=CH2 98-100 42 H H H H CH3 CH3 H CH20CH2C--CH 91-93 43 H H H H CH3 CH3 H CE20 t 107-8 44 H H CH3 H CH3 CH3 H CH20CH3 79-80 45 H H H H CH3 CH3 H CE2N 56 142-4 46 H H H H C2H5 C2H5 H 47 H H H H 2E5 C H H CH2C1 88-9 48 H H H H r Br H CH20CH3 150-2 49 H H H H 1 C1 4-C1 CH20CH3 128-9 50 H H H H 2H5 C2H5 4-C1 CH20CH3 114-6 51 H H H- H r C1 4-CH3 CH20CH3 131-4 52 H H H H H3 2E5 H CH20CH3 96-8 53 H H H H H3 CH3 4-Br CH20CH3 137-8

Claims

1. A compound offormula I wherein R1 is

wherein R7 and R8, independently, are C1-4 alkyl, halogen or C1-4alkoxy, and R9 is hydrogen, O1.4alkyl or halogen, R2 is CO-R10, wheren R10 is C1-4alkoxy-C1-4alkyl, C1-4alkyl-thio-C1-4alkyl, 2-furyl, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1-imidazolymethyl, 1-pyrrazolymethyl-,2-tetrahydrofuryloxymethyl, 2tetrahydropyranyloxymethyl, or C1-4halogenalkyl, and R3, R4, R5 and R6 are independently hydrogen or C1-4alkyl.

2. A compound of Claim 1 wherein R3, R4, R5 and R6 are hydrogen.

3. A compound according to Claim 2 wherein R2 is -COCH2OCH3, -COCH2OC2H5, -CO-(2-furyl) or -CO-(5-halo-2-fury), R7 and R8 are independently CH3, Cl or Br and R9 is H, Cl, Br or CH3.

4. A compound according to Claim 3 wherein R7 and R8 are identical.

5. A compound of Claim 4, wherein R7, R8, R3 and R10 are CH3, CH3, H and CH2OCH3 respectively.

6. A compound of Claim 4 wherein R7, Re, R9 and R10 are CH3, CH3, H and CH2OC2H5 respectively.

7. A compound of Claim 3 wherein R7, R8, Re and R10 are CH3, Cl, H and CH2OCH3 respectively.

8. A compound of Claim 4, wherein R7, R8, R9 and R10 are CH3, CH3, H and 2-furyl respectively.

9. A compound of Claim 4 wherein R7, Re, Re and R10 are CH3, 4-Cl R9 and CH2OCH3 respectively.

10. A compound of Claim 2 wherein R7, R8, R9and R10 are CH3, CH3, H and CH2SCH3 respectively.

11. A compound of Claim 2 wherein R7, RB, R9 and R10 are CH3, CH3, H and CH2Cl respectively.

12. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, Cl, H and CH2CI respectively.

13. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3 CH3. H and CH2OCH(CH3)2 respectively.

14. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, Cl, H and CH2OCH(CH3)2 respectively.

15. A compound of Claim 3 wherein R7, Re, Re and R10 are CH3, Cl, H and 2-furyl respectively.

16. A compound of Claim 2 wherein R7, Re, Re and R10 are CH3, CH3, H and CH2SC4H9(n) respectively.

17. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, Cl, H and CH2SC4Hg(n) respectively.

18. A compound of Claim 2 wherein R7, Re, Re and R10 are CH3, CH3, H and CHBrC2H5 respectively.

19. Acompound of Claim 2 wherein R7 , R8, R9 and R10 are CH3, CH3, H and CHClCH3 respectively.

20. A compound of Claim 2 wherein R7, R8, Re and R10 are CH3, CH3, H and CH2Br respectively.

21. A compound of Claim 4 wherein R7, R8, R9 and R10 are CH3, CH3, H and 5-Br-2-furyl respectively.

22. Acompound of Claim 4 wherein R7, Re, Re and R10 are Cl, Cl, H and CH2OCH3 respectively.

23. A compound of Claim 2 wherein R7, Re, R9 and R10 are Cl, Cl, H and CH2CI respectively.

24. A compound of Claim 4 wherein R7, Re, R9 and R10 are Cl, Cl, H and 2-furyl respectively.

25. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, CH3, H and 1-pyrazolylmethyl respectively

26. A compound of Claim 4 wherein R7, Re, R9 and R10 are CH3, CH3, 4-CH3 R9 and CH2OCH3 respectively.

27. A compound of Claim 2 wherein R7, Re, R10 and CH3, are C2H5, R9 H and CH2CI respectively.

28. A compound of Claim 4 wherein R7, Re, R10 and CH3, are 3-Cl CH3, F9 and CH2OCH3 respectively.

29. A compound of Claim 4 wherein R7, Re, R10 and CH3, are CH3, R9 3-Br and CH2OCH3 respectively.

30. A compound of Claim 2 wherein R7, Re, CH3, and R10 are CH3, R9 3-Br and CH2CI respectively.

31. A compound of Claim 4 wherein R7, Re, R10 and R10 are CH3, 4-CH3 3-Br and 2-furyl respectively.

32. A compound of Claim 3 wherein R7, Re, R9 and R10 are CH3, Br, 4-CH3 and CH2OCH3 respectively.

33. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, Br, 4-CH3 and CH2CI respectively.

34. A compound of Claim 3 wherein R7, Re, R9 and R10 are CH3, Br, 4-CH3 and 2-furyl respectively.

35. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, CH3, H and CH(CH3)OCH3 respectively.

36. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, CH3, H and 2-tetrahydrofuryl respectively.

37. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, 4-Cl and CH2 Cl respectively

38. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, 4-Cl and 2-furylrespectively.

38. A compound of Claim 2 wherein R7, Re, R9 and r10 are C2H5, C2H5, H and CH2OCH3 respectively.

39. A compound of Claim 2 wherein R7, Re, R9 and R10 are C2H5, C2H5, H and CH2OCH3 respectively.

40. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, CH3, H and CH20O3H7(n) respectively.

41. A compound of Claim 2 wherein R7, Re, R9 and R10 are CH3, CH3, H and CH2OC4Hg(n) respectively.

42. A compound of Claim 2 wherein R7, Ra, R9 and R10 are CH3, CH3, H and CH2OCH(CH3)C2H5 respectively.

43. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, H and CH2OCH2--CH2 respectively.

44. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, H and CH2OCH2-C=CH respectively.

45. A compound of Claim 2 wherein R7, R8, Rs and R10 are CH3, CH3, H and 2-tetrahydropyranyloxymethyl respectively.

46. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, H and 1 -pyrazolylmethyl respectively.

47. A compound of Claim 2 wherein R7, R8, R9 and R10 are C2H C2H5, H and 2-furyl respectively.

48. A compound of Claim 2 wherein R7, R8, R9 and Rio are C2H5,. C2H5, H and CH2CI respectively.

49. A compound of Claim 4 wherein R7, R8, R9 and R10 are Br, Br, H and CH2OCH3 respectively.

50. A compound of Claim 4 wherein R7, R8, R9 and R10 are Cl, Cl,4-Cl and CH2OCH3 respectively.

51. A compound of Claim 2 wherein R7, R8, R9 and R10 are C2H5, C2H5,4-CI and CH2OCH3 respectively.

52. A compound of Claim 3 wherein R7, R5, R9 and R10 are Br, Cl, 4-CH3 and CH2OCH3 respectively.

53. A compound of Claim 2 wherein R7, R8, Rs and R10 are CH3, C2H5, H and CH2OCH3 respectively.

54. A compound of Claim 2 wherein R7, R8, R9 and R10 are CH3, CH3, 4Br and CH2OCH3 respectively.

55. A method of combating phytopathogenic fungi in plants, seeds or soil, which comprises applying to the plants, seeds or soil a fungicidally effective amount of a compound claimed in any one of claims 1 to 54.

56. A method of combating phytopathogenic fungi in plants or soil according to Claim 55, which comprises applying to said locus 0.05 to 5 kg of a compound claimed in any one of Claims 1 to 54 per hectare treated locus.

57. A method according to Claim 56, in which the dosage rate is from 0.1 to 3 kg of a compound claimed in any one of Claims 1 to 54 per hectare treated locus.

58. A method of combating phytopathogenic fungi in seeds according to Claim 55, which comprises applying from 0.05 to 0.5 g of a compound claimed in any one of claims 1 to 54 per kg seed.

59. A method of combating phytopathogenic fungi in a locus which comprises applying to the locus to be treated fungicidally effective amounts of a component a) comprising a compound of formula las defined in any one of Claims 1 to 54, and of a component b) selected from a component b1) a copper fungicide or a component b2) captan orfolpet or a component b3) mancozeb or maneb.

60. A method according to Claim 59, wherein component b) is mancozeb.

61. A method according to Claim 59, wherein component b) is cuprous oxide, copper (Ill oxychloride, cupric hydroxide our a mixture of copper (II) calcium sulphate with copper (II) oxychloride.

62. A method according to any one of Claims 59 to 61 which comprises applying component a) at a rate of 100-400 g per hectare and component b) at a rate of 200-2000 g/ha.

63. A method according to Claim 62 which comprises applying the components a) and b) in a weight ratio of 1:1 to 1:10 of component a) : component b).

64. A method according to Claim 63 wherein the weight ratio component a) : component b) is 1:2 to 1:7.

65. A composition comprising a compound of formula I as defined in any one of Claims 1 to 54 in association with an agriculturally acceptable carrier or diluent.

66. Afungicidal composition comprising a component a) and a component b) as defined in Claim 59 in a weight ratio of 1:1 to 1:10 of component a) : component b).

67. A fungicidal composition wherein the weight ratio component a) : component b) is from 1:2 to 1 :7.

68. A composition according to any one of Claims 65 to 67 in comprising from 0.01 to 90% by weight of a compound of formula I as claimed in any one of Claims 1 to 54 or mixtures thereof with component bi as defined in Claim 59.

69. Concentrate forms of compositions according to any one of Claims 65 to 68 comprising from 2 to 80% of component a) or of a mixture of component a) and component b) as defined in Claim 59.

70. Liquid application forms of compositions according to any one of Claims 65 to 68 comprising from 0.01 to 20% by weight of component a) or of a mixture of component a) and component b) as defined in Claim 59.

71. A process for the production of a compound of formula I as claimed in Claim 1 characterized by intramolecular condensation of a compound of formula Il

wherein R1, R. R4, R. Re and R. are as defined in Claim 1 and Y is halogen.

72. A process for the production of a compound of formula I substantially as hereinbefore described with reference to any one of the Examples.

73. A compound of formula I whenever produced by a process according to Claim 71 or 72.

74. Acompound of formula Il

wherein R1, R3, R4, R5, R6 and R10 are as defined in Claim 1 and Y is halogen.