DE3030026A1 - Fungicidal 3-acylamino-oxazolidinone derivs. - prepd. by cyclisation of 2-haloethyl 2-acyl-2-phenyl-hydrazine carboxylate cpds. - Google Patents

Abstract

New 3-amino-oxazolidin-2-one derivs. are cpds. of formula (I). R1 is a gp. of formula (Ia) in which R7 and R8 are 1-4C alkyl, halogen or 1-4C alkoxy and R9 is H, 1-4C alkyl or halogen; R2 is -CO-R10 in which R10 is (1-4C alkoxy)-(1-4C alkyl), (1-4C alkylthio) -(1-4C alkyl), 2-furyl, tetrahydro-2-furyl, halogenated 2-furyl or tetrahydro-2-furyl, 1-imidazolylmethyl, 1-pyrazolylmethyl, tetrahydro-2-furyloxymethyl, tetrahydro-2-pyranyloxymethyl or 1-4C haloalkyl; and R3, R4, R5 and R6 are H or 1-4C alkyl. (I) are fungicides useful for combating phytopathogenic fungi, esp. those of the order Oomycetes. Results of tests demonstrating the activity of (I) are given. In tests against Phytophthora infestous on young potato plants, 2-methoxy-N-(2,6-dimethylphenyl)-N-(2-oxo- 3-oxazolidinyl)-acetamide in a concn. of 8 ppm gives 80% control of fungal infection; the same concn. as a tank mixt. with 2 ppm copper oxide (which by itself gives 20% control) gives 100% control.

Description

Fungiz ide

The subject matter of the invention includes compounds which for the Control of phytopathogenic fungi are suitable.

In particular, the invention relates to new compounds of the formula in which R1 is a radical R7 and R8 independently of one another (1-4C) -alkyl, halogen or (1-4C) -alkoxy, Rg hydrogen, (1-40) -alkyl or halogen, R2 -CO-10, R10 (1-4C) -alkoxy - (1-4C) -alkyl, (1-4C) -alkylthio- (1-4C) -alkyl, 2-furyl, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1-imidazolyl-methyl, l -Pyrrazolylmethyl, 2-tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl or halo- (1-4C) alkyl and R3, R4, R5 and R6 are independently hydrogen or (1-4C) -alkyl.

If each of the radicals R3, R4, R5, R6, R7, R8 or Rg is an alkyl radical indicated or contains an alkyl radical (e.g. in an alkoxy radical) it is mainly for (1-3C) -alkyl, e.g. methyl, ethyl, n-propyl or i-propyl.

If R7 or R8 are each halogen, it is F, Cl, Br or I, mainly F, C1 or Br, especially C1 or Br or especially C1.

If Rg or R10 each denotes halogen or contains halogen, stand she for F, C1, Br or I, especially £ forF, C1 or Br, in particular for C1 or Br.

Preferred halogenated 2-furyl radicals in the meaning of R10 are monohalogenated 2-furyl radicals, e.g. 5-chloro-2-furyl and 5-bromo-2-furyl.

Preferred halogenated (1-4C) -alkyl radicals in the meaning of R are Chloro- (1-4C) -alkyl or bromo- (1-4C) -alkyl, e.g. chloromethyl, bromomethyl and C2H5CHBr-preferred Halogenated 2-terahydrofuryl radicals with the meaning of R10 are monohalogenated 2-tetrahydrofuryl residues, especially monochlorinated or monobrominated 2-tetrahydrofuryl residues, e.g. 5-chloro-2-tetrahydrofuryl.

Preferred (l-4C) -alkoxy- (l-4C) -alkyl radicals in the meaning of R10 are (1-30) -alkoxymethyl, especially CH30aI2- and C2H5-OCH2-.

Preferred (1-4C) -alkyltnio- (1-4C) -alkyl radicals in the meaning of R10 are (l-3C) -alkylthiomethyl, e.g. CH3S-CH-.

R10 particularly represents (1-4C) -alkoxy- (1-4) alkyl, 2-furyl or 5-halo-2-furyl.

In the event that one of the radicals R3 or R4 is (1-40) -alkyl, the other especially stands for hydrogen.

If one of the radicals R5 or R6 is (1-40) -alkyl, the is other remainder especially for hydrogen.

A preferred group of compounds are the compounds of the formula wherein R2 '-CO-CH2-OCH3, -CO-CH2-OC2H5, -CO- (2-furyl) or -CO- (5-halo-2-furyl), R71 and R8 independently of one another -CH3, Cl or Br and R9 'denote H, C1, Br or -CH3, where R7' and R81 advantageously have the same meanings.

The invention further provides a process for the preparation of the compounds of the formula I, which is characterized in that a compound of the formula wherein R1, R2, R4, R5, R6 and R, have the meanings mentioned above and Y is halogen, condensed intramolecularly.

Y is advantageously chlorine or bromine, especially chlorine.

The intramolecular condensation can be carried out according to methods known per se be performed. The reaction is exothermic. The reaction can take place in an anhydrous Medium using an ether, such as dimethoxyethane, carried out as a solvent or a hydrocarbon such as toluene or another solvent, which is inert under the reaction conditions.

The reaction temperature is not critical and can be approximately between 0 ° and 1000C. Since the reaction is exothermic, it is expedient to start the reaction at room temperature in order to be able to gradually increase the reaction temperature.

The reaction is expediently carried out in the presence of an acid-binding agent such as sodium hydride, sodium amide or a sodium alcoholate, such as sodium ethylate, The intramolecular condensation can also be carried out in an aqueous organic Two-phase system in the presence of an inorganic base, e.g. sodium hydroxide and optionally with a catalytic amount of a phase transfer catalyst be performed.

The organic phase can usefully not be any inert with water miscible solvents include, such as hydrocarbons or halogenated hydrocarbons, e.g. xylene, toluene, ortho-dichlorobenzene or dichloromethane.

Appropriate phase transfer catalysts are ammonium compounds, such as benzyltrimethylammonium bromide quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride and "Crown" ethers such as 18- "Crown" -6.

The compounds of the formula II are new. You can acylate a compound of the formula in which R1, R3, R4, R5, R6 and Y have the meanings given above, with a compound of the formula in which R10 has the meanings mentioned above and Z is halogen, especially chlorine or -O-CO-R10, in which R10 has the meanings mentioned above, are obtained.

Suitable solvents for this acylation reaction are hydrocarbons, such as toluene or halogenated hydrocarbons such as chlorobenzyl. The reaction is conveniently used at temperatures from about 500 to about 100 ° C, e.g. 80 ° C carried out.

The compounds of the formula III can be prepared by reacting a compound of the formula R1-NH-NH2 V, in which R1 has the meanings mentioned above, with a compound of the formula in which R3, R4, R5, R6 and Y have the meanings given above and X is halogen, especially chlorine, are obtained.

This reaction can take place at a temperature of about 00 to 1000 in water or in an organic solvent, whichever among these Reaction conditions Is inert, are carried out, conveniently in the presence of a base, e.g. a organic amine or sodium hydrogen carbonate.

The starting compounds and reactants in those previously described Procedures are either known or, if not known, they can prepared according to the methods described herein or methods known per se will.

The compounds of formula I have a useful and excellent one fungicidal activity, especially against phythopathogenic fungi, especially against fungi from the order of the Oomycetes as by a significant effect in the following Tests shown: T e s t M e t h o d e A Fungicidal effect against Phytophthora infestans.

Young potato plants planted in pots (in a 3 to 5 leaf stage) are sprayed with an aqueous suspension, which is 0.003% (weight / volume) a compound of formula I, e.g. 2-'I2thoxy-NT- (2,6-dimethylphenyl) -X- (2-oxo-3-oxazolidinyl) -acetamide (composed according to the formulation in Example I). Will be two hours later the treated plants inoculated with a spore suspension of Phytophthora infestans, or vaccinated.

The plants treated in this way are then transferred to a tent, in which a 100% relative atmospheric humidity at an ambient Temperature of 1600 and a day length of 16 hours prevails.

The dying, resp. the control of the disease will be 4 to 5 days later estimated by comparing the treated plants with untreated, but non-oculated similar plants.

A considerable fungicidal inundation can occur when checked (a search) are observed but with no evidence of phytotoxicity on the Host plants.

Test M e t h o d e B Fungicidal effect on Plasmopara viticola.

Young vines planted in pots (in a 3 to 6 leaf stage) xerden sprayed with an aqueous suspension, which 0.0008 (weight / volume) a Compound of formula I contains, for example 2-Nethoxy-N- (2> 6-di-ethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (composed according to the formulation of Example I). Will be two hours later the plants treated in this way with a suspension of spores of Plasmopara viticola inoculated and the treated plants then transferred into a tent, in which 100% relative atmospheric humidity at one for 24 hours continuous ambient temperature of 15 to 22 ° C and a day length of 16 Hours prevail.

Disease control is assessed 6 days after inoculation by comparing the treated with the untreated non-oculated similar Plants. A considerable fungicidal infection can be observed during the control but without any signs of phytotoxicity on the host plants.

Test M e t h o d e C Healing fungicidal effect against Plasmopara viticola.

Young vines planted in pots (in a 3 to 6 leaf stage) are inoculated in the same way as in test method B, but with the compound of the formula I 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (composed according to the formulation of Example I) only 3 days after inoculation he follows. The incubation conditions were the same as in test method B. The Checking for death is estimated in the same way as in test method B.

A considerable fungicidal infection can be observed during the control will.

T e s t M e t h o d e D Against an eradicating fungicidal effect Plasmopara viticola.

The procedure for assessing this type of activity is in the test method C. described with the exception that the treatment did not take place until 6 days after inoculation is carried out when the sporulation of the leaf surface of the withered leaves is already visible or has progressed.

The control of the death or the disease was 7 days after the use of 0.012% of the compound 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-oxazolidinyl) -acetamide (composed according to the formulation of Example I) estimated and shows a Stopping effect in the areas already infected with spores, so that further spore formation completely stops.

T e s t M e t h o d e E Relocation of treated leaves during Vine.

Any selected sheets of white sticks are marked with a sprayed with an aqueous suspension containing 0.012X of a compound of the formula 2-methoxy-N- (2,6-dimethylphenyl) -N '- (2-oxo-3-oxazolidinyl) acetamide Contains (composed according to the formulation of Example I), with only the lower one Half of these leaves are treated. Two hours after treatment, the whole will be Leaf inoculated with a spore suspension of Plasmopara viticola, and then the leaves are incubated in a tent, which is 100% atmospheric has relative humidity and under the conditions as in the test method B. Although only the lower half of the leaves were treated as described above, considerable disease can be observed all over the leaf surface. The same effect of the disease can also be observed over the whole leaf, if only the upper half of the leaves iirde i-oculated. This test method shows accordingly that the 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (composed according to the formulation in Example 1) distributed over the entire sheet will, even if the spray is only at the base or even only at the tip of the leaf took place.

T e s t M e t h o d e F (in vivo) Pythium aphanidermatum is used in a sterile mixture of sand and cornmeal (97: 3 V / V) to which water in a ratio 1: 4 (V / V) is added, cultivated for 4 days at 250C. The fungus will then mixed with a semi-sterile mixture of peat and sand and then with a suspension treated, which contains the active ingredient in a concentration of 10 to 160 ppm (e.g. 10, 40 and 160 ppm calculated per volume of substrate). The subs is stepped in Put pots of 5 cm in diameter in which cucumber seeds are sown. The pots will at 240C and 60-70% relative humidity in an incubation zizzer for 7 Days, and the number of healthy plants with untreated, analogous compared inoculated control plants. The compound according to Example 1 is used in the wettable powder formulation according to formulation example 1, results in a complete control.

Similar tests with beets and sugar beets give comparable results.

Each of the following compounds in the following examples possesses fungicidal properties and indicates its usefulness as a fungicide.

A particularly effective fungicidal activity is according to the above listed tests with the compounds of formula Ia found: in which R2 -CO-CH2-O-C2H5, R7 and R8 'are each -OH3 and R9 are hydrogen; or in which R2 -CO- (2-furyl), R7 'and R8' are each -CH3 and R9 'are hydrogen; or in which R2 '-CO- (5-bromo-2-furyl), R7 'and R8' are each -OH3 and R9 'are hydrogen; or in which R2 '-CO-CH2-0-CH3, R7 'and R81 each represent C1 and R9' hydrogen; or in which R2 '-CO-CHz-O-CH3, and R8 'are each CH3 and R9' 3-Br and especially with the compound of the formula Ia, where R2 'is -CO-CH2-0-CE3, R7' and R8 'are each -OH3 and R9' are hydrogen.

9 The subject matter of the invention also includes a method for Control of phytopathogenic fungi, in particular of the genus Oomycetes Plants, seeds or in the ground with a fungicidal effect Amount of a compound of the formula I.

Fungi of the genus Oomycetes against which the method according to the invention particularly effective are those of the genus Phytophthora in plants such as for potatoes, tomatoes, tobacco, citrus, cocoa, gum, apples, conquered berries, useful plants and ornamental plants, e.g. Phytophthora infestans in potatoes and tomatoes: in which Genus Plasmopara viticola in the vineyards; in the genus Peronospora Plants such as tobacco, e.g. Peronospora tabacina in tobacco; in the Genus Pseudoperonospora in plants such as hops and cucumber, e.g. Pseudoperonospora humuli in hops; in the genus Bremia in plants such as lettuce or lettuce, e.g.

Bremia lactucae for lettuce or lettuce; at the genus Pythium, which causes decay and rotting of the roots in a large number of plants, for example in crops, sugar beets, ornamental plants and conifers, e.g. Pythium aphanidermatum in sugar beet; in the genus Sclerospora in plants, as with sorghum and maize, e.g. Sclerospora sorghis with sorghum.

When using the method according to the invention, the amount is the preparation to be used depending on various factors, so on the species of fungi to be controlled, the time and method of application, and the amount and nature of the compound of the formula I as used in the preparation is used.

In general, satisfactory results are obtained when using On the spot, e.g. in crops or in the soil in large quantities of the order of magnitude of 0.05 to 5 kg, advantageously between 0.1 to 3 kg of a compound of formula I per hectare of the treated site, whereby the procedure, if necessary, can be repeated.

In the event of treatment in the preparation of seeds or seeds, e.g. as a seed coating, satisfactory results will be obtained when in large quantities from about 0.05 to 0.5, advantageously from about 0.1 to 0.3 g of a compound of the formula I is used per kilo of seed.

According to a special process according to the invention, the compounds of the formula I in combination with those fungicides which are used against phytopathogenic Fungi are used effectively against which the compounds of formula I are not or are not sufficiently effective. This procedure enables treatment of a wider range of phytopathogenic fungi than the compounds of Formula I.

A particularly advantageous method according to the invention comprises the use at the place to be treated with a fungicid effective Amount of a component a) which is a compound of the formula I and a component b) includes which is to be selected from one of the components bl) a copper fungicide or a component b2), referred to as "captan" or "folpet", or a component b3), referred to as "mancozeb" or "maneb".

Examples of copper fungicides which are suitable for use as a component bl) are suitable are copper carbonate, copper TI calcium sulfate, copper II calcium oxychloride, Tetracupric oxychloride, Bordeaux mixture, Burgundy mixture, copper oxide, copper III hydroxide, Copper (II) oxychloride or coupling complexes such as copper triethanolamine hydroxide of the formula [CuN (CH2OH2OH) 3] - (OH) 2, commercially available under the trademark "K-Lox", or bis (ethylenediamine) copper sulfate, commercially available under the trademark "Comes", as well as mixtures thereof, in particular copper oxide, copper-III-oxychloride, Copper hydroxide and a mixture of copper (II) calcium sulfate and copper (II) oxychloride.

"Captan", "Folpet", "Hancozeb" and "Maneb" are the most common Names for protected fungicides, which are particularly effective against diseases of the foliage are effective. (Pesticide Manual, 5th Ed. By B. Martin and C.R. Worthing, pp 76, 281, 328 and 329).

The inventive method, wherein a component a) and a Component b) used is particularly effective in a wide range of phytopathogenic fungi.

In particular, component a) is in a range from 100 to 400 g per hectare and component b) in a range from 200 to 2000 g per hectare used.

The preferred weight ratio of a component a) to a component b) is in a range from 1: 1 to 1:10, in particular 1: 2 to 1:10 and quite especially from 1: 2 to 1: 7.

The inventive method, wherein a component a) and a Component b) is particularly effective against phytopathogenic fungi in plants such as potatoes, tomatoes and other Solanaceae, tobacco, citrus, Cocoa, gum, apples, strawberries, vegetables and ornamental plants, e.g. against fungi of the genus Plasmopara, e.g. Plasmopara viticola in the vine, in the genus Guignardia e.g. - Guignardia bidwelli in the vine, or in the genus Phoma in the vine, in the genus Pseudopeziza, e.g. Pseudopeziza tracheiphila. at the Vine, in the genus Gloeosporeum, e.g. Gloeosporeum ampelo? Hagum in the vine> in the genus Botrytis in the vine and lettuce or lettuce, e.g. Botrytis cinerea in the vine, in the genus Phytophthora, Phytophthora infestans in the potato, of the tomato or other Solanaceae, Phytophthora parasitica of the tomato or other Solanaceae, Phytophthora cryptogaea in the tomato and other Solanaceae, Phytophthora mexicana in tomatoes and other Solanaceae, Phytophthora nicotinae in tobacco and Phytophthora palmivora in gum or cocoa; in the genus Peronospora, e.g. Peronospora tabacina in tobacco, in the genus Pseudoperonospora, e.g. Pseudoperonospora humuli in hops, in the genus Bremia in plants such as lettuce or lettuce, e.g. Bremia lactucae, in the genus Pythium, e.g. Pythium aphanidermatum in the Sugar beet.

in the genus Alternaria, e.g. Alternaria solani in the potato, Tomato and other Solanaceae, Alternaria tenuis in tobacco, in the genus Spondylocladium, e.g. Spondylocladium atrovirens in the potato, in the genus Rhizoctonia, e.g. Rizoctonia solani in the potato, tomato or other Solanaceae, in the Genus Cladosporiu, e.g. Oladosporium fulvum in the tomato or other Solanaceae, at of the genus Colletotrichum in plants such as cocoa or tomatoes, z.3.

Colletotrichum atrar..entarium in the tomato or other Solanaceae, in the genus Glomerella, e.g. Glomerella lycopersici in the tomato or others Solanaceae, in the genus Corticium spp in the tomato and other Solanaceae and in the genus Botryodiplodia, e.g. Botryoaiplodia theobromae in cocoa.

The method according to the invention allows the verification of a more significant one wider range of fungicidal diseases than just treating one of the two components.

In general, a larger than the calculated additive effect will be observed by both components; especially treatment with concentrations the component a) and component b) grants a practically complete, more specific and more than 50 years of examinations of fungi, especially with the use of cupric oxychloride, Copper oxide, “captan”, “mancozeb or 'maneb” as component b) and in particular if they are used against phytopathogenic fungi from the class of Oomycetes, mainly against Oomycetes of the genus Phytophthora, e.g. Phytophthora infestans, in the genus Flasmophora, e.g. Plasmophora viticola, in the genus Peronospora, e.g. Peronospora tabaccina, in the genus Pseudoperonospora, e.g. Pseudoperonospora humuli, in the genus Bremia, e.g. Bremia lactucae and in the genus Pythium, e.g. Pythium aphanidermatum.

The process according to the invention wherein components a) and b) are used is particularly suitable for combating or preventing or

before mushrooms with fine vines, tomatoes and other Solanaceae and with cocoa, if a component b1) is used, with weistock or grapevine if a component b2) is used and with heinstock, potatoes, tomatoes or other Solanaceae, tobacco and hops, if a component b3) is used.

Components a) and b) can be used in the form of formulations and can be applied from a tank mix or in separate forms. They are advantageous in a mixture and in the form of an aqueous spray or used on the basis of an oil concentration.

A suitable fungicidal activity, which after treatment with a component a) and a component b) is obtained in the following Test methods shown: T e s t - M e t h o d e G Fungicidal effectiveness against Phytophthora infestans.

The test is carried out according to the specifications of test method A, where the plants from a tank mix with an aqueous suspension in the form of a Spray solution are treated, the spray solution a component a) and a Kopmonente b) contained in such concentrations as in the following Tables A1 to A6 are given.

The review of the disease, respectively. the infestation or death, is estimated 4 to 5 days later by comparing the results to that Effect that would have been obtained if only the additive effect had arisen. It but a greater effect than the additive effect is obtained in the experiment, such as the following Tables A1 through A6 illustrate.

Table A1 Table A SomponanlW 2) Semass or. «Oncrlçe a) according to Example 1 in ppm Example 1 in ppm 2 1 8 1 32 lo 1 2 1 8 1 32 80 100 030 70 1 70 1 90 (o where 1 40 2 0 40 80 lloo 8 o 50 jloo 100 ii 2 j | (100) 2 0) (40) (l 0 v) s zu2! (4) (80) (100) x og 1120 60 90 100 8 es 30 80 'lC0 100 (45) (90) | (4 5) | (9 o) (, O) o 8 (60) (85) (1C) z <2 i yes 80 100 100 wz (805) 1100 1100 (70) (90) 1 (90) (9O) 2 175 9 1 (95) 1 (1 °: The individual symbols have the following meanings: () calculated additive effect.

(1) Commercially available product in "Kupfer-Sandoz" form.

(2) Commercially available product in "Kocide 101" form.

Table A3 Table Ao Konporente a) oem: »sJ Koll.vonente a) ueTass Example 1 in ppm Example 1 in tra 0 O 2 1 8 32 0 O 1 2 1 8 32 z OO 80 1 80 100 0 80 50 iCO 1C3 to 2 30 40 1 2 20 (45) 1CO 100 100 ~ 2 30 70 90 (lCO) (45) (85) (100) (40) (80) 100) k 8 80 100 lGO lCO to 8 23 | 9O | 100 CO 8 40 (60) (90) (1cm) 8 20 (50) (85) (100) 0 32 j70 90 lOO lCO to 32 80 l 100 j 100 j 1C3 32 L (80) (95) (100) l ~; j (90) | (95) (100) () calculated additive effect.

Table A5 Table A6 Component a) semass component a) geruass Example 1 in ppm Example 1 in ppm 0283201218 32 0I20I80I95O03070 95 2 2 1 20 80 90 I 100 2 ~ 30 70 | o0 l 100 (35) (35) I (95) (50) (80) (100) 40 o 90 (80 100, 0 40 85 100 100 o 8 (50) (90) (lCO)> 8 (50) 0) 1 (5Co) 75 75 95 100 iVO r 00 100 100 E: OC) (95) (100): z 851 (90) (95) 1 (1cm) () calculated additive effect. Test method H Fungicidal effectiveness against Plasmopara viticola.

This test method is carried out according to test method B, whereby the plants with an aqueous solution in the form of a spray from a tank mix are treated, the one component a) and one component b) in concentrations as given in Tables B1 to B6 below. The observed Effect illustrated by Tables -B to B below.

1 6 Table B1 Table B2 t "ontponents a 'I according to component a) geinas Example 1 in ppm Example 1 in ppm I 0 2 8 r 32 0 O 1 ° 8 30 1 70 l 100 ~ O 14 ° to 32 0 100 lot30 70 100 to ~ 20 40 1 70 j lOO 2 2 (35) (75) (lCO)% 2 1 (t5) l (75)! (Ico) O ffi 150 60 100-140 (66%) <° 160 jlCO I) 100 S 8 l 651 (85) (CC) Affi 8 80) (100) F'0 a: 65) (90) za 85 1 80j85 100 lOO 32 80 100 j CO 100 32 (85) 1 (95) (100) (80) (100) The individual symbols have the following meanings: () calculated additive effect.

(1) Commercially available product in "Copper Sandoz" form.

(2) Commercially available product as "Rocide 101" form.

Table B Table 34 -Com-oente - Kcmcnerrt & Component a) according to Kcmper! E.it a) geinäss Example 1 in ppm Example 1 in ppm I To = -2 pe 7 32 04080Z¼0? 040 70 1CO g OOO z ~ ~ lz <2 40 60 100 1CO 2 <0 d0 80 1CO (65) (90) (100 '+ 2 (40) (70) (1cm) 70 80 100 100 I 'L70 95 100 1C3 3 70 oO 100 100 8 70 95 100 100 (80) (95) (lU) (80) (90) (100) O 103 100 100 100 to 32 100 100 100 I (100) (100) (lot) U 32 i (lCO) (lot) (1cm) () calculated additive effect.

Table B5 Table 36 - - | - Xom.ponente a) seress component a) according to »ss Example 1 in ppm Example 1 in ppm 0 O 2 8 1 32 O 2 1 8 32 af- o AOO 40 1 80 l 100 0 OO 35 1 80 l 100 F = 2 20 5C! IcO -I 20 20 60 100 100 z 2 20 5Q 90 100 2 ~ ~ (50) (85) (100) 2 ~ (50) I (85) (0 ' O 70 95 100 100 Y 8 60 90 ICO 100 No 8 (80) (95) (100) 8 (75) (90) (1cm) g:. c) 90 32 9O 100 100 9S a 32 Ws5 lCO 100 32 32 1 (95) (100) (100) 2 0 r (100) j (10u) 132 (-> calculated additive effect.

The compounds of formula I are conveniently in the form of fungicides Compositions in conjunction with agriculturally acceptable carriers or solvents or other auxiliaries are used. Such compositions resp. Formulations also form part of the invention. You can next a compound of the formula I contain other active ingredients as the active compound, such as fungicides, in particular a fungicide from the group of component b) such as which have been previously defined.

They can be used in both solid and liquid forms e.g. in the form of a wettable powder, an emulsified concentration, a water-dispersible suspension concentration, the "flowing" properties possesses, a dust powder, a granulate of a depot form which the effectiveness the active compound gradually releases, these forms the usual carriers may contain, as well as solvents and / or other auxiliaries. Such compositions can be prepared by conventional methods.

The formulations according to the invention which contain components a) and b) can contain, for example, by mixing these two components a) and b) obtained, principally with a carrier and other ingredients, which are common in the formulations.

In particular, formulations which are used in the form of a spray such as water-dispersible concentrations or wettable powders, Surface-active compounds can be used as wetting or dispersing aids contain, e.g. the condensation product of formaldehyde with naphthalene sulfate Alkyl aryl sulfate, a lignium sulfate, a fatty alkyl sulfate, an ethoxylated alkylphenol or an ethoxylated fatty alcohol.

In general, the formulations contain from 0.01 to 90 percent by weight Active substance, this active substance either consisting of at least one compound of formula I or mixtures of compounds of formula I exist, if desired also with other active ingredients, for example with fungicides, e.g. one component b) as previously described.

Concentrated forms of the compositions generally contain between about 2 and 80, mainly between about 5 and 70 percent by weight of active ingredient. Liquid application forms of formulations generally contain from 0.01 to 20, advantageously from 0.01 to 5 parts by weight of active ingredient.

The invention can be illustrated by the following examples5 where the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

Formulation example 1 wettable powder.

50 parts of 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide are fine with 2 parts of lauryl sulfate, 3 parts of sodium lignosulfate and 45 parts ground kaolinite ground until the mean particle size is smaller than 5 microns. The wettable powder thus obtained is used before use diluted with water up to a concentration between 0.01 and 5 of active substance. The spray liquid thus obtained can be used as a foliar spray as well as a soaking spray on roots.

Formulation Example 2 Granules.

Place 0.5 parts on 49.5 parts of quartz sand in a rotary mixer a binder (a non-ionic surfactant) is sprayed on and the whole thing mixed vigorously. 5 parts of 2-methoxy-N- (2,6dimethylphenol) -N- (2-oxo-3-oxazolidinyl) acetamide in powder form are added and vigorous mixing continued, with a formulation is available in granulate form with a particle size in the order of magnitude of 0.3 to 0.7 mm. The granules can be entered into the earth in the Near plants to be treated.

Formulation Examples 3 to 6 Wettable Powders. Weight percent Example 3 4 5 1 6 Component a) (1) 12.65 6.25 12.5 6.25 Copper (II) oxychloride (56% copper) 47 47 Copper oxide (~ 88% copper) 29 29 Sodium Lauryl Sulphate 1 1 1 1 Lignin sulfate i 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 components of the formulations are mixed, ground and mixed again according to known methods.

Formulation Examples 7 to 9 Wettable Powders Weight percent Example 7 1 8 89 Component a) (1) 25 12.5 6.25 Component b) 2 (2) 50 50 50 Sodium oleoyl methyl tauride 2 2 2 Condensation product of sodium alkylnaphthalene sulfonate and formaldehyde 5 5 5 Silica gel 5 5 5 Kaolin 13 25.5 31.75 (1) e.g. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide.

(2) e.g. "Folpet".

All components of the formulations were made according to known methods mixed, ground and mixed again.

Formulation Examples 10 to 12 Wettable Powders. Weight percent Examples 10 11 12 Component a) 25 12> 5 6.25 Component b) 3 (2) 50 50 50 Sodium Lauryl Sulphate 1 1 1 Lignin sulfate 4 4 4 Silica gel 5 5 5 Kaolin 15 27.5 33.75 (1) for example 2-metoxy-N- (2,6-dimethylfenyl) -N- (2-oxo-3-oxazolidinyl) -aCet- '-amide.

(2) e.g. "Mancozeb".

The formulations are made by mixing the components, followed by Grinding the mixture and remixing obtained, all operations according to known Methods are carried out.

Example 1 2-Methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolinidyl) acetamide.

11.8 g (0.0375 mol) of 2-chloroethyl 2- (methoxy-acetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate are at room temperature in portions to form a suspension consisting of 2.0 g Sodium hydride (in the form of an approximately 55% mineral oil) and 100 ml of absolute Toluene added under a nitrogen atmosphere. The reaction temperature rises at this point Add up to 400. After the addition is complete, the mixture is left for 30 minutes stirred without cooling and then cooled to 100. The unreacted sodium hydride is then destroyed with ethanol, the solution obtained is washed with water and dried with MgSO4 and the solvent removed in vacuo. Rembebted as a residue the title compound, which is recrystallized from ethanol. The colorless one is obtained Title compound in crystal form with a melting point of 1030 to 1040.

For example, 2-chloroethyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate.

The starting compound used in Example 1 can be obtained as follows are: A mixture consisting of 14.7 g (0.06 mol) of 2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate and 16.2 g (0.1 mol) elethoxyacetic anhydride ((OH3OCH2CO) 20] are in 100 ml of absolute toluene for 1 hour at 800. After cooling, the solution becomes washed with water, then with a 5% aqueous NaHOO solution and then again with 3 water. The solution is dried with bIgSO4 and then the solvent removed in vacuo, the title compound according to the example la is obtained.

For example, 2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate.

To a mixture consisting of 127 g (0.935 mol) 2,6-dimethylphenylhydrazine, 102.5 g (1.3 mol) of pyridine and 400 ml of water, is 133.5 g (0.935 mol) at Oo to 50 Chloraneic acid-ß-chloroethyl ester added. When the addition is complete, the The mixture was stirred at room temperature for 2 hours, the precipitate formed was filtered off, washed with water and dried. The title compound thus obtained is made from toluene recrystallized and results in colorless crystals which melt at 74-75 °.

A preferred alternative method of Examples 1, la and lb can be carried out as follows: Example 2 2-Methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide.

A mixture of 236.1 g (0.75 mol) of 2-chloroethyl (2-methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate, 375 ml of xylene and 187 ml of water are stirred, with cooling from the outside; to 82.5 ml (0.82 mol) of an aqueous solution of is added to this mixture in portions Sodium hydroxide (containing approximately 0.4 g NaOH per ml) and the internal reaction temperature keep at around 200. After the addition is complete, the mixture becomes during Stirred for 1 hour at 200 and for 2 hours at 0 °. The residue is filtered off, washed with 150 ml of water and dried; the weakly colored solid is obtained Title compound with a melting point of 1020-1030.

B e 1 s p i e 1 2a 2-chloroethyl 2- (methyloxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate.

A mixture consisting of 200 g (0.825 mol) of 2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate and 500 ml of xylene, is heated to 800 and to a solution of heated to 80Q 2-methoxy-acetyl chloride in 250 ml of xylene was added [prepared by treating 73.5 g (0.826 mol) of 2-methoxyacetic acid dissolved in 250 ml of xylene with 107.1 g (0.9 mol) Thionyl chloride at 800 for 2 hours. The mixture is for 30 minutes at 800 heated and then worked out the product according to the information in Example la.

B e i s p i e 1 2b 2-chloroethyl 2- (2,6-dimethylphenyl) hydrazine carboxylate.

A mixture consisting of 17.7 g (0.1 mol) of 2,6-dimethylphenylhydrazine hydrochloride, 21.2 g (0.2 mol) of sodium carbonate in 50 ml of water and 50 ml of xylene are at room temperature Stirred for 30 minutes and then cooled to 500. 14.3 g (0.1 mol) of 2-chloroethyl chloroformate are then added over the course of an hour, the temperature being kept at 5 ° will. The mixture is stirred at 50 for an additional hour and finally 100 ml of water was added. The precipitate thus formed is filtered off with water washed and dried. The work-up is carried out according to the information in Example Ib carried out.

In a manner similar to that described in Examples 1 and 2, the following compounds of Formula 1 can be prepared. S & ir: .ei 3sP 'R3 R4 R5 R6 R7 R8 R9 R10 point No. 0 3 II HHH CH3 CH3 H CH20C 2H5 62-4 4 HHHH CH3 Cl H C1120CH3 99-100 5 HHHH CH3 CH3 H t 190-1 6 HH II H CH3 CH3 4-C1 CH2OCH3 107-9 7 H CH3 CH3 H CH3 CH3 H CH20CH3 8 HHHH CH3 CH3 H CH2SCH3 113-5 9 HHHH CH3 CH3 H CH2Cl 134-6 10 HHHH CH3 Cl H CH2C1 135-6 11 HHHH CH3 CH3 H CH20CH (CH3) 2 12 HHHH CH3 Cl H CII20CH (CH3) 2 13 HHHH CH3 Cl H t 166-7 14 HHHH CH3 CH3 H CH2SC4H9 (n) oil 15 HHHH CH3 Cl H CH2SC4H9 (n) oil 16 HHHH CH3 CH3 H, CH-C2H5 123-4 Br 17 HHHH H3 CH3 H C1 147-8 Cl 18 II HH 1 H3 H3 H CIl2Br 143-4 9 HH H1 i EI3 EI H L- 119-20 20 11 H EI Cl Cl EI CH2OCH3 107-9 "EI EI 1 Cl Cl CH2C1 142-4- 5 cnrelz No. R3 R4 R5 R6 R7 R8 R9 R point 10 (0C) 22 HHHH C1 C1 H t 173-4 23 HHHH CH3 CH3 H CH2 1 139-41 24 HHHH CH3 CH3 4-CH3 CH20CH3 Oil 25 HHHH CH3 C2H5 H CH2C1 oil 26 HHHH CH3 CH3 3-C1 CH2OCH3 90-2 27 HHHH CH3 CH3 3-Br CH2OCH3 96-7 28 HHHH CH3 CH3 3-Br CH2C1 182-3 29 HKKK CH3 CH3 3-Br t 145-8 30 HHHH CH3 Br 4-CH3 CH20CH3 125-6 31 H 11 EI EI CEI3 Br 4-CH3 CH2C1 124-6 32 HHHH CH3 Br 4-CH3 193-4 33 HHHH CH3 CH3 H CHOCH3 90-4 CH3 34 HHHH CH3 CH3 K NftO 149-52 35 HHHH CH3 CH3 4-C1 CH2Cl resin 36 KH EI H CH3 CH3 4-C1 m 11 164-5 37 HHH EI H 2H5 C 2H5 H CH20CH3 109-12 38 HHHH CH3 CH3 H CH2OC3H7 (n) oil cnir1z RRRRR R6 R7 R8 ru 10 point ("c) 39 HHKH CH3 CH3 H CH2OC4H9 (n) 40 EI EI EI EI CH3 CH3 EI CH2OCR-C2H5 CH3 41 H EI EI H CH3 CH3 H ES oH2CH2CH = CH2 98-100 42 HHHH CH3 CH3 EI CH2OCH2C-CH 91-93 43 HHH EI CH3 CH3 H CH2 ° t 107-8 44 H EI INCH3 H CH3 CH3 H CH2OCH3 79-80 45; HHH CH3 CH3 H CEI2N 56 1 3 3 46 HHHH C2H5 C2EI5 H 142-4 47 H EI HH 2H5 2 2H5 EI CH2C1 88-9 48 HHHH r Br EI CH2OCH3 150-2 49 EI H EI H> 1 C1 4-Cl CH2OCH3 128-9 50 H EI H EI H C2H5 4-C1 CH2OCH3 114-6 r2--5 3 114-6 1 H EI H Br 1 4-CEI3 CH2OCH3 131-4 2 H EI EI EI3 2EI5 EI CH2OCH3 96-8 53 EI HHH CH3 CH3 4-Br CH 137-8

Claims (10)

Claims 1. Compounds of the formula wherein R1 is a radical R7 and R8 independently of one another are (1-4C) -alkyl, halogen or (1-4C) -alkoxy, R9 hydrogen, (1-4C) -alkyl or halogen, R2 -CO-R10, R10 (1-4C) -alkoxy - (1-4C) -alkyl, (1-4C) -alkylthio- (1-4C) -alkyl, 2-furyl, 2-tetrahydrofuryl, halogenated 2-furyl, halogenated 2-tetrahydrofuryl, 1-imidazolylmethyl-, l- Pyrrazolylmethyl, 2-tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl or halo (1-4C) -alkyl and R3, R4, R5 and R6 independently of one another denote hydrogen or (1-4C) -alkyl. 2. Compounds according to claim 1 of the formula wherein R2 '-CO-CH2-OCH3, -CO-CH2-O-C2H5, -CO- (2-furyl) or -OO- (5-alogen-2-furyl), R7' and R8 'independently of one another are CH3, C1 bder Br and R9 'are H, C1, Br or -OH3, where b 7' and R8 'advantageously have the same meanings. 3. Process for the preparation of compounds of the formula I according to claim 1, characterized in that a compound of the formula in which R1, R3, R4, R5, R6 and R10 have the meanings given in claim 1 and Y is halogen, intramolecularly condensed. 4. Methods of combating fungi, in particular phytopathogens Fungi, characterized in that one has a fungicidal effect Amount of a compound of formula 1 according to claim 1 used. 5. Fungicidal composition containing a compound of the formula I according to claim 1 in conjunction with an agriculturally compatible one Carrier or solvent. 6. Agents for combating fungi, containing a compound of Formula 1 according to claim 1 as an active ingredient. 7. Agent for combating fungi according to claim 6, containing a fungicidal composition according to claim 5. 8. Compounds according to claim 2 of the formula Ia, wherein R2 '-CO-CH2-O-C2H5 , R7 and R each denote -OH and 8 3 R9 'denote hydrogen. 9. Compounds according to claim 2 of the formula Ia, wherein R '-CO- (2-furyl), 2 R7 'and R8' each mean -CH3 and R9 'are hydrogen. 10. Compounds according to claim 2 of the formula Ia, wherein R2 '-CO-CH2-OCH3, R7 'and R8' are each -OH3 and R9 'are hydrogen.