DE3231606A1 - FUNGICIDES - Google Patents

Description

ϋΙ-3 IbUb

Case 130-3918

FUNGICIDES

The present invention relates to compounds used for control of phytopathogenic fungi are useful.

More specifically, the present invention relates to compounds of Formula I.

N-NO

where R, for

wherein R ₇ and R _ß, independently of one another, C, _ ₄ alkyl, halogen

or C, "alkoxy, and R q is hydrogen, C, _" alkyl or halogen, R ₂ is CO-CH ₂ -AR ₁₀

where A stands for 0 or S,

R ₁₀ hydrogen, COR ₁₁ , COOR ₁₁ ,

, CSR ₁₁ , CSNR ₁₁ R ₁₂ or CSOR ₁₁ means

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R ,, C, .Alkyl, Cpgalkenyl, Cogalkynyl, C ₃ -Cycloalkyl unsubstituted or substituted by one or more substituents from the series halogen, alkoxy, alkylthio, CN or SCN; or phenyl is unsubstituted or substituted by one or more substituents from the series consisting of halogen, alkyl, alkoxy or NOp

R ₁₂ signifies hydrogen or R ,, signifies, Rgj R-, R ₅ and R ,, independently of one another, signify hydrogen or C, .Alkyl.

If one of the symbols R ₃ , R ^, R ₅ , R _g , R ₇ , Rg, R _g , R ₁₁ or R ₁₂

stands for or contains an alkyl group (e.g. alkoxy),

this is preferably C ₁ -alkyl, such as methyl, ethyl, n-propyl or i_-propyl.

If one of the symbols R ₇ or R ₈ denotes halogen, this is F, Cl, Br or I, in particular F, Cl or Br, more preferably Cl or Br, preferably Cl.

If one of the symbols R _g , R -, -. or R ₁₂ denotes or contains halogen, this is F, Cl, Br or I, in particular F, Cl, Br, preferably Cl or Br.

R ₇ and R "are preferably in the 2- and 6-position of the phenyl radical to which they are attached. They are preferably identical.

If one of the symbols R ₃ and R. C-, _. Is alkyl, the other is preferably hydrogen.

If one of the symbols Rr and R _g C, .Alkyl means, then the other is preferably hydrogen.

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If R, ₂ does not represent hydrogen, this is preferably identical to R,.

If R ₁₁ and / or R _{12 are} C 1 -C 4 alkyl, C ₂ -C alkenyl, C ₂ -C alkynyl, C ₃ -C cycloalkyl substituted by one or more substituents from the group consisting of halogen, alkoxy, alkylthio, CN or SCN, these are preferably monosubstituted.

Preferred C _2-6 alkenyl or C ₂ _galkynyl meanings of R ₁₁ and / or R ₁₂ are C _2-4 alkenyl or C ₂ _.alkynyl.

If R ₁₁ and / or R _{12 are} phenyl substituted by one or more substituents from the series consisting of halogen, alkyl, alkoxy or NO ₂ , they are preferably mono- or disubstituted.

A preferably denotes 0.

R ₁₀ is preferably COR ₁₁ , SO ₂ R -.- ,, SO ₂ NR ₁₁ R ₁₂ or H.

The compounds are accordingly a preferred group of compounds of formula Ia,

Yes

wherein R ' _{2 is} -COCH ₂ OH, -COCH ₂ OCOCH ₃ , -COCH ₂ OSO ₂ CH ₃ , -C0CH ₂ OS0 ₂ N (CH ₃ ) ₂ ,

R'y and R'o independently of one another denote CH ₃ , Cl or Br and R 'denotes H, Cl, Br or methyl, R' ₇ and R 'are preferably identical.

The invention also relates to methods of making the compounds of formula I by

··· ■■ V2J IGOS

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a) Compounds of the formula Ib

Y> N - N 0

) rL _Q ^Ib

0 <Λ ^R 5 ^R 6 in which R ', q has the above meanings of R, _Q , but not H, and R ₁ »R ₃ . R ₄ . R ₅ and R _{ß have the} above meaning

obtained by compounds of the formula II

"°

N -C-O-C-C-Y II

R ₁ - f <

¹ X-CH ₉ -A-R '

Il C. IU

where R ,, R ,, R., Rj., R _fi and A have the above meaning

R'iq has the above meaning and Y is halogen
subjected to intramolecular condensation or

b) Compounds of the above-defined compounds of the formula Ib are obtained by adding a compound of the formula III

R ₁ - NN 0 ΠΙ

COCH ₉ W

^R 3 R ₄ R ₅ 6

wherein R ₁ , R 3, R ₄ , R ₅ and R _{g have the} above meaning

and W is a leaving group with a compound of of formula IV

BA R _'1O IV

wherein B is hydrogen or a metal equivalent and A and R _'ln ohige meaning, are reacted.

G -X-

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c) compounds of the formula

HA-CH ₀ -C

t ii

Ic

_R 4 ^K 5 ^Κ 6

wherein R ,, R ₃ , R., R ₅ , R _ß and A have the above meaning, by alcoholysis of the corresponding compounds of the formula Id,

R "-ACH ₀ -

IU c- it

N-N

Id

where R ¹ 'COR ,, or SO ^ R ,, and R ,, has the above meaning,

and R ₁ , R 3, R ₄ , R ₅ , Rg and A are as defined above.

The above intramolecular condensation according to process a) can be carried out analogously to known processes. The reaction is exothermic. It can be carried out, for example, in an anhydrous medium using as solvent, an ether such as dimethoxyethane, a hydrocarbon such as toluene or another solvent which is inert under the reaction conditions. The reaction temperature is not critical and can be between about 0 ° and 100 ⁰ C. Since the reaction is exothermic, the reaction is expediently started at room temperature and the reaction temperature is allowed to rise gradually.

Y is especially chlorine or bromine, especially chlorine.

The reaction is conveniently carried out in the presence of an acid-binding agent Means such as sodium hydride, sodium amide or a sodium alcoholate,

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e.g. sodium ethoxide.

The intramolecular conversion can also take place in an aqueous / organic two-phase system in the presence of an inorganic base such as sodium hydroxide and optionally a catalytic amount a phase transfer catalyst can be carried out.

Any suitable organic phase is not suitable with water Miscible, inert solvents such as hydrocarbons or halogenated hydrocarbons, e.g. xylene, toluene, or dichlorobenzene or dichloromethane. Suitable phase transfer catalysts are quaternary ammonium compounds such as benzyltrimethylammonium bromide, quaternary phosphonium compounds such as benzyltriphenylphosphonium chlorides and crown ethers such as 18-crown-6.

In process b), W preferably represents halogen or sulfonyloxy an organic sulfonic acid, for example, a C ₁₅ alkyl SOPO group such the mesyloxy or a phenyl-S0 ₂ 0 group, wherein the phenyl group is optionally substituted by C -, _ ₅ alkyl, NOp, CN or halogen is substituted, such as £ -tosyloxy.

The reaction is expediently carried out in an organic solvent which is inert under the reaction conditions, such as alcohols, Hydrocarbons, halogenated hydrocarbons, nitriles such as acetonitrile or amides such as dimethyl formamides carried out.

The reaction temperature is not critical and can be between room temperature and the boiling point of the solvent used. As is known, the exact reaction conditions vary with the choice of W and R ¹ ^ ₀ -AB. B is preferably a metal equivalent, for example Na, K or \ Ca.

The compounds of the formula Ic are expediently by base

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catalyzed alcoholysis of the compounds of formula Id prepared. Such alcoholysis is expedient under mild conditions, e.g. at room temperature, preferably in a large excess an alcohol such as methanol and in the presence of a catalytic amount of a sodium alcoholate such as sodium methanol at.

It is clear that implementation of a compound of formula I in a other compound of the formula I can be carried out by known methods.

The compounds of the formula I in which R, _{o is} not hydrogen, for example, by acylation of the corresponding compounds of the formula I in which R, q is hydrogen, using an acylating agent such as an acid halide (preferably acid chloride or acid bromide) or an acid anhydride of R '., _Q (where R', Q has the above meaning) or with R ,, NCO, according to known methods.

The compounds of the formula II are new. You can by acylation of the compounds of formula V

0 R ₁ - Rf- R, R, R ₁ -NH-NH-COC-CY V

where R ,, R ^, R ₄ , Rr, R _ß and Y have the above meaning, with compounds of formula VI

R ' _1O -A-CH ₂ -CZ VI

where R ', _o and A have the above meaning, and Z is halogen, especially chlorine, or OCOCHpAR ¹ , _Q is

wherein A and R ', _{Q have the} above meaning are obtained.

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Suitable solvents for this acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is carried out zweckm'ässig 80 ⁰ C at a temperature between about 20 ° and about 120 ⁰ C, for example.

The compounds of the formula B can be prepared by reacting the compounds of the formula VII

- NH-NH ₂ VII

wherein R, has the above meaning, with compounds of the formula VIII

0 \> «3/4

X-C-O- C C-Y VIII

wherein R ₃ , R ₄ , R ₅ , R _ß and Y have the above meanings

and X represents halogen, in particular chlorine, can be obtained.

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This reaction can be up to about 1O ⁰ C in water or in an organic, inert under the reaction conditions, advantageously in the presence of a base, eg an organic amine or sodium bicarbonate can be carried out at a temperature of about 0 °.

The compounds of formula III can be by intramolecular Condensation can be obtained analogously to process a).

The starting materials and reagents used in the above procedure are either known or, if they are not known, can be prepared analogously to known processes.

The compounds of formula I have valuable fungicidal properties, inshosondore against phytopathogenic fungi, more particularly against fungi of the oomycete class as shown by a significant effect in the following tests.

TEST A

Fungicidal effect on Phytophthora infestans

Planting young potatoes in pots (at the 3 to 5 leaf stage) are sprayed with an aqueous suspension, which Contains 0.003% (weight / volume) of a compound of the formula I, for example 2-methylsulfonyl-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (formulated according to formulation example I). Two hours later the treated plants are inoculated with a spore suspension of Phytophthora infestans Tent placed in which there is 100% relative atmospheric humidity. At a room temperature of 16 ° C and at a day length of 16 hours.

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Disease control is determined 4 to 5 days later by comparing the treated plants with untreated, similarly inoculated plants.

The above test substance is a considerable control of fungicidal infection observed with no evidence of phytotoxicity on the host plants.

TEST B

Fungicidal effect on Plasmopara viticola .

Young vines planted in pots (in the 3 to 6 leaf stage) are sprayed with an aqueous suspension containing 0.0008% Contains (weight / volume) a compound of the formula I, e.g. 2-methylsulfonyl-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyI) -acetamide (according to formulation example I). Two hours later the plants treated in this way are inoculated with a suspension of spores of Plasmorpara viticola and the plants treated in this way then transferred to a tent, in which a 100% relative atmospheric humidity prevails at a room temperature of 15 to 22 ° C (fluctuating over a 24-hour period) and a day length of 16 hours.

Disease control is assessed 6 days after inoculation by comparing the treated with the untreated similar inoculated plants. Considerable control of the fungicidal infection is observed with the test substance significant signs of phytotoxicity on the host plants.

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TEST C

Curative fungicidal effect against Piasmopara viti cola .

Young vines planted in pots (3 to 6 leaf stage) are inoculated in the same way as in test method B, except that the compound, e.g. 2-methylsulfonyloxy-N-2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (formulated according to formulation example I) not applied until 3 days after inoculation becomes: the incubation conditions are the same as described in test method B. The infestation is controlled as in Test B indicated. With the test compound, a considerable Control of the infestation observed.

TEST D

Eradicative fungicidal effect against Piasmopara viti cola .

The procedure to determine this type of activity is as in Test C described performed with the exception that the treatment is only carried out 6 days after inoculation, when the spore formation is already visible on the lower leaf surface.

Control of the infestation 7 days after application of e.g. 0.012% of the Compound 2-Methy1sulfonyloxy-N- (2,6-dimethy! Phenyl) -N- (2-oxooxazolidinyl) -acetamide (formulated according to formulation example I) shows a stopping effect on already sporulating zones.

TEST E.

Translocation in treated vine leaves

Cut vine leaves are sprayed with an aqueous suspension which contains 0.012% of a compound of the formula I, e.g. 2-methylsulfony1oxy-N- (2,6-dimethyl phenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (formulated according to formulation example I) contains, only the

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the lower half of these leaves is treated. Two hours after the treatment, inoculated the entire sheet with a spore suspension of Plasmopara viti cola, and then the leaves are incubated in a tent having a 100% atmospheric relative humidity and as described under the conditions of Test Method B. Although only the lower half of the leaves were treated as described above, considerable control can be observed over the entire leaf surface. The same effect can also be observed over the entire leaf if only the upper half of the leaves has been treated . This test accordingly shows that the 2-methylsulfonyloxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (formulated according to formulation example I) is transported acropetally and basipetally into the leaf.

TEST F.

In vivo, using Pythium aphanidermatum .

The fungus is cultivated in a sterile mixture of sand and corn meal (97: 3 V / V): the cultivation lasts 4 days at 25 ° C. Of the Fungus is then treated with a semi-sterile mixture of peat and sand mixed and then treated with a suspension containing the active ingredient in a concentration of 10 to 160 ppm (e.g. 10, 40 and 160 ppm calculated per volume of substrate). The substrate is placed in pots 5 cm in diameter in which cucumber seeds are sown will. The pots are at 24 ° C and 60-70% relative humidity incubated in an incubation room for 7 days, and the number of healthy emerged plants with that in untreated, analogous inoculated comparison pots. The compound according to Example 1, used in the wettable powder formulation according to Formulation Example 1 gives a significant control. Analogous tests with beets and sugar beets give comparable results.

130-3918

Each of the following compounds in the following examples possesses and has fungicidal properties Usefulness as a fungicide.

Particularly effective fungicidal activity is demonstrated in the above experiments with the compounds of the formula Ia in which R ' _? and R ' _g CH ,, R' _g hydrogen and R ' ₂ COCH ₂ OH or COCH ₂ OSO ₂ CH ₃ found.

The invention accordingly also relates to a method for combating phytopathogenic fungi, in particular the class of the Oomycetes, on plants, seeds or in soil with an amount of a compound of the formula I exhibiting a fungicidal effect.

Fungi of the class of the Oomycetes , against which the inventive method is particularly effective, are those of the genus Phytophthora on plants such as potatoes, tomatoes, tobacco, citrus, cocoa, gum, apples, strawberries, vegetables and ornamental plants, for example

Phytophthora infestans on potatoes and tomatoes; of the genus Plasmopara viti cola on vines; of the genus Peronospora on plants such as tobacco, for example Peronospora tabacina, on tobacco;

of the genus Pseudoperonospora on plants such as hops and cucumber, for example Pseudoperonospora humuli on hops; of the genus Bremia on plants such as lettuce, for example Bremia Lactucae on lettuce;

of the genus Pythium , which causes the roots of a large number of plants to rot and rot, for example vegetables, sugar beets, ornamental plants and conifers, for example Pythium aphanidermatum on sugar beets;

of the genus Sclerospora on plants such as sorghum and maize, e.g.

Sclerospora sorghis on sorghum.

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When using the method according to the invention, the amount is of the preparation that is to be used depends on various factors, such as the species of fungus to be controlled, the time and the type of application, as well as the amount and type of compound of formula I contained in the preparation.

In general, however, satisfactory results are obtained when applied to the site to be treated, e.g. on crops or used in the soil in amounts in 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 area to be treated, the treatment being repeated if necessary.

If used in seed coating, satisfactory results are obtained when in an amount of from about 0.05 to 0.5 advantageously used from about 0.1 to 0.3 g of a compound of the formula I per kilo of seed.

Depending on requirements, the compounds of the formula I can be used in combination with other pesticides, e.g. fungicides, bactericides, insecticides, acaricides, herbicides or plant growth regulators are used to improve their effectiveness or to expand its spectrum of activity.

A particularly preferred method according to the invention relates to Application, to the site to be treated, of a fungicidally effective amount of a component a) containing a compound of the formula I and one or more compounds of the series copper fungicide, captan, Folpet, Mancozeb or Maneb.

Examples of copper fungicides suitable for use in association with a compound of formula I are Copper (II) carbonate, copper (11) ca! Egg sulfate, copper (11) calcium oxy-

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chloride, tetracupric oxychloride, Bordeaux mixture, Burgundy mixture, copper oxide, copper (II) hydroxide, copper (II) oxychloride or copper complexes such as copper triethanolamine hydroxide of the formula [CuN (CH ₂ CH ₂ OH) ₃ ] ( OH) ₂ , commercially available under the name "K-Lox", or bis (Ä'thylenediamine) copper-II sulfate, commercially available under the name "Komeen", and mixtures thereof, in particular copper oxide, copper II-oxychloride, copper-II-hydroxide and a mixture of copper-II-calcium sulfate and copper-II-oxychloride.

"Captan", Folpet "," Mancozeb "and" Maneb "are the most common Names for protective fungicides which are used against diseases of the Foliage are effective. (Pesticide Manual, 5th Ed. By H. Martin and CR. Worthing, pages 76, 281, 328 and 329).

The compounds of formula I are conveniently in the form of fungicidal compositions in connection with for agriculture compatible carriers or diluents or other auxiliaries funds used. Such formulations also form one Part of the invention. In addition to a compound of the formula I, they can contain other active ingredients such as fungicides as active compounds.

They can be used in both solid and liquid forms e.g. in the form of a water-dispersible powder, an emulsion concentrate, a water-dispersible suspension concentrate ("flowable"), a dust powder, a granulate, a depot form from which the active substance is released with delay , these forms containing the usual carriers, diluents and / or other auxiliaries. Such compositions can be prepared by conventional methods, e.g. by Mixing the active ingredient with a carrier and other formulation aid sniittel η.

130-3918

In particular, formulations which are used in the form of a spray such as water-dispersible concentrates or powders, surface-active compounds such as wetting or dispersing aids can be used contain, e.g. the condensation product of formaldehyde with naphthalene sulfate, an alkyl aryl sulfate, a lignin sulfonate, an alkyl sulfate, an ethoxylated alkyl phenol, or a ethoxylated fat alcohol.

In general, the formulations contain from 0.01 to 90 percent by weight Active substance, this active substance either from at least one compound of the formula I or from mixtures of Compounds of the formula I with other active ingredients, for example with fungicides. Concentrated forms of the compositions generally contain between about 2 and 80, mainly between about 5 and 70 weight percent active. 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 examples, where the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

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Formulation example 1

50 parts of 2-methylsulfonyloxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide are so with 2 parts of lauryl sulfate, 3 parts of sodium lignosulfonate and 45 parts of finely divided kaolinite Long milled until the mean particle size is below 5 microns. The wettable powder obtained in this way is with prior to use Water is diluted to a concentration between 0.01 and 5% of the active substance. The spray liquid obtained in this way can be used both as Foliar spray as well as for soaking the roots or as a root spray can be used.

Formulation example 2
granules

On 94.5 parts of quartz sand in a drum mixer, 0.5 part of a binder (a nonionic surfactant) is sprayed and that whole vigorously mixed. 5 parts of 2-methylsulfonyloxy-N- (2,6-dimethylphenol ) -N- (2-oxo-3-oxazolidinyl) -acetamide in powder form v / ground added and the vigorous mixing continued to form a granulate formulation with a particle size in the order of magnitude from 0.3 to 0.7 mm. The granulate can be added to the soil of the plants to be treated.

Formulation example 3

25 parts of a compound of formula 1, e.g. the compound according to the following Example 8.1, 65 parts of xylene, 10 parts of the mixed reaction product of an alkylphenol with ethylene oxide and calcium dodecyl benzenesulfonate are mixed thoroughly until

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a homogeneous solution is obtained. The emulsion concentrate obtained is diluted with water before use.

Example 1 : 2 - [- methylphenyl) -sulfony_loxy _] - N- [2,6-d ^ methyj phenyl} -

A slurry of 95.5 g (0.21 mol) of 2- (4-methyl phenyl sulfonyloxyacetyl) -2- (2,6-dimethylphenyl) hydrazine-carboxyl-2-chloroethyl ester in 500 ml of dry methanol is slowly, while resting, a solution of 12.4 g (0.23 mol) of sodium methanol at in 200 ml of dry methanol were added. After the exothermic reaction has ended, the mixture is stirred for a further 2 hours at room temperature and the solvent is then removed in vacuo. The residue is dissolved in CH ₂ Cl ₂ , washed twice with water, dried over MgSO and the reaction mixture is evaporated.

The residue is chromatographed on silica gel using of toluene / ethyl acetate as the eluent, and gives the title compound as a yellow oil, which solidifies after treatment with toluene and gives a colorless substance with a melting point of 122-5 °.

Example 2 :

The procedure of Example 1 is repeated, except that the corresponding starting compounds of the formula II are used, and the following compounds of the formula I are obtained (Table A: R ^, R *, R ₅ and Rg are H).

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TABLE A

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example ^R 7 ^R 8 ^R 9 ^A - ^R io 2-1 2-CH ₃ 6-CH ₃ 3-Cl OSO ₉ - (Oy-CH ₃ 2-2 2-CH ₃ 6-CH ₃ 3-Br ^OSO 2 "{°) ~ ^CH 3 2-3 2-CH ₃ 6-CH ₃ 3-CH ₃ OSO ₂ -Q) -CH ₃

Beis £ i_el__3: 2 _: Ethgxy. _: N _: [2,6 _: dimethj;} phenylhN _: (2 _: oxo _: 3 _: gxazolidiny.l> acetaniid

A mixture of 70.6 g (0.25 mol) of 2-chloro-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide and 49-2 g (0.6 mol) of dry sodium acetate are added with stirring , heated to 110 ° for 3 hours in 500 ml of dry dimethylformamide. The cooled mixture is filtered off with suction, the residue is washed thoroughly with dimethylformamide and the combined filtrates are concentrated in vacuo. The residue is dissolved in CH ₂ Cl ₂ , washed with water, dried, the solvent removed and, after crystallization from ethanol, gives the title compound as colorless crystals, melting point 102-106 °.

Example 4:

The procedure is analogous to Example 3, but using the corresponding starting compounds of the formula III, in which W is Cl or p-tosyl and of the formula IV in which B is Na, and the following compounds of the formula I are obtained (Table B: R ₃ , R ₄ , R ₅ and R _ß mean H).

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TABLE B.

example V V ^R 9 ^A " ^R io Characteri
ization
Melting point 4-1 CH ₃ Cl H O
-OC-CH ₃ 122-5 ° 4-2 CH ₃ CH ₃ H O
-OC-CH ₂ OCH ₃ oil 4-3 CH ₃ Cl H O
-OC-CH ₂ OCH ₃ 4-4 CH ₃ CH ₃ H O
-SC-CH ₃ 4-5 CH ₃ CH ₃ 3-Cl O
-OC-CH ₃ 4-6 CH ₃ CH ₃ 3-Br O
-OC-CH ₃ 115-7 ° 4-7 CH ₃ CH ₃ H S.
-SCN (CH ₃ ) ₂ 17 3-5 ° 4-8 CH ₃ CH ₃ H S.
-SCOCH ₃ 4-9 CH ₃ CH ₃ H O
-OC-O

* R_ and R _Q are in the 2,6 position / ο

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Example 5:

A solution of 24.8 g (0.46 mol) sodium methoxide in 200 ml dry methanol is slowly, with stirring, a slurry of 258 g (0.843 mol) of 2-acetoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide, prepared as in Example 3, added in 2.5 liters of dry methanol. The mixture which after 30 minutes becomes a clear solution, is a total of 2 hours at room temperature stirred, and the solvent then removed under vacuum. The remaining oil is poured into water and the pH adjusted to pH 2 by means of 2N aqueous HCl. The product is extracted with 3 portions of chloroform, the combined organic phases washed with water, over MgSO. dried, and the solvent removed under vacuum, a colorless solid being obtained. The title compound is in the form of colorless crystals obtained from ethanol (melting point 138-9 °).

Example 6:

The procedure is analogous to Example 5, and by alcoholysis of the corresponding starting compounds of the formula I, in which Rp is COCHpOCOCHo, the following compounds of the formula I, in which Rp is COCHpOH (Table C: R ₃ , R ₄ , R ₅ and R are H. ).

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TABLE C

example ^R 7 ^R 8 ^R 9 ^A " ^R 10 Characteri
ization
Melting point 6-1 2-CH ₃ 6-Cl H OH 169-71 ° 6-2 2-CH ₃ 6-CH ₃ 3-Cl OH 6-3 2-CH ₃ 6-CH ₃ 3-CH ₃ OH 6-4 2-CH ₃ 6-CH ₃ 3-Br OH 139-41 °

Example 7 : 2 _: [Diniethy_l ami Qosul fοηγΐοχγ_} _: Ν _: {2 ₂ 6 _: α1 methyl phenyl} -iili? Z2i2l3-oxazole i di nyl} -acetami d

13.2 g (0.05 mol) of 2-hydroxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide are added in portions while stirring at 10-15 ° under a ^ atmosphere added to a slurry of 2.2 g (about 0.05 mol) of sodium hydride (as a 55-60% dispersion in oil) in 100 ml of dry dimethoxyethane. The mixture is stirred for half an hour at room temperature and 7.5 g (0.055 mol) of dimethyl sulfonic acid chloride are then added. The mixture is heated to 50 ° and stirred at this temperature overnight. The mixture is filtered, the filtrate, after cooling, concentrated in vacuo, the remaining oil is dissolved in CHCl ₃ , washed with water, dried over MgSO ₄ and the solvent is removed in vacuo.

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The title compound is obtained as a yellow, viscous oil Chromatography on silica gel using toluene / ethyl acetate 1: 1 as a superplasticizer.

Example 8 :

The procedure is analogous to Example 7, except that the corresponding starting materials of the formula Ic and acid chlorides R Cl are used, and the following compounds of the formula I are obtained (Table D: R-, R., R _1. And R ₆ are H).

TABLE D.

example V V ^R 9 ^A " ^R io Characteri
ization
Melting point 8-1 CH ₃ CH ₃ H -OSO ₂ CH ₃ 142-5 ° 8-2 CH ₃ CH ₃ H O
-OCOCH ₃ 133-8 ° 8-3 CH ₃ CH ₃ H O
-OCNHCH ₃ 174-7 ° 8-4 CIl ₃ CH ₃ H O
-OCNH-0-C1 115-20 ° 8-5 CH ₃ CH ₃ 3-Cl -OSO ₂ CH ₃ 8-6 CH ₃ CH ₃ 3-Br -OSO ₂ CH ₃ 168-72 ° 8-7 CH ₃ CH ₃ 3-Cl O
-OCNHCH

* R-, and R ₀ are in the 2,6-position
/ ο

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example V V ^R 9 ^A - ^R io Characteri
ization
Melting point 8-8 CH ₃ CH ₃ H O
OCN (CH ₃ ) ₂ 157-61 ° 8-9 CH ₃ CH ₃ H O
Il
OCSCH ₂ CH-J oil

and Rg are in the 2,6 position

Output connections

The starting compounds used in Example 1 can be prepared as follows.

Example A: _{2: (4; MethYlßheriYlsulfgnYlgxYacetYl}: 2:} {2 _i 6-dimGthYl-

A solution of 112 g (0.45 mol) 2- (4-methylphenyl-sulfonyloxy) -acetyl chloride in 100 ml of toluene is slowly, with stirring at room temperature, a slurry of 2- (2,6-dimethylphenyl) hydrazine carboxyl-2-chloroethyl ester in 500 ml of toluene was added, and the mixture was stirred for 4 hours at room temperature. The reaction mixture is then successively with water, an aqueous NaHCO., - solution and washed with water, dried over MgSO and evaporated in vacuo to give a yellowish solid which after crystallization from ethanol, the title compound results in the form of colorless crystals with a melting point of 125-7 °.

.ΟΔΟ Ι OUO

130-3918

Example B : 2- {2,6-Dimeth ^ lBheny2] -h ^ drazin-carbox ^ l; {2-chloroethy] jester

A mixture of 17.7 g (0.1 mol) of 2,6-di methyl phenyl hydrazine hydrochloride and 21.2 g (0.2 mol) of sodium carbonate in 50 ml water / 50 ml of xylene is stirred for 30 Minuton at room temperature and then cooled to 5 ^Ü.

14.3 g (0.1 mol) of chloroformic acid - (2-chloroethyl) ester then added over the course of an hour, the temperature being kept at 5 °, by cooling.

The mixture is stirred for a further hour at 5 °, then 100 ml of water is added, the precipitate formed is filtered off, washed with water, dried, the title compound being obtained as a light-colored solid substance with a melting point of 69 ° -70 °. After recrystallization from diethyl ether / light petroleum fraction the melting point rises to 74τ75 °.

Example C

The procedure is analogous to Example 1, but using compounds (analogous to compounds of the formula II) in which AR ^ _{0 is,} however, Cl or Br, and the following compounds of the formula III, Table E are obtained: R ₃ , R ₄ , R ₅ and R ₅ are H) .

TABLE E.

■ U3 1606

130-3918

example R ₇ ^R 8 ^R 9 W. Characteri
ization
Melting point C-1 ^ -CH * j 6-CH ₃ H Cl 134-6 ° C-2 2-CH ₃ 6-CH ₃ 3-Cl Cl 154-7 ° C-3 2-CH ₃ 6-CH ₃ H Br 143-4

Claims (4)

32316Q6 IS Case 130-3918 claims 1.) A compound of the formula I. stands wherein R, and R ", independently of one another, C, .Alkyl, halogen or C, .Alkoxy, and Rg is hydrogen, Ci-alkyl or halogen, R _{2 is} CO-CH ₂ -AR ₁₀ , where A is 0 or S, R ₁₀ hydrogen, COR ₁₁ , COOR ₁₁ , , CSR ₁₁ , CSNR ₁₁ R ₁₂ or CSOR ₁₁ means ■ \ Y? .2 I G06 ι9 - 130-3918 C ₂ _ _g alkenyl, CggAlkinyl, C ₃ _gCycloalkyl unsubstituted or substituted by one or more substituents selected from halogen, alkoxy, alkylthio, CN or SCN; or phenyl is unsubstituted or substituted by one or more substituents from the series consisting of halogen, alkyl, alkoxy or NO ₂ R, "means hydrogen or R ^ _{1 has} meaning, R-, R, R and R _fi , independently of one another, hydrogen or C, _. Mean alkyl . 2. A method for controlling phytopathogenic fungi in plants, Seeds and soil, characterized in that a fungicidally effective amount of a compound is added to the plants, seeds or soil applied according to claim 1. 3. A fungicidal preparation containing a compound according to Claim 1 together with one acceptable in agriculture Carrier or diluent. 4. A process for the preparation of a compound according to claim 1, characterized in that one a) Compounds of the formula Ib > N - NO 0 R ₃ ^ ₄ R wherein R ¹ -in has the meaning of R _1n given in claim 1, but is not H, and Rh, R-., R., R ₁ - and R _{fi have the} above meaning obtained by adding compounds of the formula II 3ο 130-3918 Rr R / r R> H Λ / ⁶ ^ NCOCCY II R ₁ - ¹ "t - CH ₀ - A - R ' ■ ι C- IU wherein R ,, R ₃ , R ₄ , R ₅ , Rg and A have the above meaning, R ', 0 has the meaning given in this claim, and Y is halogen subjected to intramolecular condensation or b) the compounds of the formula Ib defined in claim 1 are obtained by adding a compound of the formula III R ₁ - NNQ HI COCH ₀ W ² -Ί ¹ ^ R, wherein R ₁ , R 3, R., R ₅ and Rg have the above meaning and W is a leaving group with a compound of Formula IV BA R _'lo IV where B is hydrogen or a metal equivalent and A and R '-, ^ in claim 1, respectively. 4 given meaning own, implement, c) compounds of the formula Ic Rt Ic / \ / HA-CH ₉ -C <- ti wherein R ₁ , R ^, R ₄ , R ₅ , Rg and A have the meaning given in claim 1, . .ο ο ο -X- 130-3918 by alcoholysis of the corresponding compounds of the formula Id, • w A. N-Np Id ^l V ^A - ^CH 2 - S '
0 wherein R " _lo COR ₁₁ or SO ₂ R ₁₁ , and R _{11 has} the meaning given in claim 1, and R ₁ , R ₃ , R-, Rj-, R ₆ and A are those given in claim 1 Have meaning
.receives. 3Ζό IbUb (new) - ^ Si- 130-3918 Claims (amended according to PCT Article 19 (1) "!. (Amended)" A compound of the formula I. where R, for N O stands wherein R ₇ and , Independently of each other, Cj ^ alkyl, halogen or C -._ "alkoxy, and R q is hydrogen, C ^ alkyl or halogen, R ₂ is CO-CH ₂ -AR ₁₀ where A stands for 0 or S, R ₁₀ hydrogen, COR ₁₁ , COOR ₁₁ ^ n ND D PQD CONR ₁₁ R ₁₂ , "or CSOR _11th means, R ₁₁ C ₁₆ alkyl, C ₂₆ alkenyl, C _2-5 alkynyl, C ₃ alkyl unsubstituted or substituted by one or more substituents from the series halogen, alkoxy, alkyl thio, CN or SCN; or phenyl unsubstituted or substituted by one or more substituents from the series halogen, alkyl, alkoxy or NO ₂ . means R ₁₂ denotes hydrogen or an R ₁ -. Has meaning, but if R _{2 is} COCH ₂ OCOCH ₃ , COCH ₂ OSO ₂ CH ₃ or COCh ₂ OSO ₂ NHCH ₃ , R-. does not represent 2,6-dimethylphenyl or 2-chloro-6-methylphenyl and if R ₂ denotes COCH ₂ OH, R ₁ does not denote 2,6-dimethylphenyl. lh - 32 "- 130-3918 "2. (new)" A compound according to claim 1, wherein AR, _Q either for SH, S-COR ₁₁ , S-SO ₂ R ₁₁ , S-SO ₂ NR ₁₁ R ₁₂ , ArCONR ₁₁ R ₁₂ , A-CS-R ₁₁ , A-CS-NR ₁₁ R ₁₂ or A-CS- OR ₁₁ and A, R ₁₁ and R _{12 have} the meaning given in claim 1 own,
or represents 0-COR ₁₁ and R _{11 has} the meaning given in claim 1, where, if R _{11 is} alkyl, this Alkyl contains 2 to 6 carbon atoms, or represents 0-SO ₂ RI ₁ and R .., has the meaning given in claim 1, where, if R -, -. Alkyl is this Alkyl contains 4 to 6 carbon atoms, or represents 0-SO ₂ NR ₁₁ R ₁₂ and R ₁₁ and R _{12 have} the meaning given in claim, where R, -. is not Cl-L if R _{12 is} H. "3. (new)" A compound according to claim 1 or 2, wherein R _{g is} Ci-alkyl or halogen. "4. (new)" A compound according to claim 1, wherein AR _{10 is} OH, and Rg is C-1, alkyl or halogen. "5. (new)" A compound according to claim 4, in which R _ß 6 " _{denotes CH 3} , and R _g denotes 3-Cl or 3-Br. "6. (new)" A compound according to claim 2, wherein AR _1n O-SOpNiC-joAlkyl) is Ri-j, and R _{11 has} the meaning given in claim 1. "7. (new)" A compound according to claim 6, wherein AR-. _Q di (C, ~ ₃ alkyl) aminosulfonyloxy means. "8. (new)" A compound gomä'ss claim 7, wherein R, ./; L · ο luuu - 23 - 130-3918 2,6-Dimethy! Phenyl and AR ₁₀ 0S0 ₂ N (CH ₃ ) ₂ mean. "9. (originally claim 2)" A compound for controlling phytopathogenic fungi in plants, seeds and soil, thereby characterized in that one adds a fungicidally effective amount of a compound according to a to the plants, seeds or soil of claims 1 to 8 applied. "10. (originally claim 3)" A fungicidal preparation
Containing a compound according to any one of claims 1 to 8 together with a carrier or diluent which is acceptable in agriculture. "11. (originally claim 4)" A process for the preparation of a compound according to claim 1, characterized in that one a) Compounds of the formula Ib R ₁ wherein R ' _{1Q has} the meaning of R ₁₀ given in claim 1, but does not mean H and A and R, which have the meaning given in claim 1, are obtained by adding compounds of the formula II -ST- 130-3918 H, NCO-CH _{0 -CH 9} -Y II ^R l ■ ^N <v, X - CHo - A - R wherein R 1 and A have the meaning given in claim 1, R ' _{lo has} the meaning given in this claim, and Y is halogen
subjected to intramolecular condensation or b) the compounds of the formula Ib defined in claim 1 are obtained by adding a compound of the formula III - N N O ΠΙ \ - ' wherein R has the meaning given in claim 1 and W is a leaving group with a compound of formula IV BA R _'1O IV wherein B is hydrogen or a metal equivalent and A and R ', _o in claim 1, respectively. 11 given meaning own, implement,
c) compounds of the formula Ic \ X HA-CH ₉ -C ^ ^N - ' C- H wherein R ^ and A have the meaning given in claim 1, sJ IUUO -3Gr- 130-3918 by alcoholysis of the corresponding compounds of the formula Id, ^ N-NO Id 0 where R " _1Q COR,. Or SOpR ₁ 1, and R ,, has the meaning given in claim 1, and R, and A have the meaning given in claim 1, is obtained.