CS219857B2 - Fungicide means - Google Patents

Abstract

2-(N-Aryl-,N-isoxazolylcarbonyl)aminobutyrolactones of the formula <IMAGE> in which R<1> denotes C1-C3-alkyl, R<2> denotes hydrogen, C1-C3-alkyl or halogen, R<3> denotes hydrogen, C1-C3-alkyl or halogen, R<4> denotes hydrogen or an optionally substituted C1-C3-alkyl radical, and R<5>, R<6> and R<7> denote hydrogen or methyl, and fungicides containing them.

Description

The invention is. relates to novel 2- (N-aryl-N-isoxazolylcarbonyl) aminobutyrolactones, method. . their manufacture, fungicides containing these compounds as. as well as a method for controlling harmful fungi using such active compounds.

Fungicidally active 2- (N-aryl-N-arylcarbonyl) aminobutyrolactones are known from U.S. Pat. No. 3,933,860, such as 2- (N-2,6-dimethylphenyl-N-3,4-dichlorophenylcarbonyl) aminobutyrolactone (see example 2 of the aforementioned patent specification). However, the activity of these compounds against lower fungi such as Phytophthora is not sufficient.

It was now. found to be 2- (N-aryl-N-isoxazolylcarbonyl) aminobutyrolactones in general

in which

R1 represents a C1-C3 alkyl group (such as a methyl or ethyl group),

R2 represents a group having 1 to 3 carbon atoms (such as a methyl or ethyl group) or a halogen atom. (such as chlorine or bromine),

R 3 represents a hydrogen atom or a C 1 -C 3 alkyl group (such as a methyl or ethyl group); and

R ⁴ represents a hydrogen atom or a C 1 -C 3 alkyl group (such as a methyl or ethyl group), optionally substituted by a methoxy group, exhibits excellent fungicidal activity and is superior to known 2- (fungi) of Phytophthora N-aryl-N-arylcarbonyl) aminobutyrolactones.

The 2- (N-aryl-N-soxazolylcarbonyl) aminobutyrolactones of the formula I contain an asymmetric center on the carbon atom in the 2-position of the butyrolactone ring.

Optically pure enantiomers may be annealed by conventional methods. Both the mixture of these enantiomers, usually resulting from the synthesis, and the pure enantiomers are fungicidally effective. The invention encompasses both pure enantiomers and mixtures thereof.

2- (N-aryl-N-isoxazolylcarbonyl) aminobutyrolactones of formula I can be prepared by reacting 2- (N-aryl) aminobutyrolactone of formula II

in which

R1, ^R2 and R3 have the above meanings, is reacted with a derivative isoxazolylkarboxylové acid of formula III

in which

R4 is as defined above and

A represents a nucleophilically cleavable group, optionally in the presence of a solvent or diluent, optionally in the presence of an inorganic or organic base, and optionally in the presence of a reaction accelerator, at a temperature ranging from 0 to 120 ° C.

In the above general formula (III), A represents, for example, a halogen atom such as chlorine or bromine, alkoxycarbonyloxy, such as methoxycarbonyloxy or ethoxycarbonyloxy, benzyloxycarbonyloxy or azolyl, such as imidazolyl or triazolyl.

The reaction may be carried out in the presence of a solvent or diluent. Preferred solvents or diluents include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane or chlorobenzene, aliphatic or aromatic hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene or xylene esters such as ethyl acetate, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, ketones such as acetone or methyl ketone, ethers such as diethyl ether, tetrahydrofuran or dioxane, or mixtures of these solvents.

The solvent or diluent is suitably used in an amount of 100 to 2000% by weight, preferably 100 to 1000% by weight, based on the starting materials of the formulas II and III, respectively.

Suitable inorganic or organic bases which may optionally be added to the reaction mixture as acid binding agents are, for example, alkali metal carbonates such as potassium carbonate or sodium carbonate, alkali metal hydrides such as sodium hydride, or tertiary amines such as trimethylamine, triethylamine, N , N-dimethylaniline, Ν, Ν-dimethylcyclohexylamine, N-methylpiperidine or pyridine, and azoles such as

1,2,4-triazole or imidazole. However, other conventional bases may also be used.

Suitable reaction accelerators are preferably metal halides such as sodium bromide or potassium iodide, azoles such as imidazole or 1,2,4-triazole, pyridines such as 4-dimethylaminopyridine or mixtures thereof. Suitably, 0.9 to 1.3 moles of the acid derivative of formula III and, optionally, 0.5 to 2 moles of base and, optionally, 0.01 to 0.1 moles of reaction accelerator are used per mole of aniline derivative of the formula II.

The reaction is generally carried out at a temperature in the range of 0 to 120 ° C, for 1 to 60 hours, without or under pressure, continuously or discontinuously.

According to a preferred embodiment of the process according to the invention, the starting compound of the formula II is optionally mixed with a base and optionally a diluent, an acid derivative of the formula III and optionally a reaction accelerator are added, and the reaction mixture is left to 0.5-12. hours, preferably 1 to 6 hours, to react at a temperature between 0 and 120 ° C.

The isolation of the novel compounds is accomplished by, for example, removing the diluent, if present in the reaction mixture, dissolving the residue in a suitable solvent, and removing the excess base and starting materials of formulas II and III, washing the solution with dilute acid then aqueous. dilute caustic solution and finally water.

The products remaining after solvent distillation generally do not need any further purification, but can optionally be further purified by known methods, for example, recrystallization, extraction or chromatography.

The anilines of the formula II are known or can be prepared in a known manner.

The isoxazolylcarboxylic acid derivatives of the formula III used as starting materials are partly known or can be prepared from known isoxazolylcarboxylic acids of the formula IV by known methods

COOH (IV) wherein

R4 is as defined above.

Some of the carboxylic acids of formula IV are known [see Gazz. chim. Italian. 72, 458-474 (1942), ibld 78, 764-768 (1948)] or can be prepared by oxidation of known carbinols [see Gazz, chim. Italian 69, 536-539 (1939)].

The preparation of the isoxazolylcarboxylic acids of formula IV from the corresponding carbinols by oxidation is illustrated by the following example of the preparation of 2-ethylisoxazol-5-ylcarboxylic acid:

A mixture of 750 ml of water, 164 g of sodium dichromate dihydrate and 124 ml of concentrated sulfuric acid is added dropwise at 15-20 ° C to 63.5 g of 3-ethyl-5-hydroxymethylisoxazole dissolved in 250 ml of diethyl ether. After stirring for 12 hours at 20-25 ° C, the organic phase is separated and dried over sodium sulfate. After evaporation of the solvent, 59 g of 3-ethylisoxazol-5-ylcarboxylic acid of melting point 194 DEG C. are obtained.

Analysis:

for C8H7NO3 (141)

Table 1 calculated:

51.1% C,

H, 5.0; N, 9.9;

found:

51.9% C,

H, 5.2%; N. 10.7%

The following table gives an overview of the melting points of several carboxylic acids of formula IV:

R ⁴ position of the carboxyl group on the isoxazole ring melting point (° C)

H

H

H

5-CH3

3-CH3

149

123

144

176

211

Several examples of isoxazolylcarboxylic acid derivatives of formula III (A = chloro) used as starting materials are shown in Table 2.

Table 2

R4 position of the COC1 group boiling point (° C / Pa) on the isoxazole ring

H

H

3-CH3—

3-C2H5—

5-CH3OCH2— up to 34/20 to 70/1400 to 45/25 to 55/30 to 73/20

The following example illustrates the preparation of 2- (N-aryl-N-solaxazolylcarbonyl) aminobutyrolactone corresponding to the general formula

I. Parts by weight shall be parts by volume in the same proportion as kilograms to liters.

Example 1

To a solution of 16.4 g of 2- (N-2,6-dimethylphenyl) aminobutyrolactone in 100 ml of methylene chloride was simultaneously added dropwise from two dropping funnels. 8.5 g of triethylamine and 10.5 g of 3-isoxazolylcarboxylic acid chloride. The reaction mixture is stirred overnight (12 hours), the precipitate formed is filtered off with suction, the organic phase is washed three times with water and, after drying, evaporated.

16 g of 2- (N-2,6-dimethylphenyl-N-isoxazol-3-ylcarbonyl) -amino-butyrolactone, m.p. 112 DEG-114 DEG C. (compound 1), crystallized from the oily residue upon trituration with diethyl ether.

Analysis:

calculated for C 18 H 16 O 2 N 2 (300):

64.0% C, 5.3% H, 9.3% N;

found:

64.2% C, 5.5% H, 9.2% N.

For example, the following compounds of formula I can be prepared in an analogous manner

compound R1 R2 R3 R4 group position melting point CO on isoxa- number zolového circle

2 СИз с1 No. 3 СНз СИз No. 4 СИз СИз No. 5 СИз СИз з-СИз 6 СИз СИз з-СИз 7 СНз СИз No. 8 СНз СИз з-СИз 9 С2Н5 СИз No. 10 СИз С2И5 No. 11 СИз С1 No. Effectively substances according to invention report

strong fungitoxic effect and are suitable for combating phytopathogenic fungi. The substances in concentrations necessary for combating fungi and bacteria do not damage crop plants and can therefore be used as a means of protecting plants against fungal diseases.

The active compounds described are suitable for combating, for example, the following fungi:

Phytophthora cactorum on apples, Phytophthora infestans on tomatoes and potatoes,

Phytophthora parasitica on strawberries, Pseudoperonospora cubensis on cucumbers :, Pseudoperonospora humuli on hops, Peronospora destructor (onion mold) on onions,

Peronospora tabacina on tobacco,

Peronospora sparsa on roses, Plasmopara viticola (vine peronospora) on vines,

Plasmopara halstedii (sunflower mold) on sunflowers,

Sclerospora macrospora on corn, Bremia lactura (lettuce) on lettuce.

Depending on the type of effect desired, the consumption varies between 0.025 and 5 kg of active substance per hectare.

Some of the active ingredients described have curative properties, i.e. the composition can be applied even after infection of the plant by the causative agent to achieve a reliable result. In addition, many of the novel compounds are systemically active so that

No. з 100 to 10 ° C No. 5 124-128 ° C No. 4 No. з 1з2 ° С 5-СИ2ОСИз з oil з-СИз 5 162 ° С з-СИз 5 156-158 ° C No. з З-СИз 5 З-СИз 5 156-158 ° C

by conserving roots with such compounds to achieve 1 protection of the above-ground parts of the plant.

In addition, fungi causing diseases of germinates and young emerging plants, such as Pythium and Aphanomyces in legumes and cotton, can also be combated with the novel compounds of the invention. Consumption ranges from 10 to 200 g of active substance for every 100 kg of seed. In this case, the active compounds are applied as seed dressings.

The compounds of the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds of the plants with the active compounds. Application is carried out before or after infection of the plants or seeds by the fungus.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms depend entirely on the intended use, but in any case are intended to ensure a fine and uniform distribution of the active ingredient. These compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, where organic solvents can also be used as co-solvents when water is used as a diluent. Suitable carriers and auxiliaries are, in particular, the following: solvents, such as aromatics (e.g. xylene or benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions),

210857 alcohols (for example methanol or butanol), amines or amides (for example ethanolamine or dimethylformamide) and water: carriers such as natural stone meal (for example kaolins, alumina, talc or chalk) and synthetic stone meal (for example highly disperse silica or silicates);

emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The concentrates generally contain between 0.1 and 95 wt. % of active ingredient, preferably 0.5 to 90 wt. % active substance.

The concentrates, or compositions which can be prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, pickling or dressing.

Examples of the above-mentioned compositions are as follows:

I. 90 parts by weight of the active substance No. 1 are admixed with 10 parts by weight of N-methyl-o-pyrrolidone to give a solution which is suitable for application in the form of small droplets.

II. 20 parts by weight of the active substance No. 1 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide per 1 mol of N-monoethanol oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid; 5 parts by weight of the addition product of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

III. 20 parts by weight of the active substance No. 5 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of active substance No. 2 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide per mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

V. 20 parts by weight of active substance No. 5 are mixed well with 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sulphonic acid, 17 parts by weight of sodium salt of ligninsulphonic acid from waste sulphite lyes and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

VI. 3 parts by weight of active substance No. 3 are mixed intimately with 97 parts by weight of finely divided kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts by weight of the active substance No. 6 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, an effective formulation with good adhesion is obtained.

VIII. 40 parts by weight of active substance No. 2 are intimately mixed with 10 parts of sodium salt of the condensation product phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water to obtain a stable aqueous dispersion. By diluting this dispersion with 100,000 parts by weight of water, an aqueous dispersion containing 0.04% by weight of the active ingredient is prepared.

IX 20 parts of active ingredient No. 6 are mixed intimately with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenolsulfonic acid, urea and formaldehyde, and 68 parts of paraffinic mineral oil fraction to obtain a stable oily dispersion.

The active compounds according to the invention can be present in these compositions, together with other active substances, such as herbicides, insecticides, growth regulators and fungicides, or they can also be mixed with fertilizers and applied in this form. In many cases, when mixed with fungicides, the spectrum of activity is broadened.

The following list of fungicides with which the compounds of the invention may be combined illustrates these combination possibilities in greater detail, but is not intended to limit them in any way.

Fungicides with which the compounds of the invention may be combined are, for example, dithiocarbomates and derivatives thereof, such as ferric dimethyldithiocarbamate, dithiocarbamates and derivatives thereof, such as manganese ethylene-bis-dithiocarbamate, manganese-zinc manganese-zinc dithiocarbamate, ethylenediocarbamate, ethylene-bis-zinc di-ethylenediocarbamate, tetramethylthiuram disulfide, zinc ammoniacal complex of N, N-propylene-bis-dithiocarbamate and N, N'-polypropylene-bis- (thiocarbamoyl) di-sulfide;

Zinc N, N‘-propylene-bis-dithiocarbamate, an ammoniacal complex of N, N‘-propylene-bis-dithiocarbamate zinc and N, N polypropy-polypropylene-bis- (thoshocarbamoyl) -disulfide;

derivatives, such as dinitro (1-methylheptyl) phenylcrotonate,

2-sec-butyl-4,6-di-nitrophenyl-3,3-dimethyl-acrylate,

2-sec-butyl-4,6-din-trophenyl isoproryl carbonate;

heterocyclic compounds such as

N-trichloromethyl hylt! His - ethydroftaИmid,

N- (1,1,2,2 + 2-hydroxy-1: ШуШ 11o) tetrahydrophthalimide,

N-trichloromethylthio-phthalimide, 2-hertadecyl-2-imidazoline acetate,

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl]

-3-phenyl-1,2,4-triazole,

5-ethoxy-3-richloromethyl-1,2,4-thiadtzole,

2,3-dicyano-1,4-dithioanthraquinone, -thio-1,3-dithio [4,5-b] quinoxaline, 1-butylcarbamoyl 2-benzimidazolecarbamic acid methyl ester,

2-methoxycarbonylaminobenzimidazole, 2-thiocyanomethylthiobenzthiazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, ryridine-2-thiol-1-ol, hydroxyquinoline or its copper (II) salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine-4,4-doxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2- (2-furyl) benzimidazole, piperazine-1,4-dtylbis- [1- (2,2,2-trichloroethyl) formamide],

2- [4-thiazolyl (benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis- (p-chlorophenyl) pyrimidine-methanol,

1,2-bis- (3-ethoxycarbones of 1- (2-methyl) benzene),

1,2-bis- [3-methoxycarbonyl-2-thioureido) benzene;

and various other fungicides such as dodecylguanidine acetate,

3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N ‘, N‘-dimethyl

-N-: Sulfuric acid di-amide,

2,5-dimethylfuran-3-carboxanide, cyclohexylamide 2,5-dimethylfuran-3-carboboxylic acid, 2-methylbenzoic anilide, 2-iodo-benzoic acid anilide, 1- (3,4-dish-orangeilino) -tetyl-amino-2,2,2- trichloroethane,

2,6-Dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, S-nitroisophthalic acid diisopropyl ester, 1- (1 ', 2', 4'-triazol-1'-yl) 4- (4'-chlorophenoxy) -3 ₎ 3-dimethylbutan-2-one,

1- [1‘, 2‘, 4'-triazol-1'-yl) -1- [4'-chlorophenoxy) -

3,3-Dimethylbutan-12-ol,

N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N-imidazolylurea, N-cyclohexyl-N-methoxy-2,5-dimethylfran-4-carboxamide, 2,4,5-trimethylfuran-3-carboxamide 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 5-methoxymethyl-5-methyl-3- (3,5-dichlorophenyl) -2,4 -dioxo-1H-oxazolidine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine.

The following experiment demonstrates the fungicidal activity of the novel compounds of the invention.

Activity against Phytophthora infestans (potato late blight) on tomatoes

The leaves of tomato plants (variety "Grosse Fleischotomate") are sprayed with aqueous suspensions containing 0.025, 0.006 and 0.003% (w / w) of the active ingredient. After the spray coating has dried, the leaves of the test plants are infected with a zoospore suspension of Phytorhthora infestans and the plants are placed in a water-saturated chamber maintained at 16 to 18 ° C. After 5 days the disease develops on untreated but infected plants to the extent that the fungicidal activity of the test substances can be evaluated.

The results obtained are shown in the following table using a scale of 0 to 5, where 0 means no attack and 5 means complete fungal attack.

Claims (2)

Table Active Substance Influence Number After Spraying Active Substrate Suspension [%] 0.025 0.006 0.003 1 0 0 1 2 0 0 2 3 0 1 2 5 0 1 2 6 1 1 3 7 2 2 2—3 8 1 2 3 Example 2 of U.S. Patent No. 3,933,860 4-5 4-5 4-5 Inspection (Untreated) 5 OBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as active ingredient, a 2- (N-aryl-N-isoxazolylcarbonyl) aminobutyrolactone of the formula I in which: R 1 represents an alkyl group having 1 to 3 carbon atoms, R ² represents an alkyl group having 1-3 carbon atoms or halogen, R 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ⁴ represents a hydrogen atom or a C 1 -C 3 alkyl group optionally substituted by a methoxy group. 2. A composition according to claim 1 which comprises 2- (N-aryl-N4soxazolylcarbonyl) aminobutyrolactone selected from the group consisting of 2- (N-2,6-dimethylphenyl-N-isoxazol-3-ylcarbonyl) aminobutyrolactone 2- (N-2-methyl-6-chlorophenyl-N-isoxazol-3-ylcarbonyl) aminobutyrolactone; and 2- [N-2,6-dimethylphenyl-N-isoxazol-5-ylcarbonyl] aminobutyrolactone.