CS196433B2 - Fungicide - Google Patents

Abstract

The present invention provides fungicidal compositions which contain as active ingredient an imidazole derivative of the general formula <IMAGE> where R<1> denotes halogen or methoxy and R<2>, R<3> and R<4>, which may or may not be identical, denote hydrogen or halogen, or a salt thereof. The active ingredients and fungicidal compositions containing them are used for crop protection, particularly against fungi of the Ascomycetes and Basidiomycetes classes. A wide variety of other active agents may be present in the compositions if desired; in particular, a synergistic effect is obtained by using the imidazole derivatives as bases or salts in admixture with N- tridecyl-2,6-dimethyl morpholine or its salts.

Description

BACKGROUND OF THE INVENTION The present invention relates to a fungicidal plant protection composition containing, as active ingredient, imidazolylderivatives, in particular .beta.-imidazolyl alcohols.

It is already known that 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole has fungicidal activity (see DOS 2,063,857). Therefore, the compound is not suitable for use as a plant protection agent for combating fungi.

It has now been found that imidazole derivatives of the general formula

in which

R ¹ is halogen (fluoro, chloro, bromo or iodo) or methoxy,

R ^2, R ³ and R ⁴ denote hydrogen or halogen (fluorine, chlorine, bromine) and their salts are highly active against harmful fungi, in particular from the Ascomycetes and Basidiomycetes classes.

Salts are, for example, hydrochlorides, hydrobromides, sulfates, oxalates, dodecylbenzenesulfonates or nitrates.

The imidazole derivatives and their salts can be prepared by converting them to the halogen derivatives of the formula

x-C ^-c

in which ·

R ^1, R ^2, R ³ and R ⁴ have the previously mentioned meanings ·, and

X is halogen, preferably chlorine or bromine, with an imidazole, optionally in the presence of an acid-binding agent or vein. tor196433 has an alkali metal salt thereof, such as a sodium methoxide salt in a suitable solvent, and then optionally treated with an acid to convert it to a salt.

The reaction of the halogen derivatives with the imidazole or its alkali metal salts can be carried out. in both the presence and absence of diluents. The diluents used are predominantly organic solvents, for example dimethylformamide, hexamethyltriamidophosphoric acid, acetonitrile and benzene.

This reaction, if not used with an alkali metal salt of imidazole, is preferably carried out in the presence of an excess, but at least approximately stoichiometric, amount of acid binding. An excess of the imidazole used is preferably suitable as an acid binding agent. Furthermore, all conventional acid-binding agents, such as, for example, alkali, alkaline earth metal and alkaline earth metal hydroxides, carbonates and alkoxides, as well as organic bases such as targets, amines, are suitable.

The reaction temperatures can be varied within a wide range. In general, the reaction is carried out at temperatures of 0 to 150 ° C, preferably at temperatures between 30 and 1 (20 ° C).

The preparation of halogeno derivatives can be carried out, for example, according to methods for the preparation of targets, alcohols from the corresponding ketones or carboixylic acid derivatives and Grignard compounds in a known manner (Houben-Weyl, Methoden der organischen Chemie, 13 / 2a, 46-527 (1973)).

Halogen derivatives are obtained, for example, by the ketone of the formula

wherein R ¹ , R ² and X are as defined above, acts by the Grignard compound of formula

R ³

R * in which

R ³ and R ⁴ are as defined above, and

Y is halogen, preferably chlorine or bromine, in a solvent customary for Grigard reaction, preferably diethyl ether or tetrahydrofuran.

Halogenated derivatives are usually not isolated but reacted with iiriidazole after preparation as described above. However, in particular cases, the batogenderivatives can be isolated and then reacted with the imidazole as described above, which may have the advantage of achieving higher yields.

The active compounds are present as optically active isomeric d- and 1-forms and as a mixture (racemates).

The invention is described in more detail by the following examples.

Example 1

5.35 g of magnesium chips in 50 ml of ether, together with 39.1 g of 2,4-diclorobenzyl chloride, dissolved in 200 ml of diethyl ether, are reacted at boiling point. 22.4 g of 2,2 ‘, 4‘-trichloiracetophenone dissolved in 150 ml of diethyl ether are added dropwise to this solution. An aqueous ammonium chloride solution was then added to decompose the reaction. the organic phase is separated and dried over sodium sulphate. After concentration in vacuo, the residue is added to the melt with 68.1 g of Imidazole and the reaction mixture is reacted with stirring at 120 ° C. Then the reaction mixture is cooled, first water is added and then methylene chloride. The white residue was filtered off, dissolved in chloroform while hot, and 100% nitric acid dissolved in diethyl ether precipitated nitrate.

After recrystallization from a mixture of isopropyl alcohol and ethyl acetate, 33.5 g of 1,2-bis- (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol-nitrate are obtained. m.p. 170-172 ° C (active substance No. 5).

Example 1 a d 2

32.2 g of 2-chlorobenzyl chloride, which is dissolved in 450 ml, are added dropwise to 5.3 g of magnesium chips in 50 ml of diethyl ether. diethyl ether, at boiling point. After completion of the reaction, 18.6 g of 2-chloro-4'-methoxyacetophenone which is dissolved in 1'50 ml of tetrahydrofuran is added. Aqueous ammonium chloride solution was then added for decomposition. thereto, the organic phase is separated, washed neutral and dried over sulfate. sodium. After concentration in vacuo, the residue was dissolved in 75 ml of dimethylformamide, and this solution was stirred overnight at room temperature, together with a solution of sodium fumazole in 7.5 ml of dimethylformamide prepared from 3 g of sodium in 50 ml of methanol and 15 g of imidazole. . The solvent was distilled off. under vacuum, the residue was dissolved in chloroform, washed with water and dried over sodium sulfate.

Addition of an ethereal nitric acid solution resulted in the formation of a white nitrate. Recrystallization twice from n-propanol and once from ethanol yielded 8.7 g of 1- (2-chlorophenyl) -2- (4-methoxyphenyl) -3- (imidazol-1-yl) propan-2-ol-nitra -TU mp 167 ^Q C (active ingredient no. 9).

198433

Examples 3-9

The following compounds were prepared by the corresponding procedure as in Examples 1 and 2:

3. ·. ' ''. -

-1- (2,4-dichlorophenyl) -2- (4-chlorophenyl) -3-

- (imidazol-1-yl) propan-2-ol hydrochloride, m.p. 22-5 ° C (active substance No 1),

4.

1- (4-chlorophenyl) -2- (2,4-dichlorophenyl) -3-

- (imidazol-1-yl) propan-2-ol-metrate, melting point 181 43 (active substance No 2),

5.

1- (2-Clorophenyl) -2- (2,4-dichlorophenyl) -3-

- (imidazol-1-yl) propan-2-ol-nitrate of melting point 1-9 ° C (active substance No 3) ,.

6.

1,2-bis - (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol, m.p. 196-200 ° C (active substance No 4),

7.

1-phenyl-2- (2-bromo-4-chlorophenyl) -2- (imidazol-1-yl) propan-2-ol-nitrate, m.p. 183-184 (active substance 6) )

8.

1- (2,6-dichlorophenyl) -2- (2-bromo-4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol-1-nitrate, m.p. C (active substance No 7),

9. '

1- (2,4-dichlorophenyl) -2- (4-iodophenyl) -3-

(imide ^: zol-1) propan-2-ol-nitrate, m.p. 195-197 43 (active ingredient no. 8). .

Imidazole derivatives and their salts show a broad spectrum of fungicidal effects and are better tolerated by plants than the known 1- (2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H-imidazole (active ingredient A) ).

The active compounds can also be used in the form of their salts, for example, hydrochlorides, hydrobromides, sulphates, oxalates, di-benzylsulphonates or nitrates.

Of great importance are fungicidal compositions of the invention in combating fungal diseases on various crop plants, such as e.g.

Ustilago · scitaminea,

Hemileia Vastatrix, bean rust (Uromýces fa-bae or appendiculatus), Puccinia species, 'powdery mildew (Erysiphe gr.ami.nls), gray mold (Botrytis cinerea) on vines and strawberry plants, powdery mildew (Uncinula necator),

Sphaerotheca fuliginea, Powdery mildew (Erysiphe cichoracearum), Powdery mildew (Podosphaera leucotrichaj.

In this context, crop plants are in particular wheat, rye, barley, oats, rice, maize, apple, cucumber, god, coffee, sugarcane, grapevine, strawberry and ornamental horticultural plants.

The active substances are systemically active. The systemic effectiveness of these compositions is of particular importance in combating internal plant diseases such as cereal and mildew rust. .

The compositions of the invention can simultaneously suppress the growth of two or more of these fungal species and are well tolerated by plants. The application rate required to combat phytopathogenic fungi is between 0.05 and 2 kg of active ingredient / ha of culture area.

Suitable active compounds are, for example, the following compounds:

Active substance no. Ri Rž R ⁵ R < Salt PC melting point) 1. '4-01 H 2-C1 4-Cl HCl 225 2, 2-C1 4-01 4-Cl H HNOs 181 3 2-C1 4-01 2-C1 H ‘ HNOs 1'59 4 2-01 4-01 2-C1 4-Cl - 196 - '200 5 2-C1 4-01 2-C1 4-Cl ΗΝΌ3 170-172 6 2-Br 4-Cl H H HNOs 183-184 7 '2-Bir 4ЧЛ 2-C1 6-C1 ΗΝΌ3 219-2'22 8 4-J ' H 2-C1 4-01 HNOs 195-197 9 4-О'СНз H 2-C1 H HNOs l'S7

The active compounds can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These compositions are prepared in a manner known per se, for example by mixing the active compound with solvents and / or carriers and, if appropriate, emulsifiers and dispersants, where further organic solvents can be used in the case of water as a diluent. Basically suitable auxiliaries are: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine, dimethylf) ormamide) and water; carriers such as natural stone meal (for example kaolins, clays, talc, chalk) and synthetic stone meal (for example highly disperse silicic acid, silicates); emulsifiers such as non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfoinates) and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. The compositions or preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in a known manner, for example by spraying, fogging, spraying, spreading, pickling or dressing.

These compositions can also be applied in these dosage forms together with other active substances, for example herbicides, insecticides, growth regulators and fungicides, or also with fertilizers. Fungicides which may be combined with the compounds of the invention are, for example, dithtocarbamates and derivatives thereof, such as:

ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-dithiocarbamate, manganese zinc ethylenediamine-bis-dithiocarbamate, zinc ethylene-bis-dithiocarbamate, bis (tetramethylthiuramodisulfate), netramethylenediamine ammonium disulfate,

N, N‘-polyethylene-bis- (thiocarbamoyl) disulfide,

Zinc N, N‘-prbpylene-bis-dithiocarbamate, zinc ammoniacal complex, N, N‘-propylene-bis-dithiocarbamate, and

N, N: ‘-polypropylene-bls- (thiocarbamoyl) disulfide;

nitrophenol derivatives such as dinitro (1-methylheptyl) phenyl cronate,

2-sec-butyl-4, 6-dinitrophenyl-3,3-dimethyl acrylate,

_{2-sec-butyl-4,6-1} díinitirofenyliso propyl carbonate;

heterocyclic compounds such as <

N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthlophthalimide, 2- ¹ heptadecyl-2-imidazoline acetate,

2,4-dichloro-6- (o-chloroanilino) -s-trlazine, O, O-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] J-

-3-phenyl-1,2,4-triaZO1,

5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,

2,3-dicyano-1,4-dithiaanthraquinone,

2-thio-1,3-dithio- (4,5-b) quinoxaline, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester,

2-methoxycarbonylaminobenzimidazole,

2-rhodanomethylthiobenzthiazole,

4- (2-chlorophenylhydropyono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide;

8-hydroxyquinoline or its copper salt,

2,3-dihydro-5'-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

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

2- [fur-2-yl] benzimidazole, piperazine-1,4-diyl-bis-1- (2,2,2-trichloroethyl) -formamide,

2- [thiazol-4-yl] benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6 ^{J-methylpyrimidine} 'bis (p-chlorophenyl] -3-pyridinemethanol,

1,2-bis- (3-ethoxycarbonyl-2-thioureido) berizene,

1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene; - various fungicides, such as dodecylguanidine acetate,

3- [2- (3,5-dimethyl-2-oxycyclohexyl) -2-hyaroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N, N-dimethyl-N-phenyldiamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide;

2-methylbenz ⁱ zanilld,

2-iodobenzanilide,

1- (3,4-detranilino) -1-formylainino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine or its salts,

2,6-dimethyl-N-cyclodecylmorpholine or its salts,

2,3-dichloro-1,4-naphthoquinone,

1.4- dichloro-2, ^l 5-dimethoxybe.nzen p dimethylaminobenzendiazonátriumsuilfonát-l-chloro-2-nltropropan, polychloronitrobenzenes such as pentachloronitrobenzene, methyl isocyanate, an antifungal as antibiotics such as griseofulvin and kausgamycin, tetrafluoro luordichloraceton · 1 f enylthiosemikarbazin, a mixture of Bordeaux, a compound containing nickel and sulfur.

In combating powdery mildew and rust on cereals, a synergistic effect has been achieved ^by using the new active substances either in the form of bases or in the form of their salts in admixtures with N-tridecyl-2,6-dimethylmorpholine and its salts. A particularly pronounced synergistic effect was observed at ratios of 1: 2 to 1: 4 parts by weight.

The fungicidal effect of the new active compounds is illustrated by the following examples.

In the examples as comparative active ingredients used in well-known and effective l- (2- (2,4-dichlorophenyl) -2- ^(2; propenyloxy) ethyl] -lH-imidazole (A).

active substance·

6.

A (known) control (untreated)

3

Example 10.

Test for rust on wheat (Puccinia recondita) i ·; - · .., ·. <· ’

The leaves of wheat plants growing in pots of the species "Caribo" are dusted with spores of Puccinia recondita rust. The pots were then placed in a high humidity chamber (90-96%) for 2 hours at 20-2 ° C. During this time spores germinate and the germs penetrate the leaf tissue, the infected plants are then sprayed until moistened with 0.025 and 0.0125% (w / w) aqueous suspension, which contains 80% active ingredient and 20% lignin sulphonate in dry matter. After the spray layer has dried, the test plants are placed in a greenhouse at a temperature between 20 and 22 ° C and at 65 to 70% relative humidity. After 8 days, the degree of rust development on the leaves was determined.

infestation of the leaves after spraying,% and suspension of the active ingredient

0.025 0.0125 _ _ _ _ __. 12 oo

3 ', = no attack, graded up to 5, which means total attack

Example 11

Batter for rust bobsled

Leaves in pots of growing bean plants are artificially infected with spores of bean rust (Uromyces fabae) and then the plants are placed in the chamber for 48 hours. at 20 to 25 ° C and at 100% humidity. The plants are then sprayed with aqueous suspensions containing a water-soluble or emulsified mixture consisting of 80% of the active ingredient tested and 20% of lignin sulphonic acid sodium salt and placed in a greenhouse at temperatures between 20-22 ° C and 75-80% relative humidity. humidity. After 10 days, the degree of rust development is evaluated.

Effective infestation of leaves after spraying substance · 0.05% suspension of active substance '20 '5'0

9 · 2 · control (untreated) 5

Example 12

Test for cucumber powdery mildew (Erysiphe cichoria- / cear um)

Leaves in pots of growing plants o- /. The bark is sprayed with an aqueous emulsion composed of 80% active ingredient and 20% emulsifier and, after the spraying layer has dried, is dusted with powdery mildew (Erystphe cichoriacearum). The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days, the stage of development of powdery mildew is found.

effective spraying the leaves O- substance ¹ 0.05% active substance suspension

0

0 • 5 ·

9 inspection (untreated)

Example 13

Test for gray mold (Botrytis clnerea) on paprika

Peppers of the Neusledler Ideal Elite species are then sprayed until they are moistened, after having developed well 4 to 5 leaves. 0.1% (weight percent) aqueous suspension containing 80% active ingredient and 20% sodium sulphonic acid in the dry matter. After the spray has dried, the plants are sprayed with a conidia suspension of the fungus Botrytis cinerea and then placed at 22-24 ° C in a high humidity chamber to achieve optimum conditions for fungal development. After 5 days the disease will not. treated control plants develop so greatly that the resulting necrosis of the leaf covers the bulk of the leaf area.

effective infestation of leaves after spraying substance 0.1% suspension of active substance control (untreated) 5

Example 14 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution which is suitable for application in the form of minimal drops.

Example 15 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide with 1 mole of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid; 5 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 16 parts by weight of compound 3 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 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide. mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

EXAMPLE 17 parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 to 280% and 10 parts by weight of an adduct of 40 moles ethylene oxide with 1 mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

EXAMPLE 18 parts by weight of active compound 5 are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing this mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example 19 3 parts by weight of compound 6 are intimately mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example 20 parts by weight of compound 7 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 the silica gel. In this way, an active substance preparation with good adhesion is obtained.

198433

Example 21 parts by weight of the active compound 9 are intimately mixed with 10 parts by weight of the sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution of 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active ingredient.

Example 22 parts of the active ingredient 8 are intimately mixed with 2 parts, dodecylbenzenesulfonic acid calcium salt, 8 parts of fatty alcohol ¹ polyglycol ether, 2 parts of phenol, urea and formaldehyde condensate sodium and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Claims (1)

OBJECT OF THE INVENTION A fungicidal plant protection composition comprising a solid or liquid carrier and, as active ingredient, at least one imidazole derivative of the general formula: R ¹ is halogen or methoxy, and R ^2, R ³ and R ⁴ represent hydrogen or halogen or a salt thereof.