CH635481A5 - FUNGICIDE AGENT. - Google Patents

Description

The present invention relates to fungicides for crop protection which contain imidazolyl derivatives, in particular .beta.-imidazolyl alcohols, and to methods for controlling fungi with these compositions.

It is known that l- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -IH-imidazole has a fungicidal activity (DE-OS 20 63 857). Its effect is particularly inadequate against mildew and rust fungi. For this reason, it is not very suitable for use as a crop protection agent for combating fungi.

It has been found that imidazole derivatives of the formula I

Oh

I ^ N-ch2-C

3 (I)

ch in which R1 is halogen (F, Cl, Br, J) or methoxy, R2, R3 and R4 are hydrogen or halogen (especially F, Cl, Br), and their salts are highly effective against harmful fungi, in particular from the class of the Ascomycetes and Basidiomycetes. Salts are e.g. Hydrochloride, hydrobromide, sulfate, oxalate, dodecylbenzenesulfonate or nitrate.

The imidazole derivatives and their salts can be prepared by using a halogen compound of the formula II

ntr r1 x- ° Vè ^ 2

_ "R3

in which X represents halogen, preferably chlorine or bromine, with imidazole, if appropriate in the presence of an acid-binding agent or in the form of its alkali metal salt, as obtained, for example, by treatment with sodium methylate in a suitable solvent, and then optionally the compound obtained with an acid transferred to a salt.

The reaction of the halogen compounds with imidazoi or its alkali salts can be carried out either in the presence or in the absence of diluents. Organic solvents, for example dimethylformamide, hexamethylphosphoric triamide, acetonitrile and benzene, are predominantly used as diluents.

Unless an alkali salt of imidazole is used, the reaction is preferably carried out in the presence of an excess, but at least about the stoichiometrically required amount of an acid-binding agent. An excess of the imidazole used is preferably suitable as the acid-binding agent. Furthermore, all common acid binding agents, such as Hydroxides, carbonates and alcoholates of alkali and alkaline earth metals as well as organic bases such as tertiary amines.

The reaction temperatures can be varied over a wide range. Generally one works at 0 to 150 ° C, preferably at temperatures between 30 and 120 ° C.

The halogen compounds can be prepared, for example, in a known manner by the methods for preparing tertiary alcohols from the corresponding ketones or carboxylic acid derivatives and Grignard compounds ((Lit .: Houben-Weyl, Methods of Organic Chemistry, 13 / 2a, 46 to 527 ( 1973)].

Halogen compounds are obtained, for example, by using a ketone of the formula III

0

(III)

with a Grignard compound of formula IV

™ 8-ck2 ^ (it) j

5

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635481

in which Y represents halogen, preferably chlorine or bromine, in a solvent customary for Grignard reactions, preferably diethyl ether or tetrahydrofuran.

The halogen compounds are generally not isolated, but after their preparation are reacted with an imidazole, as described above. In special cases, however, the halogen compounds can be isolated and then reacted with an imidazole in the manner described, which can be advantageous in order to achieve higher yields.

The active substances are in the form of optically active isomeric d and 1 forms and their mixture (racemates).

Production of the Active Ingredients Example 1

5.35 g of magnesium spheres in 50 ml of ether are reacted with 39.1 g of 2,4-dichlorobenzyl chloride, dissolved in 200 ml of diethyl ether, at the boil. 22.4 g of 2,2 ', 4'-trichloroacetophenone, dissolved in 150 ml of diethyl ether, are added dropwise to this solution. It is then decomposed with aqueous ammonium chloride solution, the organic phase is separated off and dried over sodium sulfate. After concentration in vacuo, the residue is placed in a melt of 68.1 g of imidazole and reacted with stirring at 120 ° C. The mixture is then cooled, water is added first and then methylene chloride. The white residue is filtered off, dissolved in chloroform under heat and the nitrate precipitated with 100% nitric acid, dissolved in diethyl ether.

After recrystallization from isopropanol / ethyl acetate, 33.5 gl, 2-bis- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propan-2-ol nitrate with a melting point of 170 to 172 ° C. are obtained (Active ingredient No. 5).

Example 2

To 5.35 g of magnesium shavings in 50 ml of diethyl ether, 32.2 g of 2-chlorobenzyl chloride, dissolved in 450 ml of diethyl ether, are added dropwise at the boiling point. After the reaction has ended, 18.6 g of 2-chloro-4'-methoxy-acetophenone, dissolved in 150 ml of tetrahydrofuran, are added. The mixture is then decomposed with aqueous ammonium chloride solution, the organic phase is separated off, washed neutral and dried over sodium sulfate. After concentration in vacuo, the residue is dissolved in 75 ml of dimethylformamide and stirred with a solution of sodium imidazole in 75 ml of dimethylformamide, prepared from 3 g of sodium in 50 ml of methanol and 15 g of imidazole, at room temperature overnight. The solvent is distilled off in vacuo, the residue is dissolved in chloroform, washed with water and dried over sodium sulfate.

When etheric nitric acid is added, a white nitrate precipitates. After recrystallization twice from n-propanol and once from ethanol, 8.7 g of l- (2-chlorophenyl) -2- (4-methoxyphenyl) -3- (imidazol-l-yl) -propan-2-ol-nitrate are obtained with a melting point of 167 ° C. (active ingredient No. 9).

Examples 3 to 9

The following compounds were prepared in accordance with Examples 1 and 2:

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3.1 - (2,4-dichlorophenyl) -2- (4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol hydrochloride with mp: 225 ° C (active ingredient no. 1).

4. 1 - (4-chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propan-2-ol nitrate with mp: 181 ° C (active ingredient no. 2 ).

5. l- (2-chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazole-

1-yl) propan-2-ol nitrate with mp: 159 ° C (active ingredient No. 3).

6.1,2-bis- (2,4-dichlorophenyl) -3- (imidazol-1-yl) -propane-

2-ol with mp: 196 to 200 ° C (active ingredient no. 4).

7. l-Phenyl-2- (2-bromo-4-chlorophenyl) -3- (imidazol-l-yl) propan-2-ol nitrate with mp: 183 to 184 ° C (active ingredient no. 6 ).

8.1 - (2,6-dichlorophenyl) -2- (2-bromo-4-chlorophenyl) -3- (imidazol-l-yl) propan-2-ol nitrate with mp: 219 to 222 ° C ( Active ingredient No. 7).

9.1 - (2,4-dichlorophenyl) -2- (4-iodophenyl) -3- (imidazol-1-yl) -propan-2-ol-nitrate with mp: 195 to 197 ° C (active ingredient no.8 ).

The imidazole derivatives and their salts show a considerably broader fungicidal activity and better plant tolerance than the known l- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -lH-imidazole (active ingredient A).

The active ingredients can also be in the form of their salts, e.g. Hydrochloride, hydrobromide, sulfate, oxalate, dodecyl-benzenesulfonate or nitrate can be used.

The fungicidal compositions according to the invention are of great interest in the case of fungal diseases on various crop plants, e.g. at

Ustilago scitaminea (sugar cane fire)

Hemileia Vastatrix (coffee rust)

Uromyces fabae or (bean grate)

appendiculatus

Puccinia species (grain rust)

Erysiphe graminis (powdery mildew)

Botrytis cinerea on vine, strawberries Uncinula necator,

Sphaerotheca fuliginea,

Erysiphe cichoracearum,

Podosphaera leucotricha.

In this context we understand crops in particular wheat, rye, barley, oats,

Rice, corn, apple tree, cucumber, beans, coffee, sugar cane, grapevine, strawberries and ornamental plants in horticulture.

The active substances are systemically effective. The systemic effectiveness of these agents is of particular interest in connection with the control of internal plant diseases, e.g. Grain rust, powdery mildew.

The agents according to the invention can simultaneously suppress the growth of two or more of the fungi mentioned and are highly tolerated by plants. The application rates required to control the phytophatogenic fungi are between 0.05 and 2 kg of active ingredient / ha of cultivated area.

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

Active substance no.

R1

R2

R3

R4

salt

Mp .: ° C

1.

2-C1

H

2-C1

4-C1

HCl

225

2nd

2-C1

4-C1

4-C1

h hno3

181

3rd

2-C1

4-C1

2-C1

h hno3

159

4th

2-C1

4-C1

2-C1

4-cl

-

196-200

5.

2-C1

4-C1

2-C1

4-C1

hno3

170-172

6.

2-br

4-C1

h h

hno3

183-184

635481

4th

Active substance no.

R1

R2

R3

R4

salt

Mp .: ° C

7.

2-br

4-C1

2-cl

6-C1

HNO3

219-222

8th.

4-y

H

2-cl

4-C1

HNO3

195-197

9.

4-OCH3

H

2-cl

H

HNO3

167

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30th

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are made in known manner, e.g. by mixing the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, where, if water is used as the diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially suitable as auxiliaries: 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. 20 ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquor and methyl cellulose.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. The formulations or the ready-to-use preparations produced therefrom, such as solutions, emulsions, suspensions, powders, pastes or granules, are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

In these application forms, the agents can also be present together with other active ingredients, e.g. Herbicides, insecticides, growth regulators and fungicides or also be mixed with fertilizers. Fungicides which can be combined with the compounds mentioned are, for example, dithiocarbamates and their derivatives, such as

Ferridimethyldithiocarbamate,

Zinc dimethyldithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine bis-dithiocarbamate, zinc ethylene bisdithiocarbamate,

Tetramethylthiuram disulfide,

Ammonia complex of zinc (N, N-ethylene-bis-dithiocar-50 bamat) and

N, N'-polyethylene-bis- (thiocarbamoyl) disulfide, zinc (N, N'-propylene-bis-dithiocarbamate),

Ammonia complex of zinc (N, N'-propylene-bis-di-thiocarbamate)

andN, N'-polypropylene bis (thiocarbamoyl) disulfide;

Nitrophenol derivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate;

heterocyclic structures such as N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl- phthalimidophosphonothioate, 5-amino-l- [bis- (dimethylamino) -phosphinyl] -3-phenyl-1,2,4-triazole,

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

2,3-dicyano-l, 4-dithiaanthraquinone,

2-thio-l, 3-dithio- (4,5-b) -quinoxaline,

1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,

2-methoxycarbonylamino-benzimidazole, 2-rhodanmethylthio-benzothiazole,

4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-l-oxide,

8-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4,4-dio-

xid,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2- [furyl- (2)] benzimidazole,

Piperazin-l, 4-diyl-bis-l- (2,2,2-trichloroethyl) formamides,

2- [thiazolyl- (4)] benzimidazole,

5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene,

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

Dodecylguanidine acetate,

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

N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-schw-

rock diamond,

2,5-dimethyl-furan-3-carboxylic acid anilide,

2,5-dimethyl-furan-3-carboxylic acid-cyclohexylamide, 2-methyl-benzoic acid anilide,

2-iodo-benzoic acid anilide,

l- (3,4-dichloroanilino) -l-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclodecyl-morpholine or its salts,

2,3-dichloro-l, 4-naphthoquinone,

1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene diazo sodium sulfonate, 1-chloro-2-nitrole-propane,

Polychloronitrobenzenes, such as pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics, such as griseofulvin or kausgamycin, tetrafluorodichloroacetone, 1-phenylthiosemi-carbazine, Bordeaux mixture, nickel-containing compounds and sulfur.

When combating mildew and rust diseases on cereals, an effect-increasing effect (synergism) was achieved when the active compounds were used either as bases or in the form of their salts in mixtures with N-tridecyl-2,6-dimethylmorpholine and its salts. The increase in effectiveness can be observed particularly clearly with the mixing ratios 1: 2 to 1: 4 parts by weight.

The following examples explain the fungicidal activity of the active ingredients.

In the following examples, the known and recognized good active ingredient 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -lH-imidazole (A) was used as the comparative active ingredient.

Example 10 Wheat Brown Rust Leaves of potted wheat seedlings of the "Caribo" variety are dusted with spores of the brown rust (Puc-cinia recondita). The pots are then placed in a chamber with high atmospheric pressure at 20 to 22 ° C for 24 hours.

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635481

humidity (90 to 85 ° C). During this time, the spores germinate and the germ tubes penetrate the leaf tissue. The infected plants are then sprayed to runoff point with 0.025% and 0.0125% (by weight) aqueous spray liquors which contain 80% active ingredient and 20% lignin sulfonate in the dry matter. After the spray coating has dried on, the test plants are placed in the greenhouse at temperatures between 20 and 22 ° C. and 65 to 70% relative atmospheric humidity. After 8 days, the extent of the rust fungus development on the leaves is determined.

Active ingredient

Infection of the leaves after spraying with 0.05% active ingredient broth

Active ingredient

1

2nd

3rd

4th

5

6

7

A (known)

Control untreated)

0

0

1 0 0 0 0 0

2 2 5

0 2 2 0

0 2

1 0

2nd

3rd

0 = no infection, graded to 5 = total infection

Example 11 Bean Grate

Leaves of bean plants grown in pots are artificially infected with spores of the bean grate (Uromyces fabae) and placed in a steam-saturated chamber for 48 hours at 20 to 25 ° C. The plants are then sprayed with aqueous spray liquors which contain a mixture of 80% of the active ingredient to be tested and 20% sodium lignosulfonate in the water or emulsified and in a greenhouse at temperatures between 20 to 22 ° C. and at 75 to 80% relative atmospheric humidity set up. After 20 days, the extent of the rust fungus development is assessed.

Active ingredient

1 0

2 0

3 0

4 0

5 0

6 0

7 0 9 2 control (untreated) 5

Example 12 Cucumber Powdery Mild Leaves of cucumber seedlings grown in pots are sprayed with aqueous emulsions of 80% active ingredient and 20% emulsifier and, after the spray coating has dried on, are dusted with oidia (spores) of the cucumber powdery mildew (Erysiphe cichoracearum). 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 extent of the mildew development is determined.

xo

Control (untreated)

0 0 0 0 0 5

Infestation of the leaves after spraying

..% active ingredient broth is 0.025 0.0125

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Example 13 Botrytis cinerea on paprika Pepper seedlings of the "Neusiedler Ideal Elite" variety, having developed 4 to 5 leaves well, were mixed with 0.1% (% by weight) aqueous spray liquors containing 80% active ingredient and 20% sodium lignin sulfonate the dry substance contained, sprayed soaking wet. After the spray coating has dried on, the plants are sprayed with a conidia suspension of the botrytis cinerea fungus and placed at 22 to 24 ° C. in a chamber with high atmospheric humidity in order to obtain optimum conditions for the development of the fungus. After 5 days, the disease on the untreated control plants developed so much that the resulting leaf necrosis covered most of the leaves.

Active ingredient

Infection of the leaves after spraying with 0.1% active ingredient broth

Infection of the leaves after spraying 45 with 0.05% active ingredient broth

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6 0

7 0 control (untreated) 5

Production of fungicidal agents

Example 14

90 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, and a solution is obtained which is suitable for use in the form of minute drops.

Example 15

20 parts by weight of compound 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 16

20 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 the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

Example 17

20 parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol and 65 parts by weight of a mineral oil fraction with a boiling point of 210

635 481 6

to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient. 5

Example 18

20 parts by weight of active ingredient 5 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

Example 19

3 parts by weight of compound 6 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.

Example 20

30 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 this silica gel. In this way a preparation of the active ingredient with good adhesiveness is obtained.

Example 21

40 parts by weight of active ingredient 9 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formal-dehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.

Example 22

20 parts of active ingredient 8 are intimately mixed with 2 parts of calcium salt of the dodecylbenzosulfonic acid-urea-formaldehyde condensate and 68 parts of sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

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s

Claims (4)

635 481 1,2-bis- (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol, 1-phenyl-2- (2-bromo-4-chlorophenyl) -3- (imidazole -1 -yl) -pro-pan-2-ol, l- (2,6-dichlorophenyl) -2- (2-bromo-4-chlorophenyl) -3- (imida- zol-1 -yl) -propan-2-ol, l- (2,4-dichlorophenyl) -2- (4-iodophenyl) -3- (imidazol-l-yl) -pro-pan-2-ol, l- (2-chlorophenyl) -2- (2-methoxyphenyl) -3- (imidazol-l-yl) - propan-2-ol existing group, or a salt thereof. 1 - (2,4-dichlorophenyl) -2- (4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol, 1- (4-chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propan-2-ol, 1- (2-chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazol-l-yl) propan-2-ol, 2. Fungicidal composition according to claim 1, containing an imidazole derivative selected from the group 2nd PATENT CLAIMS 1. Fungicidal agent for crop protection, containing an imidazole derivative of the formula I oh in which R1 is halogen or methoxy, R2, R3 and R4 are hydrogen or halogen, or its salt. 3. A method for combating fungal diseases in plants, characterized in that the plants to be protected are treated with a fungicidal agent according to claim 1. 4. The method according to claim 3 for the treatment of fungal diseases in plants, characterized in that that the plants to be protected are treated with a fungicidal agent according to claim 2.