HU179925B - Fungicide composition containing imidazole derivatives as active substances and process for preparing the active materials - 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

FIELD OF THE INVENTION The present invention relates to agricultural fungicides containing imidazole derivatives, in particular β-imidazolyl alcohols, as active ingredients, and to processes for their preparation.

1- [2- (2,4-Dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole is known to be used as an active ingredient in fungicides (German Patent Publication No. 2,063,857). . However, these agents are moderately effective against powdery mildew and rust fungi and therefore have limited use as an agricultural fungicide.

It has now been found that agents containing imidazole derivatives of the formula I and their salts have very good activity against harmful fungi, in particular fungi of the Ascomycetes and Basidiomycetes classes. In the formula (I), R ^{1 is} halogen, i.e. fluorine, chlorine, bromine or iodine or methoxy, and R ² , R ³ and R ⁴ independently of one another are hydrogen or halogen, especially fluorine, chlorine or bromine.

Examples of salts include hydrochloride, hydrobromide, sulfate, oxalate, dodecylbenzene sulfonate and nitrate.

The imidazole derivatives of formula (I) and salts thereof may be prepared by reacting a halogen compound of formula (II) wherein R ¹ , R ² , R ³ and R ^{4 are} as defined above and X is halogen, preferably chloro; or bromine - with imidazole, optionally in the presence of an acid acceptor or an alkali salt thereof, which may be prepared, for example, with sodium methylate in a suitable solvent, and optionally converted to the acid salt thereof.

The reaction of the halogen compounds with an imidazole or an alkali salt thereof may optionally be carried out in a diluent. Suitable diluents are, in particular, organic solvents such as dimethylformamide, hexamethylphosphoric triamide, acetonitrile and benzene.

If an alkali salt of imidazole is not used, the reaction 10 is carried out in the presence of at least one equivalent but preferably in excess of an acid acceptor. In particular, an excess of imidazole is used as an acid binder; however, conventional acid scavengers such as hydroxides, carbonates and alcoholates of alkali and alkaline-earth metals as well as organic bases such as tertiary amines may also be used.

The reaction temperature may be varied within a wide range, generally from 0 to 150 ° C, preferably from 30 to 120 ° C.

The halogen compounds used as starting materials can be prepared from the corresponding ketones or carboxylic acid derivatives and Grignard compounds by known methods for the preparation of tertiary alcohols (HoubenWeyl, 1973, Methods 13, 2a, 46-2527).

For example, the preparation of the halo-ketone compounds of the general formula (III): - wherein, R ^1, R ^2, and

X has the meaning given above - a formula IV

The Grignard compound in which R ³ and R ⁴ are as defined above and Y is halogen, preferably chloro 179925 or bromine, is reacted in a solvent used for the Grignard reactions, preferably in diethyl ether or tetrahydrofuran.

The halogen compounds are generally not isolated, but directly reacted with imidazole. In some cases, the halogen compounds may be isolated and then reacted with imidazole; this has the advantage of higher yields.

The compounds may be in optically active isomeric d- and 1-forms or mixtures thereof in the form of their racemates.

The following examples illustrate the preparation of compounds of formula (I). Temperature data is given in degrees Celsius.

Example 1

Magnesium filings (5.35 g) in ether (50 ml) were reacted with boiling (39.1 g) in 2,4-dichlorobenzyl chloride (200 ml) in diethyl ether. A solution of 22.4 g of 2,2 ', 4'-trichloroacetophenone in 150 ml of diethyl ether is added dropwise to the reaction solution. The reaction mixture was quenched with aqueous ammonium chloride solution, the organic phase was separated and dried over magnesium sulfate. After evaporation in vacuo, the residue is added to a melt of imidazole (68.1 g) and heated to 120 ° with stirring. After cooling, water was added followed by methylene chloride. The precipitated white residue is filtered off, dissolved in chloroform with heating and the nitrate is precipitated with 100% nitric acid in diethyl ether.

Recrystallization from a mixture of isopropanol and ethyl acetate gave 33.5 g of 1,2-bis (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate; mp 170-172 °. 35 (Active ingredient 5)

Example 2

A solution of 32.2 g of 2-chlorobenzyl chloride in 450 ml of diethyl ether is added dropwise to 5.35 g of magnesium turnings in 50 ml of diethyl ether. After the reaction was completed, a solution of 18.6 g of 2-chloro-4'-methoxyacetophenone in 150 ml of tetrahydrofuran was added. The reaction mixture was quenched with aqueous ammonium chloride solution, the organic phase was separated, washed with neutral and dried over sodium sulfate. The residue was concentrated in vacuo and dissolved in dimethylformamide (75 mL) and stirred with a solution of sodium imidazole (3 g sodium and 15 g imidazole in 50 mL methanol) in 75 mL dimethylformamide at room temperature overnight. The solvent was evaporated in vacuo, the residue was dissolved in chloroform, washed with water and dried over sodium sulfate.

Addition of ethereal nitric acid gives off a white nitrate. This was recrystallized twice from η-propanol and once from ethanol to give 8.7 g of 1- (2-chlorophenyl) -2- (4-methoxyphenyl) -3- (imidazol-1-yl) propan-2-ol. yielding nitrate; mp 167 °. (Active ingredient 9)

3-9. examples

The following compounds were prepared as described in Examples 1 and 2:

3. 1- (2,4-Dichlorophenyl) -2- (4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol hydrochloride, m.p. 225 ° (active ingredient 1);

4. 1- (4-Chloro-phenyl) -2- (2,4-dichloro-phenyl) -3- (imidazol-1-yl) -propan-2-ol nitrate, m.p. 181 ° (active ingredient 2);

5. 1- (2-Chloro-phenyl) -2- (2,4-dichloro-phenyl) -3- (imidazol-1-yl) -

-propan-2-ol nitrate, m.p. 159 ° (active ingredient 3);

6. 1,2-bis (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol, m.p. 196-200 (active ingredient 4);

7. 1-phenyl-2- (bromo-4-chlorophenyl) -3- (imidazol-1-yl) -propan-2-ol nitrate, m.p. 183-184 ° (active ingredient 6);

8. 1- (2,6-Dichlorophenyl) -2- (2-bromo-4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate, m.p. 219-222 ° (active ingredient 7);

9. 1- (2,4-Dichlorophenyl) -2- (4-iodophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate, m.p. 195-197 ° (active ingredient 8).

The compounds containing the imidazole derivatives of the formula I and their salts have a much better fungicidal activity than the known 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] - Plants are more tolerant to fungicides containing 1 H-imidazole (active ingredient A) and the new agents.

The imidazole derivatives of the formula I can also be used in the form of their salts, such as their hydrochlorides, hydrobromides, sulfates, oxalates, dodecylbenzenesulfonates or nitric salts thereof.

The fungicides of the present invention are particularly significant for fungal infections of various crop plants, e.g. and Strawberries against Botrytis cinerea, Uncinula necator, Sphaerotheca fuliginea, Erysiphe cichoracearum, Podosphaera leucotricha.

Crops include, but are not limited to, wheat, barley, oats, rye, rice, corn, apples, cucumbers, beans, coffee, cane sugar, grapes, strawberries and ornamental horticultural plants.

The agents of the invention have systemic activity. The systemic efficacy of the agents is particularly effective in controlling internal plant damage, such as corn rust and corn flour.

The fungicides of the present invention can simultaneously inhibit the development of two or more fungi and are well tolerated by crop plants. The amount of active ingredient against phytopathogenic fungi may be between 0.05 and 2 kg per hectare.

Preferred active ingredients are, for example:

agent R ^{2 *} R® R ⁴ Salt Melting point, ° C First 4-Cl H 2-Cl 4-Cl HCI 225 Second 2-Cl 4-Cl 4-Cl H hnoj 181 Third 2-Cl 4-Cl 2-Cl H HNO ₃ 159 4th 2-Cl 4-Cl 2-Cl 4-Cl - 196-200

17992.5

agent R ¹ R ^a R ⁸ R ' Salt Melting point »° C 5th 2-Cl 4-Cl 2-Cl 4-Cl hno ₃ 170-172 6th 2-Br 4-Cl H H hno ₃ 183-184 7th 2-Br 4-Cl 2-Cl 6-Cl hno ₃ 219-222 8th 4-J H 2-Cl 4-Cl hno ₃ 195-197 9th 4 — OCH ₃ H 2-Cl H hno ₃ 167

Agents of the invention may be in the form of conventional preparations such as solutions, emulsions, suspensions, powders, pastes and granules. They may be prepared in known manner, for example, by mixing the active ingredient with a solvent and / or carrier, optionally in the presence of a surfactant such as an emulsifier or dispersant; if water is used as a diluent, other organic solvents may be used as co-solvents. Suitable excipients are in particular solvents such as aromatic hydrocarbons such as benzene or xylene, chlorinated aromatic hydrocarbons such as chlorobenzenes, paraffins such as petroleum fractions, alcohols such as methanol or butanol, amines such as ethanolamine or dimethylformamide and water. ; carriers such as natural mineral grinds such as kaolin, clay, talc and chalk, and artificial mineral grinds such as highly dispersed silica and silicates; emulsifiers, such as nonionic and anionic emulsifiers such as polyoxyethylene fatty alcohol ether, alkylsulfonates and arylsulfonates, and dispersants such as lignin, sulfite waste water and methylcellulose.

The compositions contain from 0.01 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The agents or the ready-to-use formulations thereof, such as solutions, emulsions, suspensions, powders, pastes and granules, are used in known manner, for example by spraying, spraying, spraying, dressing or dusting.

Other agents such as herbicides, insecticides, growth regulators and fungicides, as well as fertilizers, may be incorporated into the agents of the present invention. Examples of fungicides that can be mixed with the agent of the present invention include dithiocarbamate and derivatives such as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene bis (dithiocarbamate), manganese zinc ethylene diamine bis. (dithiocarbamate), zinc ethylene bis (dithiocarbamate);

tetramethyl thiuram disulfides; an ammonium complex of zinc [N, N-ethylene bis (dithiocarbamate) J and N, N'-polyethylene bis (thiocarbamoyl) disulfide;

Zn [N, N'-propylene-bis (dithiocarbamate) J; an ammonium complex of zinc [N, N'-propylene bis (dithiocarbamate)] and N, 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 compounds such as

N- (trichloro-methyl-thio) -tetrahydrophthalimide;

N- (trichloromethylthio) phthalimide;

2-heptadecyl-2-imidazoline acetate;

2.4-dichloro-6- (o-chloroanilino) s-triazine;

O, O-diethyl-phthalimido foszfonotioát;

5-amino-l- [bis (dimethylamino) phosphinyl] -3-phenyl-l, 2,4-triazole;

5-ethoxy-3- (trichloromethyl) -1,2,4-thiadiazole;

2.3-diciano-1,4-dithia-anthraquinone;

2-thio-l, 3-dithio [4,5-b] quinoxaline;

Methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate;

2- (methoxycarbonylamino) -benzimidazole;

2- (thiocyano-methylthio) benzothiazole;

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

8-hydroxyquinoline or its copper salt;

2.3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine-4,4-dioxide;

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxatin;

2- (2-furyl) benzimidazole;

piperazine-1,4-diylbis-1- (2,2,2-trichloroethyl) formamide;

2- (thiazolyl-4) -benzimidazole;

5-butyl-2- (dimethylamino) -4-hydroxy-6-methylpyrimidine; bis (p-chlorophenyl) -3-pyridinemethanol;

1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene;

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

and various other active ingredients such as dodecylguanidine acetate;

3- [2- (3,5-Dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] -glutarimide;

hexachlorobenzene;

N- (dichlorofluoro- methylthio) -N ', N'-dimethyl-N-phenyl-sulfuric acid diamide;

2,5-Dimethyl-furan-3-carboxylic acid anilide;

2,5-Dimethyl-furan-3-carboxylic acid cyclohexylamide;

2-methyl-benzoic acid anilide;

2-iodobenzoic acid anilide; l- (3,4-dichloro-phenylamino) -l- (formylamino) -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-2,5-dimethoxybenzene; p- (dimethylamino) benzenesulfonyl diazonátrium sulfonate;

-chloro-2-nitropropane;

polychlorinitrobenzenes, such as pentachloronitrobenzene;

methyl isocyanate;

fungicidal antibiotics such as griseofulvin or caustic gamycin;

tetrafluoro-dichloroacetone;

1-phenyl-thiosemicarbazide;

Bordeaux mixture;

nickel compounds and sulfur.

-3179925

In cereals, potentiation against powdery mildew and cereal rust was observed when synergism was observed when N-tridecyl-2,6-dimethylmorpholine or its salts were used together with the active compounds of the formula I or their salts. The potency enhancement is particularly pronounced for 1: 2 to 1: 4 weight ratio of active ingredients.

The following examples illustrate the fungicidal activity of the agents of the invention.

The known and well-known fungicide containing 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole (A) was used as comparator.

Example 10

Bama wheat rust

Leaves of potted wheat cultivars ('Caribo') were pollinated with spores of Puccinia recondita. The pots were then placed in a high humidity (90-95%) chamber for 24 hours at 20-22 °. During this time the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then spray-dripped with an aqueous spray solution containing 0.025% and 0.125% by weight of active ingredient, 80% active ingredient and 20% lignin sulfonate. After drying of the spray layer, the experimental plants were kept in a greenhouse at 20-22 ° and 65-70% RH. After eight days, we determined the degree of brown rust infection on the leaves.

The results are shown in Table I below.

Table I

agent Leaf infestation 0.025% After spraying 0.0125% First 0 0 Second 0 2 Third 1 2 4th 0 0 5th 0 0 6th 0 2 7th 0 1 8th 0 0 9th 2 2 The (known) 2 2 Untreated control 5

0 = no infection, 5 = total infection.

Example 11

bean rust

Leaves of bean plants grown in pots were artificially infected with spores of bean rust (Uromyces fabae) and placed in a humidified chamber at 20-25 ° for 48 hours. The plants were then sprayed with an aqueous spray solution containing 0.05% active ingredient, 80% active ingredient and 20% sodium lignin sulfonate dissolved or emulsified in water, and kept in a greenhouse at 20-22 ° C and 75-80% RH. After ten days, the rate of rust infestation was determined.

II. spreadsheet

agent Leaf infestation, After spraying with 0.05% spray liquid First 0 Second 0 Third 0 4th 0 5th 0 6th , 0 7th 0 9th 2 Untreated control 5

0 = no infection, 5 = total infection

Example 12

ITborkalisztharmat

The leaves of cucumber shoots grown in pots were sprayed with 0.05% aqueous emulsion (made from a mixture of 80% active ingredient and 20% oxyethylated castor oil emulsifier (Eriulphor EL)), and after spray drying, the leaves were dusted with cucumber cystic fever spores. The plants were then kept in a greenhouse at 20-22 ° C and 75-80% RH. Ten days later, the degree of powdery mildew infection was determined.

Xz results are shown in Table III. Table 1.

III. spreadsheet

agent Leaf infestation, After spraying with 0.05% spray liquid First 0 Second 0 7th 0 8th 0 9th 0 Untreated control 5

= no infection, 5 = total infection.

Example 13

Botrytis cinerea in peppers

Pepper shoots containing four to five well-developed leaves (Neusiedler Ideal Elite variety) were spray-dripped with 0.1% aqueous spray juice with a dry matter content of 80% active ingredient and 20% sodium lignin sulfonate. After drying, the plants were sprayed with a spore suspension of Botrytis cinerea and

2.2-24 ° C, placed in a high humidity chamber to ensure favorable conditions for fungal growth. Within five days, untreated control plants were so severely infected that most of the leaves were covered with necroses.

The results are shown in Table IV. Table 1.

ARC. spreadsheet 5 agent Leaf contamination after spraying with 0.1% spray 6th 0 10 7th 0 Untreated control 5

0 = no infection, 5 = total infection.

Example 14 sr. 1- (2,4-Dichlorophenyl) -2- (4-chlorophenyl) -3- (imidazol-1-yl) -propan-2-ol hydrochloride was mixed with 10 v / v. A solution containing 90% by weight of the active compound is obtained in the form of 20 drops of N-methyl-x-pyrrolidone and thus used as tiny droplets.

Example 15 sr. 1- (4-Chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate was dissolved in 80 µl. xylene, 8 molar ethylene oxide and 1 molar oleic acid N-monoethanolamide in 30 parts by weight, 5 parts by weight. in a mixture of the calcium salt of dodecylbenzenesulfonic acid and 40 mol of ethylene oxide and 1 mol of castor oil in 5 parts by weight. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion of 0.02% w / w.

from 17 sr. lignin sulfonic acid sodium salt and 60 µl of powdered silica gel and grind the mixture in a hammer mill. The mixture was added at 20,000 sr. uniformly distributed in water to give a spray liquid containing 0.1% by weight of the active ingredient.

Example 19 sr. 1-Phenyl-2- (2-bromo-4-chlorophenyl) -3- (imidazol-1-yl) -propan-2-one nitrate is thoroughly mixed with 97 parts by weight of powdered kaolin to give a powder containing 3% by weight of active ingredient. .

Example 20 sr. 1- (2,6-Dichlorophenyl) -2- (2-bromo-4-chlorophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate is thoroughly mixed with 20 µl. powdered silica gel and previously sprayed onto the silica gel surface with 8 sr. paraffin oil. A good adhesive composition is obtained.

Example 21 sr. 1- (2-Chlorophenyl) -2- (4-methoxyphenyl) -3- (imidazol-1-yl) propan-2-ol nitrate is thoroughly mixed with 10 parts by weight of sodium salt of phenolsulfonic acid urea-formaldehyde condensate , 2 sr. silica gel and 48 sr. water. A stable aqueous dispersion was obtained. 100,000 sr. diluted with water to give an aqueous dispersion of 0.04% w / w.

Example 16 sr. 1- (2-Chlorophenyl) -2- (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate was dissolved in 40 µl. cyclohexanone, 30 sr. isobutanol in a mixture of 10 parts by weight of a product of addition of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 40 mol of ethylene oxide and 1 mol of castor oil. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion of 0.02% w / w.

Example 22 sr. 1- (2,4-Dichlorophenyl) -2- (4-iodophenyl) -3- (imidazol-1-yl) propan-2-ol nitrate is thoroughly mixed with 2 volumes. dodecylbenzenesulfonic acid urea-formaldehyde condensate sodium salt, phenolsulfonic acid urea45-formaldehyde condensate calcium salt and 68% paraffinic mineral oil. A stable oily dispersion is obtained.

Example 17 50 sr. 1,2-Bis (2,4-dichlorophenyl) -3- (imidazol-1-yl) propan-2-ol was dissolved in 25 sr. Cyclohexanol, 65 sr. In a mixture of petroleum fractions having a boiling range of 210-280 ° C and 40 mol of ethylene oxide and 1 mol of castor oil in 10 parts by weight. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion of 0.02% w / w.

Example 18 sr. 1,2-Bis (2,4-dichlorophenyl) -3- (imidazol-1-yl) -propan-2-ol nitrate is mixed well with 3 parts by weight. diisobutylnaphthalene-a-sulfonic acid, sodium salt, sulphite content 65

Claims (2)

Patent claims An agricultural fungicide, characterized in that it is present in an amount of 0.01 to 95% by weight of the active ingredient (I). Imidazole derivative 55 talános formula: - wherein R ¹ is halogen or methoxy, R ^2, R * and R ⁴ independently represent a hydrogen or halogen atom - or a salt, preferably a hydrochloride or nitrate containing a solid or liquid carrier - preferably a mineral powder, petroleum fraction, aromatic or cyclic hydrocarbon, and a surfactant, preferably a nonionic or anionic emulsifier or wetting agent. Process for the preparation of the imidazole derivatives 5179925 of the formula I and their salts, preferably their hydrochlorides or nitrates, in which R ^{1 is a} halogen or methoxy group, R ² , R ⁸ and R ⁴ independently of one another are hydrogen or halogen. characterized in that a halogen compound of the formula II, in which R ¹ , R ² , R ⁸ and R ^{4 are} as defined above and X is a halogen atom, preferably a chlorine or bromine atom, is reacted with an imidazole or an alkali metal salt thereof; converting the resulting compound into its salt, if desired.