CS203930B2 - Fungicide means - Google Patents

Description

The invention relates to a fungicidal composition comprising, as active ingredient, at least one new azolylaeetophenone oxime ether. The invention further relates to a process for the preparation of these novel azolylacetophenone oxime ethers.

It is already known to use triazolylacetoenone derivatives as fungicides (cf. DOS No. 2,431,407). However, their effect is insufficient in various fungi.

It has now been found that the novel azolylacetophenone oxime ethers of the general formula n-o-R in which is

R ^{1 is} C 1 -C 2 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, isoxazolylmethyl optionally substituted with C 1 -C 2 alkyl or halogen (fluoro, chloro, bromo) or optionally substituted benzyl radical with one or more halogen atoms,

R ² is hydrogen or halogen (fluorine, chlorine, bromine), n is 1, 2 or 3 and

A 2 is a residue of imidazole or 1,2,4-triazole, and their salts and metal complexes have good fungicidal activity which exceeds that of the known fungicides mentioned above.

According to the invention, the novel azolylacetophenone oxime ethers are prepared by producing an azolylacetophenone oxime of the general formula wherein:

R ² , to Az, as defined above, is reacted with hydroxylamine to give the corresponding azolylacetophenoxime, which is then reacted with a halogen derivative of the formula

R1-X in which

R ¹ is as defined above, and X represents a halogen atom (fluorine, chlorine, bromine or iodine).

Etherification alkyl radicals (R ¹ = alkyl) can also be used preferably dialkyl. Another possibility is to react the azolylacetophenones with O-substituted hydroxylamines of the general formula

HzN — O — R ¹ in which

R ¹ has the above meanings.

Azolylacetophenone oxime ethers, due to the C = N double bond, occur as geometric isomers (syn / anti-forms) and often have an oily consistency as the free bases. To characterize them, they can be converted into the corresponding salts or complex metal salts, which are mostly crystalline and also have excellent fungicidal activity.

For the preparation of salts, the azolylacetophenone oxime ethers can be reacted with an acid (such as hydrochloric, nitric, sulfuric or carboxylic acid) and the azolylacetophenone oxime ethers can be reacted with a water-soluble inorganic metal salt (copper, zinc, tin) to produce complex metal compounds. .

The azolylacetophenones required as starting materials are known (cf. DAS 2,431,407, DOS 2,610,022).

The following examples illustrate the preparation of the compounds according to the invention.

Example 1

(a) 2,4-dichloro-η 4 - [1,2,4-triazol-1-yl] acetophenone oxime

10.4 parts (parts by weight) of hydroxylamine hydrochloride and 10.6 parts of sodium acetate are dissolved in 100 parts of water. To this solution was added 25.6 parts of 2,4-dichloro [1,2,4-triazol-1-yl] acetophenone in 250 parts ethanol and the mixture was refluxed for 2 hours. The reaction mixture was then cooled to 0 ° C, the precipitate was filtered off, washed with water and dried. 16 parts of 2,4-dichloro-ω- [1,2,4-triazol-1-yl] acetophenonoxime are obtained, m.p. 197 ° C.

bj To 200 parts of absolute tetrahydrofuran was added 3.12 parts of sodium hydride under a nitrogen atmosphere. 27.2 parts of 2,4-dichloro-ω- [1,2,4-triazol-1-yl] acetophenonoxime (dissolved in 80 parts of dimethylformamide) are added dropwise at 50-60 ° C and the mixture is boiled 2 hours under reflux. 23.5 parts of 2,4-dichlorobenzyl chloride are then added dropwise at 50-60 ° C and the mixture is refluxed for a further 2 hours. 280 parts of water are then added dropwise, the mixture is extracted three times with 100 ml of ether and the organic phases are dried over sodium sulfate. Hydrogen chloride is then reintroduced until saturation, the precipitate is filtered off and recrystallized from acetonitrile. 16 parts of 2,4-dichloro [1,2,4-triazol-1-yl] acetophenone oxime-O- (2,4-dichlorobenzyl) ether are obtained in the form of the hydrochloride, m.p. 173 ° C.

Example 2 parts 2,4-dichloro-1- [1,2,4-triazol-1-yl] acetophenone oxime-O- (2,4-dichlorobenzyl) ether are dissolved in 10 parts ethanol and at 70 ° C 2.2 parts of copper (II) chloride dihydrate in 7 parts of ethanol (saturated solution) are added dropwise. The mixture is concentrated in vacuo, the solid residue is triturated with ether and filtered off. There are obtained 4 parts of a copper (II) chloride 2,4-dichloro-N- [1,2,4-triazol-1-yl] acetophenone oxime-O- (2,4-dichlorobenzyl) ether complex with a decomposition temperature of 142-143 ° C. (olive green color).

The compounds listed in the following table can be prepared accordingly:

Number

R ^{2 Λ η}

2,4-Cl

2,4-Cl

2,4-Cl

2,4-Cl

2.4- Cl

4-C1

4-Br

4-Br

4-Br

4-Br

4-Br

4-C1

4-C1

4-C1

4-C1

2.4- Ch

2.4- Clz

2,4-Clz

2,4-Cl-iodine

NORWEGIAN

Rl

2,4-dichlorobenzyl

CHj

C2H5 allyl

CH3

CH3

Cl

Cl

Cl

Salt / Complex Temperature

salt X melting point (° C) HCl N 173 HCl N 141 HCl N 159 HNO3 N 115 *) HNO3 H 108 *) HCl CH 127 HCl N 157—159 HCl N 167—169 HCl N 168—170 1/2 C11Cl2 N 182-1841) 1/2 C11Cl2 N 1711) HCl N 156—158 - N 91 V2 CuClZ N 2071) 1 µl CuCl 2 N 158—1601) HCl N HCl N HCl N

Cl

CuCl2 N 142 - 1431)

WITH

Number R _n ²

R ¹ Salt / complex Temperature salt X melting (° C)

2,4-Cl

Z0

CH 2 O

2,4-Cl

,Whose

2,4-Cl

2,4-Cl

Cl CH, &

'and.

CH- O

24 2,4-Cl CH 2 —C-CH 25 2,4-Cl 26 2,4-Cl 27 Mar: 2,4-Cl

- N oil ² ] - N oil ² ) - N oil ² ) - N oil ² )

CuCl 2 N 152 ¹ ) - N oil

NO3 N 99-101

HCl N 158-160

*) with decomposition

1) with decomposition

3) characterized by NMR spectrum

The azolylacetophenone oxime ethers of the present invention exhibit excellent activity against a broad spectrum of phytopathogenic fungi. In part, they are systemically active and can be used as foliar or soil fungicides, in particular as mordants.

The novel compounds are particularly suitable for combating the following fungal diseases:

powdery mildew (Erysiphe graminis) on cereals, powdery mildew (Erysiphe cichoriacearum) on pumpkin plants, apple powdery mildew (Podosphaera leucotricha) and apple scab (Venturia inaequalis) on apple trees beans, powdery mildew (Sphaerotheca pannosa) on roses, rust species (Puccinia) on cereals, rust species (Uromyces) on beans.

These compounds are applied by taking the plants. they are sprayed with or dusted with active substances or plant seeds are treated with active substances. Application is carried out before or after infection of plants or seeds by fungi.

The compounds of the invention may be converted into conventional compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The dosage forms are entirely governed by the purposes of use; in any case, these forms 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 using emulsifiers and dispersants, where further organic solvents can be used as co-solvents when water is used as a diluent. Basically suitable excipients are: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanol203930 amine, dimethylformamide) ) 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 (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) 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.

Depending on the type of effect desired, the application rate is 0.01 to 3, but preferably 0.01 to 1 kg of active substance per ha.

The compositions of the invention may be present in these dosage forms together with other active ingredients such as herbicides, insecticides, growth regulators and fungicides, or they may be mixed and co-administered with a fertilizer. When mixed with fungicides, in many cases an increase or decrease is achieved. enlargement of the spectrum of fungicidal effects.

The following list of fungicides with which the compounds of the present invention may be combined serves to illustrate the combination possibilities, but not to limit them to the above.

Fungicides which may be combined with the complex metal compounds of the invention include, for example: dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-dithiocarbamate, ethylenediamine bis-dithiocarbamate, manganese zinc dithiocarbamate, tetramethylthiuram disulfides, ammoniacal complex of N, N-ethylene-bis-dithiocarbamate zinc and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide,

Zinc N, N‘-propylene-bis-dithiocarbamate, an ammoniacal complex of N, N‘-propylene-bis-dithiocarbamate zinc and N, N‘-propylpropylene-bis- (thiocarbamoyl) disulfide;

N-Trichloromethylthiotetrahydrophthalimide

N-Trichloromethylthiophthalimide

2-Heptadecyl-2-imidazoline acetate

2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0,0-diethylphthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

S-ethoxy-S-trichloromethyl-1H-thiadiazole,

2,3-dicyano-1,4-dithiaanthraquinone, 2-thio-1,3-dithio- (4,5-b) quinoxaline, 1- (butylcarbamoyl) -2-beta-diisidazolecarbamic acid methyl ester, 2-methoxycarbonylaminobenzimidamethyltetamine, 2-rhodanmethylthiobenzthiobenzthiobenzthiobenzyl

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-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-methylpyrimidine, 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 dodecyclguanidine acetate,

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

Sulfuric acid N-dichlorofluoromethylthio-N ‘, N‘-dimethyl-N-phenyldiamide,

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

2-methylbenzanilide,

2-iodobenzanilide,

1- (3,4-dichloroanino) -1-formyl-amino-2,2,2-trichloroethane,

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

2,6-dimethyl-N-cyclodecylmorpholine or salts thereof.

For comparative purposes, the following known active substances have been used for comparative purposes, such as nitro derivatives, such as dinitr- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate;

heterocyclic compounds such as?

N, N-CH 2 CS ₃ -C 1'UNO ₃

Cl (compound A) (known from DOS 24 31407) <2 n-n-ch-c

FWNO ₃ (compound B) (known from DOS 24 31 407) |

N, N-CH 2 CO

C · HNO ₃ (Compound C) (known from DOS 24 31 407).

Example 3

Effect against powdery mildew on barley

The leaves of the barley plants growing in pots are sprayed with aqueous emulsions prepared from 80% (w / w) of active ingredient and 20% of emulsifier, and after drying of the spraying layer, they are dusted with powdery mildew of Erysiphe graminis var. hordei. The test plants are then placed in a greenhouse where they are stored at temperatures between 20 and 22 ° C and at 75 to 80% relative humidity. After 10 days, the degree of mildew development was determined.

Active substance

Attack of leaves after spraying ...% of active substance suspensions 0,05 0,025 0,012

2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 25 0 0 0 26 0 0 0 27 Mar: 0 0 0 A (known) 0 2 2 B (known) 3 5 5 untreated (control) 5 5 5 0 = no attack, graded to 5 (total attack)

Example 4

Effect against wheat rust

The leaves of 'Caribo' wheat plants growing in pots are dusted with spores of wheat rust (Puccinia recondita). The pots were then placed in a high humidity (90-95%) chamber at 20-22 ° C for 24 hours. During this time the spores germinate and the germs penetrate the leaf tissue. The infected plants are then sprayed with aqueous suspensions of 0.05, 0.025 and 0.012% of active ingredient concentration (% by weight) containing 80% active ingredient and 20% lignin sulphonate in dry matter. Spraying is carried out until dew. After the spray layer has dried, the test plants are placed in a greenhouse at temperatures 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.

The test results are shown in the following table:

active substance infestation of leaves after spraying ...% active substance suspensions 0.05 0,025 0.012 2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0 25 0 0 0 26 0 0 0 27 Mar: 0 0 0 C (known) 5 5 5 untreated (control) 5 5 5

= no attack, graded up to 5, which is the total attack

Example 5

Explanatory notes to the table:

Effect against oat rust

In the same manner as in Example 3, the leaves of oat plants of the species Flfimings Krone that grow in pots are dusted with spores of oat rust (Puccinia coronata) and placed in a chamber with high humidity. The infected plants are then sprayed with 0.05% (w / w) aqueous suspension containing 80% active ingredient and 20% lignin sulphonate in the dry state until dripping. After drying, the plants are placed in a room temperature of 20-22 ° C and 65-70% relative humidity. After 8 days, the degree of rust development was determined on the leaves.

The results of this test are shown in the following table:

effective infestation of the leaves after spraying with a 0.05% suspension of the active substance

0

0

0

0

0

A (known) 2

B (known) 0

C (known) 0 untreated 5 (control) = no attack, graded up to 5, which is the total attack.

Example 6

Effect on barley powdery mildew (pickling application)

100 g - 'Asse' barley seed samples are pickled in glass bottles for about 5 minutes each with 300 mg (= 0.3% by weight) of the mordant listed in the table carefully. Then, each of the 8 grains is placed in a pot and covered with soil. 10 days after emergence of the cereal, the leaves are dusted with powdery mildew of Erysiphe graminis var. hordei. The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and at the corresponding relative humidity. After a further 10 days, the degree of mildew development on the leaves was determined.

The test results are shown in the following table:

Active substance% of active substance Degree of mildew infestation in mordant on the leaves 10 days after artificial infection

2 40 0 4 40 0 5 40 0 A (known) 40 1 - 2 B (known) 40 5 C (known) 40 5

untreated (control) = no attack, graded to 5, which is the total attack

Example 7

The following example illustrates the particularly excellent action of the active substance No. 5 against apple scab:

Four-year-old Golden Delicious apple trees are treated a total of four times with aqueous suspensions containing, as active substance, 0,012% (w / w) 2,4-dichloro-ω- [1,2,4-triazole-1] from the end of August until mid-July. -yl-acetophenone oxime-O-propargyl ether nitrate (active substance No. 5). At the end of July, naturally occurring apple scab infestation (Venturia inaequalisj on leaves of untreated apple trees was evaluated and compared to infestation on the treated leaves. Dichloro-N- [1,2,4-triazol-1-yl] acetophenone oxime-O-propargyl ethernitrate detect any attack.

Example 8 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 9 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 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight. parts of an 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 10 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 mol of isooctylphenol and 10 parts by weight of an adduct. oils. 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 11 parts by weight of compound 1 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 ° C and 10 parts by weight of an adduct of 40 moles of 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 12 parts by weight of active compound 2 are well mixed with 3 parts by weight of sodium salt of dlisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of sodium salt of ligninsulfonic acid 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 13 parts by weight of compound 3 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 14 parts by weight of compound 4 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.

Example 15 parts by weight of active ingredient 1 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 16 parts of active ingredient 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Claims (1)

A fungicidal composition comprising a solid or liquid carrier and, as the active ingredient, at least one azolylacetophenone oxime ether of the general formula n- ¹ wherein: R ^{1 is} C 1 -C 2 alkyl, C 2 -C 4 alkenyl, YnAlez C 2 -C 4 alkynyl, isoxazolylmethyl radical optionally substituted by C 1 -C 2 alkyl or halogen or optionally one or more halogen atoms substituted benzyl radical, R ² is hydrogen or halogen, n is 1, 2 or 3 and And the remainder of the imidazole or 1,2,4-triazole, or a salt thereof or a metal complex thereof.