JPH0136828B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ¹ is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, ^R2 represents 3-pyridyl or 2-pyrazinyl, ^R3 represents hydrogen or linear _C1-4 -alkyl,
and R ⁴ is C _1-6 -alkyl, C _3-6 -cycloalkyl,
C _3-6 -alkenyl or C _3-6 -alkynyl) and acid addition salts of these compounds. The compounds of the formula and their acid addition salts have fungicidal properties and are suitable as fungicidal active substances, in particular for use in agriculture and horticulture. The present invention further provides a process for producing compounds of the formula and their acid addition salts, compounds of the formula and their acid addition salts as fungicidal active substances, and fungicidal compositions containing the compounds of the formula or their acid addition salts as active substances. , and the use of said compounds, acid addition salts and compositions for mold control in agriculture and horticulture. The term "halo" in the formula definitions includes fluoro, chloro, bromo and iodo, with chloro being preferred. The halogen atoms in the 2,4-dihalo-phenyl group represented by R ₁ may be the same or different. The terms " _C1-6 -alkyl", " _C3-6 -alkenyl" and " _C3-6 -alkynyl" include straight-chain as well as branched hydrocarbon groups. Alkyl may be understood by the specified number of carbon atoms, such as the following groups: methyl, ethyl, n-
Propyl, isopropyl, n-butyl, tert-butyl, isoamyl and n-hexyl come into consideration. If R ⁴ represents C _1-6 -alkyl, C _3-6 -alkenyl or C _3-6 -alkynyl, then this radical is C _1-4 -alkyl, C ₃ or 4-alkenyl or C ₃ Or ₄ -alkynyl is preferred. The allyl group is particularly preferably an alkenyl group, and the propargyl group is particularly preferably an alkynyl group. R ¹ preferably represents 4-chlorophenyl or 2,4-dichlorophenyl, particularly preferably the latter group. R ³ preferably represents hydrogen, methyl or ethyl, particularly preferably hydrogen. Particularly preferred compounds of the formula are 2′,4′-
Dichloro-2-(3-pyridyl)-acetophenone O-methyloxime. Representative compounds of the formula are 4'-chloro-2-(3-biridyl)-acetophenone O-allyloxime and 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-isopropyloxime. Geometric isomers result from the presence of a C=N double bond in the compound of formula. Additionally, asymmetric carbon atoms may be present, so that the compounds may exist as optical antipodes. The formula is therefore meant to include all these possible isomers. Physiologically compatible salts are considered as acid addition salts of the compound of formula. These salts include inorganic or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, mono- or difunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) as well as sulfonic acids (e.g. 1,5-naphthalene-
Disulfonic acid) is preferred. The method of the present invention for producing compounds of formula (a) and their salts comprises: (a) (In the formula, R ¹ , R ² and R ³ have the above meanings)
An oxime of the formula R ⁴ U {where R ⁴ has the above meaning and U represents a leaving group (e.g. chlorine, bromine, iodine, mesyloxy,
tosyloxy or alkyl sulfate group), or (b) (In the formula, R ¹ , R ² and R ³ have the above meanings)
reacting a ketone of the formula R ⁴¹ ONH ₂ with an O-substituted hydroxylamine of the formula R 41 ONH 2 , in which R ⁴¹ represents C _1-6 -alkyl, C _3-6 -cycloalkyl or C _3-6 -alkenyl;
and, if desired, converting the obtained compound of formula into an acid addition salt. Variant (a) comprises starting with a compound of the formula, conveniently in the presence of a base, in an organic solvent at 0°C.
and the reflux temperature of the reaction mixture. The solvent may be protic or aprotic. If protic solvents such as alcohols, especially methanol or ethanol, are used, preference is given to using alkali metal hydroxides (eg sodium or potassium hydroxide) or alkali metal alcoholates as bases. When using aprotic solvents such as ethers or ether-like solvents, especially tetrahydrofuran or dimethoxyethane, and dialkylamides, especially dimethylformamide, preference is given to using alkali metal hydrides (e.g. sodium hydride) as the base. . In a preferred embodiment of variant (a), sodium hydride is used as base and an ether or ether-like compound, especially tetrahydrofuran or dimethoxyethane, or a dialkylamide, especially dimethylformamide, is used as solvent. In variant (b), which gives compounds of the formula in which R ₄ represents C _1-6 -alkyl, C _3-6 -cycloalkyl or C _3-6 -alkenyl, the reaction is carried out in an organic solvent, such as an alcohol such as methanol or ethanol. , a dialkylamide such as dimethylformamide or a tertiary amine such as pyridine. Preferably, the reaction is carried out within a temperature range between room temperature and the reflux temperature of the reaction mixture. Since the starting materials of the formula are preferably used in the form of acid addition salts (for example hydrochlorides or sulphates), it is expedient to add a base such as sodium or potassium carbonate, triethylamine or pyridine to the reaction mixture. For the preparation of acid addition salts, compounds of the formula are reacted, if desired, with inorganic or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, mono- and difunctional carboxylic acids and hydroxycarboxylic acids or sulfonic acids. Isolation and purification of the compounds of the formula and their acid addition salts thus prepared are carried out by methods known per se. The formulas and compounds used as starting materials are known or can be prepared by methods known per se. For example, oximes of the formula can be prepared from the corresponding ketones of the formula by reaction with hydroxylamine;
It can be manufactured by the method described in DOS2800010 and British Patent Specification No. 2015524. The compounds according to the invention (i.e. the compounds of formula and their acid addition salts) have fungicidal activity;
Therefore, it can be used for controlling mold in agriculture and horticulture. They are particularly suitable for eradicating or controlling plant pathogens on plant parts (e.g. leaves, stems, roots, stems, fruits or flowers) and seeds, and in soil, and in particular for the eradication or control of powdery mildews, e.g. Erysiphe graminis (powdery mildew of grains), Erysiphe cichoracearum (mildew of cucumbers), Podosphaera leucotricha (mildew of apples) and Erysiphe cichoracearum (mildew of cucumbers) Sphaerotheca pannosa (powdery mildew of roses)
Venturia ainequaris (Venturia
inaequalis (apple scab), rust fungi such as Puccinia, Uromyces and Hemileia, especially Puccinia coronata
coronata (crown rust of oats), Puccinia recondita (red rust of grains), Uromyces appendiculatus (bean rust) and Hemileia
It is effective in controlling coffee rust (coffee rust). Additionally, various compounds of the invention also have activity against plant pathogens of the following genera: Helminthosporium, Rhizoctonia, Septoria, Cercospora, Corticium. , Tilletia and Ustilago. Furthermore, the individual compounds of the invention may be used in wood-destroying fungi such as Coniophora
puteana) and range test labia (Lenzites)
trabea). Furthermore, each compound also has activity against phytopathogenic bacteria such as Xanthomonas oryzae. The compounds of the invention have systemic activity (systemic activity).
activity) as well as good plant tolerance. The compounds of the invention are active under greenhouse conditions even at concentrations of active substance from 5 mg to 500 mg per spray liquid. In the field, 50g per hectare
Active substance concentrations and treatments of the formula 1000 g are advantageous for application. For example, effective control of apple powdery mildew and apple rust requires a
Active substance concentrations of formulas from g to 400 g are used. For controlling mold on seeds during disinfection processes, it is advantageous to use from 0.1 to 2.5 g of active substance per kg of seeds. The compounds of the invention can be formulated to provide a variety of compositions, such as spray solutions, aqueous suspensions, emulsions, emulsion concentrates, and powder formulations. The fungicidal compositions of the present invention contain an effective amount of at least one compound of the general formula as defined above or an acid addition salt of such a compound and an inert carrier material. The composition is generally 0.0001 depending on its type.
and 95% by weight of the compound of the invention as active substance. Various inert powder carrier materials such as kaolin,
Bentonite, talc, chalk, magnesium carbonate and siliceous earth can be used to make powdered fungicidal compositions. The active ingredient can be mixed with such a carrier material (e.g. by grinding together) or an inert carrier material can be impregnated with a solution of the active ingredient and the solvent can be evaporated, heated or filtered off with suction under reduced pressure. Twist and remove. Such a powder composition can be applied as a wiping composition to the plants to be protected using conventional wiping equipment. By adding wetting and/or dispersing agents, such pulverulent compositions can be made easily wettable with water, so that they can also be used in the form of aqueous suspensions as spray compositions. . To produce emulsified concentrates, the active substance is mixed with an emulsifier, for example, or dissolved in an inert solvent and mixed with an emulsifier. By diluting such a concentrate with water, a ready-to-use emulsion is obtained. Such concentrates contain 5 to 95% by weight of active substance, in particular 25 to 75% by weight. The fungicidal compositions of the present invention contain, in addition to the active substance of the formula, other active substances such as other fungicides,
(insecticides and acaricides, other fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for broadening the spectrum of activity or for influencing specific plant growth. The compounds of the invention can be used in plant protection or in agriculture by conventional application methods. The method for controlling mold according to the invention is characterized in that the article to be protected (for example a plant, a part of a plant or a seed) is treated with an effective amount of a compound according to the invention or a composition according to the invention. The following examples illustrate the invention. All temperatures are in °C. Example of Preparation of Active Substances 1 A solution of 13.3 g of 2',4'-dichloro-2-(3-pyridyl)-acetophenone in 40 ml of ethanol is mixed with 10 g of sodium carbonate and 8.3 g of O-methylhydroxylamine hydrochloride. treated with salt,
The mixture is then heated to reflux temperature with stirring. After 4 hours, the mixture is poured onto ice and extracted with ethyl acetate. Wash the organic layer, dry over sodium sulfate and concentrate under reduced pressure. 2′,4′-dichloro-
2-(3-Pyridyl)-acetophenone O-methyloxime is obtained as an E,Z-isomer mixture in the form of a yellow oil. n-hexane/on silica gel
Chromatographic separation was performed using ethyl acetate (4:1) to first separate the E-isomer (n ²⁰ _D = 1.5845).
and then the Z-isomer (n ²⁰ _D =1.5745). Similarly, 4'-chloro-2-(3-pyridyl)-acetophenone O-methyloxime, mp55-58, was prepared from 4'-chloro-2-(3-pyridyl)-acetophenone and O-methyl-hydroxylamine hydrochloride. 4'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride, mp53-58℃ , obtained from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-ethylhydroxylamine hydrochloride, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-ethyloxime, mp44-46° obtained; 4'-chloro-2-(2-pyrazinyl)-acetophenone O-allyl oxime as a yellow oil from 4'-chloro-2-(2-pyrazinyl)-acetophenone and O-allylhydroxylamine hydrochloride. Obtained; 2',4'-dichloro-2-(3-pyridyl)- from 2',4'-dichloro-2-(3-pyridyl)-acetophenone and O-allylhydroxylamine hydrochloride.
Acetophenone O-allyl oxime is obtained as a colorless oil. Example 2 3 g of 2'-chloro-2-(2-pyrazinyl)-acetophenone and 0.8 g of O-methylhydroxylamine hydrochloride are dissolved in 10 ml of pyridine and the mixture is heated at 80 DEG C. for 30 minutes. The pyridine is then removed under reduced pressure and water is added to the crude product. Thereupon, the mixture is extracted with ethyl acetate, the organic layer is dried over sodium sulfate and concentrated.
2'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime is obtained as an oil. Similarly, 4'-fluoro-2-(2-pyrazinyl)-acetophenone O-methyloxime, mp52-54°, was prepared from 4'-fluoro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride. ,
4'-bromo-2-(2-pyrazinyl)-acetophenone O-methyloxime, mp81-84°, from 4'-bromo-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride; 4'-Chloro-2-(2-pyrazinyl)-propiophenone O-methyloxime was obtained as an oil from 4'-chloro-2-(2-pyrazinyl)-propiophenone and O-methylhydroxylamine hydrochloride. Obtained as a product; 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-methyl from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride The oxime was obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-methylhydroxylamine hydrochloride. O-ethyloxime was obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl) was obtained from 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and O-allylhydroxylamine hydrochloride. )-acetophenone O-allyloxime obtained as an oil; 2',4'-dichloro-2-(2-pyrazinyl)-propio-phenone and O-methylhydroxylamine hydrochloride to obtain 2',4'-dichloro-2 -(2-pyrazinyl)-propiophenone O-methyloxime is obtained as an oil. Example 3 A solution of 3 g of 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime in 25 ml of dimethoxyethane is diluted with 0.51 g of a sodium hydride dispersion (55% in oil). The mixture is stirred for 30 minutes at room temperature. Then 2.0 g of ethyl iodide are added and the mixture is heated to reflux temperature. 4
After some time, the mixture is poured onto ice, extracted with ethyl acetate, the organic layer is dried over sodium sulfate and concentrated under reduced pressure. The crude product is purified by chromatography on silica gel. 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-ethyloxime is obtained as a yellow oil. Similarly, from 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime and isopropyl bromide, 2',
4'-Dichloro-2-(3-pyridyl)-acetophenone O-isopropyloxime obtained as a yellow oil; from 2',4'-dichloro-2-(3-pyridyl)-acetophenone oxime and propargyl bromide. 2′,
4'-dichloro-2-(3-pyridyl)-acetophenone O-propargyloxime, mp60-62°,
obtained; 4'-chloro-2-(2-pyrazinyl)-acetophenone O- from 4'-chloro-2-(2-pyrazinyl)-acetophenone oxime and propargyl bromide.
Propargyl oxime, mp76−77°, was obtained from 2′,4′-dichloro-2-(2-pyrazinyl)-acetophenone oxime and propargyl bromide.
2',4'-di-chloro-2-(2-pyrazinyl)-acetophenone O-propargyloxime is obtained as an oil. Preparation of Starting Materials Example 4 The 2',4'-dichloro-2-(3-pyridyl)-acetophenone required as starting material in Example 1 may be constituted as follows: 27.6 g of ethyl 2,4-dichlorobenzoic acid and
A mixture of 20.81 g of ethyl 3-pyridyl acetate is treated in portions at 20-25° with 10.59 g of sodium methoxide. The mixture is then heated to 65-70° and the resulting highly volatile product is blown off with dry nitrogen. After 20 hours, the mixture is treated with 40 ml of concentrated hydrochloric acid and heated at reflux temperature for 18 hours. The mixture was washed with diethyl ether, the aqueous layer made basic by addition of concentrated ammonia,
Extract with methylene chloride. The organic layer is concentrated and the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2).
The purified product, 2',4'-dichloro-2-(3-pyridyl)-acetophenone, was dissolved in diethyl ether/n
- Recrystallization from pentane. mp55−56°. Example 5 The 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone required as starting material in Example 2 is prepared as follows; 20 g of 2-methylpyrazine is added to the suspension of sodium amide in liquid ammonia. Add dropwise to the suspension (from 200 ml of ammonia and 4.83 g of sodium) at -30° and stir the mixture for 30 minutes. 20.5 g of methyl 2,4-dichlorobenzoic acid are then slowly added dropwise and the mixture is allowed to react for 1 hour at -30°. The mixture was then treated with ammonium chloride,
Remove ammonia and add diethyl ether. The organic layer is washed with water, dried over sodium sulfate, and concentrated. Upon treatment with a small amount of ethanol, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone crystallizes from the crude reaction product. The product melts at 96-98°. In a similar manner, 2'-chloro-2-(2-pyrazinyl)-acetophenone was obtained as an oil from 2-methylpyrazine and methyl 2-chlorobenzoic acid; 4 from 2-methylpyrazine and methyl 4-fluorobenzoic acid. '-Fluoro-2-(2-pyrazinyl)-
Acetophenone, mp100-103°, was obtained; 2-methylpyrazine and methyl 4-bromobenzoic acid gave 4'-bromo-2-(2-pyrazinyl)-acetophenone, mp121-122°; 2-ethylpyrazine and 4'-chloro-2-(2-pyrazinyl)-propiophenone, mp85°, is obtained from methyl 4-chlorobenzoic acid; 2',4' dichloro is obtained from 2-ethylpyrazine and methyl 2,4-dichlorobenzoic acid. -2-(2-pyrazinyl)-propiophenone is obtained as an oil. Example 6 4'-Chloro-2- required as starting material in Example 3
(2-pyrazinyl)-acetophenone oxime may be prepared as follows; 10 g of 4'-chloro-2-(2-pyrazinyl)-acetophenone, 10 g of hydroxylamine hydrochloride and 12 g of anhydrous sodium carbonate at 60° Stir in 100 ml of ethanol for 2 hours. The mixture is then treated with water, extracted with ethyl acetate, and the organic layer is dried over sodium sulfate and then concentrated. The residue is recrystallized from acetone/n-hexane.
4'-chloro-2-(2-pyrazinyl)-acetophenone oxime, mp 134°, is obtained. In a similar manner, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone and hydroxylamine hydrochloride were prepared.
2',4'-dichloro-2-(2-pyrazinyl)-acetophenone oxime obtained as a viscous oil; from 2',4'-dichloro-2-(3-pyridyl)-acetophenone and hydroxylamine hydrochloride. 2′,
4'-dichloro-2-(3-pyridyl)-acetophenone oxime, mp 134-136°, is obtained. EXAMPLE 7 FORMULATION EXAMPLE 7 1 Spray Powder (for active substance that is liquid or melts below 75°) Parts by weight of active substance 50 Hydrated silicic acid 37 Kaolin 5 Alkylphenol ethoxylate 4 Sodium polynaphthalene sulfonate 4 100 Liquid or absorbing the molten active substance into silicic acid;
Mix the remaining ingredients and finely grind the mixture in a suitable mill. 2 Spray powder (based on solid active substances melting above 75°) Parts by weight of active substance 50 Hydrated silicic acid 5 Kaolin 42 Sodium uralyl sulfate 1 Sodium lignosulfonate 2 100 The components are mixed together and this The mixture is finely ground in a suitable mill. Example 8 Emulsified concentrate (for active substance liquid at 20-25°) Parts by weight Active substance of the formula 500 Castor oil ethoxylate 100 Calcium dodecylbenzene sulfonate 25 C ₁₀ -Mixture of alkylbenzenes
Add 1000 parts by volume of each component to each other and mix until a clear solution is obtained. Evaluation of fungicidal activity Test: Powdery mildew of cucumber (Erysiphe
Aqueous dispersion of the test compound (prepared in a conventional manner as a powder for spraying) was thoroughly applied to each of two cucumber plants at the two-leaf stage of the Chinese Snake species. The plants were thoroughly sprayed from all directions and then cultivated in a greenhouse. 24 hours after this treatment, on the first leaf of the plant
Infection was achieved by sprinkling with spores of Erysiphe cichoracearum. After a further 7-9 days, the degree of protection conferred by the test compound was determined by comparing the infections found on the leaf surface of the test plants with Erysiphe, without treatment with the test compound.
It was evaluated by comparing the infection found on the leaf surface of control plants infected with Cichoracearum. Test: Apple scab (Venturia inaequalis)
Activity against “Golden Delicious”
Delicious) 3 seedlings of apple seeds
A suspension of Venturia inaequalis spores was sprayed and then incubated at 18° C. under dew point conditions. After 24 hours, the plants were thoroughly sprayed from all directions with an aqueous dispersion of the test compound (prepared in a conventional manner as a powder for spraying). The apple seedlings thus treated were further cultivated in a greenhouse. After 9 to 10 days, the degree of protection conferred by the test compound was determined by the amount of infection and Venturia found on the leaf surface of the test plants.
inaequalis similarly infected, but not treated with the test compound. The activity of both tests for these test compounds, expressed as percent activity, is shown in the following table:

【table】

Table: In each of the two tests above, representative compounds of the invention showed fungicidal activity, with few exceptions, even at low application rates of 16 mg/ and 5 mg/. The activity at the highest application rate of 160 mg/was 100% in most cases. Contrary to these excellent results, the compounds of the prior art, i.e. the 9th and 10th compounds of Example 1 of JP-A-55-19288 (European Patent Application Publication No. 7679), have a maximum application rate of 160 mg/ However, it shows even lower fungicidal activity, and at even lower application rates it shows little or no activity. Based on the above test results, the compounds of the present invention were proved to have excellent fungicidal activity, whereas the compounds of the prior art were shown to have excellent fungicidal activity based on these test results.
It was demonstrated that they had little or no fungicidal activity.

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, R ² represents 3-pyridyl or 2-pyrazinyl, R ³ represents hydrogen or chain-like C _1-4 -alkyl,
and R ₄ is C _1-6 -alkyl, C _3-6 -cycloalkyl,
_C3-6 -alkenyl or _C3-6 -alkynyl) and acid addition salts of these compounds. 2. A compound according to claim 1, wherein R ¹ represents 4-chlorophenyl or 2,4-dichlorophenyl. 3. A compound according to claim 1 or claim 2, wherein R ³ represents hydrogen. 4. The compound of claim 1 which is 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-methyloxime. 5 4'-chloro-2-(3-pyridyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl) )-acetophenone O-ethyloxime, 4'-chloro-2-(2-pyrazinyl)-acetophenone O-allyloxime, 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-ethyloxime, 2 Claims selected from ',4'-dichloro-2-(3-pyridyl)-acetophenone O-isopropyloxime and 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-propargyloxime Compound of item 1. 6 2',4'-dichloro-2-(3-pyridyl)-acetophenone O-allyloxime, 2'-chloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-fluoro-2-( 2-pyrazinyl)-acetophenone O-methyloxime, 4'-bromo-2-(2-pyrazinyl)-acetophenone O-methyloxime, 4'-chloro-2-(2-pyrazinyl)-propiophenone O-methyloxime , 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-methyloxime, 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-ethyloxime, 2',4' -dichloro-2-(2-pyrazinyl)-acetophenone O-allyloxime, 2',4'-dichloro-2-(2-pyrazinyl)-propiophenone O-methyloxime, 4'-chloro-2-(2 -Pyrazinyl)-acetophenone O-propargyl oxime and 2',4'-dichloro-2-(2-pyrazinyl)-acetophenone O-propargyl oxime. 7. At least one general formula for effective amounts (In the formula, R ¹ is 2-halo-, 4-halo- or 2,4
-dihalo-phenyl, ^R2 represents 3-pyridyl or 2-pyrazinyl, ^R3 represents hydrogen or linear _C1-4 -alkyl,
and R ₄ is C _1-6 -alkyl, C _3-6 -cycloalkyl,
_C3-6 -alkenyl or _C3-6 -alkynyl) or an acid addition salt of such a compound and an inert carrier material. 8. The fungicidal composition of claim 8 containing an effective amount of 2',4'-dichloro-2-(3pyridyl)-acetophenone O-methyloxime and an inert carrier material. 9 General formula (R ¹ represents 2-halo-, 4-halo- or 2,4-dihalo-phenyl, R ² represents 3-pyridyl or 2-pyrazinyl, R ³ is hydrogen or linear C _1-4 - represents alkyl,
and R ₄ is C _1-6 -alkyl, C _3-6 -cycloalkyl,
C _3-6 -alkenyl or C _3-6 -alkynyl) and an acid addition salt thereof (wherein R ¹ , R ² and R ³ are as defined above), an oxime compound of the formula R ₄ U (wherein R ⁴ is as defined above and U is chlorine,
bromine, iodine, mesyloxy, tosyloxy or an alkylsulfate group and, if desired, converting the resulting compound of the formula into an acid addition salt. 10 General formula 1 (R ¹ represents 2-halo-, 4-halo- or 2,4-dihalo-phenyl, R ² represents 3-pyridyl or 2-pyrazinyl, R ³ is hydrogen or linear C _1-4 - represents alkyl,
and R ⁴ is C _1-6 -alkyl, C _3-6 -cycloalkyl,
C _3-6 -alkenyl or C _3-6 -alkynyl) and acid addition salts thereof, the method comprising: (wherein R ¹ , R ² and R ³ are the same as defined above), a ketone compound having the formula R ⁴¹ ONH ₂ () (wherein R ⁴¹ is C _1-6 -alkyl, C _3-6 -representing cycloalkyl or _C3-6 -alkenyl) and, if desired, converting the obtained compound of the formula into an acid addition salt.