DE3309466A1 - PYRIDINE AND PYRAZINE DERIVATIVES - Google Patents

Description

β β *

DipHng. Reiner F. Meyer-Roxlau :: ·· ..:: · ... ··. . ο ο η ο / c £>

ÖGOO Munich i »O.:. *„. · * .. * · .. * · .. ** .. * O O U D q. D O

Lucfle-Grahn-Str. 22, iel. (OaS?) 472947 * ~ -5 -

F. Hoffmann-La Roche & Co. Aktiengesellschaft, Basel / Switzerland

1 6th MSiz 1983

RAN 6103/23

10 _ Pyridine and Pyrazine Derivatives

The invention relates to compounds of the general formula

N
20 OR ⁴

wherein R 2-halo-, 4-halo- or 2,4-dihaiο-phenyl,

2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide,

2-pyrazinyl-4-oxide or 2-pyrazinyl-1,425 dioxide,

_{R is hydrogen or straight-chain C 1} -alkyl and R C ^ __ g-alkyl, G 3 _g-cycloalkyl, C ₃ _ _g -alkenyl

or C ₃ - alkynyl,

and acid addition salts of these compounds. 30th

The compounds of the formula I and their acid addition salts have fungicidal properties and are suitable as fungicidal active ingredients, in particular for use in agriculture and horticulture. 35

Pa / 1/13/83

* Μ »

The invention also relates to a process for the preparation of the compounds of the formula I and their acid addition salts, Compounds of the formula I and acid addition salts thereof as fungicidal active ingredients, fungicidal agents, the Compounds of the formula I or acid addition salts thereof as active ingredients, and the use of such compounds, Acid addition salts and agents for combating fungi in agriculture and horticulture.

The term “halo” in the definition of formula I includes fluorine, chlorine, bromine and iodine, with chlorine being preferred is.

The halogen atoms in the radical R, which means 2,4-dihalophenyl, can be identical or different.

The terms "C _1-6 -alkyl" include "C ₃ _ ₆ alkenyl" and "C _3-6 alkynyl" includes both straight and branched chain hydrocarbon radicals. Alkyl is to be understood as meaning, depending on the number of carbon atoms, for example the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isoamyl and n-hexyl.

4th
R means C-. _, - alkyl, C -, _--- alkenyl or C _1-4 alkynyl is preferably C 1-4 -alkYl, C, - or C.-alkenyl or C-, - or C.-alkynyl. A particularly preferred alkenyl or alkynyl group is the allyl or propargyl group.

R preferably denotes 4-chlorophenyl or 2,4-dichlorophenyl, especially the latter group.

R preferably denotes hydrogen, methyl or ethyl, in particular hydrogen.

A particularly preferred compound of the formula I is 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide.

O * * OC *> ft

Further representatives of compounds of the formula I are:

2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-ethyloxime-1" oxide,

2 ¹ , 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-1" -oxide,

2 ', 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-4" -oxide,

4 '-chloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide,

4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl", 4 "-dioxide,

4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-ethyloximl", 4 "-dioxide,

4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-allyloxime-4" -oxide,

2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-allyloximl" -oxide,

2'-Chloro-2- (2 "-pyrazinyl) -acetophenone-O-methyloxime-4" -oxide,

4'-Fluoro-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl" -oxide,

4'-Bromo-2- (2 "-pyrazinyl) -acetophenone-O-methyloximl", 4 "-dioxide,

4'-chloro-2- (2 "-pyrazinyl) -propiophenone-O-methyloxime-4" -oxide,

2 ¹ , 4'-dichloro-2- (2 "-pyrazinyl) -butyrophenone-0-methyloxime-1", 4 "-dioxide,

2 ', 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-allyloxime-1" -oxide,

2 ', 4'-dichloro-2- (2 "-pyrazinyl) -propiophenone-O-methyloxime-1" , 4 "-dioxide,

2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-cyclopropyloxime-1" oxide,

2 ¹ , 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-isopropyloxime-1" oxide,

2 ¹ , 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-propargyloxime-1" -oxide,

4'-chloro-2- (2 "-pyrazinyl) -acetophenone-O-propargyloxime-4" -oxide,

2 ' , 4 ■ -Dichloro-2- (2 "-pyrazinyl) -acetophenone-O-propargyloxime-1" -oxide and

4'-Iodo-2- (3 "pyridyl) propiophenone-O-cyclohexyloxime" oxide.

The presence of the C = N double bond in the compounds of the formula I results in geometric isomerism (E and Z isomers). In addition, asymmetric carbon atoms can be present, so that the compounds as optical Antipodes may be present. The formula I is therefore intended to encompass all of these possible isomeric forms.

The acid addition salts of the compounds of the formula I are physiologically acceptable salts with strong acids in question. These preferably include salts of the compounds I with inorganic acids, such as hydrochloric acid and nitric acid and phosphoric acid, and with sulfonic acids such as 1,5-naphthalene-disulfonic acid.

The process according to the invention for the preparation of the compounds of the formula I and of their salts is characterized in that one
25th

a) a pyridine or pyrazine derivative of the general formula

R ³

1 '2 ¹

R C CH R II

Ii
N

I 4

OR

13 4
wherein R, R and R have the meanings given above

2 '

and R is 3-pyridyl or 2-pyrazinyl, N-oxidized, or

b) a ketone of the general formula

2 ■ C CH R III

12 3

wherein R, R and R have the meanings given above

own,

with an O-substituted hydroxylamine of the general formula

R ⁴¹ ONH ₀ IV

¹⁰ 41

wherein R C-. _ _fi -alkyl, C - ,, - cycloalkyl or C, _ _fi -

Alkenyl means
implements,

and, if desired, a compound obtained from the general Formula I converted into an acid addition salt.

Process variant a) can expediently be carried out by converting the starting material of formula II using hydrogen peroxide or a peracid oxidized in the presence of an inert diluent.

In the case of using hydrogen peroxide as an oxidising agent suitable diluents particular '* ■ 25 lower alkanols such as methanol, ethanol and isopropanol, in question, and the oxidation is preferably carried out in a temperature range between 0 ° and 60 ⁰ C, in particular between 20 ° and 40 ⁰ C, made.

Peracids are preferably peracetic acid, perbenzoic acid and m-chloroperbenzoic acid, the diluent being preferably used in a halogenated hydrocarbon, for example methylene chloride or chloroform. The oxidation with a peracid is preferably carried out in a temperature range between 0 ^° C. and the reflux temperature of the reaction mixture, in particular between 0 ^° C. and room temperature. A particularly preferred embodiment of this method is

it says that the oxidation is carried out with m-chloroperbenzoic acid in chloroform in a temperature range between 0 ^° C. and room temperature.

According to process variant b), which lead to compounds of

4th
Formula I leads, in which RC ₁ , .- alkyl, C ₀ , - cycloalkyl or

JL- D J-O

C ₃ , -alkenyl, the reaction is conveniently carried out in an organic solvent, for example an alcohol such as methanol or ethanol, a dialkylamide such as dimethylformamide, or a tertiary amine such as pyridine. One works preferably in a temperature range between room temperature and the reflux temperature ^v ** ^{/ of} the reaction mixture. Since the starting material of the formula IV is preferably used in the form of an acid addition salt, for example the hydrochloride or hydrosulfate, a base such as sodium or potassium carbonate, triethylamine or pyridine is expediently added to the reaction mixture.

For the preparation of acid addition salts, if desired the compounds of formula I with the desired acids, such as hydrochloric acid, nitric acid, Phosphoric acid, or a sulfonic acid, are implemented.

The uses of the formula I and their acid addition salts prepared in this way are isolated and purified according to methods known per se.

The starting materials of formula II can be prepared by adding an oxime of the general formula

R ³

R ¹ C CH R ² 'V

If

I.

^J0 OH

12 '3
wherein R, R and R have the meanings given above

own,

• β 9 *

«• Ο * β β 9 _# »

»Β ·» β to e »

with a compound of the general formula

R ⁴ U VI

4th
wherein R has the meaning given above

and U is a leaving group, e.g., chlorine, bromine, iodine, mesyloxy, tosyloxy or one Alkyl sulfate radical, means, reacts, or a ketone of the general formula

1 ι 2 '

R C CH R VII

K 0

12 '3
wherein R, R and R have the meanings given above,

with an O-substituted hydroxylamine of the general formula

R ⁴¹ ONH ₂ IV

41
wherein R is C-, _g -alkyl, C ₃ _ _g -cycloalkyl or C_ e-

Alkenyl means
implements.

The reaction of the oxime of the formula V with the compound of the formula VI can be carried out by mixing the oxime V with the compound VI, conveniently in the presence of a base, in an organic solvent and in a temperature range between 0 ^° C. and the reflux temperature of the reaction mixture offset. The solvent can be protic or non-protic. In the case of protic solvents, such as alcohols, in particular methanol or ethanol, the base used is preferably an alkali metal hydroxide, for example sodium or potassium hydroxide, or an alkali metal alcoholate. When using non-protic solvents such as ali-

phatic or alicyclic ethers, especially tetrahydrofuran or dimethoxyethane, and dialkylamides, in particular Dimethylformamide, the base is preferably an alkali metal hydride such as sodium hydride. In a preferred

_ An embodiment of this process is sodium hydride 5

as a base and an aliphatic or alicyclic ether, especially tetrahydrofuran or dimethoxyethane, or a Dialkylamide, especially dimethylformamide, is used as a solvent.

The implementation of the ketone of the formula VII with the

Hydroxylamine of the formula IV, leading to compounds of the formula

4th
II leads, wherein R Cg-alkyl, _C3 g-cycloalkyl, or C _3-6 -

Alkenyl is conveniently carried out analogously to

process variant b) described above. 15th

The starting materials of formula III can be prepared by using the above-mentioned ketone of general formula VII analogously to process variant a) described above N-oxidized.

The compounds usable as starting materials

of the formulas IV, V, VI and VII are either known or can be prepared by methods known per se. For example, the oximes of the formula V from the corresponding ketones of the formula VII by reaction with 25th

Hydroxylamine, and the ketones themselves according to the DOS 2,221,546, DOS 2,800,010 and British Patent No. 2,015,524, e.g. by condensation of the corresponding methylated hetero- "_ Cycle with a halogenated benzoic acid alkyl ester, getting produced.

The compounds of the invention, i.e. the compounds of the formula I and their acid addition salts have fungicidal activity and can accordingly be used for ^ Fungi control in agriculture and horticulture Find use. They are particularly suitable for curbing growth or for killing phytopathogens Fungi on parts of plants, e.g. leaves,

Stems, roots, tubers, fruits or flowers, and on seeds as well as in the ground and are particularly effective at the fight against Botrytis cinerea (gray rot); of powdery mildew, such as Uncinula necator (Powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Podosphaera leucotricha (apple powdery mildew) and Erysiphe graminis (Barley powdery mildew); from Venturia inaequalis (apple scab); of Helminthosporium oryzae (brown spot disease of rice); and of harmful fungi of the genera Puccinia, Uromyces, Rhizoctonia, Penicillium, Septoria and Cercospora.

Individual representatives of the compounds according to the invention also have a pronounced effect against wood-destroying fungi, such as Coniophora puteana and Gloeophyllum trabeum.

The compounds according to the invention are distinguished by

local and / or systemic effect. 20th

The compounds according to the invention act under greenhouse conditions already at a concentration of 10 mg to 500 mg of active substance per liter of spray liquid. in the In the field, concentrations of 50 g to 2000 g of active ingredient of the formula I per hectare and treatment are advantageous applied.

Using formulation auxiliaries you can the compounds according to the invention, that is to say the fungicidally active ingredients, are converted into the customary formulations such as dusts, powders, granulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the same. The fungicidal agent according to the invention is characterized in that it is an effective amount at least one compound of the general formula I, as defined above, or an acid addition salt of a contains such a compound as well as formulation auxiliaries. The means expediently contain at least one of the

the following formulation auxiliaries:

Solid carriers; Solvents or dispersants; Surfactants (wetting and emulsifying agents); Dispersants (without surfactant effect); and stabilizers.

The following solid carriers are essentially: natural minerals such as kaolin, clay, Kieselguhr, talc, bentonite, chalk, e.g. whipped chalk, magnesium carbonate, limestone, quartz, dolomite, attapulgite, Montmorillonite and diatomaceous earth; synthetic minerals such as highly dispersed silica, aluminum oxide and Silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and Nitrates, whereby such carriers can be in the form of granulates or powders, for example.

The following are essentially suitable solvents or dispersants: aromatics, such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons, such as cyclohexane and paraffins, for example petroleum fractions; Alcohols, such as butanol and glycol, and their ethers and esters; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solution bzx-i. Dispersants such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, such solvents or dispersants preferably having flash points of at least 30 ^° C. and boiling points of at least 50 ^° C., and water.

Among the solvents or dispersants, so-called liquefied gaseous extenders or are also suitable Carriers that are products that are gaseous at room temperature and under normal pressure. Examples such products are in particular aerosol propellants such as halogenated hydrocarbons, e.g. dichlorodifluoromethane. in the If water is used as the solvent, organic solvents can also be used as auxiliary solvents, for example

β β · Λ O -Q * i

β O β α · »α β β» «ο

be used.

The surfactants (wetting and emulsifying agents) can be nonionic compounds, such as condensation products of Fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; Fatty acid esters and ethers of sugars or polyhydric alcohols; the products made from sugars or polyhydric alcohols by condensation with ethylene oxide obtained; Block polymers of ethylene oxide and propylene oxide; or alkyl dimethyl amine oxides.

The surfactants can also be anionic compounds, such as soaps; Fatty sulfate esters, e.g. dodecyl sodium sulfate, Octadecyl sodium sulfate and cetyl sodium sulfate; Alkyl sulfonates, aryl sulfonates and fatty aromatic sulfonates, such as alkylbenzenesulfonates, e.g. calcium dodecylbenzenesulfonate, and butylnaphthalene sulfonates; and more complex fatty sulfonates, e.g. the amide condensation products of oleic acid and N-methyl taurine and the sodium sulfonate of dioctyl succinate.

Finally, the surfactants can be cationic compounds, such as alkyldimethylbenzylammonium chlorides, Dialkyldimethylammoniumchlori.de, Alkyltrimethylammonium-. chlorides and ethoxylated quaternary ammonium chlorides.

The dispersants (without surfactant effect) are im essential question: lignin, sodium and ammonium salts of ligninsulphonic acid, sodium salts of maleic anhydride-diisobutylene copolymers, Sodium and ammonium salts of sulfonated polycondensation products from naphthalene and formaldehyde, and sulfite waste liquors.

As dispersants, which are particularly suitable as thickeners or anti-settling agents, e.g. methyl cellulose, Carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, alginates, caseinates and blood albumin are used will.

Examples of suitable stabilizers are acid-binding agents, e.g., epichlorohydrin, phenyl glycidyl ether and Soy epoxide; Antioxidants such as gallic acid esters and butylated hydroxytoluene; UV absorbers e.g. substituted benzophenones, Diphenylacrylonitrile acid esters and cinnamic acid esters; and deactivators, e.g. salts of ethylenediaminetetraacetic acid and polyglycols.

The fungicidal agents according to the invention can in addition to the active ingredients of the formula I also contain other active ingredients, e.g. other fungicidal agents, insecticides and acaricides, bactericides, plant growth regulators and fertilizers. Such combination means are suitable for broadening the spectrum of activity or for specifically influencing plant growth.

In general, the fungicides according to the invention contain Agent, depending on the type, between 0.0001 and 95 percent by weight of compound according to the invention or according to the invention Compounds as active ingredient (s). They can be in a form that is convenient for storage and use Suitable for transport. In such forms, e.g. emulsifiable concentrates, the active ingredient concentration is normally in the higher range of the above concentration series.

These forms can then be mixed with the same or different formulation auxiliaries up to active ingredient concentrations suitable for practical use, and such concentrations are usually in the lower range of the above concentration series.

Emulsifiable concentrates generally contain 5 to 95 percent by weight, preferably 25 to 75 percent by weight, of the compound or compounds of the formula I. The use forms include ready-to-use solutions and emulsions and suspensions, which are suitable, for example, as spray liquors, in question. In such spray mixtures you can e.g. concentrations between 0.0001 and 20 percent by weight are present. Spray mixtures can be used in the ultra-low-volume process be formulated in which the active ingredient concentration

tion is preferably from 0.5 to 20 percent by weight, while those in the low-volume process and in the high-volume process formulated spray mixtures preferably have an active ingredient concentration from 0.02 to 1.0 or 0.002 to 0.1 percent by weight.

The fungicidal agents according to the invention can thereby be prepared that at least one compound of the general formula I or an acid addition salt such a connection with formulation auxiliaries mixed.

The preparation of the agents can be carried out in a known manner, for example by mixing the active ingredient with solid carriers, by dissolving or suspending in suitable solvents or dispersants, possibly with the use of surfactants as wetting or emulsifying agents or dispersants, by dilution already prepared emulsifiable concentrates with solvents or dispersants etc.

In the case of powdered agents, the active ingredient can mixed with a solid carrier, e.g., by grinding together; or you can use the solid carrier impregnate with a solution or suspension of the active ingredient and then the solvent or dispersant through Steaming, heating or by suction under reduced conditions Remove pressure. Such pulverulent agents can be mixed with water by adding surfactants or dispersants Make them easily wettable, so that they are transferred into aqueous suspensions that are suitable, for example, as sprays can be.

The compounds according to the invention can also be used with a surfactant and a solid carrier to form a wettable powder, which is dispersible in water, or they can be pre-granulated with a solid Carrier for the formation of a granular

β β 9 «* 9 αν» «« «» Β »β« »

Product are mixed.

If desired, a compound according to the invention can be dissolved in a water-immiscible solvent, such as an alicyclic ketone, which advantageously contains dissolved emulsifier, so that the solution is self-emulsifying when added to water works. Otherwise, the active ingredient can be mixed with an emulsifying agent and then the mixture with water on the

"Ό the desired concentration can be diluted. In addition, the Active ingredient dissolved in a solvent and then mixed with an emulsifying agent. Such a mixture can also be diluted with water to the desired concentration. In this way, emulsifiable ones are obtained Concentrates or ready-to-use emulsions.

The compositions according to the invention can be used by the application methods customary in crop protection or in agriculture, such as spraying, spraying, dusting, watering or scattering. The method according to the invention for combating fungi is characterized in that the material to be protected, for example plants, parts of plants or seeds, is mixed with an effective amount of a compound according to the invention or a substance. _f ^ 5 means according to the invention treated.

The following examples illustrate the invention.

30th

35

3303466

I. Preparation of the active ingredients of the formula I:

example 1

A solution of 10 g of 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone-O-methyloxime in 100 ml of chloroform is added at 0 ⁰ C with 7.2 g of m-chloroperbenzoic acid followed by 24 hours in the refrigerator stored at approx. 4 ° C. It is then diluted with 200 ml of chloroform and extracted with 250 ml of 10% strength potassium carbonate solution. The organic phase is dried over anhydrous sodium sulfate and concentrated. The residue obtained is 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide as E, Z isomer mixture in the form of a yellowish paste.

15th

In an analogous manner, by oxidation of 2 ·, 4'-dichloro-2- (2-pyrazinyl) -acetophenone-O-ethyloxime using m-chloroperbenzoic acid as oxidant, a reaction product is obtained which can be separated by chromatography on silica gel with ethyl acetate , namely in a mixture of 2 ¹ , 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-O-ethyloxime-1" -oxide and 2 ', 4'-dichloro-2- (2 "-pyrazinyl ) -acetophenone-0-ethyloxime-4 "oxide (viscous oil) and 2 ', 4'-dichloro-2- (2" -pyrazinyl) -acetophenone-O-ethyloxime-1 ", 4" -dioxide, m.p. * ■ * 25 164-168 ° C.

Example 2

1.41 g of 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-1" oxide are dissolved in 5 ml of ethanol, 1 g of sodium carbonate and 0.83 g of 0-methylhydroxylamine hydrochloride are added and then heated under reflux for 3 hours. Then it is poured onto ice and extracted with ethyl acetate, and the organic phase is dried over anhydrous sodium sulfate and then concentrated. Of the The residue consists of 2 ', 4'-dichloro-2- (3 "-pyridyl) -acetophenone-O-methyloxime-1 "-oxide.

II. Production of the raw materials:

Example 3

A solution of 13.3 g of 2,4'-dichloro-2- (3-pyridyl) acetophenone in 40 ml of ethanol, 10 g of sodium carbonate and 8.3 g of O-methylhydroxylamine hydrochloride are added and then heated to reflux temperature with stirring. After 4 hours the reaction mixture is poured onto ice and extracted with ethyl acetate. The organic phase is washed, dried over anhydrous sodium sulfate and concentrated under reduced pressure. You get 2 ', 4'— Dichloro-2- (3-pyridyl) -acetophenone-O-methyloxime as E, Z-isomer mixture in the form of a yellowish oil.

15th

In an analogous manner, 2 ', 4'-dichloro-2- (2-pyrazinyl) acetophenone is obtained and O-ethylhydroxylamine hydrochloride the 2 ', 4'-dichloro-2- (2-pyrazinyl) -acetophenone-O-ethyloxime as OeI.

20th

Example 4

A solution of 5 g of 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone in 20 ml of chloroform at 0 ⁰ C with 3.6 g of m-chloro- "offset 25 perbenzoic acid followed by 24 hours in the refrigerator stored at about 4 ° C. It is then diluted with 100 ml of chloroform and extracted with 100 ml of 10% strength potassium carbonate solution. The organic phase is dried over anhydrous sodium sulfate and concentrated. 2, 4'-dichloro-2- ( 3 "-pyridyl) acetophenone-l" oxide, mp. 137-140 ⁰ C.

Example 5

A mixture of 27.6 g of ethyl 2,4-dichlorobenzoate and 20.81 g of ethyl 3-pyridyl acetate at 20-25 "C. 10.59 g of sodium methylate are added in portions. The reaction mixture is then increased to 65-

70 ° C heated, and resulting volatile products are blown off with dry nitrogen. After 20 hours, 40 ml of concentrated hydrochloric acid are added and heated at reflux temperature for 18 hours. The mixture is washed with diethyl ether and the aqueous phase is made basic by adding concentrated ammonia placed and extracted with methylene chloride. The organic phase is concentrated and the crude product on silica gel Chromatographed with methylene chloride / methanol (98: 2).

The product, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone may be selected from diethyl ether / n-pentane are brought to crystallization and melting at 55-56 ⁰ C.

III. Formulation examples

Example 6

1. Wettable powder (for liquid active ingredients or those that melt below? 5 ° C)
20th

Parts by weight

Active ingredient of formula I 50

Hydrated silica 37

Kaolin 5

Alkyl phenol ethoxylate 4

Sodium polynaphthalene sulfonate 4

100

The liquid or molten active ingredient is absorbed onto the silica and the other components are mixed in and the whole thing finely ground in a suitable mill.

2. Wettable powder (for solid active ingredients that melt ^{above 75 0 C)}

Parts by weight

Active ingredient of formula I 50

Hydrated silica 5

Kaolin 42

Sodium Lauryl Sulphate I.

Sodium lignosulfonate 2_

100

The components are mixed together and the whole thing finely ground in a suitable mill.

Example 7

Emulsifiable concentrate (for active ingredients that are liquid ^{at 20-25 0 C)}

Parts by weight of active ingredient of the formula I castor oil ethoxylate calcium dodecylbenzenesulfonate

Mixture of C, "- alkylbenzenes to 1000 parts by volume

The components are mixed together until a clear solution is obtained.

Claims (10)

3 3 O 9 4 6'6 10 Claims (1.j compounds of the general formula R ³ R ¹ C CH R ² Il 1 4 OR wherein R 2-halo-, 4-halo- or 2,4-dihalophenyl, R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide, 2-pyrazinyl-4-oxide or 2-pyrazinyl-1,4-dioxide,
R hydrogen or straight chain C - ^ .- Alkyl
and R C _{1-6 alkyl, C 3 g} cycloalkyl, C ₃ -C alkenyl or C _{3 fi} alkynyl, and acid addition salts of these compounds. 20th 2. Compounds according to claim 1, wherein R is 4-chlorophenyl or 2,4-dichlorophenyl. 3. Compounds according to claim 1 or 2, wherein R f ** _ 25 means hydrogen. 4. 2 ', 4'-Dichloro-2- (3 "-pyridyl) -acetophenone-0-methyloxime-1" -oxide. 5. A compound according to claim 1, selected from: 2 ¹ , 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-0 ~ ethyloxime-1" oxide, 2 ', 4 ■ -Dichloro-2- (2 "-pyrazinyl) -acetophenone-O-ethyloxime-4-oxide and 2 ', 4'-dichloro-2- (2 "-pyrazinyl) -acetophenone-0-ethyloxime-1", 4 "-dioxide. 6. A compound or an acid addition salt according to any one of claims 1 to 5 as a fungicidal active ingredient. 7. Fungicidal agent, characterized in that it contains an effective amount of at least one compound of the general formula -. 1 2 R C CH R I Il ! 4th OR wherein R 2-halo-, 4-halo- or 2,4-dihalophenyl, 2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide, 2-pyrazinyl-4-oxide or 2-pyrazinyl-1,4- dioxide, R is hydrogen or straight C. _1-alkyl 4th
and R C. g-alkyl, C _{1-10 cycloalkyl, C 3} -C alkenyl or C-j, alkynyl, or an acid addition salt of such a compound, as well as formulation auxiliaries. 8. Fungicidal agent according to claim 7, characterized in that it contains an effective amount of 2 ', 4'-dichloro- 2- (3 "-pyridyl) -acetophenone-O-methyloxime-1" oxide and formulation auxiliaries. 9. Process for the preparation of compounds of the general formula ^R. 1 I 2 R C CH R I OR ⁴ wherein R 2-halo-, 4-halo- or 2,4-dihalophenyl, 2
R 3-pyridyl-1-oxide, 2-pyrazinyl-1-oxide, 2-pyrazinyl-4-oxide or 2-pyrazinyl-l, 4- e ff * « to m flow dioxide, R is hydrogen or straight C. _1-alkyl 4 and R is C _{1 6} alkyl, C ^ g-cycloalkyl, C _{3 6} alkenyl or C, - alkynyl, and of their acid addition salts, characterized in that one a) a pyridine or pyrazine derivative of the general formula 1 t R C -CH R II Il 1 ^0R 13 in which R, R and R have the meanings given above 2 ■ and R is 3-pyridyl or 2-pyrazinyl, N-oxidized, or 20 b) a ketone of the general formula R ³ R ¹ c CH ^ -R ² III ti O 12th wherein R, R and R have the meanings given above have, with an O-substituted hydroxylamine of the general Formula 30 R ⁴¹ ONH ₂ IV 41 wherein R Ci is g-alkyl, C ₃ _g-cycloalkyl or C ₃ ^ ₆ -alkenyl, converts, and, if desired, a preserved connection of the general Formula I converted into an acid addition salt. W ο «* α« «μ ·) β * «es * ΰ» »ö <a 10. A method of combating fungi in agriculture and horticulture, characterized in that the property to be protected with an effective amount of at least one of those mentioned in claims 1 to 5 5 compounds or an agent mentioned in claim 7 or 8 treated. 11. Use of one of the compounds mentioned in claims 1 to or one of claims 7 or 8 ge 10 named agents for combating fungi in agriculture and horticulture.