CS214753B2 - Fungicide means and method of making the active component - Google Patents

Abstract

1. Cycloalkane- and cycloalkene-carboxylic acid anilides of the general formula see diagramm : EP0023669,P12,F6 in which R**1 represents hydrogen, alkyl or halogen, R**2 represents hydrogen or alkyl, R**3 represents hydrogen or alkyl, R**4 represents hydrogen or alkyl, R**5 represents hydrogen, alkyl, halogen or optionally substituted phenyl and R**6 represents optionally substituted cycloalkyl or cycloalkenyl.

Description

The present invention relates to a fungicidal composition comprising as active. a cycloalkane (alkane) carboxylic acid anilide component. The invention further relates to a process for the preparation of these new active substances and their use as fungicides.

It is already known that alkyl esters of chloroacetyl-N- (2,6-dialkylphenyl) alanine, such as ethyl N-chloroacetyl N- (2-ethyl-6-methylphenyl) alanine, can be successfully used to combat · Plant fungal diseases (cf. DOS 2,350,944). However, their effect is not always entirely sufficient, especially at low application rates and concentrations, particularly as regards combating Phytophthora species.

We have now found novel cycloalkalkyline carboxylic acid anilides of the formula I

in which

R ¹ to R ⁵ are hydrogen or methyl. group, and

R ⁶ represents a cycloalkyl or cycloalkenyl group having 3 to 6 carbon atoms, which groups are optionally substituted methyl · acid, ethyl, vinyl or dichlorvinylovcu groups that have strong fungicidal properties and can therefore be used as active ingredients · fungicidal compositions.

The present invention relates to a fungicidal composition comprising, as an active ingredient, at least one cyclic-alkane (alkene) carboxylic acid anilide of the aforementioned general formula (I).

According to the invention, the novel anilides, cycloalkane (alkene) carboxylic acids, of the formula I are prepared by the formation of the N-propargylanilines of the formula II ......

in which

^R1 to R5 have the meaning indicated above, are allowed. reacted with carboxylic acids or derivatives thereof of formula III

R ⁶ —C — X

II 0 (III), in which:

R ⁶ is as defined above, and

X is chlorine, bromine, hydroxyl or a group ^-0-CO-R6 wherein R6 is as defined above, in the presence of a diluent and optionally in the presence of an activating agent, - and optionally in the presence of an acid binding agent at temperatures from 0 to 120 degrees Celsius . . .......... ..........

New. cycloalkane alkenyl carboxylic acid anilides have potent fungicidal properties. Surprisingly, the compounds according to the invention exhibit a considerably higher effect. - than. N-chloroacetyl-N- (2-ethyl-1-6-methylphenyl) alanine ethyl ester, which is the closest chemical compound in terms of action and activity, is known from the prior art. The substances according to the invention thus represent. state enrichment. techniques.

The cycloalkane alkenyl carboxylic acid anilides of the invention are generally defined by formula I. In this formula, R 1, R 2, R 3, R 4 and R ^{5 are} preferably hydrogen or methyl. R @ 1 is preferably an optionally substituted cycloalkyl group. Or (C6 -C6) cycloalkyl or (C až-C výhodně) cycloalkylene, the preferred substituents being: (C až-C alky) alkyloyl, vinyl and dichlorvinyl.

Especially preferred are the cyanoalkane (alkene) carboxylic acid anilides of formula I wherein R1, R2 and R3 are hydrogen or methyl; R4 is hydrogen or methyl; R5 is hydrogen or methyl; R6 is cyclopropyl, cyclobutyl, cyclopentyl a cyclohexyl group, a cyclobutenyl group, a cyclopentenyl group or a cyclohexenyl group which may be substituted one or more times by the same or different substituents selected from the group consisting of methyl, ethyl, vinyl and dichlorvinyl.

Individually. in addition to the compounds mentioned. the following compounds of the general formula I are mentioned in the examples illustrating the preparation of the active compounds:

II ⁰ (I)

R1 R2, R3 CH3 6-CH3 H CH3 3-CH5 6-CH3 CH3 H H CH3 6-CH 2 H CH3 6-CH3 H CH3 6-CH5 H

R -. . -. R5 R® ...... CH3 ČH3 “< Ř CH3 H - < CH3 H CH3 H -O CH3 H -Ό CH3 H

-Se When used as starting materials, for example 3- (2,6-di <methylanilino) ^-l-: butyne and cyclopropanecarboxylic acid chloride, the reaction can then be represented as follows · Reaction: scheme:

+ base

Ct-C— <J-: *

II -wct

CH

CH 1 '/ CH-C = CH

-O

СН _Ь O 'Ч.

When used as starting materials, e.g. - reaction shown by the following reaction sequence of 3- (2,6-dimethylanilino) -1-butyne and the cyclo scheme:

pentanecarboxylic acids, then a course can be performed

activation

Reagent ->

HCt

N-propargy.la.nilins that · are. .needed as. starting materials- at. The process according to the invention is generally defined by formula II. In this formula meant -Symbol R1, ^R2, R3, R4. and R ⁵ . preferably those residues already. were related to the description. The compounds according to the invention of the formula I are mentioned as being advantageous for these. symbols.

The N-pyrargylanilines of the formula II are partially known (cf. U.S. Patent Nos. 3,535,377 and 4,001,325) or can be obtained by known methods by reacting, for example, the corresponding anilines with propargyl halides of the formula V

Hal — CH — C = C — R3

R4 (V) wherein

R4 and R5 are as defined above, -a

Hal represents chlorine or bromine, or. with the corresponding propargylsulfonates, such as -s-mesylates or tosylates, in the presence of an acid-binding agent such as sodium carbonate or potassium carbonate, optionally in the presence of a catalyst such as copper (I) chloride as well as an inert organic solvents, such as dioxane, at temperatures between 20 and 150 ° C, whereby an excess of aniline may advantageously be used.

The N-propargylanilines of the formula - II in which R 4 is a methyl group - can also be obtained by reacting the corresponding anilines with acetylene in the presence of copper acetyldide under pressure [cf. Liebigs Ann. Chem. 596, 1 [19515)).

Examples of starting materials of formula II include:

(II)

R1 R2 rs R4 R5 CHs 6 — CHs H H H CHs s — CHs H H H CHs 5 — CHs H H H CHs s — CHs 6 — CHs H H CHs 6 — CHk H CHs H CHs 6 — CHB H H CHs CHs 16 — CHs .. H CHs CHs CHs s — CHs Й — CH5 CHs H CHs H H • CHs H

Furthermore, the carboxylic acid chlorides, bromides or anhydrides as well as the carboxylic acids used as starting materials for the process according to the invention are generally defined by formula III. In this formula, R @ preferably have those meanings which have already been in connection with the description of the compounds of formula I of the invention, mentioned as preferred for this · symbol.

Chlorides or - bromides. the carboxylic acid anhydrides and the carboxylic acid anhydrides of the formula III are generally known compounds of organic chemistry.

The halides which are used as starting materials for the preparation of the compounds of formula (II) are generally defined by formula (V). In this formula, R ⁴ and -R ^{5 are} preferably those already present in the formula. in the context of the description of the compounds of the formula I according to the invention, are said to be advantageous for these substituents.

The propargyl halides of the formula V are generally known compounds of organic chemistry.

They come as diluents for the reaction according to the invention. preferably inert organic solvents. These preferably include ketones, such as dimethyl ketone, in particular acetone and dimethyl ketone, nitriles, such as propionitrile, in particular acetonitrile, ethers such as tetrahydrofuran or dioxene, aliphatic and aromatic hydrocarbons such as petroleum ether, benzene, toluene or -xylene, halogenated hydrocarbons such as methylene chloride, tetrac-1-bromoethane, chloroform or chlorobenzene and esters such as ethyl acetate.

The process of the invention may optionally be carried out in the presence of an acid binding agent (hydrogen halide acceptor). As such, all conventional acid binding agents may be used. These include, preferably, bases, such as tertiary amines, for example triethylamine, pyridine, and further inorganic bases, such as alkali metal hydroxides and carbonates. If desired, a catalyst such as dimethylformamide may also be used.

The reaction temperatures can be varied within a wide range when carrying out the process according to the invention. In general, temperatures of between 0 DEG and 120 DEG C., preferably between 20 DEG and 100 DEG C., are employed.

The process according to the invention is preferably carried out using molar amounts. The isolation of the compounds of formula I is carried out in a conventional manner.

When carrying out the process using a carboxylic acid of formula III (X = -OH), a mixture of phosphorus oxychloride and pyridine is preferably used as the activating agent. The isolation of the reaction products is carried out in the usual manner;

The active compounds according to the invention have a broad microbicidal action and can be used on a practical scale to combat undesirable microorganisms. The active compounds are suitable as plant protection agents.

Fungicides - are used in plant protection - to control fungi in the PlasmodiophbiOmycetes, OMpycetes., CysticBetes, - Zygonrycetes, - Ascomycetes, © ^ s-idibmycetes,

The good tolerability of the active substances in the concentrations necessary for combating plant diseases of the crops allows the treatment of above-ground parts of the plants, seedlings and seeds as well as the soil. '·

As plant protection agents, the active compounds according to the invention can be used with particular success in combating fungi of the Oomycetes class, for example the pathogen of Phytophthora infestans in tomatoes and potatoes. In particular, the active compounds according to the invention have not only a protective but also a curative-eradicative effect. They also have systemic properties. Thus, it is possible to protect the plants against fungal attack, if the active ingredient is fed through the roots and soil or through the stalk to the above-ground parts of the plant.

The active substances can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, natural and active substances impregnated with active substances, small particles - coated with polymeric substances and with seed coating materials, further with flammable additives such as smoke cartridges, smoke ddzy, smoke coils, etc., as well as compositions in the form of active ingredient concentrates for fog scattering. cold or hot.

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants, and / or foaming agents. In the case of using water as a filler, organic solvents can also be used as auxiliary solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glyco-1, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol proipelants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, att.apulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Crushed and fractionated natural stone materials such as limestone, marble, pelmza, sepiolite and dolomite, as well as synthetic granules of inorganic and organic sap and granules of organic material such as sawdust, coconut shells are suitable worn granules for the preparation of granulates. , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers, such as polyoxythylene fatty acid esters, fatty alcohol polyoxyethylene ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, arylsulfates and hydrolysates of protein, for example, and dispersants of sulfonates, and cellulose dispersants.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Concentrates generally contain between 0.1 and 95 percent by weight, preferably between 0.5 and 90 percent by weight, of the active ingredient.

The active compounds according to the invention may be present in the formulations in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, anti-ozone preservatives, growth agents, plant nutrients with soil improvers.

The active compounds according to the invention can be applied as such, in the form of concentrates or from further use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Application is carried out in a conventional manner, for example by watering, dipping, spraying, fogging, evaporating, injecting, in the form of suspensions, painting, dusting, tossing, dry pickling, wet pickling, wet pickling or suspension or incrustation.

In the treatment of plant parts, the concentrations of the active ingredient in the dosage forms can vary widely. In general, they are between 1 and 0, 000% by weight, preferably between 0.5 and 0.001% by weight.

In the treatment of seed, the active compound is generally required in an amount of from 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g.

In soil treatment, concentrations of active compound of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, are required in the area where the effect is to be achieved.

In the following examples, the following compound A is used as a comparative:

(A) =

II

CH-C'OC H _{2 C-CH?} an *

C _L H _S o

N-Chloroacetyl-N- (2-ethyl-6-methyl-phenyl) -alanine ethyl ester.

Example A

Test for potato late blight (Phytophthora infestans) - prolongative effect (tomato)

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95.0 parts by weight

The active ingredient in an amount necessary to achieve the desired concentration of the active ingredient in the spray liquid is mixed with said amount of solvent and the concentrate is diluted with said amount of water containing said ingredients.

Spray liquid is sprayed on young tomato plants with 2 to 4 blades until dripping. The plants are kept for 24 hours at 20 ° C and 70% relative humidity in a greenhouse. Thereafter, tomato plants are inoculated with an aqueous suspension of fungal fungi (Phytophthora infestans). The plants are then transferred to a humidified chamber at 10% relative humidity at 18-20 ° C.

After 5 days, the infestation of tomato plants is determined.

The values obtained by the evaluation are converted to percent of attack. 0% means no infestation and 100. ^β / α means that the plants are completely infested.

The test results are shown in Table A below:

Table A

Test for potato late blight (Phytophthora) - pratective effect (tomato)

Active substance Infestation in% at active substance concentration 0.0005%

СН _Ъ / Сн-c-ocfy о

Q-ch?

(known)

CH ³

CH-Cl £H

Test for potato late blight (Phytophthora infestans] - systemic effect (tomato)

Solvent: 4.7 parts by weight of acetone

Dispersing agent: 0.3 part by weight of alkylaryl polyglycofether

Water: 95.0 parts by weight

The amount of active ingredient required to achieve the concentration of the active ingredient in the dressing is diluted with the stated amount of solvent and the concentrate is diluted with the amount of water containing the ingredients.

1.1

Plants of 2 to 4 leaf tomatoes grown in standard soil are covered with 10 ml of water of the indicated concentration, based on 100 ml of soil.

The treated plants are inoculated with an aqueous suspension of spores of the fungus (Phytoiphthoira infestans) after treatment and then transferred to a humid chamber where the relative air humidity is 100% and the temperature is 18-20 ° C. After 5 days, the infestation of tomato plants is determined. 0% means no attack, 10Ό% means that the plants are completely infected.

The following table shows the test results:

Table B

Test for potato late blight (Phyt-o-pithora) - systemic effect (tomato)

Active ingredient Infestation in% at an active substance concentration of 100 ppm

^CH _O

I ^ó

CH C-OCJ-S II a o c-ch-cj.

O (A) (known)

/

X сн _д CH-C5.CW c— <3 »1 o

(1)

Examples illustrating the method of manufacture of the active ingredient:

Example 1

To a boiling solution of 9.0 g (0.05 mol) of 3- (2,6-dimethylamino) -1-butyne and 5.95 g (0.075 mol) of pyridine in 50 ml of tetrahydrofuran was added dropwise over 5 minutes. g (0.075 mol) of cyclopropanecarboxylic acid chloride and the mixture was heated under reflux for 5.5 hours. R ^ j ^ <^ i ^ u ^{^,} t4Šdlo · the • distilled off · vacuo, the residue was partitioned between ethylaceitát and dilute hydrochloric acid, the organic phase · washed with 5% · by a sodium hydroxide are solution and water, dried over and evaporated. The oily residue (9.7 g) was dissolved in chloroform, transferred to a silica gel column (24 X 3 cm) and eluted with 250 ml of chloroform. Evaporation of solvent left 8.9 g (73.9% of theory) of 2,6-anilide dlme Ithylo-N- (l-methyl-2-propynyl) cyklopropainkarboxylové acid as a brown OLE classes of refractive index = 1 · ²⁴ , 5263.

The following compounds of formula I are obtained in an analogous manner and according to processes a), b) and c)

R * ¹ D ⁵ 'CH-C 2 -C' ^R

ON

II o (l)

Example number R1 R2 R3 R4 R5 Re Melting point (° C) 2. <5> H5 6-OH 3 H CH3 H 60—83 3 CHs 6-CH3 H CH3 H "O n _D 20 1.5389 4 CHs 6-CH3 H CH3 H "IN <4 101—102 5 CHs 6-CH3 H CH3 H Ό 112—113 6 CHs 6-CH3 H CH3 H 72—73 7 CH5 6-CH3 H H H 72—76 6 CH3 6-CH3 H H H )Е) ^ CH2Cl2, nD20: 1.5400 9 CHs 6-CH3 H H Ή in сц _ь 62—63

I will invent the subject

Claims (2)

A fungicidal composition, characterized in that it contains at least one cycloalkane (alkene) carboxylic acid anilide of the formula I in which: R 1 to R ⁵ are hydrogen or methyl, and R ⁶ represents a cycloalkyl or a cycloalkeinyl group having in each case 3 to 6 carbon atoms, these groups being optionally substituted by a methyl, ethyl, vinyl or dichlorviyl group. 2. A process according to claim 1, wherein the N-propargylanilines of the formula II are: R1 to R5 are as defined in 1, reacted with carboxylic acids or derivatives thereof of formula III R ⁶ —C — X II o (ΠΙ) in which R 6 is as defined above and X is chlorine, bromine, hydroxyl or -O-CO-R 6, wherein R ⁶ has the meaning given Shiori, in the presence of a diluent and optionally in the presence of an activating agent and in the optional presence of an acid binding agent at temperatures -from 0 to 120 degrees Celsius .