CS199223B2 - Fungicide - Google Patents

Abstract

1. N-substituted 3,5-dimethyl-piperidin-4-one derivatives of the general formula see diagramm : EP0002222,P11,F1 where X is a linear or branched alkylene radical of 3 to 10 carbon atoms, R is an alkyl or alkoxy group of 1 to 8 carbon atoms, and the salts of these compounds.

Description

The present invention relates to a fungicidal composition comprising as active ingredients novel valuable aralkyl-3,5-dimethylpiperidin-4-ones and salts thereof.

It is known from German Patent Nos. 1,164,152, 1,173,722, 1,198,125 and DOS 2,461,513 to use N-alkyl substituted morpholines and their salts as fungicides.

It has now been found that 3,5-dimethylpiperidin-4-one derivatives of the general formula

in which

X represents a straight or branched alkylene radical having 3 to 10 carbon atoms,

R represents an alkyl or alkoxy group having from 1 to 8 carbon atoms, preferably an isopropyl or tert-butyl group, and their salts have a good fungicidal activity which exceeds that of the known morpholine derivatives.

Suitable salts are those with inorganic or organic acids, such as, for example, hydrohalic acids (hydrochloric acid, hydrobromic acid), sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid , butyric acid, acrylic acid, oxalic acid, adipic acid, lactic acid, tartaric acid, citric acid, trichloroacetic acid, stearic acid, oleic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid , dodecanesulfonic acid or perfluorooctanoic acid.

X is, for example, a group

СНз —CH — CH2 — CH2—,

СНз —CH2 — CH — CH2—,

НзС СНз \ /

-CH2-C-CH2-,

НзС СНз \ / —С — СНг — СНз—, —СН2 — СН — СН2—,

С2Н5 — СНг — СН — СНг—.

НзС СНз

R is, for example, methyl, ethyl, isopropyl, butyl, sec-butyl, target, butyl, methoxy, ethoxy, isopropoxy.

The N-substituted 3,5-dimethylpiperidin-4-ones of the invention can be prepared by reacting the corresponding primary amines with 2,4-dimethylpenta-1,4-dien-4-one:

wherein R and X are as defined above.

The desired primary amines can be prepared by reductive amination from the corresponding aldehydes or ketones (Houben-Weyl " Methoden der organlschen Chemie "), Vol. 11/1, p. 802 and others). 2-Methyl-3- (p-tert-butylphenyl) propylamine can be prepared, for example, according to the following protocol.

800 parts by weight of 2-methyl-3- (p-tert-butylphenyl) propanal are dissolved in 800 parts of methanol and this solution, together with 150 parts of Raney-nickel, is introduced into a 3 liter hydrogenation autoclave. 540 parts of ammonia are charged into the autoclave and then the reaction mixture is heated to 90 ° C. At 90 [deg.] C. hydrogen is introduced into the autoclave until a total pressure of 10 MPa is reached. Hydrogenation is carried out at this constant pressure for 30 hours.

The reaction product is filtered and the filtrate is worked up by distillation. 750 parts (about 93% of theory) of 2-methyl-3- (p-tert-butylphenyl) propylamine, b.p. 97 DEG C./0.1 mbar, are obtained.

The synthesis of 2,4-dimethylpenta-1,4-dlen-3-one can be carried out from dlisopropyl ketone by bromination and hydrogen bromide cleavage (O. Sorokin, Izv. Akad Nauk USSR 1961, 460-466) or according to the Houben-Weyl Methoden der organischen Chemie ', Vol. 7 / 2a ,. 743 or S.F. Reed, J. Org. Chem. 27, p. 4 116 (1962).

Among the compounds of the invention, the following are summarized in the table, for example:

Compound number

Boiling point ° C / Pa

Melting point (° C)

CH ₃

152 / 66.7

188

200

187 / 666.7

205 / 666.7

210 сн _ъ

184

Compound number

Boiling point ° C / Pa

Melting point (° C)

143 / 1.3

155 / 1.3

140 / 2.7

162 / 1.3

154 / 6.7

200

108

100 / 1,3

Β

Examples illustrating the method of production of active ingredients:

Example 1 parts by weight of 3- (p-tert-butylphenyl) -2,2-dimethylpropylamine are dissolved in 100 parts of methanol. A solution of 12.6 parts of 2,4-dimethylpenta-1,4-dien-3-one in 30 parts of methanol is added at room temperature and then the mixture is heated to temperature for 5 hours. (65 ° C) under reflux. The reaction mixture is worked up by distillation to give 32 parts (approximately 85% of theory) of N- [3- (p-tert-butylphenyl) -2,2-dimethylpropyl] -3,5-dimethylpiperidin-4-one of boiling point. 162 ° C / 1.3 Pa (Compound No. 12).

P. k i 1 and d 2

6.3 parts of N- [2- (p-tert-butylphenyl) propyl] -3,5-diinethylpiperidin-4-one are dissolved in 50 parts of methanol and added at room temperature by adding 32.5 parts by volume of 0.5 M methanolic solution. dodecylbenzenesulfonic acid adjusts the pH to 5. Then the solvent is distilled off completely to obtain 10.5 parts (about 82% of theory) of the N- [2- (p-tert-butylphenyl) propyl] -3,5-dimethylpiperidine salt. -4-one with dodecylbenzenesulfonic acid, m.p. 112 ° C (Compound No. 19).

The active compounds according to the invention and the corresponding fungicidal compositions are particularly suitable for combating fungal diseases of plants, such as. for example, powdery mildew (Erisiphe graminis) on cereals, beet mildew (Erysiphe cichoriacerum) on plants, powdery mildew (Podosphaera. leucotricha) on apple trees,.

powdery mildew (Unicinula. necator) on grapevine, powdery mildew (Erysiphe polygoni) on beans, powdery mildew (Sphareotheca pannosa) on roses, powdery mildew (Microsphaera querci) on oaks, powdery mildew (Mycosphaerella musicola) on banana trees, mushrooms Puccinia) on cereals, bean rust (Uromyces appendlculatus and Uromyces phaseoli) on beans, Hémtleía, vasťatrix on coffee plants and potato root (Rhlzoctonia solani).

These substances are systemically active. Both roots and leaves are taken up and transported to plant tissue from there.

When applying new active substances for the treatment of plants against fungal diseases, the application rate is between 0.025 and · kg of active substance / ha. In order to protect the surface of trees or fruits, the active compounds can also be used in combination with a plastic dispersion in a concentration of 0.25 to 5%, based on the weight of the dispersion. Fungicides generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds may be mixed with other known fungicides. In many cases, an increase in the spectrum of the fungicidal effect is achieved; some mixtures of fungicides in weight ratios of 1: 10 to 10: 1 also exhibit synergistic effects, i.e. the fungicidal activity of the combined product is greater than the sum of the effects of the individual components. Fungicides which may be combined with the compounds of the invention are, for example:.

dithiocarbanates and their derivatives, such as zinc dirtyldi thiocarbamate, manganese ethylene bis-dithiocarbamate, ethylenedianine bis-dithiocarbamate, zinc manganato-zinc, zinc ethylenebis-dithiocarbanate, N-ethylenediethene disulfate, N-ethylenediureth disulfate, stannous dithiocarbamate and N, N'-polyethylene bis- (thiocarbamoyl) disulfide, N, N'-propylene bis-dithiocarbanate zinc '.

the ammoniacal complex of N, N-propylene-bis´dithiocarbanate zinc and N, N‘-polypropyl len-bis- (thiocar bamoy 1) disulfide;

heterocyclic compounds such as N-trichloromethylthiotetrahydrophthalide, N-trichloromethylthiophthalide, N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzenesidazolkaibanoic acid methyl ester, 2-methyloxycarbonylaminobenzyl

2,3-dihydro-5-carboxanilide O '6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 5-butyl-2-dimethylanino-4-hydroxy-6-methylpirimidine,

1,2-bis- (3-ethoxycarbonyl-2-thloureldo) benzene,

1,2-bis- (3-methoxycarbonyl-2-thioureldo) benzene, and various other fungicides such as dodecylguanidine acetate, N-dichlorofluoromethylrhio-N ', N'-dimethyl-N-phenyldiamine sulfuric acid, 2,5-dimethylfuran-3 -carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide, 2-iodobenzoic acid anilide, 2-bromobenzoic acid anilide, 3-nitroisophralic acid diisopropyl ester,

1- (1,2,4-triazol-11-yl) - [1- (1- (4'-chlorophenoxy)] -3,3-dimethylbutan-2-one,

1- (1-imidazolyl) -2-allyloxy-2- (2,4-dichlorophenyl) ethane, piperazine-1,4-diyl-bis-1- (2,2,2-triclilorethyl) formamide, 2,4 , 5,6-Etrachloroisophthalonitrile, 1,2-Dimethyl-3,5-diphenylthiazolinium methylsulfate, β- (4-chlorophenoxy) -α- (1,1-dimethyl) -1H1,2,4-riazol-1- ethanol.

The application is carried out, for example, in the form of - directly - sprayable solutions, - powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters, granulates by spraying, fogging, dusting, spreading or potting. The dosage forms are entirely governed by the purposes of use: in any case, they should, as far as possible, ensure the finest possible distribution of the active compounds according to the invention.

For the preparation of directly injectable solutions, emulsions, pastes and oil dispersions, suitable are mineral oil fractions of medium to high boiling point, such as kerosine or. oil for diesel engines, tar oils, etc., and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tttramydronaphthalene, - alkylated packaged or derivatives thereof, - for example methanol , ethanol, propanol, butanol, chloroform, ether-chloromethane, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents such as dimethelformamide, dimethylsulfoxide, N -ethelpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by the addition of water. In order to prepare paste emulsions or oil dispersions, the substances as such or dissolved in an oil or solvent may be homogenized in water by means of wetting agents, adhesives, dispersing or emulsifying agents. However, concentrates may also be prepared which consist of the active ingredient, wetting agent, adhesive, dispersing or emulsifying agent and, optionally, solvent or oil, which are suitable for dilution with water.

Surfactants include:

salts of lignisulfonic acid with alkali metals, with alkaline earth metals or salts and mono, naphealenesulfonic acids, phenolsulfonic acids, alkanol sulfonate, alkyl sulfates, - alkelsulfonate, dibutelnafealtnsulfonic acid salts - with alkali metals and with alkaline earth metals, laurel ether sulfates, sulfated fatty alcohol salts alkali and alkaline earth metal acids, salts of - sulphated hexadecanols, heptadecanols, octadecanols, salts of sulphated glycol tetra fatty alcohol, condensation products of sulphonated naphthalene and naphthalene derivatives - with - formaldehyde, condensation products of naphthalene, or naphthalenesulphonic acid- polyoxyethylenoctylphenol terethers, ethoxylated isooctelfenol-, octylphenol-, nonylphenol-, alkylphenolpolyglycol ether, tributelfenelpoleglekoletmer, alkylareloletoltralcohol, isotridecyl alcohols, condensation products of fatty alcohols with ethylene oxide, - ethoxylated castor oil, polioxyet: hylenalkyltthere, ethoxylated polyoxepropylene, laurelalcoholpoleglecol acetate, sorbitol esters, lignin, sulphite waste liquors and methylcellulose.

Powders, dusts and dusts can be made by mixing or comminuting the substances with a solid carrier.

Granules, for example coated granules, impregnated and homogeneous granules, can be produced by binding active ingredients to solid carriers. Solid carriers are, for example, mineral clays. such as silica gel, silicic acid, silica gel, silicates, talc, kaolin, attaclay, limestone; lime, - chalk, bolus, loess, - clay, dolomite, diatomite, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers such as ammonium sulphate, ammonium phosphate, urea and plant products such as cereal flour, meal from tree bark, wood and walnut shells, powdered cellulose and other solid-carrying materials.

Various types of oils, herbicides, fungicides, bactericides, trace elements, fertilizers, antioxidants (eg silicones), growth regulators, antidotes or other active compounds can be added to the mixtures or individual active ingredients.

The following known comparatives were used for the following experiments:

1 «

active substance No. 21 (German patent No. 1 164 152) ^ -N O.C ^ COON •

Active ingredient no. 22 (German Patent No. 1,173,722)

Active substance No 23 (DOS 2 461 513)

Example · 3

The leaves of "Jubilar" wheat plants growing in pots are sprayed with aqueous emulsions consisting of .80% (w / w) of the active ingredient and. 20% emulsifier and, after the spraying layer has dried, · are dusted with oid powders · Erysiphe gra minis var. The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and at 75 to 75 ° C. 80% relative humidity. After 10 days, the degree of mildew development is determined.

The test results are shown in the following table:

Active substance

Infestation of leaves after spraying x-% active substance suspensions x = 0.025 0.05

21) known

22) control (untreated)

0 0 0 0 0 0 0

0 0 1 1 = No assault. Graduated to

5, which is an overall attack

Example 4

In a further experiment, as described in Example 3, the leaves of barley plants of the species "Firlbecks. Union" growing in pots are treated and powdery mildew (Erysiphe graminis var. Hordeij) is sprayed.

Active substance

Infestation of the leaves after spraying x-% active substance suspensions x = 0.025 0.05

2 0 0 3 0 0 4 0 0 5 0 0 7 0 0 12 0 0 14 0 0 15 Dec 0 0 16 0 0 17 0 0 18 0 0 19 Dec 0 0 20 May 0 0 22 known 1 1

inspection (untreated)

Explanatory notes:

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

Example 5

Leaves of wheat plants growing in pots are artificially infected with wheat rust (Puccinia recondita) and left in a room saturated with water vapor at 20-25 ° C for 48 hours. The plants are then sprayed with aqueous suspensions containing a mixture of 80% test substance and 20% sodium ligninsulfonic acid dissolved or emulsified in water and placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. After 10 days the degree of rust development is assessed.

The test results are shown in the following table:

Table

Attacking leaves after spraying x-% active substance suspensions

0.1

Active substance

X == 0.05

3 2 1 4 0 0 5 0 0 6 0 0 7 0 0 16 0 0 17 0 0 21) known 3 2 22) 4 3 23) 3 3 inspection (untreated) 5

- no attack - graduated until

5, which is an overall attack. Examples of 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 1 - 7 parts by weight of compound 2 are dissolved in a mixture consisting of 80% by weight of xylene, 10% by weight of an addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid salt and 5 parts by weight, addition product 40, mol 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 8 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 with 10 parts by weight of an adduct. mol of ethylene oxide - with 1 mol of castor oil. By pouring this solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Example 9 parts by weight of compound 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight - mineral oil fraction - boiling point 210-280 ° C - and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil . By pouring this solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion is obtained which contains 0.02% by weight of active ingredient.

it is well mixed with - 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulfonic acid sodium salt from sulphite waste liquors and 60 parts by weight of silica gel and the mixture is ground in a hammer mill. By finely distributing the mixture in 20000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of the active ingredient.

Example 11 parts by weight of compound 3 are mixed intimately with 97 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 3% by weight of active ingredient.

Example 12 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 1 13 parts by weight of the active compound-1 are intimately mixed with 10 parts of 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 with 100,000 parts by weight of water yields an aqueous dispersion containing 0.04% by weight of the active ingredient.

Example 14

....... “parts of active substance 2 are intimately mixed with 2 parts of calcium salt - dodecylbenzenesulfonic acid. acids, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenolsulfonic acid, urea and formaldehyde and 68 parts of paraffinic mineral oil. A stable aqueous dispersion is obtained.

Example 10 parts by weight of active ingredient 2 are

Claims (1)

I will invent the subject A fungicidal composition comprising a solid or liquid carrier and, as an active ingredient, at least one N-substituted 3,5-dimethylpiperidin-4-one derivative of the general formula wherein: X represents a straight or branched alkylene radical having from 3 to 10 carbon atoms, R represents an alkyl or alkoxy group having from 1 to 8 'carbon atoms, or a salt thereof.