CS195346B2 - Fungicide - Google Patents

Abstract

The morpholine derivatives of the formula I and their salts show a fungicidal activity. The substituents in formula I have the meaning given in Claim 1. The fungicides, which contain the morpholine derivatives of the formula I, are used for controlling fungi. The plant or its seeds are treated. <IMAGE>

Description

The invention relates to fungicidal compositions containing, as active ingredients, valuable new morpholine derivatives and their salts and reaction products with higher molecular weight acids, for example dodecylbenzenesulfonic acid. Said compositions are used to combat fungi.

It is already known that N-tridecyl-2,6-dimethylmorpholine and its salts as well as its molecular and addition compounds can be used as fungicides (German patent, 1,164,162, German patent 1,173,722 and DOS 2). 461 514) ..

It has now been found that the novel morpholine derivatives of the general formula

For example, with dodecylbenzenesulfonic acid, they have a good fungicidal effect which exceeds that of known morpholine derivatives.

Salts are, for example, salts with inorganic or organic acids, such as chlorides, fluorides, bromides, iodides, sulfates, nitrates, phosphates, acetates, propionates and fumarates. Reaction products with higher molecular weight acids are formed, for example, by the action of surfactant acids such as dodecylbenzenesulfonic acid.

The novel compounds can be isolated in the case of 2,6-dimethyl derivatives, such as cis and trans isomers. They are prepared, for example, by reacting 2,6-dimethylmorpholine with 3-p-tert-butylphenyl-2-methylpropanal in the presence of a diluent, for example formic acid, at temperatures of from 50 to 110 ° C.

The following examples illustrate the preparation of the novel compounds:

Example 1

Synthesis of N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -cis-2,6-dimethylformoline

The 2,6-dimethylmorpholine, which was obtained by the cyclization of diisopropanolamine catalysed with sulfuric acid, was separated by fractional desillation in which

R ¹ , R ² , R ³ and R 4 are hydrogen, methyl or ethyl, and their salts and their reaction products with higher molecular weight acids, via a distillation column filled with stainless steel wire cis- and trans-form. About 75% (w / w) of 2,6-dimethylformoline is present in the cis-configuration, the remainder in the trans-configuration The isomer separation by fractional distillation is carried out on a column with about 40 separation steps. The trans-form of 2,6-dimethylmorpholine can be obtained under the same transition conditions between 88-89 ° C / 13.3 kPa as the product containing over 95% pure material.

575 g of 98% formic acid are introduced into the apparatus, which is equipped with a reflux condenser, a thermometer and a dropping funnel. While stirring and cooling, 345 g of 99% 2,6-cis-dimethylmorpholine are added dropwise. The mixture was then slowly heated in a water bath to 70 ° C. 612 g of 3-p-tert-butylphenyl-2-methylpropanal are added dropwise to the reaction mixture over a period of 4 hours while maintaining a temperature of about 100 ° C. With strong carbon dioxide evolution, condensation is complete. After completion of the reaction, the mixture was maintained at 100 ° C for 2 hours with stirring.

The excess formic acid is then distilled off under reduced pressure. Far-reaching removal 'of formic acid is carried out under water pump vacuum at 100 ° C ^e

Release of the base from the formate is effected by dropwise addition of a 40% aqueous sodium hydroxide solution. The addition of sodium hydroxide is expediently carried out at 80 to 100 ° C in order to favorably influence the formation of the amine phase. sodium hydroxide. Toluene (200 g) was added to reduce viscosity. The organic phase is washed twice with 250 g of water after separating the sodium hydroxide phase.

. For further purification, the amine is fractionally distilled at 5 mbar over a 5-well distillation column. . Next to the small front fraction (up to

143 [deg.] C / 27 Pa; 50 g) gave 865 g of N- (3-tert-butylphenyl-2-methyl-11-propyl) -2,6-cis-dimethylmorpholine. This passes at 27 Pa at a temperature between 143 and 146 ° C. According to chromatographic analysis, the amine contains more than 98% pure substance. Based on. The aldehyde was achieved in 84.5% yield.

To convert to the hydrobromide, 30 g of pure product was dissolved in 50 g of ethanol, which was saturated at room temperature with hydrogen chloride. After cooling, 23 g of hydrochloride are obtained in pure form, which melts at 220 ° C.

Example 1 a d 2

Synthesis of N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -2,6-transdiethylethylmorpholine

To 70 g of 98% formic acid 29 g of 2,6-transdimethylmorpholine are added under ice-cooling. 41 g of 3-p-tert-butylphenyl-2-methylpropanal are then added with stirring. The reaction mixture was heated at 100 ° C for 6 hours. At the beginning of the reaction there is a very strong release of carbon dioxide, which ceases noticeably after about 1 hour. Further processing is carried out in the manner described in more detail in Example 1.

At 670 mbar, N- (3-p-tert-butylphenyl-2-methyl-1-propyl) -2,6-trans-dimethylmorpholine is passed at 168-169 ° C. Yield 52 g = 86% based on aldehyde. 11 g of the amine are dissolved in 20 g of ethyl acetate, which is saturated with dry hydrogen chloride. Upon cooling, the hydrochloride crystallizes. Melting point 165 ° C.

Other compounds are obtained accordingly. '

Among the compounds of the invention, for example,

frCH-C-active substance no.

boiling point:

123 ° C / 1.3 Pa

Melting point:

108 ° C, active ingredient no.

1 »5> 346 _N ^R ~ ^N \ ^ CTS- form ^{_v% c} / -γ

Irans- farm

RN * э - на • г ^CH 3 as-form

CH ₃ . RN p-Hórans-form θ ^ 3 boiling point:

143 to 146 ° C / 27 Pa Boiling point:

168-169 ° C / 670 Pa • Melting point:

220 DEG

Melting point:

165 [deg.] C

10 № ^R + '. m _a boiling point: 128 ° C / 2.7 Pa 11 RN RN RN ^CH * boiling point: 133 ° C / 6.7 Pa 12 ^{1 C} ^ 3 RN 0 boiling point: 125 ° C / 2.7 Pa 13 Í ~ V ^R Nj ° boiling point: 170 ° C / 667 Pa

195 & 4B Active ingredient no.

14 r-'nO · m Melting point: 206 ° C 15 Dec R-NO ⁷ H $ C boiling point: 145 ° C / 40 Pa 16 H ₃ c R-n'Э'НС1 λ- ⁷ n ₃ c Melting point: Mp 172 ° C IN 17 C ₂ H ₅ l · JR-. 0 Ws boiling point: 148 ° C / 40 Pa 18 R-NO no boiling point: 146-148 ° C / 40 Pa .19 The Chk _N / R 'HBr crs form Melting point: 228 ° C i. . 20 May R-N p · HOOC-CH (¾ hc-cooh 0 cta-form Melting point: 174 ° C

The active compounds according to the invention and the fungicidal compositions according to the invention are particularly suitable for combating plant diseases, such as, for example, Erysiphe graminis (powdery mildew), for cereals, Erysiphe cichoriacearum (powdery mildew) on pumpkin plants, Podosphaera leucotricha on apple trees, Uncinula necator on vines, Erysiphe polygoni on beans, Sphaerotheca on roses, Microsphaera dacha and grape vines, Mycosphaerella musicola on banana trees, Puccinia and Uulatus appulatus species. phaseoli on beans, Hemileia vastatrix on coffee plants and Rhizoctonia solani. They are systemically effective. They are transported both through plant roots and through plant leaves to plant tissue.

The application is carried out, for example, by watering, spraying, dusting or pickling plants or seeds with the active ingredients. When using new active substances for the treatment of plants against fungal infections, the application rates are between 0.025 and 5 kg of active substance per 1 ha of area. For the surface protection of trees or fruits, the active compounds can also be used in combination with plastic dispersions as 0.25% to 5% by weight of the dispersion. The fungicides generally contain between 0.1 and 95% by weight of active compound, preferably without 0.5 and 90%.

The active compounds may be mixed with other known fugicides. In many cases, an improvement in the spectrum of fungicidal effects is achieved. Many combinations of these fungicides in weight ratios of 1: 10 to 10: 1 also exhibit synergistic effects, i.e. the fungicidal efficacy of the combination preparation is greater than the sum of the individual efficacies. ingredients. Fungicides which may be combined with the compounds of the invention are, for example: dithiocarbamates and derivatives thereof, such as zinc diimethyldithiocarbamate, manganese zinc ethylenedi-dithiocarbamate, manganosodium bis-dithiocarbamate, ethylene-bis-dithiocarbamate N, zinc ethylenebistocarbamate and N, N'-polyethylene bis- [thiocarbamoyl] disulfide, zinc, Ν'-propylene-bis-dithiocarbamate, ammoniacal complex of N, N'-propylene-bis-dlthiocarbamate, zinc and N n-Polypropylene-bis- (thiocarbamoyl) disulfide;

heterocyclic compounds such as

N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide,

N- (1,1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester,

2-methyloxycarbonylaminobenzimidazole,

2,3-dihydro-5-carboxanilido-6-methyl-

-1,3-oxathiine-4,4-dioxide,

2,3-dihydro-5'-carboxanilido-6-methyl-1,4-oxathiin,

5-butyl72-dimethylamino-4-hydroxy-6-methylpyrimidine,

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

1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, and various other fungicides such as dodecylguanidine acetate, N-dichlorofluoromethylthio-N 'diamide, N'-dimethyl-N-phenylsulphuric acid, 2,5-dimethylfuran-3-carboxanilide 2,5-dimethylfuran-3-carbonyl-SS346 xylic acid cyclohexylamide; 2-iodobenzanilide,

3-brombenzanilid, diisopropyl 3-nitro isophthalic acid ,, 1- (1,2,4-triazol-r-yl) - [1 ^(T 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-trichloroethyl) formamide,

2,4,5,6-tetrachlorispthalonitrile,.

1,2-dimethyl-3,5-diphenylpyrazolinium methylsulfate

The application is carried out, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions. emulsions, oil dispersions, pastes, dusts, sprinkles, granulates by spraying, fogging, dusting, sprinkling or watering.

The dosage forms are entirely governed by the purposes of use; these dosage forms are in any case intended to ensure the finest possible distribution of the active compounds according to the invention.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions are those of a medium to high boiling point mineral oil, such as kerosene or a diesel engine oil, as well as tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by adding water. For the production of emulsions, pastes 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 agents or emulsifiers. Concentrates may also be prepared which consist of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water.

The surfactants include: alkali metal, alkaline earth metal or ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal dibutylnaphthalenesulfonic acid salts and alkaline earth metal salts, lauryl ether sulfates, sulfated , alkali metal and alkaline earth metal fatty acid salts, sulphated hexadecanols, heptadecanols, octadecanols, sulphated glycol ethers of fatty alcohols, condensation products of sulphonated derivatives of naphthalene, naphthalene with formaldehyde, condensation products of naphthalene and polyphenol sulfone polyol, , ethoxylated isooctylphenol-, octylphenol-, nonylphenol-, ajkylphenol glycol ether, trbutylphenylpolyglycol ethers, alkylarylpolyether.alcohols, isoiridecyl alcohol, mass condensation products % of alcohols with ethylene oxide, ethoxylated castor oil, nitroglycerin, ethoxylated polyoxypropylene, lauryl alcohol polyglycol etheracetal, sorbitol esters, lignin, sulphite waste liquors and methylcellulose.

Dusts, dusts and powders can be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules sp can be prepared by binding the active ingredient to solid carriers. Fixed

Ю the carrier substances are, for example, mineral clays, such as mica, silica, silica, silica, talc, kaolin, attaclay, limestone, lime, chalk, this, loess, clay, dolomite, silica, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and plant products such as cereal flour, ground tree bark, wood flour, and nutshell flour, powdered cellulose and other solid carriers.

Oils of various types, herbicides, fungicides, nematicides, insecticides, bactericides, trace elements, fertilizers, antifoams (for example silicones), plant growth regulators, antidotes and other active compounds can be added to the mixtures or to the individual active substances.

The following known comparatives were used for the following tests:

active substance no.

(znah *> a9)

^C , 27;

CH3COOH

CH>

Cl 3 ^H 27;

About ·

(known)

CH ₃

Example 3

The leaves of wheat seedlings growing in the 'Jubilar' pot are sprayed with aqueous emulsions consisting of 80% (by weight) of active ingredient and 20% of emulsifier and, after the spraying layer has dried, are dusted with Erysiphe graminis var. trltici. The test plants are then kept in a greenhouse at temperatures between 20 and 22 ° C and at 75 to 80% relative humidity. After 10 days, the degree of development of powdery mildew on plants was determined.

The results are shown in the following table:

1Θ5346

active substance no.

Table of leaf attack after spraying x '% active ingredient suspension x 0.006 0.012 0.025 0.05

1 1 to 2 1 0 to l · 0 2 1 0 to 1 0 0 3 Ό 0 0 0 4 1 0 0 0 5  O 0 0 0 6 .1 0 0 0 19 Dec 0 0 0 0 20 May 0 0 0 ΰ 7 (Known) 3 to 4 3 2 1 8 (known). 4 4 2 1 9 (known) 2 and 1 0 inspection (untreated) 4

= no attack graded to 5 = £ complete attack

Example 4

In another experiment, the leaves in a pot of cultivated barley plants of the species Firlbecks are treated as described in Example 3.

Union ”and dusted with spores (conidia) of powdery mildew of Erysiphe graminis varhodei.

The test results are shown in the following table:

Table

active substance no. infestation of leaves after spraying x% active substance suspensions x = 0.006 0.012 0.025 1 . 0 0 0 2 0 0 0 3 D 0 0 4 0 0 0 5 O 0 0 6 0 O· 0 19 Dec 0 0 0 20 May 0 0 0 7 (Known) . 2 1 0 to 1 8 (Known) 3 1 1 inspection (untreated) 4 0 = no attack graduated to 5 = total attack

Example 5

The leaves in the pot of growing wheat plants are artificially infected with Puccinia recondita spores and then kept at 20-25 ° C for 48 hours in a water-saturated chamber. Then the plants are sprayed with aqueous suspensions containing a mixture of 80 1% of the test compound and 20% of sodium lignisulfonic acid dissolved or emulsified in water and placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity. air. After 10 days, the degree of rust development on the plants is evaluated.

The test results are shown in the following table:

195348 --18

Table.

active substance no. Λ. _ ____. ... .. Λ infestation of leaves after spraying x% suspensions x = 0.025 active substance 0,05 ....... 0,1 ... - 1 2 to 3 1 to 2 0 3 0 0 0 4 0 0 0 5 0 0 0 6 0 0 0 19 Dec 0 0 0 20 May 0 0 0 7 (Known) 4. 3 2 8 (Known) 4 4 3 9 (known) 4 3 9 inspection (untreated) 4

О = no attack, graded to 5 = complete attack

Example 6 parts by weight of compound 3 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution which is suitable for application as minimal drops.

Example 7 parts by weight of compound 4 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the 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. 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 the addition product of 7 moles of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide. mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely dissolving the resulting aqueous dispersion contains 0.02% by weight of the active ingredient.

Example 9 parts by weight of compound 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a temperature of 210 to 280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water ^and finely distributing it yields an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 5 parts by weight of the active substance No. 5 are mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of sodium ligninsulphonic acid from sulphite waste liquors and 60 parts by weight of powdered silica gel and grind well with hammer. mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

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

EXAMPLE 12 parts by weight of compound 4 are intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil onto which the liquid portion has been sprayed. In this way, a composition with good adhesion is obtained.

Example 13 parts by weight of active ingredient No. 3 are intimately mixed with 10 parts of sodium salt of the condensation product phenolsulfonic acid, urea and formaldehyde and 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution of 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active ingredient.

Example 14 parts of active ingredient No. 4 are intimately mixed with 2 parts of dodecylbenzenesulfonic acid calcium salt, 8 parts of fatty alcohol polyglycol ether, 2 parts of phenolsulfonic acid, urea and formaldehyde condensate sodium salt and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Claims (1)

SUBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and, as an active ingredient, at least one morpholine derivative of the general formula: R ¹ , R ² , R ³ and R 4 are hydrogen, methyl or ethyl, or a salt thereof or a reaction product thereof with a higher molecular weight acid, for example dodecylbenzenesulfonic acid.