CS212230B2 - Fungicide means and method of making the active agent - Google Patents

Abstract

1. N,N-Disubstituted ethylglycine esters of the general formula see diagramm : EP0017850,P37,F1 in which R represents alkyl, hydroxyalkyl, cyanoalkyl, alkenyl, alkinyl, halogenoalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, acyloxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, dialkylaminoalkyl or optionally substituted aralkyl, R**1 represents hydrogen, alkyl, alkoxy or halogen, R**2 represents hydrogen, alkyl, alkoxy or halogen, R**3 represents hydrogen or alkyl, R**4 represents furyl, tetrahydrofuryl, thienyl or tetrahydrothienyl ; isoxazolyl which is optionally substituted by alkyl ; hydroxyalkyl ; alkyl, alkenyl or alkinyl which is optionally substituted by cyano or thiocyano ; cycloalkyl ; dihalogenoalkyl ; or the grouping -CH2 -Az -CH2 -OR**5 -CH2 -SR**5 -OR**5 -SR**5 -CH2 -OSO2 R**5 -CH2 OCOR**5 or see diagramm : EP0017850,P37,F2 wherein R**5 represents optionally substituted alkyl, alkenyl, alkinyl or alkoxyalkyl and Az represents pyrazol-1-yl, 1,2,4-triazol-1-yl or imidazol-1-yl.

Description

BACKGROUND OF THE INVENTION The present invention relates to novel esters of N, N-dsubsubstituted ethyl glycines, to a process for their preparation and to their use as fungicides.

It is also known that haloacceiilides, such as alkyl esters of N-chloroacetyl-N- (2,6-dialkylphenylslanine or glycine), can be successfully used for combating fungal diseases of plants (cf. DOS No. 2 350 944 or U.S. Pat. However, the effect of these substances, in particular in their use in lower quantities and concen- trations, and in particular also in the sweat control of the fungi of the species Ph (1) (1), is not entirely satisfactory.

New esters of Ν, Ν-dL.substituted ethyl ethers of the formula I have been found,

-O-R (I)

II o

in which

R represents an alkyl group containing up to 4 carbon atoms,

3

R, R₁ and R ^J are independently shows, all modes are hydrogen or alkyl obsahnící to 4 carbon atoms, Ar * is a furyl group, a hydroxyalkyl group having 1 or 2 carbon atoms, cycloalkyl having 3 AI 7 carbon atoms, dihaloalkyl of 1 or 2 carbon-cast ^with the ^uP and ^{nu -} · CH ^{2 -A,} -CH-oR ^5, -CH ₂ -SR ^5, R ^{5 a -CH?} O-SO ^ -R ^5, -CH-O- CO-R ⁵ or

2122230

-СН ₂ -0

where

Az represents a pyrazolyl or triazolyl residue and

R 8 represents an alkyl group having 1 to 4 carbon atoms.

It has also been found that the esters of N, N-131-ethylglycine of the above-mentioned formula (I) are obtained by reacting the N-phenylethylglycine esters of the formula (II),

(II) in which

2 3

R, R *, R *, and L are as defined above, reacted with the acid chlorides, bromides or aritydrides of the formulas IMa or Iib,

R ⁴ -C-Cl (Br), (lo), (B ⁴ -? -) ₂ ⁰ o

wherein r 4 is as defined above, in the presence of a diluent and optionally in the presence of an acid binding agent.

In addition, it has been found that the novel Ν, Ν-disubstituted ethylglycine esters of formula (I) above have potent fungicidal properties.

Surprisingly, the esters of the β, β-di-β-β-β-γ-ethylglycines according to the invention exhibit a significantly higher fungicidal activity, in particular against Pltythophthora species than the known alkyl esters of N-chloro-oleo-N- (2,6- dialkylphenyl) alanine or glycine, which are closely related compounds chemically and efficiently. The substances according to the invention therefore represent an enrichment of the prior art.

If, for example, N- (hydroxyethyl) glycol ethyl ester and methanol are used as starting materials, the reaction according to the invention can be carried out as follows:

-C-OCH ₃ ³ Cl-CO-CH ₂ OCH ₃

-HCI

CH ₃ CH ₃

The esters of N-fenr-ethylglycine of the above formula (II) are described in part (see U.S. Pat. No. 4,096,167 and DOS No. 28 05 525). These compounds can be obtained by, for example, reacting the corresponding anilines with the corresponding alpha-halo-butyric acid esters in the presence of an acid binding agent such as carbonate

potassium, and in the presence of an inert organic solvent, such as dimethylformamide, and optionally in the presence of a catalyst, such as potassium iodide, at a temperature between ²⁰ and ¹⁰⁰ ° C.

The N-phenyl-ethyl-glycine esters of formula (II) can also be obtained by esterifying N-fen-1-ethylglycine with a known method with dry alcohols, for example in the presence of boron trifluoride.

The chlorides, bromides and / or ankylsides of the acids of formulas IIIa and IIIb used as further starting materials in the process according to the invention are generally known compounds in organic chemistry.

Suitable diluents for use in the process according to the invention are preferably inert organic solvents, which preferably include ketones, such as diethyl ketone, and in particular acetyl and metal methyl ketone; ρrosiIonttil particular ^ «^ tl Egon, ethers such as tetrahydrofuran or dioxane, Hifatccké and aromatic hydrocarbons such as petrsletler, benzene, toluene or xylene, halogenated hydrocarbons such as ⁿ meeihl® chloride, carbon tetrachloride, chloroform, chlorobenzene, and esters such as ethyl acetate.

The reaction according to the invention may optionally be carried out in the presence of acid binding agents (hydrogen chloride acceptors or bromoaluminum). All of the customary acid acceptors to which organic bases belong, such as tertiary amines such as triethylamine and pyridine, and inorganic bases such as hydroxides and carbonates of alkoxides, can be used. Suitable catalysts are, in particular, dimethylformamide.

The reaction temperatures of the process according to the invention can be varied within a wide range. In general, the reaction is carried out at a temperature between 0 and 120 ° C, preferably between 20 and 100 ° C.

In the process according to the invention, preferably 1 to 1.5 mol of the compound of the formula (III) and optionally 1 to 1.5 mol of the acid binding agent are used per mole of the compound of the formula II. The isolation of the compounds of formula (I) is carried out in a conventional manner.

that

Alternatively, the compounds of the above formula (I) may also be prepared with N-cyano-N-phenyl-ethylylglycines of formula (IV),

c, H_o

I ^{2 5} II

CH-C-O-H (IV) which

R ^2, in r 'necCna!

4

R3 and R are as defined above, to react with alcohols of formula V,

C-R «

II

O

R-O-H (V) wherein

R is in the presence of a condensing agent and optionally wherein the N-α-N-phenyl-ethylylglycine sulfides of the above meaning, the formula VI, the diluent (variant b)), or

CnHc o ⁵ II

CH-c -Cl

(VI)

CR ⁴

II

O in which

3 4

R, R, R and R are as defined above, reacted with alcohols of formula (V) in the presence of a diluent and optionally in the presence of a base (variant c) 1, and some of the compounds of formula (I) may also be obtained that the esters of N-haloacetyl-N-phenyl-ethylglycines of the general formula У11,

7 I ^{2 5} » _л

R ² y - / CH-COR

3®> u _-K-CH2 -Hal

II o

(VII) wherein

2 3

R, R, R and R are as defined above and

Hal is chlorine, bromine or iodine, reacted with compounds of formula VIII,

B-X (VIII) wherein

X is the radical Az, grouping * 0R ⁵ or -SR ^, wherein R ^ is as defined above, or an alkylcarbonyloxy group having 1 to 4 carbon atoms in the alkyl part and

V represents a hydrogen atom or an alkali metal, in the presence of a diluent and optionally in the presence of an acid binding agent (variant d)], or that the esters of N-hydroxyacetyl-N-phenyl-ethylglycind of the general formula IX

c ₂ h ₅ o

I ^D | L _* CH-C-OR c _-CH2 -OH

II ² o

(IX) wherein

R, R ^1, R ² and R have the abovementioned meaning, are reacted (1), optionally after activation with an alkali metal halide of the formula X

Hal-R ⁶ (X) wherein

Hal is as defined above and

R ⁶ represents a radical R ⁵ or a moiety of the formula -SO 2 R ⁶ or -CO 2 -, wherein R 6 is as defined above, in the presence of a diluent and optionally in the presence of an acid binding agent or

in the presence of a diluent and optionally in the presence of a catalyst [variant e / 1 resp. e / 2)].

The N-Acyl-N-phenyl-ethylglycine of formula (IV) used as starting material in the process of variant b) is not yet known, but can be easily obtained by reacting the N-phenyl-ethylglycine with the acid chlorides of the above. of formula (IIIa) in the presence of an acid binding agent, for example sodium hydroxide, and in the presence of an inert organic solvent, for example methylcellide, at a temperature between 0 to 120 ° C.

The alcohols of formula (V) used as starting materials in the variant variations

b) and c) are generally known compounds in organic chemistry.

The N-acyl-N-phthylglycine < RTI ID = 0.0 > ltridl < / RTI > of formula VI, used as starting materials in the work of variant c), are not yet known. IV are reacted advantageously with a hypochlorous acid chloride, in dimethylfomiamide or pyridine,

The esters of the H-chloroacetyl-N-phthylglycine of the general formula (VII) required as a starting material in the process of variant (d) are already described in some cases (see U.S. Pat. No. 4,096,167 and DOS No. 28,055,525) Said compounds can be obtained in such a way that, for example, the N-phenyl-ethyl-esters of the above-mentioned formula (II) are not reacted with the chloroacetic acid according to the invention.

Compounds of formula (VIII) used as further starting materials in the process of variant (d) are generally known in organic chemistry.

Esters of N-N-Ίydrotyleetyl felnl. ^tthllgly-c and ⁿ in formula IX required as starting materials in the smslu variant e) spadaaí the scope of the compounds of the invention is the custom can also be obtained by reacting an ester of N- acyl O-ethyl-N-phenylethylglycines of formula XII,

(XII)

C-CH ₂ -O-CO-R ⁸

O in which

2 λ

R, R, R and R 'mmaí above meanings, ^R B represents an alkyl group having from 1 ^and 4 of ^Y coal ^ z ^ Seni NaOH or draselrým in aqueous or alcoholic solution. For example ^the in metihanolu or e-anol, at a temperature of ^between-20 and ⁶⁰ ° C and ^P of acidification, esterification of a compound of the formula V in přítomnoosi esterífkaaČního catalyst such as boron trifluoride.

The halides of the formula (X) used as starting materials in the mixture of variant e / 1 are generally known compounds.

The DH-tropes used as starting material in the process of variant (e) (2) is also known in organic chemistry.

Suitable solvents for working in the variant b) are preferably inert organic solvents, which preferably include aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as chloroform or dichloromethane, esters such as ethyl acetate, ethers such as as well as the alcohols themselves used as reactants.

The reaction in the mixture of variant b) is carried out in the present. a condensing agent. For this purpose, all conventional condensation agents, such as, in particular, cyclic tert-butylcarbodiimium, ethyl chloroformate or benenenfluorohexia, may be used.

The reaction temperatures when working in variant b) can be varied within a wide range.

In general, the reaction is carried out at a temperature between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C, optionally under the boiling point of the solvent used.

Preferably, 2 to 8 moles of alcohol and 1 to 2 moles of condensing agent are used for the reaction of variant b) with 1 mole of the compound of formula (IV). The isolation of the compounds of formula (I) is carried out in a conventional manner.

Suitable solvents for working in the mixture of variant c) are preferably inert organic solvents, which preferably include those already mentioned in the description of the reaction according to the invention. Said reaction may optionally be carried out in the presence of an inorganic or organic base. Preferred bases have already been mentioned in the description of the reaction according to the invention.

Reaction. the working temperatures within the meaning of variant c) can be varied within a wide range. In general, the reaction is carried out at a temperature of between 0 and 120 ° C, preferably between 20 and 100 ° C, optionally under boiling. of the solvent used. For the reaction according to variant c), the mono-reactive reactants are preferably used in moss blue. The isolation of the compounds of formula (I) is carried out in a conventional manner.

As a diluent for working in the mix. variants d) are preferably inert organic solvents, which preferably include those already mentioned in the description of the reaction according to the invention.

Optionally, the reaction of variant d) may be carried out in the presence of an acid binding agent. For this purpose, all customary inorganic or organic acid-binding agents can be used, such as alkali metal nitrates, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate, or as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example . Preferably, an excess of the starting azole is used.

Relative temperatures when working in the cover of variant d) can be varied within wide ranges. Generally working at temperature between about 20 DEG and 150 DEG _F, preferably between 60 and 120 ° C. In the case of use of the solvent, it is expedient to work with and boil the solvent.

When crying in the direction of variant d), preferably 1 to 2 mol of the compound of the formula (VIII) and optionally 1 to 2 mol of the acid binding agent are used per mole of the compound of the formula (VII). The isolation of the compounds of formula (I) is carried out in a conventional manner.

The diluents to be used for the process according to variant e) are preferably inert organic solvents, which include the solvents mentioned above for the description of the reaction according to the invention.

Reaction variants in Smela E / 1) may be conducted in the presence of the binding agent ky ^ee linoleum. For this purpose, all customary inorganic or organic acid acceptors can be used, preferably the substances mentioned above in the description of the reaction according to the invention.

The reaction temperatures at work in the sense of variant e / 1) may be dimensional.

In general, the reaction is carried out at a temperature of from 20 to 150 ° C, preferably at the boiling point of the solvent used, for example at temperatures between 60 and 100 ° C.

In the process of variant e / 1), 1 mol of a halide X and optionally 1 to 2 mol of a reagent-binding agent are used per mole of the compound of the formula (IX), optionally after addition of 1 to 2 mol of a strong base such as an alkali metal hydride. acid. To isolate the resulting product, the mixture was freed from solvent and water and organic solvents were added to the residue. The organic phase is separated and worked up in the usual manner.

In context,! Preferably, the process of variant e / 1) is suitably started from the hydroacetate of the formula IX, which is converted into an alkali metal alkoxide in a suitable inert solvent by treatment with an alkali metal hydride or amide, which is then immediately isolated without isolation. reacting with a halide of formula (X) to give the desired compound of formula (I) of the invention by cleavage of the alkali metal halide in a single step.

The reaction in the mixture of variant e / 2) can optionally be carried out in the presence of a catalyst. Hydrogen chloride is preferably used for this purpose [see J. Am. Chem. Soc. 69, 2 246, (194 * 7), ibid. JO, 4 187 (1948)].

The reaction temperatures when operating in variant e / 2) may be within wide limits. Generally RAC ^{p p} s ^p te lo ^t of between ⁰ and ¹⁰⁰ ° C, preferably between ²⁰ and ⁶⁰ ° C.

For the reaction in the mixture of variant e / 2), the reactants are preferably mixed molar. mnnoisvích. The isolation of the compounds of formula (I) is carried out in a conventional manner.

The active compounds according to the invention exhibit a strong mild activity and can be used in practice for controlling undesirable microorganisms. The active compounds described can be used as plant protection agents.

Fwnjicidní agents are employed in plant protection for our ^ i pooírání fungi from the classes Plasmoddophoromcctes, Oomyceees, Clhtridiomycetes, zygote ^c ®ees, Ascoimcetes, Basidiomycetes and Deuteromycetes read.

Since the plants of the active compound according to the invention which are well tolerated for the control of plant fungal diseases are well tolerated by plants, they can be used for the treatment of above-ground parts of plants, seedlings and seeds, and for the treatment of soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good results in the fight against fungi of the class of the oceycees, for example by the pathogen of potato fungi (tomatoes) on tomatoes and potatoes. It is particularly advantageous that the active compounds according to the invention exhibit not only a curative-eradicative effect, but also a curative-eradicative effect. The compounds of the present invention may act to enable fungal plants to be attacked by fungi by delivering the active ingredients to the above-ground parts of the plants through the soil and root system or through seeds.

The active compounds may be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, grams, aerosols, natural and synthetic substances impregnated with the active compounds, small particles coated with polymeric substances and coatings for seeds, furthermore to formulations with flammable additives such as smoke cartridges, smoke jars, smoke sprays and the like, as well as formulations in the form of active substance scattering agents for cold or hot fog.

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied with gases. and / or solid carriers, optionally with surfactants, i.e., emulsifiers and / or dispersants and / or foaming agents. In the case of water problems as fillers, for example, organic solvents can also be used as co-solvents. Suitable liquid solvents are, in principle, aromatics, such as xylene, toluene or alkanol, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, hydrocarbons, or else hydrocarbons, such as hydrocarbons, such as cyclohexane or petroleum fractions, e.g. . such as butanol or glycol, and their ethers and esters; furthermore ketones such as acetone, methylcyclohexyl, yetthi-butylbutyl ketone or cyclohexanone, strongly polar solvents such as dimethylphosphonamide and ^di- methylphosphoric acid, and water.

Liquefied gaseous fillers. or carriers means liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone flours such as kaolins, alumina, talc, chalk, quartz, attapuugite, montmorillonite or silica, and synthetic stone flours such as highly dispersed silica, alumina and silicates.

Suitable solid carriers for the preparation of granulates are crushed and not natural stone materials such as limestone, marble, pumice, eeppolite and dolomite, as well as synthetic granules of inorganic and organic flours and organic maerule granules such as sawdust, coconut shells. , corn sticks and tobacco stalks.

Suitable emulsifiers and / or foaming agents are noninogenetic and anionic e-promoters, such as poly (fatty acid) esters of fatty acids, poly (ethyl ether) esters, fatty ₄ alcohols, for example, alkylsulphates, sulfates. proteins, trisulfonyl and protein hydrolysates, and as dispersants, for example, lignin, network waste liquors and meet the gel.

The compositions of the invention may contain an adhesive, such as _L karbOlqyιloellyll·lUlóau natural and synthetic powdered, granular or polymers such as gum arabic, alcohol and polyvinrXal-

In addition, these compositions may contain colorants such as inorganic pigments such as iron (III) oxide, extrinsic oxide and ferrocyanide blue, and organic dyes such as electrolyte dyes and metallic tz (1-phthalocyanine dyes) as well as trace elements such as iron, manganese, boron, odi, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight of the monomer, preferably between 0.5 and 90% by weight of the active compound.

The active compounds according to the invention may be present in the respective compositions in a salt with other active substances, such as fungicides, bactericides, bird preservatives, growth agents, plant nutrients and soil improvers.

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

In the treatment of above-ground parts of plants, the concentrations of the active compounds in the application forms can vary within wide limits. These concentrations generally lie between 1 and 0.0001%, preferably between 0.5 and 0.001% by weight. % «

In the treatment of seed, it is generally necessary to use from 0.001 to 50 g, preferably 0.01 to 10 g, of active compound per kilogram of seed.

For the treatment of the soil, it is necessary to use the active compounds in concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, depending on the type of effect desired.

In the examples below, the following is used as a comparator:

A = N-chlooaaeeml-N- (2, β-: χrPyP) illegal ester of formula

Β = N-chloroacetyl-N- (2-ethyl-6-methylphenyl) alenine ethyl ester of formula

CH ₃ o

CH-COC ₂ H ₅

Example A

Potato (Phytophthora) - Protective Effect TestTurn Solvent: 4, 7 w / w aceOon Emulsifier: 0.3. % by weight of water-glycol glycol water: 95 parts by weight.

The amount of active ingredient required to achieve the desired concentration of active ingredient in the spray liquid is then mixed with said solvent level and diluted with a blowing team of water containing said ingredients.

Young tomato plants of 2 to 4 leaves are sprayed with the spray liquid until dripping. Ponec RoosIío ¹ to 24 ^ ^h Odin at ²⁰ ° ^C and a relative humidity of 70% vlhkjsti in a greenhouse. Then the tomato plants are inoculated with an aqueous suspension of spores of the fungus (Phytophthora ioflstjos). The Rossiins are transferred to a humid comic, where they are maintained at 100% relative humidity and 18-20 ° C.

After 5 days, the infestation of tomato plants is determined and the infestation is calculated in%. 0% means no 100% means complete infestation of plants.

The active substances, the active substance concentrations and the results obtained are given in the table below.

Table A

Test for potato late blight (Phytophthora) - protective / tomato active substance (example number)

attack in% at active substance concentration 0.0005% / СН ₂ -С-ОСНз ^ C-CHo-CI

II o

(known)

(known) θ ^Η 3 O

I ii ^ CH-C-OC ^ C-CHh-Cl ^С 2 ^Н 5 (A)

2 ^H 5 (B) continued Table A active substance (example number) infestation in% at active substance concentration 0.0005%

^Γ э II R- ^ C-OCH

(12)

* 2 2 ^H 5 O

Even и _X-C CH ₃ -OCH ^{ч с} _{сн-2--о сн} а

II ³ o

(1)

^ _C-CH2 II of

(10)

Example B

Systemic Effect Test on Potato Mold (Ptytoppora) / Tomato Solvent: 4.7 parts by weight of acetone dispersant: 0.3 parts by weight of alkylanyl polyglycoletteau water: 95 parts by weight

The amount of active ingredient required to achieve the desired concentration of the active ingredient in the dressing is mixed with the same amount of solvent and the concentrate is diluted with the specified amount of water containing the above ingredients.

Roosiioy tomato planted in standard Pooh <36, at the stage of 2-4 leaves watered with 10 ml zálivty below Uve ^d enou frorccenCirecí. ^EFFECTIVE nn ^{e l ubstances} per ¹⁰⁰ cm @ soil.

The plants thus treated are inoculated with an aqueous suspension of spores of potato (Phytophttora infestans) and then transferred to a shallow chamber. with a 100% wavelength of air and at a temperature of 18 to 20 ° C. After 5 days, infestation of the tomato plants is determined and converted to infestation in%. 0% means no infestation, 100% means complete infestation of plants.

The active substances, the active compound concentrations and the results obtained are given in Table B below.

Table В

Systemic effect test on potato late blight (Phytophthora) / tomato active substance (example number) attack in% at active substance concentration 100 ppm

(known) (B)

(12)

c ₂ h ₅ o

CH 2 -CHO-CH ³ -CH ² -OCH ³ pho

(1)

Italy (9)

(10)

The following examples illustrate the preparation of the active compounds according to the invention.

Example

^ч с-сн, -о-сн,

II ³ о

(method according to the invention)

To a solution of 18.4 g (0.0816 mol) of N- (2,6-xylyl) ethylglycine methyl ester and a few drops of dimethylformamide in 80 ml of toluene at room temperature was added dropwise 13.3 g (0.122 mol) of methoxyacetyl chloride and the mixture was stirred for 3 hours. was stirred at 80 ° C. After cooling, the resulting solution was diluted with ethyl acetate, washed with dilute hydrochloric acid, water and sodium bicarbonate solution, dried over sodium sulfate and evaporated. The residue was crystallized from ligroin to give 10.4 g (43.5% of theory) of N-methoxyacetyl-N- (2,6-xylyl) ethylglycine methyl ester, m.p. 96-97 ° C.

Preparation of starting material:

A mixture of 387.3 g (2.1 mol) of 2-bromobutyric acid methyl ester, 127.0 g (1.05 mol) of 2,6-xylidine, 121.8 g (2.1 mol) of potassium fluoride and 100 ml of dimethylformamide is added. under nitrogen at 100 ° C for 39 hours. After cooling, the mixture is filtered, the filtrate is poured into water, the oily product obtained is extracted with methylene chloride, the extract is washed with water and, after drying with sodium sulphate, evaporated. The residue was subjected to fractional distillation in vacuo using a distillation column. 112.0 g (48.3%) of N- (2,6-xylyl) ethylglycine methyl ester having a boiling point of 100-110 [deg.] C./90 Pa are obtained.

Example 2

(method according to the invention)

To a solution of 11.1 g (0.05 mol) of N- (2,6-xylyl) ethylglycine methyl ester, 7.9 g (0.1 mol) of pyridine and 1.2 g (0.01) of 4-dimethylaminopyridine were 18.4 g of 1-pyrazolylacetyl chloride hydrochloride (prepared from 0.1 mol of 1-pyrazolylacetic acid) was added over 35 minutes under reflux and the mixture was heated under reflux for 22 hours. The reaction mixture is evaporated, the residue is partitioned between ethyl acetate and 1M citric acid, the organic phase is washed with 5% sodium hydroxide solution and water, dried over sodium sulphate and evaporated. The residue was crystallized from toluene / petroleum ether (1: 4). 11.3 g (68.7% of theory) of N- (1-pyrazolylacetyl) -N- (2,6-xylyl) ethylglycine methyl ester of melting point 113 DEG-115 DEG C. are obtained.

To a suspension of 12.6 g (0.1 mol) of 1-pyrazolylacetic acid in 40 ml of toluene was added 1 drop of dimethylformamide and then added dropwise at 25-30 ° C (ice-cooling).

19.5 g (0.15 mol) of oxalic acid chloride. After stirring at room temperature for 6 hours, the mixture is filtered off with suction and the residue on the filter is evaporated twice with toluene. 13.4 g of crude 1-pyrazooyl-acetyl chloride hydrochloride are obtained, which is used without further cross-linking.

Preparation of starting material:

x HCl

Example 3

III-CH-C-OCH ₃ ^X C-CH ₂ -OH

II o

[variant f)]

To a solution of 61.1 g (0.19 mol) of N- (2,6-xyryl) ethers of N- (2,6-xyryl) ethers in 200 ml of methanol is added dropwise a solution of 21.3 g (0.38 mol) of powdered solution at room temperature over 15 minutes. of potassium hydroxide in 200 ml of methanol / methanol, the resulting mixture was first stirred at room temperature for 1 hour and then at 50 ° C for 3.5 hours. The solution is evaporated, the residue is dissolved in water, the aqueous solution is shaken with ether, acidified with dilute hydrochloric acid and extracted with itlylacitate. The extract was dried over sodium sulfate and evaporated.

The residue was dissolved in 180 ml of methanol and heated to reflux for 17 hours after addition of 81.0 g (0.571 mol) of 48% bootrifluoride nitrate. The reaction solution is poured into 1000 ml of 10% sodium hydrogen carbonate solution under ice-cooling, extracted several times with methylene chloride, the extracts are washed with water and, after drying over sodium sulphate, evaporated. There was obtained 48.1 g (90.6% of theory) of melhirestir N- (ΊddJJχcecececececeylyl--N- (2,6-N-llllyl) -tiline), m.p. 101-102 ° C.

Example 4

C2H5 O

I 11 ^ СН-с-ОСНз ^X C-CH ₂ -O-SO _? -CH ₃

II ^{of J} o [variant e / 1) J

To a solution of 13.95 g (0.05 mol) of melthlestir N - (hydroxyethyl) - (2,6-hexyl) ethllelycine (Example 3) and 12.3 g (0.11 mol) of 1,4-dicocbicylo [ 2,2,2] octane vi 150 ml of reethrench chloride were added dropwise at 20-25 ° C (cooling to humans) with 11.5 g (0.1 mol) of melhanesulfonic acid chloride and the mixture was stirred at room temperature for 17 hours. The residue is crystallized from lignin and toluene (7: 2) to give 13.9 g (78.8% of theory) of melhilestir, which is washed with water, 10% aqueous pyridine, dilute hydrochloric acid and again with water, dried over sodium sulfate and evaporated. N-MMT ltian: ^ ffnnlox ^ i ^ c ^ t ^ and ^ ir 1 N (22 - ^ X ^^ D Ethly lglycinu about ^l OTE tip T ^and the ⁹² ° ^C "

AT

Example 5

⁹ 2 ^H S ^o

-E-Ochoa CH ^ _C-CH2 -O- (\ [version e / 2)]

To a mixture of 11.2 g (0.04 mol) of N-tyroxyacetyl-N- (2,6-xylyl) ethylglycine methyl ester (Example 3) and 13.8 g (0.16 mol) of 3,4-dilyrdro-2H- Pyrene (4 ml) was added and the mixture was stirred at room temperature for 23 hours. The oily residue is freed from volatile impurities by evaporation in an oil pump vacuum. 14.4 g (99.2% of theory) of N-tetrahydro-diployl-ethyl-acetyl-N- (2-6-yl) -thiyl-glythine methyl ester are obtained in the form of an oil having a refractive index n = 1.4959.

The following compounds of formula I are prepared in an analogous manner:

'with - <CH-C-O-R II 0 (AND) example number H ¹ r2 R ³ r4 R melting point (° C) or refractive index 6 CH ₃ H H -O CH3 np '' ⁵ - 1 ^, 5417 7 CHj H H -CH 2 -O-CH 3 ch ₃ NP ^{1 '5} = ¹ 5037 8 CH3 _6-CH3 H -C1-O-COCH3; ch ₃ 79 to β0 9 CH _{3 6-CH3} H -CHCl ₂ CH ₃ 101 to 102 10 ^CH 3 _6-CH3 H - ^ch ^ ⁿ CN CH ₃ 141 to 143 11 ^CH 3 _6-CH3 H -OC ₂ H ₅ CH ₃ n * ¹ & apos ^; = 5 ^, 4865 12 CHj 6-CH-J H -Q CH ₃ 107 13 CH3 _6-CH3 H CH ₃ 66 to 68 14 ^CH 3 _6-CH3 H -C ^ SCH? CH ₃ np = ^{1 1,} 5470

Claims (2)

SUBJECT OF THE INVENTION A fungicidal composition, characterized in that it contains at least one Ν, Ν-disubstituted ethylglycine ester of the general formula I as an active ingredient, in which: R represents an alkyl group containing up to 4 carbon atoms, 12 3 W, R, R are each independently hydrogen or alkyl of up to 4 carbon atoms and is furyl, hydroxy of 1 or 2 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, dihaloalkyl of 1 or 2 atoms carbon or a group -CHg-Az, -CH ₂ -OR ⁵ , -CHg-SR ⁵ -OR ⁵ , -CH ₂ -O-SO ₂ -R ⁵ , -CHg-O-CO-R ⁵ or wherein Az represents a pyrazolyl or triazolyl radical and represents an alkyl group having 1 to 4 carbon atoms; 2. A process for the preparation of active substances according to the point of ethylglycine of the general formula II, 1, characterized in that the esters of N-phenyl- (II) in which 12 3 R, R, R and R are as defined above, reacted with the acid chlorides, bromides or anhydrides of formulas IIIa or IIIb, R ⁴ -C-Cl (Br) II o (R ⁴ -C-), O II o (lila) (Illb) in which R1 is as defined above, in the presence of a diluent and optionally in the presence of an acid binding agent.