DD152274A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal agents, the 1,2,4-Triazolylenolether d. general formula I in which Ar, R and X d. have meaning given in the description as active ingredients. These agents are suitable for use as crop protection agents and can be used to combat cereal diseases such as powdery mildew and barley powdery mildew, Podosphaere species and Erysiphe species with particular success.

Description

Berlin, 1.8.1980 57 876/11

Fungizi de Mittel Field of application of iHrfi

The present invention relates to fungicidal agents containing novel 1,2,4-tiazolyl enol ethers as active ingredients

Characteristics of the known technical solutions

It has already been disclosed that 1,2,4-triazolyl ether, v / e, for example, 1- (4-chloropheno 2: y) -2- (2 _f 4-dichlorobenzyl oxy) -3,3-dimethyl-i ~ (1 , 2,4-triazol-1-yl) -butane, and 1,2,4-5! Riazolyl-pentanone, v / ie, for example, 1- (4-chlorophenyl) - = 4 _f 4-dimethyl-2- (1 , 2,4-triazol-1-yl) -3-pentanone, good fungicidal properties, have (see DE-OS 27 20 949 and DE-OS 27 34 426) _β The effect of these compounds, however, especially at low application rates and concentrations, not always quite satisfactory,

Aim of the invention;

The new 1,2,4-triazolyl enol ethers of the formula (I) have strong fungicidal properties. Surprisingly, the compounds of the invention exhibit a considerably higher activity than those known from the prior art compounds 1- ^(4-c hlorphenoxy) ~ 2- (2,4-dichlorobenzyloxy) -3,3-dimethyl ~ 1 "(1.2 , 4-triazol ~ 1 ~ yl) -butane and 1- (4-chlorophenyl) ~ 4,4-dimethyl-2- (1,2,4-tria7 _J ol-1-yl) ~ '3 ~ pentanone which chemically and functionally obvious compounds are · The substances according to the invention thus represent an enrichment of the art »

-2- 57 876/11

Explanation of the _m essence of the invention

Bs were new 1j2 _t 4-riazolyl enol ethers of the general formula

OR I

Ar-X-C = rC-CCCILOo (I),

if *

Il it

in which

Ar is optionally substituted aryl,

R is alkyl and

Σ is oxygen or methylene,

found, as well as their acid and Hetallsalz addition compounds «

The compounds of the formula (I) according to the invention are present in the geometric isomers E (trans) and Z (cis) * In E, Z-Homenklatur the substituents on the double bond react according to the Cahn-Ingold-Prelog rule decreasing priority. If the preferred substituents are on the same side of the double bond _s is the configuration Z (derived from Together), they are on the opposite side, E (derived from opposite). Both the individual isomers and the mixtures are claimed according to the invention »

-3- 57 876 /

It has furthermore been found that the 1,2,4-triazolyl enol ethers of the formula (I) are obtained when 1,2,4-triazolyl ketones of the formula I are obtained

Ar-X-CH-C-C (CEJo (II),

j

^H'h

in which

Ar and X are as defined above,

with alkyl sulfates or * halides in the blessing of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, and optionally subsequently adding an acid or a metal salt.

2229 83

The 1,2,4-triazolyl enol ethers according to the invention are generally defined by the formula (i). In this formula, Ar preferably represents optionally mono- or polysubstituted by identical or different substituents aryl having 6 to 10 carbon atoms, preferably phenyl and naphthyl, wherein as substituents are preferably: halogen; Alkyl of 1 to 6, especially 1 to 4 carbon atoms; Alkoxy of 1 to 4, especially 1 to 2 carbon atoms; Haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, in particular having up to 2 carbon atoms and up to three identical or different halogen atoms, halogens being in particular fluorine and chlorine; nitro; cyano; and, optionally substituted by halogen, in particular chlorine-substituted phenyl. R preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms. X is preferably oxygen and the methylene group.

Very particular preference is given to those 1,2,4-triazolyl enol ethers of the formula (I) in which Ar is phenyl which is optionally monosubstituted or disubstituted, identical or different, by fluorine, chlorine, bromine, iodine, methyl, Ethyl, isopropyl, trifluoromethyl, nitro, phenyl or chlorophenyl; R is methyl, ethyl, isopropyl, isobutyl or tert-butyl; and X has the meaning given in the definition of the invention.

Specifically, in addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (i) may be mentioned:

Le A 1Q 818

83

OR Ar -XC = C-C (CH ₃ )

₃

(D

ü

Ar

CH ₂

CH ₂

CH ₂

CH ₂

CH ₂

i-C 4 H ₉ CH ₃ i-C 3 H ₇ i-C 4 H ₉ CH ₃ C ₂ H 5 CH ₃ C ₂ H 5

CH,

tr

2 ** 5

CH,

C ₂ H ₅

O O

CH,

C ₂ H ₅

Le A 19 818

2229

Ar

Cl

Cl

CH,

CH ₃

CH, CH, CH, CH, O ₂ N-

0 ₂ N ~ <

O ₂ N-

O ₅ N-

CH,

CH, CH ₂ CH ₂ O

CH ₂

CH ₂

CH ₂ CH ₂

O CH ₂

CH ₅

CH ₃

C ₂ H ₅

CH ₃

Cp, H ₅

CH ₃

C ₂ Hf.

CH ₃

C ₂ H ₅

CH ₃

C ₂ H ₅

CH ₃

C ₂ H ₅

CH ₃

C ₂ H ₅

CH ₃

Le A 19

2229 83

Ar

CH,

CH,

CH ₂ CH ₂

CH ₂ CH ₂

CH,

C ₂ H ₅

CH ₃ C ₂ H ₅ CH ₅ C ₂ H ₅

If, for example, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butan-2-one and dimethyl sulfate are used as starting materials, the course of the reaction can be followed by the following Formula scheme are reproduced:

0 5 Cl. "'

) -O-CH-CC (CH ₃ ) ₃ + (CH ₃ ) ₂ SO ₄

base

OCH ₃ -O-C = CC (CH ₃ ) ₃

The starting materials to be used in carrying out the process according to the invention. 1,2,4-triazolyl ketones are generally defined by the formula (II). In this formula, Ar and X are preferably those radicals which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.

Le A 19 818

ύ &»& α 4ka W KJ W ο

The 1,2,4-triazolyl-ketones of the formula (II) are known (cf. DE-AS 22 01 063 [le A 14 118 ^ and DE-OS 27 34 426) and know by the methods specified therein v / earth by eg corresponding HaIogenketone with 1,2,4-triazole in the presence of a diluent and in the presence of an acid binder is reacted (see also the preparation examples).

The alkyl sulfates or halides which are furthermore required as starting materials for the process according to the invention are generally known compounds of organic chemistry. Examples include: dimethyl sulfate, diethyl sulfate, methyl bromide, methyl iodide, ethyl bromide, "ethyl iodide, isopropyl iodide and isobutyl iodide.

Suitable inert diluents for the reaction according to the invention are inert organic solvents. These include, preferably, aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; Esters, such as ethyl acetate; Formamides, such as dimethylformamide; as well as dimethylsulfoxide.

The reaction according to the invention is carried out in the presence of a base. In this case, all customary organic and in particular inorganic bases can be used, such as preferably alkali metal hydroxides or alkali metal carbonates, for example sodium and potassium hydroxide.

22 28 83

The reaction temperatures can be varied within a relatively wide range when carrying out the process according to the invention. In general, one works between 0 and 100 ⁰ C, preferably between 20 and 80 ⁰ C.

In carrying out the process according to the invention is preferably used for 1 mole of 1,2,4-triazolyl-ketone of the formula (II) 1 to 2 moles of alkyl sulfate or halide. The compounds of the formula (I) are obtained in the form of the geometric isomer mixtures. The isolation of the individual geometric isomers by conventional methods, such as due to different solubility, by salt formation, by Craig distribution or by chromatographic separation methods or by combining these methods. A clear structure assignment occurs on the basis of the ¹ H NMR data, in particular using displacement reagents. The effected by these reagents signal shifts are all the greater, the smaller the spatial distance between the central atom of the complexed Ver-Schiebungsreagenzes and the observed proton (see also the preparative examples).

In a preferred embodiment, the reaction according to the invention is carried out in a two-phase system, such as, for example, aqueous sodium or potassium hydroxide / toluene or methylene chloride, optionally with the addition of 0.1-1 mol of a phase transfer catalyst such as, for example, ammonium or phosphonium compound fertilize, for example, be benzyl-dodecyl-dimethyl ammonium chloride and triethyl-benzyl-ammonium chloride, carried out (see also the preparation examples).

The compounds of formula (I) which can be prepared according to the invention can be converted into acid addition salts or metal salt complexes.

Le A 19 813

2229 S3

- ίο -

For the preparation of physiologically acceptable acid addition salts of the compounds of the formula (I), preference is given to the following acids: The hydrogen halides, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid. The acid addition salts of the compounds of formula (i) can be readily prepared by conventional salt formation techniques, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid, and in known manner, e.g. by filtration, isolated and optionally purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of the formula (I) are preferably salts of metals of II. To IV. Main and I .. and II., And IV. To VIII «. Subgroup in question, copper, zinc, manganese, magnesium, tin, iron and nickel are exemplified.

Suitable anions of the salts are those which are preferably derived from the following acids: hydrogen halides, such as e.g. hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of compounds of the formula (I) can be obtained in a simple manner by customary methods, for example by dissolving the metal salt in alcohol, for example ethanol and adding to the compound of Forrol (i). Metal salt complexes can be prepared in known way .z. 3 * by filtration, isolation and optionally aurcr; Recrystallize.

Le A 19 818

2 0 O Q R &, £. C? Ό

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active compounds are suitable for use as plant protection agents.

Fungicides in crop protection are used to; Control of Plasmodiophoronycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

., ₀ The good plant tolerance of the active ingredients in the concentrations necessary for the control of plant diseases allows treatment of aboveground .. Plant parts, of plant and seed, and the soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good success to combat cereal diseases, such as powdery mildew and barley powdery mildew; of Podosphaera species, such as the powdery mildew (Podosphaera leucotricha) pathogen; and Erysiphe species, such as the causative agent of cucumber powdery mildew (Erysiphe cichoracearum),. be used. It should be emphasized that the active compounds of the invention not only have a protective effect, but are also partially systemically effective. Sp succeeds. To protect plants against fungal attack, when the active ingredient on the soil and the root or on the seed feeds the aerial parts of the plant.

Le A 19 B18

22 29 8 3

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with Fuel sets, such as smoked cartridges, cans, spirals, etc., as well as ULV cold and low-fog emulsions.

These formulations are prepared in known ways, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate by use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlcrbenzoie, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, 2.3. Petroleum fractions, alcohols such as butanol or glycol, as well as esters and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water; by liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, ζ .3. Aerosois propellant, such as halogenated hydrocarbons as well as 3utane, propane, nitrogen

'Q

22 29 83 - 13 -

and carbon dioxide; as solid carriers there are suitable: e.g. ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and snionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcelluic, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate can be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyanobiau and organic dyes such as alizarin, azole metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between C 'and 95% by weight of active ingredient, preferably between 0.5 and 90%.

Le A 19 81S

2229 83

The active compounds according to the invention may be present in the formulations or in the various application forms in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or by diluting them therefrom.

1.0 rode application forms, such as read-only readings,. Emulsions, suspensions, powders, pastes and granules are applied. The application is done in the usual way, e.g. by pouring, dipping, spraying, spraying, atomizing, vaporizing, injecting, silting, spreading, dusts, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied over a wider range. They are generally between V and 0.0001 wt .-%, preferably between 0.5 and 0.001 %.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably · 0.01 to 10 g, required.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

Le A 19 β

2229 83

In the following examples, the compounds indicated below are used as comparative substances:

(A) Cl- (O) -CH ₂ -CH-CC (CH ₃ )

Cl

(B) Cl-

O - CH ₂ - <p) -Cl 0 -CH-CH-C (CH ₃ ) ₃

e A 19 SIS

22 29 8 8 _ _1β -

Example a

Sprout Treatment Test / Mildew / Protective (Foliar Mycosis)

To prepare a suitable preparation of active compound, 0.25 part by weight of active compound in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkylaryl polyglycol ether) are added and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for protective activity, the monocled barley seedlings of the variety Amsel are sprayed with the preparation of active compound dewatered. After drying, the barley plants are dusted with spores of Erysiphe graminis var.hordei.

After 6 days residence time of the plants at a temperature of 21-22 ⁰ C and a humidity of 80 ~ 90% one evaluates the .Besatz of plants with mildew pustules. The level of infestation is expressed as a percentage of the infestation of the untreated control plants. 0 % means no infestation and 100 % the same degree of infestation as in the untreated control. The lower the powdery mildew case, the more effective the active ingredient.

The test results are shown in the following table:

Le A 19 818

Table A

Sprout Treatment Test / Cereal Mildew / Protective

Active ingredient infestation in % concentration of

T "ic" s + rt-F-Pe ^ ^the injection negotiated RKSI: oiie _ broth in wt% control.

-CH-CO-C (CH ₃ ) ₃ N

N U (A)

(known)

0.001

72.5

Cl

»0

C = C.

,, C (CH _{3) 3} '0-CH (CH ₃₎

 3/2

ff ^X N

LJ

(3)

0.001

26.9

Cl-OQ ^ ^ C (CH ₃ ),

"c = c

* N

0-C ₂ H ₅

(D

0.001

25.0

Cl- (C)> - O _N / C (CH ₃ ) ₃ , C = C

N.

0-CH ₃ (2)

0.001

0.0

Le A 19 818

2223 83

Barley mildew test (Erysiphe graminis var.hordei) / systemic (fungal cereal disease)

The application of the active ingredients is carried out as a powdered seed treatment agent. They are prepared by stripping the active ingredient with a mixture of equal parts by weight talc and diatomaceous earth to a finely powdered mixture with the desired drug concentration.

For seed treatment, barley seed is shaken with the stripped active ingredient in a sealed glass bottle. The seed is sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of one part by volume of Fruhstorfer unit earth and one part by volume of quartz sand. The germination and the casserole are done under favorable conditions in the greenhouse. 7 days after sowing, when the barley plants have unfolded their first leaf, they are pollinated with fresh spores of Erysiphe graminis var.hordei and further cultivated at 21-22 ⁰ C and 80-90% relative humidity and 16-hour exposure , Within 6 days the leaves form the typical mildew pustules. out

The level of infestation is expressed as a percentage of the infestation of the untreated control plants. Thus, 0% means no infestation and 100% the same degree of infestation as in the untreated control. The active ingredient is the more effective the lower the mildew case is.

The test results are shown in the following table:

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83

Table b

Barley mildew test (Erysiphe graminis var.hordei) /

systemic

  Active ingredient- dressing agent infestation

Concentration in% of the active substances ^{in the pickling center in} g / kg seed untreated

in% by weight

control

Cl

• O-CH-CH N

N-

C-CH ₂ - <O) -C1 Cl ^ ~ ^

(B) (known)

10

100

C = C

0-CH (CH ₃ )

₃ ) ₂

(3)

10

50.0

3/3

0-C ₂ H ₅

_J

(D

25

10

0.0

C = C

C (CHj) ₃

0-CH ₃

25

10

0.0

Le A 19 813

83

Table B (continued)

Barley powdery mildew test (Erysiphe graminis var.hordei) / systemic

Active drug seed dressing infestation concentration in the application rate of the mordant in g / kg seed unbehanin weight in%.% Good punched

control

C (CH ₃ )

3 'Z

_{/ C} = c _s

LJ

0-C ₂ H ₅ 25

33.8

Cl

CH,

C = C

, C (CH ₃ ),

OC ₂ H ₅ (5)

0.0

Le A 19 318

222883

Example C

Podosphaera test (apple) / protective

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 amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned. With the spray liquid splashed young apple seedlings, which are in the 4- to 5-leaf stage, to dripping wet. The plants remain for 24 hours at 2O ⁰ C and a relative humidity of 70? ^ In the greenhouse. Subsequently, they are inoculated by dusting with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse with a temperature of 21 to 23 ⁰ C and a relative humidity of about 70 °.

Ten days after the inoculation, the infestation of the seedlings is determined. The obtained rating values are converted into percent infestation. 0 % means no infestation, 100 % means that the plants are completely infested.

The test results are to be taken from the following table

to take :

Le A 19 SIS

2229

table

Podopshaera - test (apple) / protective

active substance

Infestation in % at a drug concentration of 0.001 %

Il

C1- (O) - ^CH 2 -CH-CC (CH ₃₎

^L 3/3

I-U (A) (known)

C (CH ₃ ),

= c

(3)

Cl- (C) VO / C (CH ₃ ) ₃ C = C

- "0-CH ₃

(2)

₃ ) ₃

ci- <y> - ^CH 2 / C (CH ₃₎ ^x c = c

oc ₂ h ₅ 32

Le A 19 818

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Example D

Erysiphe test (cucumbers) / Protective

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 amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned,

The spray liquid sprays young cucumber plants with about three leaves to dripping wet.

The cucumber plants remain for drying in the greenhouse for 24 hours. Then they are pollinated with conidia of the fungus Erysiphe 'cichoracearurn for inoculation. The plants are then placed at 23 to 24 ⁰ C and at a relative humidity of about 75 % in the greenhouse.

After 12 hours, the infestation of cucumber plants is determined. The obtained rating values are converted into percent infestation. 0% means no infestation, 100 % means that the plants are completely infested.

The test results are shown in the following table:

Le A 19 818

Table D

Erysiphe test (cucumbers) / Protective

Active ingredient infestation in % at an active substance concentration of 0.0005%

0 Cl- (O) -CH ₂ -CH-CC (CH ₃ ) ₃

On

Lji (a)

Cl- (Q) -O

C = C

! Uli

(3)

Vc

tr

N.,

¹ OC ₂ H ₅

(D 19

Le A 19 B16

22 29 83

MANUFACTURING EXAMPLES Example 1

_C (CH ₃ ) ₃

C = C. (E) form

• N \ 0 - CH ₂ - CH ₃

To 29.5 g (0.1 mol) of 1- (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butan-2-one, 16 g (0, 1 mol) of ethyl iodide and 0.5 g of benzyl-dodecyl-dimethyl-ammonium chloride in 50 ml of dimethyl sulfoxide are slowly added at room temperature 4.4 g (0.11 mol) of sodium hydroxide solution, dissolved in a little water, added dropwise. The reaction is slightly exothermic (up to 50 ° C). Then allowed to stir for 3 hours at room temperature, the reaction mixture is water, neutralized with acetic acid and extracted with methylene chloride '. The organic phase is extracted by shaking with water, dried over sodium sulfate and concentrated. After separation by Craig distribution, 6.0 g '(22% of theory) of 1- (4-chlorophenoxy) -3,3-dimethyl-2-ethoxy-1- (1,2,4-triazol-1-yl ) -1-butene as a mixture of isomers (Z / E = 1/3). Preparative HPLC gives the (Z) and (E) form of 1- (4-chlorophenoxy) -3,3-dimethyl-2-ethoxy-1- (1,2,4-triazol-1-yl ) -l-butene, wherein the (E) -form has a melting point of 57-62 ° C.

The structural assignment der.beiden isomers by means of ¹ H-NMR spectroscopy using Eu (TFC) ₃ = europium tris [3-trifluoromethylhydroxymethylene) -d-camphorato] as a shift reagent. The measurements are carried out in CDCl ₃ . The results are shown in the following table:

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Table.: Shift values and shift differences of the resonance signal with and without shift reagent (VR)

Fragment: (Z) isomer δ (ppm) with VR Δε • (E) isomer δ (ppm) with VR: AS δ (ppm) without VR: 2.77 1.77 δ (ppm) without VR: 2.16 1.01 C (CH ₃ ) ₃ 1.00 1.80 0.58 1.15 2.70 1.68 CH ₃ 1.22 5.10 1.08 1.02 6.45 3.12 CH ₂ 4.02 > 12 > 4 3.33 > 12 > 4 Triaz.-H 7.94 7.91 8.10 7.80 0.78 8.31 7.58 0.66 arom. H 7.02 8.60 1.35 6,92 ^: 8.46 1.27 7.25 7.19

Explanations:

"Craig distribution" = countercurrent distribution HPLC = high pressure liquid chromatography To Eu (TFC) ^ see Merck, Contacts, Issue 2/1978, p. 9

Le A 19 818

2 2 2 9 8 3

Cl

- (Cj) - ω - ch - co - C (CH ₃ ),

4l8g (6.6 mol) of 1,2,4-triazole are dissolved in 3000 ml of acetone. 934 g (7.2 mol) of anhydrous, pulverized potassium carbonate are added, the suspension is heated to the boil and a solution of 1565 g (6 mol) of 1- (4-chlorophenoxy) -1-chloro-3,3-dimethyl-butane is added. 2-on in 1500 ml of acetone is added dropwise so that the mixture boils without heating at reflux. When the addition is complete, the mixture is refluxed for 15 hours to complete the reaction; then the resulting precipitate is filtered off, washed with acetone and discarded. The filtrate is freed of solvent in a water-jet vacuum, the residue taken up in 3000 ml of toluene and once

washed with a solution of 100 g of 37% hydrochloric acid in 2000 ml of water. The aqueous phase is separated and discarded; The organic phase is washed with 50C0 ml of water and - after adding a further 4000 ml of toluene with a solution of 145 g of sodium hydroxide in 3500 ml

Water stirred for 6 hours at room temperature. Thereafter, the organic phase is separated, washed neutral with water and freed of solvent in a water-jet vacuum. This gives 1535 g (87 % of theory) of 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one of melting point 75-76 ⁰ C.

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2229 8

- 28 -

^Cl - (CJ) - O - CH - CO - C (CH ₃ ) ₃

I Cl

771 g (6 mol) of 4-chlorophenol are dissolved in 3600 ml of acetone. 3 g of anhydrous sodium iodide and 910 g (6.6 mol) of anhydrous, powdered potassium carbonate are added, and 895 g (6.3 mol) of 94.6% monochloropinacolin are added dropwise under reflux. After 20 hours of stirring at reflux temperature, the precipitate is filtered off, washed with acetone and discarded. The filtrate is freed of solvent in a water-jet vacuum. The

Sultierende white residue is taken up with 3000 ml of carbon tetrachloride and heated to 60 ⁰ C. 891 g (6.6 mol) of sulfuryl chloride are added dropwise without further heating to this solution in such a way that a steady evolution of gas takes place. After completion of the addition, 15 hours at the end of the

heated river. Finally, the solvent is distilled off in a water-jet vacuum. 1565 g of 1- (4-chlorophenoxy) -1-chloro-3,3-dimethylbutan-2-one are obtained in quantitative yield, which can be used without further purification for the reaction described above.

Example 2

_x , C (CH ₃ ) ₃

C = C. (E) form

0 -CH ₃ NJ

Le A 19 818

2 2 2 9 8 3

.- 29 -

To become 146.5 g (0.5 mol) of 1- (4-chlorophenoxy) -3,3-dimethyl-1- (l, 2,4-triazol-1-yl) -butan-2-one in 250 ml of dimethyl sulfoxide 30 g of potassium hydroxide, dissolved in a little water, added dropwise. The mixture is stirred for 1 hour and then added dropwise 65g (0.51 mol) of dimethyl sulfate. The temperature of the reaction mixture is maintained at about 40 ° C by means of ice bath. The mixture is stirred for 2 hours, mixed with water, the crystalline precipitate is filtered off with suction and crystallized from petroleum ether. This gives 51 g (33 % of theory) of (E) -1- (4-chlorophenoxy) -3,3-dimethyl-2-methoxy-1- (1,2,4-triazol-1-yl) -1-butene of melting point 134-138 ° C.

In a corresponding manner, the following examples of the general formula

QR I Ar -XC = C-C (CH ₃ ) ₃ (i)

ii ^N I! η

N Ll

receive:

Bsp.Nr. Ar XR melting point ( ⁰ C)

° iC ₃ H ₇ 129-32 (E-form)

^{CH2 C} 2 ^H5 103-05 (Z-form)

Cl-O-CH ₂ C ₂ H ₅ ng = 1, 537O

(E-form)

Le A 19 818

Claims (4)

-30- 57 876/11 invention claim 1 _β Fungicidal agent, characterized by a content of at least one 1,2,4-Sriazolyl-enoläther of the formula OR
Ar-X-C = C - C (CH ₃ ) ₃ (I), κ - in which Ar is optionally substituted aryl, R is alkyl and X is oxygen or methylene, and their acid and metal salt addition compounds, in addition to extenders and / or surfactants. 2, "Method of combating fungi, characterized in that 1,2,4-iriazolyl enol ether of the formula I is allowed to act on fungi or their habitat. 3 ', use of 1,2,4'-riazolyl enol ethers of the formula I, characterized in that they are used for combating fungi. 4. A process for the preparation of fungicidal agents, characterized by mixing 1,2,4-iriazolyl enol ether of the formula I with extenders and / ocu = x · surface-active agents.