Fungicide and method of producing active compounds

The present invention relates to novel complexes of 1-phenyl-2-trlazolylethyl derivatives with metal chlorides, to a process for their preparation and to their use as fungicides.

It is already known that 1- [β-aryl-4- (R-oxy) ethyl] imidazoles such as 1- [β-butoxy- [3- (4'-chlorophenyl) ethyl] imidazole, and 1 - [ R-aryl- [S- (R-pxy) ethyl] triazoles, such as 1- [O-allyloxy- [3- (4'-chlorophenyl) ethyl] -1,2,4-triazole, show good fungicidal activity (see DOS Nos. 2,063,857 and 2,640,823). However, in certain areas of indication, the effect of these substances, especially when applied at lower levels and concentrations, is not always entirely satisfactory. Furthermore, it has long been known that zinc ethylene-1,2-bis-dithiocarbamate is a good means of combating fungi in plant diseases [see Phytopathology 33, 1113 (1963)]. However, the use of this substance as seed dressing is only possible to a limited extent, since the compound is less effective when applied in lower amounts and concentrations.

It has now been found that the novel complexes of 1-phenyl-2-triazolylethyldervlates with metal chlorides of formula I

<img file="CS199530B2_D0001.tif" />

(D in which R¹ represents an allyloxy group or tert. R represents a chlorine atom or a phenoxy-butylcarbonyloxy group, _ч Me is a metal selected from the group consisting of copper, manganese, zinc and tin, n is a number of 1 or 2 and p is a number of 2 or 4, having a strong fungicidal property.

It has further been found that the novel metal complexes of the above-mentioned general formula (I) are obtained by substituting 1-phenyl-2-triazolylethyl derivatives of the general formula (II). ^Rand R⁴ (Kterém in which

R, R¹ and are as defined above, reacted with the metal chlorides of the formula III

MeClp x kH2O (ΠΙ), in which

Me and p are as defined above and k is any number from 0 to 12 in the presence of a solvent.

Surprisingly, the complexes of 1-phenyl-2-trlazolylethyldervates with the metal chlorides of the formula I according to the invention surprisingly show considerably higher fungicidal activity, in particular against various types of rust and powdery mildew, (R-oxy) ethyl-imidazoles and -trlazoles, for example 1- [$ -butoxy-β- (4'-chlorophenyl) ethyl] imidazole, which are chemically and efficiently related, and than ethylene-1,2 -bls-zinc dlthiocarbamate, which is a known substance of the same focus. The active compounds according to the invention thus represent an enrichment of the prior art.

When [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether and copper (II) chloride are used as starting materials, the reaction according to the invention can be described as follows: by the scheme:

<img file="CS199530B2_D0002.tif" />

Some of the starting materials of formula (II) are known (cf. DOS No. 25 47 953 and DOS No. 26 40 823). The hitherto unknown starting materials of the formula II can be obtained, for example, by one of the following processes:

a) reaction of alkoxides derived from 1-hydroxy-1-phenyl-2-trlazolylethane derivatives of the general formula IV (IV) in which:

Wounds have the meanings given above and

M represents an alkali metal, preferably lithium, sodium or potassium, a quaternary ammonium or phosphonium group, with a halide of formula V

Hal — Ri (V) in which

R¹ is as defined above and

Hal represents chlorine or bromine, in the presence of an organic solvent, for example dioxane or chloroform, at a temperature between 20 and 12 ° C.

To isolate the resulting product, the reaction mixture was freed from the solvent and the residue was stirred with water and an organic solvent. The organic phase is separated, worked up and purified in the usual manner.

According to a preferred embodiment, it is expedient to proceed from a 1-hydroxy-1-phenyl-2-triazolylethane derivative, which in a suitable inert solvent is converted into an alkali metal alkoxide corresponding to the above general formula IV by treatment with an alkali metal hydride or amide. which, without isolation, is immediately reacted with the halide of the general formula

V, whereby compounds of formula II are obtained in a single stage to produce the alkali metal halide.

According to another preferred embodiment, both the preparation of the alkoxide IV and the reaction with the halide V are conveniently carried out in a two-phase system, such as a mixture of aqueous, sodium or potassium hydroxide and toluene or methylene chloride, with the addition of a phase transfer catalyst such as ammonium or phosphonium compounds.

The starting materials of the formula (II) can also be obtained by the addition of:

b) reacting the corresponding 1-hydroxy-1-phenyl-2-trlazolylethanes corresponding to the aloxides of the general formula IV with the corresponding acid anhydride in a manner known per se, for example in molar amounts, in the presence an acid in the presence of an acidic or basic catalyst, for example sodium acetate, at a temperature between 0 and 150 ^CThe compounds of formula (II) are then isolated in the usual manner.

The 1-hydroxy-1-phenyl-2-triazolylethane derivatives from which the alkoxides of formula (IV) are derived are known (see DOS No. 24 31417 and DOS No. 25 47 953).

Examples of the 1-phenyl-2-triazolylethyl derivatives of the general formula (II) used as starting materials in the process according to the invention are the compounds summarized in Tables 1 and 2 below.

TABLE 1

<img file="CS199530B2_D0003.tif" />

<td> Rn,. ·</td><td>R²</td><td>Melting point (° C) or refractive index</td>

<td>2,4-Cb</td><td>—CH2 —CH = CH2</td><td>n_D²⁰ = 1,545</td>

<td>4-0— / о /</td><td>—CH2 —CH = CH2</td><td>n_D²² = 1,570</td>

<td>4-Cl</td><td>—CH2 —CH = CH₂</td><td>140 (x HCl)</td>

<td></td><td>TABLE 2</td><td></td>

<img file="CS199530B2_D0004.tif" />

<td rowspan="2">R "</td><td colspan="2">WHAT-"* (lib)</td>

<td>R⁴</td><td>Melting point (° C)</td>

<td>4-Cl</td><td>С (СНз) з</td><td> 135—136</td>

<td>2,4-CL ·</td><td>С (СНз) з</td><td>149—151 (x HNO3)</td>

The starting metal chlorides of formula III are generally known, readily available compounds.

Suitable diluents for use in the process according to the invention are all inert organic solvents, which preferably include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone,

Like 1 ethers such as diethyl ether and dioxane.

The reaction temperatures of the process according to the invention can be varied within a wide range. Generally, the temperature is between 0 and 40^CC, preferably at a temperature of 15 to 30 ° C.

In the process according to the invention, a stoichiometric amount (depending on the oxidation degree of the metal) of the compound of the formula II is used per mole of the metal salt of the formula III. This ratio can be exceeded up to 20 rpm without reducing the yield.

199330

The reaction mixture is worked up in the 'organic-chemistry' manner by conventional means, for example by suctioning off the precipitated complex and purifying the product by recrystallization, for example from alcohol.

The active compounds according to the invention show a strong fungitoxic effect. The substances at concentrations necessary for combating fungi do not damage crop plants. For these reasons, these compounds are suitable for use as agents for protecting plants against fungal diseases. The fungicidal agents are used in plant protection to combat fungi from the classes of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ashcomycetes, Basidiomycetes. and Deuteromycetes.

The active compounds according to the invention have a broad spectrum of action and can be used against parasitic fungi attacking above-ground parts of plants, attacking plants from soil, as well as agents of fungal diseases transmitted by seed. The active compounds described above have been particularly effective against parasitic fungi on aerial parts of plants.

As plant protection agents, the active compounds according to the invention can be used with very good results in combating various types of Venturia, such as against the agent of scabs against true powdery mildews such as apple powdery mildew (Podosphaera leucotricha) and powdery mildew and other diseases. cereals.

Particularly preferred is the partial systemic effect of the disclosed compounds, which makes it possible to protect plants against infestation by the fungus of the apple tree (Fusicladium dendriticum), by applying to the conventional means, such as solutions, the aerial parts of the plants.

The active compounds according to the invention can be applied by spraying the seed or soil, or for treating the active substance with water into above-ground parts of plants by means of soil and roots.

As plant protection agents, the active compounds according to the invention can be used for emulsions, suspensions, powders, pastes and granules. These compositions are prepared in a manner known per se, for example - by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases present - under pressure and / or - solid carriers, optionally with surfactants, i.e. emulsifiers and and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. As a liquid solvent, the following are possible in principle: aromatics such as xylene, toluene, benzene or alkylnaphthalenes, - chlorinated aromatics or chlorinated - aliphatic hydrocarbons, such as chlorobenzenes, - chlorethylenes or methylene chloride, - aliphatic hydrocarbons, - such as cyclohexane or paraffins, - for example petroleum fractions, alcohols, - - as butanol - or glycol, as well as 1 - their ethers and esters, further - ketones such as acetone, methyl ethyl ketone, methyl isobutyl8 ketone - or cyclohexane, strongly polar - solvents, such as dimethylformamide and dimethylsulfoxide; and water. By liquefied gaseous fillers or carriers is meant those liquids which are - at normal temperature and at normal pressure - gaseous, for example, aerosol propellants, for example dichlorodifluoromethane or trichlorofluoromethane. Suitable solid carriers are: - natural stone - meal, such as kaolins, alumina, - talc, - chalk, - quartz, attapulgite, montmorillonite - or - diatomaceous earth, - and synthetic - stone meal, - - such as highly disperse silicic acid, alumina and silicates. Suitable emulsifiers are non-ionic and anionic emulsifiers, such as polyoxyethylene esters of fatty acids, polyoxyethylene ethers of fatty alcohols, e.g.

The active compounds according to the invention may be present in the formulations in admixture with other active substances, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird preservatives, growth agents, plant nutrients and soil improvers.

The concentrates according to the invention generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight. '

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

When the active ingredients are used as foliar fungicides, their concentrations in the application formulations can be varied within a wide range. These concentrations generally lie between 0.1 and 0.00001 wt. %, Preferably between 0.05 and 0.0001 wt.

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.

To treat the soil should be used on. every m³ 1 to 1000 g, preferably 10 to 200 g, of active compound.

The versatility of the compounds of the invention follows from the following examples.

Example 1 - A

Protective test for apple scab (Fusiclaudium)

Solvent:

4.7 parts by weight - acetone.

Emulsifier:

·· .. ..⁹

0.3 parts by weight of alkylaryl polyglycol ether.

Water: ..... ......

parts by weight.

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

By spraying, young apple seedlings in the 4-6 leaf stage are sprayed until wet. The plants are kept in a greenhouse at 20 ° C and a relative humidity of 70% for 24 hours, after which they are inoculated with an aqueous suspension of a fungus of Fusicladium dendriticum (apple scab) and incubated for 18 hours in a humid chamber at. 18 to 20 ° C and 100% relative humidity.

The plants are then transferred again to the greenhouse for 14 days.

days - after inoculation - an infection of the treated seedlings is found. The values ​​obtained are recalculated to% attack.

0-% means no attack, 100% represents - complete attack of plants.

The active substances, active substance concentrations and - results obtained - are given in the following table:

TABLE A

Protective test for apple scab (Fusicladium)

Active substance . - x

Attack in%. active substance concentration 0,0025%

<img file="CS199530B2_D0005.tif" />

186669

Active substance

Attacking in% at Mtisa concentration

0.0025% X

<img file="CS199530B2_D0006.tif" />

<img file="CS199530B2_D0007.tif" />

Ρ-ΙΜΚΜλ-Φ® · .. ·· ......

Protektlvní - --test - on apple powdery mildew (Podosphaera)

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 to achieve the desired concentration of the active ingredient in the spray is mixed with the stated amount of solvent and the concentrate is diluted with the indicated amount of water containing the above ingredients.

By spraying, young apple seedlings having 4-6 leaves are sprayed until wet. The plants are kept for 24 hours in a greenhouse at 20 ° C and a relative air humidity of 70 ° / o, then inoculated by dusting with spores of Podosphaera leucotricha (powdery mildew) and - placed in a greenhouse at 21 ° C. to 23 - = C and relative - air humidity of about 70 percent.

The infestation of the treated seedlings was determined on days after inoculation. The obtained values ​​are converted to the attack in ° / o.

% - means no infection - 100% represents complete infestation of plants.

Active substances, concentrations of active substances - as well as - achieved - results are shown in the following table:

TABLE B.

Protective test for apple powdery mildew - Podosphaera.

% Attack

Active substance at concentration of active substance

0,0025 %

<img file="CS199530B2_D0008.tif" />

Active substance

Infestation in ® / o at active substance concentration of 0.0025%

<img file="CS199530B2_D0009.tif" />

CC (CH₃)₃

<img file="CS199530B2_D0010.tif" />

^WHOSEAND

<img file="CS199530B2_D0011.tif" />

И)

<img file="CS199530B2_D0012.tif" />

(9)

953'0

Example С

Protective test (treatment of shoots) for Erysiphe graminis var. hordei (leaf-destroying mycosis),

To prepare a suitable active ingredient, 0.25 part by weight of the active compound is stirred in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether as emulsifiers and 975 parts by weight of water are added. The concentrate is then diluted with water to the desired final concentration.

To determine the protective effect, young barley plants [species ^: In the single leaf stage, they are sprayed with the right active ingredient until wetted and sprayed with spores of Erysiphe graminis var. hordei.

After six days at which the plants were grown at a temperature of 21 ° C to 22 ° C, and at a temperature of 21 ° C. 80 to 90% air humidity, the extent of the disease on the plants is 'evaluated'. The degree of infestation is expressed as a percentage of infestation of the untreated control plants, with 0% meaning. no attack and 100 ° / o. the same infestation as in the untreated control plants. Test substance. is ... the more effective the lower the degree of attack. .

active ingredient, spray concentration of active ingredient and range.

TABLE · C

Protective test (treatment of shoots) for Erysiphe graminis var. 'hordei

Active substance

Concentration of the active substance in the spray (w / w%)

Challenge v. % infestation of untreated control plants untreated

<img file="CS199530B2_D0013.tif" />

<td></td><td> 100</td>

<td> 0,025</td><td> 100</td>

M) (z)

CH_OFCH * CH_OF , ^whoseof

Cl *

0,025;·.' 12,5

0,025 8,8

0.025 3.8 (S)

Active substance

- Concentration of the active substance in the spray (mass%)

Infestation in% attack on untreated control plants

<img file="CS199530B2_D0014.tif" />

0,025

0,0

<img file="CS199530B2_D0015.tif" />

0,025

0,0

<img file="CS199530B2_D0016.tif" />

0,0

<img file="CS199530B2_D0017.tif" />

0.0 x 4 H2O

<img file="CS199530B2_D0018.tif" />

(9)

0,0

Example D

Test for systemic action on powdery mildew (Erysiphe graminis var. Hordei) - fungal disease of grain shoots

The active ingredient is used in the form of powdered seed. This mordant is prepared by mixing the respective active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered concentration.

The barley seed is treated by shaking with prepared mordant in a closed glass container. The seed is then sieved (3 x 12 grains) 2 cm deep into pots containing a mixture of one volume of standard peat - soil and one volume of quartz sand. Germination and emergence of plants takes place under favorable conditions in the greenhouse. - 7 - days after sowing, when the barley plants develop their first leaf, they shall be dusted. fresh spores of the fungus Erysiphe graminis var. hordei and further cultured at a temperature of 21 - to - 22 ° 0 and 80 - to - 90 -% -relative air humidity under a 16-hour illumination daily. - Within - 6 days - the leaves of the plants will also form - typical - patches of powdery mildew.

The degree of infestation is - expressed as a percentage - infestation of untreated - control plants, - - where 0 - o / o means - no infestation and - 100 - -% - - same - infestation - as - for untreated control - plants. The active substance is, the more effective the lower the extent of the disease.

Active substances, - the concentration of active substances in mordants, mordant consumption and the percentage of disease content are given in the following table:

TABLE - D

Systemic effect test on powdery mildew of Erysiphe graminis var. hordei

Active substance - Concentration of active substance in the mordant (m / m) not infested

Infestation Consumption in% - infestation agents - not (in g / kg of seed-borne seed) of control plants

S Ca-NW &amp; S. I Ztt CH-NUCS 'II,}

<td></td><td></td><td> 100</td>

<td> 25</td><td> 10</td><td> 100</td>

<img file="CS199530B2_D0019.tif" />

(?)

10 0,0

10 - - - 0,0

Active substance ¹⁸

End- Consumption Challenge trace morldla v. % 'ineffective (in g / kg daily' not * seed ') treatment in mollusc control (% by weight) of plants

<img file="CS199530B2_D0020.tif" />

10 0,0

Í0 ^; 0,0

<img file="CS199530B2_D0021.tif" />

10 0,0

10 0,0

Example E

Test of the effect on mycelial growth

Nutrient medium used:

parts by weight of agar-agar,

200 parts by weight of potato broth, 5 parts by weight of malt, parts by weight of dextrose, parts by weight of peptone, parts by weight of sodium phosphate,

0.3% by weight of calcium nitrate.

Ratio of solvent mixture to medium:

ШтоСпоПШ lysysuccinic mixtures

100 ALIGN! parts by weight of agar broth. :

Composition of solvent mixture:

0.19 parts by weight of dimethylformamide or acetone,

0.01 part by weight of alkylaryl polyglycol colether as emulsifier,

1.80 parts by weight always

- parts by weight of the solvent mixture.

20

The amount of active ingredient required to achieve the desired concentration of active ingredient in the broth is mixed with said amount of solvent mixture. The concentrate was thoroughly mixed with the liquid broth cooled to 42 ° C at the indicated weight ratio and poured into 9 cm diameter Petri dishes. Control plates are also prepared without admixtures of the active preparation.

After the culture medium has cooled and solidified, the plates are inoculated with each of the fungi listed in the table below and incubated at a temperature of approx.^CC.

Evaluation is based on fungal growth rates after 4 to 10 days. The evaluation compares the radial growth of the mycelium on the treated broths with that on the control broths. Mushroom growth is assessed using the following scale:

no fungus growth, up to 3 very strong growth suppression, up to 5 moderate growth inhibition, up to 7 moderate growth inhibition, growth same as untreated control plates.

The active substances, active substance concentrations and results obtained are shown in the following table. Individual trial fungi are indicated in the table by Roman numerals with the following meaning:

I = Colletotrichum coffeanum

II = Botritis clnerea

III = Verticilllum alboatrum

IV = Phytophthora cactorum

V = Pyrlcularia oryzae

VI = Helminthosporium gramlneum

TABLE E

Test of mycella growth (active substance concentration 10 ppm)

Active substance

Experimental mushrooms

I II III IV V VI

CHrCH = CH x HCl (2 / 2АЫ)

<img file="CS199530B2_D0022.tif" />

Preparation of effective,. The following examples illustrate the invention but are not intended to limit the scope of the invention in any way. ·

Example 1

<img file="CS199530B2_D0023.tif" />

4.25, (0.025 mol) of copper (II) chloride hydrate. dissolve - in - 40. ml of water and solution were added dropwise to a solution of 14.9 g (0.05 mol) of [1- (2,4-chlorophenyl) -2- (1,2,4-triazole) After stirring for 3 hours at room temperature, the solid material is filtered off with suction and washed with diethyl ether and dried to give 13.5 g (75%) of the title compound. - -%⁴ theory) of the bis- | - (1- (2,4-dichlorophenyl) -2- (1,2,4,4-l-4-l-1-enyl) ethyl 1-allyl ether) complex; cuprous chloride, m.p. 158-160 ° C.

Preparation of starting materials

Cl o

25.7 g of -0.1 mol) 1-hydroxy-1- (2,4-dichlorophenyl) -2- (1,2,4-riazol-11-yl) ethane was dissolved in 125 ml dioxane and added dropwise with stirring. to the suspension. 4 g of 80% sodium hydride in 150 ml dioxane. The mixture is refluxed for 1 hour and, after cooling to room temperature, 22.1 g (0.1 mol) of allyl bromide are added to the sodium salt thus obtained. The reaction mixture was refluxed for 8 hours, then allowed to cool and the solvent. distills off. Water and methylene chloride were added to the residue, the organic phase was separated and dried over sodium sulfate; se²² «Evaporate., Like &lt;. residaksseasian.29r-3g. {1- (2,4сИаМоПеау 1) 32, - [lL ^^ - itilieazclr-l.yjeethyj ·] uallylethermo, index -, house. hb²2 - == J, S45, which corresponds to .. Practically Aquantitous. .

<img file="CS199530B2_D0024.tif" />

jOH

25.6 g (01.1 mol) óZój.1_ч2_and4: 1- (1-yl) -2,4-dihydroiiloacetophenone. 300 ml (of methanol) to the solution was filtered at 5 ° C to 10 ° C at room temperature._!11, part 4, type 4, -g _; m.p. The mixture is still present. . 1 hour, .mix for - ^ ед ^ ё. .then. se. After heating for 1 hour, the solvent was distilled off and the residue was briefly heated with 200 ml of water and 40 ml of concentrated hydrochloric acid. After alkalization with sodium hydroxide solution. The solid product may be filtered off and recrystallized from ligroin / isopropanol to give 21.3 g. (82,% (theory)., 1-: 1-cyano) -1- (2,4-dichlorophenyl) -2- (1,2,4-chloro-1-) ethane o melting point - 90 ec.

Whose

<img file="CS199530B2_D0025.tif" />

N

269 g (1 mol) of n-bromo-2,4-dichloroacetophenone is dissolved in 250 ml of aietonitrile and the solution obtained. to a suspension of 69 g (1 mol) was added dropwise. 1,2,4-triazole and 150 g of potassium carbonate in 2 L of refluxing acetonitrile. cooler. . After heating for 20 hours to reflux, the soils were cooled. the suspension is filtered, - the solvent is evaporated from the filtrate,. the residue is taken up in ethyl acetate. solution^: The mixture was washed with water and dried (Na2 SO4) and the solvent was evaporated. The residue - after evaporation of the ethyl acetate crystallizes after addition of -isopropanol. After recrystallization from a mixture of ligroin and isopropanol, 154-g (60% of theory) of ω- (1,2,4-triazol-1-yl-2-N-dichloroacetophenone) having a temperature of -1 ° C was obtained.

Example 2

<img file="CS199530B2_D0026.tif" />

)199330

1.7 g (0.0083 mol) of manganese chloride are dissolved in 40 ml of water and the solution is added dropwise to the solution with 5.3 g (0.0166 mods). . [Ir (4-Phenoxy-phenyl) -2- (1,2,4-trlazol-1-yl) -ethyl] -ethyl ether in 1100 ml of ethanol. After stirring for 1.5 hours at room temperature, the precipitated oil was decanted and triturated with petroleum ether to crystallize. Aspiration and drying of the solid material yielded 5.5 g (87%) of bis (l- (4-phenoxyphenyl) -2- (1,2,4-triazolr-1-yl) ethyl) allyl ether complex | 180 DEG-200 DEG C .;

<img file="CS199530B2_D0027.tif" />

Dissolve 3.5 g (0.025 mol) of zinc chloride in 40 ml of water and dissolve the solution. with stirring, dropwise addition of 17 g (Q; 05 mol). 1-trichlorophenyl) (1-trimethylacetoxy) -2-

(1,2 ', 4-trlazol-1-yl) ethane in 100 ml of ethanol. After stirring at room temperature for 3 hours, the solid was filtered off with suction and dried. There was obtained 13.1% (72% of theory) of the hippocuplex; melting point 160^CC.

Transport of the starting substance

Cí o

CO-C₃) э

Dissolve 25.8 g (0.1 imol) of 1- (2,4-dichlorophenyl) -1-η 6 -benzoyl-2- (1 ', 2,4-η 5 -gol-1-ol) ethane in 200 ml dioxane and dissolve the solution. 6 g of 80% sodium hydride and 100 ml of dioxane are added dropwise with stirring. The resulting mixture was stirred. approx. The mixture was heated at reflux for 0.5 hour. under a reflux condenser, then cooled to temperature. 24 g (0.2 mol) of chlorobenzoyl chloride was added dropwise to the room and the sodium salt thus obtained. acids.ve. 100 ALIGN! The reaction mixture is stirred overnight at room temperature, then the solvent is distilled off in vacuo and the residue is stirred for 30 minutes. excerpts. chloroform. . The chloroform solution is washed with water, dried with sodium hydroxide and washed with water._t it evaporates again. The residue is directly_Řuse for further reaction.

The compounds summarized in Table 4 can also be prepared in an analogous manner to Examples 1 to 3:

TABLE 4

<img file="CS199530B2_D0028.tif" />

<td>Example number</td><td>Me</td><td>Rn</td><td>R¹</td><td>X</td><td>AND_p</td><td>Melting point ГС)</td>

<td> 4</td><td>Cu</td><td>4-O-</td><td>—О — CH2 — CH == CH2</td><td> 2</td><td>C12</td><td> 90—100</td>

<td> 5</td><td>Šn</td><td>4-0- &lt;g&gt;</td><td>—О — CH2 — CH = CH2</td><td> 2</td><td>C14</td><td> 139—142</td>

<td> 6</td><td>Sn</td><td>2,4-С12</td><td>—O — CH2 — CH = CH2</td><td> 2</td><td>C14</td><td> 126—131</td>

<td> 7</td><td>Cu</td><td>2.4-C12</td><td>—О — СО — С (СНз) з</td><td> 2</td><td>C12</td><td> 190—198</td>

<td> 8</td><td>Mn</td><td>2,4-Clz</td><td>—O — CH2 — CH = CH2</td><td> 2</td><td>C12</td><td>148—152 (x 4HZO)</td>

<td> 9</td><td>Zn</td><td>2,4-CL ·</td><td>—O — CH2 — CH = CH2</td><td> 2</td><td>C12</td><td> 128—130</td>

L