DE3921502A1 - New fungicidal imidazolyl-substd. di:phenyl-propyne cpds. - e.g. 3-(2,4-di:fluorophenyl)-3(1-imidazolyl)-3-phenyl-1-propyne - Google Patents

Abstract

Imidazolyl-substd. diphenyl-propynes (I) and their addn. salts and metal salt complexes are new, where R1, R2 = H or fluorine; Y = halogen; 1-4C alkyl; 1-4C alkoxy; 1-4C alkylthio; 1-2C haloalkyl or haloalkoxy contg. 1-5 halogens; phenyl; or phenoxy; m = 0, 1, 2 or 3. Starting materials (II) are also claimed. USE/ADVANTAGE - Cpds. (I) are plant fungicides. They have a good plant tolerance and are esp. useful against fungal diseases on cereals and rice. Cpds. (I) can be formulated conventionally and can be used in concns. of 0.0001-1 wt.% to treat plants and 0.00001-0.1 wt.% to treat soil, and in amts. of 0.01-50 g/kg to treat seeds. Cpds. (I) have better activity than 3,3-diphenyl-3-(1-imidazolyl)-propyne known from DE2128700 and DE3307909. Starting materials (II). In an example, (i) 2,4-difluoro-benzophenone (VII) (20.3g) was converted in a metal-organic reaction using acetylene in the presence of potassium tert. butylate into 1-(2,4-difluorphenyl)-1-phenyl-2-propyn-1-ol (II) (22.8g) and (ii) acetic anhydride (14.5g) was added at 60-70 deg.C to a mixt. of the prod. from (i) and imidazole (45g). The mixt. was treated at 120 deg.C, cooled, taken up in dichloromethane, washed, dried and concd. Chromatography gave 3-(2,4-difluorophenyl)-3-(1-imidazolyl) -3-phenyl-1-propyne (I) (5.6g); m.pt. 100 deg.C.

Description

The present invention relates to new imidazolyl-propyne derivatives, a process for their manufacture and their use as fungicides.

It has already been known that certain 3-azolyl propynes possess fungicidal properties (cf. DE-PS 21 28 700 and DE-OS 33 07 909). For example, 3,3-Diphenyl-3- (imidazolyl-1-yl) propin to combat of mushrooms. The effect of this substance but is not always with low application rates quite satisfactory.

There have now been new imidazolyl propyne derivatives of formula  

in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or phenoxy and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes.

It was also found that imidazolyl-propyne derivatives of formula (I) and the acid addition salts and metal salt complexes when propinols formula  

in which R¹, R², Y and m have the meanings given above, either

• a) with imidazole of the formula in the presence of an anhydride of the formula (R³-CO) ₂O (IV) in which R³ is alkyl having 1 to 4 carbon atoms or phenyl, or in the presence of an acid chloride of the formula R⁴-CO-Cl (V) in which R⁴ is alkyl with 1 to 4 carbon atoms or represents phenyl, or
• b) with imidazole derivatives of the formula in which X represents oxygen or sulfur, if appropriate in the presence of a diluent,

and, if appropriate, subsequent to those thus obtained Compounds of formula (I) an acid or a metal salt added.

Finally, it was found that the new imidazolyl propyne derivatives of the formula (I) and their acid addition salts and metal salt complexes very good fungicidal Possess properties.  

The substances according to the invention surprisingly show a much better one when fighting fungi Effectiveness as the 3,3-diphenyl-3- (imidazol-1-yl) propyne, which is a constitutionally similar, previously known Active ingredient is the same direction of action.

The imidazolyl propyne derivatives according to the invention are generally defined by formula (I). In this Formula are preferably

R¹ is hydrogen or fluorine,
R² for hydrogen or fluorine,
Y for fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trichloromethyl, trifluoromethyl, trichloromethoxy, trifluoromethoxy, phenyl or phenoxy and
m for the numbers 0, 1, 2 or 3.

If m is the number 2 or 3, Y can be the same or different leftovers.

Preferred substances according to the invention are also addition products from acids and those imidazolyl-propyne derivatives of formula (I) in which R¹, R², Y and m have the meanings for these residues or this index has already been mentioned as preferred.  

The acids that can be added preferably include Hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, Nitric acid, mono- and bifunctional carboxylic acids and Hydroxycarboxylic acids, such as. B. acetic acid, maleic acid, Succinic acid, fumaric acid, tartaric acid, citric acid, Salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids, such as B. p-toluenesulfonic acid and 1,5-naphthalene disulfonic acid.

Preferred compounds according to the invention are also Addition products from salts of metals from II to IV. Main and I. and II. As well as IV. To VIII. Subgroup of the periodic table of the elements and those Imidazolyl-propyne derivatives of the formula (I) in which R¹, R², Y and m have those meanings for this Residues or this index already mentioned as preferred were.

Here are salts of copper, zinc, manganese, magnesium, Tin, iron and nickel are particularly preferred. Anions of these salts are those which derived from those acids that are too physiological compatible addition products. Particularly preferred such acids are in this context the hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, also phosphoric acid, Nitric acid and sulfuric acid.

Examples of substances according to the invention are those in Imidazolyl propyne derivatives listed in the following table called.  

Table 1

If 1- (2,4-difluorophenyl) -1-phenyl-2-propyn-1-ol is used and imidazole as starting materials and acetic anhydride as a further reaction component and as a diluent, so can the course of the method according to the invention Variant (a) using the following formula are illustrated:  

If 1- (2,4-difluorophenyl) -1-phenyl-2-propyn-1-ol is used and thionyl-bis-imidazole as starting materials, so the course of the method according to the invention can be variant (b) Illustrated by the following formula scheme will:

The in the implementation of the method according to the invention Propinols required as starting materials are generally defined by formula (II). In this Formula R1, R2, Y and m preferably have those Meanings already related to the description the substances of the formula (I) according to the invention preferably called for these residues or the index m were.

The propinols of the formula (II) have not yet been used known. They can be made by using ketones of the formula

in which R¹, R², Y and m have the meanings given above, with acetylene in the presence of a base and in the presence a diluent.

The in the preparation of the propinols of the formula (II) ketones of the formula (VII) required as starting materials are known or can be made by known methods produce in a simple manner.  

The bases come in the manufacture of the propinols Formula (II) according to the above procedure all for such Reactions usual strong organic and inorganic Bases into consideration. Are preferably usable Alcohols, such as potassium tert-butoxide, also amides, such as Sodium hydride, and further organo-lithium compounds, like butyl lithium.

As diluents come in the manufacture of Propinols of formula (II) all according to the above procedure inert organic solvents customary for such reactions Solvents in question. Ether can preferably be used, such as diethyl ether, dioxane or tetrahydrofuran.

The reaction temperatures can be in the preparation of the Propinols of formula (II) according to the above procedure can be varied within a certain range. Generally one works at temperatures between 0 ° C and 30 ° C, preferably between 5 ° C and 25 ° C.

The above process for the preparation of the propinols Formula (II) is just like the process according to the invention generally carried out under normal pressure.

When performing the above manufacturing process of propinols of the formula (II) is set to 1 mol an excess of ketone of formula (VII) in general of acetylene and 1 to 3 moles of base. The workup takes place according to usual methods. Generally goes one so that the reaction mixture with aqueous Ammonium chloride solution added, the organic phase separates, washes and constricts.  

The in the implementation of the method according to the invention Variant (a) required as reaction components Anhydrides are generally defined by the formula (IV). In this formula, R³ is preferably Methyl, ethyl or phenyl. The anhydrides of formula (IV) are known.

The in the implementation of the method according to the invention Variant (a) continues as reaction components usable acid chlorides are represented by the formula (V) generally defined. In this formula, R⁴ is preferably for methyl, ethyl, n-propyl or phenyl.

The acid chlorides of formula (V) are just like that Compounds of the formulas (III) and (VI) are generally known Organic Chemistry Substances.

When carrying out the method according to the invention according to variant (b), all for such reactions customary inert organic solvents be used. Are preferably usable polar solvents such as dimethylformamide and dimethyl sulfoxide, and also halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzenes.

The reaction temperatures can be carried out of the inventive method both when working according to variant (a) and variant (b) can be varied within a wide range. in the generally one works at temperatures between 20 ° C. and 160 ° C, preferably between 50 ° C and 140 ° C.  

The method according to the invention is used both when working according to variant (a) and variant (b) in generally carried out under normal pressure.

When carrying out the method according to the invention variant (a) is based on 1 mol of propinol Formula (II) generally 2 to 8 moles of imidazole Formula (III) and 1.5 to 3 moles of anhydride of the formula (IV) or an acid chloride of the formula (V). The workup takes place according to usual methods. In general one proceeds in such a way that the reaction mixture in one absorbs little miscible organic solvent with water, washes with water, dries and concentrates.

When carrying out the method according to the invention According to variant (b), 1 mol of propinol is used Formula (II) generally 2 to 8 moles of imidazole derivative of the formula (VI). The processing takes place again according to usual methods.

The imidazolyl propyne derivatives of the formula (I) can be found in Acid addition salts or metal salt complexes transferred will.

For the preparation of acid addition salts of the compounds of formula (I) are preferably those Acids in question that are already associated with the Description of the acid addition salts according to the invention were mentioned as preferred acids.  

The acid addition salts of the compounds of formula (I) can be made in a simple manner using conventional salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. B. hydrochloric acid can be obtained and in a known manner, e.g. B. isolated by filtering and optionally by washing with an inert organic solvents can be cleaned.

For the production of metal salt complexes of the compounds of the formula (I) are preferably those salts of metals in question that are already related to the description of the metal salt complexes according to the invention were mentioned as preferred metal salts.

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary methods be so. B. by dissolving the metal salt in Alcohol, e.g. As ethanol, and adding to compounds of formula (I). One can know metal salt complexes in known Way, e.g. B. by filtering, isolating and optionally clean by recrystallization.

The active compounds according to the invention have a strong microbicidal action Effect on and can be used as fungicides will.

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

Some pathogens are exemplary but not limiting of fungal and bacterial diseases that under the generic terms listed above fall, called:

Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus;
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the concentrations necessary to combat plant diseases allows treatment from above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention are particularly suitable to combat cereal and rice diseases, such as Erysiphe, Leptosphaeria, Pseudocercosporella, Pyricularia and pellicularia.

The active ingredients can depend on their respective physical and / or chemical properties in usual formulations are transferred, such as solutions, Emulsions, suspensions, powders, foams, pastes, granules, Aerosols, very fine encapsulations in polymers Substances and in coating compositions for seeds, as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surfactants Agents, ie emulsifiers and / or dispersants  and / or foam-generating agents. In case of Use of water as an extender can e.g. Belly organic solvents used as auxiliary solvents will. Essentially come as liquid solvents in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, Alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous Extenders or carriers are such liquids meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers in question: e.g. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; come in as solid carriers for granules Question: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents  come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used in the formulations in a mixture with other known active ingredients are present such as fungicides, insecticides, acaricides and herbicides as well as in mixtures with fertilizers and growth regulators.  

The active ingredients as such, in the form of their formulations or the application forms prepared from it such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble powders, dusts and granules be applied. The application is done in the usual way Way, e.g. B. by pouring, spraying, spraying, scattering, Dusting, foaming, brushing, etc. It it is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or inject the active ingredient into the soil yourself. It can also treat the seeds of the plants will.

When treating parts of plants, the drug concentrations can in the application forms in one larger range can be varied. They generally lie between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g is required.

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

The production and use of the invention Active ingredients are illustrated by the following examples.

Manufacturing examples Example 1

In a mixture of 22.8 g (993 mmol) of 1- (2,4-difluoro phenyl) -1-phenyl-2-propin-1-ol and 45 g (0.66 mol) Imidazole 14.5 g at 60-70 ° C with stirring (142 mmol) acetic anhydride was added dropwise. More are heated 6 hours at 120 ° C and the reaction mixture takes off upon cooling in dichloromethane. The mixture is with Shaken water, dried over sodium sulfate and by removing the solvent under reduced pressure Pressure reduced. The remaining residue is with a mixture of dichloromethane / ethanol = 99: 1 as the eluent chromatographed on silica gel. By narrowing of the eluate, 5.6 g (20.5% of theory) of 3- (2,4-difluorophenyl) -3- (imidazol-1-yl) -3-phenyl-1-propyne in the form of a solid with a melting point of 100 ° C.  

Production of the starting substance

Acetylene is introduced into a mixture of 14.6 g (0.13 mol) of potassium tert-butoxide in 140 ml of tetrahydrofuran at 20 ° C. with stirring for 1 hour. A solution of 20.3 g (93 mmol) of 2,4-difluoro-benzophenone in 90 ml of tetrahydrofuran is then added dropwise while acetylene is still passed in. The reaction mixture is stirred for a further 1 hour and then 400 ml of saturated, aqueous ammonium chloride solution are added. The organic phase is separated off and the aqueous phase is extracted with dichloromethane. The combined organic phases are concentrated by stripping off the solvent under reduced pressure. The remaining residue is taken up in dichloromethane, the resulting solution is washed with water, dried over sodium sulfate and the solvent is removed under reduced pressure. This gives 22.8 g (100% of theory) of 1- (2,4-difluorophenyl) -1-phenyl-2-propyn-1-ol.
1 H-NMR (CDCl₃, 200 MHz):
δ = 2.85 (s, 1H), 3.6 (broad, 1H), 6.66-6.92 (m, 2H), 7.22-7.39 (m, 3H), 7.53- 7.62 (m, 2H), 7.67-7.82 (m, 1H) ppm.

According to the method given in Example 1 the substances listed in Table 2 below Formula (I) prepared.

Table 2

Examples of use

In the following examples of use, the Compound of the formula below as Comparative substance used:

(Known from DE-PS 21 28 700 and DE-OS 33 07 909).  

Example A Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective effectiveness, spray dew dampens young plants with the active ingredient preparation. After the spray coating has dried on, the plants sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain at 20 ° C and 48 hours 100% relative humidity in an incubation cabin.

The plants are grown in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

This test shows that in Examples 1 and 3 disclosed substances according to the invention an essential better efficacy than the comparison substance (A).  

Example B Erysiphe test (barley) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective efficacy one splashes dew dampens young plants with the active ingredient preparation. After the spray coating has dried on, the plants with spores of Erysiphe graminis f.sp. hordel pollinated.

The plants are grown in a greenhouse at a temperature of 20 ° C and a relative humidity of about 80% set up to develop mildew pustules to favor.

Evaluation is carried out 7 days after the inoculation.

This test shows that in Examples 1, 2 and 4 disclosed substances a much better effectiveness than the reference substance (A).

Claims (10)

1. Imidazolyl propyne derivatives of the formula in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or phenoxy and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes. 2. Imidazolyl propyne derivatives of the formula (I) according to Claim 1, in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trichloromethyl, trifluoromethyl, trichloromethoxy, trifluoromethoxy, phenyl or phenoxy and
m stands for the numbers 0, 1, 2 or 3. 3. Process for the preparation of imidazolyl-propyne derivatives of the formula in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or phenoxy and
m represents the numbers 0, 1, 2 or 3,
as well as their acid addition salts and metal salt complexes, characterized in that propinols of the formula in which R¹, R², Y and m have the meanings given above, either

• a) with imidazole of the formula in the presence of an anhydride of the formula (R³-CO) ₂O (IV) in which R³ is alkyl having 1 to 4 carbon atoms or phenyl, or in the presence of an acid chloride of the formula R⁴-CO-Cl (V) in which R⁴ is alkyl with 1 to 4 carbon atoms or represents phenyl, or
• b) with imidazole derivatives of the formula in which X represents oxygen or sulfur, if appropriate in the presence of a diluent,

and, if appropriate, subsequent to those thus obtained Compounds of formula (I) an acid or a metal salt added. 4. Fungicidal agents, characterized by a content on at least one imidazolyl propyne derivative Formula (I) according to claim 1 or on an acid addition salt or metal salt complex of an imidazolyl propyne derivative of formula (I). 5. Use of imidazolyl propyne derivatives Formula (I) according to claim 1 or of its acid addition salts and metal salt complexes Fighting mushrooms.   6. Process for combating fungi, characterized in that that one imidazolyl propyne derivatives of the formula (I) according to claim 1 or the acid addition salts thereof or metal salt complexes on the Mushrooms and / or their habitat. 7. Process for the preparation of fungicidal compositions, characterized in that imidazolyl propyne derivatives of formula (I) according to claim 1 or their Acid addition salts or metal salt complexes with Extenders and / or surfactants mixed. 8. Propinols of the formula in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or phenoxy and
m stands for the numbers 0, 1, 2 or 3. 9. Process for the preparation of propinols of the formula in which
R¹ represents hydrogen or fluorine,
R² represents hydrogen or fluorine,
Y represents halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, phenyl or phenoxy and
m represents the numbers 0, 1, 2 or 3,
characterized in that ketones of the formula in which R¹, R², Y and m have the meanings given above, with acetylene in the presence of a base and in the presence of a diluent.