DD209100A5 - PESTICIDES - Google Patents

Abstract

The invention relates to crop protection agents for use in agriculture and forestry. The aim of the invention is the provision of new agents with a strong fungicidal and, in addition, plant growth-regulating action. The plant protection products according to the invention are characterized by a content of azolyl-butyne derivatives of the general formula I in which Ar is 1, optionally substituted phenyl, Ar 2 is optionally substituted phenyl, Az is imidazol-1-yl, 1,2 , 4-triazol-yl or 1,2,4-triazol-4-yl and X is hydrogen or halogen, and their acid addition salts and metal salt complexes in addition to extenders and / or surface-active agents.

Description

AP G07 D / 250 609 62 117 12 j9

2699.83

Pesticides Field of application of the invention

The present invention relates to crop protection compositions containing new azolyl-butyne derivatives, to a process for their preparation and to their use as fungicides and fungi acidity regulators.

Characteristic of the known technical solutions

It has already been disclosed that H-3-rityl-azoles, for example 1-triphenylmethylimidazole or 1-triphenylmethyl-1,2,4-triazole, have good fungicidal properties (cf. US Pat DS-PS 1 670 976 and DE-PS 1 795 249). However, their action is not always fully satisfactory in all indications of calibration, especially in the case of low Aufwecfimengen and Konzentra!

Object of the invention

The aim of d & r Srfiadups is to provide new compounds with improved fungicidal activity.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties, which are suitable as "tVirkstoff in pesticides.

AIa active ingredient in the new Schädlebbeksmungsungsniteln were new azolyl-butyne derivatives of the general formula

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Ar ¹

X-CSO-CH ₂ -C-Az (I),

²

in which

Ar is optionally substituted phenyl,

ρ Ar represents optionally substituted phenyl, Az represents imidazol-1-yl, 1,2,4-triazol-1-yl or 1,2,4-tria-

zol-4-yl and X is hydrogen or halogen,

and their acid addition salts and metal salt complexes are found ·

It has furthermore been found that the azolyl-butyne derivatives of the formula (I) are obtained when oarbinols of the formula

AT ¹

Η-ΟΞΟ-OH ₂ -O-OH (II),

¹ Я

in which

1 2 Ar and Ar have the abovementioned meaning,

with azolides of polybasic inorganic acids of the formula O =Y (Az) _n (IH),

in which

Az has the meaning given above and

Y is sulfur or carbon and η is 2, or

Y is phosphorus and η is 3,

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in the presence of a diluent? and optionally thereafter, the thus obtained Azolylbutin derivatives of Pormel ^, 1

H - C 2 C - CH ₂ - C - Az (Ia),

2

* ¹

in which

1 2 Ar, Ar and Az have the abovementioned meaning,

in a conventional manner with Alkalihypohalogenit.

Optionally, an acid or a metal salt can be added to the compounds of the formula (I) thus obtained.

Finally, it has been found that the new azolyl-butyne derivatives of the formula (I) and their acid addition salts and metal salt complexes have strong fungicidal and plant growth-regulating properties.

Surprisingly, the erfindmigsgeffiäßec. Compounds of formula (I) have a better fungicidal activity than those known from the prior art ST-Tr4.t7l-aeau.e, such as 1-triphenylmethyl-imidazole and I-triphenylmethyl-1,2,4-triazole, which are chemically and operatively obvious compounds. In addition, the compounds of the formula (I) according to the invention show surprisingly good plant growth-regulating action. The active compounds according to the invention thus represent an enrichment of the art.

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The azolyl-butyne derivatives of the invention are generally defined by the formula (I). In this formula, they are preferably

Ar is phenyl which is optionally monosubstituted to disubstituted by identical or different substituents, of which the following are preferably mentioned: halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl and haloalkoxy each having 1 to 2 carbon atoms and 1 to 5 or different halogen atoms, such as fluorine and chlorine atoms, and optionally substituted by halogen-substituted phenyl; Ar represents optionally mono- to disubstituted, identically or differently substituted phenyl, wherein as substituents preferably the phenyl substituents already mentioned for Ar are preferably suitable;

Az is imidazol-1-yl, 1,2,4-triazol-1-yl or 1,2,4-iriazol-4-yl and

represents hydrogen, iodine, bromine or chlorine.

Particular preference is given to those compounds of the formula (I) in which

Ar is optionally monosubstituted to disubstituted by identical or different substituents phenyl, wherein as 3 substituents may be mentioned in particular: fluorine, chlorine, bromine, methyl, 'trifluoromethyl, trifluoromethoxy, phenyl and chloro-phenyl;

ArAr ¹ "represents optionally mono- to disubstituted, identically or differently substituted phenyl, with

in particular, the substituents already mentioned in particular for Ar are suitable phenyl substituents;

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Az for imidazol-1-yl, 1,2,4-triazol-1-yl or 1,2,4-tria-

zol-4-yl and X is hydrogen, iodine or bromine.

Preferred compounds of the invention are also addition products of acids and those azolyl-butyne derivatives

Λ 2 of the formula (I) in which the substituents Ar, Ar, Az and X have the meanings which have already been mentioned as preferred for this ester

The acids that can be added are preferably hydrogen halides, ie ζ. 3. the hydrochloric acid and the hydrobromic acid, in particular the hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as. Acetic acid, maleic acid, behenic acid, fumaric acid, tartaric acid, salicylic acid, sorbic acid and 1,5-2f. Phthalindisulfonic acid.

Other preferred compounds of the invention are addition products of salt © A ѵead metals of II. To IV. Main and the I and II and IV * to VIII · NebengEuppe and those azolyl-butta «derivatives of the formula (I), la To whom the

1 2

Substituents Ar, Ar, Az and X have the meanings that have already been mentioned as preferred for this Heste. Here, salts of copper, zinc, manganese, magnesium, tin, sisens and nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred such acids are in this context, the hydrogen halide acids, such as. 3. the hydrochloric acid and hydrogen fluoride

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acid, phosphoric acid, nitric acid and sulfuric acid,

For example, using 4- (4-СЫогрЬепу1) -4-раепу1-1-butyn-4-ol and thionyl-bis-imidazole as starting materials, the course of the reaction can be represented by the following scheme:

-so.

HH

If, for example, 4,4-diph8nyl-4- (1,2,4-triazol-1-yl) -1-butyne and potassium hypobromite are used as starting materials, the course of the reaction can be represented by the following formula scheme: t

KOBr

- KOH

3r-C = C-CH.

The carbinols required as starting materials for carrying out the process according to the invention are

ael (II) generally defined. In disser omel stand Ar '

ρ and Ar preferably for those meanings that already

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in connection with the description of the substances of the formula (I) according to the invention have preferably been mentioned for these radicals

The Garbinole of formula (II) are known or can be obtained in a known manner by z. 3. reacting the corresponding ketones in the presence of activated aluminum in an aprotic solvent, such as tetrahydrofuran, with propargyl halides at temperatures between -70 and 60 ^° C. (see D3-PS 1 217 368, J. Agr. Food Chem. 78 (1970) and Liebigs Ann. Chenu 682 , 62 (1965)).

The azolides of inorganic acids additionally required as starting materials for the process according to the invention are generally cSe-substituted by the formula (III). In this Forsel, Az preferably represents those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention preferably for this test. I and the indes are preferably the meanings given in the definition of the invention.

The azolides of the formula (III) are generally known compounds of organic chemistry. They werclen preferably generated in situ by z. 3. Thionyl chloride at room temperature to give a solution of N-trimethylsilylinidazole in absolute toluene.

For the reaction according to the invention of the carbinols of the formula (II) with the azolides of the formula (III), preference is given to using polar organic solvents as diluents

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Question. These include, for example, nitriles, such as acetonitrile; Sulfoxides, such as dimethylsulfoxide; Formamides, such as dimethylformamide; Ketones, such as acetone; Ethers, such as diethyl ether and tetrahydrofuran; and chlorinated hydrocarbons, such as methylene chloride and chloroform.

The reaction temperatures can be varied within a larger range in this reaction according to the invention. In general, one works between -60 ⁰ C and 100 ⁰ C, preferably between -50 and 85 ⁰ C,

In carrying out this reaction according to the invention, preferably 2 to 3 mol of the azolide of the formula (III) are employed per mole of the carbinols of the formula (II), the azolide of the formula (III) preferably being generated in situ » Isolation of the compounds of formula (I) is carried out in the usual manner.

For the reaction according to the invention of the azolyl-butyne derivatives of the formula (Ia) with alkali metal hypohalite, suitable diluents are water and also alkali metal hypohalite inert organic solvents. Hierau include, for example, alcohols, never ethanol or ethanol; Ether, Tjie diethyl ether, dioxane or tetrahydrofuran; as well as Zueiphasengemische, such. 3. Et her / 7 / ass he.

The reaction temperatures can be varied in this reaction according to the invention in a larger range. "In general, one works between 0 and 50 ⁰ C, preferably between 0 and ⁰

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In carrying out this reaction according to the invention, 1 to 1.5 mol of hypohalogenite is preferably employed per mole of the compound of the formula (Ia), the alkali metal hypohalite being produced in situ from the corresponding halogen and the alkali hydroxide, in particular sodium and potassium hydrosides ( See also Houben-Weyl, Volume V / 2a, pages 608-10 (1977)). The isolation of the end products takes place in the usual way,

For the preparation of acid addition salts of the compounds of the formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention

The acid addition salts of the compounds of the formula (I) can be prepared in a simple manner by customary salt formation methods, for. 3. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. 3. hydrochloric acid, are obtained and in a known 7 / eise, z. 3. by filtration, isolated and, if appropriate, purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of the formula (I), preference is given to salts of metals of the IIth to IVth major groups and the I. to II. Soraie IVth to VIIIth iTebengruppe, -sobei copper, zinc,. Manganese, magnesium, tin, iron and nickel are exemplified. Possible anions of the salts are those 3etracht derived preferential Tjeise from the following acids: hydrohalic acids, * ліе ζ "3rd acid, hydrochloric and hydrobromic acid, furthermore phosphoric acid, nitric acid and ос

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feisäure.

The metal salt complexes of compounds of the formula (X) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, cf. Ethanol, and addition to the compound of the formula (I). Metal salt complexes can be isolated by filtration in a known manner, z, 3, and optionally purified by crystallization.

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

Cytotoxic fungicides are used to control Plasmodiophoromycetes, Qomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, 3asidiomycete, Эеиъего-myceties.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of above-ground parts of plants, planting and seed and the soil.

As plant protection agents, the active compounds according to the invention can be used with; particularly good result for the control of cereal diseases, such as, for example, the 3rd instar virus (Srysiphe graminis), from Леiskrankneіт: еп, т? іэ s. 3. Pyricularia огузае, of Sphaerotheca species, -.vie з. 3. the organism of the cucumber (opaerotheca fuliginea) as well as PhTtophora-Arrren, 7iie z. 3. against Зггедзг brown blight

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tomatoes (Pnytophthora infestans) are used «

The active compounds which can be used according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

For the mode of action of plant growth regulators gil according to previous experience that an active substance can also exert several different effects on plants. The effects of the substances depend essentially on the time of application, based on the stage of development of the plant, on the amounts of active substance applied to the plants or their environment and on the mode of administration. In any case, growth regulators are intended to influence crops in some desired manner.

Plant growth-regulating substances may, for. B. be used to inhibit the vegetative growth of plants. Such growth inhibition is of economic interest among grasses, among other things, because this can reduce the frequency of grass clippings in ornamental gardens, parks and sports facilities, on roadsides, at airports or in orchards. Also of importance is the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overland pipelines or, more generally, in areas in which heavy plant growth is undesirable.

Also important is the use of growth regulators to inhibit grain elongation. As a result, the risk of killing ("storage") of the plants before harvest is reduced or completely eliminated. In addition, wax

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The use of growth regulators for stalk shortening and stalk augmentation makes it possible to apply higher quantities of fertilizer in order to increase the yield without the risk of the grain being stored.

Sine inhibition of vegetative growth allows for a denser planting in many crops, so that more yields can be achieved relative to the 3odenfläche. The goal of the smaller plants thus obtained is that the crop can be processed and harvested more easily.

The inhibition of the vegetative growth of plants may also result in increased yields, that the nutrients and assimilates are more beneficial to fruit and fruit formation than to the vegetative parts of plants.

Frequency regulators can often be used to promote vegetative growth. This is of great benefit when the vegetative parts of the plant are harvested, but the promotion of vegetative growth may at the same time result in the promotion of generative growth, in that more assimilates are formed, so that more or more fruits are produced.

Yield increases can be achieved in some cases by зідеп squeezing into the plant metabolism, without making changes in vegetative growth noticeable. Furthermore, with Jachatuas regulators, a change in the composition of the plants can be achieved

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in turn can lead to a quality improvement of the Srnteprodukte. For example, it is possible to increase the sugar content in sugar beet, sugar cane, pineapple and citrus fruits, or to increase the protein content in soya or cereals. It is also possible, for example, the degradation of desirable ingredients such. Sugar in sugar beet or cane, with growth regulators before or after harvesting. In addition, the production or the discharge of secondary plant ingredients can be positively influenced. An example is the stimulation of the lata flow in gum trees.

Under the influence of growth regulators, parthenocarp fruits may develop. Furthermore, the sex of the flowers can be influenced. Also, a sterility of the pollen can be produced, which has a great importance in the breeding and production of hybrid seed.

On the one hand, the development of side shoots can be promoted by breaking the apicoid dominance, which may be very desirable, especially in ornamental plant cultivation, even in the presence of inhibition of the plant, but on the other hand it is also possible 3, there is great interest in growing tobacco or planting tomatoes.

Under the influence of regulators of vacuums, the plants of the plants were controlled in such a way that the leaves were exfoliated at a convenient time; becomes. Such defoliation plays an important role in the mechanical Зеегп-ting of the cotton tree, but is also

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ren cultures like ζ. B, in viticulture to facilitate the crop of interest. Defoliation of the plants may also be done to minimize the transpiration of the plants before transplanting.

Likewise can be controlled with growth regulators the fruit case. On the one hand, a premature fruit drop can be prevented. On the other hand, however, the fruit fall or even the fall of the flowers can be promoted to a desired level ("thinning") to break the alternance. Alternating means the peculiarity of some types of fruit to yield very different yields year after year. Finally, it is possible with growth regulators at the time of harvesting to reduce the forces required to detach the fruits in order to facilitate mechanical harvesting or facilitate manual harvesting.

With growth regulators can also accelerate or even delay of the soap of the crop before or after harvest reach. This is a special part of the goal, because this can bring about an optimal adaptation to the needs of the market. In some cases growth regulators may improve fruit colouration. In addition, with growth regulators, a temporal concentration of the soap can be achieved. This creates the "prerequisites for, for example, that tobacco, tomatoes or coffee can undergo a complete mechanical or manual consultation in one operation.

By applying growth regulators, furthermore, the seed or bud rest of the plants can be influenced by ornamental plants

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that the plants, such. As pineapples or ornamental plants in nurseries, germinate, sprout or flower at a time when they usually do not show willingness to do so. Delay of bud sprouting or germination of seeds by growth regulators may be desirable in areas prone to frost to avoid damage from late frosts.

Finally, with growth regulators , a resistance of the plants to frost, drought or high salt content of the soil can be induced. This makes it possible to cultivate plants in areas which are normally unsuitable for this purpose.

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, superfine encapsulations in polymeric substances and in coating compositions for seeds, such as ÜL7-]? ormulierungen.

These formulations are prepared in a known manner, for. 3. by mixing the active compounds with extenders, that is liquid solvents »liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of the use of water as extender, z. 3. also uses organic solvents as auxiliary solvents; яerden. The most suitable liquid solvents are: aromatics, tert-butyl, toluene, or alkyl naphthalenes, ciliary aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes

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or methylene chloride, aliphatic hydrocarbons, cyclohexane or paraffins, S B. Srdölfraktionen, alcohols such as 3utanol 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, and water By liquefied gaseous extenders or carriers are meant those liquids which are gaseous at normal temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and sole dioxide. Suitable solid carriers are: 3. Ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as high-silica, alumina and silicates. Suitable solid carriers for granules are: 3. broken and fractionated natural rocks such as calcite, marble, bins, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalk · Smuigiar- and / or foam-forming agents are suitable: for example, nonionic and anionic emulsifiers, such as polyosylethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, z, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, and 3-hydrolyzates. Suitable dispersants are: z. 3 · Lignin-sulphite liquors and ilethyicellulose »

3s may be used in the tamping adhesives, in carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetal

t.

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For example, dyes such as inorganic pigments, e.g. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo-bSetallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, Zupfer, cobalt, molybdenum and zinc.

The formalizations generally contain between 0.1 and 95% by weight of 7%, preferably between 0.5 and 90%.

The active substances according to the invention can be present in admixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and other estrogen regulators.

The insects may be used as saline solutions ready for use in the form of their preparations or prepared forms of preparation, ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, powders, pastes, soluble powders, dusts and granules. V'eis ^, z. _В л by casting, Terspri-CZEN, atomizing, scattering, dusting, foaming, brushing usa * ^ s is further möglictt, the 7 / irkstoffe by the ultra-low-Volu2ae method ausaubr-rings or Injecting the active substance preparation or the active ingredient into the soil itself can also be used to process the seeds of the plants.

Зеіа use of the invention TerbindunoSa as a pest control adjusters, the Aufndndren ^ en in еілзп can be varied gross range. In general, nanoparticles per hectare of soil use 0.01 to 50 kg, preferably 0.05 to 10 kg.

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When using the substances according to the invention as plant growth regulators, the application is carried out in a preferred period of time, the exact delimitation of which depends on climatic and vegetative conditions.

Even when using the substances according to the invention as fungicides, the application rate can be varied within a substantial range, depending on the nature of the application. Thus, the treatment concentrations in the treatment of parts of plants in the forms of application are generally between 1 and 0.0001 Gev.%, Preferably between 0.5 and 0.001% by weight. In the seed treatment, in general, active ingredient amounts of from 0.001 to 50 g of QS kg of seed, preferably from 0.01 to 10 g, are required. In the treatment of the soil, active compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.2%, are required at the site of action.

Execution game

The invention will be explained in more detail below with reference to some examples.

Production Examples Example 1

To a solution of 224 g (1.5 h) of trimethylnylsilyl imidazole in 15 ml of absolute toluene is added 952 g at room temperature

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(0.8 mol) of thionyl chloride stirred within half an hour. The toluene is decanted from the precipitated thionylbis-imidazole, taken up in 800 ml of acetonitrile, the solution is cooled to -40 ⁰ O and added dropwise at this temperature, a solution of 102.6 g (0.4 mol) of 4- (4-chlorophenyl ) -4-phenyl-1-butyn-4-ol with stirring. The mixture is kept for a further 1 hour at -40 ⁰ C and then at 0 ⁰ C for 3 hours. The solvent is distilled off under reduced pressure, the residue is taken up in 300 ml of silicate, washed three times with 100 ml of water and the organic phase is evaporated. The remaining liquid residue (124.1 g) is dissolved in 300 ml of acetone and treated slowly with 43.2 g (0.15 mole) of naphthalen-1,5-disulfonic acid dissolved in 150 ml of acetone. After standing for one hour, the crystallized salt is filtered off and washed with acetone. (Yield: 54.7 g "23% of theory} # 3 ha |> 209 to 211 ⁰ C.). Sor release of the base becomes the naphtha! in-1,5-disulfonate distributed between .je 150 ml of water and Diehlormethan and treated with 100 ml of aqueous sodium carbonate solution. The organic phase is separated off, dried over anhydrous sodium sulfate and the solvent is distilled off under reduced pressure. 3s are thus 27.6 g (22.5% of theory) of 4- (4-chlorophenyl) -4- (1-imidazolyl) -4-phenyl-i-butyne in orm colorless crystals of melting point 117 to 118 ⁰ O. receive.

Preparation of the starting product

[6:

H - C Ξ G - Cj p - G - CH

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52 g of aluminum shavings are covered with 240 ml of dry tetrahydrofuran. After addition of a spatula tip of iodine and ^ mercury (II) chloride, the mixture is stirred at room temperature for twelve hours. Then it is heated to 60 ⁰ G and a solution of 338 g (2.84 mol) of propargyl bromide in 340 ml of tetrahydrofuran within Dripped with stirring for 1 hour.

The reaction mixture is cooled to -60 ⁰ C and added dropwise within 1.5 hours 432 g (2 mol) of 4-Ghlorbenzophenon dissolved in 660 ml of tetrahydrofuran to. Then allowed to warm to 0 ⁰ G, mixed with 680 ml of a saturated aqueous Aimaoniumcnlorid solution, filtered and the majority of the tetrahydrofuran distilled off under reduced pressure. The residue is treated with 1000 ml Bssigester and the mixture washed four times with 700 ml of water. The organic phase is dried over sodium sulfate, the solvent is distilled off in a flier-jet vacuum and the remaining oily residue is treated with petroleum ether. ! Lan thus obtained 366.3 g (71.6 % of theory) 4- (4-0Ы.огрЬ.еп7І) -4-раепу1-1-butyn-4-ol of melting point 58 to 59 ⁰ G.

Example 2 and 3

 "" 2

(Example 2) (Example 3)

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With stirring 5 to 10 ⁰ G 47.5 § (0.4 mol) of thionyl chloride are added dropwise to a solution of 112.8 g (0.8 mol) of N-trimethylsilyltriazole in 1000 ml of dry toluene. The precipitated thionyl-bis-triazole is filtered off, suspended in 400 ml of acetonitrile and stirred into this suspension at -40 ⁰ C, a solution of 55 g (0.2 mol) of 4- (4-chlorophenyl) -4- (4 -fluorophenyl) -1-butyn-4-ol in 80 ml of acetonitrile within 30 minutes. The mixture is stirred for a further hour at -40 ⁰ G and 3 hours at 0 ⁰ C after and then concentrated the heatscape under reduced pressure. The residue is taken up in 300 ml of siliceous ester and washed three times with 50 ml of water each time. ZTach of the organic phase is obtained 63 g of a viscous liquid by column chromatographic separation on silica gel (Sluierungsmittel: a) cyclohexane / Ghloroform 3 ί 1> b) Chloroform) gives 9 »5 S (14, £ % of 2аѳогіѳ§ 4 ~ <4 * ^ hiorphenyl) -4- (4-fluorophenyl) -4 ~ (1,2,4-triazole-1-7l) -1 Butyl (Example 2) of melting point 84 to 85 ⁰ C and 13.9 g (21.3% ae ^ theory) of 4- (4-chlorophenyl) -4- (4-fluorophenyl) -4- (1,2, 4-triazol-4-yl) -1-butyne of melting point 139 to 140 ⁰ G (Example 3).

1 - G Ξ С - GH ₂ - С -

To a solution of 13.7 g (0.05 mol) of 4,4-Diphen7l-4- (1,2,4-Griazol-1-yl) -1-butyne in 150 ml of methanol at 20 to 25 ⁰ G under concurrently adding 24 ml of concentrated ITatroniausje. 15j3 S (0.06 Hol) iodine entered. IT After four hours, the precipitated crystals are filtered off with filtration / water and ethanol and washed in vacuo

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This gives 12.0 g (60 % of theory) of 4-, 4-diphenyl-1-iodo-4- (1,2,4-triazol-1-yl) -1-butyne of melting point 158 to 160 ⁰ G. ,

In appropriate manner and according to the indicated reactions according to the invention, the following compounds are described

si

general Pormel

1-G = C-GH ₂ -G-Az

receive; Ex,

No.

az

Melting point ( ⁰ G)

10 11 12

14

-JS

93 - 95

232 (Zers.)

(χ 1/2 2TBS) 222 (Zers.) (s 1/2 ITDS)

90 - 92 133 - "Об

116-117

105-106

13s -

139

156 - 153

16

114

125 -

115

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Ex. Hr.

Ar

az

Z Melting point ( ⁰ C) Я 118-119 H 108-109 H 188 - 189 I 173 - W 3r 114-115 150 (x 1/2 NDS)

Br

-gl

22 ^) ^Ѵ - ^) " ⁰¹ " ⁰ ^ -J

HDS = 1,5-naphthalenedisulfonic acid

-г

ЯГ

In the following fungicidal Anbeendebeispiei the compounds listed below are used as comparative substances:

(A)

(3)

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Example A

Erysiphe test (barley) / protective

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

For the preparation of a suitable active compound preparation is mixed Λ weight part of active ingredient with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient in a dewy manner. Subject to drying of the spray coating, the plants are spotted with Srysiphe graminis f. sp. hordei pollinated.

The plants are placed in a greenhouse at a temperature of about 20 ⁰ C and a relative humidity of about 80 % to promote the development of mildew pustules.

7 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds according to the following preparation examples: 5 »6, 20, 21, 12, 8, 1, 9, 10 and 11.

Example B

Stimulation of C0 ₂ -binding in soybeans

Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

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To prepare a suitable active ingredient preparation, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier and the mixture is filled with water to the desired concentration.

Soybean plants are grown in the greenhouse until full deployment of the first pole leaf. At this stage, the plants are sprayed dripping wet with the active compound preparations. In the further course of the experiment, the citration of the plants is measured by customary methods. The values are compared with those of control plants which have not been treated with active ingredients.

Further experimental data and the results of this experiment are shown in the table below.

The active ingredient of the invention according to Preparation Example 14 shows in this test compared to the control of a very strong stimulation of

Claims (4)

- 26 - 62 117 12/39 26/9/83 Srfindungsans-Pruch 1 · crop protection agent, characterized by a content of at least one azolyl-butyne derivative of the general formula Ar σ - с s σ - сн ₂ - σ - Az (ι), 2 in which Ar is optionally substituted phenyl, Ar represents optionally substituted phenyl, Az represents imidazol-1-yl, 1,2, A-triazol-1-yl or 1,2,4- TrisLZol-4-yl stands and
X is hydrogen or halogen, as well as their acid addition salts and metal-salt sompleses, in addition to extenders and / or surface-active agents, 2 · Pesticides according to item 1, characterized by Ar represents phenyl which is optionally monosubstituted to disubstituted, identically or differently, by fluorine, chlorine, bromine, methyl, trifluoromethyl, trifluoromethoxy, phenyl and chlorophenyl, Ar is optionally mono- to disubstituted by identical or different substituents by the phenyl substituents already mentioned for Ar, Az is imidazol-1-yl, 1,2,4-triazol-1-yl or 1,2,4-triasol-4-yl and X is hydrogen, iodine or bromine. 27 - 62 117 12/39 26/9/33 3. Fungicidal agents and the growth of plant regulating agents, characterized by a content of at least one azolyl-butyne derivative of the formula I in points 1 and 2 4 »A method for controlling fungi and for the regulation of plant growth, characterized in that azolyl-butyne derivatives of the formula I in points 1 and 2 act on fungi, plants to be treated or their Lebensrauia · 5, use of azolyl-butyne derivatives of the formula I in points 1 and 2, characterized in that they are used as crop protection agents. 5 * use of aaclylbatin derivatives of the formula I in points 1 and 2, characterized in that they are used for controlling fungi, Use of azoljl-butyne derivatives of the formula I in the items 1n and 2, characterized in that they are used for the regulation of plant growth. 8. A process for the production of vegetable cyanogens, characterized in that Azolji-butyne derivatives of the formula I in the points 1 and 2 are mixed with extenders and / о the surface-active Дхігсеіп.