CS236691B2 - Agent for regulation of plant growth and fungicide agent and production method of its efficient components - Google Patents

Abstract

1. Azolyl-alkenones and -ols of the formula see diagramm : EP0079006,P19,F1 in which R**1 represents the grouping see diagramm : EP0079006,P19,F2 in which Z**1 and Z**2 are identical or different and represent hydrogen, halogen or alkyl with 1 to 4 carbon atoms, and, furthermore, R**1 represents phenyl which can be mono- or polysubstituted by identical or different substituents selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio each with 1 to 4 carbon atoms, alkyl- and dialkylamino each with 1 to 4 carbon atoms in each alkyl part, and also halogenoalkyl, halogenoalkoxy and halogenoalkylthio each with 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, phenyl and/or phenoxy, it being possible for the two last-mentioned radicals in turn to be substituted by halogen and/or alkyl with 1 to 2 carbon atoms, R**2 represents straight-chain or branched alkyl with 1 to 12 carbon atoms, and also phenyl which can be mono- or polysubstituted by identical or different substitutents selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy and alkylthio each with 1 to 4 carbon atoms, alkyl- and dialkylamino each with 1 to 4 carbon atoms in each alkyl part, and also halogenoalkyl, halogenoalkoxy and halogenoalkylthio each with 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, phenyl and/or phenoxy, it being possible for the two last-mentioned radicals in turn to be substituted by halogen and/or alkyl with 1 to 2 carbon atoms, or R**2 represents cycloalkyl which has 3 to 7 carbon atoms and is optionally substituted by halogen and/or alkyl with 1 to 4 carbon atoms or cycloalkylalkyl which has 3 to 7 carbon atoms in the cycloalkyl part and 1 to 2 carbon atoms in the alkyl part and is optionally substituted by halogen and/or alkyl with 1 to 4 carbon atoms, X represents the CO or CH(OH) group and Y represents a nitrogen atom or the CH group, and acid addition salts and metal salt complexes thereof.

Description

The invention relates to a process for the production of novel azolyl-alkenones and -alkenols, and their use as plant growth regulators and fungicides.

It is already known that certain 6,6-disubstituted 2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-hexen-3-ones and -ols have good effects as plant growth regulators and good fungicidal effects (see DOS No. 2,905,981). However, the effect of these compounds, especially when applied in lower amounts and concentrations, is not always entirely satisfactory.

New azolyl-alkenones and -ols of the formula I have now been found

R-K-CH-CH 2 CH-R ²

(I) in which

R ¹ represents a moiety of the formula -CH ² Z ¹

I — C — CH ₃

AND

CH ₂ Z ² wherein each of Z ¹ and Z ² , which may be the same or different, represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl group, or R ¹ represents a phenyl group optionally substituted by one to three substituents selected from the group consisting of halogen atoms, (C 1 -C 4) alkyl groups and (C 1 -C 4) alkoxy groups,

R ² represents a C 1 -C 12 alkyl group, optionally a halogen and / or C 1 -C 4 alkyl group substituted by a phenyl group, a C 3 -C 7 cycloalkyl group or a C 3 -C 7 cycloalkylalkyl group, and 1 or 2 carbon atoms in the alkyl moiety,

X is -CO- or -CH (OH) - and

Y represents a nitrogen atom or a CH group and their acid addition salts and complexes with metal salts, in particular with copper chlorides.

The compounds of the formula I according to the invention are present in the form of the geometric isomers E (trans) and Z (cis). In the nomenclature using the symbols E and Z, the substituents on the double bond are arranged according to the decreasing priority according to the Cahn-Ingold-Prelog rule. If the preferred substituents are on the same side of the double bond, it is the Z configuration (zusammen from the German), if they are on the opposite sides it is the E configuration (from the German entgegen).

In addition, when X is CH (OH), the compounds of the formula I according to the invention contain two asymmetric carbon atoms and can therefore exist in the form of both geometric isomers (threo- and erythto-form) which can be used in the production of the abovementioned compounds. result in different weight ratios. In both cases, said substances occur as optical isomers.

It has further been found that the azolyl-alkenones and -ols of the formula I, as well as their acid addition salts and metal salt complexes, are obtained by reacting the compounds of the formula II

in which

R ^1, R ² and Y have the abovementioned meaning, are heated in the presence of a diluent and optionally in the presence of a catalyst, optionally in the presence of alumina, formed azolyl-alkenony of the invention of formula Ia

in which

R ¹ , R ² and Y are as defined above, optionally reduced in a known manner, and optionally the acid or metal salt is added to the compounds of the formula I thus obtained.

Finally, it has been found that the novel azolyl-alkenones and -ols of the formula I, as well as their acid addition salts and metal salt complexes, show strong effects as plant growth regulators and strong fungicidal effects.

In addition, the new azolyl-alkenones and

-ols of formula I interesting intermediates for the production of other plant protection agents.

In ketoderivatives, a keto group is possible

R ¹

Reduce R ² to --CH (OH) -. Additionally, functional derivatives of the keto group, such as oximes and oximethers, hydrazones and ketals, can be obtained by appropriate modifications. Carbinol derivatives can be converted to the corresponding ethers in a conventional manner. Furthermore, the acyl or carbamoyl derivatives of the compounds of the formula I can be prepared by reaction with, for example, acyl halides or carbamoyl chlorides in a manner known per se.

Surprisingly, the compounds according to the invention show a better plant growth regulating effect and a better fungicidal effect than the known 6,6-disubstituted 2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5 -hexen-3-ones and -ols, which are closely related in chemical and potency terms. The active compounds according to the invention thus represent an enrichment of the prior art.

The present invention relates to a plant growth regulating agent and to a fungicidal composition comprising, as an active ingredient, at least one compound of the above general formula (I) or a salt or a complex thereof with copper chloride, and a process for the preparation thereof.

In addition to the compounds mentioned in the examples, the following compounds corresponding to the general formula (I) in which Y represents a CO or CH (OH) group and Y represents a nitrogen atom or a CH group are preferred compounds of the invention:

RX-CH-CH = CH-R ² (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C (CH3) ₃ C _(CH! J ₃ C (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C (CH3) ₃ C (CH3) ₃ C (CH3) ₃ C- (CH _{3] 3} C- (CH3) ₃ C-

(CH ₃ ) ₃ C - (N (CH ₃ ) ₃ C -

R ¹ R ² ch ₂ fh ₃ c — οΙ

F _and CH [CH3) ₃ C-

-CH ₂ -CH (CH ₃ ) ₂ (CH ₃ ) ₃

-CHO -CH (CH ₃₎ C ₂ H, -CH ₂ CH (CH ₃₎ C ₃ H ₇ -CH = CH (OH ₃₎ C ₄ H 9 -CH ₂ -C (CH ₃₎ -CH _{3 2} -CH (C ₂ H ₅ ) ₂

- CH ₂ -CH (C ₃ H ₇ ) ₂ -CH (CH ₃ ) -CH (CH ₃ ) ₂ —C (CH ₃ ) ₂ —CH (CH ₃ ) ₂

CH ₃

CH ₃

CH ₂ C1

AND

H ₃ c - C - CH _{2 -} CH (CH ₃ ) ₂

CH ₂ Cl (CH ₃ ) ₃ c (CH ₃ ) ₃ c - _ _{CH -} <2>

ct

Preferred substances according to the invention are also acid addition products and the above-mentioned preferred azolyl-alkenones and -ols of the general formula (I).

Preferred acids include hydrohalic acids such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, mono- and dibasic carboxylic acids and hydroxycarboxylic acids such as acetic acid. maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids, for example p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Preferred substances according to the invention are furthermore addition products formed from metal salts II. to IV. the main groups а I. а II. as well as IV. to VIII. side groups of the Periodic Table of the Elements, in particular from copper chloride, and from the above-mentioned preferred azolyl-alkenones and -ols of the formula I

Possible anions of these salts are those derived from acids leading to the formation of physiologically tolerable addition products. Particularly preferred acids of this type are hydrohalic acids such as hydrochloric acid.

For example, when 6-cyclohexyl-2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-hexen-3-one is used as the starting material, alumina and a diluent are used. methanol, the reaction may be described by the following reaction scheme:

(СH ₃ ) ₂ C-СО-ОС ó N - ^y

If, for example, 6-cyclohexyl-2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-hexen-3-one is used as the starting material and sodium borohydride is used as a reducing agent, The reactions of the invention can be described by the following reaction scheme:

(CH ₃ C-CO-CH-CH = CH 2 H 4

A fcHJ ₄ C -? - CM-CW = C ^ - / ř7 \

The compounds required as starting materials in the process of the invention are generally defined by the above formula II. In this general formula, R ^1, R ² and Y preferably have those meanings which have for these substituents already mentioned as preferred in connection with the description of compounds of formula I.

Compounds of formula (LL) are known or can be prepared by a simple method known per se (see DOS No. 30 00 643 and the literature cited therein). Thus, the compounds of formula (II) may be obtained by ketoenamines of formula (III)

R-CO-CH2-CH-N

(U1) in which

R ¹ and Y are as defined above and each of R ³ and R \ which may be the same or different, represents an alkyl group having 1 to 4 carbon atoms, especially methyl, are reacted with organomagnesium compounds of the formula IV

Hal-Mg-R ³ (IV) wherein

R ² has the abovementioned meaning and

Hal represents halogen, in the presence of an inert organic solvent, for example an ether, and optionally in the presence of an inert gas, for example nitrogen, at a temperature between -20 and 120 -C (see also DOS No. 30 00 643 and examples).

The ketoenamines of formula (III) are known or can be easily obtained in a manner known per se (cf. DOS No. 30 00 643). Thus, the ketoenamines of the formula III can be obtained by reacting the azolyl ketones of the formula V

(V) in which

R ¹ and Y have the abovementioned meanings, are reacted with amide acetals or amlnalestery formulas VIa, respectively. VIb

R ⁵ OR \ /

CH — N (Via) / \

R ⁵ OR

NR ³ R ⁴ /

R ⁵ O-CH (VIb) \

NR ³ R ⁴ in which

R ³ and R ⁴ are as defined above and

R @ ⁵ represents a C1 -C4 alkyl group in a manner known per se in the presence of an inert organic solvent, for example an aromatic hydrocarbon or, in particular, an excess of the amidacetal or aminalester of the formulas VIa and II, respectively. VIb, boiling [see also Chem. Ber. 101, 41-50 (1968); J. Org. Chem. 43, 4248-4250 (1978), as well as exemplary embodiments].

The azolyl ketones of formula V are known (see, for example, DOS No. 24 31 407, DOS 6.

Alternatively, they can be obtained in a manner known per se by reacting the corresponding haloketones in the presence of an acid binding agent with 1,2,4-triazole or imidazole.

The amidacetals and / or aminalesters of the general formula (VIa) and (IIa) respectively. VIb, are generally known compounds in organic chemistry [see, for example, Chem. Ber, 101, 41-50 (1968) and J. Org. Chem. 43, 4248-4250 (1978)].

The organomagnesium compounds of formula IV are well known compounds in organic chemistry.

Suitable diluents for the process according to the invention for the preparation of the azolylalkenones of the formula (Ia) are organic solvents inert under the reaction conditions, which preferably include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol or isopropanol, aliphatic and aromatic hydrocarbons such as benzene, toluene or xylene as well as halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene.

The process for preparing the azolylalkenones of formula (Ia) according to the invention is optionally carried out in the presence of a base as a catalyst. These basic catalysts preferably include organic nitrogen bases (such as morpholine, pyridine, triethylamine and N, N-dimethylbenzylamine).

The reaction temperatures for the preparation of the azolylalkenones of the formula Ia according to the invention can be varied within wide limits. In general, the reaction is carried out at a temperature of between 30 and 150 ° C, preferably between 50 and 120 ^° C.

The reaction according to the invention leading to the formation of the azolylalkenones of the formula Ia is carried out either purely by thermal heating of the compounds of the formula II or under basic catalysis, using 0.1 to 1 mol of base per mole of the compound of the formula II. aluminum. The compounds of the invention are in all cases isolated in the usual manner.

The reduction according to the invention leading to the azolylalkenols of the formula I is carried out in a customary manner, for example by reacting the azolylalkenone of the formula Ia with complex hydrides, optionally in the presence of a diluent, or by reaction of the azolylalkenones of the formula I and with aluminum isopropoxide.

When working with complex hydrides, suitable diluents for the reaction according to the invention are polar organic solvents, which preferably include alcohols such as methanol, ethanol, butanol and isopropanol. and ethers such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at a temperature of 0 to 30 ° C, preferably at a temperature of 0 to 20 ° C. Approximately 1 reaction equivalent of a complex hydride such as sodium borohydride or lithium alanate is used per mole of the ketone of the formula Ia. In order to isolate the reduced compounds of the formula I, the residue after any evaporation of the reaction mixture is taken up with dilute hydrochloric acid, the solution is rendered alkaline and extracted with an organic solvent.

Further processing is then carried out in the usual manner.

When working with aluminum isopropoxide, suitable solvents for the reaction according to the invention are preferably alcohols, such as isopropanol, or inert hydrocarbons, such as benzene. Again, the reaction temperatures can be varied within a wide range. In general, the reaction is carried out at a temperature between 20 and 120 degrees Celsius, preferably between 50 and 100 ° C. To carry out this reaction, about 1 to 2 moles of aluminum isopropoxide are used per mole of the ketone of formula (Ia). To isolate the reduced compounds of formula (I), excess solvent is distilled off in vacuo and the resulting aluminum compound is decomposed with dilute sulfuric acid or sodium hydroxide. Further processing is then carried out in the usual manner.

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

Acid addition salts of compounds of formula (I) may be obtained in a simple manner by conventional methods used to prepare salts, for example by dissolving a compound of formula (I) in a suitable inert solvent and adding an acid such as hydrochloric acid. The resulting salts can be isolated in a conventional manner, for example by filtration, and optionally purified by washing with an inert organic solvent.

For the preparation of the azolyl-alkenone complexes and the metal salts of the general formula (I), preference is given to salts containing those anions and cations which have already been mentioned in connection with the description of the metal salt complexes according to the invention.

Complexes of compounds of formula I with metal salts can be obtained in a simple manner by conventional methods. Thus, for example, the metal salt is dissolved in an alcohol, for example ethanol, and the solution is added to the compound of formula I. The metal salt complexes can be isolated in a known manner, for example by filtration and optionally purified by recrystallization.

The active substances used in the context of the invention interfere with the metabolism of plants and can therefore be used as growth regulators.

For the type of action of the plant growth regulators, it has been hitherto known that the active substance can have several different effects on plants. The effects of the substances depend essentially on the duration of application, depending on the developmental stage of the plant, as well as on the amount of active substance applied to or in the vicinity of the plants, and further on the mode of application. In any case, plant growth regulators are intended to positively influence crop plants in a certain desirable manner.

Plant growth regulators can be used, for example, to suppress vegetative plant growth. Such growth suppression is of economic importance, inter alia, in grassland, since the suppression of grass growth can, for example, reduce the frequency of mowing in ornamental gardens, parks and sports facilities, at the roadside, at airports and orchards. It is also important to suppress the growth of herbaceous and woody plants at roadside and near pipelines and overhead lines, or quite generally where strong growth is undesirable.

It is also important to use plant growth regulators to suppress crop growth in grain, as this will reduce or eliminate the risk of plants lying down before harvest due to crop shortening. In addition, plant growth regulators can cause grain stalks to increase, which also counteracts lodging. The use of growth regulators to shorten the stalks and strengthen the stalks allows the application of higher amounts of fertilizer to increase yields without the need to worry about the lodging of grain.

Suppression of vegetative growth allows for many crops to be denser or planted, so that yields per unit area can be increased. The smaller plants thus grown also have the advantage that the culture is easier to cultivate and harvest.

Suppression of vegetative plant growth can also lead to increased yields, as nutrients and assimilates are used more intensively for the formation of flowers and fruits than for the growth of vegetative parts of plants.

Stimulators of vegetative growth can also often be achieved with growth regulators. This is of great importance when vegetative parts of plants are harvested. However, stimulation of vegetative growth can also simultaneously lead to stimulation of generative growth by producing more assimilates, so that for example more fruits can be formed or larger fruits can be produced.

Increased yields can also be achieved in many cases by interfering with plant metabolism without observing changes in vegetative growth. Growth regulators can also act on changes in the composition of plants, which in turn can achieve a better quality of harvested products. Thus, for example, it is possible to increase the sugar content of sugar beet, cane, pineapple as well as citrus fruits or to increase the protein content of soy or grain. Furthermore, it is also possible, by means of growth regulators, to inhibit the degradation of desired substances contained in plants, such as sugar in sugar beet or sugar cane, before or after harvesting. In addition, the production or efflux of secondary plant substances can be positively influenced. By way of example, stimulation of latex and rubber flow can be accomplished at 236969.

Parthenocarpic fruits (fruits without seeds) may also develop under the influence of growth regulators. Furthermore, it is possible to influence the sex of the flowers with these regulators. Pollen sterility can also be achieved, which is of great importance in breeding and hybrid seed production.

By using growth regulators, it is possible to control the formation of side shoots in plants. On the one hand, the development of side shoots can be promoted by violating apical dominance, which may be very desirable, especially in the cultivation of ornamental plants, even in conjunction with growth suppression. On the other hand, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in tobacco growing or tomato planting.

The effect of the active substances on the foliage of the plants can be controlled so that the plants can be completely de-leafed at the desired point in time. Such defoliation is important for facilitating the mechanical harvesting of cotton, but it also plays a major role in other crops, such as the vine, where it facilitates harvesting. Plant defoliation can also be performed to reduce plant transpiration before transplanting.

Growth regulators can also be used to control the fall of fruit. On the one hand, premature fruit loss can be prevented. On the other hand, it is also possible to support the fall of fruits or even flowers in the sense of a “chemical thinning” in order to break the so-called “alternative”. An alternative is the special behavior of some fruits, based on endogenously conditioned very different yields from year to year. Growth regulators can also serve to reduce the force required for harvesting fruit at harvest time so that mechanical harvesting or manual harvesting is facilitated.

By means of growth regulators, it is furthermore possible to accelerate or slow down the ripening of the harvested products before or after harvesting. This is particularly advantageous since it can be optimally adapted to market requirements. Furthermore, growth regulators can in many cases serve to improve the coloring of the fruit. In addition, growth regulators can achieve a concentration of fruit ripening within a certain period of time. This creates the prerequisites for, for example, tobacco, tomatoes or coffee plants to be able to carry out fully mechanical or manual harvesting in only one working stage.

The use of growth regulators can also affect seed or bud rest periods in plants such that plants such as pineapple or horticultural ornamental plants germinate, sprout or bloom when they do not germinate under normal conditions. nerašíly, respectively. nekvetly.

Growth regulators can also achieve delayed bud buds, delayed seed germination, for example to prevent late frost damage in areas with colder climates.

Finally, frost, drought or high salt content in the soil can be induced by the growth regulators in the plants, allowing the plants to be grown in areas that would normally be unsuitable for the plants.

The active compounds according to the invention also show a strong microbicidal action and can be used in practice to combat undesirable microorganisms. The active compounds described are suitable for use as plant protection agents.

Fungicides are used in plant protection to combat fungi of the classes Oomyceies, Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Since the plants of the present invention are well tolerated at the concentrations required for combating fungal diseases of the plants, they can be used for the treatment of aboveground parts of plants, seedlings and seeds, and for the treatment of soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good results for combating powdery mildew-inducing fungi such as Erysiphe species, for example against powdery mildew on barley or cereals (Erysiphe graminis), for combating barley stiffness (Drechslera) graminea), to combat Venturia species, for example to combat the causal agent of apple scab (Venturia inaequalis), or to combat rice diseases such as Pyricularia oryzae and Pellicularia sasakii.

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with the active compounds, small particles coated with polymeric substances and seed coatings, as well as formulations for application by the so-called ULV procedure (Ultra-Low-Volume).

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure or with solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated fatty acids such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as 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 fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks.

Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metallic phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

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

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

The active compounds according to the invention can be applied as such, in the form of concentrates or further dilution forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, spray powders, pastes, soluble powders, dusts and granules. The application is carried out in the usual manner, for example by watering, spraying, tossing, dusting, foaming, painting and the like.

Furthermore, the active compounds can be applied by the so-called ULV method (Ultra-Low-Volume) or the active agent or the active compound itself can be injected into the soil. Plant seeds may also be treated.

When using the compounds of the invention as plant growth regulators, their consumption can vary within wide limits. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active compound are used per hectare of soil surface.

When using the compounds according to the invention as growth regulators, the application is carried out for a preferred period of time, the definition of which is governed by climatic and vegetative conditions.

Also, when the active compounds according to the invention are used as fungicides, their consumption may, depending on the method of application, be varied within a wide range. In the treatment of plant parts, the concentration of active compound in the dosage forms is generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment of seed, from 0.001 to 50 g of active compound, preferably 0.01 to 10 g of active compound, are generally used per kilogram of seed. In soil treatment, it is desirable that the concentration of active ingredient is from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, at the point where the effect is to be achieved.

The preparation and use of the active compounds according to the invention are illustrated by the following non-limiting examples.

Example 1

(ch, lc-co-ch-ch = ch - / h) ώ

A mixture of 20 g (0.073 mol) of 6-cyclohexyl-2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-hexen-3-one and 200 g of alumina in 300 ml of methanol The mixture was heated at reflux for 24 hours. The reaction mixture was allowed to cool, sucked through a pad of diatomaceous earth and the filtrate was evaporated. 19.9 g (99% of theory) of 6-cyclohexyl-2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-hexen-3-one are obtained with a refractive index no of ²⁰ = 1.4890.

Preparation of the starting material

Dissolve 44.4 g (0.2 mol) of 2,2-dimethyl-5-dimethylamino-4- (1,2,4-triazol-1-yl) -4-pyridin-3-one in 600 ml of ether and a solution of 48.2 g (0.24 mol) of cyclohexylmethylmagnesium bromide in 200 ml of ether was added at -20 DEG C. The reaction mixture was stirred for 1.5 hours while warming to room temperature and then diluted with acid. The organic phase is separated, washed twice with water and dried over sodium sulphate and evaporated. It is obtained

27.4 g (49.8% of theory) 6-cyclohexy-2,2-dimethyl-4- (1,2,4-triazol-1-yl-4-hexen-3-one with refractive index n ₀ ²⁰ = 1.4910.

Ь (CH 2 O 2 CH-N (CH ₃ ) ₂ )

250.8 g (15 mol) of 2,2-dimethyl-4- (1,2,4-triazol-1-yl) -3-butanone were heated together with 196 g (1.65 mol) of dimethylformamide dimethyl acetal for 5 hours. the excess acetal is distilled off. There were obtained 306 g (92%) of 2,2-dimethyl-5-dimethylamino-4- (l, 2,4-triazol-l-yl) -4-penten 3-one having a refractive index n _D ² 0 = 1.531 .

с / (сн ^ с-со-сн ^ ')

138 g (2 mol) of 1,2,4-triazole are added in portions at room temperature to 276.4 g (2 mol) of ground potassium carbonate and 296.2 g (2 mol) of α-chlorpinacoline in 500 ml of acetone, whereby the temperature of the reaction mixture rises to boiling. The mixture was stirred at reflux for 5 hours, then cooled to room temperature, filtered and the filtrate was steamed by distilling off the solvent in vacuo. The oily residue crystallized upon the addition of gasoline. 240.8 g (72% of theory) of 2,2-dimethyl-4- (1,2,4-triazol-1-yl) t-butanone of melting point 62-64 ° C are obtained.

EXAMPLE 2 R ^H (сщс-сн-сн-сн-сн

10.4 g (0.038 mol) of 6-cyclohexyl-2,2-dimethyl-4T (L ₁ 2,4-triazol-l - yl) -5-hexen-3-one (see Example 1) were dissolved in 100 A solution of 0.38 g (0.01 mol) of sodium borohydride in 5 ml of ice-water is added dropwise at -10 ° C. The reaction mixture was stirred for 2 hours and then adjusted to pH 6-7 with dilute hydrochloric acid. The solvent was distilled off in vacuo, the residue was taken up in methylene chloride, washed with water, dried over sodium sulfate and evaporated. 8.9 g (86%) of 6-cyklohexylt2,2-dimethyl-4- (1,2,4 - г1а2оМ-у1) -5-hexen-S-ol of refractive index n _D ^20-1, 4920.

The following compounds corresponding to formula (I) are obtained in an analogous manner as described above

R 1 -X-CH-CH 2 CH-R ^2,

Table 2

Ri X YR ² melting point (° C) refractive index n ₀ ^: (CH ₃ ) ₃ C- what N -c _r h ₁₃ 1,5388 (CH ₃ ) ₃ C- what N -c ₇ h ₁₅ 1,4778 (CH ₃ ) ₃ C- what N -C ₃ H ₇ Cl 1.4880 (CH ₃ ) ₃ C- what N 105—108 (CH ₃ ) ₃ C- what N - ^objectives 1.5512 (CH ₃ ) ₃ C— what N —C ₃ H ₇ -i 1.4871 (CH ₃ ) ₃ C— what N —CH ₂ —C ₃ H ₇ -i 1.4868 (CH ₃ ) ₃ C- what N OF* 1.5434 (CH ₃ ) ₃ C- what N - @ Hct A 138—140 (CH ₃ ) ₃ C— what N ct 1,5624

(CH ₃ ) ₃ C— WHAT C1CH ₂ C (CH ₃ ) ₂ - what FCH ₂ C (CH ₃ ) ₂ - what

(CH3) ₃ C (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C- (CH3) ₃ C- (CH _{3) 3} C (CH _{3) 3} C-

CH (OH)

CH (OH)

CH (OH)

CH (OH)

CH (OH) CH (OH) CH (OH)

CH (OH)

CH (OH)

N

N N

N

N

N

N

N

-CH [C ₂ H ₅ ) ₂ —CH -> - C ₃ H ₇ -i —CH ₂ —C ₃ H ₇ -1

-c ₃ H ₇ —ύβΗι ₃

ЧоУ-сг —C ₃ H ₇ -i —CH ₃ —C ₃ H ₇ -i -cH ₁₅

1,4885

1.4969

1.4777 viscous oil

1.4898

1.4798

1.5633

1.4841

1,4857

1.4807

112—124

154—156 (A-form)

46—48 (B-form)

(CH ₃ ) ₃ C—

CH (OH)

N

R ¹

XYR ² Example Number Melting point (° C) Refractive index η ₀ ' ^2υ

26 (CHshC- CH (OH) N 27 Mar: (CH ₃ ) ₃ C- СН N 28 (CH _with hC- СН N 29 C1CH ₂ C (CH ₃₎ - СН N 30 FCH ₂ C (CH ₃ ) ₂ - СН N 31 Ci- <Q- СН N 32 (CH ₃ ) ₃ C- со сн 33 (CH ₃ ) ₃ c- со сн 34 (CH ₃ ) ₃ C— со сн 35 (CH ₃ ) ₃ C— со сн 36 (CH ₃ ) ₃ C- со сн 37 (CH ₃ ) ₃ c- со сн 38 (CH ₃ ) ₃ c- со сн 39 (CH ₃ ) ₃ C— со сн 40 (CH ₃ ) ₃ C— со сн 41 (СНз) зС- СН сн 42 (СНз) зС- СН сн 43 ₃ С- СН сн 44 £? R со N 45 ΒΓ - @> - со N 46 C ₃ H ₇ -C (CH ₃ ) ₂ - СН N

^С Ч -¼ 180 г (A-form) ct —СЩСоЦ-ЛС / Д) 1,4832 -СН (С ₂ Н ₅ ) С ₄ Н ₉ 1,4832 —СН ₂ —C3H7-I 1,5001 - СН2 — C3H7-1 1,4852 50—60 -С ₃ Н ₇ 1.4915 —СбН ₁₃ 1,4773 —С ₇ Н ₁₃ 1,4808 —С ₈ Н ₁₇ 1,4742 —С ₉ Н ₁₉ 1.4770 —С5Н11 а 1.4890 viscous oil 1,5018 —С ₅ Н _И 1.4892 Ct ~ ^ ^_ct 92—96 -c ₆ H ₁₃ 1,4742 1.5050 © 46 © 107-111 (x _CuCl2) —СН ₂ —C ₃ H ₇ -i 1,4849

A- and B-form = both possible geometric isomers

47 сн ₃ о- <р> - CH (OH) N c ₂ h ₅ 1.5320 (A-form) 48 (CH ₃ ) ₃ C- what N -CH ₂ -C (CH _{3) 3} 1,4828 49 (CH ₃ ) ₃ c- what N -CH ₂ -0 1,4884 50 (CH ₃ ) ₃ C— CH (OH) N 1,4887 51 (CH ₃ ) ₃ c- CH (OH) N -CH ₂ -C (CH ₃ ) ₃ 62

R ¹

X

YR ² Example Number Melting point (° C) Refractive index no ²⁰ ci

52 CH (OH) N —CH ₂ —C ₃ H ₇ -i 49 53 p CH (OH) N C ₂ H ₅ 40 (B-form) 54 ^Cl ~ ^ ~ CH (OH) N с- ₂ н ₅ 67 55 C ₃ H ₇ —C (CH ₃ ) ₂ - what N. -CH ₂ -C ₃ H ₇ -i 1,4819 56 (СНз) зС- what N -CH ₂ -CH (CH ₃ i-C ₂ H ₅ 1.4772 57 (CH ₃ ) ₃ C- CH (OH) N -CH = CH (CH ₃ i-C ₂ H ₅ 1,4819

In the following examples of use of the active compounds according to the invention, the following compounds are used as comparators:

(A) =

(C)

Example А

Soybean growth inhibition solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

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

Soybean plants are grown in a greenhouse until the first assimilation leaf unfolds. At this stage, the plants are sprayed with the active ingredients until wet. After 3 weeks, the increment was measured for all plants and the growth retardation was calculated as a percentage of the increment of the control plants. 100% growth inhibition means that there is no further growth and 0% means growth corresponding to the growth of control plants.

The active substances, the active substance concentrations and the results obtained are given in the following Table A.

Table A

Soybean growth inhibition active ingredient concentration of growth inhibition (Example No.) (%) (%) control

(known)

0.05

OH (CH ^C -H-CH-CHCH-CHjCjHp III)

0.05

70 *>

(21) (c ^ ₃ c- ř f-Н-.СН = СН- ^ ОУ “С1

('19}

Italy (27) 0.05 29 *> (30) 0.05 50 *> (51) 0.05 59 (54) 0.05 87 *>

Legend:

· * Dark green leaves

Example В

Growth retardation (fescue - Festuca pratensis)

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To make a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Grass (fescue) is grown up to 5 cm in the greenhouse. At this stage, the plants are sprayed until moistened with the active ingredients. After 3 weeks, the increment is measured and the growth retardation is calculated as a percentage of the increment of the control plants. 100% inhibition of growth means a state of rest (no further growth) and 0% means growth corresponding to the growth of control plants.

The active substances, the active substance concentrations and the results obtained are given in the following Table B.

Table В

Grass growth inhibition (Festuca pratensis) Active substance Concentration (example.) (%) Growth inhibition (%) Control

0.05 (known)

OH

I (с ₃ ) _э с-сн-сн-сн A

O

0.05 (8) (known)

OH (CH ₃ ) ₃ C-CH-CH-CH = CH-Cl-C ₃ HL

Legend:

* ´ dark green leaf color

0.05

70 *>

Italy (21)

238691

Example C

Effect on sugar beet growth solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To make a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Sugar beet plants are grown in the greenhouse until the cotyledons are fully formed. At this stage, the plants are sprayed with the active ingredient until wet. After 14 days, the plant growth is measured and the growth influence in percent growth of the control plants is calculated. A 0% effect on growth means growth corresponding to that of the control plants.

Negative values impede growth, positive values imply growth stimulation compared to growth controls.

The active substances, active substance concentrations and results obtained are given in the following Table C.

Table C

Effect on sugar beet growth active substance concentration influence on growth (example no.) (%) [%]

OH _X CH ₃

0.05 - 5 (C) (known)

OH (CH _{3 I 3} C-CH-Ch-CH

A (known) γ (ch- ₃ -ch-ch-ch-ch / ch)

(1в)

OH (c-c-ch-ch-ch-c-c)

Дм

0.05

0.05

0.05 —5 —65 * ’··’ —10 ‘>

(13) the active ingredient (Example No.) concentration

C%) Influence of growth (%)

0.05

0.05

0.05 —95 * ’**>

_35 ·) **) +10 (26) (A-form) (CH 3) 3 C — CO — CH — CH = CH — C 9 H 19

0.05 +10

(36)

0.05 +25 (47)

(24) 0.05 —17 * ’ (28) 0,025 —83 *> i *) (29) 0.05 —71 ») (31) 0.05 —30 ») (46) 0.05 —17 *) (48) 0.05 —25 * ’ (50) 0.05 __ίο ») **) (51) 0.05 —40 *> (56) 0.05 —40

Legend:

* 'dark green leaves' ** thickened leaves

Example D

Cotton growth retardant solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To make a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Cotton plants are grown in a greenhouse until the fifth assimilation leaf unfolds completely. At this stage, the plants are sprayed with the active ingredient until dripping. After 3 weeks, the percent increase is measured and the growth retardation is calculated as percent of the control plants. 100% means growth arrest and 0% represents the same growth as untreated control plants.

The active substances, active substance concentrations and results obtained are given in Table D below.

Ta b u · 1k and D

Cotton growth inhibition active substance (example number) concentration (%) growth inhibition (%) control

0.05 (known)

0.05 (known)

0.05 (known as

0.05

23В691 active substance (example number) growth retardation (%) concentration (θ / ο)

Cl (CH 2 CH 2 -CO-CH 2 CH-CH 2 CH 33 i)

Λ

0.05 (6)

Whose

0.05

0.05

45 * '^ ί ^Ί Ν ιϋ-У (ю)

(111

0.05

55

Cl

0.05

35 * '(B-form)

Legend:

* 'dark green leaf color * ^#) thick leaves (25)

Example E

Stimulation of carbon dioxide fixation in soybean solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

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

Soybean plants are grown in the greenhouse until the first assimilation leaf unfolds. At this stage, the plants are sprayed with the prepared active ingredient until wet. In the further course of the experiment, the fixation of carbon dioxide by plants is measured in a conventional manner. The measured values are compared with those found in control plants not treated with the active substances.

Individual values are denoted by symbols with the following meaning:

- inhibition of carbon fixation fixation of carbon dioxide fixation as with control plants + low stimulation of carbon fixation ++ strong stimulation of carbon fixation +++ very strong stimulation of carbon fixation.

The active substances, the active substance concentrations and the results obtained are given in the following Table E.

Table E

Stimulation of carbon dioxide fixation in soybean active substance (Example No.) concentration (%) effect

0.05 (known)

0.05 (known)

0.05 <E>

(known)

(11

0.05 ++ ^; + concentration effect active substance (example no) (%)

OH

and 0.05 +++ Italy (22) (37) 0.05 +++ (48) 0.05 (52) 0.05 + + +

Example F

Powdery mildew test (Erysiphe) / protective effect (barley) solvent:

100 parts by weight of dimethylformamide emulsifier:

0.25 parts by weight of alkylaryl polyglycol ether

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

To determine protective activity, young barley plants are sprayed with the active agent until wet. After the spray coating has dried, the plants are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are then placed in a greenhouse at a temperature of about 20 ° C, where the relative humidity of the air is about 80 ° / o, thereby favorably influencing the development of powdery mildew piles.

The experiment is evaluated 7 days after the inoculation.

The active substances, active substance concentrations and results obtained are given in Table F below.

Table F

Powdery mildew test (Erysiphe) / protective effect (barley) active substance concentration of the active substance (example no.) In spray suspension (% by weight) infestation in% compared to that of untreated control plants

0.05

68.8 (known)

0,025

0.0 (5) (C H & C-CO-C H-CH 3 C H-C 6a)

0,025

0.0 (321

238691 active substance (example no.) Concentration of active substance infestation in% versus in spray suspension state in untreated (% w / w) control plants (СН ₃ ) ₂ С-СО-СН-СН = СН-С _? Н.

'7 15

0,025

0.0 (34J ёЧ?

0,025

0.0

0,025

0,025

0,025

0,025

0.0

0.0

0.0

0,025

active substance (example #) concentration of active ingredient infestation in% versus in spray suspension state in untreated (% by weight) of control plants

ОН

(CH ₃ - CH - CH - CH - C HC ₃ H ₇ 0,025 0.0 (17) OH AND (CH 2 C-CH-CH-CH 2 CH-C ₆ H ₁₃ O (18) 0,025 0.0 OH (снрСн-сн-сн = сн - (& .. _а n ___ ^{) (} 19 ⁾ 0,025 0.0 G ^H ! X j> 1, ch. P Л Э π ή ' 0,025 0.0 (20) OH CH ⁷³ and CH, Cs (20 OH j (CH 2 C-CH-CHCHCH-CH 0,025 0.0 0,025 0.0

(22) concentration of the active substance in the spray suspension (% by weight) active substance (Example No) infestation in% compared to that of untreated control plants;

and

r (10)

Italy (11)

B-form

0,025

0,025

0,025

0,025

0.0

0.0

0.0

Example G

Seed dressing test - barley streak [Drechslera graminea (syn. Helminthosporium gramineum)]

The active ingredient is used in the form of a dry seed dressing, for which the respective active ingredient is mixed with stone flour to form a fine powder mixture ensuring uniform distribution of the active ingredient on the seed surface.

To soak, the infected seed is shaken with stain in a sealed glass bottle for 3 minutes.

The seed is then kept in a refrigerator at 4 gc for 10 days in a sieved, moist standard soil presented in closed Petri dishes, in which the barley germinates and eventually the spore of the fungus is germinated. The germinated barley seed is then sown in a 2 x 50 grain 3 cm depth into standard soil and cultivated in sowing boxes in a greenhouse at a temperature of about 18 ° C under 15-hour illumination daily.

Approximately 3 weeks after sowing, symptoms of streaking on the plants are detected.

The active substances, the active substance consumption and the results obtained are given in the following Table G.

Table G

Seed pickling test - barley stiffness active substance (example no.) Consumption of active substance (mg / kg seed) diseased plants in ° / o total emerging plants not infested

Claims (2)

pRedmet vynalezu К 1. A plant growth regulating and fungicidal composition, characterized in that the active substance comprises at least one azolyl-alkenon or -ol of the formula I X- ^R ^ ^C ^ H ^ C ^ H ^ = CH- ^RL (!) in which R 1 represents a grouping of the formula CH ₂ Zi I — C — CH ₃ CH ₂ Z ² wherein each of Z 1 and Z 2, which may be the same or different, represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl group or R 1 represents a phenyl group optionally substituted by one to three substituents selected from the group including halogen atoms, C 1 -C 4 alkyl groups and C 1 -C 4 alkoxy groups, R 2 represents a C 1 -C 12 alkyl group, optionally halogen and / or C 1 -C 4 alkyl substituted phenyl, C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkylalkyl; or 2 carbon atoms in the alkyl moiety, X is -CO- or -CH (OH) - and Y represents a nitrogen atom or a CH group, or an acid addition salt or a copper chloride complex thereof. 2. A process according to claim 1, wherein the compound of formula (II): EMI2.0 wherein: EMI2.0 [0015] wherein: EMI2.0 [0060] R ¹ , R ² and Y are as defined above, heated to a temperature of 50 to 120 ° C in the presence of a diluent and optionally in the presence of a catalyst, optionally in the presence of alumina, the azolyl alkenones formed according to formula Ia RIO-CH-CH = CH '/? ² (laJ in which R ¹ , R ² and Y are as defined above, optionally reduced in a known manner, and optionally the acid or copper chloride is added to the compounds of the formula I thus obtained.