DE3025242A1 - 2-Phenyl-1-triazolyl-vinyl halo-tert-butyl ketone and carbinol derivs. - with plant growth regulant, herbicide and fungicide activity - Google Patents

Abstract

2-Phenyl-1-(1,2, 4-triazol-1-yl)-vinyl halo-tert-butyl ketone and carbinol derivs. (I) and their acid. addn. salts and metal salt complexes are new. A is CO or CHOH; X is H or halogen; Y is halogen; R is halogen, alkyl, haloalkyl, halo- alkoxy, alkoxy, alkylthio, haloalkylthio, alkylamino, dialkyl- amino, NO2, CN, OH, alkylcarbonyloxy, opt. substd. phenyl, opt. substd. phenoxy or opt. substd. benzyloxy; and n is 0, 1, 2 or 3. (I) have plant growth regulant and fungicidal activity. As plant growth regulants (I) can be used for inhibiting or promoting vegetative growth, modifying plant metabolism without affecting vegetative growth (e.g. stimulating latex flow), inducing parthenocarpic fruit, influencing the sex of flowers, inducing pollen sterility, controlling branching, inducing defoliation, controlling fruit drop, accelerating or retarding fruit ripening, controlling seed or bud dormancy, or inducing resistance to frost, drought or high soil salinity. As fungicides, (I) can be used in plant protection esp. against true mildews, and not only exert a protective effect but also are systemically active. At appropriate rates of applicn. (I) can also be used as herbicides.

Description

Halogenated triazolylvinyl keto and carbinol

Derivatives, processes for their preparation and their use as Plant Growth Regulators and Fungicides The present invention relates to new ones halogenated triazolylvinyl keto and carbinol derivatives, a process for their Manufacture and their use as plant growth regulators and fungicides.

It has already become known that certain 4,4-dimethyl-1-phenyl-2-triazolyl-penten-3-ones and oils have good fungicidal effectiveness (cf. Japanese patent application J5 3130 661 and DE-OS 28 38 847) The effect of these compounds is, however, in particular with low wall quantities and concentrations, not always fully satisfactory. The plant growth-regulating effect of these azole derivatives is also not always completely satisfactory.

There were new halogenated triazolylvinyl keto and carbinol derivatives of the formula in which A stands for the keto group or the CH (OH) group, X stands for hydrogen or halogen, Y stands for halogen, R for halogen, alkyl, haloalkyl, haloalkoxy, alkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, nitro, Cyano, hydroxy, alkylcarbonyloxy, optionally substituted phenyl, optionally substituted phenoxy or optionally substituted benzyloxy and n is the numbers 0, 1, 2 or 3, and their physiologically acceptable acid addition salts and metal salt complexes have been found.

The compounds of the formula (I) according to the invention come in the geometric Isomers E (trans) and Z (cis).

In the E, Z nomenclature, those on the double bond are used Substituents classified according to the Cahn-Ingold-Prelog rule in decreasing priority. If the preferred substituents are on the same side of the double bond, is the configuration Z (derived from together) in front, they are opposite Side, is the con- figuration E (derived from "opposite").

If A stands for the CH (OH) group, there is an asymmetric one Carbon atom, so that the compounds of formula (I) in this case also occur in two optical isomer forms.

The present invention relates both to the individual isomers also isomer mixtures.

It has also been found that the halogenated triazolylvinyl keto and carbinol derivatives of the formula (1) and their acid addition salts and metal salt complexes are obtained when triazolyl ketones of the formula in which X and Y have the meaning given above, with aldehydes of the formula in which R and n have the meaning given above, reacts in the presence of a solvent and in the presence of a catalyst, optionally then the halogenated triazolylvinylketo derivatives of the formula in which X, Y, R and n have the meanings given above, reduced in the generally customary manner, and optionally then an acid or a metal salt is added to the compounds of the formula (I) obtained.

Finally it was found that the new halogenated triazolylvinyl-keto- and carbinol derivatives of the formula (I) and their acid addition salts and metal salt complexes have strong plant growth regulating and strong fungicidal properties.

Surprisingly, the compounds according to the invention show the Formula (I) a better fungicidal and growth-regulating effect than that from 4,4-Dimethyl-1-phenyl-2-triazolyl-1-penten-3-ones known from the prior art and oils, which are chemically and functionally obvious compounds. the Active ingredients according to the invention thus represent an enrichment of technology.

The halogenated triazolyl vinyl keto and carbinol derivatives according to the invention are generally defined by the formula (I). In this formula, X is preferably for hydrogen, fluorine, chlorine and bromine. Y preferably represents fluorine, chlorine and Bromine. The radical R is preferably for fluorine, chlorine, bromine; straight chain or branched alkyl, alkoxy and alkylthio each having 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio each with 1 to 2 carbon and up to 5 identical or different halogen atoms, such as in particular fluorine and chlorine atoms; Alkylamino and dialkylamino each having 1 to 2 carbon atoms in each alkyl part; Nitro, cyano, hydroxy and alkylcarbonyloxy of 1 to 4 carbon atoms in the ALkyLteil; R also preferably represents optionally substituted phenyl, Phenoxy and benzyloxy, where preferred substituents may be mentioned: fluorine, Chlorine, bromine and alkyl of 1 to 2 carbon atoms. A and the index n are preferably the meaning given in the definition of the invention.

Those compounds of the formula (I) in are particularly preferred where X is hydrogen and Y is fluorine or chlorine, or X and Y are the same and stand for fluorine or chlorine. ' R for fluorine, chlorine, methyl, isopropyl, tert-butyl, Methoxy, methylthio, isopropoxy, trifluoromethyl, difluorochloromethyl, fluorodichloromethyl, Trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluoromethoxy, trifluoromethylthio, l, l, 2-trifluoro-2-chloro-ethoxy and -ethylthio, dimethylamine, nitro, cyano, hydroxy, Acetoxy, tert-butylcarbonyloxy, and optionally single or double, the same or phenyl, phenoxy which is differently substituted by fluorine, chlorine and / or methyl and benzyloxy; A and the index n that specified in the definition of the invention Have meaning.

In addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (I) may be mentioned in detail: Table 1 Rn A x 4-Cl CO Cl Cl 4-Cl CH (OH) Cl Cl 4-C (CH3) 3 CO Cl Cl 4-C (CH3) 3 CH (OH) Cl Cl 2,4-Cl2 CO Cl Cl 2 , 4-Cl2 CH (OH) Cl Cl 2-Cl CO Cl Cl 2-Cl CH (OH) Cl Cl 4-C1 CO FF 4-C1 CH (OH) FF 4-C (CH3) 5 CO FF 4-C (CH3) 3 CH (OH) FF 2,4-Cl2 CO FF 2,4-C12 CH (OH) FF 2-C1 CO FF 2-C1 CH (OH) FF 4-CF3 CO H Cl 2-CF3 CO H Cl 2-Cl, 4-CF3 CO H Cl 4-OCH3 CO H Cl 4-SCH3 CO H Cl 4-OH CO H Cl 2 -OH, 3,5-Cl2 CO H Cl 4-NO2 CO H Cl 4 -OH , 3-OCH3 CO H Cl Table 1 (continued) AAXY CO H C1 44-C1 CO H C1 4-oe CO H C1 4-O4-C1 CO H C1 4-O-CH2%) 0 CO H C1 4-o-CH2 eC1 CO H C1 4-CF3 CH (OH) H C1 2-CF3 CH (OH) H C1 2-Cl'4-CF3 CH (OH) H C1 4-OCH3 CH (OH) H C1 4-SCH3 CH (OH) H C1 4-OH CH (OH) H C1 2-OH, 3,5-Cl2 CH (OH) H C1 4-NO2 CH (OH) H C1 4-OH, 3-OCH3 CH (OH) H C1 4 <CH (OH) H C1 4 <) - C1 CH (OH) H C1 4-043 /; ?? CH (OH) H C1 4-O-Cl CH (OH) H C1 4-o-CH2 4 CH (OH) H C1 4-O-CH2 4-C1 CH (OH) H C1 4-CF3 CO HF 2-CF3 CO HF 2-Cl, 4-CF3 CO HF 4-OCH3 CO HF 4-SCH3 CO HF Table 1 (continued) Rn AXY 4-OH CO HF 2-OH, 3,5-Cl2 CO HF 4-NO2 CO HF 4-OH, 3-OCH3 CO HF 4 <CO HF 4-Cl CO HF 4-0 to CO HF 4-0 - C1 CO HF 4-O-CH2 4 CO HF 4-0-CH, C1 CO HF 4-CF3 CH (OH) HF 2-CF3 CH (OH) HF 2-Cl, 4-CF3 CH (OH) HF 4-OCH3 CH (OH) HF 4-SCH3 CH (OH) HF 4-OH CH (OH) HF 2-oHs3s5-Cl2 CH (OH) HF 4-NO2 CH (OH) HF 4-OH, 3-OCH3 CH (OH) HF 4 <CH (OH) HF 4 v Cl CH (OH) HF 4-0 4 CH (OH) HF 4-0 <-Cl CH (OH) HF 4-O-CH2 4 CH (OH) HF 4-O-CH2Cl CH (OH) HF If, for example, chloropinacolyl-1,2,4-triazole and 4-chlorobenzaldehyde are used as starting materials, the sequence of the process according to the invention can be represented by the following equation; If, for example, 1-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4-t1,2,4-triazol-1-yl) -4-penten-3-one and sodium borohydride are used as starting materials, then the sequence of the method according to the invention can be represented by the following equation: The triazolyl ketones required as starting materials when carrying out the process according to the invention are generally defined by the formula (II). In this formula, X and Y preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The triazolyl ketones of the formula (II) are known (see DE-OS 2,820,361) or can be synthesized by known processes. Triazolyl ketones of the formula (II) are thus obtained, for example, by using haloketones of the formula in which X and Y have the meaning given above and Hal is chlorine or bromine, with 1,2,4-triazole in the presence of a diluent such as acetone, and in the presence of an acid binder such as potassium carbonate, at temperatures between 20 and 1500C implements.

The haloketones of the formula (IV) are known (compare, for example, DE-OS 2 632 603 and DE-OS 2 843 767) or are obtained in a generally known manner by using compounds of the formula in which X and Y have the meaning given above, chlorine or bromine are added in the presence of an inert organic solvent at room temperature; or e.g.

with common chlorinating agents, such as sulfuryl chloride, at 20 to 600C implements.

Also used as starting materials for the process according to the invention Aldehydes to be used are generally defined by the formula (III). In this Formula, R and the index n preferably represent the radicals that are already related with the description of the substances of the formula (I) according to the invention preferably for this substituent or for this. Index were named the Aldehydes of the formula (III) are generally known compounds in organic chemistry.

The preferred solvents for the process according to the invention are inert organic solvents. These preferably include alcohols, such as Methanol and ethanol; Ethers such as tetrahydrofuran and dioxane; aliphatic and cycloaliphatic Hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons, such as Benzene, voluene and cumene; halogenated aliphatic and aromatic hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform, chlorobenzene and dichlorobenzene.

The inventive method is carried out in the presence of a catalyst carried out. You can use all commonly used acidic and especially basic Use catalysts and their buffer mixtures. These preferably include Lewis acids such as boron trifluoride, boron trichloride, tin tetrachloride, or titanium tetrachloride; organic bases such as pyridine and piperidine; and in particular piperidine acetate.

The reaction temperatures can when carrying out the invention Procedure can be varied over a wide range. Generally one works between 20 and 1600C, preferably at the boiling point of the respective solvent.

When carrying out the process according to the invention, one sets up 1 mole of triazolyl ketone of the formula (II) 1 to 1.5 moles of aldehyde of the formula (and catalytic to 0.2 molar amounts of catalyst. The end products of formula (T) fall preferably as E / Z isomer mixtures.

Separation into the pure isomers is in the usual manner possible, e.g. by crystallization or by chromatographic separation processes.

The reduction according to the invention is carried out in the usual way, e.g. by Reaction with complex hydrides, optionally in the presence of a diluent, or by reaction with aluminum isopropoxide in the presence of a diluent.

If you work with complex hydrides, then come as a diluent Polar organic solvents are suitable for the reaction according to the invention preferably include alcohols such as methanol, ethanol, butanol, isopropanol, and Ethers such as diethyl ether or tetrahydrofuran. The reaction is generally at -10 to + 30 ° C, preferably carried out at -10 to 20 ° C. To do this, you put on 1 mole of the ketone of the formula (Ia) about 1 mole of a complex hydride, such as sodium borohydride, Calcium borohydride or lithium alanate.

To isolate the reduced compounds of the formula (I), the The residue was taken up in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent. The further work-up takes place in the usual way, as well as a possible separation of the E / Z isomer mixtures.

If you work with aluminum isopropylate, then come as a diluent alcohols such as isopropanol, or inert ones, are preferred for the reaction according to the invention Hydrocarbons such as benzene can be used. The reaction temperatures can turn can be varied over a wider range; in general one works between 20 and 120 ° C, preferably at 50 to 1000C. To carry out the re- action 1 to 2 moles of aluminum isopropoxide are added to 1 mole of the corresponding ketone of the formula (Ia) a.

To isolate the reduced compounds of the formula (I), the Excess solvent removed by distillation in vacuo and the resulting Aluminum compound decomposed with dilute sulfuric acid or caustic soda. the further work-up takes place in the customary manner.

The reduction with aluminum isopropylate gives only the Z isomers.

A clear characterization feature for the two geometrical ones Isomer is the H1 nuclear resonance of the two triazole protons, the difference in the shift values for these two protons is roughly twice as large in the E forms as in the corresponding Z-shapes.

For the production of physiologically compatible acid addition salts of the compounds of the formula (I) are preferably the following acids: The Hydrohalic acids, such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid. Sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, dumaric acid, tartaric acid, citric acid, salicylic acid, Sorbic acid, lactic acid, and sulfonic acids, such as p-toluenesulfonic acid and 1, 5-naphthalenedisulfonic acid.

The acid addition salts of the compounds of the formula (I) can be used in simply by using common salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. hydrochloric acid, and in a known manner, e.g. by filtering off, isolated and optionally by washing with an inert organic solvent getting cleaned.

For the preparation of metal salt complexes of the compounds of the formula (I) are preferably salts of metals of the II. To IV. Main group and the I. and II. as well as IV. to VIII. subgroup of the periodic table in question, whereby copper, Zinc, manganese, magnesium, tin, iron and nickel may be mentioned by way of example.

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

The metal salt complexes of compounds of the formula (I) can be used in can easily be obtained by conventional methods, for example by dissolving the Metal salt in alcohol such as ethanol and adding to the compound of formula (1). Metal salt complexes can be used in a known manner, e.g. by filtering off or isolating and, if necessary, purify by recrystallization.

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

The following applies to the mode of action of plant growth regulators previous experience that an active ingredient also has several different effects can exert on plants. The effects of the substances depend essentially on the time of application based on the stage of development of the plant as well of the amounts of active ingredient applied to the plants or their environment and of the kind of A ?? likaticn. In any case, the crop plants should be growth regulators influence in a certain desired way.

Substances regulating plant growth can be used, for example, to inhibit the vegetative growth of the plants are used. Such an inhibition of growth is of economic interest for grasses, among other things, because it can the frequency of grass cuttings in ornamental gardens, parks and sports facilities, at roadsides, at airports or in self-contained systems. Inhibition is also important the growth of herbaceous and woody plants on and near roadsides of pipelines or overland lines or more generally in areas where a strong growth of the plants is undesirable.

The use of growth regulators for inhibition is also important the growth in length of grain. This reduces the risk of the primary buckling ("storage") of the plants before harvest or eliminated whole grains. You can also use growth regulators cause a stalk reinforcement in grain, which also counteracts storage. The use of growth regulators for shortening and strengthening the stalk is permitted it is to apply higher amounts of fertilizer in order to increase the yield without the danger insists that the grain is stored.

Inhibition of vegetative growth is made possible in many cultivated plants a denser planting, so that additional yields are achieved in relation to the soil area can be. One advantage of the small natural plants is also that the culture can be worked and harvested more easily.

This can also inhibit the vegetative growth of the plants that the nutrients and assimilates lead to increases in yield to a greater extent the flower and fruit formation benefit than the vegetative parts of the plant.

Growth regulators can often also be used to promote the achieve vegetative growth. This is of great use when the vegetative Plant parts are harvested. However, vegetative growth can be promoted also at the same time lead to a promotion of generative growth by the fact that more assimilates are formed, so that more or larger fruits arise.

In some cases, yield increases can be achieved through an intervention in the vegetable metabolism can be achieved without any changes in the vegetative Make growth noticeable. Furthermore, a change can be made with growth regulators the composition of the plants can be achieved, which in turn leads to an improvement in quality which can lead to harvested products. For example, it is possible to check the sugar content in sugar beet, sugar cane, pineapple as well as in citrus fruits or to increase the protein content Boost in soy or grain. It is also possible, for example, to dismantle desired ingredients, such as e.g.

Sugar in sugar beet or sugar cane, with growth regulators or to inhibit after harvest. In addition, the production or the outflow positive influence of secondary plant constituents.

An example is the stimulation of the latex flow in rubber trees called.

Under the influence of growth regulators it can lead to training parthenocarpic fruits come. The sex of the flowers can also be influenced will. Sterility of the pollen can also be created, which is what happens during breeding and the production of hybrid seeds is of great importance.

Through the use of attitude regulators, the depravity can be reduced control of plants. On the one hand, by breaking the apical dominance, the development are promoted by side shoots, which is particularly in connection with ornamental plants with stunted growth can be very desirable. On the other hand, it is also possible inhibit the growth of the side shoots. There is great interest in this effect, for example when growing tobacco or when planting tomatoes.

Under the influence of growth regulators, the leaf population of the Plants are controlled so that a defoliation of the plants to a desired one Time is reached. Such defoliation takes place in mechanical harvesting But cotton also plays an important role in other crops such as viticulture to facilitate the harvest of interest. A defoliation of the plants can also be made to reduce transpiration of the plants before transplanting.

Likewise, the fruit fall can be controlled with growth regulators. On the one hand, premature fruit fall can be prevented. On the other hand, can but also the fall of the fruit or even the fall of the flowers to a desired one Measures are encouraged ("thinning") in order to break the alternation. Under alternation one understands the peculiarity of some types of fruit, endogenously from year to year to bring different yields. Finally, it is possible with growth regulators to reduce the forces required to detach the fruit at the time of harvest, to enable mechanical harvesting or to facilitate manual harvesting.

Growth regulators can also be used to accelerate or also delay the ripening of the crop before or after the harvest. This is of particular advantage because it allows an optimal adaptation to the needs of the market.

Furthermore, growth regulators can in some cases reduce the color of the fruit to enhance. In addition, growth regulators can also be used to concentrate over time maturity can be achieved. This creates the conditions for e.g. with tobacco, Tomato or coffee a full mechanical or manual harvesting can be carried out in one operation.

By using growth regulators, the seed or Bud rest of the plants can be influenced, so that the plants, e.g. pineapple or ornamental plants in nurseries, germinate, sprout or bloom at a time, on which they normally show no willingness to do so. A delay in the Budding or germination of seeds with the help of growth regulators may be desirable in frost-prone areas to prevent damage from late frosts to avoid.

Finally, growth regulators can make the plants more resistant against frost, drought or high salinity of the soil. Through this the cultivation of plants is possible in areas that are normal for this are unsuitable.

The active ingredients according to the invention also have a strong microbicidal effect Effect on and can come in handy for combating unwanted microorganisms The active ingredients are for use as pesticides suitable.

Fungicidal agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in the control Concentrations necessary for plant diseases allow the treatment of above-ground parts of plants, of plant material and seeds, and of the soil.

The active compounds according to the invention can also be used as crop protection agents particularly good success for combating such fungi are used, the real ones Cause powdery mildew diseases; so for the control of Erysiphe species, such as e.g. against the pathogen of barley or powdery mildew (Erysiphe graminis) and of cucumber powdery mildew (Erysiphe cichoracearum); as well as to combat Pyricularia oryzae and Pellicularia sasakii.

It should be particularly emphasized that the active ingredients according to the invention not only have a protective effect, but are also systemically effective In this way it is possible to protect plants against fungal attack if the active ingredient is used the soil and the roots or, via the seeds, the above-ground parts of the plant feeds.

The compounds according to the invention show when applied in appropriate amounts also has a herbicidal effect.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Active ingredient-impregnated natural and synthetic materials, fine encapsulation in polymers Substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, coils and the like, as well as ULV cold and warm smoke formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents Liquefied gases under pressure and / or solid carriers, if appropriate with the use of surface-active agents, that is, emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, retones 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 meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates, e.g.

broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-generating agents are possible: e.g.

non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular and latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo 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 Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in the formulations or in the various application forms mixed with other known active ingredients present, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, Protective substances against bird damage, growth substances, plant nutrients, soil structure improvers and plant growth regulators.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, emulsions, suspensions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by watering, dipping, spraying, Spraying, atomizing, vaporizing, injecting, silting up, spreading, dusting, Spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting. It is also possible to apply the active ingredients using the ultra-low-volume method or to prepare the active ingredient or to inject the active ingredient itself into the soil. The seeds of the plants can also be treated.

When using the compounds according to the invention as plant growth regulators the application rates can be varied over a wide range. In general 0.01 to 50 kg, preferably 0.05 to 10 kg of active ingredient are used per hectare of soil area.

When using the substances according to the invention as plant growth regulators applies that the application is carried out in a preferred period of time, its exact Delimitation itself according to the climatic and vegetative Realities.

Even when the substances according to the invention are used as fungicides the application rate varies over a wide range depending on the type of application will. This is how the active ingredient concentrations are in the treatment of parts of plants in the use forms generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment of 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, the active ingredient concentrations are 0.00001 up to 0.1% by weight, preferably from 0.0001 to 0.02, required at the site of action.

Preparation examples Example 1 E / Z isomer mixture Example 2 E isomer 201.5g (1 mol) of 1-chloro-2,2-dimethyl-4- (1,2,4-triazol-1-yl) -butan-3-one, 140.5g (1 mol) 4 -Chlorobenzylaldehyde and 9.9 ml of piperidine and 30 g of glacial acetic acid are refluxed in 300 ml of toluene for 8 hours, the resulting water of reaction being removed azeotropically. The reaction mixture is then washed with water and with dilute sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated in vacuo. 305.9 g (94.4% of theory) of crude l-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4- are obtained penten-3-one with a boiling point of 1650C / 0.1 Torr as an E, Z isomer mixture.

The E-isomer can be obtained by stirring with isopropanol or ethanol isolate in crystalline form. It has a melting point of 1120C.

Manufacture of the starting product 43.3 g (0.32 mol) of l-chloro-2,2-dimethyl-butan-2-one are dissolved in 250 ml of ether and 52 g (0.325 mol) of bromine are added dropwise at 20 ° C. while cooling. the ethereal solution was washed five times with 100 ml of water each time, dried over sodium sulfate and concentrated in vacuo. The resulting 4-bromo-1-chloro-2,2-dimethylbutan-2-one is taken up in 50 ml of acetone and, at room temperature, with cooling, dropwise to a mixture of 23.1 g (0.33 mol) i, 2.4- Triazole and 46.2 g (0.4 mol) of potassium carbonate in 250 ml of acetone. The mixture is stirred for 4 hours at 20 ° C., the inorganic precipitate is filtered off with suction and the filtrate is concentrated in vacuo. 57.9 g (90% of theory) of 1-chloro-2,2-dimethyl-4- (1,2,4-triazoll-yl) -butan-2-one, which can be further reacted directly, are obtained.

11.6 g (01 mol) of 2,2-dimethyl-1-hydroxy-butan-3-one are at 50 to 600C (ice cooling) was added dropwise to 20.5 g (0.1 mol) of N, N-diethyl-1,2,2-trichlorovinylamine. After stirring for two hours at 60 ° C., the mixture is distilled in a water jet vacuum.

8.1 g (60% of theory) of 1-chloro-2,2-dimethylbutan-3-one are obtained from melting point 60 - 620C / 12mm.

(The 1-chloro-2,2-dimethyl-butan-3-one is obtained in a yield of 90% if equimolar amounts of 2,2-dimethyll-hydroxy-butan-3-one and triphenylphosphine are added in ten times the amount of carbon tetrachloride Heated under reflux for 12 hours, the solvent was distilled off, the residue was taken up in ether, filtered and distilled.) To 172 g (2 mol) of methyl isopropyl ketone in 1000 ml of methanol, 66 g (2.2 mol) of paraformaldehyde and 1 g of potassium hydroxide in 10 ml of methanol are added dropwise. The mixture is refluxed for 15 hours and the methanol is then distilled off through a column at an internal temperature of 820C. The residue is distilled in a water jet vacuum. 152.7 g (68% of theory) of 2,2-dimethyl-1-hydroxy-butan-3-one with a boiling point of 80-820C / 12mm are obtained.

EXAMPLE 3 Mixture of isomers 162g (0.5 mol) of l-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-penten-3-one ( Example 1) are dissolved in 500 ml of isopropanol and, while stirring, 9.5 g (0.25 mol) of sodium borohydride are added in portions. The reaction mixture is allowed to stir for 10 hours at room temperature and then concentrated in vacuo. The residue is taken up in toluene, washed with dilute acetic acid and then with water, dried over sodium sulfate and concentrated in vacuo. 156.6 g (96% of theory) of 1-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-pentene-3 are obtained -ol with a refractive index n2D0 = 1.5579 as an E / Z isomer mixture.

Example 4 Z-isomer 48.6g (0.15 mol) l-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-pentene- 3-one (Example 1) and 30.6g (0.15 mol) of aluminum isopropoxide are refluxed in 200 ml of isopropanol for 7 hours, with isopropanol and acetone continuously distilled off via a 30 cm Vigreux column until acetone can no longer be detected in the distillate . The reaction mixture is then concentrated, and ice / hydrochloric acid is added to the residue. Extract with methylene chloride. The combined methylene chloride extracts are dried over sodium sulfate and concentrated in vacuo. The oily residue is separated by column chromatography (silica gel / chloroform). The unreduced E-isomer of l-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-l-yl) penten-3-one is obtained (Example 2) and pure 1-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2ffi4-triazol-1-yl) penten-3-ol with a melting point of 1200C as the Z isomer. Example 5 2.0 g (6.13 moles) of the E isomer of 1-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-tria701-1-yl) -4-pentene -3-ons (Example 2) and 0.467g (4.11 mol) of calcium chloride are dissolved in 30 ml of isopropanol and a solution of 0.167g (4.3 mmol) of nadrium borohydride is added dropwise at -50C. After 6 hours, the reaction mixture is heated to 250 ° C. and concentrated in vacuo. The residue is poured into water and extracted with ethyl acetate.

The combined ethyl acetate extracts are dried over sodium sulfate and concentrated in vacuo. The oily residue crystallizes on stirring with diisopropyl ether. 1.1 g (55% of theory) of l-chloro-5- (4-chlorophenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) -4-pentene-3 are obtained -oil of melting point 1700C as E-isomer.

The following compounds of the general formula (I) are obtained in a corresponding manner: Table 2 E.g. melting point (° C) No. Rn AXY or refractive index nD20 6 4-Cl CO HF 1.5672 7 4-C (CH3) 3 CO HF 1.5565 8 4-C (CH3) 3 CO H Cl 1.5655 (Z-Isom.) 9 4-N (CH3) 2 CO HF 100 10 4-N (CH3) 2 CO H Cl 84 11 2-C1 CO HF 1.5632 (E-Isom.) 12 4-Cl CH (OH) HF 230 (x NDS) 13 4-C1 CH (OH) HF 11O (Z-Isom.) 14 4-C (CF3) 3) 3 CH (OH) HF 1.5250 15 4-C (CH3) 3 CH (OH) H Cl 1.5820 (Z-Isom.) 16 4-N (CH3) 2 CH (OH) HF 118 (Z-Isom.) 17 4-N (CH3) 2 CH (OH) H Cl 120 (Z-Isom.) 18 2-C1 CH (OH) HF 116 (Z-Isom.) 19 2-C1 CH (OH) HF 140 (E-Isom.) 20 4-OCF3 CH (OH) H Cl 100 (Z-Isom.) 21 4-OCF3 CH (OH) H Cl 140 (E-Isom.) 22 2,4-Cl2 CH (OH) HF 150 (Z-Isom.) 23 2,4-Cl2 CH (OH) HF 158 (E-Isom.) NDS = 1,5-naphthalenedisulfonic acid E.g. melting point (° C) No. Rn AXY or refractive index n20 D. 24 4-C1 CO FF 1.5728 25 2,4-C12 CO FF 1.5778 26 4-C1 CO C1 Cl 1.5942 27 2,4-Cl2 CO Cl Cl 1.5868 28 4-C1 CH (OH) FF 74 (E-Isom.) 29 4-C1 CH (OH) FF 110 (Z-Isom.) 30 2,4-C12 CH (OH) FF 157 (E-Isom.) 31 2,4-C12 CH (OH) FF 154 (Z-Isom.) 32 4-Cl CH (OH) Cl Cl 150 (Z-Isom.) 33 2,4-Cl2 CH (OH) Cl Cl 148 (Z-Isom.) Application examples In the application examples below, the compounds specified below are used as comparison substances: Example A Growth inhibition in soybeans Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and made up to the desired concentration with water.

Soybean plants are grown in the greenhouse to full development of the first following sheet tightened. At this stage the plants will become dripping wet sprayed with the active ingredient preparations. After 3 weeks, the Growth measured and the inhibition of growth as a percentage of the growth of the control plants calculated. Loo S growth inhibition mean the standstill of growth and 0 ° a Growth similar to that of the control plants.

A very clear superiority in effectiveness over the Compounds (A), (B), (D), (E), (F) and (G) known from the prior art show in this test, for example, the compounds according to the following preparation examples: 3, 4, 7, 12, 13 and 14.

Example B Inhibition of growth in cotton Solvent: 30 parts by weight Dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active compound, 1 part by weight is mixed Active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Cotton plants are grown in the greenhouse until the 5. Follower sheet tightened. At this stage the plants will become dripping wet with the Sprayed active ingredient preparations. The growth of the plants is measured after 3 weeks and the inhibition of growth is calculated as a percentage of the growth of the control plants. It loo t0 growth inhibition means the standstill of growth and 0% a growth accordingly that of the control plants.

A very clear superiority in effectiveness over the show compounds (A), (B), (E), (F) and (H) known from the prior art in this test, for example, the compounds according to the following preparation examples: 3, 4, 7, 13 and 14.

Example c Inhibition of growth in sugar beets Solvent: 30 parts by weight Dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate for To produce an appropriate preparation of active compound, 1 part by weight is mixed active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Sugar beets are grown in the greenhouse until the cotyledons are fully developed dressed. At this stage the plants become dripping wet with the active compound preparations sprayed. After 14 days, the growth of the plants and the inhibition of growth are measured calculated as a percentage of the wax of the control plants. It means O% inhibition of growth a growth corresponding to that of the control plants. 100% growth inhibition means Growth stagnation.

The active ingredients 3, 4, 12 and 13 according to the invention show in this Test a better growth inhibition than the compounds known from the prior art (E) and (F).

Example D Drought resistance in sugar beets When treating young ones Sugar beet plants with the active compound preparation was particularly useful in the case of the one according to the invention Example 3 in the concentrations 250 and 125 ppm a resistance to soil drought established.

Example E Erysiphe test (barley) / protective / solvent: 100 parts by weight Dimethylformamide emulsifier: 0.25 part by weight of alkyl aryl polyglycol ether for production 1 part by weight of active ingredient is mixed with an appropriate active ingredient preparation the indicated tongues solvent and emulsifier and tinned the concentrate with Water to the desired concentration.

To test for protective effectiveness, young plants are sprayed dew damp with the active ingredient preparation.

After the spray coating has dried on, the plants become infected with spores Erysiphe graminis f.sp.hordei pollinated.

The plants are in a greenhouse at a temperature of approx. 200C and a relative humidity of approx. 80% set up for the development to benefit from powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

A clear superiority in effectiveness compared to the off Compounds (B) and (E) known from the prior art show in this test e.g. the compound according to the following preparation examples: 6,7,3,4,12,13 and example w Barley powdery mildew test (Erysiphe graminis var.hordei) / systemic (fungal cereal sprout disease) The active ingredients are used as powdered seed treatment agents. They are made by stretching the active ingredient with a mixture of the same Parts by weight of talc and diatomaceous earth to a fine powdery mixture with the desired Active ingredient concentration.

For seed treatment, barley seeds are shaken with the barley seed Active ingredient in a sealed glass bottle. The seeds are sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of one volume of Fruhstorfer standard soil and a volume of quartz sand. Germination and emergence take place under favorable conditions in the greenhouse. 7 days after sowing when the barley plants when their first leaf has unfolded, they are filled with fresh spores of Erysiphe graminis var.hordei pollinated and at 21-220C and 80-90% relative humidity and for i6 hours Exposure further cultivated. Form on the leaves within 6 days the typical powdery mildew pustules.

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

A clear superiority in effectiveness compared to the off Prior art compound (H) shows, for example, the compound in this test according to preparation example 3.

Example G wrysiphe test (cucumber) / Protective solvent: 4.7 parts by weight Acetone emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether, water 95.0 parts by weight : n mixes the concentration required for the desired active substance in the spray liquid necessary amount of active ingredient with the specified amount of solvent and diluted the concentrate with the specified amount of water, which contains the additives mentioned Young cucumber plants with around three leaves are sprayed with the spray liquid until dripping wet.

The cucumber plants remain in the greenhouse to dry for 24 hours. They are then pollinated with conidia of the fungus Erysiphe cichoracearum for inoculation.

The plants are then at 23 to 240C and at a relative Humidity of about 75% in the greenhouse.

The attack on the cucumber plants is determined after 12 days. The received Rating values are converted into percent infestation. 0% means no infestation, 100 ffi means that the plants are completely infected.

In this test, the following compounds, for example, show very good results Effect similar to that of the compounds (D) and (E) known from the prior art is superior: compounds according to preparation examples: 6, 7, 14, 2 and 13.

Claims (10)

Claims 1) Halogenated triazolylvinyl keto and carbinol derivatives of the formula in which A stands for the keto group or the CH (OH) group, X stands for hydrogen or halogen, Y stands for halogen, R for halogen, alkyl, haloalkyl, haloalkoxy, alkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, nitro, Cyano, hydroxy, alkylcarbonyloxy, optionally substituted phenyl, optionally substituted phenoxy or optionally substituted benzyloxy and n stands for the numbers 0, 1, 2 or 3, and their physiologically acceptable acid addition salts and metal salt complexes. 2) Halogenated triazolyl vinyl keto and carbinol derivatives of the formula (1), in which A stands for the keto group or the -CH (OH) group, X for hydrogen, Stands for fluorine, chlorine or bromine, Y stands for fluorine, chlorine or bromine, R stands for fluorine, chlorine, Bromine, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and up to to 5 halogen atoms, haloalkoxy with 1 or 2 carbon atoms and up to 5 halogen atoms, Haloalkylthio with 1 or 2 carbon atoms and up to 5 halogen atoms, alkylamino with 1 or 2 carbon atoms, dialkylamino with 1 or 2 carbon atoms per alkyl group, Nitro, cyano, hydroxy, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl group, for optionally by fluorine, chlorine, bromine and / or alkyl with 1 or 2 carbon atoms substituted phenyl, for optionally by fluorine, chlorine, bromine and / or alkyl with 1 or 2 carbon atoms substituted phenoxy or for optionally by Fluorine, chlorine, bromine and / or alkyl substituted with 1 or 2 carbon atoms Benzyloxy stands and n stands for the numbers =, lt 2 or 3, as well as their acid addition salts and metal salt complexes. 3) Halogenated triazolylvinyl keto and carbinol derivatives of the formula (I) in which X is hydrogen and Y is fluorine or chlorine. 4) Halogenated triazolylvinyl keto and carbinol derivatives of the formula (I) in which X and Y are the same and represent fluorine or chlorine. 5) Halogenated triazolylvinyl keto and cabinol derivatives of the formula (I), in which R stands for fluorine, chlorine, methyl isopropyl, t-butyl, methoxy, methylthio, Isopropoxy, trifluoromethyl, difluoromethyl, fluorodichloromethyl, trichloromethyl, 1,1,2-trifluoro-2-chloro-ethyl, trifluoromethoxy, trifluoromethylthio, 1,1,2-trifluoro-2-chloro-ethoxy and -ethylthio, dimethylamino, nitro, cyano, hydroxy, acetoxy, t-butylcarbonyloxy, as well as for optionally single or double, identical or different by fluorine, Phenyl, phenoxy and benzyloxy substituted with chlorine and / or methyl. 6) Process for the preparation of halogenated triazolylvinyl keto and carbinol derivatives of the formula (I) and their acid addition salts and metal salt complexes, characterized in that triazolyl ketones of the formula in which X and Y have the meaning given above, with aldehydes of the formula in which R and n have the meaning given above, in the presence of a solvent and in the presence of a catalyst, optionally then reacts the halogenated triazolylvinylketo derivatives of the formula in which X, Y, R and n have the meanings given above, reduced in the generally customary manner, and optionally then an acid or a metal salt is added to the compounds of the formula (I) obtained. 7) Plant growth regulating and fungicidal agents, labeled by a content of at least one halogenated triazolylvinyl-keto or carbinol derivative of the formula (I) or an acid addition salt or Metal salt complex of a halogenated triazolylvinyl-keto or. carbinol derivative of the formula (I). 8) Methods of regulating plant growth and combating them of fungi, characterized in that halogenated triazolylvinyl-keto or carbinol derivatives of formula (I) or their acid addition salts or metal salt Complexes on the plants and / or their habitat or on the fungi and / or their habitat. 9) Use of halogenated triazolylvinyl keto and carbinol derivatives of formula (I) or of acid addition salts or metal salt complexes of halogenated Triazolylvinyl keto and carbinol derivatives of the formula (I) for regulating plant growth or to combat fungi. 10) Process for the production of plant growth regulating and fungicidal agents characterized in that halogenated triazolylvinyl-keto- or carbinol derivatives of the formula (I) or acid addition salts or metal salt complexes of halogenated triazolylvinyl keto or carbinol derivatives of the formula (I) with Mixing extenders and / or surfactants.