DE3018866A1 - 1-Hydroxy-1-azolyl-ethane derivs. and oxirane precursors - useful as fungicides and plant growth regulators - Google Patents

Abstract

Azole derivs. of formula (I), their acid addn. salts and metal salt complexes are new. R is alkyl or opt. substd. cycloalkyl or phenyl. X is nitrogen or CH. Y is OCH2, CH2CH2 or CH=CH. Z is halo, alkyl (opt. substd. by halo), cycloalkyl, alkoxy or alkylthio (both opt. substd. by halo) or opt. substd. phenyl, phenoxy, phenylalkyl or phenylalkoxy. m is 0-3. Also new are intermediates of formula (II). (I) are useful as fungicides (esp. against true mildews such as Erysiphe species and have both preventative and systemic actions and as plant-growth regulators. Typical responses include inhibiting vegetative growth of cereals etc., increasing sugar content of beet, and protein content of soya; stimulating latex flow in rubber trees; induction of parthenocarpic fruiting; breaking apical dominance, defoliation, acceleration of ripening; improving resistance to adverse climatic conditions etc. They are more effective than known cpds. such as 2-chloroethylphosphonic acid.

Description

l-Hydroxyethyl-azole derivatives, process for their preparation

position and their use as plant growth regulators and Fungicides.

The present invention relates to new l-hydroxyethylazole derivatives, a process for their production and their use as plant growth regulators and fungicides.

It is already known that certain -haloethyl-trialkyl-ammonium halides have plant growth regulating properties (see US patent 3 156 554). For example, 2-chloroethyl-trimethyl-ammonium chloride can be used influencing plant growth, especially inhibiting vegetative growth Achieve plant growth in important crops. However, the effectiveness is this substance, especially at low application rates, is not always sufficient.

It is also known that 2-chloroethylphosphonic acid regulates plant growth Has an effect (compare DE-OS 1 667 968). The ones achieved with this substance However, results are not always satisfactory either.

Furthermore, it has already become known that Zimk-ethylene-1,2-bisdithiocarbamidate is a good means of combating fungal plant diseases (compare Phytopathology 33, 1113 (1963)). However, its use is only possible to a limited extent, since it is not always the case, especially when the application rates and concentrations are low is satisfactorily effective.

There were new l-hydroxyethyl-azole derivatives of the general formula in which represents alkyl, optionally substituted cycloalkyl or optionally substituted phenyl, X represents a nitrogen atom or the CH group.

Y stands for the groupings -OCH2-, -CM2 CH2 -or -CH = CH-, Z stands for Halogen, alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, optionally substituted phenyl, optionally substituted tuated Phenoxy, optionally substituted phenylalkyl or optionally substituted Phenylalkoxy and m stands for the numbers 0, 1, 2 or 3, as well as their acid addition salts and metal salt complexes found.

The compounds of the formula (I) have an asymmetric carbon atom and can therefore occur in the two optical isomer forms. If Y is for the Grouping -CH = CH-, the compounds of formula (I) can additionally in two geometric isomeric forms exist. The present invention relates to both the isomer mixtures and the. individual isomers.

It has also been found that the l-hydroxyethylazole derivatives of the formula (I) are obtained when oxiranes of the formula in which R, Y, Z and m have the meaning given above, with azoles of the formula in which X has the meaning given above, is reacted in the presence of a diluent and, if appropriate, in the presence of a base and, if appropriate, an acid or a metal salt is then added to the compounds of the formula (Ij).

It was also found that the new l-Mydroxyethylazoi derivatives of formula (I) strong plant growth regulating and strong fungicidal properties own.

Surprisingly, the 1 * hydroxy-azole derivatives according to the invention show of formula (I) a better plant growth regulating effect than the known 2-chloroethyltrimethylammonium chloride and as the also known 2-chloroethylphosphonic acid, which are recognized as effective substances of the same type of effect. Also own the compounds according to the invention surprisingly have a better fungicidal effect, than the zinc-ethylene-1,2-bisdithiocarbamidate known from the prior art, which is an effective connection. The active ingredients according to the invention thus represent an enrichment of the technology.

The e rfindungsgemä3 en l-hyd ^ oxyethyl-azole derivatives are by the Formula (i) generally defined. In this formula, R preferably stands for straight chain or branched alkyl having 1 to 4 carbon atoms, optionally through alkyl cycloalkyl substituted by 1 to 2 carbon atoms and having 3 to 7 carbon atoms and for those which are optionally substituted one or more times, identically or differently Phenyl, the following preferably being possible as substituents: halogen, alkyl with 1 to 4 carbon atoms and haloalkyl with 1 to 2 carbon and 1 to 5 identical or different halogen atoms, such as in particular fluorine and chlorine atoms. Z preferably represents halogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, alkoxy and alkylthio each having 1 to 4 carbon atoms, haloalkyl and haloalkoxy and haloalkylthio each with 1 to 2 carbon and 1 to 5 identical or different halogen atoms, such as, in particular, fluorine and chlorine atoms and for each optionally substituted one Phenyl, phenoxy and phenylalkyl and phenylalkoxy with 1 to 2 carbon atoms in the alkyl part or in the alkoxy part, the following preferably being mentioned as substituents: Halogen and alkyl of 1 to 4 carbon atoms. X, Y and the subscript m are preferably the meaning given in the definition of the invention.

Particularly preferred are those compounds of the formula (I) in where R is tert-butyl, isopropyl or methyl, for each Cyclopropyl, cyclopentyl or cyclohexyl which is optionally substituted by ethyl stands as well as optionally single or double, equal or different through Fluorine, chlorine, methyl or trifluoromethyl substituted phenyl; Z for fluorine, Chlorine, bromine, methyl, tert-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyl, Trifluoromethoxy, trifluoromethylthio and for each optionally simple or Twice, identically or differently substituted by fluorine, chlorine and / or methyl Phenyl, phenoxy, benzyl or benzyloxy, and X, Y and the index m denote in the meaning given in the definition of the invention.

In addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (I) may be mentioned: Table 1 YYRX m -O-CH2- CH3) 3 N (CH) Cl C 1? 1 1? II 4-0 1 Cl 11 kl 4-CEZ 4 II 11 4-CII2 C1 according to II 11 4-O-CH2 1? t, II 4-O-CEI24SC1 l1 II 3, 4-C12 fl n fl 4-CF3 1l 11 4-OCF3 lt lt " 4-SCF3 lv II I1 4SCIj II vi iv 4-C (CMs (II iv vi Table 1 (continued) Zz, YRX 4 -O-CK, CN (CH) Cl lt vi ti 4-OD tv II acc 4-OX Cl lv iv iv 4-CM2 4 lv Ir 4-CH2 Cl vi iv lv 4-0-CM2 vi according to 4-O-CM2Cl lt vi iv 3, 4-C12 iv according to tr 4-CF3! 1 ii acc 4-OCF3 "according to 4-SCF3 iv lv lt 4-SCM3 lv lv vi 4-C (CM3) iv ii II Table 1 (continued) Zm YR 4> -O-CH2- -CM (CH) 2 N (CM) 4 lv lv lv 4-OD lv "n ii cm in iv vi 4-CH2 4 Q according to II 4-CH2 e Cl lv lv lv 4-o-cH2 4 e 4-0-CM2 #Cl lv rt 3, 4-C12 vi lv,. 4-CF3 II lv acc 4 OCF3 II iv iv 4-SCF ii vi iv 4-SCH3 lt lv Ii 4-C (CM3) ii ii Ii Table 1 (continued) Zm YRX -0-CM2 4 N (CM) Cl vi iv 4-OD lv ii iv 4-OX ci lt vi iv 4-CM2 In tor 4-CH4ZE C1 4-0-CM2 4 lv lt ii 4-0 -CM2 Cl vi Ii lt 3, 4-C12 lv vi ii 4-CF3 ii Ii ii 4-OCF3 l, iv iv 4-SCF lv II ii 4-5CM3 vi ii lt 4-C (CH3) ii ii iv Table 1 (continued) Zm YRX . ; {KDi; {1 CM) Cl vi 4-OD iv 1 ii 4-049 Cl lt fl vi 4-CH2 4 vi Ir 4-CH2 e Cl Ir tr 4-o-cH2 4 ii iv vi 4-0-CH, C1 Ir Ir 11 3, 4-C12 lt Ii lt 4-CF3 "lv ii 4-OCF3 vi iv vi 4-SCF3 lv tl acc 4-SCM3 vi iv ii 4-c (CH, CH3 lt vi Table 1 (continuation) Zm YRX - (O) N -C (CM3) 3 N (CM) Cl lt ii ci 4-OD lv iv vi 4-OE Cl iv lt II 4-CH2 4 vi Ir 4-CHa Cl Cl lt ii 4-owCH2 D lt Ii lt 4-O-CH2 C1 iv lv iv 3, 4-C12 iv ii iv 4-CF3 iv II dd 4-OCF3 iv iv ii 4-SCF3 vi Ii lt 4-SCH3 lv lv ii 4-C (CHS) 3 1l n lv Table 1 (continued) Zm YRX -CM2 -CM2 - Cl N (CH) Cl ii ii ii 4-0 4 vi ii 4-0 to Cl lv Ii iv 4-CH2 D " 4-Ci, Cl Cl t 4-O-CH2 rt n 4 ~ 0 ~ GH2 C1 3, 4-C12 iv iv iv 4-CF3 lv iv ii 4-OCF3 lv iv iv 4-SCF3 4-SCH3 lt iv iv 4-C (CM3) ii ii lv Table 1 (continued) zin YRX -CM2-CM2- -CM (CM3) 2 N (CM) Cl ii vi vi 4 ~ ° 43 11 ii 4-OE Cl iv vi iv 4-CH4 ,, vi ii 4-CM2 Cl (II, 4-o-cH2 vi 1 4- ° -CH2 vi ii vi 3, 4-Cl2 lv lv vi 4-CF3 vi vi ii 4-OCF3 ii ii iv 4-SCF ii ii vi 4-SCH, Ir rr 4-C (CHÇ), rt iv vi Table 1 (continued) Zm YRX -CM2 -CH2 -CH2 Cl lv vi ii 4-OD lv It 4-OX C1 lv vi iv 4-CM2 D iv ii Ii 4-CtI2 e Cl lv Ii 4-Q-CH2 4 vi vi ii 4-0-CM2 C1 't 3, 4 - C1a iv vi iv 4-CF3 ii vi vi 4-OCF'3 ii iv iv lv iv 4-SCF3 n vi 4-5CM3 vi vi vi 4-C (CH3) 3 1 n 4-C (CM1) lv vi Table 1 (continued) zin YRX 44 -CM2-CH2- ix N (CM) CH3 Cl iv iv ii 4-0 ii iv t 4-C e Cl "" 4-CM2 4 lv vi iv 4-CH2 e C1 n vi lv 4-0-CM2 4 lv lv vi 4-0-CM2 -O trl iv lt vi 3, 4-Cl2 II Z ii 4-CF3 ii t lv 4-OCF3 iv vi ii 4-SCF3 ii vi vi 4-SCM3 ii iv ii 4-C (CH3) ii iv iv Table 1 (continued) Zm YRX -CH = CH- -C (CH3) 3 N (CH) 4 vi iv lv 4-O ii iv ii Cl ii vi iv 4-CH2 lv vi vi 4-CH2 e Cl ii iv n 4-0-CM2 lv ii vi 4-0 CH2 vi lv 7, 4-C12 II vi iv 4-CF vi ii vi 4-OCF3 vi iv n 4-SCF5 iv vi iv 4-SCH3 4-c (cr, lv iv Table 1 (continued) YYRX -CM = CH- c, OCl N (CM) Cl iv ii iv 4-OD iv Z ii 4-OX C1 iv,! ,. 2 4 4-CH2 Cl iv lv vi 4-o-cH2 4 iv ii iv LO-CTI, .C1 tr iv lv lv ii 3, 4-C12 4-CF3 ii lv ii lv 4-OCF3 iv ii iv 4-SCF3 ii ii iv 4-5CM3 iv ii 4-C (CMs) 3 Ii iv vi Table 1 (continued) YYRX 4 4 ~ CH-CH ~ -CH (CH3) 2 N (CH) Cl iv lv ii 4-O Ii ii iv 4-0 Cl vi Ir 4-CM2 - (C, D ii lv iv 4-CH2 Cl iv vi iv 4-G-CH2 4> 4-0-CM2 e) -1 ii vi ii 3, 4-Cl2 lv lt ii 4-CF3 lv ii Ii 4-OCF3 4-SCF3 iv iv vi 4-SCH3 Ii lv iv 4-C (CM3) ii lt ii Table 1 (continued) YYR -CH = CH- ff \ N (CH) Cl C1 iv 4-OD ii iv ii 4-0 ii iv iv 4-CM2 4 vi Ii It 4-CM2 e Cl vi vi vv Lc-O-CH, 4 ii vi iv 4-0-CM2-Cl iv iv ii 3, 4-Cl2 iv iv ii 4-CF3 lv iv vi 4-OCF3 ii vi iv 4-SCF3 lv vi iv 4-SCM3 lv iv vi 4-C (CMs) 3 iv vv Ii Table 1 (continued) Zm YRX - -CH = CH- NN (CH) 4 e CM311 lv 4-0 4 iv ii Cl iv C1 "Ii 4-CM2 D vi ii Ii 4-CH2 e C1 ii iv vi iv / 7n ii 2 vi 4-0-CII, -V1 vi Ii ii 3,4-C1Z vi iv lv 4-CF3 n 11 1. 40CFj lv iv ii 4 - SCF3 iv vi iv 4-SCEI3 lv ii iv 4-C (CH3) vi lt ii Table 1 (continued) YYR x m 4-C1 -O-CH, - CH (CH, N (CM) 4-F nn,. 4-CH3 ii iv n 4-C1 -O-CH, e N (CH) 4-F n Ii vi 4-CH3 vi iv iv 4-C1 -0-CM2- g N (CM) CH3 4-F "Ii ii 4-CM3 iv iv ii 4-C1 -CM2-CM2- -CM (CM3) 2 N (CH) 4-F rt n ii 4 ~ CH3 IL ii Table 1 (continued) Zm YR 4-C1 -CM2 -CM2- e N (CH) 4-F rt 4-CH3 "11 II / 1 N (CM) 4-C1 -CM2 -CM2- N (CTi) V 3 4-F tr I rl 4-CM3 iv vi il 4-C1 -CH = CH- -CH (CH3) 2 N (CH) 4-F "iv iv 4-CE, ii ii Ii 4-Cl -CM = CM- NM (CH) 4-F "iv ii 4-CH3 ii iv ii Table 1 (continued) Zm YRX 4-C1 -CH = CH- N (CM) CH, 4-F ru is 4-CH3 iv ii ii 2,4-C12 -CM2-CM2- -C (CH3) 3 N (CH) 4-CM3 ii ii acc 4-C1, 2-CH3 vi rt ii 2,4-Cl2 -CH = CM- -C (CH3) 3 N (CM) 4-CH3 iv ii 4-C1, 2-CH3 rr no rr 4-F -O-CH, -C (CH3) 3 N (CM) 2-CH3 -CM2 -CH2 ~ - -C (CH3) 3 N 4-F-CH = CH- -C (CH3) 3 N If, for example, 2- (4-chlorophenoxymethyl) -2-tert-butyl-oxirane and ls2,4-triazole are used as starting materials, the sequence of the process according to the invention can be represented by the following equation: The oxiranes to be used as starting materials when carrying out the process according to the invention are generally defined by the formula (II). In this formula, R, Y, Z and the index m preferably represent the radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention, preferably for these substituents or for the index m.

The oxiranes of the formula in which R represents alkyl, optionally substituted cycloalkyl or optionally substituted phenyl, Y represents the groups -OCH2-, -CH2CH2- or -CH = CH-, Z represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, Haloalkylthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylaklyl or optionally substituted phenylalkoxy and m represents the numbers 0, 1, 2 or 3 are new.

The oxiranes of the formula (II) can be prepared by using ketones of the formula in which R, Y, Z and m have the meaning given above r either oc) with dimethyloxosulfonium methylide of the formula Reacts in the presence of a diluent, ß) with trimethylsulfonium methyl sulfate of the formula or in the presence of an inert organic solvent and in the presence of a base.

The starting materials used in the preparation of the oxiranes of the formula (II) required ketones of the formula (IV) are known (cf. DE-PS 22 01 063, DE-OS 27 05 678, DE-OS 27 37 489, Tetrahedron 31, 3 (1975) and Chemical Abstracts 84, 73 906 n) or can be produced by processes that are known in principle.

The dimethyloxosulfonium methylide required in process variant (a) of the formula (V) is also known (cf. J. Amer. Chem. Soc. 87, 1363-1364 (1965)). In the above implementation, it is processed in a freshly prepared state by it is done in situ by reacting trimethyloxosulfonium iodide with sodium hydride or sodium amide generated in the presence of a diluent.

The trimethylsulfonium methyl sulfate required in process variant (β) of formula (VI) also known (cf. Heterocycles 3, 397 (1977)).

It is also freshly made in the above implementation State used by making it by reacting dimethyl sulfide with dimethyl sulfate generated in situ.

In the variant (<) of the process for the preparation of the oxiranes of the formula (II), the preferred diluent is dimethyl sulfoxide.

The reaction temperatures can in the process variant described above (α) can be varied within a larger range. Generally works one at temperatures between 200C and 300C.

Carrying out the process for the preparation of the oxiranes of the formula (II) according to variant () and the work-up of the resulting from this synthesis The reaction mixture is carried out by customary methods (cf. J. Amer. Chem. Soc. 87, 1363-136 (1965)).

In the preparation of variant (ß) for the preparation of the oxiranes of the Formula (II) is preferably acetonitrile as the inert organic solvent into consideration.

Strong inorganic bases can be used as bases in the variant (ß) or organic bases can be used.

Sodium methylate is preferred.

The reaction temperatures can be as described above Process variant (ß) can be varied within a certain range. Generally works one at temperatures between 0OC and 600C, preferably at room temperature.

Carrying out the process for the preparation of the oxiranes of the formula (II) according to variant (B) and the work-up of that obtained in this synthesis The reaction product is carried out by customary methods (cf. Heterocycles 8, 397 (1977)).

The oxiranes of the formula (II) can be used in the process according to the invention optionally further reacted directly without isolation.

They are also used as starting materials for the process according to the invention Azoles to be used are generally defined by the formula (III). In this Formula X preferably represents the radicals that are already in the definition of the invention for this substituent.

The azoles of the formula (III) are generally known compounds of organic chemistry.

All diluents can be used for the reaction according to the invention inert organic solvents. These include preferred alcohols, such as.

Ethanol and methoxyethanol; Ketones such as 2-butanone; Nitriles, like e.g., acetonitrile; Esters such as ethyl acetate; Ethers such as dioxane; aromatic Hydrocarbons such as benzene and tolucl; or amides, like e.g. Dimethyllormamide.

The bases for the reaction according to the invention are all customary usable inorganic and organic bases. These preferably include Alkali carbonates such as sodium and potassium carbonate; Alkali hydroxides, e.g. Sodium hydroxide; Alkali alcoholates such as sodium and potassium methylate and ethylate; Alkali hydrides such as sodium hydride; as well as lower tertiary alkylamines, cycloalkylamines and aralkylamines, such as, in particular, triethylamine.

The reaction temperatures can when carrying out the invention Procedure can be varied over a wide range. Generally one works at temperatures between 0 and 2000C, preferably between 60 and 1500C.

The reaction according to the invention can optionally be carried out under increased Printing can be carried out. In general, between 1 and 50 bar is used, preferably between 1 and 25 bar.

When carrying out the process according to the invention, one sets up 1 mol of oxirane of the formula (II), preferably 1 to 2 mol of azole and optionally 1 to 2 moles of base. The end products are isolated in a generally customary manner Way.

The compounds obtainable by the process according to the invention of the formula (I) can be converted into acid addition salts or metal salt complexes will.

For the production of physiologically compatible acid addition salts of the compounds of formula (I) come preferably the following acids In question: The hydrohalic acids, such as e.g. hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, Maleic acid, succinic acid, fumaric 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 conventional 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, nitric acid and sulfuric acid.

The metal complexes of compounds of formula (I) can be in simple Way obtained by conventional methods e.g. by drawing lots of the metal salt in alcohol e.g. ethanol and adding to the compound of the formula (I) Q One can use metal salt complexes in known manner, e.g.

by filtering off, isolating and optionally by recrystallization clean.

The active ingredients that can be used according to the invention intervene in the metabolism of the 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 substance 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 type of application. In any case, the cultivated 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 grassers, among other things, because it can the frequency of grass cuttings in ornamental gardens, parks and sports facilities, at roadsides, at airports or in commercial facilities. The inhibition is also important the growth of herbaceous and woody plants on and near roadsides of pipelines or power 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 twisting ("storage") of plants reduced or completely eliminated before harvest. Also can Growth regulators in cereals cause a stalk reinforcement, which also counteracts the storage. The use of growth regulators for shortening and strengthening the stalk allows higher amounts of fertilizer to be applied, to increase the yield without the risk of the grain being stored.

Inhibition of vegetative growth is made possible in many cultivated plants a denser planting, so that additional yields are achieved based on the soil area can be. An advantage of the smaller plants obtained in this way is also that the Culture can be processed and harvested more easily.

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

lit 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 lead at the same time to a promotion of generative growth by the fact that more assimilates are formed, so that more or larger fruits arise.

In some cases, increases in yield can be achieved through an intervention in the plant 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

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.

By using growth regulators, the - control of plants. On the one hand, by breaking the apical dominance, the development are promoted by side shoots, which is especially 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 number of leaves can of plants @o are controlled that defoliation of the plants to a desired Time is reached. Such defoliation takes place in mechanical harvesting Cotton 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.

Fruit fall can also 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 ger fruit species, endogenous to bring very different yields from year to year. Finally it is possible with growth regulators at the time of harvest, the ones required to detach the fruit Reduce forces to allow mechanical harvesting or manual harvesting To facilitate harvesting.

Hit growth regulators can also accelerate or also delay the ripening of the crop before or after the harvest. This is of particular advantage, as it enables 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 8 prerequisites for E.g. for tobacco, tomatoes or coffee a complete mechanical or manual Harvesting can be done in one operation.

By using growth regulators, the seed or Bud rest of the plants can be influenced, so that the plants, such as pineapples 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 Sprouting of buds or germination of seeds with kilfe 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 normally used 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 can be used. The active ingredients are for use as pesticides suitable.

Fungicidal agents in crop protection are used for control of Piasmodiophoromycetes, 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 ingredients which can be used according to the invention can be used as crop protection agents The real ones are used with particularly good success to combat such fungi Cause powdery mildew diseases; so to combat Erysiphe species, such as against the pathogen of barley or powdery mildew (Erysiphe graminis).

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 root or via the seed the above-ground parts of the plant feeds.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Finest encapsulation in polymeric substances and in coating compounds for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, for example by mix the active ingredients with extenders, i.e. liquid solvents Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or Dispersants and / or foam-generating agents. In the case of using Water as an extender can, for example, also use organic solvents as auxiliary solvents be used. The following liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylenes 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, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

With liquefied gaseous extenders or carriers are such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide. The following can be used as solid carriers: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly dispersed Silica, alumina and silicates. Come as solid carriers for granules in question: e.g. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flour sourie granules made from organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks. Come as emulsifying and / or foam-producing agents in question: 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. As a dispersant are possible: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or 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, azole-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 9o.

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

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. The application happens in the usual Way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, Brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method to apply or the active ingredient preparation or the active ingredient itself in the soil to inject. 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, are used per hectare of soil area Active ingredient.

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 is based on the climatic and vegetative conditions.

Even when the substances according to the invention are used as fungicides the application rate varies in a coarser 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. 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. at Treatment of the soil are active ingredient concentrations of 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02%, required at the site of action.

Preparation examples Example 1 72.15 g (0.3 mol) of 2- (4-chlorophenoxymethyl) -2-tert-butyl-oxirane and 24.15 g (0.35 mol) of 1,2,4-triazole are dissolved in 120 ml Ethanol heated under reflux for 48 hours. It is then concentrated, the residue is taken up in 200 ml of ethyl acetate and heated. It is then cooled in an ice bath, the solid is filtered off with suction and washed with ethyl acetate. The filtrate is concentrated, the residue is dissolved in ether / hexane and gassed with hydrogen chloride. The precipitate is filtered off with suction, washed with ether and the free base is obtained by adding ethyl acetate / 1N sodium hydroxide solution. 60.2 g (65% of theory) of 2- (4-chlorophenoxymethyl) -3,3-dimethyl-1- (1,2,4-triazol-l-yl) butan-2-ol vom Melting point 84-870C.

Manufacture of the starting product A solution of 189 ml (2.0 mol) of dimethyl sulfate in 1200 ml of absolute acetonitrile is treated at room temperature with a solution of 162 ml (2.2 mol) of dimethyl sulfide in 400 ml of absolute acetonitrile. The reaction mixture is allowed to stir overnight at room temperature. Then 118.8 g (2.2 mol) of sodium methylate are added. The mixture is stirred for 30 minutes and then a solution of 272 g (1.2 mol) of 1- (4-chlorophenoxy) -3,3-dimethyl-butan-2-one in 600 ml of absolute acetonitrile is added dropwise over the course of 30 minutes. The reaction mixture is allowed to stir overnight. It is then concentrated, the residue is partitioned between water and ethyl acetate, the organic phase is separated off, washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate and concentrated, and the residue is distilled in vacuo. 242.4 g (84% of theory) of 2- (4-chlorophenoxymethyl) -2-tert are obtained. -butyl-oxirane with a boiling point of 115-220C / 0.003 mm Hg column and a melting point of 50-520C.

Example 2 2.71 g (0.1178 mol) of sodium in 250 ml of absolute ethanol are mixed with 8.02 g (0.1178 mol) of imidazole.

A solution of is left at room temperature within 30 minutes 14.17 g (0.0589 mol) of 2- (4-chlorophenoxymethyl) -2-tert-butyl-oxirane in 100 ml of ethanol drip. The reaction mixture is then refluxed for 8 hours and concentrated and the residue taken up in ether. It is extracted three times with 1N hydrochloric acid, neutralized the combined hydrochloric acid phases with sodium hydrogen carbonate and extracted then with ethyl acetate. After concentration and recrystallization from cyclohexane obtained 11.6 g (64% of theory) 2- (4-chlorophenoxymethyl) -3, 3-dimethyl-1- (imidazol-l-yl) -butan-2 ol, melting point 154-550C.

Example 3 A solution of 17.75 g (0.075 mol) of 2- (4-chlorophenylethenyl) -2-tert-butyl-oxirane and 6.9 g (0.1 mol) of 1,2,4-triazole in 30 ml of ethanol is 20 Heated for hours at 1500C in a bomb tube. The reaction mixture is then concentrated and the crystalline residue is stirred with ether. The solid is then filtered off with suction and recrystallized from acetonitrile. 17.7 g (77 of theory) of 1- (4-chlorophenyl) -4, 4-dimethyl-3- (imidazol-l-yl-methyl) -l-penten-3-ol with a melting point of 139-41 "are obtained" C.

Example 4 A solution of 17.9 g (0.075 mol) of 2- (4-chlorophenylethyl) -2-tert-butyl-oxirane and 6.9 g (0.1 mol) of 1,2,4-triazole in 30 ml of ethanol is used Heated for 20 hours at 1500C in a bomb tube. It is allowed to cool and the reaction solution is concentrated. The residue is dissolved in ether, washed three times with water and once with sodium chloride solution, dried over sodium sulfate and concentrated. The residue is chromatographed on a silica gel column (mobile solvent: dichloroethane / ethyl acetate 1: 1). 12.3 g (53.2% of theory) of 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) pentane-3- are obtained oil as a viscous oil.

The following compounds of the general formula (I) were obtained in an analogous manner: Table 2: No. Zm YRX melting point I- 5 4-C1,2-CH3 -0-CM2- -C (CH3) 3 N 125.5-29 6 2,4-C12-O-CH, -C (CH3) 3 N 120.5-23.5 7 4-CH3 -0-CM2- -CSCH3) 3 N 98-101.5 8 2CH3 -O-CH2 - -c (CM3) 3! § 89-101 9 4-F -CH2-CH2- -C (CH3) 3 g 91-95.5 10 2-CH3 -CH = CH- -C (CM3) 3 NOel 11 4-C1 -CM2-CM2- -c (CM3) 3 N 212 (decomp.) / 3 12 2,4-C12-0 CM2- -C (CH3) 3 CH 152-54 13 4-CH3-0-CM2- -C (CH1), CH129-31 14 2-CH3 -O-CH, -C (com3) 3 CH 123-24 15 4-C1,2-CH, -OC -C (CH3) 3 CH 157-59 16 4-C1-CHCM2- -C (CFT,), CH 157.5-59.5 17 4-F -CH2CHZ - -C (CL,), CH 124-25 18 2-CH3 -CH2 -CM2 -C (CM3) 3 CH 94-99 19 4-C1-CH = CH- -C (cH3) 3 CH 158.5-62 20 4-F-CH = CH- -C (CH3) 3 CH144-46 21 2-CH3 -CH = CH- -C (CM3) 3 CM 127-32 22 4-C1-O-CH, -Cl CH 216-17 (x 1/2 ND) * NDS = 1,5-naphthalenedisulfonic acid E.g. Zm YR x melting No. point (° C) 23 4-CH3 -CH = CH- -C (CH3) 3 N 117-19 24 4-CH3 -CH = CH- -C (CH3) 3 CH144-46 25 2,6-C12-CH = CH- -C (CM3) 3 CH 110-16 26 4-CH3 -CH2-CH2- -C (CM3) 3 N oil According to Example 1, the following intermediates of the general formula (II) are obtained: Table 3: E.g. boiling point (° C) / No. Zm YR mm Hg column II- 2 2,4-C12-O-CH2- -C (CH3) 3 125-27 / 0.3 II- 3 4-CH3 -O-CH2- 85 / 0.07 II- 4 2-CH3 -O-CH2- - 89 / 0.07 II- 5 4-C1,2-CH3 -O-CH2- "114-17 / 0.33 II- 6 4-C1-CH2 -CH2- 99-103 / 0.005 II- 7 2,4-Cl2 -CH2-CH2- 79 / 0.004 II- 8 4-F -CH2 -CH2- 79-89 / 0.003 II- 9 4-CH3 -CH2 -CH2- 74-78 / 0.003 11-10 2-CH3 -CM2 -CH2- 95 / 0.005 II-11 4-Cl -CH = CH- m.p. 61-62.5 II-12 2,4-C12 -CH = CH- "not isolated II-13 4-CM3 -CH = CH- "not isolated II-14 4-F-CH = CH- "75 / 0.005 II-15 2-CH3 -CH = CH- "71-74 / 0.01 II-16 2,6-C12 -CH = CH- not isolated The good effectiveness of the substances according to the invention can be seen from the following examples.

In these examples, the compounds given below are used as comparison substances: 2-chloroethylphosphonic acid + - (B) = Cl- CH2 - CH2 - N (CH3) 3 Cl 2-chloroethyl-trimethylammonium chloride Zinc ethylene 1,2-bisdithiocarbamidate Example A Growth inhibition in sugar beets 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 with water the desired concentration on.

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 growth 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 1 and 7 according to the invention show better in this test Growth inhibition as the substance (B) known from the prior art.

Example B Inhibition of growth in the presence of a solvent: 10 parts by weight Methanol emulsifier: 2 parts by weight of polyethylene sorbitan monolaurate 1 part by weight of active ingredient is mixed with an appropriate active ingredient preparation the specified amounts of solvent and emulsifier and fill with water on the desired focus on.

Young soybean plants are at the stage at which the first Subsequent leaves are unfolded, sprayed to runoff with the active ingredient preparations. To The increment is measured for 2 weeks and the inhibition of growth in% of the increment of the control plants calculated. 100% means the growth has come to a standstill and 0% means growth accordingly that of the untreated control plants.

The active ingredients 5 and 1 according to the invention show a in this test better growth inhibition than the substance (B) known from the prior art.

EXAMPLE C Thermal 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 ingredient, 1 part by weight is mixed Active ingredient with the specified amount of solvent and emulsifier and fill with water on the desired concentration.

Cotton plants are grown in the greenhouse until the 5. Follow-up 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 100% growth inhibition means a standstill in growth and 0% means growth accordingly that of the control plants.

The active ingredients 1 and 7 according to the invention show a in this test better growth inhibition than the substance (A) known from the prior art.

Example D Stimulating CO21 Assimilation in Soybeans Soybeans are, as described in Example (B), treated with the active ingredient preparations. 7 days after the treatment is applied to leaf disks of these plants and the like Control plants measured the CO2 assimilation with the help of an infrared analyzer. The active ingredients according to the invention 5, 9 and 18 show in the concentrations 250, 500 and 1000 ppm a significantly increased CO2 assimilation compared to the controls. This effect suggests that the active ingredient will increase the yield.

Example E Erysiphe test (barley) / protective / solvent: 100 parts by weight Dimethylfor: r.ami'd emulsifier: 0.25 part by weight of alkyl aryl polyglycol ether Zur To produce an appropriate preparation of active compound, 1 part by weight is mixed Active ingredient with the indicated: acn Menger. Solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed be thawed with the active compound preparation, after the spray coating has dried on the plants are pollinated with spores of Erysiphe graminis f.sp.hordei.

The plants are in a greenhouse at a Te = temperature of approx. 200C and a relative humidity of approx. 80% set up for the development to favor mildew pustules, the evaluation is carried out 7 days after the inoculation.

A clear superiority in effectiveness compared to the off Substance (C) known from the prior art, for example, show the compounds in this test according to the following production examples: 5,6,1,7,8,9,2,12,13 and 15.

Example F Barley powdery mildew test (Erysiphe graminis var.hordei) / systemic (Fungal cereal sprout disease) The active ingredients are used in powder form Seed treatment agents. They are made by stretching the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered Mixture with the visible 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 16 hours Exposure further cultivated. Form on the leaves within 6 days the typical mildew from.

The degree of infection is expressed as a percentage of the infection of the untreated control plants expressed. So 0% means no infestation and 100% the same degree of infestation as 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 Substance (C) known in the art shows, for example, the compound in this test according to the following production example ^ 5.

Claims (9)

Claims 13 1-Hydroxyethyl-azole derivatives of the formula in which R represents alkyl, optionally substituted cycloalkyl or optionally substituted phenyl, X represents a nitrogen atom or the CH group, Y represents the groupings -OCH2-, -CH2CH2- or -CH = CH-, Z represents halogen, alkyl , Cycloalkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally substituted phenylalkoxy and m represents the numbers 0, 1, 2 or 3, and their acid addition salts and metal salts -Complexes. 2) 1-hydroxyethyl-azole derivatives of the formula (I) in which R is alkyl with 1 to 4 carbon atoms, optionally by alkyl with 1 or 2 carbon atoms substituted cycloalkyl of 3 to 7 carbon atoms or for optionally by halogen, alkyl having 1 to 4 carbon atoms and / or Haloalkyl substituted with 1 or 2 carbon atoms and 1 to 5 halogen atoms Phenyl, X represents a nitrogen atom or the -CH group, Y represents the groupings -OCH2-, -CH2-CH2- or -CH = CH-, Z stands for halogen, alkyl with 1 to 4 carbon atoms, Cycloalkyl with 5 to 7 carbon atoms, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkylthio with 1 or 2 carbon atoms and 1 to 5 halogen atoms, optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms Phenyl, optionally by halogen and / or alkyl having 1 to 4 carbon atoms substituted phenoxy, optionally by halogen and / or alkyl with 1 to 4 Carbon atoms substituted phenylalkyl with 1 or 2 carbon atoms in the alkyl part or for optionally by halogen and / or alkyl having 1 to 4 carbon atoms substituted phenylalkoxy with 1 or 2 carbon atoms in the alkoxy part and m stands for the numbers 0, 1, 2 or 3, as well as their acid addition salts and metal salt complexes. 3. Process for the preparation of 1-hydroxyethylazole derivatives of the formula (I) and their acid addition salts and metal salt complexes, characterized in that one oxiranes of the formula in which R, Y, Z and m have the meaning given above, with azoles of the formula in which X has the meaning given above, is reacted in the presence of a diluent and, if appropriate, in the presence of a base, and if appropriate then an acid or a metal salt is added to the compounds of the formula (I) obtained. 4) Plant growth regulating and fungicidal agents, labeled by a content of at least one 1-hydroxyethyl-azole derivative of the formula (I) or an acid addition salt or metal salt complex of a 1-hydroxyethyl-azole derivative of formula (1). 5) Methods of regulating plant growth, as well as control of mushrooms, characterized in that 1-hydroxyethyl-azole derivatives of the 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. 6) Use of 1-hydroxyethyl-azole derivatives of the formula (I) or of acid addition salts or metal salt complexes of 1-hydroxyethyl azole derivatives of formula (I) for regulating plant growth or to combat fungus. 7) Process for the production of plant growth regulators and fungicidal agents characterized in that 1-hydroxyethyl-azole derivatives of the formula (I) or acid addition salts or metal salt complexes of 1-hydroxyethyl azole derivatives of the formula (I) mixed with extenders and / or surface-active substances. 8) Oxiranes of the formula in which R represents alkyl, optionally substituted cycloalkyl or optionally substituted phenyl, Y represents the groupings -OCH2-, -CH2-CH2- or -CH = CH-, Z represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, Haloalkoxy, haloalkylthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally substituted phenylalkoxy and m represents the numbers 0, 1, 2 or 3. 9) Process for the preparation of oxiranes of the formula (II), characterized in that retones of the formula in which R, Y, Z and m have the meaning given above, either>) with dimethyloxosulfonium methylide of the formula reacts in the presence of a diluent, or B) with Timethylsulfonium methyl sulfate of the formula in the presence of an inert organic solvent and in the presence of a base.