KR840001772B1 - Process for preparing the 1-hydroxyethyl-azole derivatives - Google Patents

Abstract

Title compds. I(R=alkyl, (un)substituded cycloalkyl, Ph; Z=halo, alkyl, cycloalkyl, alkoxy, alkylthio, etc.; X=N, CH; m=0-3), useful as plant growth regulators and fungicides, were prepd. by reaction of II and III. Thus, 2-(4-chlorophenylethenyl)-2-ter-buty-oxirane and 1,2,4-triazole in EtOH refluxed at 150oC for 20hr to give I(Z=Cl, m=l, R=CMe3, X=N)

Description

[Name of invention]

Method for preparing 1-hydroxyethyl-azole derivative

Detailed description of the invention

The present invention relates to novel 1-hydroxyethyl-azole derivatives of the general formula (I) below, which are useful as plant growth regulators and fungicides, and acid addition salts and metal salt complexes thereof.

(Ⅰ)

(Ⅰ)

Wherein R is an alkyl radical, an optionally substituted cycloalkyl radical, or an optionally substituted phenyl radical, X is a nitrogen atom or a CH group, Z is a halogen atom, alkyl, cycloalkyl, alkoxy, alkylthio, halogeno Alkyl, halogenoalkoxy or halogenoalkylthio radical, optionally substituted phenyl radical, optionally substituted phenoxy radical, optionally substituted phenylalkyl radical, or optionally substituted phenylalkoxy radical, m is 0, 1, 2 or 3 to be.

It is already known that certain 2-halogenoethyl-trialkyl-ammonium halides exert plant growth regulation (see US Pat. No. 3,156,554). 2-Chloro-ethyl-trimethyl-ammonium chloride can be used to inhibit nutrient growth of important crops. However, the activity of these compounds is not always satisfactory, especially when a small amount of the material is applied.

It is also known that 2-chloroethyl phosphonic acid acts as a plant growth regulator (see Publication No. 1,667,968). However, the results presented with these materials are also not always satisfactory.

Zinc ethylene-1,2-bisdithiocarbamidate is also known to play an excellent role in controlling parasitic fungi on plants (see Phyto-pathology 33, 1113 (1963)). However, these substances can be used only in a limited range because their action is not always satisfactory, especially when used in small amounts and low concentrations.

Since the compound of general formula (I) has one asymmetric carbon atom, two optical isomers can be obtained. The compound of general formula (I) may have two further geometric isomers. The present invention relates to isomeric mixtures and to individual isomers.

The process for preparing the compound of formula (I) according to the present invention is carried out by reacting the oxirane of formula (II) with the azole of formula (III) below in the presence of a weighting agent, if necessary in the presence of a base: After the preparation of the compound of (I), if necessary, the compound of the general formula (I) produced is characterized by being converted into its acid addition salt or metal salt complex compound.

(Ⅱ)

(Ⅱ)

(Ⅲ)

(Ⅲ)

In the general formula, R, X, Z and m are as defined above.

1-hydroxyethyl-azole derivatives according to the present invention has a strong plant growth regulation and bactericidal action.

Surprisingly, the 1-hydroxyethylazole derivatives according to the invention are superior to 2-chloro-ethyl-trimethylammonium chloride and 2-chloroethyl-phosphoic acid, which are already known as good actives having the same form of action. It shows plant growth regulation. The compounds according to the invention also surprisingly show a stronger bactericidal action than zinc ethylene-1,2-bisdithio carbamates, compounds which are known in the art and closely related in function. Therefore, the effective compound according to the present invention has made a great contribution to the industrial development in this field.

Preferred 1-hydroxyethyl-azole derivatives according to the present invention are cycloalkyl radicals in which R has 1 to 4 straight or branched chain alkyl radicals, 3 to 7 carbon atoms and is optionally substituted by alkyl having 1 to 2 carbon atoms, or Phenyl radicals optionally substituted mono- or polysubstituted with the same or different substituents (preferably including substituents halogen, alkyl of 1 to 4 carbon atoms and 1 to 5 halogen atoms, such as fluorine and chlorine atoms) And halogeno alkyl having 1 to 2 carbon atoms;

Z is a halogen atom, a straight or branched chain alkyl radical having 1 to 4 carbon atoms, a cycloalkyl radical having 5 to 7 carbon atoms, an alkoxy or alkylthio radical having 1 to 4 carbon atoms, and a halogen atom having the same or different carbon atoms as 1 to 2 ( For example, halogenoalkyl, halogenoalkoxy or halogenoalkylthioradicals each having 1 to 5 fluorine and chlorine atoms, or phenyl, phenoxy, phenylalkyl or phenylalkoxy radicals (they are halogen, of 1 to 4 carbon atoms) Each of which may be optionally substituted by a preferred substituent such as alkyl, and the alkyl or alkoxy moiety of the phenylalkyl and phenylalkoxy radical have 1 to 2 carbon atoms); X and m are the compounds as defined above.

More preferred compounds of formula (I) are optionally monosubstituted by tertiary butyl, isopropyl or methylradical, or cyclopropyl, cyclopentyl or cyclosil radical, each optionally substituted with a methyl group, or by the same or different substituents Substituted phenyl (substituents include fluorine, chlorine, methyl trifluoromethyl); Z is fluorine, chlorine or bromine atom, methyl, tert-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio radical, or optionally mono- or di-substituted phenyl, Phenoxy, benzyl or benzyloxy radicals (substituents here being fluorine, chlorine or methyl); X and m are compounds as defined above.

In addition to the compounds mentioned in the preparation examples, the following compounds may be mentioned as compounds of general formula (I).

(Ⅰ)

(Ⅰ)

Table 1

For example, when using 2- (4-chlorophenyl-ethyl) -2-tert-butyl-oxirane and imidazole as starting materials, the preparation of the compound of the present invention is shown in the scheme shown below.

Preferred oxiranes of the general formula (II) used as starting materials for carrying out the process according to the invention are those compounds in which R, Z and m have already been described in the preferred compounds (I) of the invention.

The oxirane of the following general formula (II) is a novel compound.

(Ⅱ)

(Ⅱ)

Wherein R is an alkyl radical, an optionally substituted cycloalkyl radical or an optionally substituted phenyl radical, and Z is a halogen atom, alkyl, cycloalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy or halogenoalkyl thio Radical, optionally substituted phenylradical, optionally substituted phenoxy radical, optionally substituted phenylalkyl radical or optionally substituted phenylalkylalkoxy radical, m being 0,1,2 or 3.

The oxirane of formula (II), a novel compound, reacts the ketone of formula (IV) with the dimethyloxo sulfonium methylide of formula (V) in the presence of α) diluent, or β) inert organic It can be prepared by reacting with trimethylsulfonium methyl-sulfate of formula (VI) in the presence of a solvent and a base.

(Ⅳ)

(Ⅳ)

(Ⅴ)

(Ⅴ)

[(CH ₃ ) ₃ S ⁽⁺⁾ ] CH ₃ SO ₄ ^(-) (VI)

In the general formula, R, Z and m are as defined above.

Ketones of formula (IV), which are required as starting materials in the preparation of the oxirane of formula (II), are known or can be prepared by known methods. (Formula (V) required by New Zealand Patent Nos. 169,509 and 186,409, U.S. Patent No. 4,243,405 Tetrahedrom 31,3 (1975) and Chemical Abstracts 84,73 906n) or required by Method (α). Dimethyl oxo sulfonium methylide is also a known compound. See J. Amer. Chem. Soc 87, 1363-1364 (1065). This compound can be used for the reaction in the pure state produced in the place by reacting trimethyloxosulfonium iodide with sodium hydride or sodium amide in the presence of a diluent.

Trimethylsulfoniummethyl-sulfate of the general formula (VI), which is required in the process (β), is also a known compound (Hetercoycles 8, 397 (1977)). The compound can also be used for the reaction in the pure state produced by the reaction by reacting dimethyl sulfide with dimethyl sulfate.

Preferred diluent in process (α) for preparing oxirane of general formula (II) is dimethyl sulfoxide.

The reaction temperature can be changed within a substantial range in the above-described method (α). In general, the reaction proceeds at a temperature between 20 and 80 ° C. The method for preparing the oxirane of general formula (II) according to the method (α) and for treating the reaction mixture obtained in this synthesis process are carried out in a conventional manner. See J. Amer. Chem. Soc. 87,1363 to 1364 (1965).

A preferred inert organic solvent in the method (β) for preparing the oxirane of formula (II) is acetonitrile.

The base usable in the method (β) is a strong inorganic or organic base, and sodium methylate is preferably used. The reaction temperature can be varied within a certain range in the above-described method (β), and generally the reaction is carried out at a temperature of 0 to 60 ° C, preferably at room temperature. The preparation of the oxirane of general formula (II) by the method (β) and the treatment of the reaction product obtained in this synthesis are carried out by conventional methods (Hoterocycles 8,397 (1977)).

If necessary, the oxirane of general formula (II) may be further reacted directly according to the method according to the present invention without separating the oxirane.

The azoles of general formula (III) are compounds known in the field of organic chemistry.

In the reaction according to the present invention for preparing the 1-hydroxyethyl-azole derivative of general formula (I), an inert organic solvent may be mentioned as a diluent which can be preferably used. Examples thereof include alcohols (eg, Ethanol and methoxy ethanol), ketones (e.g. 2-butane silver), nitriles (e.g. acetonitrile), esters (e.g. ethyl acetate), ethers (e.g. dioxane), aromatic hydrocarbons (e.g. Benzene and toluene) and amides (e.g., dimethylformamide).

Bases usable in the reaction according to the present invention include inorganic and organic bases that can be used conventionally, and preferred examples thereof include alkali metal carbonates (e.g. sodium carbonate and potassium carbonate), alkali metal hydroxides (e.g. sodium hydroxide). Alcohols in alkali groups, eg sodium methylate and ethylate and potassium methylate and ethylate), alkali metal hydrides (eg sodium hydride) and lower tertiaryalkylamines, cycloalkylamines and aralkylamines (preferably Triethylamine).

The reaction temperature can be varied within the practical range of carrying out the process according to the invention and is generally carried out at a temperature of 0 to 200 ° C, preferably 60 to 150 ° C.

If necessary, the reaction of the present invention can be carried out under increased pressure, and the reaction is generally carried out at 1 to 50 bar, preferably 1 to 25 bar.

In the production process according to the present invention, 1 to 2 moles of azole per mole of oxirane of formula (II), and 1 to 2 moles of base are preferably used if necessary. The final product is generally separated by conventional methods.

Compounds of formula (I) which can be prepared by the process according to the invention can be converted into acid addition salts or metal salt complexes.

The following acids are preferably used in the preparation of the physiologically toxic acid addition salts of general formula (I): hydrochloric acid (e.g., full acid, preferably hydrochloric acid), phosphoric acid, nitric acid, sulfuric acid, monofunctional and dual Functional carboxylic acids and hydroxy carboxylic acids (e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids (e.g. p-toluene sulfonic acid and 1,5-naphthalene disulfonic acid)>

Acid addition salts of the compound of general formula (I) may be prepared by a simple method using a conventional salt forming method, for example, by dissolving a compound of general formula (I) in a suitable inert solvent and then adding an acid (eg, hydrochloric acid). It can be prepared, can be separated by a known method (eg, filtration), and, if necessary, can be purified by washing with an inert organic solvent.

In order to prepare metal salt complexes of the general formula (I) compounds, metal salts of the main groups of Groups II to IV and the subgroups of Groups I, II and IV to VIII of the periodic table can be preferably used. Examples of the metal include copper, zinc, manganese, magnesium, tin, iron, and nickel.

Salt anions derived from the following acids are preferably used. Hydrochloric acid (eg hydrochloric acid and bromic acid), phosphoric acid, nitric acid and sulfuric acid.

The metal complex of the compound of formula (I) may be prepared by a simple method by conventional methods (e.g., by dissolving a metal salt in an alcohol such as ethanol and then adding the solution to the compound of formula (I)). . This metal salt complex can also be purified by known methods (e.g., by filtration, separation and recrystallization if necessary).

The compounds according to the invention can be used as growth regulators because they are involved in the metabolism of plants.

Periodic experiments on the mode of action of plant growth regulators revealed that the active compounds may exhibit a variety of different actions in plants. The action of the compounds depends on the timing of their use, the stage of plant growth, the amount of active compound used around the plant or their surroundings and the method of using the active compound. In all cases, growth regulators can affect the crop in a specific manner.

Compounds that regulate plant growth can also be used, for example, to inhibit trophic growth of plants. This growth inhibition is economical, especially in grasses, because it reduces the number of mowings in ornamental gardens, parks, playgrounds, roads, airports or orchards. It is also important to inhibit plant and herbaceous plant growth in roads, around pipelines, in line areas on land, or in areas where plants are undesirably spoiled.

The use of growth regulators to inhibit the lengthy growth of tall grains is also important because it reduces or eliminates the risk of the plant falling down before harvesting. Moreover, growth regulators can increase yields by using larger amounts of fertilizers because they shorten and enjoy grain enjoyment, thus preventing plants from falling over.

In the case of many cereals, suppression of trophic growth allows the grain to be grown more densely, resulting in higher yields per unit area. As a result, grown short plants have the advantage of being easier to harvest.

Inhibition of vegetative growth of plants can also increase yields because more amount contributes to flowering and fruit formation than zero-field and assimilation contributes to vegetative growth of plants.

Promoting nutrient growth can also be accomplished using growth regulators. If the nutrient part is harvested from plants, the use of such growth regulators is very easy. Promoting nutritional growth also promotes reproductive growth at the same time, so that more or larger fruits can be formed.

If you nourish the plant's metabolism, you can increase your harvest without major changes in nutrient growth. Moreover, growth regulators may alter the composition of the plant to improve the quality of the crop.

For example, sugar content in beets, sugar cane, pineapples and citrus fruits can be increased or protein content in soybeans or grains can be increased.

In addition, growth regulators are used to inhibit the amount of sugar in the desired components, such as sugar cane or sugar beet, from decreasing before and after harvesting. It may also have a beneficial effect on the outflow or production of secondary plant components. As an example, it stimulates the fluid flow in a rubber tree.

Unit deletions may be formed under the influence of growth regulators, and may also affect the gender of flowering. Pollen can also be made male, which is very important for the production and breeding of hybrid seeds.

Growth regulators may be used to tighten the branches of the plant. It can also promote branching while breaking the dominant dominant, which may be very desirable, especially when growing ornamental plants or in terms of growth inhibition. On the other hand, it can also inhibit the growth of branches, which is very useful when growing tobacco or tomatoes.

Growth regulators can also control the amount of plant leaves so that they defoliate at the desired time. Such defoliation enhances the harvest of grapes or cotton and the like, and also has the advantage that less transpiration occurs before the plant is transplanted.

Growth regulators can also be used to inhibit the escape of deletions. It can also prevent premature detachment of the fruit, while promoting to some extent the fruition or fallout of the fruit to prevent alternation. Due to alternating endogenous reasons, they are produced at very different yields each year. Growth regulators reduce the force needed to harvest fruit from crops during the harvester and can be harvested mechanically or easily harvested manually.

The use of growth regulators can also promote or delay the ripening of the harvested crop, before and after harvesting. Therefore, there is a unique advantage that can be optimized for demand needs. In addition, growth regulators may sometimes enhance the coloration of the fruit. In addition, growth regulators may be used to ripen for a period of time. This provides a preliminary condition that allows, for example, tobacco, tomatoes or coffee to be fully harvested only mechanically or manually at one time.

The use of growth regulators also affects the incubation period of the seeds or shoots of plants, causing plants, such as pineapples or ornamentals, grown in greenhouses to germinate, branch, or bloom during normal germination, branching, or flowering periods. . Also, in late frost areas, growth regulators can be used to delay seed germination or shoots to prevent late frost damage.

Growth regulators can be used to make plants resistant to frost, drought, or salt-containing soils. Therefore, growth regulators enable plant cultivation in areas not suitable for plant cultivation.

The preferred timing of using growth regulators depends on the climate and nutritional status. Individual compounds may not exhibit all of the effects described above in plants. The effects exerted by a compound in an unusual environment must be measured empirically.

Since the active compound according to the present invention exhibits a strong bactericidal action, it can be used to combat undesirable microorganisms. For this reason the active compounds are suitable for use in plant protection agents. Plant protection fungicides are used to combat plasmodio phoromycetes, Oomycetes chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. .

When the active compound is applied to plants, stems, seeds and soil in the ground at a concentration capable of eradicating plant pathogens, it has excellent tolerability.

As a plant protection agent, the active compounds according to the invention are in particular fungi which induce powdery mildew diseases, for example, Erysiphe species [e.g. microorganisms that cause powdery mildew in barley and cereals]. It may be particularly useful to combat the problem. The compounds according to the invention not only act as protective but also systemic. Therefore, the administration of the active compounds to the above-ground plants through soil and roots or via seeds can protect the plants from the infestation of fungi.

The active compounds can be made from conventional formulations such as microcapsules, aerosols, granules, pastes, foaming agents, powders, suspensions, emulsions and solutions and ULV formulations in seed coating compositions and polymerization compositions.

These formulations can be prepared by known methods such as mixing the active compound with a promoter (ie, liquid, liquefied gas, solid weight or carrier) and optionally with surfactant (ie, emulsifier and / or dispersant and / or blowing agent). When water is used as an enhancer, an organic solvent can be used as a cosolvent.

Liquid weight agents or carriers, in particular solvents, include aromatic hydrocarbons (e.g. xylene, toluene or alkyl naphthalene), aromatic or aliphatic hydrocarbons (e.g. chlorobenzene, chloroethylene or methylenetolo-lide), cyclohexane or paraffin. Aliphatic or substituted hydrocarbons (e.g. mineral oil fractions), alcohols (e.g. butanol or glycols, and ethers and esters thereof), ketones (e.g. acetone, methylethylketone, methyl isobutyl ketone or cyclohexane) Or strong polar solvents (e.g., dimethylformamide is dimethyl sulfoxide), water and the like are mainly preferably used.

Liquefied gaseous weight or carrier means a liquid that is in a gaseous state at normal temperature and normal pressure, and examples thereof include halogenated hydrocarbons, butane, propane, aerosol propane, such as nitrogen and carbon dioxide. Solid carriers include ground natural minerals (e.g. kaolin, clay, talc, choke, quartz, attapulgite montmorillonite or diatomaceous earth) and ground synthetic minerals (e.g., highly dispersible citric acid, alumina or silicate) Can be used. Solid carriers for granulation include pulverized natural rock (eg calcite, marble, pumice, calcite and dolomite), synthetic granules of inorganic and organic wheat, and granules of organic matter (eg sawdust, coconut husk, corn). Genus and tobacco stem) may be used.

Emulsifiers and / or foaming agents include nonionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol esters, for example alkylaryl polyylglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and Albumin hydrolysis products and the like can be used. Examples of dispersants are lignin sulfide liquids and methylcellulose.

Electrodeposition agents such as carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinylacetate) in powder or granule or latice form may also be used in the formulation.

Also colorants such as inorganic pigments (e.g. iron oxide, titanium oxide and plusian blue) and organic dyes (e.g. alizarin dyes, azo dyes or metal phthalocyanine dyes), nutrients of interest (e.g. iron, manganese, boron, copper , Salts such as cobalt, molybdenum and zinc) can also be used.

The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight.

The active compounds according to the invention can be present in the formulation as a mixture with other known active compounds (eg fungicides, pesticides, acaricides, and herbicides) or as a mixture of fertilizers and other growth regulators.

The active compounds may be in the form of their preparations or in the forms of use prepared therefrom [e.g., solution emulsifiable concentrates, emulsions, foaming agents, suspensions, wetting ingredients, pastes, molten ingredients, dusting agents and granules ready for use]. Can be used. These compounds are used by conventional methods (eg, watering, spraying, spraying, dispersing, dusting, foaming, coating, etc.). It is also possible to inject the active compound itself or the active compound preparation into the soil or to use the active compound according to the microvolume method. Seed treatment of plants is also possible.

When the compound according to the present invention is used as a plant growth regulator, the dosage can be changed within a substantial range. Generally, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active compound per hectare of soil surface is used.

When the substance according to the present invention is used as a bactericide, the application amount may vary within a substantial range depending on the application form. In particular, in the case of treating only a part of plants, the concentration of the active compound in the form of application is generally 1 to 0.0001% by weight, preferably 0.5 to 0.001% by weight. When applied to seeds, 0.001 to 50 g, preferably 0.01 to 10 g of active compound per kg of seed are required. When applied to soil, it is necessary to apply the active compound at a concentration of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, at the place of application.

The present invention also provides a plant growth regulating and bactericidal composition containing the compound of the present invention as an active ingredient in the form of a solid or a liquefied gas weighting agent or a carrier or a liquid weighting agent or a carrier containing a surfactant.

The present invention also discloses a composition containing a mixture of the compound of the present invention as a weighting agent and a carrier as an active ingredient, or a method for eliminating fungi by applying only the compound of the present invention to fungi. The present invention also proposes a composition containing a mixture of the compound of the present invention as a weighting agent or a carrier as an active ingredient or a method of controlling plant growth by applying only the compound of the present invention to a plant.

The present invention also suggests that the compounds of the present invention are applied alone or during the growth period alone or in combination with a weighting agent or a carrier to protect crops grown in the region from damage by fungi.

The present invention also suggests plants whose growth is controlled at the time of application by applying the compounds of the invention, either alone or in admixture with a weighting agent or a carrier, immediately before and / or during growth.

It will be appreciated from the above description that the conventional method of harvesting crops can be improved by the present invention.

Production Example

Example 1

(Ⅰ-1)

(Ⅰ-1)

Made by adding 17.75 g (0.075 mole) of 2- (4-chlorophenyl-ethenyl) -2-tertbutyl-oxirane and 6.9 g (0.1 mole) 1,2,4-triazole to 30 ml of ethanol The solution is heated to 150 ° C. for 20 hours in a bomb tube. After the reaction mixture is concentrated, the crystalline residue is stirred with ether. The solid is filtered off and then recrystallized from acetonitrile. Thus 17.7 g of 1- (4-chlorophenyl) -4,4-dimethyl-3- (imidazol-1-yl-methyl) -1-phenen-3-ol having a melting point of 139 to 141 ° C. (77 of theory) %) Is obtained.

In a similar manner, the following compounds of formula (I) are prepared.

(Ⅰ)

(Ⅰ)

The following intermediate product of NDS = 1,5-naphthalene disulfonic acid general formula (II) is prepared by a method analogous to the method described in Example 1 of 1981 patent 1169, the parent application of the present application.

Table 3

(Ⅱ)

(Ⅱ)

Plant growth regulation and bactericidal activity of the compounds of the present invention will be described in the Examples relating to the following biological tests.

In these examples, the compounds according to the invention are the same as the compounds represented by the compounds represented by parentheses in number 9 in the corresponding corresponding preparation examples described above.

Known comparative compounds are as follows.

2-클로로에틸포스포트산(A)

2-chloroethylphosphoric acid

2-클로로에틸-트리메틸-암모늄 클로라이드(B)

2-Chloroethyl-trimethyl-ammonium chloride

아연 에틸렌-1,2-비스디티오카바미데이트.(C)

Zinc ethylene-1,2-bisdithiocarbamidate.

Example A

Influences on the growth of sugar beet

Solvent: 30 parts by weight of dimethyl formamide

Emulsifier: 1 part by weight of polyoxy ethylene sorbitan monolaurate

In order to prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent and emulsifier and then the mixture is used to the desired concentration.

Beet grows in greenhouses until cotyledon formation occurs. In this step, the active compound preparation is sprayed until the plant is completely wet. After 14 days, the degree of further growth of the plant is measured and compared to that of the control plant, the percentage of growth inhibition is calculated. A growth inhibition of 0% means a growth that corresponds to the growth of a control plant, and a growth inhibition of 100% means that growth has stopped.

In this test, the active compounds according to the invention were found to have better growth inhibition than the material (B) known in the art.

Example B

Soybean Growth Inhibition

Solvent: 10 parts by weight of methanol

Emulsifier: 2 parts by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent and emulsifier, and then the mixture is diluted with water to the desired concentration. In the stage where the second leaf is fully opened for the first time, the young soybean plants are sprayed with the active compound preparation to sufficiently wet the plants. After 2 weeks, the degree of further growth of the plant is measured and the growth inhibition is calculated in% compared to the degree of further growth of the control plant. 100% means that the growth has been stopped, and 0% means that the growth is commensurate with the growth of untreated control plants.

In this test, the active compound according to the present invention showed better growth inhibition rate than the material (B) known in the art.

Example C

Inhibit the growth of cotton

Solvent: 30 parts by weight of dimethyl formamide

Emulsifier: 1 part polyoxyethylene sorbitan monolaurate

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

Cotton plants are grown in greenhouses until the fifth leaf is opened. In this step, the active compound preparation is sprayed until the plant is wet. After 3 weeks, the degree of further growth of this plant is measured and the percent growth inhibition is calculated by comparison with that of control plants. 100% means that the growth has been stopped, and 0% means that the growth is commensurate with that of the control plant.

In this test, the active compound according to the present invention showed better growth inhibition than the material (A) known in the prior art.

Example D

Promote CO ₂ assimilation in soybean

Soybeans are treated with the active compound formulation as described in Example (B) for biopsy. Seven days after the treatment, an infrared analyzer is used to measure the promotion of CO ₂ in the leaves of the treated plants and the leaves of the control plants. The active compounds of the present invention have been shown to significantly increase CO ₂ assimilation at concentrations of 250,500 and 1000 ppm compared to the control plants. Due to this effect, it can be expected that the yield is increased by using the active compound.

Example E

Eritife Test (Botti / Protection)

Solvent: 100 parts by weight of dimethyl formamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To prepare a formulation of the appropriate active compound, 1 part by weight of the active compound is mixed with this amount of solvent and emulsifier and diluted with water to the desired concentration.

To test for protective action, spray the active compound preparation until the young plant is slightly wet.

After the spray coating layer was dried, the plants were subjected to E. sigtaminis F. SP. Sprinkle holiday spores.

The implants are planted in a greenhouse maintained at a temperature of about 20 ° C. and an air humidity of 80% so as to raise the barley of barley.

Evaluate 7 days after vaccination.

In this test, it was found that the compounds according to the invention perform significantly better than the material (c) known in the art.

Example F

Test for powdery mildew disease [Erysiphe graminis var hordei] / invasive (bottle caused by fungi of cereal veins) of barley.

Use the active compound as a medicine to treat well-seed seeds. These agents are prepared by mixing the active compound with a mixture of equal parts of talc and diatomaceous earth into a finely ground mixture containing the active compound in the desired concentration.

To treat the seed, the barley seed is shaken with the active compound mixed in a closed glass jar. This seed is planted in a mixture of 1 volume of hurrupper standard soil and 1 volume of quartz sand in a flower pot at a depth of 2 cm at the rate of 3 x 12 grains. Germinates under favorable conditions in the greenhouse. After 7 days of sowing, when the first leaves of barley are opened, the spores of Erysiphe graminis var hordei are sprayed and grown at 21-22 ° C. and 80-90% relative atmospheric humidity. Destroy for 16 hours. Typical fungal ridges appeared on the leaves within 6 days.

The extent of this infection is compared to the extent of infection of the untreated control plants to determine the percent infection. 0% means no infection and 100% means the same degree of infection as for untreated control plants. The greater the activity of the active compound, the less susceptible to bacterial infection.

In this test, the compounds according to the invention showed significantly better action than material (c) known in the art.

Claims (1)

The oxirane of the general formula (II) is reacted with the azole of the general formula (III) in the presence of a weighting agent, whereby the 1-hydroxyethyl-azole derivative of the general formula (I), an acid addition salt thereof And a method of preparing a metal salt complex.

(Ⅰ)

(Ⅱ)

(Ⅲ) In the above general formula, R is alkyl having 1 to 4 carbon atoms, X is nitrogen or CH-group, Z is halogen or alkyl having 1 to 4 carbon atoms, and M is 0.1 or 2.