RU2043026C1 - Composition for decreasing growth of culture plants - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: proposed composition contains E-isomer of 1-phenyl(substituted or unsubstituted)-2-(1,2,4-triasolyl-1)propene or its salt as active compound, its quantity being 1-80 mass Said compound has formula R₂-C₃-C₆ where R₃-alkyl, cyclopropyl, methylcyclopropyl, C₁-C₄-halogen, C₁-C₂-alkyl, trifluoromethyl,

Description

C

R₂ (I) в которой R₁ представляет атом водорода, С₁-С₄ алкильную, С₃-С₄алкенильную или 2-пропильную группу, R₂ представляет С₁-С₆ алкильную, циклопропильную или 1-метилциклопропильную группу, элемент R₃, который может иметь одинаковые или различные значения, представляет атом галогена, С₁-С₄ алкильную группу, галоидзамещенную С₁-С₃ алкильную группу, С₁-С₄ алкокси, фенокси, фенильную циано или нитрогруппу, и является целым числом от 0 до 3, и термин: "галоген" означает атомы хлора, брома и фтора, его соли, способ его получения и фунгицид, гербицид и/или регулятор роста растений для применения в сельском хозяйстве, и садоводстве, содержащий указанное соединение в качестве активного ингредиента.The subject of the invention is the geometric isomer of the E form (a compound defined as I A isomer in the description below) of a triazole compound represented by the formula (I)

C

R ₂ (I) in which R ₁ represents a hydrogen atom, a C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl or 2-propyl group, R ₂ represents a C ₁ -C ₆ alkyl, cyclopropyl or 1-methylcyclopropyl group, element R ₃ , which may have the same or different meanings, represents a halogen atom, a C ₁ -C ₄ alkyl group, a halogen-substituted C ₁ -C ₃ alkyl group, a C ₁ -C ₄ alkoxy, phenoxy, phenyl cyano or nitro group, and is an integer from 0 to 3, and the term: "halogen" means the atoms of chlorine, bromine and fluorine, its salts, its production method and fungicide, herbicide / Or plant growth regulator for use in agriculture and horticulture containing said compound as an active ingredient.

C C

(III)
Эти два изомера отличаются друг от друга температурой плавления, спектром ядерного магнитного резонанса или газовой хроматографией, но различие между ними можно более широко и ясно охарактеризовать исходным материалом, триазольным соединением формулы (II)

C

-R₂ (II) в которой R₂, R₃ и n имеют указанные выше значения.Each triazole compound of the formula (1) has two geometric isomeric forms, the z-form and the E-form, represented by the formulas

CC

(III)
These two isomers differ from each other by their melting point, nuclear magnetic resonance spectrum or gas chromatography, but the difference between them can be more broadly and clearly characterized by the starting material, the triazole compound of formula (II)

C

-R ₂ (II) in which R ₂ , R ₃ and n are as defined above.

C C

где R₁ является атомом водорода, с последующей этерификацией полученного соединения:

C

-R₂

C

где R₁, R₂, R₃ и n имеют указанные ранее значения.A triazole compound of formula (I) is prepared by reducing a triazole compound of formula (II) to form a triazole compound of formula (I)

CC

where R ₁ is a hydrogen atom, followed by esterification of the obtained compound:

C

-R ₂

C

where R ₁ , R ₂ , R ₃ and n are as previously defined.

 Hence one of the two geometric isomers of the triazole compound (II), the olefin proton of which appears in the stronger magnetic field of the NMR spectrum in deuterochloroform, is defined as the II-A isomer, and the other, the olefin proton of which appears in the lower magnetic field of the NMR spectrum in deuterochloroform, defined as isomer II-B.

C C

Соединения II-B опиcаны в опубликованной, еще не прошедшей экспертизу японской патентной заявке N 130661/1978 и соединения I-B описаны в опубликованной нерассмотренной (выложенной) японской патентной заявке N 41875/1979 (бельгийский патент N 870243).These links are illustrated below.

CC

Compounds II-B are described in published Japanese patent application No. 130661/1978, which has not yet been examined, and compounds IB are described in published unexamined (laid out) Japanese patent application No. 41875/1979 (Belgian patent No. 870243).

Further, the compound (I) in which R ₁ is a hydrogen atom obtained by reduction of the isomer II-A is defined as the I'-A isomer, the compound (I) in which R ₁ is the specified substituent other than the hydrogen atom obtained during the esterification of the isomer I'-A is defined as the isomer I '' - A, while the I'-A isomer and I '' - A isomer is usually defined as the IA-isomer. The corresponding compounds obtained from the II-B isomer are likewise defined as the I'-B isomer, the I ″ -B isomer and the IB-isomer, respectively. The invention relates to the IA-isomer and the II-A isomer, which is an intermediate for the IA-isomer.

 Until then, a large number of synthetic organic compounds were obtained, which have made a great contribution as agricultural chemicals for agricultural and horticultural crops due to their activity against diseases and pests that harm these crops. However, the fact is known that a significant number of problems still need to be resolved. These problems are sometimes solved, for example, by creating new and more desirable pesticides, or it can be considered that they can also be solved by studying conventional pesticides to establish suitable forms of application of agricultural chemicals.

 There are many synthetic organic compounds that may also be present as geometric or optical isomers. In practice, there are many cases in which pesticides containing these isomers are used in practice as agricultural chemicals. It is well known not only for agricultural chemicals, but also in many other fields that among many ingredients having isomeric forms, differences in biological activity are observed. The problem of environmental pollution in agriculture and horticulture is currently gaining serious importance, and it is important to mitigate this problem using one of the two isomers, which is more active. In addition, it is necessary to take into account the greater economic effect of obtaining this compound, as well as in practical use as pesticides. Therefore, from this point of view, the fact of the creation of an isomer with stronger activity can be considered favorable.

 Based on this invention, a further study of compounds already found by them was carried out (Japanese / Cocai Open Patent Application No. 130661/1978, Belgium Patent No. 870248 and UK Patent No. 2004276). As a result of this, it was found that the present invention, defined as the IA isomer (i.e., the E-form), namely one of the two geometric isomers of the triazole compound represented by formula (I), has a higher fungicidal activity in a wider the range of plant diseases, as well as a higher herbicidal effect and a stronger effect regulating plant growth compared with compounds defined as the I-B isomer (i.e., Z-form), in other words, they have excellent properties as a pesticides atov.

C C

в которой R₁ представляет атом водорода, С₁-С₄-алкильную, С₃-С₄алкенильную или 2-пропинильную группу, R₂ представляет С₁-С₆ алкильную, циклопропильную или 1-метилциклопропильную группу, элемент R₃, который может иметь одинаковые или различные значения, представляет атом галогена, С₁-С₄ алкильную группу, галоидзамещенную С₁-С₃ алкильную группу, С₁-С₄ алкокси, фенокси, фенильную, циано- или нитрогруппу, и n является целым числом от 0 до 3, или его соль.Therefore, this invention provides a geometric isomer or its salt in an E-form having the formula

CC

in which R ₁ represents a hydrogen atom, a C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl or 2-propynyl group, R ₂ represents a C ₁ -C ₆ alkyl, cyclopropyl or 1-methylcyclopropyl group, an element of R ₃ , which may have the same or different meanings, represents a halogen atom, a C ₁ -C ₄ alkyl group, a halogen-substituted C ₁ -C ₃ alkyl group, a C ₁ -C ₄ alkoxy, phenoxy, phenyl, cyano or nitro group, and n is an integer from 0 to 3, or its salt.

 There are also many well-known triazole compounds described in Great Britain Patent No. 1364619, Belgian Patent No. 345433, West Germany Patent Nos. 2610022, 2654890 and 2734426, as well as US Patent No. 4086351. However, a distinctive feature of the invention is that the following new information is obtained: one of the two geometric isomers of the triazole compound (I) characterized in that it has both (1) a double bond (benzylidene group) and (2) a hydroxyl group or its ethers.

H

обладает гораздо более сильными характеристиками в качестве сельскохозяйственных химикалиев по сравнению с другими геометрическими изомерами. В этом плане соединения настоящего изобретения имеют структурные характеристики, отличающиеся от характеристик указанных ранее хорошо известных соединений, и, кроме того, они обладают гораздо более ценными свойствами, по сравнению с хорошо известными соединениями. Соответственно оригинальность настоящего изобретения такова, что она никак не следовала из известного ранее уровня знаний.

H

possesses much stronger characteristics as agricultural chemicals in comparison with other geometric isomers. In this regard, the compounds of the present invention have structural characteristics that differ from those of the previously well-known compounds, and, in addition, they have much more valuable properties compared to the well-known compounds. Accordingly, the originality of the present invention is such that it did not follow from the previously known level of knowledge.

 As diseases against which the compounds of the present invention (1-A) (isomer) have high protective activity, rice pyriculariasis (pyricularia oryzae), rice shell rot (pellicularia sasakii), apple cancer (valsa mali), apple flower rot ( Sclirotinia mali), powdery mildew of apples (podosphaera lencotricha), scab of an apple tree (venturia inaegualis), spotting of apples (Mucosphaerella ponni), leaf spotting of an apple tree (Alternaria mali), black spotting of a pear (Alternaria kikuchiana), and powdery mildew , pear rust (Gymnosporangium haralanun), pear scab (venturia Rashicola), citrus melanz (Duaporthe citri), citrus scab (Elsinol fawсetti), ordinary green mold of citrus fruits (penicillium otigitatum), blue mold of oranges (penicillium italicum), brown rot of peaches (selerotinia cinerea), grape anthracose (Elsinoe ampelina céléra gingulata), rot grapes (Botrytiv cinerea), powdery mildew of grapes (Uncinula necator), rust of grapes (phakopsora avupelopsidis), rust of the tops of oats (puccinia coronota), powdery mildew of barley (Erysiphe graminis), spotting of the leaves of barley (Phynchosporium sec. ), loose smut of barley (ustilago huda), firm smut of barley (ustilago hord ei), snow rot of barley (Typhula incarnata), stem rust of barley (puccinia graminis), leaf rust of wheat (puccinia recondita), loose smut of wheat (ustilago tritici), durum wheat smut (Tilletia caries), leaf spottedness (Tilletia caries), leaf spotty , spotting of spikelets of wheat (Septoria nadorum), yellow rust of wheat (puccinia striiformis), stem rust of wheat (puccinia graminis), powdery mildew of wheat (Erysiphe graminis), powdery mildew of cucumbers (Sphaerotheca fuliginea), sulfuric rot of cucumbers, cucumbers stem rot of cucumbers (Mycosphaerella melonis), rot of cucumber achene (Sclerotinia sclerotiorum), anthracose cucumber c (Colletotrichum aegenarium), deciduous rot of tomatoes (Cladosporium fulvum), powdery mildew of tomatoes (Erysiphe cichora cearum), early rot of tomatoes (Alternaria solahi), gray rot of eggplant (Botrytis cinirea), unclean withered eggplant eggplant dew (Erysiphe cichoracearum), powdery mildew of allspice (Levcillula tanrica), gray rot of wild strawberry (Botrytis cinirea), powdery mildew of wild strawberry (Sphaerotheca humuli), brown blotch of tobacco (Alternaria longipes), powdery mildew of porcini (powdery mildew) beets (cercospora Beticola), leaf spotting of green peas (cercospora personata), brown spot the validity of pea leaves (cercospora arachilicola) and the like.

 In further studies of the antimicrobial activity of the compounds of the present invention, the IA isomer, it became apparent that the compounds of the present invention also have antimicrobial activity against Trichophyron rubrum. Thus, it was found that it is possible to use the compounds of the present invention as a fungicide for medical purposes.

 Further, the compounds of the invention, the IA isomer, can also be used as plant growth regulators used to control the growth of beneficial plants. So, for example, they can be used to prevent spindle-shaped growth of rice, wheat, turf, hedge trees and fruit trees, as well as to obtain dwarf forms of garden plants, for example, potted chrysanthemums.

 When growing rice and wheat, lodging of rice and wheat is often a serious problem due to the introduction of more than necessary fertilizers or strong winds. The introduction of the compounds of the present invention at the right time is effective for controlling the weight of rice and wheat and preventing their lodging.

 When growing a potted culture of chrysanthemums, the introduction of the compounds of the present invention is useful for increasing the commercial value of chrysanthemums, as they can shorten the length of the stem without harming the flowers.

 The compounds of the invention IA isomers have high herbicidal activity against grassy field weeds such as millet rooster (Echinochloa crus-galli), high dewdrop (Digitaria sanguinalis) and green bristles (Setaria viridis), such broad-leaved field weeds as umbrella plants (Cyperus difformis Z.), red gauze (Amaranthus retroflexus), ordinary white gauze (Chenopodium album), garden purslane (portulaca oleracea) and starfish (Stellaria media), and such annual and perennial weeds and marshy poles as millet rooster (Echinoehloa crus galli), buttercup (Monochoria viaginalis), rotala branched (Rotala oudica Koe hue) (Dopatrium junceum Bulrush sp / Seirpus jumcoides var Hotarui ohwi) and Sliuder spikerush (Ellocharis acicularis).

 If the compounds of the invention are applied to the fields, they are also good from the following points of view, they have high herbicidal activity against the main field weeds, they are active both in the tillage before the weeds germinate and in the treatment of foliage in the initial growth phase, and in addition , they can be applied without fear of harming the main crops (e.g. rice, cotton, soybeans, corn, peas, sunflowers, beets), as well as vegetable crops (e.g. lettuce, radishes, tomatoes). If the compounds of the invention are applied to marshy fields, they also exhibit high herbicidal activity against the main weeds, either during processing before germination or during processing of foliage in the initial growth phase, and in addition, they are completely safe for rice plants.

 Further, the compounds of the invention are extremely useful as herbicides not only for rice fields, but also for various cereals, vegetables, orchards, peat bogs, pastures, tea plantations, alkaline plantations, rubber plantations, forests and uncultivated land.

 It further became apparent that the compounds of the invention are highly safe for mammals and fish, and, moreover, they can be used in practice without harming beneficial crops.

 Triazole compounds II-A, intermediate for the preparation of compounds of the invention I-A, also have fungicidal activity against various pathogens harmful to agriculture, as well as herbicidal activity and action as plant growth regulators. However, the fact is that the compound of the present invention IA has a much higher activity against a wide range of plant pathogens as well as a much higher herbicidal activity and activity as plant growth regulators than compound II-A.

 More specifically, methods for preparing the compounds of the invention will be described below.

 Method A.

где R₂, R₃ и n имеют указанные ранее значения. Изомер I'-А получают, восстанавливая изомер II-А в подходящем растворителе металлогидридным комплексом (например, литийалюминийгидридом, натрийборгидридом) или алкоголятом алюминия (например, изопропилатом алюминия).Reduction of tetrazole compound II
(R ₃ )

where R ₂ , R ₃ and n are as previously defined. I'-A isomer is prepared by reducing isomer II-A in a suitable solvent with a metal hydride complex (e.g., lithium aluminum hydride, sodium borohydride) or an aluminum alcoholate (e.g., aluminum isopropylate).

 The II-A isomer to be reduced can be obtained in pure form, for example, by performing fractional crystallization or column chromatography of a mixture of geometric isomers of the triazole compound (II) obtained in accordance with the following reaction scheme. Isomer II-A can also be easily obtained in good yield, for example by irradiating the mixture with ultraviolet rays for photoisomerization. A more detailed explanation will be given below regarding method C and D.

CHO +

-R ₂

C

-R

где R₂, R₃ и n имеют указанные ранее значения.

CHO +

-R ₂

C

-R

where R ₂ , R ₃ and n are as previously defined.

Solvents that can be used in the reduction with the metal hydride complex include, for example, ethers (e.g. diethyl ether, tetrahydrofuran) and alcohols (e.g. methanol, ethanol, isopropanol). If sodium borohydride is used as the metal hydride complex, the reaction is carried out by adding 1 mol of the II-A isomer and from 0.25 to 2 moles of sodium borohydride to the solvent. The reaction temperature is preferably in the range of from 0 ° ^C to room temperature. Useful solvents include, for example, ethers (e.g. diethyl ether, tetrahydrofuran), and alcohols (e.g. ethanol, methanol, isopropanol). If lithium aluminum hydride is used as the metal hydride complex, the reaction is carried out by dissolving lithium aluminum hydride in an amount of 0.25 to 0.8 mol based on the II-A isomer in the solvent, and adding the resulting solution to a solution of the isomer in the same solvent. The reaction temperature is maintained, preferably in the range of -60 to 70 ^° C. Solvents used include ethers (e.g. diethyl ether, tetrahydrofuran). After completion of the reaction, water or acid diluted with water is added to the reaction solution, and after neutralization with alkali, if necessary, the precipitated crystals are collected by filtration or extraction with an organic solvent sparingly soluble in water. Subsequent processing is carried out by conventional methods.

If aluminum isopropylate is used as the reducing agent, it is preferable to use solvents such as alcohols (e.g. isopropanol) or aromatic hydrocarbons (e.g. benzene). Usually allow 1 mol of II-A isomer to interact with 1-2 moles of aluminum isopropoxide at a temperature between room temperature and 100 ^C. The resulting aluminum compound is decomposed with dilute sulfuric acid or aqueous sodium hydroxide, followed by extraction with an organic solvent sparingly soluble in water . Subsequent processing is carried out by conventional methods.

 Salts of the I'-A isomer refer to salts derived from plant and physiologically acceptable acids, for example, hydrohalic acids (e.g., hydrobromic acid, hydrochloric acid, hydroiodic acid), carboxylic acids (e.g., acetic acid, trichloroacetic acid, maleic acid, succinic acid) , sulfonic acids (e.g. paratoluene sulfonic acid, methanesulfonic acid), nitric acid, sulfuric acid, and phosphoric acid. If necessary, these salts are obtained by conventional methods.

 Method B.

C

R₂
где R₁, R₂, R₃ и n имеют указанные ранее значения.Etherification of I'-A isomer

C

R ₂
where R ₁ , R ₂ , R ₃ and n are as previously defined.

The compounds of the present invention, I'-A isomers, are prepared by reacting the I'-A isomers with a reactive C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl or 2-propynyl derivative in a suitable solvent in the presence of a base. Reactive derivatives include, for example, alkyl alkenyl or alkynyl halides (e.g. methyl iodide, allyl bromide, propargyl bromide), sulfates (e.g. dimethyl sulfate, diethyl sulfate) and sulfonates (e.g. paratoluene sulfonate, naphthalenesulfonate). Solvents include, for example, common inert organic solvents, for example diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, and dimethylformamide. This reaction can be carried out in the presence of water using a phase transfer catalyst known as a reaction accelerator (e.g. triethylbenzylammonium chloride, trimethylbenzylammonium bromide). Bases include, for example, suitable strong bases (e.g., alkali metal hydrides such as sodium hydride, alkali metal amides, e.g. sodium amide), carbonates (e.g. sodium carbonate, potassium carbonate) and alkali metal hydroxides (e.g. potassium hydroxide, sodium hydroxide).

This reaction is carried out by mixing the I'-A isomer, a reactive, C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl or 2-propynyl derivative and a base, preferably in an equimolar ratio in a suitable solvent. The reaction is conducted at temperatures ranging from 0 ^to 100 ° C and preferably from 20 to 60 ^C. The I'-A isomer with a suitable strong base (e.g., alkali metal hydrides, alkali metal amides) in an inert solvent and then the resulting alkali metal salt reacted with reactive C ₁ -C ₄ alkyl, C ₃ -C ₄ alkenyl, or 2-propynyl derivative.

 In some cases, the following route may be desirable to isolate the compounds of the invention I ’- A: the reaction mixture is isolated from the solvent by evaporation, water and an organic solvent sparingly soluble in water are added to the residue, the organic layer is isolated after extraction and then purified by conventional methods .

 Salts I '' - A isomers refer to those salts which are obtained using physiologically acceptable acids, such as, for example, hydrohalic acids (e.g. hydrobromic acid, hydrochloric acid, hydroiodic acid), carboxylic acids (e.g. acetic acid, trichloroacetic acid, maleic acid, succinic acid), sulfonic acids (e.g. paratoluenesulfonic acid, methanesulfonic acid), nitric acid, sulfuric acid and phosphoric acid. If necessary, these acids are obtained by conventional methods.

 In more detail, the invention will be illustrated with reference to the following examples.

 Unless otherwise indicated, the NMR spectra in the examples indicate δ values for deuterochloroform as a solvent and tetramethylsilane as an internal standard.

PRI me R 1. Synthesis of I'-A isomer of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3- ol (compound N 1) by the method of II-A isomer (2.9 g, 0.01 mol, m.p. 108-109 ° ^C).

1- (4-chlorophenyl) -4,4-dimethyl-2) 1,2,4-triazol-1-yl) 1-penten-3-one (compound I ') was dissolved in methanol (50 ml). To this was added sodium borohydride (0.38 g, 0.01 mol), and the reaction temperature was maintained at ²⁰ ° C or less by cooling with ice. The reaction mixture was heated at 20 ^{° C} for 3 hours and then decomposed by adding water (100 ml) and acetic acid (1 mL). The organic layer was extracted with ethyl acetate (100 ml), the resulting extract was washed with 5% aqueous sodium bicarbonate (50 ml) and dried over anhydrous sodium sulfate. Then, the solvent was removed under reduced pressure and the resulting residue was recrystallized from isopropanol to obtain 2.0 g (yield 69%) I'-A isomer, melting point is 153-155 ° ^C. Elemental analysis and NMR spectrum obtained of this compound are shown below.

Elemental analysis:
Calculated C, H, N, Cl,
for C ₁₅ H ₁₈ N ₃ OCl 61.74 6.23 14.40 12.15
Found 61.82 6.33 14.38 12.15
NMR spectrum:
8.52 (1H, s, triazole proton)
7.98 (1H, s, triazole proton)
7.30 (4H, s, phenyl proton)
6.91 (1H, s, olefin proton)
4.56 (2H, broad singlet, hydroxyl proton and methine proton containing an OH group)
0.66 (9H, s, butyl proton)
Comparative Example 1. Synthesis of the 1'-B isomer of 1- (4-chlorophenyl) -4,4-dimethyl-2 (1,2,4-triazol-1-yl) -1-penten-3-ol (compound N 1).

II-B isomer (2.9 g 0.01 mol, m.p. 78-79 ^{° C)} of 1- (4-chlorophenyl) -4,4-dimethyl-2) (1,2,4-triazol-1 -yl) -1-penten-3-one (compound N 1 ′) was dissolved in methanol (50 ml). This isomer was allowed to react with sodium borohydride and then treated in the same manner as in Example 1. The resulting residue was recrystallized from a 1:10 mixture of carbon tetrachloride and n-hexane to obtain 2.2 g (yield 76%) of the I'-B isomer (m.p. 116-117 ° ^C) the compound N 1. Elemental analysis and NMR spectrum of this compound are shown below.

Elemental analysis:
C, H, N, Cl,
Calculated 61.74 6.28 14.40 12.15
for C ₁₅ H ₁₈ N ₃ OCl
Found 61.80 6.25 14.52 12.09
NMR spectrum
7.92 (s, triazole proton)
7.77 (1H, s, triazole proton)
7.05 (2H, d, phenyl proton j 9 Hz)
6.58 (2H, d, phenyl proton j 9 Hz)
6.66 (1H, s, olefin proton)
4.28 (1H, d, methyl proton carrying an OH group, j 6 Hz)
3.21 (1H, d, hydroxyl proton, j6 Hz)
0.80 (9H, s, butyl proton).

 PRI me R 2. Synthesis of I'-A isomer of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen- 1-ol (compound N 30) according to method A.

II-A isomer (2.9 g, 0.01 mol, m.p. 89-92 ^{° C)} of 3- (4-chlorophenyl) -1-methylcyclopropyl) -2- (1,2,4-triazol-1 -yl) -2-propen-1-one (compound 29 '). Characterized by NMR spectrum as described below, was dissolved in methanol (50 ml), sodium borohydride (0.33 g 0.01 mol) was added to it, and the reaction temperature was maintained at ²⁰ ° C or below by cooling with ice. The reaction temperature was maintained at ²⁰ ° C for 3 hours and then decomposed by adding water (100 ml) and acetic acid (2 mL). The organic layer was extracted with chloroform (100 ml), the extract was washed with 5% aqueous sodium bicarbonate (50 ml), and dried over anhydrous magnesium sulfate. Then the solvent was removed under reduced pressure, and the resulting precipitate was recrystallized from a mixture of carbon tetrachloride and n-hexane (1: 1) 5 ml (to obtain 2.4 g) yield 85% of the title compound.

 NMR spectrum of starting material II-A of the 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one isomer.

8.28 (1H, s, triazole proton)
8.07 (1H, s, triazole proton)
7.32 (4H, s, phenyl proton)
7.19 (1H, s, olefin proton)
1.45-1.15 (2H, m, methylene proton of the cyclopropyl group)
1.25 (3H, s, methyl proton)
0.99-0.75 (2H, m, methylene proton of the cyclopropyl group)
Comparative Example 2. Synthesis of I'-B isomer of 3- (4-chlorophenyl) -1- (1-methylcyelopropyl) -2- (1,2,4-triazol-1-yl) -2-propan-1-ol ( compound N 30).

II-B isomer (2 g, 0.007 mol, mp 74-75 ° C (3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2-1,2,4-triazol-1-yl) - 2-propen-1-one (compound N 29), characterized by an NMR spectrum described below, was reduced in the same manner as in Example 2 with sodium borohydride (0.27 g, 0.007 mol) in methanol (50 ml). 1.7 g (85% yield) of the title compound are obtained. NMR spectrum of starting material, II-B isomer of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4- triazol-1-yl) -2-propen-1-one:
8.12 (2H, s, triazole proton)
8.03 (1H, s, triazole proton)
7.55 (1H, olefinic proton)
7.21 (2H, d, phenyl proton j 8 Hz)
6.81 (2H, d, phenyl proton j 8 Hz)
1.50-1.25 (2H, m, methylene proton of the cyclopropyl group)
1.28 (3H, s, methyl proton)
0.90-0.65 (2H, m, methylene proton of the cyclopropyl group).

 PRI me R 8. Synthesis of I '' - A isomer of 1- (4-chlorophenyl) -4,4-dimethyl-3-methosi-2) -1.2.4-triazol-1-yl) - pentyl (compound N 35) according to method B.

 I'-A isomer (2 g) 1-para-chlorophenyl-4,4-dimethyl-2 (1,2,4-triazol-1-yl) -1-penten-3-ol (compound N 1) was dissolved in dimethylformamide (20 cm3) and 65% sodium hydride in oil (0.26 g) was added thereto. After stirring for 1 at room temperature, the reaction mixture was cooled to 10 ° C and methyl iodide (1 g) was added. After standing at room temperature for 20 h, the solvent was removed under reduced pressure, and the obtained residue was extracted by adding ice water (100 g) and chloroform (100 cm3). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained oily crude product was purified by silica gel column chromatography (acetone n-hexane 1:10), and then recrystallized from a mixture of carbon tetrachloride and n-hexane (1: 2) to obtain 1.6 g of the title compound (mp 63-66 ° C).

0.99-0.75 (2H, m, methylene proton of the cyclopropyl group)
Comparative Example 2. Synthesis of I'-B isomer of 3- (4-chlorophenyl) -1- (1-methylcyelopropyl) -2- (1,2,4-triazol-1-yl) -2-propan-1-ol ( compound N 30).

II-B isomer (2 g, 0.007 mol, m.p. 74-75 ^{° C)} of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2-1,2,4-triazol-1-yl ) -2-propen-1-one (compound N 29 ′), characterized by the NMR spectrum given below, was reduced in the same manner as in Example 2, with sodium borohydride (0.27 g, 0.007 mol) in methanol (50 ml) . Thus, 1.7 g (85% yield) of the title compound are obtained. NMR spectrum of starting material, II-B isomer of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one:
8.12 (2H, s, triazole proton)
8.03 (1H, s, triazole proton)
7.55 (1H, s, olefin proton)
7.21 (2H, d, phenyl proton j 8 Hz)
6.81 (2H, d, phenyl proton j 8 Hz)
1.50-1.25 (2H, m, methylene proton of the cyclopropyl group)
1.28 (3H, s, methyl proton)
0.90-0.65 (2H, m, methylene proton of the cyclopropyl group).

 PRI me R 3. Synthesis of I ″ - A isomer of 1- (4-chlorophenyl) -4,4-dimethyl-3-methoxy-2) -1, 2.4-triazol-1-yl) - pentyl (compound N 35) according to method B.

I'-A isomer (2 g) 1-para-chlorophenyl-4,4-dimethyl-2 (1,2,4-triazol-1-yl) -1-penten-3-ol (compound N 1) was dissolved in dimethylformamide (20 cm ³ ) and 65% sodium hydride in oil (0.26 g) was added thereto. After stirring for 1 at room temperature, the reaction mixture was cooled ^to 10 ° C and was added methyl iodide (1 g). After standing at room temperature for 20 hours, the solvent was removed under reduced pressure, and the obtained residue was extracted by adding ice water (100 g) and chloroform (100 cm ³ ). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting oily crude product was purified by silica gel column chromatography (acetone n-hexane 1:10), and then recrystallized from a mixture of carbon tetrachloride and n-hexane (1: 2) to obtain 1.6 g of the title compound (mp. . 63-66 ^about C).

Comparative Example 3. Synthesis of I ″ - The isomer of 1-para-chlorophenyl-4,4-dimethyl-3-methoxy-2- (1,2,4-triazole) -1-or-1-pentene (compound N 35 )
I'-B isomer (2 g) 1- (4-chlorophenyl) -4,4-dimethyl-2 (1,2,4-triazol-1-yl) -penten-3-ol (compound N 1) was dissolved in dimethylformamide (20 cm) and 65% sodium hydride (0.26 g) was added thereto. After stirring at room temperature for 1 h, the reaction mixture was cooled ^to 10 ° C and 1 g of methyl iodide was added. The reaction mixture was heated at 10 ^{° C} for 1 hour and then left to stand at room temperature for 16 hours. Dimethylformamide was removed under reduced pressure and the resulting residue was extracted by adding ice water (100 g) and chloroform (100 cm ^3). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel (acetone) n-hexane column chromatography (1:10) to obtain 1.0 g of the title compound as an oily product.

Refractive index n _D ²⁷ 1.5435.

Calculated C, H, N, Cl,
62.90 6.60 13.77 11.50
for C ₁₆ H ₂₀ N ₃ ClO
Found 62.84 6.59 13.74 11.59
The compounds of the present invention (IA isomers) obtained by methods A and B are shown in table 1. For comparison, the data for I-V isomers are shown nearby. Unless otherwise indicated, the NMR spectra in the table are given in δ for CDCl ₃ as solvent and tetramethylsilane as internal standard. I'-A isomer and I '' - A isomer is usually referred to as A I-A isomer, and I'-B isomer is also commonly called I-B isomer. This generic term is also used in the test cases below.

 The following is an explanation for obtaining the II-A isomer of the triazole compound (II), which is the starting material for the I'-A isomer of the triazole compound (I).

где R₂, R₃ и n имеют указанные ранее значения.Method C
Isomerization of the II-B isomer or a mixture of II-B and II-A isomers of the triazole compound (II):

where R ₂ , R ₃ and n are as previously defined.

The II-A isomer can be obtained by irradiating the II-B isomer or a mixture of the II-B and II-A isomers with UV lamps or xenon lamps, or experimentally with fluorescent lamps or sunlight, in a solvent inert with respect to these rays. As a commonly used solvent, for example, alcohols (e.g. methanol, ethanol, popanol) can be mentioned; ethers (e.g. tetrahydrofuran, dioxane), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone), aliphatic hydrocarbons (e.g. hexane, cyclohexane, petroleum ether) and aromatic hydrocarbons (e.g. benzene, toluene, xylene). The reaction can be conducted at temperatures at which usually proceeds photoisomerization, but in practice the preferred temperatures are between 0 and 100 ° ^C. Naturally reaction may be carried out by adding a sensitizer, used in conventional photoreaction e.g. phenyl ketone such as acetophenone and propilfenon, but this advantage gives a little.

Next, a method for producing a triazole compound represented by the formula (II) will be illustrated.
Method D.

CHO

-

-R₂

C

-R₂
где R₂, R₃ и n имеют указанные ранее значения.Obtaining a mixture of geometric isomers of the triazole compound (II) and each of the isomers (II-B and II-A)

Cho

-

-R ₂

C

-R ₂
where R ₂ , R ₃ and n are as previously defined.

The triazole compound (II) is prepared by reacting 1 mol of a ketone of formula (IV) with 1-2 moles of benzaldehyde of formula (III) in a suitable solvent in the presence of a basic catalyst. Basic catalysts include, for example, alkali and alkaline earth metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal alkoxides (e.g. sodium methylate, sodium ethylate, potassium methylate), carbonates (e.g. sodium carbonate, potassium carbonate), acetates (e.g. acetate sodium, potassium acetate), secondary amines (e.g. diethylamine, dipropylamine, pyrrolidine, piperidine, morpholine) and tertiary amines (e.g. triethylamine, tributylamine, pyridine, picoline, dimethylaniline) and are used in quantities ax 0.01 to 10.0 moles. Solvents include, for example, alcohols (e.g., methanol, ethanol), aromatic hydrocarbons (e.g., benzene, toluene, xylene), ethers (e.g. diethyl ether, tetrahydrofuran, dioxane), water, and mixtures thereof. The reaction is carried out in the temperature range 0 ° ^C to the boiling temperature of the solvent.

 If acetates (e.g. sodium acetate, potassium acetate), carbonates (e.g. sodium carbonate, potassium carbonate) or tertiary amines are used as the main catalyst, glacial acetic acid or acetic anhydride can be used as a solvent for the reaction.

The triazole compound (II) thus obtained is a mixture of two geometric isomers, for example, isomer II-A and isomer II-B, each of the isomers can be isolated by column chromatography or fractional crystallization. A mixture of geometric isomers usually contains a larger amount of isomer II-B than isomer II-A. All isomers of II-A ketone compounds are naturally new compounds, and of II-B isomers, new compounds are those in which R ₂ is an I-methylcyclopropyl group.

 Next, methods C and D will be illustrated in more detail with reference to the following examples.

 PRI me R 4. Synthesis of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one (compound N 1 ') according to method D.

α - (1,2,4-triazol-1-yl) pinacolone (50 g), anhydrous potassium carbonate (41 g) acetic anhydride (200 ml) and 4-chlorobenzaldehyde (46.3 g) were mixed, and the resulting mixture was heated at 90 ^about C for 12 hours with stirring. After cooling the reaction solution, the precipitate formed was filtered. The obtained filtrate was added dropwise to warm water (500 ml) at ⁶⁰ ° C to decompose the acetic anhydride followed by potassium carbonate was added little by little for alkalizing solution. The resulting oily product was extracted with ethyl acetate (500 ml) and the organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. One drop of the obtained residue was dissolved in acetone and the acetone solution was analyzed by gas chromatography under the conditions described below. Then it was found that the retention time for the peak corresponding to the II-B isomer is 300 s, and the time corresponding to the peak of the II-B isomer is 360 s. The ratio of both isomers obtained when calculating the peak areas was 19.8 / 61.2, i.e. about 1/3.

 The conditions for gas chromatographic analysis were as follows.

 Instrumentation: Nippon Denshey 20K gas chromatograph equipped with an FID detector.

Column: 1 m glass column
Liquid phase 5% XE-60
Carrier Chromosorb W
Temperature (column): 200 ^° C
Temperature (on water): 240 ^о С
Carrier gas: nitrogen gas, 1 kg / cm ² .

The residue was dissolved in benzene (100 ml). The resulting solution was passed through a column filled with silica gel with a particle size of 100-200 mesh (1.2 kg) and chromatography was performed with n-hexane / acetone (10: 1) as a developing solvent. The fractions corresponding to each isomer were recrystallized from carbon tetrachloride, resulting in 36 g (yield 41.6%) of pure II-B isomer), so pl. 78-79 ^{° C} (and 10 g) yield 11.5% (pure isomer II-A) (m.p. 108-109 ° ^C). The developing solvent n-hexane / acetone (10/3) was then passed through a column, whereupon 8 g of - (1,2,4-triazol-1-yl) pinacolone were isolated. Elemental analysis and NMR spectra of each isomer are given below. NMR spectra were obtained in deuterochloroform as a solvent, and chemical shifts were expressed in terms of tetramethylsilane as an internal standard.

 II-A isomer of 1- (4-chlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one (compound N 1 ').

Elemental analysis
C, H, N, Cl,
Calculated for 62.17 5.58 14.50 12.23
C ₁₅ H ₁₆ N ₈ OCl
Found 62.32 5.60 14.41 12.20
NMR spectrum:
8.11 (1H, s, triazole proton)
7.00 (1H, s, triazole proton)
7.15 (4H, s, phenyl proton)
6.99 (1H, s, olefin proton)
0.99 (9H, s, butyl proton)
II-B isomer of 1- (4-chlorophenyl) -4,4-dimethyl-2-) 1,2,4-triazol-1-yl) penten-3-one (compound N 1 '):
Elemental analysis:
C, H, N, Cl,
Found: 62.35 5.59 14.38 12.18
NMR spectrum:
8.14 (1H, s, triazole proton)
7.98 (1H, s, triazole proton)
7.22 (2H, d, phenyl proton j 8 Hz)
6.73 (2H, d, phenyl proton, j 8 Hz)
7.49 (1H, s, olefin proton)
1.22 (9H, s, butyl proton)
PRI me R 5. Synthesis of II-A isomer of 1- (4-chlorophenyl) -4,4-dimethyl -2- (1,2,4-triazol-1-yl) 1-penten-3-one according to method C.

II-B isomer (8.0 g) 1- (4-chlorophenyl) -4,4-dimethyl-2 (1,2,4-triazole -1-yl) -1-penten-3-one, obtained in example 4 was dissolved in acetone (500 ml) and isolated at ⁴⁵ ° C under UV light source, equipped with a 500 W high pressure mercury lamp. During the reaction, trace amounts of the reaction solution were taken from time to time and, using gas chromatography under the same conditions as in Example 4, the isomer ratio (II-B isomer) (II-A isomer) was separated. Got the following results:
Time, min. Isomer ratio
(II-B / II-A) 0 100/0 20 10/90 60 6/94 120 6/94
After 2.5 hours, the reaction solution was transferred to an 500 ml eggplant flask and acetone was removed under reduced pressure, whereby 7.9 g of crystals were obtained. The resulting crystals were recrystallized from carbon tetrachloride to yield 6.2 g (78% yield) of crystals (m. Mp. 108-109 ^C). This compound was dissolved in acetone and chromatographed under the previously described conditions, but no peak corresponding to the II-B isomer was observed.

 PRI me R 6. Synthesis of the II-A isomer from a mixture of geometric isomers 1- (4-chlorophenyl) -4,4-dimethyl-2 (1,2,4-triazol-1-yl-1-penten-3 -one) (compound N 1 '). The reaction mixture (10 g) containing the II-A and II-B isomers in a ratio of 1 to 3, obtained in Example 4, was irradiated with ultraviolet rays under the same conditions as in Example 5. After 1.5 hours using gas chromatography again measured the ratio of the II-A isomer to the II-B isomer, and it was found that this ratio was about 19 to 1.

 After evaporation of the solvent, the obtained crystals were recrystallized from carbon tetrachloride to obtain 5.1 g of the II-A isomer.

 PRI me R 7. (A) Synthesis of 3- (4-chlorophenyl) -1- (1-methyl-cyclopropyl) -2) (1,2,4-triazol-1-yl) -2-propene- 1-one (compound N 29 ') according to method C.

1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) ethan-1-one (10 g, 0.06 mol), anhydrous potassium carbonate (8 g, 0.06 mol) and acetic anhydride (100 ml) were mixed, and the resulting mixture was heated to 100 ^C for 6 hours with stirring. The precipitate formed in the reaction was removed by filtration, and the obtained filtrate was concentrated under reduced pressure to obtain an oily product. This oily product was extracted with chloroform (300 ml) and the resulting extract was washed with water saturated with sodium bicarbonate (300 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. One drop of the obtained residue was dissolved in acetone, and the acetone solution was subjected to gas chromatography under the conditions described below. The peak corresponding to the II-B isomer was found to have a retention time of 250 s, and the corresponding peak of the II-B isomer is characterized by a retention time of 300 s. The ratio of both isomers was 19.1 / 63.5, i.e., about 1/3, which was calculated from the percentage ratios of each of the areas.

The conditions for gas chromatography were as follows:
Instrumentation: Nippon Denshey 20K gas chromatograph equipped with an F1 D detector
Column: Glass column 1 m long
Liquid phase: 5% XE-60
Carrier: Chromosorb W
Temperature (column): 181 ^{° C}
Input temperature: 240 ^о С
Carrier gas: nitrogen gas, I kg / cm ²
The resulting residue was dissolved in benzene (100 ml). The resulting solution was passed through a column filled with silica gel (300 g) with a grain size of 100-200 mesh, and chromatography was performed with n-hexane / acetone (10: 1) as a developing solvent. The fractions corresponding to each of the isomers were recrystallized from carbon tetrachloride to separate the two indicated geometric isomers.

 The NMR spectra of each of the isomers are shown in Table 2.

II-A isomer: 1.7 (10% yield)
II-B isomer: 6.7 g (33% yield)
(B) Synthesis of starting material, 1- (1-methyl-cyclopropyl) -2- (1,2,4-triazol-1-yl) -ethan-1-one.

To a mixture of methyl 1-methylcyclopropyl ketone (28 g, a well known compound described in Bull. Soc. Chem. Eg. 1708 (1960), potassium chlorate (5.8 g) and water (70 ml) was added 28 g of bromine at a temperature from 40 ^to 50 ° C for 4 hours with vigorous stirring and then the reaction solution was stirred for 2 hours at room temperature. Thereafter, the reaction solution was extracted with two portions of ether, 200 mL, and then the organic layer was dried over calcium chloride and concentrated under reduced pressure to obtain 53 g of a crude product. 1- (1-methylcyclopropyl) -1- rometan-1-one.

A mixture of 1,2,4-triazole (18.3 g), anhydrous potassium carbonate (37 g) and acetonitrile (250 ml) was refluxed for 1 hour and then cooled to 60 ^C. The crude 1- (1 -methylcyclopropyl) -2-bromoethan-1-one (53 g), obtained previously, was added to this mixture over 2 hours, after which stirring was continued overnight. Residues from the reaction solution were removed by filtration, and the resulting filtrate was concentrated under reduced pressure. The resulting residue was extracted by adding 100 ml of water and 300 ml of chloroform, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was extracted by adding 100 ml of water and 300 ml of chloroform, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting oily residue was recrystallized from 100 ml of petroleum ether to give 27 g of 1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -ethan-1-one 3, yield 57% based on methyl-1-methylcyclopropyl ketone, mp 57-60 ^about S.

 PRI me R 8. Synthesis of II-A isomer of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1 -one from the II-B isomer according to method C.

II-B isomer 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one (4 g), obtained in example 7 was dissolved in 500 ml of acetone and isomerization conducted at ⁴⁵ ° C for 2 hours using a UV light source, equipped with a 500 W high pressure mercury lamp. The ratio of the II-A isomer to the II-B isomer was measured by gas chromatography in the same manner as in Example 7. It was found that this ratio was 81.2 to 18.1. The reaction solution was concentrated under reduced pressure to obtain 3.9 g of crystals. These crystals were recrystallized from carbon tetrachloride to obtain 2.8 g (70% yield) of the II-A isomer.

 PRI me R 9. Synthesis of II-A isomer of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) - 2 (1,2,4-triazol-1-yl) -2-propen-1- it is from a mixture of geometric isomers.

 The reaction mixture (3 g) containing the II-A and II-B isomers, (II-A) II-B 1/3, obtained in Example 7, was irradiated with ultraviolet rays for 1.5 hours under the same conditions as in example 8. After that, the ratio of the II-A isomer to the II-B isomer was measured by gas chromatography. It was found that this ratio changed from 1/3 to 7/3. After removing the solvent by evaporation, the obtained crystals were recrystallized from carbon tetrachloride to obtain 1.5 g of the II-A isomer.

 PRI me R 10. Synthesis of II-B isomer of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -1-hepten-3-one (compound N 22) according method D.

To a mixture of 2-hexanone (50 g) and methanol (300 ml) was added 80 g of bromine at ⁰ ° C, and the resulting mixture was heated at 10 ^{° C} for 2 hours. To this was added 200 ml of water and 50 g of concentrated sulfuric acid and after stirring for 16 hours, another 500 ml of water was added. The reaction mixture was transferred to a separation column and extracted with 500 ml of ether. The organic layer was washed with a 5% aqueous potassium carbonate solution and dried over calcium chloride. Then, the solvent was removed under reduced pressure to obtain 89 g of crude 1-bromo-2-hexanol as an oily product.

A mixture of triazole (35 g), anhydrous potassium carbonate (69 g) and acetonitrile (300 ml) was refluxed for 1 h and allowed to cool to 50 ° ^C. The crude 1-bromo-2-hexanone (89 g) obtained previously, it was added dropwise to the resulting mixture, which was then stirred at room temperature for 16 hours. The precipitate in the reaction solution was removed by filtration, and the solvent was removed under reduced pressure. 200 ml of water and 200 ml of chloroform were added to the residue thus obtained, and the resulting mixture was transferred to a separatory funnel, after which it was extracted. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain 77 g of crude 1- (1,2,4-triazolyl) -2-hexanone as an oily product.

The obtained 1- (1,2,4-triazolyl) -2-hexanone (20 g), anhydrous potassium carbonate (20 g), p-chlorobenzaldehyde (20 g) and acetic anhydride (200 ml) was stirred and heated at 90 ° ^C for 5 hours. Then the reaction mixture was concentrated under reduced pressure, the resulting residue was dissolved in ethyl acetate (500 ml) and transferred to a separatory funnel. The ethyl acetate solution was washed with water saturated with potassium carbonate (200 ml), and the organic layer was isolated. Then, the solvent was removed from the organic layer under reduced pressure, the residue was introduced into a silica gel funnel (0.5 kg of silica gel with a size of 100-200 meshes) and chromatography was performed using n-hexane / acetone (10: 1) as a developing solvent. Thus obtained 3.7 g of II-B isomer (m.p. 117-120 ^{° C)} of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -1-heptene -3-one and 9 g of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -3-acetoxy-1,3 heptadiene (m.p. 112-114 ° ^C) .

To the obtained 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -3-acetoxy-1,3-heptadiene (9 g), concentrated hydrochloric acid (100 ml) was added and the resulting mixture was heated ^at 50 ° C for 2 hours, after which it was poured into ice water (500 ml). The aqueous solution was neutralized with potassium carbonate and extracted with ethyl acetate (300 ml). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation. The crystalline residue was recrystallized from a mixture of carbon tetrachloride (n-hexane (1: 1), whereby 6 g of II-B isomer of 1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) was obtained -1-heptan-3-one.

 PRI me R 11. Synthesis of I-A isomer of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethyl-1-penten-3 -ol (compound N 2).

 The first stage (condensation) method D.

A mixture of α - (1,2,4-triazol-1-yl) -pinakolona (200 g) of 2,4-dichlorobenzaldehyde (220 g) and acetic anhydride (700 cm ³⁾ was heated ^to 50 ° C, and thereto was added 255 g of triethylamine. The heated for 7 hours at 70 ^{° C,} after which the acetic anhydride was removed under reduced pressure. 3 L of water was added to the residue, and the resulting crystals were filtered off, washed with water and dried. The resulting crude product was recrystallized from ethanol (600 cm ³ ) to give 304 kg. II-B isomer of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) 4,4-dimethyl-1-penten-3-one (compound N 2 ′) .

 The second stage (photoisomerization) method C.

II-B isomer (300 g) of the compound N 2 'produced in the first step was dissolved in 2 L of acetone, and subjected to isomerization at ³⁰ ° C for 26 hours under a UV source equipped with a 500 W high pressure mercury lamp. Then, the solvent was removed under reduced pressure to obtain 300 g of an oily product. Using gas chromatography, it was found that this product is a mixture consisting of 75% of the II-A isomer of compound N 2 and 25% of the II-B isomer of the same compound. This product was passed on to the next step without separating the isomers.

 The third stage (recovery).

300 g of a mixture of geometrical isomers of compound N 2 'obtained from the second step was suspended in methanol (1 kg), and thereto is added sodium borohydride (38 g) in portions while cooling the reaction mixture to 10 ° ^C. After stirring at room temperature for 1 h, the reaction solution was concentrated under reduced pressure. The resulting residue was extracted by adding a 10% aqueous solution of acetic acid (2 L) and ethyl acetate (3 L). The separated organic layer was washed with a 5% aqueous potassium carbonate solution (1 L) and dried over anhydrous magnesium sulfate (100 g). After removal of the drying agent by filtration, the solvent was removed under reduced pressure, whereby 280 g of a crude product were obtained in the form of crystals. This product was a mixture of IA and IB isomers of compound N 2 (mixture ratio IA (IB 75/25). The crude product (280 g) was recrystallized from carbon tetrachloride (600 cm ³ ), resulting in 209 g of the title compound (IA isomer of compound N 2) are obtained. The mother liquor from recrystallization is concentrated to half volume, whereby 25 g of IB compound isomer of N 2 is obtained in the form of secondary crystals.

 II-A isomers of the ketone compound (II) obtained by methods C and D are shown in table. 2 along with II-B isomers. NMR spectra in table 2 in the same form as in table 1.

 In the practical application of the compounds of the invention thus obtained, they can be used alone without other components or in a mixture with carriers to facilitate their use as fungicides, herbicides and plant growth regulators. Commonly used formulations include, for example, dusts, wettable powders, oil spray formulations, emulsifiable concentrates, tablets, granules, fine granules, aerosols and expiratory preparations.

 The preparations described above usually contain 01, -95.0 wt. active ingredient (including other ingredients of the mixture). A suitable amount of the active ingredient used is usually 2-500 g per ar, and the concentration of the active ingredient used is preferably in the range of 0.001-1.0%. However, since the amount and concentration depend on the form of the preparation, time of use, devices for use, crop diseases and their nature, these values can be reduced or increased relative to the indicated intervals.

In preparing the fungicide, herbicide and plant growth regulator of the invention, suitable solid carriers or liquid carriers are mixed. As examples of solid carriers, for example, inorganic compounds, for example, clay, kaolin group, montmorilonite group and attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, lime, apatite, zeolite, silicic anhydride, synthetic calcium silicate), plant organic compounds, such as powdered soybeans, tobacco, powdered walnuts, flour, powdered wood, starch, crystalline cellulose (synthetic e or natural macromolecular compounds) such as petroleum resin, aklidnye resins, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal, damarovaya resins and waxes (e.g. carnauba wax, beeswax) and urea. filtered, washed with water and dried. The resulting crude product was recrystallized from ethanol (600 cm ³ ) to obtain 304 g. II-B isomer of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) 4,4-dime - til-1-penten-3-one (compound N 2 ').

 The second stage (photoisomerization) method C.

II-B isomer (300 g) of the compound N 2 'produced in the first step was dissolved in 2 L of acetone, and subjected to isomerization at ³⁰ ° C for 26 hours under a UV source equipped with a 500 W high pressure mercury lamp. Then, the solvent was removed under reduced pressure to obtain 300 g of an oily product. Using gas chromatography, it was found that this product is a mixture consisting of 75% of the II-A isomer of compound N 2 and 25% of the II-B isomer of the same compound. This product was passed on to the next step without separating the isomers.

 The third stage (recovery).

300 g of a mixture of geometrical isomers of compound N 2 'obtained from the second step was suspended in methanol (1 kg), and thereto is added sodium borohydride (38 g) in portions while cooling the reaction mixture to 10 ° ^C. After stirring at room temperature for 1 h, the reaction solution was concentrated under reduced pressure. The resulting residue was extracted by adding a 10% aqueous solution of acetic acid (2 L) and ethyl acetate (3 L). The separated organic layer was washed with a 5% aqueous potassium carbonate solution (1 L) and dried over anhydrous magnesium sulfate (100 g). After removal of the drying agent by filtration, the solvent was removed under reduced pressure, whereby 280 g of a crude product were obtained in the form of crystals. This product was a mixture of IA and IB isomers of compound N 2 (mixture ratio IA (IB 75/25). The crude product (280 g) was recrystallized from carbon tetrachloride (600 cm ³ ), resulting in 209 g of the title compound (IA isomer of compound N 2) are obtained. The mother liquor from recrystallization is concentrated to half volume, whereby 25 g of IB compound isomer of N 2 is obtained in the form of secondary crystals.

 II-A isomers of the ketone compound (II) obtained by methods C and D are shown in table. 2 along with II-B isomers. NMR spectra in table 2 in the same form as in table 1.

 In the practical application of the compounds of the invention thus obtained, they can be used alone without other components or in a mixture with carriers to facilitate their use as fungicides, herbicides and plant growth regulators. Commonly used formulations include, for example, dusts, wettable powders, oil spray formulations, emulsifiable concentrates, tablets, granules, fine granules, aerosols and expiratory preparations.

 The preparations described above usually contain 0.1-95.0 wt. active ingredient (including other ingredients of the mixture). A suitable amount of the active ingredient used is usually 2-500 g per ar, and the concentration of the active ingredient used is preferably in the range of 0.001-1.0%. However, since the amount and concentration depend on the form of the preparation, time of use, devices for use, crop diseases and their nature, these values can be reduced or increased relative to the indicated intervals.

 In preparing the fungicide, herbicide and growth regulator of a plant of the invention, suitable solid carriers or liquid carriers are mixed. Examples of solid carriers are, for example, inorganic compounds, for example, clay of the kaolin group, montmorilonite group and attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, lime, apatite, zeolite , silicic anhydride, synthetic calcium silicate), vegetable organic compounds, for example, powdered soybeans, tobacco, powdered walnuts, flour, powdered wood, starch, crystalline cellulose (synthetically f or natural macromolecular compounds), for example petroleum resins, aclide resins, polyvinyl chloride, polyalkylene glycol, ketone resins, ester resins, digging, damar resins, as well as waxes (e.g. carnauba wax, beeswax) and urea.

 Examples of liquid carriers are paraffinic or naphthenic hydrocarbons (e.g. kerosene, mineral oil, spindle oil, white oil), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene), halogenated hydrocarbons (e.g. carbon tetrachloride, chloroform , trichlorethylene, monochlorobenzene), o-chlorotoluol ethers (e.g. dioxane, tetrahydrofurn), ketones (e.g. acetone, methyl, ethyl, ketone, diisobutyl, ketone, cyclohexane, acetophenone, isophorone), esters (e.g. tyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate), alcohols (e.g. methanol n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol), alcohol ethers (e.g. ethyl ether, glycol, ethylene glycol phenyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether), polar solvents (e.g. dimethylformamide, dimethyl sulfoxide and water).

 Surfactants used for emulsification, dispersion, wetting, surface distribution, binding, regulation of disintegration, stabilization of the active ingredient, improved fluidity and anticorrosion properties of the non-ionic, anionic, cationic and amphoteric types can be used, but nonionic and / or or anionic agents. As suitable non-ionic surfactants, compounds obtained by the polymerization of ethylene oxide and higher alcohol (e.g. lauryl alcohol, stearyl alcohol, oleyl alcohol), ethylene oxide and alkylphenol (e.g. isoxylphenol, nonylphenol), ethylene oxide and alkylnaphthol (e.g. butylnaphthol) can be used. octylnaphthol) of ethylene oxide and higher fatty acid (e.g. palmitic acid, stearic acid, oleic acid), ethylene oxide and mono- or di-alkyl phosphate (e.g. stearyl phosphate, di auryl phosphate) or ethylene oxide and amine oxide (e.g. dodecylamine, stearic acid amide), esters of higher fatty acids and polyhydric alcohol (e.g. sorbitol), as well as compounds obtained by polymerization of these esters and ethylene oxide, as well as mixed polymers based on ethylene oxide and propylene oxide.

 Suitable anionic surfactants may include alkyl sulfate salts (e.g. sodium lauryl sulfate, amine salts of oleyl sulfate), alkyl sulfonates (e.g. sodium dioxyl sulfosuccinate, sodium 2-ethylhexenesulfonate), as well as arylsulfonates, sodium isopropylnaphthalenesulfonate sulfonate , sodium lignosulfonate, sodium dodecylbenzenesulfonate).

 In addition, the preparations of the invention may contain high molecular weight compounds and other auxiliary agents in order to enhance technological characteristics and biological activity. Such high molecular weight compounds include, for example, casein, gelatin, albumin, glue, sodium alginate, carboxylmethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol.

 The above carriers and auxiliary agents are usually used alone or in combination in accordance with the proposed use, taking into account the form of the drug and the technique of use.

 The content of the active ingredient in dusts is usually 1-25 wt. and the remainder is a solid carrier.

 As for wettable powders, the content of the active ingredient in them is usually 25-90 wt. The residue is a solid carrier and a dispersion wetting agent and, if necessary, a protective colloid, a thixotropic agent and an antifoam agent are added to the composition.

 In granules, the content of the active ingredient is usually 1-35 wt. and most of the residue is a solid support. The active ingredient is uniformly mixed with a solid carrier or uniformly fixed or adsorbed onto the surface of a solid carrier. Such particles have a diameter of 0.2-1.5 mm.

 As for emulsifiable concentrates, the content of the active ingredient in it is usually 5-30 wt. and the emulsifier takes 5-20 wt. and the remainder is a liquid carrier. If necessary, add anti-mold agents.

 In addition, the compounds of the invention can be used in a mixture with other fungicides, herbicides and plant growth regulators without reducing the regulatory effect of each active ingredient in the mixture. As fungicides, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, S-n-butyl S-p-tert-butylbenzyl dithiocarbonimidate, 0,0-dimethyl, 0- ( 2,6-dichloro-4-methylphenyl) phosphorothioate, methyl 1-butylcarbamoyl-1H-benzimidazole -2-yl-carbamate, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, cis-N- (1,1 , 2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboxyimide polyoxin, streptomycin, zinc ethylene bis (dithiocarbamate), zinc dimethyl tiscarbamate, manganese ethylene bis (dithiocarbamate), bis (N, N-dimethylthiocarbam disulfide, tetrachloroisophthalonitrile, 8-g idroxyquinoline, dodecylguanidine acetate, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide. N'-dichlorofluoromethylthio-N ', N'-dimethyl-N'-phenylsulfamyl, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -2-butanone, 1,2-bis (3-methoxycarbonyl-2-thioureido), benzene, methyl N- (2, 6-dimethylphenyl) -N-methoxyacetyl-2-methylglucinate, aluminum ethyl phosphite, etc.

 Phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and 2-methyl-4-chlorophenoxyacetic acid (including esters and salts) can also be used as herbicides. ), diphenyl ether series herbicides such as 2,4-dichlorophenyl-4-nitrophenyl ether, 2,4,6-trichlorophenyl 4'-nitrophenyl ether, 2-chloro-4-trifluoromethylphenyl, 3'-ethoxy-4'-nitrophenyl ether, 2,4-dichlorophenyl, 4'-nitro-3'-methoxyphenyl ether and 2,4-dichlorophenyl 3'-methoxycarbonyl-4'-nitrophenyl ether, triazine series herbicides such as 2-chloro-4,6-bisethylamino-1,3, 5-triazin-2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylthio 4,6-bisethylamino-1,3,5-triazine and 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine, urea series herbicides such as 3- (3,4-dichlorophenyl) -1, 1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea-1- (a, a-dimethylbenzyl) -3-p-tolylurea and 1- (2-benzothiazolyl) -1,3- dimethylurea, carbamate series herbicides such as isopropyl N- (3-chlorophenyl) carbamate and methyl N- (3,4-dichlorophenyl) carbamate, thiol carbamate series herbicides such as S- (4-chlorophenyl) N, N-diethylthiocarbamate and S-ethyl N, N-hexamethylene thiol carbamate, anilide series herbicides such as 3,4-dichloropropionailide, 2-chloro-N-methoxymethyl-2 ', 6'-diethylacetanilide , 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide, 2-chloro-2', 6'-diethyl-N- (n-propoxyethyl) acetanilide and N-chloroacetyl-N- ( 2,6-diethylphenyl) glycine ethyl ester, uracil series herbicides such as 5-bromo 3-fluoro.butyl-6-methyluracil and 3-cyclohexyl-5,6-trimethyleneuaracil pyridine salt herbicides such as 1,1'- dimethyl-4,4'-bipyridinium chloride, phosphorus-containing herbicides such as N- (phosphonomethyl) glycine, N, N-bis (phosphonomethyl) glycine, 0-ethyl 0- (2-nitro-5-methylphenyl) N-sec. butyl phosphoroamidothioate S- (2-methyl-1-piperidylcarbonylmethyl) 0,0-di-n-propyldiimophosphate and S- (2-methyl-1-piperidylcarbonylmethyl) 0,0'-diphenyldithiophosphate, toluidine series herbicides such as a, a , a-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine, 5-tert.butyl-3 (2,4-dichloro-5-isopropoxyphenyl) 1,3,4-oxadiazolin-2-one , 3-isopropyl-1H (-2,1,3-benzothiadiazine (3H) -one-2,2-dioxide, a-β-naphthoxy (propionanilide, 4- (2,4-dichlorobenzoyl) -1,3- dimethylpyrazol-5-yl p-toluenesulfonate, 3- (methoxycarbonylamino) phenyl-3-methylphenylcarbamate, 4-amino-3-methyl-6-phenyl-1,2,4-triazine, etc.

 The compounds of the invention can be used in a mixture with other insecticides, which does not reduce the regulatory effect of each active ingredient in the mixture. Organophosphorus insecticides such as 0, 0-dimethyl-0- (4-nitro-3-methylphenyl) phosphorothioate, 0- (4-cyanophenyl) -0,0-dimethylphosphorothioate, 0- (4-cyanophenyl) can be used as such insecticides. ) 0-ethylphenylphosphonothioate, 0,0-dimethyl-S- (N-methylcarbamoylmethyl) phosphorodithioate, 2-methoxy-4H-1,3,2-benzodiaxaphosphorin-2-sulfide and 0,0-dimethyl S- (1- ethoxycarbonyl-1-phenylmethyl) phosphorodithioate, and insecticides of the peretroid series such as a-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) isovalerate, 3-phenoxybenzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate and a-cyano-3- enoksibenzil 2,2-dimethyl 3- (2,2-dibromovinyl) tsikloropankarboksilat. Therefore, at the same time, one or more diseases and insects can be controlled and, in addition, a synergistic effect due to mixing can be expected.

 Further, the utility of the compounds of the present invention as fungicides, herbicides and plant growth regulators for agriculture and horticulture will be illustrated in more detail in the following test examples and production examples.

 Test Example 7

 50 g of mixed soil containing sea sand, mountain soil and peat were placed in a flower pot with a diameter of 13 cm and pot-mum were cultivated in it (different: Snow Ridge). Two weeks later, pot-mum was pressed and cultured in a 3-stem form and new buds grew. Two weeks after pressing, an aqueous dilute solution containing a predetermined concentration of each of the test compounds was applied to pot-mum, and 42 days after the application of the pesticide, the effect of plant growth regulation was studied. The results are presented in table.3.

 This effect was evaluated as follows.

 The increase in plant height was calculated as the difference between the initial plant height during application and plant height at 42 days after application and expressed by the height index with the corresponding difference in the untreated bowl, taken as one hundred. The values presented in table 3 represent the average of three parallel experiments.

 B-9 (N, N-dimethylamino succinic acid) was used as a control compound.

 Test Example 9

 Action to control the height of soy and barley plants. In a 500 ml plastic bowl, loamy soil was loaded. The soil was removed from the upper half of the bowl, well mixed with 10 ml of an aqueous diluted solution of the emulsifiable concentrate of each of the test compounds and returned to the bowl. After that, soy and barley were sown on treated soil in the amount of 3 seeds per bowl and 5 seeds per bowl, respectively.

Soybeans and barley were grown in a glass chamber at 25 ^C and after 14 days was measured the height of each plant. The results obtained are presented in table. 4. The numerical values in Table 4 mean the average height for two soy plants and for three barley plants, which is expressed as a percentage relative to the average height and untreated bowl, taken as 100.

 As a result, it was found that the IA isomer of the invention shows a pronounced strong effect on controlling the height of the plant compared to isomer IB, which is a control compound. In addition, when using both the isomer IA and IB, no phytotoxic effect, such as, for example, chlorosis and necrosis was observed, and it was found that the foliage remains dark green.

 Test Example 10

 The controlling effect on the growth of interstitial barley. Barley (different. Coseshikoku) was sown on the soil on November 20 and the next year an aqueous dilute solution of the emulsifiable concentrate IA-isomer of compound I was sprayed on the foliage once (April 4) and twice (April 4 and 24 )

 Barley in each bowl ripened by May 28th and the length of the internode of 30 barley stems per bowl was measured. As shown in table 5, the length of the fourth and fifth internodes in the treated bowl was significantly shorter than the untreated bowl and, in addition, the total length in the treated bowl was also shortened.

 Nowhere was there a phytotoxic effect such as yellowing and sterility.

 Test Example 11

 The effect of controlling peat growth.

 A soil mixture from mountain soil and peat in a ratio of 3: 1 was placed in a Wagner bowl with an area of 1/5000 macaw and on December 6, Zoysia (Zoysia metrella L.) was transplanted into the bowl.

Zoysa were cultivated in a greenhouse at 30 ^{° C} with constant fertilization and movement Zoysa to the point where it becomes uniform growth. Immediately after moving the zoisia on May 9, an aqueous dilute solution of the emulsifiable concentrate of each of the test compounds was used at a flow rate of 10 ml / cup using a hand sprayer.

 On June 2nd, the increase in Zoisia's height was measured in order to assess the control of growth caused by the test compound. This effect was expressed by the height index with a corresponding increase in height in the untreated bowl, taken as 100. The results are presented in table.6. From table 6 it is seen that the compounds of the invention have an effect that controls the growth of zoisia.

 Production Example 1. Dusty.

 1 parts by weight isomer IA of each of the compounds of the invention (1) to (52), 89 wt. including clay and 10 parts by weight talcum powder was well mixed to obtain a dust containing 1% of the active ingredient.

 Production Example 2. Dust.

 3 parts by weight IA isomer of each of the compounds of the invention (1) to (52), 67 wt. including clay and 30 parts by weight talcum powder was mixed well to obtain a dust containing 3% of the active ingredient.

 Production Example 3. Wettable powders.

 30 wt. including I-A isomer of each of the compounds of the invention (1) to (52), 45 parts by weight diatomaceous earth, 20 parts by weight white coal, 3 parts by weight wetting agent (sodium lauryl sulfate) and 2 parts by weight dispersing agent (calcium lignosulfonate) was well mixed to a powder state with the formation of a wettable powder containing 30% of the active ingredient.

 Production Example 4. Wettable Powder.

 50 wt. including I-A isomer of each of the compounds of the invention (1) to (52), 45 parts by weight diatomaceous earth, 2.5 wt. wetting agent (calcium alkylbenzenesulfonate) and 2.5 wt. a dispersing agent (calcium lignosulfonate) was well mixed with each other to a powder state to form a wettable powder containing 50% of the active ingredient.

 An example of obtaining 5. Emulsifiable concentrate.

 10 wt. including I-A isomer of each of the compounds of the invention (1) to (52), 80 wt. including cyclohexanone and 10 parts by weight an emulsifier (polyoxyethylene alkylaryl ether) was mixed to form an emulsifiable concentrate containing 10% of the active ingredient.

 Production Example 6. Granule.

 5 parts by weight IA isomer of each of the compounds of the invention (1) to (52), 40 wt. bentonite, 50 parts by weight clay and 5 parts by weight sodium lignosulfonate was well mixed to a powder state. The resulting mixture was well mixed with water, granulated and dried to form granules.

 Production Example 7. Dust.

 2 wt. including II-A isomer of each of the compounds of the invention (1 ') - (33'), 88 wt. including clay and 10 parts by weight talcum powder was well mixed until a powder was formed to obtain a dust containing 2% of the active ingredient.

 Production Example 8. Dust.

 3 wt. including II-A isomer of each of the compounds of the invention (1 ') - (33'), 67 wt. including clay and 30 parts by weight talcum powder was mixed well to obtain a dust containing 3% of the active ingredient.

 Production Example 9. Wettable Powder.

 30 parts by weight II-A isomer of each of the compounds of the invention (1 ') - (33'), 45 parts by weight diatomaceous earth, 20 parts by weight white coal, 3 parts by weight wettable agent (sodium lauryl sulfate) and 2 parts by weight a dispersing agent (calcium lignosulfonate) was well mixed to a powder state to obtain a wettable powder containing 30% of the active ingredient.

 Production Example 10. Wettable Powder.

 50 parts by weight II-A isomer of each of the compounds of the invention (1 ') - (33'), 45 wt. including diatomaceous earth, 2.5 wt.h. wettable agent (calcium alkylbenzene sulfonate) and 2.5 wt.h. a dispersing agent (calcium lignosulfonate) was mixed well with each other until a powder state was formed, to obtain a wettable powder containing 50% active ingredient.

 An example of obtaining 11. Emulsifiable concentrate.

 10 parts by weight II-A isomer, each of the compounds of the invention (1 ') - (33'), 80 wt. including cyclohexanone and 10 parts by weight an emulsifier (polyoxyethylene alkylaryl ether) was mixed with each other to form an emulsifiable concentrate containing 10% of the active ingredient.

 Production Example 12. Pellet.

 5 wt. including II-A isomer of each of the compounds of the invention (1 ') - (33'), 40 wt. including bentonite, 50 parts by weight clay and 5 parts by weight sodium lignosulfonate was mixed well with each other to a powder state. The resulting mixture was mixed with water, granulated and dried to obtain granules containing 5% active ingredient.

 Production Example 13. Wettable Powder.

 80 wt. including I-A isomer of each of the compounds of the invention (1) to (52), 15 wt. including diatomaceous earth, 2.5 wt.h. wettable agent (calcium alkylbenzenesulfonate) and 2.5 wt.h. a dispersing agent (calcium lignosulfonate) was mixed well with each other to a powder state to obtain a wettable powder containing 80% active ingredient.

 Test Example 19

 The experiments were carried out according to the same procedure as described in test example 7, using an emulsifiable concentrate with a concentration of the active ingredient of 5% (mixing example N 1 from preparative example 19) wettable powder with a concentration of the active ingredient 15% (mixing example N 3 from preparative example 17 ) (table. 8) and a wettable powder with a concentration of the active ingredient of 30% (mixing example N 8 from preparative example 17) (table. 9).

 The following tables present the obtained results, proving the positive effect of the currently claimed compounds in comparison with the comparative compounds described in Swiss patent N 587012.

 The results of test example 19 are presented in table.7. A test for slowing down the development of a pot-mum pupa in the presence of emulsified concentrates with a concentration of the active ingredient of 5% prepared according to the method of mixing example No. 1 and preparative example 19.

 Examples of obtaining 14-20.

 Production Example 14. Dust.

1 parts by weight IA isomer of each of the present compounds (1) to (56), 2 parts by weight soot (carbon) (Si, O ₂ and H ₂ O) and 97 parts by weight clay is well mixed when pulverized to obtain a dust containing 1% of the active ingredient.

 Production Example 15. Dust.

5 parts by weight IA isomer of each of the present compounds (1) to (56), 1 part by weight soot (SiO ₂ and H ₂ O) and 94 parts by weight the clays are mixed well when pulverized to obtain a dust containing 5% of the active ingredient.

Production Example 16. Dust
1 wt. including II-A isomer of each of the compounds of the invention (1 ') to (33') are mixed in the same manner as described in Production Example 14 to obtain dust containing 1% of the active ingredient.

 Production Example 17. Wettable Powder.

 The 1st isomer of each of the present compounds (1) to (56), a wetting agent, a dispersing agent and an inorganic carrier are well mixed to obtain a wettable powder containing each active ingredient.

 Wetting agents used: higher alcohols formed from polyoxyethylene (e.g. lauryl alcohol, stearyl alcohol), alkyl phenols formed from polyoxyethylene (e.g. isooctylphenone, nonylphenol), polyoxyethylene-formed alkyl naphthols (e.g. butylnaphthol, octylene, fatty acids, octylene, fatty acids paltyl acid, stearic acid, oleic acid), higher fatty acid esters and sorbitan, higher fatty acid esters derived from polyoxyethylene, and sorbitan alkyl sulfate you (e.g. sodium lauryl sulfonate, sodium oleyl sulfonate), alkyl sulfonates (e.g. sodium dioctyl sulfosuccinate, sodium 2-ethylhexenesulfonate), aryl sulfonates (e.g. sodium isopropylnaphthalene sulfonate, sodium dodecylbenzenesulfonate) and mixtures thereof.

 The dispersing agents used are: sodium naphthalenesulfonate, a condensation product of sodium naphthalenesulfonate and formalin, sodium lithosulfonate and calcium lignosulfonate.

Used inorganic carriers, diatomaceous earth, natural clay (e.g. kaolinite, montmorillonites, attapulgites, talc, mica), white soot (SIO ₂ and H ₂ O) and a mixture thereof.

 The ratios at which the active ingredient, wetting agent, dispersing agent and inorganic carrier are mixed in the respective mixing examples are given in Table 10.

 Production Example 18. Wettable Powder.

 The II-A isomer of each of the present compounds (1 ′) to (33 ′) is mixed as described in Production Example 17 to obtain a wettable powder containing each active ingredient.

 An example of obtaining 19. Emulsifiable concentrate.

 The IA isomer of each of the present compounds (1) to (56), an emulsifier and a solvent are mixed to obtain an emulsifiable concentrate containing each active ingredient.

 Useful emulsifiers include higher alcohols formed by policosiethylene (e.g. lauryl alcohol, stearyl alcohol), alkyl phenols formed by polyoxyethylene (e.g. isooctylphenol, nonylphenol), polyoxyethylene formed alkylnaphthols (e.g. butylnaphthalene, hydroxyethylate, butyloxyethylate , oleic acid), esters of higher fatty acids and sorbitan, polyoxyethylene formed esters of higher fatty acids and sorbitan, alkyl sulfates (e.g. sodium lauryl sulfate, sodium oleyl sulfate), alkyl sulfonates (e.g. sodium dioctylsulfosuccinate, sodium 2-etilgeksensulfonat), aryl sulfonates (e.g. sodium isopropylnaphthalene sulfonate, sodium dodecyl benzene sulfonate) and mixtures thereof.

 Solvents used include saturated hydrocarbons (e.g. kerosene, mineral oil, spindle oil), aromatic hydrocarbons (e.g. toluene, xylene, ethylbenzene, methylnaphthalene), chlorinated hydrocarbons (e.g. trichlorethylene monochlorobenzene, monochlorotoluene, dichlorobenzene), ketones (e.g. methylenetone ketone , isophorone), esters (ethylene glycol acetate, diethylene glycol acetate), dimethylformamide, dimethyl sulfoxide and mixtures thereof.

 The ratios for mixing the active ingredient, emulsifier and solvent in the respective mixing examples are given in table 11.

 An example of obtaining 20. Emulsifiable concentrate.

 The II-A isomer of each of the present compounds (1 ′) to (33 ′) is wetted as described in Production Example 19 to obtain an emulsifiable concentrate containing each active ingredient.

Claims (6)

1. COMPOSITION FOR SLOWING THE GROWTH OF CULTURAL PLANTS, including the active substance and auxiliary additives, characterized in that as the active substance it contains the E-isomer of the compound of the general formula

where R ₂ C ₃ -C ₆ -alkyl, cyclopropyl or 1-methylcyclopropyl;
R ₃ , the same or different, halogen, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₂ -alkoxyl, phenoxy, or cyano, or nitro, phenyl; n = 0-3,
or its salt in the following ratio, wt. Active substance 1-80
Auxiliary additives Else
2. The composition according to p. 1, characterized in that as the active substance it contains a compound of formula I, where R _{2 is} tert-butyl. 3. The composition according to p. 1, characterized in that as the active substance it contains a compound of formula I, where R _{2 is} tert-butyl, R ₃ -4-chloro, n = 1. 4. The composition according to p. 1, characterized in that as the active substance it contains a compound of formula I, where R _{2 is} tert-butyl, R ₃ 2,4-dichloro, n 2. 5. The composition according to p. 1, characterized in that as the active substance it contains a compound of formula I, where R ₂ 1-methylcyclopropyl, R ₃ halogen, n 0 or 1. Featured Priority
08/06/79 at R ₂ tert-butyl, R ₃ halogen, n 1 or 2. 09/10/79 at R ₂ 1-methylcyclopropyl, R ₃ halogen, n 0-2. 09/25/79 at R ₂ C ₃ -C ₆ -alkyl, cyclopropyl, R ₃ -C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₂ -alkoxyl, phenyl, phenoxy, cyan, nitro, n 0-3.

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