JPH04202189A - Optically active triazole derivative and plant-growth regulator - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (one of R<1> and R<2> is 2-4C straight- chain alkyl and the other is H; X is H or halogen) having (+) optical activity and a steric configuration characterized by the presence of R<1> and (substituted) phenylmethyl group at the cis-position and R<2> at the transposition of hydroxyl group. EXAMPLE:(1alpha,2alpha,5alpha)-2-[(4-Chlorophenyl)methyl]-5-ethyl-1-(1 H-1,2,4-triazol-1- ylmethyl)cyclopentanol having (+) optical activity. USE:A plant growth regulator. PREPARATION:A racemic compound synthesized from an oxaspiroheptane derivative of formula II and a triazole of formula III (M is H or alkali metal) is subjected to optical resolution to obtain the objective compound.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to an optically active triazole derivative that can be effectively used as a plant growth regulator, and a plant growth regulator containing the optically active triazole derivative as an active ingredient.

[Conventional technology]

JP-A-1-93574 describes - formation (A) (wherein R and R4 each represent a c-c alkyl group or a hydrogen atom (except when both R and R4 are hydrogen atoms) , ■ A racemic azole derivative represented by (X represents a halogen bee, an alkyl group of 01 to c5, or a phenyl group, n represents a number of 0 to 2, and A represents a nitrogen atom or CH), and a method for producing the same d describes that they have excellent bactericidal and plant growth regulating effects as agricultural and horticultural agents.

[Problem to be solved by the invention]

By the way, there is still a great demand for agricultural and horticultural chemicals that have the advantage of showing reliable effects at low doses and reducing the amount present in the environment, as well as agricultural and horticultural chemicals that cause less harm to plants and animals. There is a desire for the emergence of such agricultural and horticultural chemicals. The present invention has been made in view of these circumstances. Therefore, an object of the present invention is to provide a triazole derivative having an excellent plant growth regulating effect and a plant growth regulating agent using the same.

[Means to solve the problem]

In order to solve the above problems, the present inventors optically resolved the racemic form of the azole derivative of formula (A) and conducted extensive research on the activity of the optical isomer. As a result, the optical isomer according to the present invention is
It was discovered that this compound has a stronger plant growth regulating effect than its racemic form, and the present invention was completed. The present invention has the following structural features. That is, the present invention provides a triazole derivative with an optical activity of (+) shown by the following - formation (1), in which in its configuration, R' and an unsubstituted or substituted phenylmethyl group are present at the cis position of the hydroxyl group. It is characterized by the presence of R2 in the trans position. (In the formula, one of R1 and R2 represents a c-c4 straight chain alkyl group, the other represents a hydrogen atom, and X represents a hydrogen atom or a halogen atom.) The plant growth regulator of the present invention comprises the above-mentioned - It is characterized by containing a triazole derivative having an optical activity of (+) as shown in Formation (1) as an active ingredient. In the present invention, the triazole derivative may be used in the form of a salt with an inorganic acid, a salt with an organic acid, or a complex salt with a metal ion. These salts can be obtained by conventionally known methods. The optically active azole derivative represented by the general formula (1) according to the present invention is first prepared by the method described in JP-A-1-93574 and the oxaspirohebutane derivative of -formation (II) according to the following reaction formula. It can be obtained by synthesizing a racemate from the triazole of formula (m), followed by optical resolution. (II) -4= (I) (R1, R2 and X have the same meaning as defined above,
M represents a hydrogen atom or an alkali metal atom) In the above reaction formula, in the configuration of the triazole derivative represented by -formation (I) and the compound of general formula (II), the cis position of the oxygen atom bonded to the cyclopentane ring R1 and a substituted or unsubstituted phenylmethyl group are present at the position, and R2 is present at the trans position. To perform optical resolution, the racemic form of the triazole derivative represented by -formation (1) is dissolved in a solvent such as methanol, and a commercially available column for separating optical isomers, such as Cb ira Ice manufactured by Daicel Chemical Co., Ltd. I l −(1
1) etc., and using high performance liquid chromatography, develop with a solvent containing an appropriate amount of hexane and isopropanol, and fractionate. The resulting solvent containing each optical isomer was concentrated to dryness and recrystallized with ethyl acetate and hexadiene, resulting in
The desired optically active triazole derivative represented by general formula (1) (hereinafter simply referred to as "the compound of the present invention") is obtained. Table 1 shows specific examples of the compounds of the present invention and their physical and chemical properties (melting point, specific optical rotation). In addition, in the steric configuration of the compounds of the present invention shown in Table 1, R1 and an unsubstituted or substituted phenylmethyl group are present at the cis position of the hydroxyl group, and R2 is present at the trans position. Table 1 The compound of the present invention has a stronger plant growth regulating effect than the racemic compound, so it shows the same effect when used in a smaller amount than the racemic compound. Therefore, the compound of the present invention can prevent environmental pollution due to residual
It has higher safety against drug damage and toxicity. Plant growth regulators containing the compound of the present invention as an active ingredient can be used in the following fields. ■A field that utilizes the function of suppressing the vegetative growth of plants, especially plant height ■A field that utilizes the function of increasing the active ingredient content of plants ■A field that utilizes the function of regulating the ripening period and flowering time of plants The above-mentioned ■ Examples of using the growth suppressing function of the plant include suppressing the growth of weeds (herbicidal function), suppressing the growth of turfgrass, preventing lodging of plants that tend to lodge such as rice and wheat, and suppressing the plant height of soybeans and cotton. Examples include optimization of mechanical harvesting, promotion of leaf growth by suppressing axillary bud development in tobacco, reduction of pruning work by suppressing the growth of hedges, and improvement of commercial value by making ornamental plants dwarf. In addition, the function of increasing the content of plant components mentioned in (2) can be used to improve the quality of sugar beet, sugarcane, and citrus by increasing the sugar content, and to improve the quality of grains and soybeans by increasing the protein content. Furthermore, as for the use of functions related to fruit and flowering,
Examples include optimizing shipments of fresh fruits and fresh flowers according to the demand season. Although the compounds of the present invention can be used alone as they are, they are usually formulated together with formulation aids in various forms such as powders, wettable powders, granules, and emulsions. In that case, one or more compounds of the present invention are used in the preparation in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 70% by weight. The formulation should be formulated so that it is included. Examples of carriers, diluents, and surfactants used as formulation aids include the following. That is, as a solid carrier, talc, kaolin, bentonite, as a liquid diluent, water, xylene, I-toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethyl formamide, alcohol, etc. As a surfactant, as an emulsifier, polyoxy Ethylene alkyl allyl ether, polyoxyethylene sorbitan monolaure-1
Dispersants include lignin sulfonate, dibutylnaphthalene sulfonate, etc. Wetting agents include alkyl sulfonate, alkylphenyl sulfonate, etc. The above-mentioned preparations include those that are used as they are, and those that are diluted to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when used diluted is o. oo
A range of i to 1.0% is desirable. In addition, the amount of the compound of the present invention to be used in fields, [11, orchards,
20 to 5,000 per agricultural and horticultural land 111a in greenhouse nato
It is more preferably 50 to 1000 g. The concentrations and amounts used can of course be increased or decreased without being limited to the above ranges, since they vary depending on the dosage form, time of use, method of use, place of use, target crop, etc. Furthermore, the compounds of the present invention can also be used in combination with other active ingredients, such as bactericides, insecticides, acaricides, and acaricides.

[Examples] Below are separation examples and formulation examples for the compounds of the present invention.
The present invention will be specifically explained with reference to test examples. It should be noted that the present invention is not limited to the following separation examples, formulation examples, and test examples as long as they do not exceed the gist thereof. Separation Example 1 Optically active (+) (1α, 2α15α)-2-[(4-
chlorophenyl)methyl]-5-ethyl-1-(IH-
Separation of 1,2,4-1-riazol-1=ylmethyl)cyclopentanol [compound (I-1)] a) Racemic (1α, 2α, 5α)-2-[(4-chlorophenyl)methyl]- 5-ethyl-1-(IH-1,
Synthesis of 2,4-1-riazol-1-ylmethyl)cyclopentanol To 10 ml of anhydrous dimethylformamide, 630 mg of I. lithium hydride (60%/+11 thorium hydride washed with anhydrous benzene) was added, Then 1
1.8 g of H-1,2,4i-riazole was added, and the mixture was stirred at room temperature until foaming subsided. To the resulting solution, racemic (3α,4α,7α)-4-[(4-chlorophenyl)methylco-7-ethyl-1-oxaspiro[2,
4] Hebutane 3.3 g anhydrous dimethylformamide 6
．． 2 ml of the solution was added and stirred at 80°C for 1 hour. After cooling the resulting reaction solution, it was poured into ice water and extracted with methylene chloride to obtain an organic layer. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. was removed. The obtained residue was purified by silica gel column chromatography, and further recrystallized from hexane-ethyl acetate to obtain 2.96 g of the title compound. Yield: 70.3% Melting point = 82-846C NMR: (CI)CI3)δppm; 0, 67-
2.23 (m, lIll), 2.43 (d, 211,
J-7), 2.93 (s, 211), 4.20 (s,
211), 6.93-7.33 (m.411). 7,93(s,ill), 7.93(s,III),
8.07 (s, III) b) Separation of compound (1-1) Dissolve the racemic triazole derivative synthesized in a) in methanol and use high performance liquid chromatography using a column for separating optical isomers. , fractionated under the following conditions. The solvent was distilled off under reduced pressure from the solution containing the obtained compound (1-1), and it was recrystallized with a mixed solvent of ethyl acetate and hexane to obtain optically active (+) (1α, 2α, 5α)-2. −
[(4-chlorophenyl)methyl]-5-ethyl-1-
(LH-1.2.4-1-lyazol-1-ylmethyl)cyclopentanol [compound (I-1)] was separated. Preparation conditions: Column used: Daicel Chemical Co., Ltd. CIIIRALCEI,
L ODφlOmm
Solvent flow rate: 10 mil/min Detection wavelength: UV 268 nm Sample injection amount: 15 mg/150 μi (methanol) LI retention time: 47 minutes Separation Example 2 Optically active (+) (1α, 2α, 5β)-2-[(4-
chlorophenyl)methyl]-5-ethyl-1- (IH
-1.2.44 Separation of lyazol-1=ylmethyl)cyclopentanol [compound (1-2)] a) Racemic (1α.2α,5β)-2-[(4-chlorophenyl)methyl]-5- Ethyl-1-(IH-1,
Synthesis of racemic (3α, 4α, 7β)-4-[(4-chlorophenyl)methyl]-7-nityl-1-oxaspiro[2
,4]hebutane in a manner analogous to a) of Separation Example 1 to prepare racemic (1α. 2α, 5β)-2-[(4-chlorophenyl)methyl].
-5-ethyl-1-(LH-1,,2,4-triazol-1-ylmethyl)cyclopentanol was synthesized. Melting point: 93-95°C NMR: (CI)CI3)δppm; 0.70-2
．． 13 (m, 1lII), 2.13-2.47 (m,
211). 3.83 (s, III), 4.00 (d, III, J
-14), 4.30 (d, ill, J-14), 6
．． 88 (d, 211.J-8), 7.18 ((1,
211, J-8). 7.93 (s, 1II), 8.17 (s, 11b) Separation of compound (I-2) Dissolve the racemic triazole derivative synthesized in a) in methanol and remove the column for optical isomer separation. It was fractionated using high performance liquid chromatography under the following conditions. The solvent was distilled off under reduced pressure from the obtained solution/lk containing compound (1-2), and recrystallization was performed with a mixed solvent of ethyl acetate and hexane to obtain optically active (+) (1α, 2α, 5β ) −
2-[(4-chlorophenyl)methyl]-5-ethyl-
1-(IH-1,2,4i-lyazol-1-ylmethyl)cyclopentanol [compound (1-2)] was separated. Preparation conditions: Column used: Daicel Chemical Co., Ltd. C1111 ALCI:
Ll, 01] φ10mmXΩ500mm Model used: Hitachi 111TACIII 638-30 Elution solvent: Hexane-isopropanol mixed at a ratio of 15:1. Flow rate: 10ml! /min Detection wavelength: UV 268nm Sample injection amount: 15mg7150μg (methanol)
Target retention time: 40 minutes Formulation example containing the compound of the present invention as an active ingredient Formulation example 1: Powder Part by weight Compound (I-1) 3 Clay
40 talc
57 was ground and mixed and used as powder. Formulation Example 2: Wettable powder Compound (I-2) 50 lignin sulfonate 5 alkyl sulfonate 3 diatomaceous earth 42 are ground and mixed to prepare a wettable powder, which is diluted with water and used. 2 Formulation Example 3: Granules Part by Weight Compound (1-1) 5 Bentonite Clay 45 Lignin Sulfonate 7 were mixed uniformly, water was added and kneaded, processed into granules using an extrusion granulator and dried to obtain granules. shall be. Formulation Example 4: Emulsion parts by weight Compound (I-2) 20 polyoxyethylene alkyl allyl ether 10 polyoxyethylene sorbitan monolaurate 3 xylene 67 are uniformly mixed and dissolved to prepare an emulsion. Test Example 1 Plant growth regulating activity test Test example of a plant growth regulator containing the compound of the present invention as an active ingredient. Dilute the emulsion with water to the specified concentration, and add 5 ml per box.
00 ml was uniformly rinsed. After cultivating for 141 hours in a greenhouse, the plant height was measured, and the plant height suppression rate was calculated using the following formula. The results are shown in Table 2. Table 2 Test Example 2 Plant growth regulating activity test Test example of a plant growth regulator containing the compound of the present invention as an active ingredient The compound of the present invention in the form of an emulsion shown in Formulation Example 4 was diluted with water to a predetermined concentration. mil drug solution was prepared. Wheat seeds (Norin No. 64) 3g to 5ml of the above chemical solution 2
The seeds were soaked at 0°C for 24 hours and then sown in three-wooden pots filled with granular culture soil [manufactured by Kureha Chemical Co., Ltd.]. After cultivating in a greenhouse for 14 days, the plant height was determined at 1lllll, and the plant height suppression rate was calculated using the following formula. Table 3 shows the plant height results for the Mudokotanuki area. Table 3 [Effects of the Invention] As is clear from the comparison in the above examples, the compound of the present invention has a superior plant growth regulating effect compared to its racemate. Therefore, the plant growth regulator of the present invention exhibits reliable effects at low doses, and prevents environmental pollution due to residue, phytotoxicity, etc.
It has higher safety against toxicity. Applicant: Kureha Chemical Industry Co., Ltd. 11

Claims (2)

[Claims] (1) In the configuration of the triazole derivative represented by the following formula (I), R^1 and an unsubstituted or substituted phenylmethyl group exist at the cis position of the hydroxyl group, and R at the trans position.
A triazole derivative with optical activity (+) characterized by the presence of ^2. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are one of C_2-C
_4 represents a straight chain alkyl group, the other represents a hydrogen atom, and X represents a hydrogen atom or a halogen atom) (2) A plant growth regulator containing a triazole derivative having (+) optical activity represented by the general formula (I) according to claim (1) as an active ingredient.