JPS6232163B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, X represents a halogen atom, and n represents 0, 1 or 2. ] Among the two geometric isomers of the ketone compound represented by [] [In the formula, X and n are as described above.] ]
The present invention relates to a plant growth regulator containing one of the geometric isomer compounds represented by the formula or a salt thereof as an active ingredient. In the cultivation of plants, efforts to adjust plant growth in the direction desired by humans have long been entrusted to breeding and fertilization techniques. However, in recent years, as the mechanism of plant growth control by plant hormones has been elucidated, attempts have been made to directly control plant growth using chemical agents. As a result, the use of α-naphthalene acetic acid to promote the rooting of oak trees, the use of gibberellin for seedless fruit of grapes, and the use of N,N-dimethylamino succinium acid (trade name: B-Nine) for dwarfing chrysanthemums. The number of chemicals actually used for agricultural and horticultural purposes is also increasing. However, compared to the situations in which plant growth regulators are expected to be applied, there are very few fields in which their practical application has progressed. The present inventors have carried out intensive research with the aim of regulating plant growth using chemical agents, and have found that among the geometric isomers of triazole compounds represented by the general formula [], one is compared to the other. The present invention was completed based on the discovery that the present invention exhibits a higher plant growth regulating effect on a wider range of plants. In JP-A No. 54-41875, the use of an azole compound represented by the following general formula [] as a fungicide is known, and the specification states that ``a certain compound has plant growth regulating and herbicidal activity.'' ”. However, this publication does not include any examples of compounds that exhibit weeding and growth regulating effects, nor does it describe any test examples that demonstrate specific herbicidal and growth regulating effects. [Wherein, X represents an alkyl group, a cyano group, an alkoxy group, a phenoxy group, a phenyl group, a halogen atom or a hydrogen atom, and n represents an integer of 1 to 5. R ₁ is

Imidazole represented by the formula base or

Represents a triazole group represented by [Formula]. R ₂ represents a t-butyl group or a phenyl group that is unsubstituted or optionally substituted with an alkyl group, an alkoxy group, a phenyl group, or a halogen atom. ] A triazole compound represented by the general formula [ ] has plant growth regulating activity, and among the two geometric isomers, the olefin proton appears on the higher magnetic field side in the NMR spectrum (deuterated chloroform solution) [] The ketone compound represented by (hereinafter [
One isomer (hereinafter referred to as the [-E] isomer) obtained by reducing the isomer (hereinafter referred to as the [-E] isomer)
However, the other isomer (hereinafter referred to as [-Z] isomer) obtained by reducing the ketone compound in which the olefin proton appears on the lower magnetic field side (hereinafter referred to as [-Z] isomer)
-Z] has a higher plant growth regulating effect on a wider range of plants than the isomer), which is a completely new finding discovered by the present inventors as a result of their own research. Examples of synthesis of the [--E] isomer according to the present invention and the [--Z] isomer of the comparative compound are given below as reference examples. Reference example 1 [-E] of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol
Synthesis of isomer (compound number 1) 1- characterized by the following NMR spectrum
(4-chlorophenyl)-4,4-dimethyl-2
-(1,2,4-triazol-1-yl)-1
-E] isomer of -penten-3-one (melting point
108-109℃) 2.9g (0.01mol) of methanol 50
Dissolved in ml. While cooling this on ice and keeping the reaction liquid temperature below 20℃, 0.38 g of sodium borohydride was added.
(0.01 mol) was added. After keeping at 20°C for 3 hours, 100ml of water and 1ml of acetic acid were added to decompose, and the organic layer was extracted with 100ml of ethyl acetate. After washing with 50 ml of 5% sodium bicarbonate solution, it was dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from n-hexane to give 2.0 g of [-E] isomer with a melting point of 153-155°C (yield 69
%) was obtained. Elemental analysis values and NMR of each compound
The spectral results are shown. [-E] isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one;

[Table] NMR spectrum 8.11 (1H, singlet, triazole proton), 7.90 (1H, singlet, triazole proton), 7.15 (4H, singlet, phenyl proton), 6.99 (1H, singlet, olefin proton), 0.99 (9H,
singlet, butyl proton) [-E] isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol; elemental analysis

[Table] NMR spectrum 8.52 (1H, singlet, triazole proton), 7.98 (1H, singlet, triazole proton), 7.30 (4H, singlet, phenyl proton), 6.91 (1H, singlet, olefin proton), 4.56 (2H,
0.66 (9H, singlet, butyl proton) Reference example 2 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole) -1-il)-1-pentene-3-ol [-Z]
Synthesis of isomer (comparative compound, compound number 1*) 1- characterized by the NMR spectrum below
(4-chlorophenyl)-4,4-dimethyl-2
-(1,2,4-triazol-1-yl)-1
[-Z] isomer of -penten-3-one (melting point
78-79℃) 2.9g (0.01mol) in 50ml of methanol
dissolved in. After reacting with sodium borohydride in the same manner as in Example 1, the same treatment was performed, and the residue was recrystallized from a mixture of carbon tetrachloride and n-hexane (1:10) to give 2.2 g (yield 76%). A comparison compound ([--Z] isomer) with a melting point of 116-117°C was obtained.
Elemental analysis values and NMR spectrum results for each compound are shown. [-Z] isomer of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one;

[Table] NMR spectra 8.14 (1H, singlet, triazole proton), 7.98 (1H, singlet, triazole proton), 7.22 (2H, doublet,
Phenyl proton, J = 8Hz), 6.73 (2H,
Doublet, phenyl proton, J=8
Hz), 7.49 (1H, singlet, olefin proton), 1.22 (9H, singlet, butyl proton) 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl )-1-penten-3-ol [-Z] isomer;

[Table] NMR spectra 7.92 (singlet, triazole proton), 7.77 (1H, singlet, triazole proton), 7.05 (2H, doublet, phenyl proton, J=9Hz), 6.58 (2H, doublet, phenyl proton, J= 9Hz),
6.60 (1H, singlet, olefin proton), 4.28 (1H, doublet, methine proton with hydroxyl group, J = 6Hz), 3.21
(1H, doublet, proton of hydroxyl group, J=
6Hz), 0.80 (9H, singlet, butyl proton) The compound according to the present invention is one of two geometric isomers of the compound represented by the general formula [], and the geometric isomer of the present invention further includes two geometric isomers. Although there are various optical isomers, it goes without saying that the present invention includes any of these optical isomers. Examples of compounds according to the present invention are shown in Table 1, but the present invention is of course not limited thereto.

【table】

[Table] Examples of situations in which the compounds of the present invention can be used include increasing lodging resistance by suppressing internodal elongation in cereals such as rice and wheat, suppressing elongation in soybean and cotton, suppressing the growth of turfgrass, and suppressing the growth of fruit trees. It can suppress the formation of long branches, control the heat period of fruits, control the flowering time, improve the commercial value of ornamental crops by dwarfing them, suppress the growth of hedges, and suppress the germination and growth of weeds. The compound of the present invention may be applied directly to the foliage of the plant, or may be applied to the soil before sowing or before a certain point. It is also possible to treat soil where plants are growing. In the case of foliar spraying, the usual application amount is 1 to 5,000 ppm of the active ingredient, preferably 10 to 500 ppm, which is enough to wet the leaves of the target plant with the chemical solution and prevent drops from falling. will be processed. In the case of soil treatment, the active ingredient is treated at a treatment amount of 0.1 to 500 g/a, preferably 1 to 50 g/a, on the soil surface or in a mixed layer at a depth of 10 cm or less in the soil. The growth regulator of the present invention may be applied as a raw material itself, or may be mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as a growth regulator, such as a powder, a coarse powder, or a powder. Microgranules, Granules,
It is used after being prepared into wettable powders, emulsions, flowable preparations, aqueous solutions, aqueous solutions, oil suspensions, etc. Suitable solid carriers for use in preparing the growth regulators of the present invention include, for example, the kaolinite group,
Clays represented by montmorillonite group or attapulgite group, talc, mica, phyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium, lime, apatite, zeolite, anhydrous silica acid,
Inorganic substances such as synthetic calcium silicate, soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, vegetable organic substances such as crystalline cellulose, coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride,
Examples include synthetic or natural polymer compounds such as polyalkylene glycol, ketone resin, ester gum, cobal gum, and dammar gum, waxes such as carnauba wax and beeswax, and urea. Suitable liquid carriers include, for example, kerosene,
Paraffinic or naphthenic hydrocarbons such as mineral oil, spindle oil, white oil, benzene,
Toluene, xylene, ethylbenzene, cumene,
Aromatic hydrocarbons such as methylnaphthalene, carbon tetrachloride, chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, o-chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone,
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone, isophorone, esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate,
Alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dimethyl formamide, dimethyl sulfoxide, etc. Examples include polar solvents or water. Emulsification, dispersion, wetting, spreading, binding, disintegration control,
As surfactants used for the purpose of stabilizing active ingredients, improving fluidity, preventing rust, etc., any of nonionic, anionic, cationic, and amphoteric ionic surfactants can be used. Usually non-ionic and/or anionic ones are used. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, and those obtained by polymerizing and adding ethylene oxide to alkyl phenols such as isooctylphenol and nonylphenol. products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, palmitic acid, stearic acid,
Products in which ethylene oxide is polymerized and added to higher fatty acids such as oleic acid, products in which ethylene oxide is polymerized and added to mono- or dialkyl phosphoric acids such as stearyl phosphoric acid and dilauryl phosphoric acid, and ethylene oxide is added to amines such as dodecylamine and stearic acid amide. those obtained by polymerization addition, higher fatty acid esters of polyhydric alcohols such as sorbitan, and those obtained by polymerization addition of ethylene oxide,
Examples include those obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salts, alkyl sulfonates such as sodium sulfosuccinate dioctyl ester, and sodium 2-ethylhexene sulfonate; Examples include aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzenesulfonate. Furthermore, the growth regulator of the present invention includes polymeric compounds such as casein, gelatin, albumin, glue, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, and polyvinyl alcohol for the purpose of improving the properties of the preparation and increasing its biological effects. and other adjuvants can also be used together. The above-mentioned carriers and various auxiliary agents are used individually or in combination as appropriate depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc. Powders, for example, usually contain 1 to 25 parts by weight of the active ingredient compound, with the remainder being a solid carrier. Hydrating agents, for example, usually contain 25% of the active ingredient compound.
The remaining amount is a solid carrier, a dispersion wetting agent, and a protective colloid agent, a thixotropic agent, an antifoaming agent, etc. are added as necessary. Granules, for example, usually contain 1 to 35 parts by weight of the active ingredient compound, with the remainder being mostly solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle size is about 0.2 to
It is about 1.5mm. Emulsions, for example, usually contain 5 to 30 parts by weight of the active ingredient compound, this includes about 5 to 20 parts by weight of emulsifier, and the remainder is a liquid carrier;
Rust inhibitors are added if necessary. The formulation of this growth regulator is shown below. Formulation Example 1 Powder 2 parts of the compound of the present invention (1), 88 parts of clay, and talc
By thoroughly grinding and mixing 10 parts, a powder with a base ingredient content of 2% can be obtained. Formulation Example 2 Powder 3 parts of the present compound (2), 67 parts of clay, and talc
By thoroughly grinding and mixing 30 parts, a powder with a base ingredient content of 3% can be obtained. Formulation Example 3 Wettable powder: 30 parts of the present compound (1), 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of wetting agent (sodium lauryl sulfate), and dispersing agent (calcium lignin sulfonate)
By thoroughly grinding and mixing the two parts, a hydrating agent with a base ingredient content of 30% can be obtained. Formulation Example 4 Wettable powder: 50 parts of the present compound (3), 45 parts of diatomaceous earth, 2.5 parts of wetting agent (calcium alkylbenzenesulfonate), and dispersant (calcium ligninsulfonate)
By thoroughly grinding and mixing 2.5 parts, a hydrating agent with a base ingredient content of 50% can be obtained. Formulation Example 5 Emulsion 10 parts of the compound of the present invention (1), 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkylaryl ether) are mixed to obtain an emulsion with a base ingredient content of 10%. Formulation Example 6 Granules 5 parts by weight of the compound of the present invention (3), 40 parts by weight of bentonite, 50 parts by weight of clay and 5 parts by weight of sodium ligninsulfonate were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, followed by granulation drying. Main agent content 5
% of granules are obtained. Next, a test example will be described to clarify the usefulness of the compound of the present invention as a plant growth regulator. Test Example 1 Effect of suppressing plant height on soybean and barley A 500 ml plastic pot was filled with sandy loam, the top half of the soil was taken out, 10 ml of a water diluted solution of the test compound in emulsion form was added, and the mixture was thoroughly stirred and mixed. The pot was returned to its original pot, and 3 dice and 5 barley grains were sown in the chemically treated soil. This was cultivated in a glass room at 25°C, and the plant height of dice and barley was measured 14 days later. The result is second
As shown in the table, the values in the table indicate the index (%) when the average value of the plant height of two soybeans or three barley plants is set as 100 for the untreated plot. It has been found that the [--E] isomer of the compound (1) of the present invention exhibits a significantly stronger plant height inhibiting effect than the comparative [--Z] compound. In addition〔-
For both compounds E] and [-Z], no chemical damage such as chlorosis or necrosis was observed, but rather dark greening of the leaf color was observed.

[Table] Test Example 2 Effect of suppressing internodal elongation in barley Barley (variety: Goune Shiseki) was sown in the field on November 20th, and once on April 4th of the following year, and again on April 4th and 4th of the following year.
Twice on the 24th of each month, a diluted emulsion of compound (1) was sprayed on the leaves. On May 28th, each treated plot was harvested and the internodal length of 30 wheat culms in each plot was measured. The results are as shown in Table 3.
(1) Compared to the untreated plot, the internodes, especially the 4th and 5th internodes, were significantly shortened, and the total culm length was also suppressed. Furthermore, no chemical damage such as yellowing or sterility was observed.

[Table] Test Example 8 Potutumum (variety: Snow Ridge) was grown in a 4-inch unglazed pot with 500 g of synthetic soil made of sea sand, mountain soil, and peat, and pinched 2 weeks after the set point to grow 3 plants. Two weeks after the sprouts had grown, a diluted solution of the compound of the present invention at a predetermined concentration was applied, and the growth inhibitory effect was investigated on the 42nd day after the chemical treatment. The results are shown in Table 4. In addition, to evaluate the effectiveness, the plant height of the potsummum plants was measured in advance during the chemical treatment, and the length growth during this period was calculated from the difference with the plant height 42 days after treatment, and the height growth in the untreated area was set as 100. It is expressed as the elongation index. Values represent the average of triplicate.

[Table] Test Example 4 Grass Growth Suppression Test A 1/5,000th Earl Wagner pot was filled with synthetic soil containing a 3:1 mixture of mountain soil and peat, and Korai grass was transplanted on December 6th. The grass was cultivated in a greenhouse at 30°C, and fertilization and mowing were repeated several times until the grass grew evenly. On May 9th, immediately after mowing, the grass was treated with chemicals. The drug is diluted with water in the form of an emulsion, and is administered per pot.
A volume of 10 ml was applied with a hand sprayer. The amount of elongation of the turfgrass was measured on June 2nd, and the effectiveness was determined. The results are shown in Table 5 as an index when the elongation of the untreated area is set as 100, and the effect of the compound of the present invention on suppressing the elongation of turfgrass was clear.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, X represents a halogen atom, and n represents 0, 1 or 2. ] Among the two geometric isomers of the ketone compound shown by, the general formula obtained by reducing the geometric isomer in which the olefin proton appears on the higher magnetic field side in the NMR spectrum (deuterated chloroform solution) [In the formula, X represents a halogen atom, and n represents 0, 1 or 2. ] A plant growth regulator characterized by containing one of the geometric isomer compounds represented by these or a salt thereof as an active ingredient.