JPS6055499B2 - Alkylene glycol dibenzoate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula ゛ -・force Hj [I] (wherein, represents a group, and n represents an integer of 1 to 3.

However, this does not apply when X is a hydrogen atom, n is 2, and R is a propylene group. ) is an alkylene glycol dipenzoate shown in Conventionally, many compounds have been used as agricultural and horticultural fungicides, but these fungicides
Acute toxicity, chronic toxicity, residual toxicity, etc. have caused social problems, and there is a desire for the emergence of safe new fungicides with low toxicity and no residual toxicity.

The present inventors synthesized various compounds with the aim of developing such a safe disinfectant, and as a result of conducting repeated physiological activity tests, the present inventors found that the compound represented by the general formula [I] has excellent antibacterial properties. The present inventors have discovered that this is a novel compound that has the same properties, has low toxicity, has no residual toxicity, no drug damage, etc., and has not been described in any literature, and has completed the present invention.

1 The compound of the present invention is useful as a fungicide for agriculture and horticulture, and is particularly useful as a fungicide for rice blast, rice blight, and cucumber charcoal stain.

Next, the compounds of the present invention will be illustrated.

The compound numbers are referred to in the following description. Compound (1) Ethylene glycol dibenzoate colorless prism crystals Melting point 72.5-74. Compound (2) Ethylene glycol-di-4-chlorobenzoate colorless prism crystal Melting point 138.5-139.5 Compound (3) Ethylene glycol-di-2-chlorobenzoate colorless liquid Nr = 1.5731 Compound (4) Diethylene glycol-di-4-chlorobenzoate Colorless liquid Nr = 1.5731 2-chlorobenzoate colorless transparent liquid NVf' = 1.5592 Compound (5) Propylene glycol benzoate colorless transparent liquid Nr = 1.5440 Compound (6) Propylene glycol benzoate colorless transparent liquid n? = 1.5453 Compound (7) Diethylene glycol dibenzoate colorless transparent liquid n → = 1.5448 Compound (8) Dipropylene glycol dibenzoate colorless transparent liquid n = 1.5430 Compound (9) Triethylene glycol Loosy 2-chlorobenzoate colorless transparent liquid n? = 1.5495 compound (10 Trimethylene glycol-di-2-chlorobenzoate colorless transparent liquid n? = 1.5665 compound (11) Trimethylene glycol-di-2-bromobenzoate compound (12) Tetramethylene glycol-di-benzoate colorless prismatic crystal Melting point 82 ~8 (3zoc compound (13) Dipropylene glycol-di-2-chlorobenzoate Colorless transparent liquid Ne = 1.5453 Compound (14) Tripropylene glycol-di-2-chlorobenzoate compound (18) Tripropylene glycol-di-2-methylbenzoate Colorless transparent liquid n?=1.5320 Compound (15) Triethylene glycol-di-4-chlorobenzoate colorless needle crystal Melting point 91-97C Compound (16) Triethylene glycol-di-2-methylbenzoate colorless transparent liquid Nr=1.5651 Compound (17) Triethylene glycol-di-4-ethylbenzoate colorless transparent liquid n?=1.5454 These compounds are easily synthesized according to the following reaction.

(In the formula, RsX,.n have the above-mentioned meanings.) All insoluble organic solvents are used as reaction solvents in the above production method, such as benzene, toluene,
Xylene ● Carbon tetrachloride ● Aromatic hydrocarbons such as chloroform and methylene chloride, halogenated aliphatics, acetone ●
Ketones such as methyl ethyl ketone and isopropyl ketone, ethers such as diethyl ether and dibutyryl ether and dioxane, and nitriles such as acetonitrile and probionitrile can be used. As dehydrochloric agents, tertiary amines such as pyridine and triethylamine, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and sodium hydrogen carbonate are used. Further, the reaction temperature is suitably from 0 to 150'C, and the reaction time is suitably from 3 to 6 hours.

Next, a method for synthesizing the compound used in the present invention will be explained by giving specific examples.

Synthesis Example 1 Synthesis of ethylene glycol 4-chlorobenzoate Ethylene glycol 62y1 pyridine 166.1f.

Dissolve in 500 ml of benzene, and add 350 V of 4-chlorobenzoyl chloride dropwise at 20° C. or below while stirring. After the dropwise addition was completed, the mixture was heated and reacted at 80° C. for 2 hours to complete the reaction. After the reaction was completed, the mixture was washed with diluted hydrochloric acid and then further washed with water until it became neutral. Anhydrous sodium sulfate! After drying with thorium, benzene was distilled off under reduced pressure to obtain crude crystals 320f. Recrystallized with ligroin, melting point: 5-139.5℃
A colorless prism crystal 305fI was obtained.

Yield 89.9%. 2 Synthesis Example 2 Synthesis of Propylene Glycol Dibenzoate Propylene Glycol 76.1f1 Triethylamine 2
12.5 g was dissolved in 500 ml of toluene, and while stirring, pentazoyl chloride 291y was added dropwise at a temperature below 20°C.

After completion of the dropwise addition, the mixture was heated and reacted at 90° C. for 4 hours to complete the reaction. After the reaction is complete, wash with diluted hydrochloric acid and then with water until neutral.

Dry over anhydrous sodium sulfate; after drying, benzene was distilled off under reduced pressure to obtain a colorless transparent liquid 246y with n=1.5440. Yield 87.5% Synthesis Example 3 Synthesis of triethylene glycol di-2-chlorobenzoate Triethylene glycol 75.1f1 Pyridine 80y was dissolved in methyl ethyl ketone 500ml, and 2-chlorobenzoyl chloride 175y was added dropwise at 20°C or below while stirring. did.

After the dropwise addition was completed, the mixture was heated and reacted at 60° C. for 2 hours to complete the reaction. After the reaction is completed, wash with diluted hydrochloric acid water and then with water until neutral.

After drying over anhydrous sodium sulfate, methyl ethyl ketone was distilled off under reduced pressure to obtain a colorless transparent liquid with n=1.5495.
I got f. Yield: 93.6% When actually using the alkylene glycol dibenzoates represented by the above general formula as agricultural and horticultural fungicides, this compound may be used as it is, but when the active ingredient is applied, In order to achieve effective dispersion, it is usually desirable to mix carriers and adjuvants and use them in the form of emulsions, wettable powders, powders, etc.
When using the compound of the present invention as a disinfectant, examples of liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, ethylene glycol, etc.),
Ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (gasoline, kerosene, kerosene, fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, etc.) , xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (dichloroethane, trichlorobenzene, carbon tetrachloride, etc.), acid amides (
dimethylformamide, etc.), esters (ethyl acetate,
Solvents such as butyl acetate, glycerin esters of fatty acids, etc.), nitriles (acetonitrile, etc.) are suitable, and one or a mixture of two or more of these may be used.

In addition, examples of solid carriers include clays (kaolin,
bentonite, etc.), talc (talc powder, waxite powder, etc.),
Silicas (diatomite, mica powder, etc.), lime, alumina powder, sulfur powder, activated carbon, vegetable powder, etc. are suitable, and one or a mixture of two or more of these may be used.
Further, as auxiliary agents, emulsifiers, dispersants, spreading agents, surfactants, etc. are used.

Examples of surfactants include nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyldimethylbenzylammonium chloride, alkylpyridinium chloride, etc.), and anionic surfactants. Examples include surfactants (alkylbenzenesulfonates, ligninsulfonates, higher alcohol sulfates), amphoteric surfactants (alkyldimethylbetaine, dodecylaminoethylglycine, etc.).

These adjuvants may be used alone or as a mixture of two or more.

When applying the compound of the present invention as an agricultural and horticultural fungicide, when using it in the form of an emulsion, the compound of the present invention 10 to 5
A stock solution is prepared by mixing 10 to 4 parts of an organic solvent and 5 to 5 parts of an auxiliary agent in an appropriate ratio, diluted to a predetermined concentration before use, and applied by a method such as spraying.

In addition, when used in the form of a wettable powder, the compound 10 of the present invention
The (support) part, 10 to 4 parts of the solid carrier, and 5 to 2 parts of the auxiliary agent are mixed in an appropriate ratio, and the mixture is diluted with water and used in the same manner as in the case of an emulsion.

In addition, when used in the form of a powder, the compound 1 of the present invention is usually
A homogeneous mixture of ~5 parts with 95 to 95 parts of a solid carrier such as kaolin, bentonite, or talc is used.

Furthermore, the compound of the present invention can also be used in combination with other active ingredients that do not inhibit its fungicidal effect, such as fungicides, insecticides, and acaricides.

When using the compound of the present invention as a fungicide, the amount used is 250 to 1500 ppm solution per 10 are for foliage treatment, and 50 to 500 e per 10 are for soil treatment.
50 to 300f is used as the amount of active ingredient per are. Next, the bactericidal effect of the active ingredient when the compound of the present invention is used as an agricultural and horticultural fungicide will be specifically explained using Examples and Test Examples.

Example 1 Wettable powder compound (4) 50 parts, diatomaceous earth 47 parts, Solbol 804
8 (manufactured by Toho Chemical Industry Co., Ltd., surfactant) are uniformly ground and mixed to obtain a wettable powder.

Example 2 Wettable powder compound (5) 40ml 1 white carbon 1 ml diatomaceous earth 4
8 parts and 2 parts of sodium alkylbenzenesulfonate were uniformly ground and mixed to obtain a wettable powder.

Example 3 Emulsion compound (13) 30S! ,,Sorball 80841 prostitute,
Mix and dissolve xylene 6 to obtain an emulsion.

Example 4 A powder was obtained by mixing and pulverizing 5 parts of powder compound (5) and 95 parts of clay.

Example 5 A granule compound (116 parts, 50 parts of bentonite, 41 parts of diatomaceous earth, and 3 parts of Airol CT-1 (manufactured by Toho Chemical Co., Ltd., surfactant) were mixed uniformly, an appropriate amount of water was added, and the mixture was kneaded. The mixture is granulated and dried to obtain granules.

Test Example 1: Anthracnose disease of cucumber Pot test A solution of a prescribed concentration of the test compound was sprayed at 30 ml per two pots on cucumbers (variety: Sagami Hanshiro) grown in one pot with a diameter of 12Crf, which had grown up to two true leaves, and after air-drying, separately A spore suspension of Colletotrichum lagenarium (cultured on corn medium for 5 to 7 days) was spray inoculated to induce disease.

The solution was prepared in a simple manner by dissolving 125 ml of the test compound in 2 ml of acetone and adding 48 ml of a 300 ppm aqueous dyne solution to prepare a 250 ppm emulsion. The result is the control value (%) according to the formula below.
It is expressed as and shown in table u1. Furthermore, no drug damage was detected. Rice blast disease preventive effect test Twenty rice seedlings (variety: Aichi Asahi) at the 4- to 5-leaf stage planted in clay pots with a diameter of 9 cff1 were placed on a turntable, and a hydrating powder prepared according to Example 2 was applied. Dilute with water and use a spray gun to spray at a pressure of 0.5k91c! 3 per pot with i
Sprayed 0ml.

Three days after the spraying, rice blast was continuously inoculated at room temperature, and the spores of the blast fungus were obtained using a microscope (1 field of view (15 x 1 @) 2).
A spore suspension containing ingrown spores was inoculated by spraying at a rate of 5 ml per pot. After inoculation, a vinyl greenhouse (saturated humidity 24℃)
) for 2 hours, and then transferred to a greenhouse to allow the lesions to develop while maintaining the temperature at a high temperature. Seven days after inoculation, the number of lesions per pot was counted and the control value was calculated. The results are shown in Table 2. Furthermore, no drug damage was observed. Test Example 3 Preventive effect test against rice sheath blight A white porcelain pot with a diameter of 9 d was filled with paddy soil, water was added to form a paddy field, and rice seedlings (variety: Kinnanfu) were planted in stipules one by one and seedlings were grown. When the paddy rice reached the 6-leaf stage, the wettable powder prepared according to Example 2 was diluted with water to a predetermined concentration, and 50 ml per pot was sprayed. The length of the sheath blight lesions formed on the leaves and pods of rice plants using the diseased bacteria (circular culture with a diameter of 9WJII.) was measured.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ and n is an integer of 1 to 3. However, when X is a hydrogen atom, n is 2 and R is a propylene group.