JPS62181204A - Nonmedical germicide - Google Patents

Abstract

PURPOSE:The titled germicide, containing a specific 4(1H)-pyridinone derivative as an active ingredient, capable of exhibiting remarkable effect particularly on sheath blight of rice plants and producing preventive and remedial activity thereof and with persistence and having high safety for crops, warm-blooded animals, fishes and shellfishes. CONSTITUTION:A nonmedical germicide containing a 4(1H)-pyridinone derivative expressed by formula I (R and X are H or CH3), e.g. 3-methyl-1,2,6-triphenyl-4(1 H)-pyridinone, etc., as an active ingredient. The compound expressed by formula I is obtained by reacting, e.g. a compound expressed by formula II or a tautomer thereof with a compound expressed by formula III. The above-mentioned compound expressed by formula I is preferably blended with a carrier or adjuvant and formulated into dust, wettable powder, emulsion, granule, etc. The blending ratio of the above-mentioned active ingredient is preferably 5-20wt% for dust and granule and 5-80wt% for emulsion and wettable powder. The application amount thereof is preferably 10-500g/10 area expressed in terms of the active ingredient for dust and 10-1,000ppm concentration for emulsion etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a non-medical disinfectant characterized by containing a 4(IH)-viridinone derivative as an active ingredient.

(Prior art) JP-A-55-102504 and JP-A-56-65
Publication No. 871 describes that 4(IH)-viridinone derivatives are effective as agricultural and horticultural fungicides. Also, various types of 4(IH)-pyridino.

Derivatives of the compound are known [for example,
pp. 6-478 (1947), ■Annales d@chimis Vol. 12 No. 3,
pp. 595-444 (1948), ■ Pretan Société Simy France (Bul l, Soc, Ch.
in, France) pp. 734-739 (1954), ■Synthetic Communications (Syn
13, No. 5, pp. 411-417 (1983)].

(Problems to be solved by the invention) However, the compounds specifically disclosed in the above publication are
Rice sheath blight cannot be effectively controlled.

Furthermore, it is not known at all what kind of physiological activity the known 4(IH)- and lysinone derivatives have.

In order to develop compounds with excellent bactericidal activity, the present inventors synthesized various 4(IH)-pyridinone derivatives and investigated their bactericidal activity. disinfectant.

We have completed the present invention by discovering that it is especially excellent as a control agent for rice sheath blight.

(Means for solving problems) The non-medical disinfectant of the present invention is general formula (In the formula, R and X each represent a hydrogen atom or a methyl group.

) contains a 4(In) viridinone derivative represented by the following as an active ingredient.

Examples of the compounds represented by the general formula (I) are as follows.

It is as shown in Table 1. In addition, the compound number will be referred to in the following description.

Table 1 These compounds can be manufactured according to the method described in the aforementioned Synthetic Comics, Vol. 13, No. 5, pages 411-417, but they can also be manufactured by the following method.

A 1,5-diphenylpentantrione derivative represented by the general formula (wherein, R represents a hydrogen atom or a methyl group) or a tautomer thereof (wherein, X represents a hydrogen atom or a methyl group) and It can be produced by reacting with an aniline derivative represented by: The tautomer of (II) shown here is represented by the following general formula.

000 0HOOOHOOH This reaction is generally carried out using a pentantrione derivative represented by the general formula ([) and its tautomer and an aniline derivative represented by the general formula (III) in a suitable solvent 9 such as benzene, toluene, xylene, etc.

hydrocarbons, chlorobenzene, methylene chloride.

Halogenated hydrocarbons such as chloroform, ethers such as diisopropyl ether, tetrahydrofuran, and dioxane, and ketones such as acetone, methyl ethyl ketone, and cyclohexanone.

Esters such as ethyl acetate, nitriles such as acetonitrile, N,N-dimethylformamide.

The reaction is carried out by dissolving or suspending it in amides such as N,N-dimethylacetamide and N-methylpyrrolidone, dimethylsulfoxide, acetic acid, etc., or without a solvent, preferably by dissolving it in xylene or chlorobenzene.

In this case, the reaction can be carried out with or without adding a suitable reaction aid. Used as a reaction aid.

Suitable acids 9 For example, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid,
Lewis acids such as boron fluoride, aluminum chloride, and titanium tetrachloride can be used, and the reaction can be carried out by collecting the generated water in a Dean-Stark trap.

Further, depending on the acid and solvent used, the reaction can be carried out in the presence of a dehydrating agent such as Molecule Thieves. For example in dimethyl sulfoxide.

P-) When using luenesulfonic acid.

Molecule error sieves 5A can be used.

The amount of molecular sieves used is usually in the range of 2 to 200.9 g per 0.1 mole of the 1.5-diphenylpentantrione derivative (n), but preferably in the range of 50 to 200 g. can be reacted.

The reaction takes place at any temperature between the freezing point and boiling point of the solvent.

Preferably, it can be carried out at a temperature from 10° C. to the boiling point of the solvent.

After the reaction is completed, the acid or molecular sieves are washed with water and an alkaline solution or removed by e-filtration, the reaction product is extracted with chloroform, and the solvent is distilled off to produce the compound of the present invention. I can do it. Acetone, methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate if necessary.

It can be purified by recrystallization with chloroform, hexane, etc., or by chromatography using a silica gel column.

Further, the reaction may be carried out by dissolving or suspending in amides such as general formula tylacetamide, dimethyl sulfoxide, acetic acid, etc., or in the absence of a solvent. As an acid catalyst.

For example, polyphosphoric acid, sulfuric acid, P-)luenesulfonic acid,
Examples include aluminum chloride. The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably at a temperature from 10° C. to the boiling point of the solvent.

After completion of the reaction, the compound of the present invention can be produced by adding ice water to the reaction solution, extracting with chloroform, washing with water, drying, and then distilling off the solvent. If necessary, add benzene, toluene, methanol, chloroform, ethyl acetate, acetone,
It can be purified by recrystallization with hexane or the like or by silica gel column chromatography.

Next, a specific explanation will be given by giving a manufacturing example.

Production Example t Synthesis of 3-methyl-1,2,6-triphenyl-4Clm-viridinone 10.0 g (0,036 mol) of 2-methyl 1,5-diphenyl-1,3,5-pentantrione and aniline 3
3.2N (0.36 mol) was dissolved in xylene 350°C, and then 15.5% P-toluenesulfonic acid, V C0
,054 mol) was added. After refluxing for 2 hours using a Dean-Stark apparatus, the solids were removed from the reaction mixture and extracted with chloroform.
Washed with 10S sodium hydroxide water bath solution 100d). After further washing with water, it was dried over anhydrous sodium sulfate. The solvent was then distilled off and the resulting residue was crystallized from a mixed solvent of acetone/hexane to give 3-methyl-1,2,6-)diphenyl-4(IH) having a melting point of 224-227°C.
-Viridinone (5) 2.8 # was obtained.

Production Example 2 Synthesis of 3-methyl-1-(2-methylphenyl)-2,6-diphenyl-4(IH)-pyridinone 2-methyl-1,5-diphenyl-1,5,5-pentantrione 112. 9 (0,040 mole), 2-methylaniline (42.611C0.40 mole), P-toluenesulfonic acid 6.0 g (α032 mole), and 5.0 g of Molecular Tubes 5A were added to 300 g of xylene and refluxed for 5 hours. did. After cooling, remove the solids and prepare the organic layer with 100 g of hydrochloric acid, 100 g of 10% aqueous sodium hydroxide solution.
I washed it with After further washing with water, it was dried over anhydrous magnesium sulfate and the solvent was distilled off. The obtained residue was mixed with acetone/
Crystallized from a mixed solvent of hexane (hot), melting point 230-2
3-Methyl-1-(2-methylphenyl) showing 33℃
-2,6-diphenyl-4(In)-viridinone 4.
I got 511.

The non-medical bactericidal agent of the present invention may be used as the above-mentioned compound itself, but it is usually mixed with a carrier, a surfactant, a dispersant, or an auxiliary agent, etc., using a conventional method.

For example, it is formulated into a powder, a wettable powder, an emulsion, a fine granule, or a granule.

Suitable carriers include 9, for example, talc, bentonite, clay, kaolin, silica, white carbon, permichielite. Solid carriers such as slaked lime, silica sand, ammonium sulfate, urea,
Examples include liquid carriers such as isopropyl alcohol, xylene, cyclohexanone, and natylnaphthalene. Examples of surfactants and dispersants include alcohol sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, and lignin sulfonate salts.

Examples include diarylmethane disulfonate, polyoxyethylene glycol ether, polyoxydiethylene alkylaryl ether, and polyoxyethylene sorbitan monoalkylate. Examples of adjuvants include carboxymethyl cellulose, polyethylene glycol,
Examples include gum arabic. These preparations can be diluted to an appropriate concentration and sprayed, or applied directly.

The blending ratio of active ingredients is 1. °4 Can be adjusted as necessary.

When used as a powder or granule, 0.5 to 20 inches (ton weight) is suitable, and when used as an emulsion or wettable powder, it is 5 to 80 inches (ton weight).

The application amount of the non-medical fungicide of the present invention depends on the type of compound used, the tendency of occurrence of the target disease9, the degree of damage, the environmental conditions,
Although it varies depending on the dosage form used, etc., when used as is, such as # preparation or granule preparation, it is recommended to appropriately select the amount of active ingredient from the range of 10 to 500 g per 10 ares. Also.

When it is finally used in liquid form such as an emulsion or an aqueous phase agent, it is preferably selected appropriately from the range of 10 to 100 (7 ppm).

Next, examples of the non-medical disinfectant of the present invention will be specifically explained. In the following examples, ``chi'' means weight.

(Examples) Example 1 (Powder) 2% of compound (1), 5% of diatomaceous earth, and 93 clay were uniformly mixed and pulverized to prepare a powder.

Example 2 (Aqueous phase agent) Compound (4) 5 (Jl+, diatom ±45%, 2% sodium dinaphthylmethane disulfonate, and 3% sodium ligninsulfonate were uniformly mixed and pulverized to prepare an aqueous phase agent.

Example 3 (emulsion) Compound (5) 30%, cyclohexanone 20S.

11% polyoxyethylene alkylaryl ether,
An emulsion was prepared by uniformly dissolving 4% calcium alkylbenzenesulfonate and 35 ml of methylnaphthalene.

Example 4 (Granules) Compound (3) 5% sodium salt of lauryl alcohol sulfate, 5% sodium lignin sulfonate
, Carphoki dimethylcellulose 2 strips and Clay 8611
Mix and grind evenly.

This mixture was kneaded with 20 g of water, processed into granules of 14 to 32 mesh sizes using an extrusion granulator, and then dried to form granules.

(Effects of the Invention) The non-medical fungicide of the present invention has a wide range of resistance against paddy rice and horticultural diseases such as rice sheath blight, rice blast, cucumber downy mildew, chie cucumber powdery mildew, and komatsuna black sooty. 1 spectrum, and is particularly effective as a control agent for rice sheath blight. This activity is expressed both prophylactically and therapeutically, and is long-lasting.

Furthermore, it has excellent characteristics such as high safety against two crops, warm-blooded animals, and fish and shellfish.

Next, the effects of the non-medical disinfectant of the present invention will be specifically explained using test examples.

Test Example (Rice sheath blight preventive effect test) Paddy rice seeds (Shinatsuchi: Kinnanfu) were sown in 15 grains each in clay pots with a diameter of 70 mm, and grown in a greenhouse for 4 to 5 weeks. A hydrating powder prepared according to Example 2 was diluted with water to a predetermined concentration and sprayed at 10 M+t per pot to rice seedlings in which the fifth leaf had developed. Sheath blight 1 cultured for 7 days on rice grass bran medium after air drying
．． 11 (Rhizoctonia golani) at the base of the plant and placed in a greenhouse (28°C).

After 5 days, the length of the lesion formed on the rice leaf sheath was measured.
The control value was calculated according to the following criteria.

The results are shown in Table 2.

Table 2

Claims (1)

[Claims] The 4(IH)-pyridinone derivative represented by the general formula ▲ includes numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, R and X each represent a hydrogen atom or a methyl group). A non-medical disinfectant characterized by containing it as an ingredient.