JPH01146868A - 4(1h)-pyridinone derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The 4(1H)-pyridinone derivative of formula I [R is alkyl, cycloalkyl, pyridyl (the group may be substituted with lower alkyl, lower alkoxy or halogen), perhydroazepin-1-yl, morpholino, pyrrolidino, pyrimidinyl (the group may be substituted with halogen), furylmethyl or piperidino; X is halogen; n is 0, 1 or 2]. EXAMPLE:1-Cyclohexyl-3-methyl-2,6-diphenyl-4(1H)-pyridinone. USE:A fungicide for agricultural and horticultural use. PREPARATION:The compound of formula I can be produced either by reacting a compound of formula II or its tautomer with a compound of formula R-NH2 or by reacting a compound of formula III with a compound of formula IV in the presence of a Lewis acid.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a 4(IH)-viridinone derivative useful as an agricultural and horticultural fungicide and an IsW containing the same as an active ingredient.
This relates to Kobacterial agents for artistic use.

(Prior art) Until now, 1-substituted phenyl-2,6-cymethyl-4(
It is known that IH)-pyridinone derivatives are useful as cucumber powdery mildew control agents and slime control agents (Japanese Patent Application Laid-Open No. 1983-65871), and 2,6-diphenyl-4(LH)- It is known that viridinone derivatives are useful as control agents for rice blast and cucumber anthracnose (Japanese Unexamined Patent Publication No. 102504/1983). 1゜2.6-F-diphenyl-4(IH)-viridinone derivatives are known [
Synthetic Communication 1s (Synthet)
ic Communcatlons) Vol. 13, No. 5, pp. 411-417 (1983)].

(Problem to be Solved by the Invention) However, Synthetic Communications does not describe at all what kind of physiological activity the described compounds have, and the bactericidal activity of the compounds described in the above-mentioned specification is not disclosed. It's not necessarily sufficient.

The present inventors aimed to develop a more useful am fungicidal fungicide.

Focusing on the 4(IH)-pyridinone skeleton, we synthesized its derivatives and conducted intensive research, and as a result, we found that all of the compounds of the present invention
The present invention was completed based on the discovery that it has excellent effects as a fungicide for the arts.

(Means for solving aM) The pyridinone derivative of the present invention has the general formula ), perhydroazepin-1-yl group 1 morpholino group, pyrrolidino group, pyrimidinyl group (the core may be substituted with a halogen atom)
, a furylmethyl group or a piperidino group, X represents a halogen atom, and n represents an integer of 0 or 1.2).

The compounds of the present invention represented by general formula (1) are illustrated in Table 1. Compound numbers are referenced in the following description.

Table 1 Next, a method for producing the compound of the present invention will be explained.

(a) The compound of the present invention is a 1,5-diphenylpentantrione derivative represented by the general formula (wherein X and n have the same meanings as above) or a tautomer thereof and the general formula %formula% ) (wherein R has the same meaning as above).

The pentantrione derivative represented by general formula (II) can have the following tautomers.

- Pentantrione derivatives of maximum (II) are generally prepared by combining 1-benzoyl-1-methylacetone derivatives with benzoic acid ester derivatives in a suitable solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, etc. with sodium hydride or It can be produced by adding a base such as sodium methylate and condensing.

For example, from 1-benzoyl-1-methylacetone and methyl benzoate to 1,5-diphenyl-2-methylpentane-
1,3°5-trione can be produced.

The pentantrione derivative thus obtained (If
) or its tautomer with the amine derivative (ffl) is generally carried out by dissolving or suspending it in an appropriate solvent, or without a solvent.

Examples of solvents include hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chlorobenzene, methylene chloride, and 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, NlN-dimethylformamide,
Amides such as N,N-dimethylacetamide and N-methylpyrrolidone, as well as dimethylsulfoxide and acetic acid, may be mentioned, but the reaction is preferably carried out by dissolving them in xylene or chlorobenzene. In this case, a suitable reaction aid can be added. Examples of the reaction aid include a suitable acid, such as mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid, and boron trifluoride. , aluminum chloride, titanium tetrachloride, and other Lewis acids. Furthermore, it is also preferable to collect by-product water using 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 molecular sieves. The amount of molecular sieves used is usually in the range of 2 to 200 g per 0.1 mole of pentantrione derivative (II).

When using para-toluenesulfonic acid in dimethylsulfoxide, Molecular Sieves 5A can be used.

The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, but it is preferably carried out at a temperature from 10°C to the boiling point of the solvent. 7. After the reaction is complete, wash the acid or molecular sieves with water and an alkaline solution. The compound of the present invention can be obtained by removing the reaction product by filtration or the like, extracting the reaction product with chloroform, and then distilling off the solvent. If it is a mustard chestnut, it is purified by recrystallization with acetone, methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate, chloroform, hexane, etc., or by passing through silica gel column chromatography.

(b) The compound of the present invention can also be combined with a phenylpropynic acid ester derivative represented by the general formula (wherein, It can be produced by reacting an imine derivative or conductor represented by ) in the presence of a Lewis acid.

In this case, 1 reaction is carried out by dissolving in a suitable solvent or I! ! Shall I make it muddy?

Or do it without solvent.

Aluminum chloride, titanium tetrachloride, boron trifluoride, boron trichloride, etc. can be used as the Lewis acid, and it is preferable to add 1 equivalent of aluminum chloride, which is dissolved in toluene to form a reaction aid of 0.5 to 5 It is preferable to add the Lewis acid of the horse.

Examples of solvents include benzene, toluene, xylene,
Examples include chlorobenzene and dimethyl sulfoxide.

After the reaction is completed, the compound of the present invention can be obtained by washing with an aqueous sulfuric acid solution, water, and an aqueous alkali solution, extracting with chloroform, drying, and distilling off the solvent. If necessary, pass through silica gel column chromatography and further acetone and methanol.

Purify by recrystallizing with benzene, ethyl acetate, chloroform, etc.

Next, the method for producing the compound of the present invention will be explained with reference to Examples.

Example 1 Synthesis of 1-cyclohexyl-3-methyl-2,6-diphenyl-4(IH)-pyridinone (compound 2) 2-methyl-1,5-diphenyl-2,6-pentane trio:/
2.8g (0,010 mol), shi') to o*sil 7
9.8 g (0,099 mol) of titanium tetrachloride and 1 titanium tetrachloride
mQ (0,009 mol) was added to 150 m ft of xylene and refluxed for 2 hours. After cooling, the reaction solution was poured into 11 water and extracted with chloroform. The extract was washed with 300 mA of 10% aqueous hydrochloric acid solution, then with 300 mJl of 10% aqueous sodium hydroxide solution, further washed with water, and then dried over anhydrous sulfate. After filtering off the sulfate, the solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography, developed and eluted with chloroform. After distilling off the solvent, it is recrystallized from a mixed solution of ethyl acetate and hexane, with a melting point of 202-204℃.
0.4 g of the desired compound showing the following was obtained.

Example 2 3-methyl-1-morpholino-2,6-diphenyl-4
Synthesis of (IH)-Viridinone (Compound 7) 4.4 g (0,020
mol), ethyl phenylpropanate 3.5 g (0°020 mol) and aluminum chloride 3.2 g (0.0 mol)
24 mol) was suspended in 250 mM toluene, and then suspended under reflux for 10
Stir for hours.

After cooling, one reaction solution was diluted with 300 ml (l) of ice-cooled 2N @ acid aqueous solution.
and extracted with methylene chloride. The poured solution was washed with 150 mQ of a 10% aqueous sodium hydroxide solution and water, and then dried with anhydrous sulfate.

After filtering off the sulfate, the solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography, developed and eluted with chloroform. After the solvent was distilled off, the desired compound 0.7. was recrystallized from a mixed solution of ethyl acetate and hexane and had a melting point of 195-197°C. I got it.

Example 3 3-Methyl-2,6-diphenyl-1-(pyrrolidine-
Synthesis of 1-yl)-4(LH)-viridinone (compound 10) 3.6 g of 1-aminopyrrolidine hydrochloride (0,0
29 mol) and 2-9 g of triethylamine (0,02
9 mol) was added to 150 mff1 of xylene and refluxed for 10 minutes. After cooling, 2-methyl-1,5-diphenyl-1
,3,5-pentantrione 6.0 g (0,021 mol) and paratoluenesulfone fil hydrate 3.6 g (0
, 019 mol) was added and refluxed for 5 hours. Xylene was distilled off from the reaction mixture, and the residue was dissolved in chloroform (15Qmffi).
After extraction, the organic layer was extracted with 10% hydrochloric acid Loom (1, then 1
After washing with 100 mjl of 0% aqueous sodium hydroxide solution and further washing with water, it was dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: ethyl acetate) to obtain 0.2 g of the target compound having a melting point of 165 to 167°C.

Example 4 1-isobutyl-3-methyl-2,6-diphenyl-4
Synthesis of (IH)-pyridinone (compound 16) 2-methyl-1,5-diphenyl-1,3,5-pentantrione 4.0 g (0,014 mol) and isobutylamine 6
．． 2g (0,085 mol) of chlorobenzene 100m
1.9 g (0.01 mol) of titanium tetrachloride dissolved in R
was added and refluxed for 2 hours. After cooling, chlorobenzene was distilled off from the reaction mixture.

The residue was extracted with chloroform roomj+. The organic layer was washed with 50 mg of 10% hydrochloric acid, then 50 m of a 10% aqueous sodium hydroxide solution, further washed with water, and then dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate, chloroform was distilled off.

The residue was purified by silica gel column chromatography (elution solvent: ethyl acetate). The obtained crystals were further recrystallized with a mixed solvent of ethyl acetate and hexane (1:5) to obtain the desired compound having a melting point of 186-187°C.
7g was obtained.

The 14tIl artistic fungicide of the present invention contains the compound of the present invention as an active ingredient.The compound of the present invention may be used by itself.

Usually, carriers, surfactants, dispersants, auxiliary agents, etc. are blended and the preparation is used in the form of powders, wettable powders, emulsions, fine granules, or granules by conventional methods.

Suitable carriers include, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers such as isopropyl alcohol, xylene, and cyclohexanone. Examples of surfactants and dispersants include alcohol sulfate salts, alkylaryl sulfonates, diarylmethane disulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monomers. Examples include alkylates. Examples of the adjuvant include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like. These preparations can be diluted to an appropriate concentration and sprayed, or applied directly.

The blending ratio of the active ingredients is appropriately selected as required. When preparing powders or granules, 0.1 to 20% (by weight) is appropriate, and when forming emulsions or wettable powders, 5 to 80% (!L amount).

The application amount of the agricultural and horticultural fungicide of the present invention varies depending on the type of compound used, the tendency of occurrence of the target disease, the degree of damage, environmental conditions, the dosage form used, etc. When used, the amount of active ingredient per 10 ares should be appropriately selected from the range of 0.1 g to 5 kg, preferably 1 g to I kg.

In addition, when it is finally used in liquid form such as an emulsion or a wettable powder, it is 0.1-10,0OOr+pm, preferably 10-10.
It is preferable to appropriately select from the range of 3,000 ppm.

The agricultural and horticultural fungicide of the present invention can be used in combination with other fungicides and insecticides.

Next, the agricultural and horticultural fungicide of the present invention will be specifically explained with reference to examples, where 0% indicates weight percentage.

Example 5 Powder 2% of compound (1), ±5% of diatoms and 93% of clay were uniformly mixed and ground to obtain a powder.

Example 6 Wettable powder Compound (2) 50%, diatom ±45%, sodium dinaphthylmethane disulfonate 2% and sodium ligninsulfonate 3% were uniformly mixed and ground to prepare a wettable powder.

Example 7 Emulsion An emulsion was prepared by uniformly dissolving 30% of compound (3), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene.

Example 8 Granule Compound (4) 5%, sodium salt of lauryl alcohol sulfate ester 2%, sodium lignin sulfonate 5%
, 2% carboxymethylcellulose and 86% clay are uniformly mixed and ground. Add 20 parts by weight of water to 80 parts by weight of this mixture, knead it, and use an extrusion type granulator to make a
After processing into mesh granules, it was dried and made into granules.

(Effects of the Invention) The 5m horticultural fungicide of the present invention is effective against rice sheath blight, rice blast, cucumber downy mildew, cucumber powdery mildew, cucumber gray mold, and Komatsu! ! It has a wide antibacterial spectrum against paddy rice and wheat-related diseases such as black soot, but is particularly effective as a rice sheath blight control agent.

This activity is expressed both prophylactically and therapeutically, and is long-lasting. Furthermore, it has excellent characteristics such as being highly safe for crops, blood-letting animals, and fish and shellfish.

Next, the effects of the agricultural and horticultural fungicide of the present invention will be specifically explained using test examples.

The following is a margin test example 1 Test for preventive effect on crest blight 15 seeds of water seed (variety: Zennanfu) were sown on a clay body with a diameter of 7G, and grown for 4 to 5 days in a greenhouse. A hydrating powder prepared according to Example 6 was added to rice seedlings with the fifth leaf developed, and the active ingredient was diluted with water to 500 ppm.
Q m m was sprayed.

After air-drying, rice sheath blight bacteria cultured on rice husk bran medium for 7 days was inoculated at the base of the plant, placed in a greenhouse (28°C), and after 5 days, rice was grown.
The height of the lesions formed in the 11w1 area was measured, and the control value was calculated according to the following formula.

The results of evaluation using the following evaluation criteria are shown in Tables 2 and 3.

Evaluation criteria A: Control value 90% or more B: Control value 70 to less than 90% C: Control value 40 to less than 70% D: Control value less than 40% In the table, the following comparative drugs were used.

Comparative drug] 2,6-dimethyl-1-phenyl-4(1)-viridinone (compound described in JP-A-56-65871) Comparative drug 2 2,6-diphenyl-4(IH)-viridinone (JP-A-56-65871) - Compound described in Publication No. 102504) The same comparative drug was used in the following test examples as well.

Test example 2 Rice blast prevention effect test Two paddy rice seeds (variety: Aichi M) were placed on a white porcelain backing with a diameter of 9 cm.
0 seeds were sown and grown in a greenhouse for 3 to 4 weeks. A hydrating powder prepared according to Example 6 was diluted with water to 500 ppm as an active ingredient to rice seedlings with the fourth leaf developed, and 1
0 mΩ was applied.

After air-drying, the spore liquid of the rice blast fungus was spray inoculated and placed in the greenhouse (2
5℃). Contact! After 15 days, the lesions were counted and the control value was calculated.

The results of evaluation using the following evaluation criteria are shown in Tables 4 and 5.

Evaluation Base A: Control value of 90% or more B = Control value of 70 to less than 90% C: Control value of 40 to less than 70% D: Control value of less than 40% Test Example 3 Cucumber and disease preventive effect test Vinyl chloride backing (9 cs Twelve cucumber seeds (variety: Sagami Hanshiro) were sown on X 9 (Im) and grown for 7 days in a lu room.

Apply 3iI to cucumber seedlings with expanded cotyledons according to Example 6.
! A hydrating agent was diluted with water to 500 ppm as an active ingredient, and 10 mM was sprayed per pot. After air-drying, a spore suspension of cucumber and disease bacteria was spray-inoculated and placed in a bath room (20 to 2
2°C). After 70 days of inoculation, the number of affected leaves was investigated according to the following criteria, and the disease ring and control value were determined.

Number of leaves: Degree of disease onset no: No onset of disease is observed nl: The diseased area is 173 Mishiki on the leaves. 〃　　1/3 or more and less than 273 ＃　　　273 or more N = n, + n, + n, + n.

The results are shown in Tables 6 and 7.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ), perhydroazepin-1-yl group, morpholino group, pyrrolidino group, pyrimidinyl group (the group may be substituted with a halogen atom).
, a furylmethyl group or a piperidino group, X represents a halogen atom, and n represents 0 or an integer of 1 or 2. 4(1H)-pyridinone derivative represented by ). (2) General formula ▲ Numerical formula, chemical formula, table, etc. ), perhydroazepin-1-yl group, morpholino group, pyrrolidino group, pyrimidinyl group (the group may be substituted with a halogen atom).
, a furylmethyl group or a piperidino group, X represents a halogen atom, and n represents 0 or an integer of 1 or 2. An agricultural and horticultural fungicide characterized by containing a 4(1H)-pyridinone derivative represented by ) as an active ingredient.