JPH0463069B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 6-substituted phenyl-4-substituted mercapto-4,5-dihydro-
This invention relates to a 3(2H) pyridazinone compound, an agricultural and horticultural fungicide containing the same, and a method for producing the same. (In the above formula, R ¹ and R ³ represent a hydrogen atom or a halogen atom, and R ² represents a hydrogen atom, a lower alkyl group,
Represents a lower alkoxy group or a halogen atom, R ¹ ,
At least one of R ² and R ³ represents a group other than a hydrogen atom. R ⁴ represents an alkyl group substituted or unsubstituted with a hydroxy group, a carboxy group, or a lower alkoxycarbonyl group; an unsubstituted phenyl group; an unsubstituted aralkyl group; or a pyridyl group substituted with a nitro group. ) In JP-A-52-120126, 6-substituted phenyl-
3(2H)pyridazinone has a broad antibacterial spectrum and is known as an agricultural and horticultural fungicide that is particularly useful for controlling mongale disease in rice. The present inventors have now discovered that the compound of the formula () is effective in controlling diseases of various agricultural and horticultural crops. In formula (), examples of the halogen atoms for R ₁ , R ₂ and R ₃ include chlorine, bromine, fluorine and iodine. The lower alkyl group for _R2 is methyl,
Examples include C _1-4 alkyl such as ethyl, propyl, and isopropyl, preferably methyl.
Examples of the lower alkoxy group for R ₂ include C _1-4 alkoxy such as methoxy, ethoxy, and propoxy, with methoxy being preferred. Examples of the substituted or unsubstituted alkyl group for _R4 include _C1-6 alkyl such as methyl, ethyl, isopropyl, butyl, t-butyl, pentyl, and hexyl; 2-hydroxyethyl, 3-hydroxypropyl, carboxymethyl; , 1-carboxyethyl, 2-carboxyethyl, 3-carboxypropyl, 2-carboxypropyl, ethoxycarbonylmethyl,
Examples include C _1-4 alkyl substituted with hydroxy, carboxy or C _1-5 alkoxycarbonyl, such as 2-methoxycarbonylethyl and 2-ethoxycarbonylethyl. Examples of the unsubstituted aralkyl group for R ₄ include benzyl and phenethyl. As the pyridyl group substituted with the nitro group of R ₄ ,
For example, 3-nitro-2-pyridyl is mentioned. In formula (), the groups of compounds showing excellent effects are: a Compounds in which R ₁ is a halogen atom, R ₂ and R ₃ are hydrogen atoms, b Compounds in which R ₁ and R ₃ are halogen atoms, and R ₂ is a hydrogen atom. Compounds in which c R ₄ is an alkyl group, in particular a methyl, 2-hydroxyethyl, carboxymethyl or -ethyl group or a lower alkoxycarbonylmethyl or -ethyl group. In particular, the following compound group is most preferred. d A compound in which R ₁ and R ₃ are chlorine atoms, R ₂ is a methyl group, and R ₄ is a methyl group, carboxymethyl or -ethyl group, or lower alkoxycarbonylmethyl or -ethyl group, e R ₁ is bromine A compound in which R ₂ and R ₃ are hydrogen atoms, and R ₄ is a methyl group or a 2-hydroxyethyl group. Examples of compounds of formula () are shown in the following table. In addition, compound numbers are referred to in the following description.

【table】

[Table] The compound of formula () is produced by the method shown in the flowchart below. (In the formula, R ₁ to R ₄ are the same as described above.) The first step of this method is a reaction in which a thiol is added to a compound of formula () to obtain a compound of formula (). The first step is carried out by using thiols in equimolar or large excess amounts relative to the compound of formula (), preferably in an inert solvent. The solvent is not particularly limited as long as it does not participate in the reaction, such as aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as ethyl ether, tetrahydrofuran or dioxane, methanol, ethanol or isopropanol. Examples include alcohols such as , amides such as dimethylformamide, dimethyl sulfoxide, and water, but water or a mixed solvent of water and alcohol are preferred. To accelerate the reaction, bases are preferably used, such as, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; sodium carbonate, potassium carbonate, sodium bicarbonate; and tertiary amines such as triethylamine, triethylenediamine or pyridine. Although the reaction temperature is not particularly limited, it is advantageous to carry out the reaction at room temperature or under cooling. When the reaction is carried out in the presence of a base, after the reaction is completed, the compound of formula () is converted into a free acid form by acid treatment and used in the next step. The second step of the method is a reaction in which the compound of formula () is reacted with hydrazine to obtain the target compound of formula (). Hydrazine used in this reaction is usually used in the form of its hydrate or mineral acid salt such as hydrochloride or sulfate. The reaction is usually carried out in an inert solvent, but
Such solvents include, for example, alcohols such as methanol, ethanol or isopropanol, acetic acid or water, particularly preferred are alcohols or mixed solvents of water and alcohols. The reaction temperature is not particularly limited and is between room temperature and below and the reflux temperature of the solvent, but heating is preferred in order to accelerate the reaction. After the reaction is completed, the target compound of formula () is collected by a conventional method. The compounds of the formula () are used as agricultural and horticultural fungicides and exhibit therapeutic and protective effects against plant diseases without causing damage to host plants. That is, by using it as a spray agent or a water surface application agent, rice sheath blight, which is an important disease in rice cultivation, can be particularly effectively controlled. In addition, when used as a soil treatment or seed treatment agent, it is particularly effective against seedling blight of various crops such as beets, cotton, and cucurbits caused by Rhizoctonia fungi. Soil-borne diseases such as black bruise can be effectively controlled. On the other hand, in terms of practical dosage, rice, tomatoes, potatoes,
Crops such as cotton, eggplant, kiwi, and kidney beans are not affected by chemical damage. Furthermore, the compound having the formula () can be effectively used as a fungicide in orchards, non-agricultural lands, forests, etc. The compound of the present invention can be mixed with a carrier and, if necessary, other adjuvants, to form a formulation commonly used as an agricultural and horticultural fungicide, such as a powder, coarse powder,
It is prepared and used as fine granules, granules, wettable powders, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc. The term “carrier” as used herein refers to a carrier that helps the active ingredient compound to reach the site to be treated, and also helps the active ingredient compound to be stored.
Refers to synthetic or natural inorganic or organic substances that are mixed into agricultural and horticultural fungicides to facilitate transportation or handling. Suitable solid carriers include clays such as kaolinite group, montmorillonite group, or attabulgite group, talc, mica, phyllite, pumice, vermiyukilite, gypsum, calcium carbonate, dolomite, diatomaceous earth, and magnesium. Inorganic substances such as lime, apatite, zeolite, anhydrous silicic acid, synthetic calcium silicate, etc., vegetable organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, coumaron resin,
Examples include synthetic or natural polymeric compounds such as petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, and dammar gums, waxes such as carnauba wax and beeswax, and urea. Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, chloroform, etc. , chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, O-chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone, ethyl acetate, amyl acetate, Esters such as ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether , ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, dimethylformamide,
Examples include polar solvents such as dimethyl sulfoxide, water, and the like. Emulsification, dispersion, wetting, spreading, binding, disintegration control,
Surfactants used for the purpose of stabilizing active ingredients, improving fluidity, and preventing rust can be nonionic, anionic, cationic, or amphoteric, but usually used are nonionic and/or anionic. 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 alkylphenols such as isooctylphenol and nonylphenol. products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid, stearyl phosphoric acid, dilauryl phosphoric acid, etc. mono- or dialkyl phosphoric acid with ethylene oxide polymerized and added, amines such as dodecylamine and stearic acid amide with ethylene oxide polymerized and added, higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide polymerized and added to them. 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. , aryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate. Furthermore, the agricultural and horticultural fungicide of the present invention contains casein,
Polymer compounds such as gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, and other adjuvants can also be used in combination. The above-mentioned carriers and various auxiliary agents are used in the dosage form of the preparation,
They are used individually or in combination as appropriate depending on the purpose, taking into consideration the application situation. Powders, for example, usually contain 1 to 10% of the active ingredient compound.
It contains 25 parts by weight, and the remainder is solid carrier. Wettable powders usually contain, for example, 25 to 90 parts by weight of the active ingredient compound, with the remainder being a solid carrier and a dispersing wetting agent, with protective colloid agents, thixotropic agents, antifoaming agents, etc. being added as necessary. Granules, for example, usually contain 1 to 1 active ingredient compound.
It contains 35 parts by weight, and the remainder is 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 5 active ingredients.
This includes approximately 5 to 20 parts by weight of an emulsifier, and the remainder is a liquid carrier, with a rust preventive added as needed. The agricultural and horticultural fungicides of the present invention prepared in various formulations in this way can be sprayed on the foliage of crops, or applied to the soil or water surface, for example, before or after disease outbreaks in crops in paddy fields or fields. In such cases, diseases can be effectively controlled by applying 1 to 5,000 g, preferably 10 to 1,000 g of the active ingredient per 10 acres. In addition, when using the agricultural and horticultural fungicide of the present invention as a seed treatment, for example, as a seed dressing, the active ingredient is preferably 0.1% to 2% per seed weight.
By applying powder at a concentration of 0.2 to 0.5%, soil or seed-borne diseases can be effectively controlled. The agricultural and horticultural fungicide of the present invention is preferably blended with other agricultural and horticultural fungicides in order to broaden the bactericidal spectrum, and in some cases a synergistic effect can be expected. Examples of such other agricultural and horticultural fungicides include, for example, 3,3'-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,
3,5-thiadiazine-2-thione; ethylene bisdithiocarbamate zinc salt or manganese salt; bis(dimethyldithiocarbamoyl) disulfide; propylene bisdithiocarbamate
Zinc salt; bis(dimethyldithiocarbamoyl)ethylenediamine; dimethyldithiocarbamate
Nickel salt; methyl 1-(butylcarbamoyl)-
2-benzimidazole carbamate; 1,2-
Bis(3-methoxycarbonyl-2-thioureido)benzene; 1-isopropylcarbamoyl-
3-(3,5-dichlorophenyl)hydantoin; N-hydroxymethyl-N-methyldithiocarbamate potassium salt; 5-methyl-10-butoxycarbonylamino-10,11-dehydrodibenzo(b,f) azepine, etc. Carbamate fungicide, bis(1-hydroxy-2(1H) pyridinethionate) zinc salt; 2-pyridinethiol-1-
Pyridine fungicides such as oxide sodium salt, phosphorus fungicides such as O,O-diisopropyl-S-benzylphosphorothioate; O-ethyl-S,S-diphenyldithiophosphate, N-(2,
6-diethylphenyl)phthalimide; N-(2,
6-diethylphenyl) phthalimide fungicides such as 4-methylphthalimide, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide; N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboximide Dicarboximide fungicides such as 5,6-dihydro-2
-Methyl-1,4-oxazine-3-carboxanilide-4,4-dioxide; Oxazine fungicides such as 5,6-dihydro-2-methyl-1,4-oxazine-3-carboxanilide, 2,3-dichloro -1,4-naphthoquinone, 2-oxy-3
-Chloro-1,4-naphthoquinone Naphthoquinone fungicides such as copper sulfate, pentachloronitrobenzene; 1,4-dichloro-2,5-dimethoxybenzene; 5-methyl S-triazole
(3,4-b)benzthiazole; 2-(thiocyanomethylthio)benzothiazole; 3-hydroxy-5-methylisoxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid; 5
-ethoxy-3-trichloromethyl-1,2,4
-thiadiazole; 2,4,6-dichloro-6-
(O-chloroanilino)-1,3,5-triazine; 2,3-dicyano-1,4-dithioanthraquinone; 8-oxyquinoline copper; polyoxin;
Validamycin; Cycloheximide; Methanarsonic acid iron salt; Diisopropyl-1,3-dithiolane-2-ylidenemalonate; 3-allyloxy-1,2-benziisothiazole 1,1-dioxide; Kasugamycin; Blasticidin S; 4 , 5,6,7-tetrachlorophthalide and the like, but are not limited to these. The agricultural and horticultural fungicide of the present invention can also be used in combination with the following plant growth regulators or insecticides. N-methoxycarbonyl-N'-4-methylphenylcarbamoylethylisourea, 1-(4
-Chlorophenylcarbamoyl)-3-ethoxycarbonyl-2-methylisourea, isourea-based plant growth regulators, naphthalene sodium acetate; 1,2-dihydropyridazine-3,6-dione; gibberellin and other plant growth regulators , O,O-diethyl O-(2-isopropyl-4-methyl-6
-pyrimidinyl) phosphorothioate; O, O-
Diethyl S-2-[(ethylthio)ethyl]phosphorodithioate; O,O-dimethyl O-(3-methyl-4-nitrophenyl)thiophosphate;
O,O-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate; O,O-dimethyl S-(N-methyl-N-formylcarbamoylmethyl)phosphorodithioate; O,O-dimethyl S -2-(ethylthio)ethyl phosphorodithioate; O,O-diethyl S-2 [(ethylthio)
ethyl]phosphorodithioate; O,O-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate; O,O-diethyl-O-(5
-phenyl-3-isoxazolyl) phosphorothioate; methyl (4-bromo-2,5-dichlorophenyl) phenylphosphonothioate; O,O
-dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophosphate; O-ethyl-O-p-cyanophenyl phenylphosphonothioate; O,O-diethyl S-(1,2-dicarboethoxyethyl ) Phosphorodithioate; 2-chloro-1-(2,4,5-trichlorophenyl)vinyldimethyl phosphate; 2-
Chloro-1-(2,4-dichlorophenyl)vinyldimethyl phosphate; O,O-dimethyl
O-p-cyanophenyl phosphorothioate;
2,2-dichlorovinyl dimethyl phosphate; O,O-diethyl O-2,4-dichlorophenyl phosphorothioate; ethyl mercaptophenyl acetate O,O-dimethyl phosphorodithioate; S-[(6-chloro-2- Oxo-3-benzooxazolinyl)methyl]O,O
-diethyl phosphorodithioate; 4-mercaptothiophenyl dipropyl phosphate; 2-
Chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate; O,O-diethyl-
O-(3-oxo-2-phenyl-2H-pyridazin-6-yl)phosphorothioate; O,O-dimethyl S-(1-methyl-2-ethylsulfinyl)-ethyl phosphorothioate; O,O −
Dimethyl S-phthalimidomethyl phosphorodithioate; dimethyl-methyl carbamoylethylthioethyl thiophosphorothioate; O,
O-diethyl S-(N-ethoxycarbonyl-
N-methylcarbamoylmethyl) phosphorodithioate; O,O-dimethyl-S-[2-methoxy-1,3,4-thiadiazole-5(4H)-onyl-(4)-methyl] dithiophosphate; 2-
Methoxy-4H-1,3,2-benzodioxaphosphorine 2-sulfide; O,O-diethyl-
O-(3,5,6-trichloro-2-pyridyl)
Phosphorothioate; O-ethyl-O-2,4-
Dichlorophenyl thionobenzene phosphonate; S-[4,6-diamino-S-triazine-
2-yl-methyl]O,O-dimethyl phosphorodithioate; O-ethyl O-p-nitrophenylphenylphosphonothioate; O,S-dimethyl-N-acetyl phosphoramidothioate; 2-diethylamino -6-methylpyrimidin-4-yl-diethylphosphorothionate; 2-
Diethylamino-6-methylpyrimidin-4-yl dimethylphosphorothioate; O,O-diethyl O-p-(methylsulfinyl)phenyl phosphorothioate; O-ethyl-S-propyl O-2,4-dichlorophenyl Phosphorodithioate; phosphorus insecticides such as cis-3-(dimethoxyphosphinoxy)-N-methyl-cis-crotonamide; 1-naphthyl N-methylcarbamate; S-methyl-N-[methylcarbamoyl] oxy]thioacetimidate; m-tolyl methyl carbamate; 3,4-xylyl methyl carbamate; 3,5-xylyl carbamate; 2-
sec-butylphenyl-N-methylcarbamate; 2,3-dihydro-2,2-dimethyl-7-
Benzofuranyl methyl carbamate; 2-isopropoxyphenyl-N-methyl carbamate;
1,3-bis(carbamoylthio)-2-(N,N
-dimethylamino)propane hydrochloride; 2-diethylamino-6-methylpyrimidin-4-yl
Carbamate insecticides such as dimethyl carbamate, N,N-dimethyl-N'-(2-methyl-4-
Chlorophenyl) formamidine hydrochloride, nicotine sulfate, milbemycin, 6-methyl-2,3
-Quinoxaline dithiocyclic S,S-dithiocarbonate, 2,4-dinitro-6-sec
-butylphenyl dimethyl acrylate; 1,
1-bis(p-chlorophenyl)2,2,2-trichloroethanol; 2-(p-tert.butylphenoxy)isopropyl-2'-chloroethylsulfite;azoxybenzene; di-(p-chlorophenyl)-cyclopropyl Carbinol; di[tri(2,2-dimethyl-2-phenylethyl)
Chin] oxide; 1-(4-chlorophenyl)-
3(2,6-difluorobenzoyl)-urea; S
-Tricyclohexyltine O,O-diisopropyl phosphorodithioate and other insecticides or fertilizers can be used in combination. The combination of the fungicide of the present invention with a root blight, sesame leaf blight and leaf blight agent, and a planthopper and/or leafhopper repellent agent particularly for rice cultivation has great labor-saving merits. The drugs that can be combined with the fungicide of the present invention as a simultaneous control agent are as described above. The amount to be blended varies depending on the target to be controlled and the formulation form, and is adjusted to contain the amount of active ingredient required for pest control. Powders are particularly suitable for rice disease control and soil treatment. Next, a method for producing the compound having the above formula () will be explained using Examples. Example 1 4-(3,5-dichloro-4-methylphenyl)
-4-oxo-2-butenoic acid to 4-(3,5
Production of -dichloro-4-methylphenyl)-2-methylthio-4-oxobutyric acid 4-(3,5-dichloro-4-methylphenyl)
-4-oxo-2-butenoic acid 2.59g (0.01mol)
was suspended in 10 ml of water, and 3.5 g (0.01 mol) of a 20% sodium salt aqueous solution of methanethiol was added to the mixture under stirring while cooling with water.
was added and stirred for 30 minutes. Then, add 2 ml of concentrated hydrochloric acid under water cooling.
was added dropwise, and the precipitated crystals were washed with water and air-dried to obtain 3.03 g (yield: 98.7%) of the desired product. Melting point 158~
160℃. IRν ^Nujol _nax cm ^-1 : 2400-2700, 1720, 1690 NMRδppm (DMF-d ₇ ): 2.30 (3H, s, methyl), 2.53 (3H, s, methylthio), 3.12-4.12 (3H, m, methylene and methine), 7.42 (1H, bs, hydroxycarbonyl), 8.13 (2H, s, phenyl). The following compounds were produced according to the method of Example 1. 4-(3-bromophenyl)-2-methylthio-4
-Oxobutyric acid Melting point 123-134℃ 4-(3-bromophenyl)-2-ethylthio-4
-Oxobutyric acid Melting point 125-134℃ 4-(3-bromophenyl)-2-isopropylthio-4-oxobutyric acid Melting point 136-138℃ 4-(3-bromophenyl)-2-phenylthio-
4-Oxobutyric acid Melting point 125-128℃ 4-(3-bromophenyl)-2-(2-hydroxyethylthio)-4-oxobutyric acid Oil 4-(3-bromophenyl)-2-(2-carboxyethylthio) -4-Oxobutyric acid 135-137℃ 4-(3-bromophenyl)-2-(3-nitro-
2-pyridylthio)-4-oxobutyric acid 159-162℃ 4-(3,5-dichloro-4-methylphenyl)-
2-Ethylthio-4-oxobutyric acid Melting point 168-172℃ 4-(3,5-dichloro-4-methylphenyl)-
2-isopropylthio-4-oxobutyric acid Melting point 166-169℃ 4-(3,5-dichloro-4-methylphenyl)-
2-Benzylthio-4-oxobutyric acid Melting point 132-135℃ 4-(3,5-dichloro-4-methylphenyl)-
2-(2-hydroxyethylthio)-4-oxobutyric acid Melting point 129-131℃ 4-(3,5-dichloro-4-methylphenyl)-
2-(2-carboxyethylthio)-4-oxobutyric acid Melting point 149-151℃ 4-(3,5-dichloro-4-methylphenyl)-
2-Ethoxycarbonylmethylthio-4-oxobutyric acid Melting point 95-97℃ 4-(3,5-dichloro-4-methylphenyl)-
2-(2-methoxycarbonylethylthio)-4-
Oxobutyric acid Melting point 125-127℃ 4-(3,5-dichloro-4-methylphenyl)-
2-Carboxymethylthio-4-oxobutyric acid Melting point 163-166℃ 4-(3,4-dichlorophenyl)-2-methylthio-4-oxobutyric acid Melting point 136-139℃ 4-(3,4-dichlorophenyl)-2-ethylthio -4-Oxobutyric acid Melting point 108-110℃ 4-(3,4-dichlorophenyl)-2-isopropylthio-4-oxobutyric acid Melting point 136-138℃ 4-(3,4-dichlorophenyl)-2-(2-hydroxy Ethylthio)-4-oxobutyric acid Melting point 110-112℃ 4-(3,4-dichlorophenyl)-2-(2-carboxyethylthio)-4-oxobutyric acid Melting point 150-152℃ 4-(3-bromo-4 -chlorophenyl)-2-methylthio-4-oxobutyric acid Melting point 143-145℃ 4-(3,5-dibromo-4-methoxyphenyl)
-2-n-hexylthio-4-oxobutyric acid Melting point 103-105℃ 4-(4-methoxyphenyl)-2-methylthio-
4-Oxobutyric acid Melting point 116-118℃ Example 2 4-(3,5-dichloro-4-methylphenyl)
-2-methylthio-4-oxobutyric acid to 6-
(3,5-dichloro-4-methylphenyl)-4
-Production of methylthio-4,5-dihydro-3(2H)pyridazinone 4-(3,5-dichloro-4-methylphenyl)
-2-methylthio-4-oxobutyric acid 1.54g
(0.005 mol) was suspended in 5 ml of ethanol, and 0.25 g of hydrazine hydrate was added thereto at room temperature, followed by stirring at room temperature for 1 hour and then heating under reflux for 6 hours. After cooling, the crystals were collected and washed with a small amount of ethanol to obtain 1.32 g (yield: 87.1%) of the desired product.
Melting point 163-165℃. IRν ^Nujol _nax cm ^-1 : 3200, 3100, 2000 ~ 2800, 1680, 1610 NMR δppm (CDCl ₃ ): 2.23 (3H, s, methyl), 2.52 (3H, s, methylthio), 3.19 (2H, d, J= 6, methylene), 3.58 (1H, dd, J=6, methine), 7.78 (2H, s, phenyl), 9.72 (1H, bs, NH). The following compounds were produced according to the method of Example 2. 6-(3-bromophenyl)-4-methylthio-
4,5-dihydro-3(2H)pyridazinone Melting point 151-152℃ 6-(3-bromophenyl)-4-ethylthio-
4,5-dihydro-3(2H)pyridazinone Melting point 126-129℃ 6-(3-bromophenyl)-4-isopropylthio-4,5-dihydro-3(2H)pyridazinone
Melting point 155-158℃ 6-(3-bromophenyl)-4-phenylthio-
4,5-dihydro-3(2H)pyridazinone Melting point 153-156℃ 6-(3-bromophenyl)-4-(2-hydroxyethylthio)-4,5-dihydro-3(2H)pyridazinone Melting point 115-118℃ 6-(3-bromophenyl)-4-(2-carboxyethylthio)-4,5-dihydro-3(2H)pyridazinone Melting point 150-152℃ 6-(3-bromophenyl)-4-(3-nitro-
2-pyridylthio)-4,5-dihydro-3(2H)
Pyridazinone Melting point 171-174℃ 6-(3,5-dichloro-4-methylphenyl)-
4-Ethylthio-4,5-dihydro-3(2H)pyridazinone Melting point 174-177℃ 6-(3,5-dichloro-4-methylphenyl)-
4-isopropylthio-4,5-dihydro-3
(2H) Pyridazinone Melting point 174-177℃ 6-(3,5-dichloro-4-methylphenyl)-
4-Benzylthio-4,5-dihydro-3(2H)
Pyridazinone Melting point 161-163℃ 6-(3,5-dichloro-4-methylphenyl)-
4-(2-hydroxyethylthio)-4,5-dihydro-3(2H)pyridazinone Melting point 192-195℃ 6-(3,5-dichloro-4-methylphenyl)-
4-(2-Carboxyethylthio)-4,5-dihydro-3(2H)pyridazinone Melting point 192-194℃ 6-(3,5-dichloro-4-methylphenyl)-
4-(2-methoxycarbonylethylthio)-4,
5-dihydro-3(2H)pyridazinone Melting point 126-128℃ 6-(3,5-dichloro-4-methylphenyl)-
4-Ethoxycarbonylmethylthio-4,5-dihydro-3(2H)pyridazinone Melting point 146-149℃ 6-(3,4-dichlorophenyl)-4-methylthio-4,5-dihydro-3(2H)pyridazinone Melting point 149- 152℃ 6-(3,4-dichlorophenyl)-4-ethylthio-4,5-dihydro-3(2H)pyridazinone Melting point 134-136℃ 6-(3,4-dichlorophenyl)-4-isopropylthio-4,5 -dihydro-3(2H)pyridazinone Melting point 136-138℃ 6-(3,4-dichlorophenyl)-4-(2-carboxyethylthio)-4,5-dihydro-3
(2H) Pyridazinone Melting point 162-165℃ 6-(3,5-dibromo-4-methoxyphenyl)
-4-n-hexylthio-4,5-dihydro-3
(2H) Pyridazinone Melting point 80-83℃ 6-(4-methoxyphenyl)-4-methylthio-
4,5-dihydro-3(2H)pyridazinone Melting point: 145-147°C Examples of formulations of the agricultural and horticultural fungicide of the present invention are given below. In the text, all parts simply refer to parts by weight. Formulation Example 1 Powder 5 parts of Compound No. 13, 50 parts of talc, and 45 parts of kaolin were uniformly mixed to obtain a powder. Formulation Example 2 Wettable powder 50 parts of Compound No. 1, 29 parts of clay, 10 parts of diatomaceous earth, 5 parts of white carbon, 3 parts of sodium lignin sulfonate, 2 parts of Newcol 1106 (trade name of Nippon Nyukazai Co., Ltd.), and polyvinyl alcohol. One part was mixed uniformly in a mixer and ground three times in a hammer mill to obtain a wettable powder. Formulation Example 3 Granules 70 parts of Compound No. 4 was finely ground, and 30 parts of clay was added thereto and mixed in a mixer to obtain a premix. Clay 10 parts of this premix.
60 parts and 30 parts of bentonite were homogeneously mixed in a mixer. An appropriate amount of water was added to this material, kneaded in a kneader, extruded through a screen with a diameter of 0.8 mm, and dried in a ventilation dryer at 50°C. This product was sized using a sifter to obtain granules. Examples of the agricultural and horticultural fungicide of the present invention prepared in this way are given below. The test drug was manufactured according to Formulation Example 2, and a wettable powder containing 50% of the active ingredient compound of the present invention was used. Example 3 Rice monge disease control test (preventive spraying) 3 pots of rice seedlings (variety: Nipponbare) at the 4th to 5th leaf stage
After spraying 50 ml of 30 ppm test drug solution and leaving it at room temperature for 24 hours, remove the Rhizoctonia bacterium in advance.
solani) cultured oat grains are added to the stalks of rice plants.
Every 5 seeds were transferred to a humid room at 25 to 27°C, and 7 days after inoculation, the degree of disease onset was examined by the height (cm) of lesion formation. The results are shown in Table 1.

[Table] Example 4 Rice monge disease control test (water surface application) Rice seedlings (variety Nipponbare) at the 4- to 5-leaf stage grown in pots were kept submerged in water at a depth of 1 cm, and the test chemical solution was applied as an active ingredient. It was applied in a pot at an amount of 800g/10a. After being left in the greenhouse for 7 days, it fell into the water.
Place 4 to 5 oat grains in which Rhizoctonia solani has been cultured in advance near the stems of rice plants, and
The plants were transferred to a humid room at 27°C, and 7 days after inoculation, the degree of disease onset was examined by the height (cm) of lesion formation. The results are shown in Table 2.

[Table] Example 5 Seedling damping-off control test (seed coating) Seedling damping-off fungus (Rhizoctonia solani) cultured in oat grain medium at 26°C for 2 weeks was mixed uniformly with soil, and the mixture was placed in a plastic box (25 cm x 35cm, depth 11cm). Add the test drug to this soil in an amount of 0.25 active ingredients.
% (relative to seed weight), 60 grains of flour-coated kidney bean seeds (variety: Masterpiece) were sown and kept in a greenhouse at 25℃ for 2 weeks, and then the number of seedlings (plants) affected by seedling blight was investigated. . The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1 formula 6-substituted phenyl-4-substituted mercapto-4,5-dihydro-3(2H) pyridazinone compound. (In the above formula, R ¹ and R ³ represent a hydrogen atom or a halogen atom, and R ² represents a hydrogen atom, a lower alkyl group,
Represents a lower alkoxy group or a halogen atom, R ¹ ,
At least one of R ² and R ³ represents a group other than a hydrogen atom. R ⁴ represents an alkyl group substituted or unsubstituted with a hydroxy group, a carboxy group, or a lower alkoxycarbonyl group; an unsubstituted phenyl group; an unsubstituted aralkyl group; or a pyridyl group substituted with a nitro group. ) 2 The compound according to claim 1, wherein R ¹ is a halogen atom, and R ² and R ³ are hydrogen atoms. 3. The compound according to claim 1, wherein R ¹ and R ³ are halogen atoms, and R ² is a lower alkyl group or a lower alkoxy group. 4 R ⁴ is an alkyl group, 2-hydroxyethyl group,
Claim 1 which is a carboxymethyl group, carboxyethyl group, lower alkoxycarbonylmethyl group or lower alkoxycarbonylethyl group
Compounds described in Section. 5 R ¹ and R ³ are chlorine atoms, R ² is a methyl group, R ⁴ is a methyl group, a carboxymethyl group,
The compound according to claim 1, which is a carboxyethyl group, a lower alkoxycarbonylmethyl group, or a lower alkoxycarbonylethyl group. 6. The compound according to claim 1, wherein R ¹ is a bromine atom, R ² and R ³ are hydrogen atoms, and R ⁴ is a methyl group or a 2-hydroxyethyl group. 7 formula An agricultural and horticultural fungicide comprising a 6-substituted phenyl-4-substituted mercapto-4,5-dihydro-3(2H)pyridazinone compound having the following as an active ingredient. (In the above formula, R ¹ and R ³ represent a hydrogen atom or a halogen atom, and R ² represents a hydrogen atom, a lower alkyl group,
Represents a lower alkoxy group or a halogen atom, R ¹ ,
At least one of R ² and R ³ represents a group other than a hydrogen atom. R ⁴ represents an alkyl group substituted or unsubstituted with a hydroxy group, a carboxy group, or a lower alkoxycarbonyl; an unsubstituted phenyl group; an unsubstituted aralkyl group. ) 8 formula (In the formula, R ¹ and R ³ represent a hydrogen atom or a halogen atom, R ² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R ¹ ,
At least one of R ² and R ³ represents a group other than a hydrogen atom. ) with 4-substituted phenyl-4-
Oxo-2-butenoic acid has the formula R ⁴ -SH (wherein R ⁴ is an alkyl group substituted or unsubstituted with a hydroxy group, a carboxy group, or a lower alkoxycarbonyl group; an unsubstituted phenyl group; an unsubstituted aralkyl group; or the nitro group represents a substituted pyridyl group),
formula A 4-substituted phenyl-2-substituted mercapto-4-oxobutyric acid compound having the formula (wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as above) was obtained, and then this was reacted with hydrazine. Let me, expression (In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as above.) 6-substituted phenyl-4-substituted mercapto-4,5-dihydro-3(2H) pyridazinone compound is produced. how to.