JPS6210992B2 - - Google Patents

Description

[Detailed description of the invention]

This invention is based on the general formula [In the formula, R ₁ and R ₃ are both the same or different and represent a halogen atom, or one is a halogen atom and the other is a hydrogen atom. R ₂ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. R ₄ represents an alkyl group, phenyl group or benzyl group. Y represents oxygen or sulfur atom. ] This relates to a novel pyridazone derivative having the following. In the definition of the general formula (), the halogen atoms for R ₁ , R ₂ and R ₃ include chlorine, bromine, fluorine or iodine, preferably chlorine or bromine. Lower alkyl groups for _R2 include methyl, ethyl, n-propyl, isopropyl, n-
1 to 4 carbon atoms such as butyl or isobutyl
Examples include straight-chain or branched-chain alkyl groups having . Lower alkoxy groups for _R2 include methoxy, ethoxy, n
- Straight-chain or branched alkoxy groups having 1 to 4 carbon atoms such as propoxy, isopropoxy, n-butoxy or isobutoxy are mentioned, and methoxy is preferable. Also, R ₄
Examples of alkyl groups include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-hexyl, n
-octyl, n-nonyl, n-decyl or n-
Examples include straight-chain or branched alkyl groups having 1 to 12 carbon atoms such as dodecyl, preferably lower alkyl groups having 1 to 4 carbon atoms, especially methyl, ethyl, n-butyl. Or isobutyl group. The most preferred compounds having the general formula () are: 1 R ₁ and R ₃ both represent a chlorine atom or a bromine atom, and R ₂ represents a methyl group or a methoxy group; or 2 R ₁ represents a chlorine atom or represents a bromine atom, and R ₂ and R ₃ represent a hydrogen atom; R ₄ represents a lower alkyl group having 1 to 4 carbon atoms or a benzyl group; Y represents an oxygen atom. Examples of the novel pyridazone derivatives of the present invention include the following. 1 2-methoxycarbonyl-6-(3,5-dichloro-4-methylphenyl)-3-pyridazone 2 2-methoxycarbonyl-6-(3-bromophenyl)-3-pyridazone 3 2-methoxycarbonyl-6-(3 ,4-dichlorophenyl)-3-pyridazone 4 2-methoxycarbonyl-6-(3,5-dichloro-4-methoxyphenyl)-3-pyridazone 5 2-ethoxycarbonyl-6-(3,5-dichloro -4-methylphenyl)-3-pyridazone 6 2-ethoxycarbonyl-6-(3-bromophenyl)-3-pyridazone 7 2-ethoxycarbonyl-6-(3,5-dichloro-4-methoxyphenyl)-3- Pyridazone 8 2-ethylthiocarbonyl-6-(3,5-
dichloro-4-methylphenyl)-3-pyridazone9 2-isopropoxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone10 2-n-butoxycarbonyl-6-(3,5
-dichloro-4-methylphenyl)-3-pyridazone 11 2-n-butoxycarbonyl-6-(3-bromophenyl)-3-pyridazone 12 2-n-butoxycarbonyl-6-(3,4
-dichlorophenyl)-3-pyridazone13 2-n-butoxycarbonyl-6-(3,5
-dichloro-4-methoxyphenyl)-3-pyridazone14 2-isobutoxycarbonyl-6-(3,5
-dichloro-4-methylphenyl)-3-pyridazone15 2-n-pentyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone16 2-n-hexyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone17 2-n-heptyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone18 2-n-octyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone19 2-n-nonyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone20 2-benzyloxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone23 2-phenoxycarbonyl-6-(3,5-
dichloro-4-methylphenyl)-3-pyridazone26 2-n-propoxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone27 2-methoxycarbonyl-6-(3-chloro-4-methylphenyl)-3-pyridazone28 2-n-butoxycarbonyl-6-(3-chloro-4- methylphenyl)-3-pyridazone29 2-n-butoxycarbonyl-6-(3-bromo-4-methylphenyl)-3-pyridazone The novel compound () according to the present invention is represented by the formula () as shown in the following formula. 6-Phenyl-
It is produced by reacting 3-pyridazones with carbonate or thiocarbonate (). (In the formula, R ₁ to R ₄ and Y have the same meaning as defined above.) In the above reaction, the compound having the general formula () is mixed with the compound having the general formula () in equimolar to large amounts. This is easily accomplished by using an excess amount and contacting the two in a suitable inert solvent or without the use of a solvent. The solvent used in the reaction is not particularly limited as long as it does not participate in this reaction; for example, aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as ethyl ether, tetrahydrofuran or dioxane; acetone. or ketones such as ethyl methyl ketone; amides such as dimethyl formamide or dimethyl acetamide; esters such as ethyl acetate or ethyl propionate; dimethyl sulfoxide, hexamethyl phosphoric triamide (HMPA), and the like. The reaction temperature is not particularly limited, and the reaction is usually carried out at 0°C to the reflux temperature of the solvent. The above reaction can also be carried out in the presence of a base. Examples of the base used include triethylamine, triethylenediamine, 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,5-diazabicyclo[5,4,
0] Tertiary amines such as undec-5-ene (DBU) or pyridine; alkali metal carbonates or bicarbonates such as anhydrous sodium carbonate, anhydrous potassium carbonate or anhydrous sodium bicarbonate; lithium hydride or Examples include alkali metal hydrides such as sodium hydride. After completion of the reaction, the target compound is collected from the reaction mixture by a conventional method. For example, after the reaction is complete, if crystals precipitate, remove them, or if they do not precipitate, add a water-immiscible organic solvent such as n-hexane or petroleum ether to remove the precipitated crystals and wash. By drying, crude crystals of the target compound are obtained, which can be further purified by conventional methods such as recrystallization, column chromatography, etc., if necessary. The raw material compound of formula () above can be obtained by the method described in Journal of American Chemical Society (J.Am.Chem.Soc.) 75 , 1117 (1953) and Japanese Patent Application Laid-open No. 12897/1983. Manufactured in accordance with The method for producing the novel pyridazone derivative () of the present invention will be explained in more detail with reference to Examples. Example 1 2-methoxycarbonyl-6-(3,5-dichloro-4-methylphenyl)-3-pyridazone 2.55 g of 6-(3,5-dichloro-4-methylphenyl)-3-pyridazone, methyl chloroformate
A mixture of 4.7 g and 25 ml of xylene was heated under reflux for 1.5 hours. The reaction mixture was allowed to cool to room temperature, and the precipitated crystals were collected and washed with n-hexane to obtain 2.94 g of the target compound as colorless prism crystals. Yield 94% Melting point 203-206°C (Recrystallization solvent: benzene) Infrared absorption spectrum ν ^Nujol _nax cm ^-1 : 1780

[Formula] 1680 (〓C=0), 1615 (〓C=C〓) Elemental analysis value (%) Calculated value as C ₁₃ H ₁₀ Cl ₂ N ₂ O ₃ C, 49.86; H, 3.22; Cl, 22.64; N, 8.95 Experimental value C, 49.72; H, 3.17; Cl, 22.77; N, 8.64 The following compound was produced according to the method of Example 1 above. 2-Ethoxycarbonyl-6-(3,5-dichloro-4-methylphenyl)-3-pyridazone mp172-177℃ 2-isopropoxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone mp163-169℃ 2-n-butoxycarbonyl-6-(3,5
-dichloro-4-methylphenyl)-3-pyridazone mp153-157℃ 2-isobutoxycarbonyl-6-(3,5
-Dichloro-4-methylphenyl)-3-pyridazone mp159-161℃ 2-n-pentyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone mp144-147℃ 2-n-hexyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone mp128-130℃ 2-n-heptyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone mp130.5～133℃ 2-benzyloxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone mp180-185.5℃ 2-ethylthiocarbonyl-6-(3,5-
Dichloro-4-methylphenyl)-3-pyridazone mp212-220℃ 2-methoxycarbonyl-6-(3-bromophenyl)-3-pyridazone mp97-100℃ 2-ethoxycarbonyl-6-(3-bromophenyl)-3-pyridazone mp88～91℃ 2-methoxycarbonyl-6-(3,4-dichlorophenyl)-3-pyridazone mp170℃ 2-n-butoxycarbonyl-6-(3,4
-dichlorophenyl)-3-pyridazone mp107~111℃ 2-methoxycarbonyl-6-(3,5-dichloro-4-methoxyphenyl)-3-pyridazone mp180~185℃ 2-ethoxycarbonyl-6-(3 ,5-dichloro-4-methoxyphenyl)-3-pyridazone mp171-176℃ 2-n-butoxycarbonyl-6-(3,5
-dichloro-4-methoxyphenyl)-3-pyridazone mp142-144℃ 2-n-propoxycarbonyl-6-(3,
5-dichloro-4-methylphenyl)-3-pyridazone mp170-173℃ Example 2 2-n-butoxycarbonyl-6-(3,5-
Dichloro-4-methylphenyl)-3-pyridazone 2.55 g of 6-(3,5-dichloro-4-methylphenyl)-3-pyridazone and chloroformic acid,
A mixture of 6.8 g of n-butyl was heated under reflux for 1 hour.
After cooling to room temperature, the precipitated crystals were collected, washed with n-hexane, and dried under reduced pressure to obtain 3.3 g of the desired compound as colorless plate-like crystals having a melting point of 153-157°C. Yield 93% Infrared absorption spectrum ν ^Nujol _nax cm ^-1 : 1775, 1770

[Formula] 1680 (〓 C=0), 1615 (〓 C=C〓) Nuclear magnetic resonance spectrum CDCl ₃ δppm: 0.8 to 2.2 (7H, multiplet, -CH ₂ CH ₂ CH ₃ ) 2.50
(3H, single line,

[Formula]) 4.47 (2H, triple line, J=7cps, -O-CH ₂ -) 6.98, 7.58
(2H, AB type quartet, J _AB = 10 cps, △ _AB =
31cps,

[Formula]) 7.80 (2H, single line,

[Formula]) Elemental analysis value (%) Calculated value as C ₁₆ H ₁₆ Cl ₂ N ₂ O ₃ C, 54.10; H, 4.54; Cl, 19.96; N, 7.89 Experimental value C, 54.15; H, 4.52; Cl, 20.37; N, 7.93 The following compound was produced according to the method of Example 2 above. 2-n-octyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone mp126-129℃ 2-n-nonyloxycarbonyl-6-
(3,5-dichloro-4-methylphenyl)-
3-pyridazone mp122-125℃ 2-phenylcarbonyl-6-(3,5-dichloro-4-methylphenyl)-3-pyridazone mp140-147℃ 2-n-butoxycarbonyl-6-(3-bromophenyl)-3 -Pyridazone mp67-69℃ Example 3 2-n-butoxycarbonyl-6-(3,5-
Dichloro-4-methylphenyl)-3-pyridazone 6-(3,5-dichloro-4-methylphenyl)-3-pyridazone 2.55g, chloroformic acid n-
A mixture of 1.43 g of butyl, 1.75 g of potassium carbonate and 100 ml of acetonitrile was heated under reflux for 7.5 hours.
After cooling, unreacted pyridazone and inorganic salt were separated from the reaction mixture, the liquid was distilled off under reduced pressure, and the residue was recrystallized from n-hexane to obtain 1.1 g of the target compound in the form of needles. Yield 31%. The melting point and spectroscopic values of this product were completely consistent with those of Example 2. The novel pyridazone derivatives () of this invention are useful 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, cucumber, and kidney beans are not affected by chemical damage. Furthermore, the compound having the general formula () is
It can also 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 attapulgite group, talc, mica, phyllite, pumice, vermiyquilite, 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, cobal 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, 0-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 or hydrogen. 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 alkyl phenols 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 isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, 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 50 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 required. 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. 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. 14, 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. 7, 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 Powder 70 parts of Compound No. 1 was finely ground, and 30 parts of clay was added thereto and mixed in a mixer to prepare a premix. Clay 10 parts of this premix.
60 parts and 30 parts of pentonite were homogeneously mixed in a mixer. An appropriate amount of water was added to this material, the mixture was mixed 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. Test 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. Test example 1 Kiyu cucumber seedling damping-off control test Seedling damping-off fungus (Rhizoctonia solani) cultured on wheat bran at 28°C for 2 weeks was uniformly mixed into the soil.
Put this soil in a pot with a diameter of 12 cm, sow 20 seeds of cucumber (variety: Sagami Hanshiro), and then
A 250 ppm test chemical solution was irrigated at a rate of 3/m ² . The pots were kept in a greenhouse at 25°C for two weeks, and the number of seedlings (plants) affected by seedling damping-off was investigated.

[Table] Test Example 2 Rice Mongare disease control test (protective effect) 3 pots of rice seedlings (variety: Koganishiki) at the 4-5 leaf stage
After spraying 50ml of 30ppm test chemical solution and leaving it at room temperature for 24 hours, 4 to 5 oat grains in which Pellularia sasakii had been cultured were placed near the rice stalks and heated at 25 to 27℃. Ten days after inoculation, the degree of disease onset was investigated by the height (cm) of lesion formation. The results are shown in Table 2.

【table】

[Table] Journal example 3 Rice mongare disease control test (therapeutic effect) Rice seedlings (variety: Koganishiki) at the 6th to 7th leaf stage were inoculated with oat grains in which the mongare disease fungus (Pellicularia sasakii) had been cultured in advance. 4 to 5 seeds were placed near the stems and transferred to a greenhouse at 25 to 27°C. Three days after inoculation, the cells were taken out of the greenhouse, sprayed with 100 ppm of the test drug solution in 3 pots of 50 ml, air-dried, and then transferred to a greenhouse at 25-27°C. The height of lesions formed at the time of chemical spraying was checked, and the newly developed lesion length (cm) was investigated 10 days after chemical spraying. The results are shown in Table 3.

【table】

【table】

Claims (1)

[Claims] 1 formula [In the formula, R ₁ and R ₃ are both the same or different and represent a halogen atom, or one is a halogen atom and the other is a hydrogen atom. R ₂ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. R ₄ represents an alkyl group, phenyl group or benzyl group. Y represents oxygen or sulfur atom. ] A compound represented by