JPS629086B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula

[Formula] or

[Formula] [In the formula, R ₁ and R ₂ ' are the same or different and represent a lower alkyl group, and R ₂ represents a lower alkyl group or a phenyl group. R ₃ represents a lower alkyl group. _R4
is a hydrogen atom, lower alkanoyl group or group

[Formula] (wherein A represents -CO- or -CH ₂ -,
X represents a lower alkyl group, a halogen atom or a nitro group. n represents 0, 1 or 2, and when n is 2, X may be the same or different from each other. )
shows. ] or a salt thereof or an organic acid ester thereof when R ₁ is a hydrogen atom, as an active ingredient. The compound of the general formula () can exist as a tautomer as shown below. (In the formula, R ₂ , R ₃ and R ₄ have the same meanings as described above.) In the general formulas () and (), R ₁ ,
The lower alkyl groups of R ₂ and R ₂ ′ are methyl, ethyl,
It refers to a linear or branched lower alkyl group having 1 to 4 carbon atoms, especially a methyl group, such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. _R3
represents a lower alkyl group as exemplified for R ₁ , particularly a methyl group. R ₄ is a hydrogen atom; acetyl,
Straight-chain or branched lower alkanoyl groups having 2 to 5 carbon atoms, especially propionyl groups, such as propionyl, butyryl, isobutyryl or pivaloyl; or , where A represents -CO- or -CH ₂ -, and X is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl,
1 carbon number such as isobutyl or tert-butyl
It represents a linear or branched lower alkyl group having 1 to 4 atoms, especially a methyl group; a halogen atom such as chlorine, bromine, fluorine or iodine, especially a chlorine atom; or a nitro group. n represents 0, 1 or 2, and when n is 2, X may be the same or different from each other. Examples of the salt of the compound of the general formula () include salts with monovalent to trivalent metal ions such as sodium, potassium, calcium, magnesium, aluminum, iron, manganese, zinc, nickel, cobalt, or copper; Cu(H ₂ O) ₂ 〕 ⁺⁺ , [Mn
(H ₂ O) ₂ ] ⁺⁺ , [Ni(H ₂ O) ₄ ] ⁺⁺ , [Al(OH)] ⁺⁺ ,
Salts with complex ions such as [Zn(OH)] ⁺ , [Cu(OH)] ⁺ , [Cu(NH ₃ ) ₂ ^{] ++} or [Co(NH ₂ CH ₂ CH ₂ NH ₂ )] ++ ;N ⁺ H ₄ , N ⁺ H(CH ₃ ) ₃ , N ⁺ H ₂
(C ₂ H ₅ ) ₂ , N ⁺ H ₃ CH (CH ₃ ) ₂ , N ⁺ H ₃ CH ₂ CH ₂ OH
or salts with ammonium ions such as N ⁺ H ₃ CH ₂ CH ₂ OC ₂ H ₅ ; salts with mineral acids such as hydrochloric, sulfuric, nitric or hydrobromic acids. The organic acid ester of the compound of the general formula () may be an ester with an organic acid that is formed at the 3-position of the pyrazole ring and produces the compound of the general formula () upon decomposition. Such organic acids include (1) aliphatic, cycloaliphatic or aromatic carboxylic acids, such as those of the formula R ₅ COOH where R ₅ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or Straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as tert-butyl; chloromethyl, bromomethyl, iodomethyl,
2,2,2-trichloroethyl, 2,2-dibromoethyl, 2,2,2-tribromoethyl,
1 carbon number substituted with 1 to 4 halogens such as 2-iodoethyl, 2,2-diiodoethyl or 1,1,2,2-tetrafluoroethyl
Lower alkyl groups having from 4 to 4, especially 1 or 2; 5- to 7-membered cycloalkyl groups such as cyclopentyl, cyclohexyl or cycloheptyl; or phenyl, 2- or 4-nitrophenyl, 2-, 3 - or 4-tolyl, 2-methoxyphenyl, 2- or 4-chlorophenyl, 2- or 4-bromophenyl, 2,4-dichlorophenyl,
Nitro, halogen, hydroxy or carbon atoms 1 to 4, especially 1, such as 2,4,6-trichlorophenyl, 4-hydroxy-3,5-di-tert-butylphenyl or 2-chloro-4-nitrophenyl represents a phenyl group with or without 1 to 3 alkyl or alkoxy groups as substituents. (2) Carbamic acid, e.g. In the above formula, R ₆ and R ₇ are hydrogen atoms; methyl,
1 to 4 carbon atoms such as ethyl, n-propyl, isopropyl, n-butyl or isobutyl
Straight-chain or branched lower alkyl group having 1 to 4 carbon atoms, especially 1 or 2 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl or a phenyl group with or without a branched alkyl, halogen such as nitro or chloro as a substituent. (3) Sulfonic acid, for example, formula R ₈ -SO ₂ -OH where R ₈ is a straight chain having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. or a branched lower alkyl group; or methyl, ethyl, n-propyl, isopropyl,
1 carbon number such as n-butyl or isobutyl
It represents a phenyl group with or without a linear or branched alkyl having 4 to 4, especially 1 or 2, or a halogen such as chloro as a substituent. (4) Thiophosphoric diesters, e.g. In the above formula, R ₉ is the same or different and represents a linear or branched lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. Examples of compounds having the general formulas () and () used in the herbicide of the present invention are as follows (compound numbers are referred to in the following description) Compound number Compound 1 4-( 2-chlorobenzoyl)-1,2,3-
Trimethyl-3-pyrazolin-5-one 2 4-(3-chlorobenzoyl)-1,2,3-
Trimethyl-3-pyrazolin-5-one 3 4-(4-chlorobenzoyl)-1,2,3-
Trimethyl-3-pyrazolin-5-one 4 4-(2,4-dichlorobenzoyl)-1,
2,3-trimethyl-3-pyrazolin-5-one 5 4-(2-nitrobenzoyl)-1,2,3-
Trimethyl-3-pyrazolin-5-one 6 4-(5-methyl-2-nitrobenzoyl)-
1,2,3-trimethyl-3-pyrazoline-5
-one 7 2-isobutyl-4-(2,4-dichlorobenzoyl)-1,3-dimethyl-3-pyrazolin-5-one 8 4-(2,4-dichlorobenzoyl)-1,3
-diethyl-2-methyl-3-pyrazoline-5
-one10 0,0-diethyl 0-(5-methyl-1-
Phenylpyrazol-3-yl) phosphorothioate 11 3-benzoyloxy-5-methyl-1-phenylpyrazole 12 3-(2-chlorobenzoyloxy)-5-methyl-1-phenylpyrazole 13 3-(3- chlorobenzoyloxy)-5-methyl-1-phenylpyrazole 14 3-(4-chlorobenzoyloxy)-5-methyl-1-phenylpyrazole 15 3-(2,4-dichlorobenzoyloxy)-
5-Methyl-1-phenylpyrazole16 3-(3,4-dichlorobenzoyloxy)-
5-Methyl-1-phenylpyrazole 17 5-methyl-1-phenyl-3-p-toluoyloxypyrazole 18 5-methyl-3-(4-nitrobenzoyloxy)-1-phenylpyrazole 19 5-methyl -3-(2-methoxybenzoyloxy)-1-phenylpyrazole20 5-methyl-3-(4-methoxybenzoyloxy)-1-phenylpyrazole21 5-methyl-3-(5-methyl-2- nitrobenzoyloxy)-1-phenylpyrazole22 3-(4-hydroxy-3,5-ditertiary-butylbenzoyloxy)-5-methyl-
1-phenylpyrazole23 3-acetoxy-5-methyl-1-phenylpyrazole24 5-methyl-3-propionyloxy-1-
Phenylpyrazole25 3-isobutyryloxy-5-methyl-1-
Phenylpyrazole26 3-chloroacetoxy-5-methyl-1-phenylpyrazole27 3-cyclohexanecarbonyloxy-5-
Methyl-1-phenylpyrazole28 3-benzoyloxy-1,5-dimethylpyrazole29 3-(2-chlorobenzoyloxy)-1,5
-dimethylpyrazole30 3-(3-chlorobenzoyloxy)-1,5
-dimethylpyrazole31 3-(4-chlorobenzoyloxy)-1,5
-dimethylpyrazole32 3-(2,4-chlorobenzoyloxy)-
1,5-dimethylpyrazole33 3-(3,4-chlorobenzoyloxy)-
1,5-dimethylpyrazole 34 1,5-dimethyl-3-p-toluoyloxypyrazole 35 1,5-dimethyl-3-(4-nitrobenzoyloxy)pyrazole 36 1,5-dimethyl-3-(4- methoxybenzoyloxy)pyrazole37 1,5-dimethyl-3-(5-methyl-2-
Nitrobenzoyloxy)pyrazole 38 0,0-diethyl 0-(1,5-dimethylpyrazol-3-yl)phosphorothioate 39 3-(N,N-dimethylcarbamoyloxy)-5-methyl-1-phenylpyrazole 40 5 -Methyl-1-phenyl-3-pyrazolyl methanesulfonate 41 5-methyl-1-phenyl-3-pyrazolyl benzenesulfonate 42 5-methyl-1-phenyl-3-pyrazolyl p-toluenesulfonate 43 1,5-dimethyl-3 -Pyrazolyl p-chlorobenzenesulfonate44 4-benzoyl-3-hydroxy-5-methyl-1-phenylpyrazole45 4-(4-chlorobenzoyl)-3-hydroxy-5-methyl-1-phenylpyrazole46 3- Hydroxy-5-methyl-1-phenyl-4-p-toluoylpyrazole47 3-hydroxy-5-methyl-4-propionyl-1-phenylpyrazole48 4-benzoyl-1,5-dimethyl-3-hydroxypyrazole 49 4-(2-chlorobenzoyl)-1,5-dimethyl-3-hydroxypyrazole50 4-(3-chlorobenzoyl)-1,5-dimethyl-3-hydroxypyrazole51 4-(4-chlorobenzoyl)- 1,5-dimethyl-3-hydroxypyrazole52 4-(2,4-dichlorobenzoyl)-1,5
-dimethyl-3-hydroxypyrazole53 4-(3,4-dichlorobenzoyl)-1,5
-dimethyl-3-hydroxypyrazole54 1,5-dimethyl-3-hydroxy-4-p
-Toluoylpyrazole55 1,5-dimethyl-3-hydroxy-4-
(4-Nitrobenzoyl)pyrazole56 3-N-methylcarbamoyloxy-5-methyl-1-phenylpyrazole57 3-N-isopropylcarbamoyloxy-
5-Methyl-1-phenylpyrazole58 5-Methyl-3-N-phenylcarbamoyloxy-1-phenylpyrazole59 3-N-(4-chlorophenylcarbamoyloxy)-5-methyl-1-phenyl Pyrazole 60 1,5-dimethyl-3-N-phenylcarbamoyloxypyrazole 61 1,5-dimethyl-3-N-(0-tolylcarbamoyloxy)pyrazole 62 1,5-dimethyl-3-N-(4- Chloro
2-Nitrophenylcarbamoyloxy)pyrazole63 4-(2-chlorobenzyl)-1,5-dimethyl-3-hydroxypyrazole64 4-(4-chlorobenzyl)-1,5-dimethyl-3-hydroxypyrazole Above Of the compounds, compound numbers 11, 23 and
Except for the compound represented by 41, all of them are new compounds that have not been described in any literature, and have the above general formulas () and ().
A compound having the formula (), an organic acid ester of the compound having the general formula (), and a salt thereof are produced by the following method. (1) 3-pyrazolin-5-one derivative () is
As shown in the following formula, it is easily produced by reacting a 5-hydroxypyrazole derivative () with an alkyl halide () or a compound having the formula () in the presence of a base. (In the formula, R ₁ ' and R ₂ ' represent a lower alkyl group, and R ₃ and R ₄ have the same meanings as defined above.) The above reaction is preferably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction, and examples include water; lower alcohols such as methanol, ethanol, or isopropanol, or a mixed solvent of these and water; diethyl ether, tetrahydrofuran, or dioxane. ethers such as;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and lower alcohols and water-lower alcohols are particularly preferably used. The reaction is also suitably carried out in the presence of a base. Examples of the base used include alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; tertiary amines such as triethylamine; sodium hydroxide is particularly preferably used. The amount of base used is preferably 1 mole of the starting compound of formula ().
~1.2 mol is used. The reaction temperature is not particularly limited, and the reaction is usually carried out at room temperature to the reflux temperature of the solvent, particularly preferably near the reflux temperature of the solvent. The reaction time varies mainly depending on the reaction temperature and the type of reagent used, but is about 1 to 10 hours. Further, the alkyl halide used in the above reaction is a chloride, bromide or iodide. After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. Incidentally, the starting compound of formula () is produced according to the method described in JP-A-50-126830. (2) Among the compounds having the general formula () of the present invention, the compound represented by the formula (-3) is a 1,2,3-trisubstituted pyrazolin-5-one () as shown in the following formula. It is easily produced by reacting acyl halide or benzyl halide in the presence of a catalyst. [In the formula, R ₄ ′ is a lower alkanoyl group or

[Formula] (wherein A, ] The above reaction is suitably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction; for example, 1,2
- halogenated hydrocarbons such as dichloroethane or 1,1,2,2-tetrachloroethane; carbon disulfide; aromatic hydrocarbons such as benzene, toluene or xylene, etc., especially carbon disulfide. Preferably used. Catalysts used in the reaction include, for example, Lewis acids such as aluminum chloride, zinc chloride or iron chloride, with aluminum chloride being particularly preferred. The amount of the catalyst to be used is 1 to 1.5 moles per mole of the compound of formula ().
There is no particular limitation on the reaction temperature, and the reaction is usually carried out at room temperature to the reflux temperature of the solvent, particularly preferably near the reflux temperature of the solvent. The reaction time varies mainly depending on the reaction temperature and the type of reagent used, but is about 2 to 10 hours. The acyl halide used in the above reaction is, for example, acid chloride or acid bromide. After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. (3) The organic acid ester of the compound having the general formula () can be easily produced by reacting the compound of the formula () with an acylating agent as shown in the following formula. (In the formula, R ₂ , R ₃ and R ₄ have the same meanings as defined above, and R ₁₀ represents an organic acid residue.) The above reaction is preferably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction, and examples include ethers such as diethyl ether, tetrahydrofuran, diethyl ether-dioxane, and tetrahydrofuran-dioxane, or mixed solvents thereof; dichloromethane, chloroform, and tetrahydrofuran. Examples include halogenated hydrocarbons such as carbon chloride; aromatic hydrocarbons such as benzene, toluene or xylene; ketones such as acetone or ethyl methyl ketone; nitriles such as acetonitrile. The acylating agent used can also be an acyl halide, such as an acid chloride, an acid bromide; a carboxylic acid in the presence of a carbodiimide, such as 1,3-dicyclohexylcarboimide; or an acid anhydride, preferably an acyl chloride. Yes, it is carried out in the presence of a deoxidizing agent. Deoxidizing agents used in the reaction include, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; tertiary metals such as pyridine or triethylamine. Examples include grade amines. The reaction temperature is not particularly limited, and the reaction is usually carried out at room temperature to the reflux temperature of the solvent. The reaction time varies mainly depending on the reaction temperature and the type of reagent used, but is about 1 to 24 hours. After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. Among the raw material compounds of formula (), compounds in which R ₂ and R ₃ both represent a lower alkyl group and R ₄ is a hydrogen atom are described in Berichte (Ber.) 55 , 2959 (1922) and Tokko Sho.
According to the method described in No. 48-11695, a compound in which R ₂ represents a phenyl group, R ₃ represents a lower alkyl group, and R ₄ represents a hydrogen atom is manufactured by the Journal of American Chemical.・Society (J.Am.Chem.Soc.) 66 ,
1959 (1944). (4) Among the compounds having general formula () of the present invention, the compound represented by formula (-3) can be obtained by reacting 3-acyloxypyrazole () with a Lewis acid as a rearrangement catalyst, as shown in the following formula. easily manufactured by (In the formula, R ₂ , R ₃ and R ₅ have the same meanings as defined above.) The above reaction is suitably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction; for example, 1,2
- halogenated hydrocarbons such as dichloroethane or 1,1,2,2-tetrachloroethane; aromatic hydrocarbons such as monochlorobenzene, benzene or toluene; carbon disulfide, etc., especially halogenated hydrocarbons; Hydrogens are preferably used. Rearrangement catalysts used in the reaction include, for example, Lewis acids such as aluminum chloride, zinc chloride or iron chloride; a particularly preferred rearrangement catalyst is aluminum chloride. The amount of the rearrangement catalyst to be used is 1.5 times or more, particularly 1.5 to 2.5 times, by mole per mole of the compound of formula (). The reaction temperature is not particularly limited, and the reaction is usually suitably carried out at room temperature to the reflux temperature of the solvent.
The time required for the reaction is usually about 1 to 6 hours. After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method. (5) The compound represented by formula (-4) of the present invention is
As shown in the following formula, it is easily produced by reacting a 3-hydroxypyrazole derivative () with an isocyanate. (In the formula, R ₂ , R ₃ and R ₄ have the same meanings as defined above, and R ₁₁ represents a lower alkyl group or an aryl group.) The above reaction is suitably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not participate in this reaction; for example, ethers such as diethyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons such as benzene, toluene or xylene; acetone or ethyl. Examples include ketones such as methyl ketone. The reaction temperature is not particularly limited, and the reaction is usually suitably carried out at room temperature. The reaction time varies mainly depending on the reaction temperature and the type of reagent used, but is about 1 to 24 hours. (6) a salt of a compound having the general formula () and a metal;
Salts with complex ions and salts with ammonium ions are formed by adjusting the pH of the solution of the compound of formula () to about 3 or higher in the presence of a cation. The solvent for forming the salt is not particularly limited, and includes, for example, water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene; and halogens such as dichloromethane and chloroform. Hydrocarbons or a mixed solvent of these organic solvents and water are preferably used. Depending on the valence of the cation and the solvent, the coordination ratio of the compound having the formula () and the cation is 1:1, 1:2, 1:
Various types of salts, such as 3, are formed. In addition, the salt of the compound having the general formula () with a metal is disclosed in JP-A No. 52-265 or JP-A-52
It can also be obtained by reacting the 3-ester of the corresponding pyrazole derivative in the presence of aluminum chloride, a basic alkali metal salt or a basic alkaline earth metal salt, according to the method described in No. 266. be able to. (7) A salt of a compound having the general formula () and a mineral acid can be easily formed by mixing the compound of the formula () and the mineral acid in an appropriate solvent. The solvent to be used is not particularly limited, and includes, for example, water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene; and halogenated hydrocarbons such as dichloromethane and chloroform. Ketones such as acetone or a mixed solvent of these organic solvents and water are preferably used. Generally, salts with mineral acids are formed when the pH of the solution is about 3 or less. Next, methods for producing compounds having the above general formulas () and () will be explained with reference to Examples. Example 1 4-(2,4-dichlorobenzoyl)-1,2,
3-Trimethyl-3-pyrazolin-5-one 2.8 g of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole, 0.6 g of sodium hydroxide and 2.0 g of methyl iodide in 20 ml of methanol. The mixture was mixed with water and heated under reflux for 5 hours.
After cooling, add 10 ml of water and 50 ml of benzene and stir for a while, then separate the benzene layer and concentrate. The precipitated crystals are taken and washed with petroleum ether, giving a melting point of 190~
1.0 g of crude crystals of the target compound having a temperature of 195°C were obtained. Yield 34% Elemental analysis value (%) C ₁₃ H ₁₂ Cl ₂ N ₂ O ₂ Calculated value C, 52.20; H, 4.04; N, 9.36; Cl, 23.70 Experimental value C, 51.91; H, 3.94; N, 9.30; Cl, 23.64 Example 2 4-(2-chlorobenzoyl)-1,2,3-trimethyl-3-pyrazolin-5-one 1,2,3-trimethyl-3-pyrazolin-5
After adding 15 ml of carbon disulfide and then 1.0 g of anhydrous aluminum chloride to 0.63 g of -one, 0.875 g of o-chlorobenzoyl chloride was added with stirring, and the mixture was heated under reflux for 6 hours. After cooling, the solvent was distilled off from the reaction mixture under reduced pressure, and the residue was poured into ice water, stirred for a while, neutralized with dilute aqueous sodium hydroxide solution, and then extracted with chloroform. After washing the extract with water and drying over anhydrous sodium sulfate, the solvent was distilled off from the extract under reduced pressure to obtain 1.0 g of crude crystals of the target compound. Yield 75.6% Melting point 236-238℃ (Re-solidification solvent: benzene) Elemental analysis value (%) C ₁₃ H ₁₃ ClN ₂ O ₂ Calculated value C, 58.99; H, 4.95; N, 10.58; Cl, 13.39 Experimental value C , 58.95; H, 4.83; N, 10.69; Cl, 13.45 Example 3 0,0-diethyl 0-(5-methyl-1-phenylpyrazol-3-yl)phosphorothioate 3-hydroxy-5-methyl-1- 1.74 g of phenylpyrazole and 1.9 g of diethylthiophosphate chloride together with 1.5 g of potassium carbonate in 30 ml of acetone
and heated under reflux for about 7 hours. After cooling, 10 ml of water and 50 ml of benzene were added to the reaction mixture and stirred, and the benzene layer was separated and concentrated to obtain 2.7 g of the target compound as a light brown liquid. Yield 91.5% Nuclear magnetic resonance spectrum CCl ₄ δppm 1.38 (6H, triplet) 2.26 (3H, singlet) 4.42 (4H, multiplet) 5.88 (1H, singlet) 7.2-7.4 (5H, arom.) Examples 4 4-(2-chlorobenzoyl)-1,5-dimethyl-3-hydroxypyrazole 3-(2-chlorobenzoyloxy)-1,5-
0.6 g of dimethyl pyrazole and 0.67 g of anhydrous aluminum chloride in 1,2-dichloroethane (DCE)
The mixture was heated under reflux for 2 hours while stirring in a 20 ml volume. After the reaction was completed, the reaction mixture was poured into ice water, the DCE layer was separated, a small amount of concentrated hydrochloric acid was added, and the mixture was stirred for 2 to 3 hours, washed with water, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was recrystallized from benzene to obtain 0.42 g of the target compound in the form of colorless platelets having a melting point of 161-163°C. Yield 70.1% Elemental analysis value (%) C ₁₂ H ₁₁ ClN ₂ O ₂ Calculated value C, 57.50; H, 4.42; N, 11.18; Cl, 14.14 Experimental value C, 58.06; H, 4.32; N, 11.15; Cl, 14.26 Example 5 1,5-dimethyl-3-N-phenylcarbamoyloxypyrazole 1,5-dimethyl-3-hydroxypyrazole
10 ml of acetone and 0.6 g of phenyl isocyanate were added to 0.56 g, and the mixture was allowed to stand at room temperature for 15 hours, and then the solvent was distilled off under reduced pressure to obtain 1.1 g of the target compound. Yield 95.2% Melting point 142-145℃ (Re-solidification solvent: ethanol) Elemental analysis value (%) As C ₁₂ H ₁₃ N ₃ O ₂ Calculated value C, 62.32; H, 5.67; N, 18.17; Experimental value C, 62.22 ; H, 5.72; N, 18.22; The following compounds were produced according to the methods of Examples 1 to 5 above. 4-(3-chlorobenzoyl)-1,2,3-trimethyl-3-pyrazolin-5-one, mp112.5-113.5℃ 4-(4-chlorobenzoyl)-1,2,3-trimethyl-3- Pyrazolin-5-one, mp183~184℃ 4-(2-nitrobenzoyl)-1,2,3-trimethyl-3-pyrazolin-5-one, mp185~187℃ 4-(5-methyl-2-nitrobenzoyl) )−
1,2,3-trimethyl-3-pyrazoline-5-
On, mp209~210℃ 3-benzoyloxy-5-methyl-1-phenylpyrazole, mp63~64℃ 3-(2-chlorobenzoyloxy)-5-methyl-1-phenylpyrazole, mp62~63℃ 3 -(3-chlorobenzoyloxy)-5-methyl-1-phenylpyrazole, mp46-47℃ 3-(4-chlorobenzoyloxy)-5-methyl-1-phenylpyrazole, mp104-105℃ 3-( 2,4-dichlorobenzoyloxy)-5
-Methyl-1-phenylpyrazole, mp69-70℃ 3-(3,4-dichlorobenzoyloxy)-5
-Methyl-1-phenylpyrazole, mp79~80℃ 5-Methyl-1-phenyl-3-p-toluoyloxypyrazole, mp61.5~62.5℃ 5-Methyl-3-(4-nitrobenzoyloxy)- 1-Phenylpyrazole, mp132-134℃ 5-Methyl-3-(2-methoxybenzoyloxy)-1-phenylpyrazole, n ²⁴ _D 1.5790 5-Methyl-3-(4-methoxybenzoyloxy)-1- Phenylpyrazole, mp83-84℃ 5-Methyl-3-(5-methyl-2-nitrobenzoyloxy)-1-phenylpyrazole, mp69-70℃ 3-(4-hydroxy-3,5-di-tert -butylbenzoyloxy)-5-methyl-1-phenylpyrazole, mp137-138℃ 3-acetoxy-5-methyl-1-phenylpyrazole, mp37-38℃ 5-methyl-3-propionyloxy-1-phenylpyrazole enylpyrazole, mp48~49℃ 3-isobutyryloxy-5-methyl-1-phenylpyrazole, ⁿ²² _D 1.5390 3-chloroacetoxy-5-methyl-1-phenylpyrazole, mp84~85℃ 3-cyclohexane Carbonyloxy-5-methyl-1-phenylpyrazole, mp29-30℃ 3-benzoyloxy-1,5-dimethylpyrazole, mp81-83℃ 3-(2-chlorobenzoyloxy)-1,5-
Dimethylpyrazole, mp77-78℃ 3-(3-chlorobenzoyloxy)-1,5-
Dimethylpyrazole, mp94-98℃ 3-(4-chlorobenzoyloxy)-1,5-
Dimethylpyrazole, mp135-137℃ 3-(2,4-dichlorobenzoyloxy)-
1,5-dimethylpyrazole, mp112.5-114℃ 3-(3,4-dichlorobenzoyloxy)-
1,5-dimethylpyrazole, mp122-123℃ 1,5-dimethyl-3-p-toluoyloxypyrazole, mp92-93℃ 1,5-dimethyl-3-(4-nitrobenzoyloxy)pyrazole, mp185-186 °C 1,5-dimethyl-3-(4-methoxybenzoyloxy)pyrazole, mp85-90°C 1,5-dimethyl-3-(5-methyl-2-nitrobenzoyloxy)pyrazole, mp113-114°C 0,0 -Diethyl 0-(1,5-dimethylpyrazol-3-yl)phosphorothioate, n ²⁶ _D 1.4970 3-(N,N-dimethylcarbamoyloxy)-
5-Methyl-1-phenylpyrazole, mp67~68℃ 5-Methyl-1-phenyl-3-pyrazolyl methanesulfonate, mp38~39℃ 5-Methyl-1-phenyl-3-pyrazolylbenzenesulfonate, mp77~78℃ 5-methyl-1-phenyl-3-pyrazolyl p
-Toluenesulfonate, mp80~81℃ 4-benzoyl-3-hydroxy-5-methyl-1-phenylpyrazole, mp211~213℃ 4-(4-chlorobenzoyl)-3-hydroxy-5-methyl-1-phenylpyrazole enylpyrazole, mp232-233℃ 3-hydroxy-5-methyl-1-phenyl-
p-Toluoylpyrazole, mp188~189.5℃ 3-hydroxy-5-methyl-4-propionyl-1-phenylpyrazole, mp215~216℃ 4-benzoyl-1,5-dimethyl-3-hydroxypyrazole, mp143~145 °C 4-(2-chlorobenzoyl)-1,5-dimethyl-3-hydroxypyrazole, mp161-163°C 4-(3-chlorobenzoyl)-1,5-dimethylpyrazole, mp214-215°C 4-(4- chlorobenzoyl)-1,5-dimethyl-3-hydroxypyrazole, mp215-217℃ 4-(2,4-dichlorobenzoyl)-1,5-
Dimethyl-3-hydroxypyrazole, mp218-219℃ 4-(3,4-dichlorobenzoyl)-1,5-
Dimethyl-3-hydroxypyrazole, mp284-286℃ 1,5-dimethyl-3-hydroxy-4-p-
Toluoylpyrazole, mp184-186℃ 1,5-dimethyl-3-hydroxy-4-(4
-Nitrobenzoylpyrazole, mp270.5-271.5℃ 3-N-methylcarbamoyloxy-5-methyl-1-phenylpyrazole, mp147-149℃ 3-N-isopropylcarbamoyloxy-5
-Methyl-1-phenylpyrazole, mp108~110℃ 5-Methyl-3-N-phenylcarbamoyloxy-1-phenylpyrazole, mp118~120℃ 3-N-(4-chlorophenylcarbamoyloxy)-5 -Methyl-1-phenylpyrazole, mp140~142℃ 1,5-dimethyl-3-N-phenylcarbamoyloxypyrazole, mp142~145℃ 4-(2-chlorobenzyl)-1,5-dimethyl-3- Hydroxypyrazole, mp233-236℃ 4-(4-chlorobenzyl)-1,5-dimethyl-3-hydroxypyrazole, mp201-202℃ Compounds of the above general formulas () and (), their salts and their organic acid esters It is used as a herbicide and has the characteristic of causing weeds to turn white and die. In paddy fields, by treating the soil before or after weed germination, weeds such as Cyperaceae and Cyperaceae, which are difficult to control with ordinary herbicides, can be removed without causing any harm to transplanted or directly sown rice. It can particularly powerfully exterminate perennial weeds such as Omodacaceae weeds such as Prunus japonicus, and monocotyledonous weeds such as Poaceae weeds such as Japanese grasshopper, Japanese grasshopper, and Poaceae weeds.
Weeds of the Weedaceae family, such as azeena, Japanese aphrodisiac moss, and Abnome;
It is also possible to effectively exterminate broad-leaved weeds such as weeds of the Lythraceae family, such as Physcomitrella japonica, and weeds of the Asteraceae family, such as Asteraceae and Asteraceae. In addition, in fields, by treating the soil before or after the germination of weeds, it is particularly effective against weeds of the Caryophyllaceae family, such as chickweed, flea weed, Japanese clover, and clover, as well as weeds of the Caryophyllaceae family, such as Purslane. , weeds of the Amaranthaceae family, such as oxalis, and oxalis; weeds of the Chenopodiaceae family, such as pigweed, white daisy, and koakaza; weeds of the genus Cypressaceae, such as dayflower; weeds of the Lamiaceae family, such as Oxalis oxalis and Oxalis oxalis;
It is possible to effectively exterminate broad-leaved weeds such as leguminous weeds such as catfish, sycamore, and crow pea, and weeds of the euphorbiaceae family such as hackberry and cornucopia. Furthermore, among narrow-leaved weeds, it is particularly effective against weeds of the Cyperaceae family, such as Cyperus japonica and Cyperus japonica, as well as weeds of the Poaceae family, such as Cyperus japonica, Cyperus japonica, Rice grass weed, Golden millet, hackberry grass, Golden foxtail grass, and Sparrow grass. On the other hand, in practical doses, rice, corn, beets, soybeans, cotton, radish, tomatoes,
Crops such as carrots, Chinese cabbage, and lettuce are not harmed by the plant. Furthermore, the compounds having the general formulas () and () can be effectively used as herbicides in orchards, non-agricultural lands, forests, etc. In addition, the active ingredient compound of the present invention exhibits an excellent bactericidal effect against field fungi and filamentous fungi that parasitize and cause harmful effects on agricultural and horticultural crops and other plants, and in particular, it exhibits an excellent bactericidal effect on field fungi and filamentous fungi that are harmful to agricultural and horticultural crops and other plants. In addition to being highly effective against diseases such as leaf blight, anthracnose of cucurbits, powdery mildew, and damping off caused by Fusarium and Rhizoctonia,
It is also useful as an insecticide and acaricide. The compound of the present invention can be mixed with a carrier and, if necessary, other adjuvants, to form a formulation commonly used as a herbicide, such as powder, coarse powder, fine granules, etc.
It is prepared and used as granules, wettable powders, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc. The carrier here refers to a synthetic or natural carrier that is mixed into the herbicide to aid in the reach of the active ingredient to the area to be treated, and to facilitate the storage, transportation, or handling of the active ingredient. means an inorganic or organic substance. 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, chroman 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, 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 acids 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 herbicide of the present invention includes casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose,
High molecular compounds such as hydroxyethyl cellulose and polyvinyl alcohol and other auxiliary agents 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 required. When the herbicide of the present invention prepared in various dosage forms in this way is used to treat soil before or after the germination of weeds in rice fields or fields, the amount of active ingredient per 10 acres is preferably 10 to 2000 g, preferably 100 to 2000 g. Weeds can be effectively exterminated by throwing 500g. In addition, when trying to non-selectively exterminate weeds in non-agricultural lands, such as roads, grounds, house grounds, railroad tracks, etc.,
Weeds can be effectively exterminated by applying 200 to 4000g of the active ingredient per 10 acres. The herbicide of the present invention is preferably blended with other herbicides in order to broaden the herbicidal spectrum.
In some cases, synergistic effects can be expected. Examples of such other herbicides include, for example, 2-methylthio-4,6-bisethylamino-1,3,5-triazine; 2-chloro-4,6
-bisethylamino-1,3,5-triazine;
2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine; 2-methylthio-4,6-bis( isopropylamino)-S-triazine; 2
- Triazine herbicides such as methylthio-4-ethylamino-6-isopropylamino-S-triazine, 2,4-dichlorophenoxyacetic acid and its methyl, ethyl or butyl ester; 2-chloro-4-methylphenoxyacetic acid; 4-chlor-
2-methylphenoxyacetic acid, ethyl 2-methyl-
Phenoxy herbicides such as 4-chlorophenoxybutyrate, 2,4,6-trichlorophenyl-
4'-nitrophenyl ether, 2,4-dichlorophenyl-4'-nitrophenyl ether, 2,4
-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether; 3,5-dimethylphenyl-
Diphenyl ether herbicides such as 4' nitrophenyl ether, 3-(3,4-dichlorophenyl)-
1-methoxy-1-methylurea; 3-(3,4
-dichlorophenyl)-1,1-dimethylurea; 1-(α,α-dimethylbenzyl)-3-(p
-tolyl)urea; 3-(4-chlorophenyl)-
Urea herbicides such as 1,1-dimethylurea, 3-
Methoxycarbonylaminophenyl-N-(3-
methylphenyl) carbamate; isopropyl-
N-(3-chlorophenyl)carbamate; Carbamate herbicides such as methyl N-(3,4-dichlorophenyl)carbamate, 5-bromo-3-
sec-butyl-6-methyluracil; uracil herbicides such as 1-cyclohexyl-3,5-propyleneuracil, S-(4-chlorobenzyl)N,
N-diethylthiol carbamate; S-ethyl N-cyclohexyl-N-ethylthiol carbamate; S-ethyl-hexahydro-1H-azepine-1-carbothioate; S-ethyl-N,
Thiol carbamate herbicides such as N-dinormalpropylthiocarbamate, pyridinium salt herbicides such as 1,1'-dimethyl-4,4'-bispyridinium dichloride, N-(phosphonomethyl)
Phosphorus herbicides such as glycine, α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine; 4-(methylsulfonyl)
Aniline herbicides such as 2,6-dinitro-N,N-dipropylaniline, 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide, 2-chloro-2',6'- Diethyl-N-(propoxyethyl)acetanilide, 2-chloro-
2',6'-diethyl-N-(methoxymethyl)acetanilide; acid anilide herbicides such as 3,4-dichloropropionanilide, 5-tert-butyl-
3-(2,4-dichloro-5-isopropoxyphenyl)1,3,4-oxadiazolin-2-one; 2-[N-isopropyl, N-(4-chlorophenyl)carbamoyl]-4-chlor -5-methyl-4-isoxazolin-3-one; 3-isopropyl-benzo-2-thia-1,3-diazinone-(4)-2,2-dioxide; 3-(2-methylphenoxy)pyridazine, etc. However, it is not limited to this list. The herbicides of the present invention may also be used as plant growth regulators such as sodium naphthalene acetate; 1,2-dihydropyridazine-3,6-dione; gibberellin;
-(Butylcarbamoyl)-2-benzimidazole carbamate; 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene; 3-hydroxy-5-methylisoxazole; 2,3-
Dichlorophenyltetrachlorophthalamic acid;
5-Methyl S-triazole (3,4-b)benzthiazole; 0,0-diisopropyl-S-benzyl phosphorothionate; Pentachloronitrobenzene; Kasugamycin; Blasticidin S; 4,5,6,7-tetra Fungicides such as chlorophthalide, 0,0-diethyl 0-(2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate; 0,0-diethyl S-2-[(ethylthio)ethyl]phosphorodithioate; 1-Naphthyl N-methyl carbamate; 0,0-dimethyl 0
-(3-methyl-4-nitrophenyl)thiophosphate; 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate; S-
Methyl-N-[(methylcarbamoyl)oxy]thioacetimidate; 0,0-dimethyl S-(N
-Methyl-N-formylcarbamoylmethyl)phosphorodithioate; 0,0-dimethyl S-2-
(Ethylthio)ethylphosphorodithioate;
0,0-diethyl S-2 [(ethylthio)ethyl]phosphorodithioate; 0,0-dimethyl-
Insecticides or fertilizers such as 1-hydroxy-2,2,2-trichloroethylphosphonate can be used in combination. Examples of formulations of the herbicide of the present invention are given below. In the text,
All parts simply refer to parts by weight. Formulation Example 1 Granules 70 parts of Compound No. 22 is finely ground, 30 parts of clay is added thereto, and the mixture is mixed in a mixer to obtain a premix. Clay 10 parts of this premix.
Mix homogeneously in a mixer with 60 parts and 30 parts of bentonite. Add an appropriate amount of water to this mixture, mix in a kneader, extrude through a screen with a diameter of 0.8 mm, and dry in a ventilation dryer at 50°C. This material is sized using a sifter to obtain granules. Formulation Example 2 Granules 35 parts of Compound No. 4 and 35 parts of S-(4-chlorobenzyl)N,N-diethylthiol carbamate were finely ground, 30 parts of white carbon was added thereto, and the mixture was mixed in a mixer. and get premixes. 20 parts of this premix are homogeneously mixed in a mixer with 50 parts of clay and 30 parts of bentonite. Add an appropriate amount of water to this mixture, mix in a kneader, extrude through a screen with a diameter of 0.8 mm, and dry in a ventilation dryer at 50°C. This product is sized using a sifter to obtain mixed granules. Formulation example 3 Wettable powder 50 parts of Compound No. 16, 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 4 Emulsion 20 parts of Compound No. 33, 65 parts of xylene, and 15 parts of Paracol pS (trade name of Nippon Nyukazai Co., Ltd.) are mixed and uniformly dissolved to obtain an emulsion. Test examples of the herbicide of the present invention prepared in this way are given below. The test drug was manufactured according to Formulation Example 3 above, and the active ingredient compound of the present invention was added to the
A hydrating agent containing %. Test example 1 Paddy weed flooded soil treatment test ³ polyethylene pots (A,
Fill pots B and C) with paddy soil, transplant one (two) seedlings of paddy rice (variety: Kinnanfu) at the 2.5-leaf stage into pot A, and add two tubers of Urikawa to represent perennial weeds. Insert. In pot B, seeds of Japanese cypress, azalea, and sycamore, representative of broad-leaved weeds, are mixed well with the soil. In addition, I transplanted one growing stock of Pinus vulgare and planted two tubers of the perennial weed Cyperus per pot. For Pot C, seeds of Japanese millet and bulrush, which are representative of narrow-leaved weeds, are mixed well with the soil. In addition, two tubers of the perennial weed Omodaka are planted per pot.
Pots A, B, and C were cultivated in a greenhouse for 3 days as a paddy field, and after the plants took root, the soil was treated with 10 c.c. of a suspension of the test chemical per pot in a flooded state. After 20 days of treatment, the herbicidal effect on each weed and the chemical damage to paddy rice were observed and determined. The results are shown in Table 1. However, the effective dose (g/a) in the table indicates the lowest dose at which the degree of growth inhibition of each plant (whitening area on the surface of the plant) is 70% or more.

[Table] Test Example 2 Pre-emergence soil treatment test for field weeds A polyethylene pot with a surface area of 150 cm ² was filled with field soil, and a field soil was added to the field to represent narrow-leaved weeds such as cane millet, cicada, cyperus, cyperus, and broad-leaved weeds. Each seed was sown and covered with soil. Separately, a polyethylene pot with a surface area of 150 cm ² was filled with field soil, and the narrow-leaved weeds, dayflower, broad-leaved weeds, chickweed, giant clover, goldenrod, purslane, and
Seeds of Shiroza were sown and covered with soil. Immediately after covering both pots with soil, a suspension of the test chemical was applied to the soil surface in an amount of 10 c.c. per pot. process
After 20 days, the herbicidal effect on each weed was observed. The results are shown in Table 2. However, the judgment criteria are the same as in Test Example 1, and are expressed in effective dose (g/a).

【table】

Claims (1)

[Claims] 1 Formula [Formula] or [Formula] [In the formula, R ₁ and R ₂ ' are the same or different and represent a lower alkyl group. R ₂ represents a lower alkyl group or a phenyl group. R ₃ represents a lower alkyl group.
R ₄ is a hydrogen atom, a lower alkanoyl group, or a group (In the formula, A represents -CO- or _-CH2- ,
X represents a lower alkyl group, a halogen atom or a nitro group. n represents 0, 1 or 2, and when n is 2, X may be the same or different from each other. )
shows. A herbicide containing a compound having the following, its salt, or its organic acid ester as an active ingredient.