JPH0118901B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel bistriazolyl ketone compound represented by the general formula () and a method for producing the same. [In the formula, X represents a hydrogen atom or a chlorine atom. ] The compound of the present invention represented by the general formula () is a triazolyl vinyl ketone compound represented by the general formula () described in JP-A-53-130661, and the compound represented by the general formula () described in JP-A-53-130661. It is an important compound as an intermediate for the production of triazolyl vinyl alcohol compounds described in JP-41875. [In the formula, X represents a hydrogen atom or a chlorine atom. ] [In the formula, X represents a hydrogen atom or a chlorine atom. ] The compounds represented by the general formulas () and () are useful as fungicides that have a high control effect against various harmful fungi parasitic on agricultural and horticultural plants, and provide intermediates for the production of such compounds. The significance of the present invention is extremely large. As a result of intensive research into how to industrially advantageously produce compounds useful as bactericides represented by general formulas () and (), the present inventors have found that the compounds of the present invention ( ), it was found that the triazolyl vinyl ketone compound () can be easily obtained, and by further reducing the compound, the triazolyl vinyl alcohol compound () can be obtained. Furthermore, the compound () of the present invention can be produced by the following reaction route using as a starting material benzalpinacolone () obtained by condensation of industrially available benzaldehydes and binacolon. It has also been found that it can be easily produced from a ketone bromide compound or a sulfonyl vinyl ketone compound represented by the general formula (). [In the above formula, X represents a hydrogen atom or a chlorine atom. ] That is, by thermally decomposing the compound of the present invention (), a triazolyl vinyl ketone compound () can be obtained in high yield (see Reference Example 7), and the compound of the present invention () is an excellent triazolyl vinyl ketone. It was revealed that it is a precursor of the compound (). On the other hand, as shown in the reaction formula, using a vinyl ketone compound () obtained by condensing industrially easily available benzaldehydes and pinacolone as a starting material, for example, ()→( )→()→or ()→()→ A sulfonyl ketone bromide compound () which is a raw material for the compound of the present invention
was found to be produced in extremely high yield (see Reference Examples 1, 2, 3, 4, and 5). By using the sulfonyl ketone bromide compound (2) obtained as described above, the compound (2) of the present invention can be produced by, for example, two routes. That is, by reacting the sulfonyl ketone bromide compound () with triazole in an appropriate solvent in the presence of a base as a hydrobromic acid scavenger, the bistriazolyl ketone compound represented by the general formula () can be directly prepared. Obtainable. Bases used include carbonates such as potassium carbonate and sodium carbonate, acetates such as potassium acetate and sodium acetate, metal hydroxides such as potassium hydroxide, sodium hydroxide, and calcium hydroxide, and triethylamine and pyridine. Examples include tertiary amines, but carbonates are preferred. Solvents used include ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran, dioxane and diethyl ether, and dimethylformamide. , dimethyl sulfoxide, hexamethyl phosphoric acid amide, etc. It is also possible to use water,
It is also possible to react with the above-mentioned solvents in a mixture or in two phases. The reaction temperature ranges from 0°C to the boiling point of the solvent used, preferably from 50°C to the boiling point of the solvent. Triazole is used in an amount of 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of the sulfonyl ketone bromide compound (). The amount of the base is required to be 2 moles or more per mole of the sulfonyl ketone bromide compound (), and the reaction product is a salt of the by-produced base and hydrobromic acid and phenylsulfinic acid. This is accomplished in accordance with conventional methods after removal by dissolving in water. A bistriazolyl ketone compound () can also be produced by converting a sulfonyl ketone bromide compound () into a sulfonyl vinyl ketone compound () and reacting this with a triazole. Although it is possible to isolate the sulfonyl vinyl ketone compound () and then react it with a triazole, it is also possible to react the sulfonyl vinyl ketone bromide compound () with a base and then react the resulting sulfonyl vinyl ketone compound () with a triazole. It is also possible to react subsequently with a triazole without isolation. The stepwise reaction method of ()→()→() is considered advantageous when the progress of the reaction is monitored over time using, for example, gas chromatography, but it requires two steps in terms of operation. In terms of the number of reaction operations, the latter method has two steps, whereas the former method has one step, and it can be said that the former method is more preferable. The dehydrobromic acid reaction with a base can be achieved using the above-mentioned solvents and bases under similar conditions. ) can be done. In this case it is also possible to use triazoles as bases. The triazolyl reaction is also preferably carried out in the presence of a base; if the reaction is carried out in the absence of a base, the reaction can proceed only in extremely low yields (see Examples 3 and 4). That is, the amount of base used throughout the reaction from () to () is preferably about 2 mol or more, usually in the range of 2.05 mol to 5 mol, based on (). The method for isolating the product can be carried out in accordance with the conventional method described above for both () and (). The compound of the present invention has two types of diastereomers, each of which has optical isomers. The present invention covers all of these isomers. The present invention will be explained in more detail with reference to Examples and Reference Examples below. Example 1 Synthesis of 1-(4-chlorophenyl)-4,4-dimethyl-1,2,bis(1,2,4-triazol-1-yl)pentan-3-one 0.56 g (0.008 mol) of triazole, Potassium carbonate 1.1g (0.008mol) and acetonitrile 30ml
After refluxing the mixture for 1 hour, acetonitrile
1.8 g (0.004 mol) of 2-bromo-1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one dissolved in 30 ml was added. After refluxing for 2 hours, insoluble matter was removed,
The mother liquor was concentrated. Ice water was added to this and extracted with chloroform. After distilling off the organic layer, 1.5 g of oil was obtained. After dissolving in carbon tetrachloride, n-hexane was added for crystallization, and after separate drying, 1.38 g (96%) of the title compound was obtained as crystals. Melting point 157-161℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Actual value 57.02 5.38 23.35 9.73 Calculated value 56.89 5.35 23.42 9.88 (as C ₁₇ H ₁₉ N ₆ OCl) Example 2 1 -(2,4-dichlorophenyl)-4,4-
Synthesis of dimethyl-1,2-bis(1,2,4-triazol-1-yl)pentan-3-one 1.4 g (0.02 mol) of triazole, potassium carbonate
2.8 g (0.02 mol) and 60 ml of acetonitrile were heated under reflux for 2 hours. After cooling the reaction solution on ice,
2-bromo-1-(2,4-dichlorophenyl)
Add 4.8 g (0.01 mol) of -4,4-dimethyl-1-phenylsulfonylpentan-3-one, and add 20
Stirred at ℃ for 1 hour. The mixture was then heated to reflux and kept for 2 hours. After the same post-treatment as in Example 1, 3.5 g of oil was obtained. This was purified by silica gel column chromatography (using n-hexane/acetone = 20/1, the same applies hereinafter unless otherwise specified) to produce 3.12 g (79%) of 1-(2,4-dichlorophenyl). -4,4-dimethyl-1,2-bis(1,2,4-triazol-1-yl)pentan-3-one was obtained as an oil. n ²⁷ _D 1.5440 Elemental analysis value C(%) H(%) N(%) Cl(%) Actual value 51.87 4.71 21.36 17.89 Calculated value 51.91 4.62 21.37 18.03 (as C ₁₇ H ₁₈ N ₆ OCl ₂ ) Obtained product The substance was a mixture of two diastereomers, and each was able to be isolated by repurifying it by silica gel column chromatography. One diastereomer was a crystal with a melting point of 115-116°C (yield: 1.5 g), and its elemental analysis values were as follows. C(%) H(%) N(%) Cl(%) Actual value 52.07 4.59 21.36 17.92 The other diastereomer is a crystal with a melting point of 88-89℃ (yield: 1.0g), and its elemental analysis value is as follows. It was like that. C(%) H(%) N(%) Cl(%) Actual value 52.23 4.69 21.15 17.71 Example 3 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonyl-1-pentene-
Synthesis of 3-one 2-bromo-1-(4-chlorophenyl)-
4.44 g (0.01 mol) of 4,4-dimethyl-1-phenylsulfonylpentan-3-one and 2.76 g (0.04 mol) of triazole were dissolved in 30 ml of dimethylformamide and heated under reflux for 2 hours. After cooling,
It was poured into 100ml of water and extracted with 100ml of chloroform. After washing three times with water, the chloroform layer was dried over anhydrous sodium sulfate. Concentrate under reduced pressure, crystallize the residue in n-hexane, and dry separately to give 2.65 g.
(73%) of the title compound was obtained. Melting point 135-136℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Actual value 62.91 5.35 8.71 9.65 Calculated value 62.88 5.29 8.83 9.77 (as C ₁₉ H ₁₉ O ₃ SCl) Triazole is brominated It is thought that it reacted as a hydrogen acid scavenger. When the crystallization mother liquor was examined by thin layer chromatography, a small amount of spots with Rf values corresponding to bistriazole compounds were observed, but they could not be isolated and identified. It is believed that in the absence of a base, the reaction of triazole to sulfonyl vinyl ketone proceeds only in extremely low yields even if triazole is present in excess. Example 4 1-(2,4-dichlorophenyl)-4,4-
Synthesis of dimethyl-1-phenylsulfonyl-1-penten-3-one 2-brom-1-(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one 9.6 (0.02 mol) and 2.23 g (0.022 mol) of triethylamine were dissolved in 100 ml of acetone and heated under reflux for 3 hours.
The reaction solution was poured into ice water and extracted with 150 ml of ethyl acetate. The organic layer was washed twice with water and then dried over anhydrous sodium sulfate. After concentrating under reduced pressure, the residue was purified by silica gel column chromatography.
4.8g (60%) of the title compound was obtained. ^n25D _{_}
1.5723 Elemental analysis value C (%) H (%) S (%) Cl (%) Actual value 57.32 4.46 8.15 7.92 Calculated value 57.43 4.58 8.07 17.84 (as C ₁₉ H ₁₈ O ₃ SCl ₂ ) 2.3 g of sodium metal at 99% ethanol 100ml
In addition, the sodium ethylate was prepared by heating and dissolving it. Add 6.9g of triazole to this
After stirring for 30 minutes, the mixture was concentrated to dryness under reduced pressure to prepare triazole sodium salt. 2-bromo-1-(2,4-dichlorophenyl)-4,
After dissolving 4.78 g (0.01 mol) of 4-dimethyl-1-phenylsulfonylpentan-3-one in 50 ml of acetonitrile and adding 0.91 g (0.01 mol) of the above triazole sodium salt,
The mixture was heated under reflux for 1 hour. After cooling, it was poured into 200ml of ice water and extracted with ethyl acetate. After similar treatment, 3.77 g (95%) of the title compound was obtained. As in Example 3, no bistriazole compound was obtained. 4.44 g (0.01 mol) of 2-brom-1-(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one was dissolved in 50 ml of tetrahydrofuran. To this was added 30 ml of water in which 0.56 g (0.01 mol) of potassium hydroxide had been dissolved under ice-cooling, and the mixture was stirred vigorously for 3 hours.
After adding 100 ml of ice water, 100 ml of chloroform was added to separate the layers. After washing twice with water, the organic layer was dried over anhydrous sodium sulfate. Concentration under reduced pressure yielded 3.61 g (91%) of the title compound. Example 5 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonyl-1-pentene-
Triazolization reaction of 3-one A mixed solution of 1.04 g (0.015 mol) of triazole, 2.07 g (0.015 mol) of anhydrous potassium carbonate, and 30 ml of acetonitrile was heated under reflux with stirring for 1 hour.
After cooling, 1-(4-chlorophenyl)-4,4-
4.44 g (0.01 mol) of dimethyl-1-phenylsulfonyl-1-penten-3-one was added and the mixture was kept at 25° C. for 1 hour and under reflux for 5 hours. After separating the insoluble matter, the same post-treatment as in Example 1 was carried out to obtain 2.52 g of residue. Purified by silica gel column chromatography, 2.12 g (79% triazole) of bistriazole compound 1-(4-chlorophenyl)
-4,4-dimethyl-1,2-bis(1,2,4
-triazol-1-yl)pentan-3-one was obtained. Melting point 157-161°C Example 6 1-(2,4-dichlorophenyl)-4,4-
Triazolization reaction of dimethyl-1-phenylsulfonyl-1-penten-3-one 1-(2,4-dichlorophenyl)-4,4-
Dimethyl-1-phenylsulfonyl-1-penten-3-one 3.97 g (0.01 mol), triazole
2.07g (0.03mol), potassium carbonate 0.69g (0.005
A mixture of 50 ml of acetonitrile and 50 ml of acetonitrile was heated under reflux for 12 hours. After cooling, it was treated in the same manner as in Example 1 to obtain 4.2 g of oil. This was purified by silica gel column chromatography to 3.85g.
(98%) of 1-(2,4-dichlorophenyl)-
4,4-dimethyl-1,2bis-(1,2,4-
Triazol-1-yl)pentan-3-one was obtained. n ²⁸ _D 1.5445 Elemental analysis value C (%) H (%) N (%) Cl (%) Actual value 51.85 4.63 21.43 7.92 Calculated value 51.91 4.62 21.37 18.03 (as C ₁₇ H ₁₈ N ₆ OCl ₂ ) Reference example 1 1 -(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfenylpentane-3-
12 g of thiophenol was added to a mixture of 22.3 g of 4-chlorobenzalpinacolone, 5 drops of triethylamine, and 250 ml of ethanol, and the mixture was kept at 70°C for 4 hours. After cooling on ice, the formed crystals were separated, washed with cold ethanol, and dried to obtain 29 g (84%) of white crystals. Melting point 127-128℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Actual value 68.55 6.33 9.72 10.45 Calculated value 68.54 6.37 9.63 10.65 (as C ₁₉ H ₂₁ OCl) Reference example 2 1-( 2,4-dichlorophenyl)-4,4-
Synthesis of dimethyl-1-phenylsulfenylpentan-3-one 2,4-dichlorobenzalpinacolone 25.7g,
Mix Triton-B (4 drops) and 300ml of ethanol, heat to 50-60℃, and then add thiophenol.
12.1 g was added dropwise and the mixture was refluxed for 6 hours. The reaction solution was concentrated, ice water was added, and then extracted with ether. After distilling off the ether, n-hexane was added to the obtained oil to crystallize it. After separate drying, 30 g (86%) of crystals were obtained. Melting point 79-80℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Actual value 62.02 5.43 8.83 19.41 Calculated value 62.12 5.50 8.73 19.30 (as C ₁₉ H ₂₀ OSCl ₂ ) Reference example 3 1- Synthesis of (4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfenylpentan-3-one 18 g was dissolved in 500 ml of chloroform. Under ice-cooling, 24 g of meta-chloroperbenzoic acid was added little by little over 1 hour, followed by stirring at 20°C for 3 hours. 55% of the reaction solution
After washing with % sodium bisulfite water and sodium bicarbonate water, it was concentrated, and the resulting solid was crystallized in ethanol. After separate drying, 18.8 g (95%) of crystals were obtained.
Melting point 145-146℃ Elemental analysis value C (%) H (%) S (%) Cl (%) Actual value 62.71 5.73 8.86 9.64 Calculated value 62.53 5.81 8.79 9.71 (as C ₁₉ H ₂₁ O ₃ SCl) Reference example 4 2 -Bromo-1-(4-chlorophenyl)-
Synthesis of 4,4-dimethyl-1-phenylsulfonylpentan-3-one 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one
5.0 g was dissolved in 100 ml of chloroform and 100 ml of acetic acid. 2.2 g of bromine was added dropwise at 50°C. After keeping at the same temperature for 3 hours, the mixture was washed with ice water and sodium bicarbonate water, and the chloroform layer was concentrated. The resulting solid was crystallized in carbon tetrachloride/n-hexane. After filtering and drying, 5.8 g (95%) of crystals were obtained. Melting point 167-168℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Actual value 51.55 4.43 7.20 8.05 Calculated value 51.42 4.55 7.22 7.99 (as C ₁₉ H ₂₀ O ₃ SClBr) Elemental analysis value Br (%) Actual value 17.90 Calculated value 18.00 Reference example 5 Synthesis of 2-bromo-1-(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one 1-(2 ,4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentane-3-
39.9 g of ion was dissolved in 500 ml of chloroform. 60
16.8 g of bromine was added dropwise at ℃ and kept at the same temperature for 4 hours. It was treated in the same manner as in Reference Example 4 to obtain 44.5 g (93%) of crystals. Melting point 135-136℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Actual value 47.82 4.22 6.65 14.71 Calculated value 47.71 4.01 6.70 14.83 (as C ₁₉ H ₁₉ O ₃ SCl ₂ Br) Elemental analysis Value Br(%) Actual value 16.72 Calculated value 16.71 Reference example 6 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-
Synthesis of sample for identification of yl)-1-penten-3-one Since the title compound has a double bond, geometric isomers exist. As shown in the following formula, the one in which the phenyl group and triazolyl group are in the cis position is referred to as the Z-isomer, and the one in the trans position is referred to as the E-isomer.

【formula】

[Formula] According to the method described in JP-A No. 53-130661, 50 g of triazolyl pinacolone, potassium carbonate
A reaction was carried out using 41 g of the crude product and 46.3 g of 4-chlorobenzaldehyde to obtain a crude product. This was dissolved in 100 ml of benzene and passed through a column containing 1.2 kg of silica gel (100-200 mesh), followed by column chromatography using n-hexane/acetone (10/1) as a developing solvent. Fractions containing the same components were combined and concentrated by thin layer chromatography, and the residue was recrystallized from carbon tetrachloride to obtain 36 g of pure Z-isomer (yield: 41.6
%, melting point 78-79°C) and 10 g of E-isomer (yield
11.5%, melting point 108-109°C). Elemental analysis values and NMR spectrum results for each isomer are shown. The NMR spectrum uses deuterochloroform as a solvent and tetramesylsilane as an internal standard, and chemical shifts are shown as δ values. E-isomer elemental analysis value of 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one C(%) H (%) N(%) Cl(%) Calculated value 62.17 5.58 14.50 12.23 (as C ₁₅ H ₁₆ N ₃ OCl) Analytical value 62.32 5.60 14.41 12.20 NMR spectrum 8.11 (1H, singlet, triazole proton), 7.90 (1H, singlet , triazole proton), 7.15 (4H, singlet,
phenyl proton), 6.99 (1H, singlet, olefin proton), 0.99 (9H, singlet, butyl proton) 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1 -yl)-1-penten-3-one Z-isomer elemental analysis value C(%) H(%) N(%) Cl(%) Analysis value 62.35 5.59 14.38 12.18 NMR spectrum 8.14 (1H, singlet, triazole proton), 7.98 (1H, singlet, triazole proton), 7.22 (2H, doublet, phenyl proton, J=8Hz), 6.73 (2H, doublet, phenyl proton, J=8Hz),
7.49 (1H, singlet, olefin proton), 1.22 (9H, singlet, butyl proton) 1-(2,4-dichlorophenyl)-4,4
-Dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one E and Z-isomers were obtained in the same manner as in the synthesis of identification sample. Its physical properties and NMR spectrum data were as follows.

[Table] Reference Example 7 Synthesis of triazolyl vinyl ketone by thermal decomposition of bistriazolyl ketone 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-
Synthesis of 1-(4-chlorophenyl)-4,4-dimethyl-1,2-bis-(1,
2,4-triazol-1-yl)pentane-3
- 0.5g of onion in an oil bath at 180℃ for 1 hour, 200℃
℃ for 3 hours, cooled and diluted with chloroform at 50
Dissolved in ml. After washing with 50 ml of water, the organic layer was concentrated to yield 0.37 g (92%) of a yellow oil. In addition, the aqueous layer was similarly concentrated to recover 0.095 g (99%) of triazole. When the oil was subjected to gas chromatography under the following conditions, it showed two peaks at retention times of 300 seconds and 360 seconds with an area ratio of 36/64. Gas chromatography conditions Equipment JEOL 20K FID detector Column 5% XE-60 Chromosome W carrier, 1
m glass column Column temperature 200℃ Vaporization chamber temperature 240℃ Carrier gas pressure 1.0Kg/cm ^2The elemental analysis values of this oil are: C(%) H(%) N(%) Cl(%) Actual value 62.20 5.45 14.38 12.42 Calculated value 62.17 5.58 14.50 12.23 (as C ₁₅ H ₁₆ N ₃ OCl), 1-(4-chlorophenyl)-4,4-
Dimethyl-2-(1,2,4-triazole-1
-il)-1-penten-3-one. On gas chromatography, the former peak corresponded to the retention time of the E-isomer shown in Reference Example 6, and the latter peak corresponded to the retention time of the Z-isomer. The NMR spectrum also showed a mixed signal of E and Z-isomers obtained in Reference Example 6. 1-(2,4-dichlorophenyl)-4,4
-Synthesis of dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one 1-(2,4-dichlorophenyl)-4,4 obtained in Example 2 1.0 g of -dimethyl-1,2-bis(1,2,4-triazol-1-yl)pentan-3-one was heated and reacted under the same conditions as for 0.73 g (89%) of pale yellow after post-treatment. In addition to obtaining an oily substance, 0.172 g (98 g) of triazole was obtained from the aqueous layer.
%) was recovered. Gas chromatography was performed under similar conditions and showed two peaks corresponding to the E/Z of the title compound at an area ratio of 37/63. Elemental analysis values of this oily substance C(%) H(%) N(%) Cl(%) Actual value 55.41 4.55 13.10 21.72 Calculated value 55.56 4.67 12.96 21.87 (as C ₁₅ H ₁₄ N ₃ OCl ₂ ), and the NMR spectrum is 1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-
Il)-1-penten-3-one E and Z-
It showed a mixed signal of isomers.

Claims (1)

[Claims] 1. General formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A bistriazolyl ketone compound represented by 2 General formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A general formula characterized by reacting a sulfonyl ketone bromide compound represented by and 1,2,4-triazole in the presence of a base. [In the formula, X represents a hydrogen atom or a chlorine atom. ] A method for producing a bistriazolyl ketone compound represented by 3 General formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A general formula characterized by reacting a sulfonyl vinyl ketone compound represented by the formula with 1,2,4-triazole in the presence of a base. [In the formula, X represents a hydrogen atom or a chlorine atom. ] A method for producing a bistriazolyl ketone compound represented by 4 General formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A sulfonyl ketone bromide compound represented by the formula is reacted with a base to form the general formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A general formula characterized by forming a sulfonyl vinyl ketone compound represented by and then reacting this with 1,2,4-triazole in the presence of a base. [In the formula, X represents a hydrogen atom or a chlorine atom. ] A method for producing a bistriazolyl ketone compound represented by