JPS634823B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel sulfonyl vinyl 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 is a triazolyl vinyl ketone compound represented by the general formula () described in JP-A-53-130661 and a triazolyl vinyl ketone compound represented by the general formula () described in JP-A-54-41875. It is an important compound as an intermediate in the production of triazolyl vinyl alcohol compounds. [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. The present inventors have conducted extensive research on how to industrially advantageously produce the compounds represented by the general formulas () and () that are useful as fungicides, and have discovered the following two facts. That is, the triazolyl vinyl ketone compound () is further reduced from the compound of the present invention () via the bis-triazolyl ketone compound represented by the general formula () to the triazolyl vinyl alcohol compound (). Compound()
can be easily obtained. [In the above formula, X represents a hydrogen atom or a chlorine atom. ] The compound of the present invention () can be obtained in high yield from the sulfonyl ketone bromide compound represented by the general formula () by reacting a base as a dehydrobromic acid agent, and the sulfonyl ketone bromide compound () can be obtained in high yield from benzalpinacolone () obtained by condensing an industrially available benzaldehyde with pinacolone, for example, as shown in the reaction formula below. [In the above formula, X represents a hydrogen atom or a chlorine atom. ] As described above, it has been discovered that the compound useful as a bactericide can be industrially advantageously produced via the compound ( ) of the present invention, and the present invention has been completed. As described above, the compound of the present invention () can be obtained in good yield by reacting the sulfonyl ketone bromide compound () with a base. 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;
Examples include tertiary amines such as triethylamine and pyridine, but carbonates and metal hydroxides are particularly preferred. When using tertiary amines, the reaction is generally preferably carried out in the presence of a solvent, such as acetone, ketones such as methyl ethyl ketone, acetonitrile,
Nitriles such as propionitrile, benzene,
Examples include hydrocarbons such as toluene and xylene, ethers such as diethyl ether, dioxane, and tetrahydrofuran, as well as dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric acid amide. Further, water can also be used, and may be mixed with the above solvents and reacted in a homogeneous phase or a heterogeneous phase. The temperature at which the reaction is carried out ranges from 0°C to the boiling point of the solvent used, and when a strong base such as a metal hydroxide is used, the reaction easily proceeds even at low temperatures near 0°C.
The amount of base used is approximately 1 mol or more per 1 mol of the sulfonyl ketone bromide compound. Considering economic efficiency, it is in the range of 1 to 5 moles,
Particularly preferably, the amount is in the range of 1 to 3 moles. To isolate the produced target product, it is extracted with a water-insoluble organic solvent and then concentrated according to a conventional method. If water-miscible solvents are used, the product can also be crystallized after dilution with water and isolated separately. The present invention will be explained in more detail below with reference to Examples. Further, as a reference example, an example of producing a triazolyl vinyl ketone compound useful as a fungicide from the compound of the present invention and an example of producing a sulfonyl ketone bromide compound which is a raw material for producing the compound of the present invention will be given. Example 1 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonyl-1-pentene-3
Synthesis of -one 2-bromo-1-(4-chlorophenyl)-4.
4.44 g (0.01 mol) of 4-dimethyl-1-phenylsulfonylpentan-3-one and 2.76 g (0.04 mol) of the triazole were dissolved in dimethylformamide 30
ml and heated under reflux for 2 hours. After cooling, 100
ml of water and extracted with 100 ml of chloroform.
After washing three times with water, the chloroform layer was dried over anhydrous sodium sulfate. It was concentrated under reduced pressure, and the residue was crystallized in n-hexane and dried 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 C ₃ SCl) Example 2 1 Synthesis of -(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonyl-1-penten-3-one 2-bromo-1-(2,4-dichlorophenyl)-4. 9.6 g (0.02 mol) of 4-dimethyl-1-phenylsulfonylpentan-3-one 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 concentration under reduced pressure, the residue was purified by silica gel column chromatography (using n-hexane/acetone = 20/1) to give 4.8 g.
(60%) of the title compound was obtained. n ²⁵ _D 1.5723 Elemental analysis value C (%) H (%) S (%) Cl (%) Actual value 57.32 4.46 8.51 17.92 Calculated value 57.43 4.58 8.07 17.84 (as C ₁₉ H ₁₈ O ₃ SCl ₂ ) Metallic sodium 2.3 g 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)-4,4
-Dimethyl-1-phenylsulfonylpentan-3-one 4.78 g (0.01 mol) was dissolved in 50 ml of acetonitrile, and the above triazole sodium salt 0.91 g (0.01 mol) was added thereto.
The mixture was heated to reflux for an hour. After cooling, it was poured into 200 ml of ice water and extracted with ethyl acetate. After similar treatment, 9.77 g (95%) of the title compound was obtained. 4.44 g (0.01 mol) of 2-bromo-1-(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one was dissolved in 50 ml of tetrahydrofuran. To this was added dropwise 30 ml of water in which 0.56 g (0.01 mol) of potassium hydroxide was dissolved under ice-cooling, and the mixture was vigorously stirred 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 8.61 g (91%) of the title compound. Reference Example 1 Synthesis of 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfenylpentan-3-one Add thio to a mixture of 22.3 g of 4-chlorobenzalpinacolone, 5 drops of triethylamine, and 250 ml of ethanol. 12 g of phenol was added and 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 the title compound as 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 OSCl) Reference example 2 1-( Synthesis of 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfenylpentan-3-one
18g was dissolved in 500ml of chloroform. While cooling, 24 g of meta-chloroperbenzoic acid was added little by little over 1 hour, followed by stirring at 20°C for 3 hours. 5% reaction solution
After washing with aqueous sodium bisulfite and aqueous sodium bicarbonate and concentrating, the resulting solid was crystallized in ethanol. After separate drying, 18.8 g (95%) of the title compound was obtained as crystals. 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 3 2 -Bromo-1-(4-chlorophenyl)-4.
Synthesis of 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, it was washed with ice water and sodium bicarbonate water, and the chloroform layer was concentrated and the resulting solid was dissolved in carbon tetrachloride/
Crystallized in n-hexane. After filtration and drying
5.8 g (95%) of the title compound was obtained as crystals.
Melting point 167-168℃ Elemental analysis value C(%) H(%) S(%) Cl(%) Br(%) Actual value 51.55 4.43 7.20 8.05 17.90 Calculated value 51.42 4.55 7.22 7.99 18.00 (C ₁₉ H ₂₀ O ₃ SClBr Reference example 4 2-bromo-1-(2,4-dichlorophenyl)
Synthesis of -4,4-dimethyl-1-phenylsulfonylpentan-3-one 1- obtained in the same manner as Reference Examples 1 and 2
(2,4-dichlorophenyl)-4,4-dimethyl-1-phenylsulfonylpentan-3-one
39.9g was dissolved in 500ml of chloroform. 16.8 g of bromine was added dropwise at 60°C, and the temperature was kept at the same temperature for 4 hours. It was treated in the same manner as in Reference Example 3 to obtain 44.5 g (93%) of crystals. Melting point 135-136℃ Elemental analysis value C (%) H (%) S (%) Cl (%) Br (%) Actual value 47.82 4.22 6.65 14.71 16.72 Calculated value 47.71 4.01 6.70 14.83 16.71 (C ₁₉ H ₁₉ O ₃ SCl ₂ Br) Reference example 5 1-(4-chlorophenyl)-4,4-dimethyl-1-phenylsulfonyl-1-pentene-3
Triazolization reaction of -one A mixture 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 residue was subjected to the same post-treatment as in Example 1 and then concentrated to obtain 2.52 g of residue. Purified by silica gel column chromatography (using n-hexane/acetone = 20/1), 2.12 g (79% vs. triazole) of the 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℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Actual value 56.77 5.28 23.53 9.91 Calculated value 56.89 5.35 23.42 9.88 (as C ₁₇ H ₁₉ O ₆ OCl) Reference example 6 1 -(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
-Synthesis of sample for identification of 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 the triazolyl group are in the cis position is called the Z-isomer, and the one in the trans position is called 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 4-chlorobenzaldehyde 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 expressed as ζ values. 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-
E-isomer elemental analysis value of 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) Analysis 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-
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) Reference example 7 Synthesis of triazolyl vinyl ketone compounds by thermal decomposition of bistriazolyl ketone compounds 1-(4-chlorophenyl)-4,4-dimethyl-2-( 1,2,4-triazol-1-yl)-
Synthesis of 1-penten-3-one 1-(4-chlorophenyl) obtained in Reference Example 5
-4,4-dimethyl-1,2-bis(1,2,4
-triazol-1-yl)pentan-3-one
0.5g in an oil bath at 180℃ for 1 hour, then at 200℃ for 3 hours.
After heating for an hour, the mixture was cooled and dissolved in 50 ml of chloroform. After washing with 50 ml of water, the organic layer was concentrated to yield 0.37 g (92%) of a yellow oil. Further, the aqueous layer was similarly concentrated to recover 0.095 g (99%) of triazole. When gas chromatography was performed on an oily substance under the following conditions, the retention time was
Two peaks were shown at 300 sec. and 360 sec. with an area ratio of 36/64. Gas chromatography conditions Equipment JEOL 20K FID detector column 5% XE-60 Chromosome W carrier, 1m
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 Calculation Value 62.17 5.58 14.50 12.28 (as C ₁₅ H ₁₆ N ₃ OCl) and 1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-
yl)-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 the E and Z-isomers obtained in Reference Example 6.

Claims (1)

[Claims] 1. General formula [In the formula, X represents a hydrogen atom or a chlorine atom. ] A sulfonyl vinyl 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 the following with a base: [In the formula, X represents a hydrogen atom or a chlorine atom. ] A method for producing a sulfonyl vinyl ketone compound.