CN109232331B - Process for preparing β -ketosulfone or β -hydroxysulfone by reaction of substituted olefin with sulfonyl hydrazide derivative - Google Patents
Process for preparing β -ketosulfone or β -hydroxysulfone by reaction of substituted olefin with sulfonyl hydrazide derivative Download PDFInfo
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- CN109232331B CN109232331B CN201811146294.3A CN201811146294A CN109232331B CN 109232331 B CN109232331 B CN 109232331B CN 201811146294 A CN201811146294 A CN 201811146294A CN 109232331 B CN109232331 B CN 109232331B
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- C07—ORGANIC CHEMISTRY
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
Abstract
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for preparing β -keto sulfone or β -hydroxy sulfone by reacting substituted olefin and sulfonyl hydrazide derivatives, wherein the substituted olefin and the sulfonyl hydrazide derivatives are used as raw materials, air is used as an oxidant, and β -keto sulfone or β -hydroxy sulfone is generated by oxidation addition reaction under the irradiation of visible light in the presence of a photosensitizer and alkali.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for preparing β -keto sulfone or β -hydroxy sulfone by reacting substituted olefin with sulfonyl hydrazide derivatives.
Background
β -ketosulfone or β -hydroxysulfone is a compound widely used in the fields of organic chemistry and polymer chemistry, and is useful in many fields as industrial applications such as fine chemicals, raw materials for pharmaceuticals and agricultural chemicals, raw materials for resins and plastics, electronic information materials, and optical materials.
As a method for producing β -ketosulfone or β -hydroxysulfone, a method is known in which a substituted olefin and sulfonyl hydrazide are used as starting materials, but these methods produce a product under heating conditions mainly using a copper salt, elemental iodine, iodide, bromide or a strong acid as a catalyst and a peroxide as an oxidizing agent.
Disclosure of Invention
The invention aims to provide a preparation method of β -keto sulfone or β -hydroxy sulfone, which uses substituted olefin and sulfonyl hydrazide as starting materials and air as a safe and cheap oxidant in the presence of a photosensitizer and under the promotion of visible light, has mild reaction conditions (room temperature reaction) and high yield.
The invention provides a novel method for preparing β -keto sulfone or β -hydroxy sulfone by using substituted olefin and sulfonyl hydrazide derivatives under the condition of visible light, which comprises the following steps of preparing (3) or (4) by using the reaction of the following general formulas (1) and (2), using the substituted olefin and the sulfonyl hydrazide derivatives as raw materials, using air as an oxidant, and carrying out oxidation addition reaction under the irradiation of visible light in the presence of a photosensitizer and alkali to generate β -keto sulfone or β -hydroxy sulfone, wherein the reaction formula is as follows:
wherein R is1，R2，R3，R4，R5Is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
The air is used by exposing the reaction vessel to the atmosphere to expose the reaction system to normal atmospheric pressure, or by using an air balloon or air cylinder.
The photosensitizer used in the reaction is one or more of Methylene blue (Methylene blue), Eosin (Eosin Y), rhodamine, Rose Bengal (Rose Bengal), a metal oxide semiconductor, a metal-ligand complex or a metal organic molecule.
The alkali is triethylamine, triethylene diamine or diisopropyl ethylamine.
The visible light is a common illumination light source, monochromatic laser or sunlight.
The solvent used in the reaction is one or more of water, ethanol, methanol, toluene, tetrahydrofuran, diethyl ether, acetonitrile, acetone, dimethyl sulfoxide or N, N-dimethylformamide.
The mass ratio of the substituted olefin to the sulfonyl hydrazide derivative is 3: 1; the ratio of the amount of the base to the amount of the sulfonyl hydrazide derivative is 1-2: 1.
The invention has the beneficial effects that:
(1) the method of β -keto sulfone or β -hydroxy sulfone provided by the invention has the advantages of cheap raw materials, simple and convenient process and easy industrial preparation.
(2) The method takes substituted olefin and sulfonyl hydrazide derivatives as raw materials, takes air as an oxidant, and generates β -keto sulfone or β -hydroxy sulfone derivatives through oxidation addition reaction in the presence of a photosensitizer and under the irradiation of visible light.
Detailed Description
The first embodiment is as follows:
2ml of ethanol as a solvent, 0.093 g (0.5mmol) of p-toluenesulfonylhydrazide, 0.156 g (1.5mmol) of styrene, 0.112 g (1mmol) of alkali triethylenediamine, and 3.2 mg (0.01mmol) of photocatalyst methylene blue were sequentially added to a 10ml reaction tube, and irradiated with a 12W blue LED, and the reaction was carried out with the open air at room temperature. After the reaction was completed, extraction was performed with water and ethyl acetate three times, the aqueous layer was removed, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator and purified by silica gel chromatography (ethyl acetate/petroleum ether-1/10) to give 0.106 g of pure 2-p-toluenesulfonylacetophenone in 78% yield.1H NMR(400MHz,CDCl3)δ7.97(d,J＝7.7Hz,2H),7.78(d,J＝8.1Hz,2H),7.64(t,J＝7.3Hz,1H),7.50(t,J＝7.6Hz,2H),7.35(d,J＝8.0Hz,2H),4.74(s,2H),2.46(s,3H).13C NMR(101MHz,CDCl3)δ188.15,145.36,135.82,134.31,129.84,129.34,128.84,128.62,63.61,21.70。
Example two
In reaction example one, the reaction was carried out in the same manner as in example one except that 0.156 g (1.5mmol) of styrene was changed to 0.275 g (1.5mmol) of 1-bromo-4-vinylbenzene. 2-p-toluenesulfonyl-4' -bromoacetophenone, yield 89%.1HNMR(400MHz,CDCl3)δ8.02(t,J＝1.8Hz,1H),7.91(ddd,J＝7.8,1.6,1.0Hz,1H),7.80–7.71(m,3H),7.38(dd,J＝15.3,7.8Hz,3H),4.70(s,2H),2.47(s,3H).13C NMR(101MHz,CDCl3)δ186.69,144.92,137.41,132.04,130.34,128.55,127.98,123.18,63.98。
EXAMPLE III
In reaction example one, the reaction was carried out in the same manner as in example one except that 0.156 g (1.5mmol) of styrene was changed to 0.275 g (1.5mmol) of 1-bromo-3-vinylbenzene. 2-p-toluenesulfonyl-3' -bromoacetophenone, yield 67%.1HNMR(400MHz,CDCl3)δ8.02(t,J＝1.6Hz,1H),7.91(d,J＝7.8Hz,1H),7.76(t,J＝6.9Hz,3H),7.38(dd,J＝15.3,7.8Hz,3H),4.70(s,2H),2.47(s,3H).13C NMR(101MHz,CDCl3)δ186.98,145.64,137.41,137.12,135.54,132.09,130.40,129.95,128.60,128.03,123.18,63.68,21.75。
Example four
In reaction example one, 2-phenyl-1-p-toluenesulfonyl-2-propanol was reacted in the same manner as in example one except that 0.156 g (1.5mmol) of styrene was changed to α -methylstyrene, 0.177 g (1.5mmol), and the yield was 72%.1HNMR(400MHz,CDCl3)δ7.50(d,J＝8.3Hz,2H),7.33–7.29(m,2H),7.24–7.14(m,5H),4.66(s,1H),3.67(dd,J＝45.6,14.6Hz,2H),2.40(s,3H),1.72(s,3H).13C NMR(101MHz,CDCl3)δ144.53,137.39,133.62,129.71,128.25,127.56,127.13,124.65,73.17,66.69,30.76,21.57。
EXAMPLE five
In reaction example one, a reaction was carried out in the same manner as in example one except that 0.156 g (1.5mmol) of styrene was changed to 0.270 g (1.5mmol) of 2, 2-diphenylethylene. 1, 1-diphenyl-2-p-toluenesulfonylethanol, yield 75%.1H NMR(400MHz,CDCl3)δ7.44(d,J＝8.3Hz,2H),7.41–7.34(m,4H),7.26–7.19(m,6H),7.15(d,J＝8.1Hz,2H),5.41(s,1H),4.21(s,2H),2.41(s,3H).13C NMR(101MHz,CDCl3)δ144.51,143.73,137.42,129.70,128.28,127.57(d,J＝18.7Hz),125.87,65.51,21.61。
Claims (6)
1. A method for preparing β -keto sulfone or β -hydroxy sulfone by using substituted olefin and sulfonyl hydrazide derivatives is characterized in that (3) or (4) is prepared by using the following general formulas (1) and (2) to react, the substituted olefin and the sulfonyl hydrazide derivatives are used as raw materials, air is used as an oxidant, and β -keto sulfone or β -hydroxy sulfone derivatives are generated by oxidation addition reaction under the irradiation of visible light in the presence of a photosensitizer methylene blue and alkali:
R2when not equal to H (4)
Wherein R is1，R2，R3，R4，R5Each independently is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
2. The method for preparing β -ketosulfone or β -hydroxysulfone by reacting a substituted olefin with a sulfonyl hydrazide derivative as claimed in claim 1, wherein air is used by exposing the reaction vessel to normal atmospheric pressure or by using an air balloon or an air cylinder.
3. The process for preparing β -ketosulfone or β -hydroxysulfone by reacting a substituted olefin with a sulfonyl hydrazide derivative as claimed in claim 1, wherein the base is triethylamine, triethylenediamine or diisopropylethylamine.
4. The method of claim 1, wherein the visible light is a general lighting source, a monochromatic laser, or sunlight, for the reaction of a substituted olefin and a sulfonyl hydrazide derivative to produce β -ketosulfone or β -hydroxysulfone.
5. The method for preparing β -ketosulfone or β -hydroxysulfone by reacting substituted olefin with sulfonyl hydrazide derivative as claimed in claim 1, wherein the solvent used in the reaction is one or more selected from water, ethanol, methanol, toluene, tetrahydrofuran, diethyl ether, acetonitrile, acetone, dimethyl sulfoxide and N, N-dimethylformamide.
6. The method for preparing β -keto sulfone or β -hydroxy sulfone by reacting substituted olefin with sulfonyl hydrazide derivative according to claim 1, wherein the ratio of the amount of the substituted olefin to the amount of the sulfonyl hydrazide derivative is 3:1, and the ratio of the amount of the base to the amount of the sulfonyl hydrazide derivative is 1-2: 1.
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Effective date of registration: 20201016 Address after: 32 Xingxing Avenue, Xinghuo Industrial Park, Yunshan Economic Development Zone, Yongxiu County, Jiujiang City, Jiangxi Province Patentee after: JIANGXI MAIHAO CHEMICAL TECHNOLOGY Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |