Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process

A ketone compound and synthesis method technology, applied in the field of organic chemical synthesis, can solve the problems of low overall utilization rate, expensive reagents, cumbersome operation, etc., and achieve good industrialization prospects, potential application value, and the effect of increasing economic benefits.

Inactive Publication Date: 2019-10-08
WENZHOU UNIVERSITY
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Problems solved by technology

[0003] In 2014, Yadav et al. reported that the aryl alkyne and sodium sulfinate in FeCl 3 and K 2 S 2 o 8 Synthesis of α-sulfone-based ketones under co-catalytic conditions. This method uses oxygen as the oxidant and water as the solvent. It can achieve efficient conversion from alkynes to target products at room temperature. It has good adaptability to aryl-terminated alkynes. But for the aryl intermediate alkyne, the yield drops significantly, and the reaction is as follows:
[0009] In 2014, the Yadav research group reported the reaction of styrene compounds and sodium sulfinate to synthesize α-carbonyl sulfone without transition metal catalysis. This method avoids

Method used

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  • Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process
  • Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process
  • Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037]

[0038]A magnetic stir bar, 2,2-dibromo-1-(4-methylphenyl)-1-propanone (61.2mg, 0.2mmol) and sodium p-toluenesulfinate (0.6mmol) were added to a Schlenk reaction tube , 3equiv.), and then added 1mL of anhydrous methanol under nitrogen protection, and stirred at 50°C for 12h. After the reaction was finished, the solvent was evaporated on a rotary evaporator, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio was 5:1) to obtain the target product, with an isolation yield of 93%, and the product was a white solid powder , melting point m.p.104-105°C.

[0039] NMR: 1 H NMR (500MHz, CDCl 3 )δ7.88(d, J=7.8Hz, 2H), 7.65(d, J=7.8Hz, 2H), 7.37–7.21(m, 4H), 5.13(q, J=6.6Hz, 1H), 2.48– 2.33(m,6H),1.54(d,J=6.7Hz,3H); 13 CNMR (125MHz; CDCl 3 ) δ 192.1, 145.3, 145.2, 133.9, 133.1, 129.8, 129.5, 129.4, 129.4, 64.9, 21.7, 21.7, 13.2.

Embodiment 2

[0041]

[0042] A magnetic stirrer, 2,2-dibromo-1-phenyl-1-propanone (58.4mg, 0.2mmol) and sodium p-toluenesulfinate (0.6mmol, 3equiv.) were added to a Schlenk reaction tube, and then Add 1 mL of anhydrous methanol under nitrogen protection, and stir at 50° C. for 12 h. After the reaction was finished, the solvent was evaporated on a rotary evaporator, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio was 5:1) to obtain the target product, with an isolation yield of 98%, and the product was a white solid powder , melting point m.p.93-95°C.

[0043] NMR: 1 H NMR (500MHz, CDCl 3 )δ7.98(d, J=7.3Hz, 2H), 7.66(d, J=8.2Hz, 2H), 7.61(t, J=7.4Hz, 1H), 7.48(t, J=7.8Hz, 2H) ,7.31(d,J=8.0Hz,2H),5.15(q,J=6.9Hz,1H),2.43(s,3H),1.56(d,J=6.9Hz,3H); 13 C NMR (125MHz; CDCl 3 ) δ 192.6, 145.3, 136.3, 134.0, 133.1, 129.8, 129.5, 129.2, 128.7, 65.1, 21.7, 13.2.

Embodiment 3

[0045]

[0046] A magnetic stirrer, 2,2-dibromo-1-(4-chlorophenyl)-1-propanone (65.3mg, 0.2mmol) and sodium p-toluenesulfinate (0.6mmol, 3equiv.), then added 1mL of anhydrous methanol under nitrogen protection, and stirred at 50°C for 12h. After the reaction was finished, the solvent was evaporated on a rotary evaporator, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio was 5:1) to obtain the target product, with an isolation yield of 96%, and the product was a white solid powder , melting point m.p.126-127°C.

[0047] NMR: 1 H NMR (500MHz, CDCl 3 )δ7.93(d, J=8.4Hz, 2H), 7.63(d, J=8.0Hz, 2H), 7.44(d, J=8.4Hz, 2H), 7.31(d, J=8.0Hz, 2H) ,5.10(q,J=6.9Hz,1H),2.43(s,3H),1.54(d,J=6.9Hz,3H); 13 C NMR (125MHz; CDCl 3 )δ191.4, 145.5, 140.7, 134.7, 132.9, 130.6, 129.8, 129.6, 129.1, 65.2, 21.7, 13.1;

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Abstract

The invention discloses a method for synthesizing a high-added-value alpha-sulfone ketone compound from an alpha, alpha-dibromo ketone compound by a one-pot process. The method has the advantages thatan alpha-sulfone ketone derivative is synthesized from alpha, alpha-dibromo ketone, which is simple and easy to obtain, by the one-pot process without separation of an alpha-bromo ketone intermediate, so that a separation process for an intermediate product is omitted, the steps are reduced, and requirements for environment protection are met; the steps of the method are simple and easy to operate, no transition metal reagents are required, and economical sulfonate with less pollution is directly used as a promoter and a sulfonating agent for reducing debromination of the alpha, alpha-dibromoketone, so that the cost is reduced, and economic benefits of reactions are increased; a system for preparing the alpha-sulfone ketone derivative by the one-pot process is developed to provide a novel synthesis method for preparation of the alpha-sulfone ketone compound, and the method has good industrialization prospect and potential application value.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, and in particular relates to a synthesis method for synthesizing α-sulfone-based ketone and its derivatives by one-pot reduction / substitution reaction of α,α-dibromoketone. Background technique [0002] The sulfonation reaction refers to the introduction of sulfonyl (-SO 2 The reaction of R), its products widely exist in natural products, medicines, materials and organic intermediates, is a very important class of organic compounds, α-sulfone ketones are the core structural units of many physiologically active molecules. Therefore, how to efficiently and greenly synthesize α-sulfone-based ketones has been widely concerned by chemical and pharmaceutical researchers. Scientists usually use copper, nickel, palladium, rhodium, iron and other metals to catalyze sulfur-containing compounds such as sulfuryl chloride, sulfonyl hydrazide, and sulfur dioxide as the main synthesis method of α-sulf...

Claims

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Application Information

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IPC IPC(8): C07C317/24C07C315/04C07C315/06C07D213/50
CPCC07C315/04C07C315/06C07C2602/08C07C2602/10C07D213/50C07C317/24
Inventor 夏远志陈建辉陈佳佳林波华振国
Owner WENZHOU UNIVERSITY
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