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

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...

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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 the use of transition metals such as Ni and Ag, and uses air as the oxidant. But need to add excess K 2 S 2 o 8 As a promotor, the yield is unstable, and the reaction is as follows:

[0021] As mentioned above, there are many methods for preparing α-sulfone-based ketones in the prior art, but there are many reaction steps and the preparation of corresponding substrates is complicated, making these methods difficult to be used for large-scale synthesis; Most of the known methods require transition metal catalysis, less sources of sulfone groups, expensive reagents, poor substrate universality, low overall utilization, cumbersome operations, and poor economic benefits.

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