Study On The N-S/C-S Bond Formation Reactions Involving Sulfinates

The sulfinates have received great attention due to their non-toxicity,low cost,and simple manipulation.In recent twenty years,due to their many advantages in the chemical field,sulfinates have been widely used in the syntheses of some organic synthons,drug intermediates,biological and chemical accelerators.For examples,sulfinates are used as sulfur source to construct N-S bond to produce a high-efficiency promoter,sulfenamide,which has a delayed effect on the vulcanization in the rubber industry,and to produce a sulfonamide which has many biological activities such as anticancer,antibacterial,anti-inflammatory,analgesic,sterilizing and herbicidal.The sulfinates can also replace sulfonyl chlorides,thioethers,thioureaes and other sulfur compounds as green,efficient and clean sulfonylation agent to participate in organic reactions.The purpose of this thesis is to introduce two new economic,environmentally friendly,and simple methods about how to construct C-S bonds and N-S bonds with sulfinates.This thesis consists of three chapters:Chapter 1:Progress on the synthesis of N-S/C-S bonds from sulfinatesThis chapter mainly introduces the synthetic methods of sulfinates and its application in syntheses.The reaction examples of sulfinates in organic synthesis are summarized,and the advantages,disadvantages and practical values of various methods are analyzed.Chapter 2:Study on the amination of aromatic sulfinates catalyzed by sodium iodideThis chapter mainly deal with the reactions of sodium arylsulfinates with primary and secondary amines.PEG-400 and water are used as solvents and sodium iodide as catalyst.Both air and 1,2-Dibromoethane are employed as oxidants to promote these reactions.The free radicals reaction mechanism was proposed based on the controlled experiments.The innovation of this method are use of non-metal catalyst,the use of 1,2-dibromoethane and oxygen in the air as a synergistic oxidant,and use of water and PEG-400 as green solvents.This method meets the requirements of green chemistry.In addition,the raw materials of the reaction,the reaction conditions,and the intermediates of the reaction have practical application values.Chapter 3:Study on the reactions of sulfonates with methyl ketones catalyzed by sodium iodideThis chapter mainly deal with the reaction of sulfinates and methyl ketones.By use of sodium iodide as catalyst,1,2-dibromoethane and air as synergistic oxidants,K₂CO₃ as base,H₂O as solvent and nano-micelle vitamin E polyethylene glycol succinate?TPGS-750-M?,the oxidative coupling reactions of sulfinates and methyl ketones take place on the surface of nano-micelles to form?-carbonyl sulfone in high yield.The novelties of this method are the dual effect of enriching oxygen and phase transfer by using nanomicelles and the oxidative coupling of the methyl ketone with the sulfinate salt by using a mild oxidizing agent,1,2-dibromoethane.The raw materials are cheap and easy to obtain,easy to operate,and can tolerate various functional groups.