2351-74-8Relevant academic research and scientific papers
The reactions of some α-halo-β-ketosulfones with hard and soft nucleophiles. A preparation of sulfinate esters
Grossert, J. Stuart,Dubey, Pramod K.,Elwood, Tom
, p. 1263 - 1267 (2007/10/02)
The α-halo-β-ketosulfonyl functionality was attacked by ethanethiolate at the halogen which, in the presence of a proton source, usually resulted in reduction to the β-ketosulfone.A range of other soft nucleophiles did not react, whereas hard nucleophiles invariably attacked at the carbonyl, with subsequent cleavage to α-halosulfones.Ambident arylsulfinate anions usually attacked at halogen to form the sulfonyl halide, which reacted with excess sulfinate to give an intermediate that is readily attacked by alcohols.This reaction resulted in the formation of alkyl arylsulfinate esters in reasonable yields.The same reaction occurred when sulfonyl chlorides were reacted with sulfinate salts and it was rationalized by using HSAB principles.Spectral properties of some sulfinate esters are presented.
THE PREPARATION, SPECTRAL PROPERTIES, STRUCTURES, AND BASE-INDUCED CLEAVAGE REACTIONS OF SOME α-HALO-β-KETOSULFONES
Grosset, Stuart J.,Dubey, Pramod K.,Gill, Glen H.,Cameron, Stanley T.,Gardner, Patrick A.
, p. 798 - 807 (2007/10/02)
The halogenation of β-ketosulfones such as α-methylsulfonylacetophenone (1) and benzenesulfonylacetone (10) can be effected with sulfuryl chloride or pyridinium bromide perbromide.Regiochemical control can be achieved by control of stoichiometry and/or the reaction conditions.Detailed 1H and 13C nmr, and mass spectra are recorded for a series of halogenated β-ketosulfones, together with structures by X-ray crystallography for 1, 2-chloro-2-methylsulfonyl-1-phenylethanone (2), chloromethyl methyl sulfone (4), and α-chloroacetophenone (21).Results from these studies are used to suggest a reason for the difficulty associated with substitution reactions of α-halosulfones.
