PART 1: THE FORMATION OF 2-METHYLAMIN0-N-0CTADECYLETHAHESULF0NAMIDE FROM 2-CHLOROETHANESULFONYL CHLORIDE. 2-Chloroethanesulfonyl chloride (2) was reacted with octadecylamine (3) in the presence of triethylamine to give N-octadecylethcnesulfonamide (4), which was reacted with methylamine to give 2-methylamino-N-octadecylethanesulfonamide (1). The first reaction involves formation of the sulfonamide and dehydrohalogenation. The second reaction is a Michael addition. The formation of 1 is favored in a polg.r, protic medium. An aprotic, less polar medium produces an unwanted di-Michael adduct CH3N(CH2CH2S02NHCl8H37)2 (8), and polymer. The intramolecular hydrogen bonded structure of 1 is discussed. PART 2: THE FORMATION OF ETHYL ETHENESULFONATE FROM 2-CHLOROETHANESULFONYL CHLORIDE OR ETHENESULFONYL CHLORIDE; A MECHANISTIC STUDY. 2-Chloroethanesulfonyl chloride (2) or ethenesulfonyl chloride (l2) when added to benzene containing ethanol-d and triethylamine produces undeuterated (l4) and some a-monodeuterated ethyl ethenesulfonate (14'). The sulfene [CH =C=SO J (c) from 11, and possibly [ClCHoCH=S0 ] (b) from 2, account for the a-monodeuterated ester. Deuterium was not incorporated by simple exchange. There is circumstantial evidence for the 1, 3-sigmatropic rearrangement of b to give 11. The reaction of 2-bromoethanesulfonyl chloride (15) with base shows that olefin formation to give 11 is greatly favored over sulfene formation, [BrCH2CH=S023 (g). The sulfene c, and the suspected sulfene b may collapse with triethylamine -HC1 to give an undeuterated ester or be trapped by ethanol-d to give an a-monodeuterated ester. The fact that a mixture of esters are produced means that no one process is operating exclusively in Scheme II.
Library of Congress Subject Headings
Chlorides; Organosulfur compounds
Department, Program, or Center
Chemical Engineering (KGCOE)
Richard s. Henion
Zielinski, Paul, "Some reactions of 2-chloroethanesulfonyl chloride" (1976). Thesis. Rochester Institute of Technology. Accessed from
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