87323-95-3Relevant academic research and scientific papers
ORGANIC SULFUR MECHANISM. 27. A REEXAMINATION OF THE REACTION OF THIIRANE 1,1-DIOXIDE WITH AQUEOUS HYDROXIDE
King, James Frederick,Hillhouse, John Henry,Khemani, Kishan Chand
, p. 1 - 5 (2007/10/02)
Reaction of thiirane 1,1-dioxide (1) with aqueous barium hydroxide gives chiefly barium ethansulfonate (3) together with some ethylene and barium sulfite, and only a small amount (5percent) of barium 2-hydroxyethanesulfinate (2), the material previously described by Hesse at al. as the major product of this reaction.Reaction of 1 with potassium hydroxide proceeds analogously except for the formation of barium 2-sulfinatoethanesulfonate (6) from reaction of potassium sulfite with unreacted 1.This revision, when taken with what is already known of the final step of the Ramberg-Baecklund reaction, provides a consistent picture of the reaction of thiirane 1,1-dioxides with hydroxide.For this reaction we suggest a common intermediate with a pentacoordinated sulfur for formation of both the sulfonate anion and the olefin, though an attempt to confirm the existence of such a species using H2(18)O was unsuccessful.
Organic sulfur mechanisms. 24. Preparation and reaction of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride
King, James Frederick,Hillhouse, John Henry
, p. 1583 - 1593 (2007/10/02)
2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqeous solution of 2-mercaptoethanol (4a) with chlorine.This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride.Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nucleophilic ring opening to form the products.In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14), the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxyl group to give the ethenesulfonate derivatives (13 or 22).Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b).A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxonium ion (27) is discussed.
