112678-63-4Relevant academic research and scientific papers
Aliphatic sulfonation, 16: Sulfonation of alkenes by chlorosulfuric acid, acetyl sulfate, and trifluoroacetyl sulfate
Bakker, Bert H.,Cerfontain, Hans
, p. 91 - 96 (2007/10/03)
An exploratory study has been made on the reaction of a number of non- branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in the presence and the absence of [D8]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv, of [D8]1,4-dioxane at 0 °C yielded quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the corresponding β-sultones 2b-g. The ClSO3H-dioxane complex acted as a sulfonating reagent with the alkenes to yield the corresponding β-sultones in a syn cycloaddition of SO3 to the carbon-carbon double bond. In the absence of [D8]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly acidic ClSO3H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2- cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans- and cis-β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in [D]chloroform at -20 °C directly afforded the products 1,2-octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-sulfonic acid (4g).
SULFONATION OF ALKENES WITH SULFUR TRIOXIDE; REVERSIBLE STEREOSPECIFIC β-SULTONE FORMATION
Bakker, Bert H.,Cerfontain, Hans
, p. 5451 - 5454 (2007/10/02)
The small differences in the rate coefficients of β-sultone formation between the internal and the terminal double bond in the octenes 2a-c and (Z)-1,10-nonadecadiene are evidence for a concerted cycloaddition of sulfur trioxide.The formation of β-sultone 1d is accompanied by 15percent of 2-octene-1-sulfonic acid, formed in a primary side-reaction.The sulfonation of the octenes 2a-d to their β-sultones 1a-d is reversible.Desulfonation of the β-sultones 1a-d by water to the olefins 2a-d proceeds in a stereospecific syn fashion.
