Sulfonation of Alkenes by Chlorosulfuric Acid, Acetyl Sulfate, and Trifluoroacetyl Sulfate

✍ Scribed by Bert H. Bakker; Hans Cerfontain

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 128 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199901)1999:1<91::aid-ejoc91>3.0.co;2-j

✦ Synopsis

An exploratory study has been made on the reaction of a [D 8 ]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the number of non-branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly the presence and the absence of [D 8 ]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 acidic ClSO 3 H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2-mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv. of [D 8 ]1,4-dioxane at 0 °C yielded cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans-and cis-quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in corresponding β-sultones 2b-g. The ClSO 3 H-dioxane complex acted as a sulfonating reagent with the alkenes to

[D]chloroform at -20 °C directly afforded the products 1,2octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-yield the corresponding β-sultones in a syn cycloaddition of SO 3 to the carbon-carbon double bond. In the absence of sulfonic acid (4g).

With diethyl ether as solvent the reaction of chlorosulfuric