L. D. Buyck, H. Pooter
Sep 1, 2010
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0
Influential Citations
4
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Journal
Bulletin des Sociétés Chimiques Belges
Abstract
Alkyl 4-chlorobutyl ethers reacted in the dark with an excess of sulfuryl chloride at 70–85°C (bath) to afford α,β,β-trichlorinated ethers. The reactions were accelerated 3− to 6-fold by N,N-dimethyl-octylammonium salts (0,12 to 1 mmol/mol ether). This catalyst promoted decomposition of sulfuryl chloride to chlorine and sulfur dioxide and thereby caused serious loss of sulfuryl chloride. The proportions of chlorination at α or α' position were identical in the catalyzed or uncatalyzed version and depended on inductive effects, correlating well with Taft's linear free energy relationship log k/kref = ρ* σ* for R = H, Me, Et, Pr in RCH2O(CH2)4Cl with ρ* = −2.6±0.1. The overall reactivity of ethers appears to vary like the nucleophilicity of the ether oxygen. It is concluded that hydride abstraction occurs indirectly, probably involving a chloroxonium ion pair.