T. Hoang, A. Michel, A. Guyot
Sep 1, 1982
Citations
0
Influential Citations
14
Citations
Journal
Polymer Degradation and Stability
Abstract
Abstract The addition of HCl to 2–4 hexadiene in chlorinated solvents leads to an equimolar mixture of isomers of chlorohexene of which the 2–3 isomer (chloro-2-hex-3-ene) is kinetically more favoured than the 4-2 (chloro-4-hex-2-ene). The reaction is catalysed by Lewis acids such as the organotin chlorides, in the order of their Lewis acidity, in the same way as the dehydrochlorination of the chlorohexenes and their isomerisation. The same carbocation intermediate is believed to be involved in these reactions and its formation can be catalysed by the Lewis acid. It may also be inhibited by organotin chlorides such as tributyltin chloride, which reacts with HCl to give dibutyltin dichloride and butane, and thus inhibits the formation of the catalyst charge transfer complex between HCl and the diene. Furthermore, because the disappearance of hexadiene, through oligomerisation, is shown to be catalysed less by organotin chlorides than by ZnCl 2 , the yield of HCl addition in the presence of tin compounds is higher.