A KINETIC STUDY OF DOUBLE-BOND MIGRATION IN ALLYLOXY POLYETHER ALKOXIDES

The rates of rearrangement of CH2=CHCH2(OC3H6)nO-M+ to cis-CH3CH=CH(OC3H6)nO-M+ have been studied kinetically at 30° in tetrahydrofuran solution. The rates are cation dependent. The Cs+ compounds react about 60 times as fast as the K+ compounds; the Na+ compounds do not rearrange under the conditions used. The rates depend on the value of n, being maximum when n = 3 in the K+ series and when n = 3 or 4 in the Cs+ series. Chelation of cation by the polyether chain is adduced as the cause of this dependence. Addition of fluorenylpotassium or potassium dodecylbenzenesulfonate greatly reduces the rearrangement rates, suggesting that mixed ion pair aggregation is occurring in these systems. © 1968, American Chemical Society. All rights reserved.