When the "migrating" substituent is deuterium, the sigmatropic shift is degenerate and essentially equal

No abstract

The solvolysis of 6 in 80% ethanol was followed conductometrically: ki = (19.4°) 5.01 X 10-4 sec-1;(25.4°) 1.09 X 10-8 sec-1; (32.9°) 2.38 X 10-8 sec-1; AH* = 20.6 kcal mol-1; AS* = -3.3 eu. Bromide 6 is very reactive in solvolysis. Its rate at 25 °is some 4.4 X 104 times faster than that of the anti epimer 74 (ki = 2.4 X 10-8 sec-1 by Volhard titration) and nearly three times faster than that of /-butyl bromide (ki = 3.85 X 10-4sec-1).6The solvolysis product from 6 in 70% dioxane containing 1.2 equiv of 2,6-lutidine was solely the syn-7alcohol 8 (mp 92.5-94°). The alcohol and ether products in 80 % ethanol were also only syn-7 derivatives.6 Similarly, the anti epimer 7 afforded only the izn//-7-alcohol 97 in aqueous dioxane. h2o O / dioxane Á. h2o j dioxane (4) J.

ed from the thesis submitted by Jack Bernstein to the Graduate School of Cornell University in partial fulfillment of the requirements for the Ph.D. degree, June, 1941; and from the thesis submitted by Jay S. Roth in partial fulfillment of the requirements for the

No abstract