Notes. The Relative Stabilities of cis and trans Isomers. X. The 1,3-Cyclohexanedicarboxylate Esters.

Conformational analysis. CV. Syn-diaxial methyl carboethoxy interaction

“…To the best of our knowledge, only one other equilibration has been attempted using 1,3-diesters, i.e., the basic equilibration of diethyl 1,3-cyclohexanedicarboxylate. 12 In that case the entropy change was assumed to be just the entropy of mixing of the dl pair in the trans isomer.…”

Conformational Analysis in Mobile Cyclohexane Systems

“…This, in essence, entails the assumption that the prccess (IOa) + (IOb), but for the equilibrium (optically active trans) + (meso-cis) daes, in fact, have the same equilibrium constant as ( l a ) F' (lb). These principles were applied to the equilibration of the diethyl hexahydroisophthalates ( l o ) , [50] for which equilibrium at 78 "C corresponds to 71 % cisand 29 7; trans-isomer, -AG being 0.63 kcal/mole. From this, applying the RT In 2 correction, -AG 3C0,C2Hs is 1.1 1 kcal/mole.…”

Kinetics of epimerization of dimethyl cis- and trans-1,2-cycloalkanedicarboxylates

“…However, reactions such as the Claisen-type condensation do involve anions which are at least partially stabilized by ester carbonyl participation in enolization.14 Base-catalyzed equilibrations of cyclic esters yield an equilibrium mixture which reflects the relative stabilities of the cis and trans isomers. [15][16][17][18][19] In order to examine the combined effects of ring size, conformation, steric factors, and chemical reactivity, we initiated a combined kinetic and equilibration study of several dimethyl 1,2-cycloalkanedicarboxy lates. This approach was chosen for several reasons:…”