Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 9, pp. 1560−1566.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.S. Grisha, A.V. de Vekki, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 9, pp. 1510−1516.
AND INDUSTRIAL ORGANIC CHEMISTRY
Positional and Geometric Isomerization
of Diacetoxy Derivatives of 1-Phenyl-1(2)-octenes
A. S. Grisha and A. V. de Vekki
All-Russia Research Institute of Petrochemical Processes, St. Petersburg, Russia
Received June 3, 2011
Abstract—Isomerization of 1,2-, 3,4-, and 1,4-diacetoxy derivatives of 1-phenyl-1(2)-octenes in the presence of
Sb/C and/or RhBi
/C as catalysts was studied. The kinetic and thermodynamic characteristics of the reaction
Acetoxylation of octa-1,3-dienylbenzene yields
a mixture of various positional isomers of 1-phenyloctene
Furthermore, each positional isomer I–III can exist
in the form of geometric (E and Z) isomers.
The previous data [1, 2] suggest that, in the presence
of catalysts of oxidative cross coupling and acetoxylation,
, the acetoxy derivatives of 1-phenyloctene
undergo mutual isomerization. This reaction is of both
theoretical and practical interest. Knowledge of the isom-
erization features will allow control of the isomerization
routes, so as to obtain one or several desirable isomers as
major products. Understanding of the mechanism of such
reactions is important, because in a few reported cases [2, 3]
the pattern differs essentially from classical interpretation
of hydrocarbon isomerization processes (see the scheme).
It is known  that addition of various groups to
conjugated dienes occurs at 1,2- and 1,4-positions of
substrate molecules, but in the latter case the derivatives
formed are more stable thermodynamically. At the same
time, 1,2-substituted derivatives are formed at a higher
rate. That is, such reactions are controlled by both ther-
modynamic and kinetic factors. In acetoxylation, this
results in formation of an equilibrium equimolar mixture
of positional isomers . In turn, the distribution of the
geometric isomers is mainly controlled by kinetic factors: