Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 7, pp. 1201−1206.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.S. Grisha, A.V. de Vekki, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 7, pp. 1129−1134.
AND INDUSTRIAL ORGANIC CHEMISTRY
Catalytic Oxidative Acetoxylation
A. S. Grisha and A. V. de Vekki
All-Russia Research Institute for Petrochemical Processes, St. Petersburg, Russia
Received May 12, 2011
Abstract—Acetoxylation of octa-1,3-dienylbenzene in glacial acetic acid in the presence of catalysts with
intermetallic phases based on Pd and Rh and Group IIIA–VIA elements was studied. The relationship between
the total selectivity of the reaction with respect to diacetoxy derivatives and the Aller–Rochow electronegativity
of second modifying elements was examined. The most efﬁ cient catalytic systems were determined.
Acetoxylation of octa-1,3-dienylbenzene, the
product of cross-combination of styrene and 1-hexene,
is of practical interest because the diacetoxy derivatives
formed can be converted into other functional
derivatives that can be used in manufacture of some
kinds of thermally stable and frost-resistant elastomers
and in syntheses of biologically active preparations.
This reaction has not been studied as applied to
alkylidene-aromatic compounds primarily because of
the poor selectivity of the process in the presence of
homogeneous catalysts limited to palladium complexes
As can be seen in the above scheme, the main
reaction products are 1,2- (I) and (II) and, to a lesser
extent, 1,4-substituted (III) derivatives (irrespective
of the chosen type of a catalyst) . In addition, Z-
and E-isomers are present in the reaction zone. The
relative amounts of these conﬁ gurational isomers are
determined by the nature of a platinum-group atom in
the catalytic formulation: Pd (Pt) directs the reaction
toward formation of mostly the E-isomer, and Rh (Ir),
mostly the Z-isomer (Table 1).
To explain the formation of nearly equimolar
amounts of isomers I and II, we used the CNDO/2
method to perform a quantum-mechanical calculation
of the charge distribution in the molecules of octa-
1,3-dienylbenzene and, for comparison, 2,4-nonadiene
(an analog of octa-1,3-dienylbenzene in which the
phenyl group is substituted with a methyl group) and