ISSN 0965ꢀ5441, Petroleum Chemistry, 2015, Vol. 55, No. 7, pp. 549–551. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.I. Bykov, O.B. Chernova, B.A. Belyaev, T.A. Butenko, E.Sh. Finkelshtein, 2015, published in Neftekhimiya, 2015, Vol. 55, No. 5, pp. 403–405.
Stereochemical Features of 1,7ꢀOctadiene Metathesis
on the MoCl5/SiO2–Me4Sn Catalytic System
V. I. Bykova, O. B. Chernovab, B. A. Belyaeva, T. A. Butenkoa, and E. Sh. Finkelshteina
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
bGubkin Russian State University of Oil and Gas, Moscow, 119991 Russia
eꢀmail: bykov@ips.ac.ru
Received November 19, 2014
Abstract—It has been established that the metathesis reaction of 1,7ꢀoctadiene (OD) proceeds smoothly by
two pathways in the direction of the formation of the product of the chain growth, 1,7,13ꢀtetradecatriene, and
intramolecular cyclization into cyclohexene. It has been shown that, at the low (9%) conversion of OD, the
content of cyclohexene is 72%, while that of 1,7,13ꢀtetradecatriene is 28%. As the reaction proceeds, the conꢀ
tent of cyclohexene increases and becomes 97% at the conversion of 99%, i.e., almost all 1,7,13ꢀtetradecatriꢀ
ene formed cyclizes into cyclohexene. At relatively low conversions of OD (9–55%), the stereoꢀcomposition
of 1,7,13ꢀtetradecatriene does not differ from the stereoꢀcomposition of the products of the homometathesis
and cometathesis of the linear structures (
decreases sharply from 8.0 to 0.9% with the increase in the conversion. This is explained by a higher proneness
of the ꢀstereoisomer to the cyclization.
Z/E=(25⎯18)/(75⎯82)). The content of 1,Zꢀ7,13ꢀtetradecatriene
Z
Keywords: olefin metathesis, heterogeneous catalysis, stereochemistry, 1,7ꢀoctadiene
DOI: 10.1134/S096554411506002X
INTRODUCTION
in the form of the mixtures of cisꢀ and transꢀstereoisoꢀ
mers of a certain composition, which is why the study
of the stereochemical regularities of the metathesis of
olefins is of both practical and theoretical interest.
The catalytic metathesis of olefins is one of the
most interesting and promising reactions for modern
petroleum chemistry and fine organic synthesis. This
reaction possesses a high synthetic and technological
potential and several industrial processes have been
implemented on its basis [1]. In 1964, the employees
of Phillips Petroleum Company Banks & Bailey
obtained ethylene and buteneꢀ2 with high selectivity
while passing propylene over Мo(CO)6/Al2O3 under
It was shown by us earlier that, during the cometꢀ
athesis of cyclopentene (CP) with
α
ꢀolefins, the conꢀ
tent of the ꢀisomers of 1, ꢀdienes was lower when
Z
Δ
compared to cyclooctene (CO), cycloheptene (CH),
and cyclononene (CN) across the range of conversions
of CP. This is explained by the fact that, in the case of
CP, the reverse reaction of cyclization of the products
of the cometathesis into initial CP proceeds to a signifꢀ
icant extent and the equilibrium conversion does not
exceed 77%. The reverse reaction proceeds to a much
smaller extent in the case of CH. In this case, the equiꢀ
librium conversion is 94%, while there is almost no
reverse reaction of metathesis cyclization in the case of
CO and CN and the equilibrium conversions reach the
values of 99% and above. In order to confirm the fact
that the reverse reaction of metathesis cyclization of
linear olefins into cycloolefin affects the stereoꢀcomꢀ
position, the stereochemical features of the metathesis
of 1,7ꢀoctadiene (OD) were studied in this work.
mild conditions (150°C) [2]. Later, the industrial Triꢀ
olefin Process was implemented on the basis of this
reaction [1]. The Nobel Prize in Chemistry 2005 was
awarded for the development of the metathesis
approach in organic synthesis.
Particular interest is associated with the use of the
metathesis for the synthesis of biologically active natꢀ
ural compounds. At the Topchiev Institute of Petroꢀ
chemical Synthesis, Russian Academy of Sciences, a
new flexible fewꢀstage strategy for the synthesis of a
wide range of pheromones (environmentally friendly
insecticides) and other natural compounds on the
basis of the cometathesis of the petrochemical feedꢀ
stock ( ꢀolefins, cyclic olefins, cyclooctadiene, ethylꢀ
α
ene) [3–5] and heterogeneous catalytic systems on the
basis of molybdenum halides developed by us was proꢀ
posed [6–8].
EXPERIMENTAL
The metathesis of OD was carried out in a thermoꢀ
The sex pheromones of the insects of the Lepiꢀ stated glass reactor with a magnetic stirrer equipped
doptera order are longꢀchain unsaturated compounds with a dropping funnel, reflux condenser, and gas
549
Bykov
