Stereochemical features of 1,7-octadiene metathesis on the MoCl5/SiO2-Me4Sn catalytic system

Article abstract of DOI:10.1134/S096554411506002X

It has been established that the metathesis reaction of 1,7-octadiene (OD) proceeds smoothly by two pathways in the direction of the formation of the product of the chain growth, 1,7,13-tetradecatriene, 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 1,7,13-tetradecatriene is 28%. As the reaction proceeds, the content of cyclohexene increases and becomes 97% at the conversion of 99%, i.e., almost all 1,7,13-tetradecatriene formed cyclizes into cyclohexene. At relatively low conversions of OD (9-55%), the stereo-composition of 1,7,13-tetradecatriene does not differ from the stereo-composition of the products of the homometathesis and cometathesis of the linear structures (Z/E=(25-18)/(75-82)). The content of 1,Z-7,13-tetradecatriene decreases sharply from 8.0 to 0.9% with the increase in the conversion. This is explained by a higher proneness of the Z-stereoisomer to the cyclization.

Full text of DOI:10.1134/S096554411506002X

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

550
BYKOV et al.
Dependence of metathesis chemoselectivity and stereoselectivity on the conversion of octadiene
Conversion
Cyclohexene content
1,7,13ꢀTetradecatriene
content C14 : 3, wt %
1,Zꢀ7,13ꢀTetradecatriene
content Zꢀ7 C14 : 3, wt %
of 1,7ꢀoctadiene
C(6 : 1), wt
C8 : 2, wt %
9
21
55
90
99
72
73
79
91
97
28
27
21
9
25
22
18
8
3
0.9
burette for the measurement of the volume of ethylene The mass spectra (EI) were registered on a Finigan
evolving during the reaction. A weighed amount of the MAT 95 XL 70 instrument (70 eV). All the reactions,
catalyst was loaded into the reactor and a certain as well as the preparation of the initial compounds and
amount of OD and cocatalyst (tetramethyltin) was solvents, were performed in the atmosphere of extraꢀ
LiAlH
4 as the drying agent.
loaded into the dropping funnel. The reaction was carꢀ pureꢀgrade argon using
ried out with the continuous removal of forming ethylꢀ
ene.
The monitoring of the purity of the initial reagents
as well as of the reaction progress was performed by
RESULTS AND DISCUSSION
The features of the stereochemistry of the metatheꢀ
means of gas–liquid chromatography (GLC) using an sis of OD in the presence of the MoCl5/SiO2–Me4Sn
LKhMꢀ8MD chromatograph equipped with a flame heterogeneous catalytic system have been studied. It
×
0.2
mm quartz capꢀ has been shown that the reaction proceeds according
ionization detector (FID) (50 m
illary column), the stationary phases were SKTFP or to the Scheme by two pathways in the direction of the
Н
SEꢀ30 and the carrier gas was 2. The analyses were formation of the products of the chain growth, Zꢀ and
performed under the conditions of linear temperature ꢀstereoisomers of 1,7,13ꢀtetradecatriene, and in the
. The H direction of the formation of cyclohexene due to the
and 13C NMR spectra were recorded on a Bruker intramolecular cyclization of initial OD and products
СDСl Ме Si
E
1
12 210°C
°
programming ( C/min) from 35 to
MSLꢀ300 spectrometer in relative to
.
of metathesis:
4
3
cyclohexene
+ CH2=CH2
1,Zꢀ7,13ꢀtetradecatriene
1,7ꢀoctadiene
+ CH2=CH2
1,Eꢀ7,13ꢀtetradecatriene
Cyclohexene is a very thermodynamically stable products of homometathesis and cometathesis of the
structure; therefore, from the two directions, the proꢀ linear structures. With the increase in the conversion,
cess of closure into cyclohexene occurs predomiꢀ the content of 1,Zꢀ7,13ꢀtetradecatriene drops sharply.
nantly.
It is seen from the table that the content of cycloꢀ
hexene is 72% and that of tetradecatriene is 28% at the
conversion of OD of 9%. As the reaction proceeds, the tions of the stereoisomers of the linear structures posꢀ
content of cyclohexene increases and becomes 97% at sessing one internal double bond are 84 : 16. In
This is explained by the higher proneness of the
Zꢀsteꢀ
reoisomer to the cyclization.
The thermodynamically equilibrium concentraꢀ
E
:
Z
≈
the conversion of 99%, i.e., almost all tetradecatriene case of the stereoisomers of 1,7,13ꢀtetradecatriene,
formed cyclizes into cyclohexene. At low conversions this value differs substantially. Thus, when the converꢀ
of OD (9–55%), the stereoꢀcomposition of 1,7,13ꢀ sion of OD is 90%, the content of Zꢀtetradecatriene is
tetradecatriene, which has two possible stereoisomers, 8%, while when the conversion of OD is 99%, less than
does not differ from the stereoꢀcomposition of the 1%. Apparently, such a difference is explained by the
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STEREOCHEMICAL FEATURES OF 1,7ꢀOCTADIENE METATHESIS
551
specific features of the process (see the reaction
scheme), in which there is a reaction of selective
cyclization of the ꢀisomer into cyclohexene along
with the equilibrium between the isomers.
Thus, the results obtained for the metathesis of OD
confirm the assumption about the possibility of the
REFERENCES
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3, 170 (1964).
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ACKNOWLEDGMENTS
5. V. I. Bykov, T. A. Butenko, L. V. Kelbakiani, and
E. Sh. Finkel’shtein, Dokl. Akad. Nauk 349 (2), 198
(1996).
This work was supported by the Russian Foundaꢀ
tion for Basic Research, project no. 14ꢀ03ꢀ00455, and
the, Russian Academy of Sciences Chemistry and
Material Sciences Division (Stereochemistry, Kinetꢀ
ics, and Mechanisms of Formation, Deactivation, and
Reactivation of the Active Centers of MoꢀContaining
Catalysts for the Metathesis of Olefins project perꢀ
formed under the fundamental research program Theꢀ
oretical and Experimental Study of the Nature of
Chemical Bond and Mechanisms of Fundamental
Chemical Reactions and Processes OKhNMꢀ1; the
coordinator is academician O.M. Nefedov).
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Translated by E. Boltukhina
PETROLEUM CHEMISTRY Vol. 55
No. 7
2015