Cyclododecene cometathesis with hexene-1 on the MoCl5/SiO2-Me4Sn catalytic system

Article abstract of DOI:10.1134/S0965544115060031

The stereochemistry of the cometathesis of cyclododecene (CDD) with hexene-1 in the presence of the MoCl₅/SiO₂-Me₄Sn heterogeneous catalytic system has been studied. It has been established that CDD is the mixture of cis- (Z) and trans- (E) stereoisomers with the ratio of 30/70, respectively. It has been shown that the reactivity of the E-stereoisomer of CDD in the reaction of cometathesis is higher when compared to the Z-stereoisomer. Thus, when the conversion of CDD is 92%, the ratio E/Z = 6: 94, i.e., the amount of the E-stereoisomer decreases from 70 to 7%, while the amount of the Z-stereoisomer increases from 30 to 93%, respectively.

Full text of DOI:10.1134/S0965544115060031

ISSN 0965ꢀ5441, Petroleum Chemistry, 2016, Vol. 56, No. 1, pp. 62–64. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.I. Bykov, B.A. Belyaev, T.A. Butenko, E.Sh. Finkel’shtein, 2016, published in Neftekhimiya, 2016, Vol. 56, No. 1, pp. 70–72.
Cyclododecene Cometathesis with Hexeneꢀ1
on the MoCl5/SiO2–Me4Sn Catalytic System
V. I. Bykov, B. A. Belyaev, T. A. Butenko, and E. Sh. Finkel’shtein
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
eꢀmail: bykov@ips.ac.ru
Received November 17, 2014
Abstract—The stereochemistry of the cometathesis of cyclododecene (CDD) with hexeneꢀ1 in the presence
of the MoCl5/SiO2– Me4Sn heterogeneous catalytic system has been studied. It has been established that
CDD is the mixture of cisꢀ (
shown that the reactivity of the
pared to the ꢀstereoisomer. Thus, when the conversion of CDD is 92%, the ratio
amount of the ꢀstereoisomer decreases from 70 to 7%, while the amount of the ꢀstereoisomer increases
Z
) and transꢀ (
ꢀstereoisomer of CDD in the reaction of cometathesis is higher when comꢀ
= 6 : 94, i.e., the
E) stereoisomers with the ratio of 30/70, respectively. It has been
E
Z
E/Z
E
Z
from 30 to 93%, respectively.
Keywords: stereochemistry, cometathesis, cyclododecene, heterogeneous catalysis
DOI: 10.1134/S0965544115060031
INTRODUCTION
weighed amount of the catalyst and 1ꢀhexene was
loaded into the reactor, while a certain amount of
CDD and cocatalyst (tetramethyltin) was loaded into
the dropping funnel. The reaction was carried out with
the continuous removal of forming ethylene. The
monitoring of the purity of the initial reagents as well
as of the reaction progress was performed by means of
gas–liquid chromatography (GLC) using an LKhMꢀ
8MD chromatograph equipped with a flame ionizaꢀ
Cyclododecene (CDD) is one of the most available
petrochemical cyclic olefins. CDD is produced indusꢀ
trially via the partial hydrogenation of cyclododecatriꢀ
ene, which is formed with high selectivity during the
cyclotrimerization of butadiene in the presence of Niꢀ
containing catalysts [1].
Earlier, the chemoselectivity and stereoselectivity
of the cometathesis of C5 and C7–C10 cyclic olefins
with
α
ꢀolefins in the presence of the MoCl5/SiO2–
×
0.2
mm quartz capillary
tion detector (FID) (50 m
Me4Sn heterogeneous catalytic system was studied by
us [2–4] and a new fewꢀstage strategy for the synthesis
of a wide range of pheromones and other natural comꢀ
pounds was developed on this basis [5–7].
column), the stationary phases were SKTFP or SEꢀ30
and the carrier gas was H2. The analyses were perꢀ
formed under the conditions of linear temperature
1
12
°
220
°
C
programming ( C/min) from 35 to
. The H
The cometathesis of CDD with 1ꢀhexene is interꢀ
esting from both practical and theoretical points of
view because 1,13ꢀoctadecadiene, from which it is
easy to obtain 1,13ꢀoctadecenol, as well as the correꢀ
sponding aldehyde and acetate, which are the compoꢀ
nents of the pheromones of the pest insects of the Lepꢀ
idoptera order, is one of the target products.
and 13C NMR spectra were recorded on a Bruker
СDСl3 Ме4Si
MSLꢀ300 spectrometer in
relative to
The mass spectra (EI) were registered on a Finnigan
MAT 95 XL 70 instrument (70 eV). All the reactions,
as well as the preparation of the initial compounds and
solvents, were performed in the atmosphere of extraꢀ
LiAlH
4 as the drying agent.
pureꢀgrade argon using
EXPERIMENTAL
RESULTS AND DISCUSSION
The cometathesis of CDD with 1ꢀhexene was carꢀ
ried out in a thermostated glass reactor with a magꢀ
netic stirrer equipped with a dropping funnel, reflux
condenser, and gas burette for the measurement of the
The cometathesis of CDD with hexeneꢀ1 proceeds
according to the scheme that is general for cyclic oleꢀ
volume of ethylene evolving during the reaction. A fins
62

CYCLODODECENE COMETATHESIS WITH HEXENEꢀ1
63
1,13ꢀtetradecadiene
C14 : 2
( )10
( )3
Mo
( )3
Mo
Mo
Mo
( )10
( )3
( )3
1,13ꢀoctadecadiene
C18 : 2
+
( )3
( )3
Mo
Mo
Mo
Mo
( )10
( )3
deceneꢀ5
( )3
( )3
( )3
5,17ꢀdocosadiene
C22 : 2
Scheme.
The chain growth reaction proceeds with the parꢀ the increase in the conversion of CDD, the content of
ticipation of CDD, while the chain termination, with
the participation of hexeneꢀ1. The reaction of
homometathesis of hexeneꢀ1 resulting in deceneꢀ5
and ethylene competes with these processes. Accordꢀ
ing to the data of the 1H NMR (Fig. 1), initial CDD is
a mixture of transꢀ and cisꢀstereoisomers. The ratio of
1,13ꢀoctadecadiene drops from 71 to 55%, while the
content of 1,13ꢀtetradecadiene changes slightly. The
reaction proceeds quite quickly and the conversion
reaches 75% within 30 min (Fig. 2).
It is interesting that reactivity of the
mer of CDD in the reaction of cometathesis is higher
when compared to the ꢀstereoisomer. Thus, the iniꢀ
tial ratio of the stereoisomers of CDD is = 70 : 30,
while it is = 6 : 94 when the conversion of CDD is
92%. The content of the ꢀstereoisomer decreases
from 70 to 7%, while, on the contrary, the content of
the ꢀstereoisomer increases from 30 to 93%.
Eꢀstereoisoꢀ
the isomers of CDD
integral intensities of the resolved multiplets of the
trans )ꢀprotons (the chemical shift of 5.36–
5.4 ppm) and cis )ꢀprotons (the chemical shift of
E/Z = 70/30 was estimated by the
Z
(
E
E/Z
(
Z
E/Z
5.3–5.35 ppm). This stereoꢀcomposition is in agreeꢀ
ment with the data of the capillary GLC.
The composition of the main products of the
cometathesis is shown in the table. It is seen that, with
E
Z
70
60
50
40
30
20
10
70%
30%
0
5
10
15
20
25
30
Time, min
5.44
5.40
5.36
5.32
5.28
1
Fig. 1. A fragment of the H NMR spectrum of initial
Fig. 2. Cyclododecene conversion as a function of the
reaction time.
cyclododecene.
PETROLEUM CHEMISTRY Vol. 56
No. 1
2016

64
BYKOV et al.
Content of the cometathesis product at various conversions
of cyclododecene
fins project performed under the fundamental
research program Theoretical and Experimental
Study of the Nature of Chemical Bond and Mechaꢀ
nisms of Fundamental Chemical Reactions and Proꢀ
cesses OKhNMꢀ1; the coordinator is academician
O.M. Nefedov).
Amounts of cometathesis products, %
Conversion
of CDD, %
C18 : 2
C14 : 2
C22 : 2 and others
40
58
81
92
71
66
58
55
14
14
14
13
15
20
28
32
REFERENCES
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Chem. 46, 110 (2006).
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As for the stereoꢀcomposition of 1,13ꢀoctadecadiꢀ
ene, the thermodynamically equilibrium stereoꢀcomꢀ
position
5 min.
Z/E = 16 : 84 is already observed within
Therefore, it was established that CDD, as well as
ꢀcyclodecene, does not exhibit any cis )ꢀregulating
E. Sh. Finkel’shtein, Kinet. Catal. 53, 353 (2012).
Z
(Z
5. V. I. Bykov, D. V. Redkin, and E. Sh. Finkelshtein,
NATO Science Series II, vol. 56: Ring Opening Metatheꢀ
sis Polymerisation and Related Chemistry, Ed. by
E. Khosravi and T. SzymanskaꢀBuzar (Kluwer Acaꢀ
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action typical for cyclopentene, cycloheptene,
cyclooctene, and cyclononene.
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (project no. 14ꢀ03ꢀ
00455) and by the Branch of Chemistry and Material
Sciences, Russian Academy of Sciences (the Stereꢀ
ochemistry, Kinetics, and Mechanisms of Formation,
Deactivation, and Reactivation of the Active Centers
of MoꢀContaining Catalysts for the Metathesis of Oleꢀ
7. V. I. Bykov and E. Sh. Finkelshtein, J. Mol. Catal. 133
,
17 (1998).
Translated by E. Boltukhina
PETROLEUM CHEMISTRY Vol. 56
No. 1
2016