Selective dimerization of higher cycloolefins in the presence of micro- and micromesoporous zeolite catalysts

Article abstract of DOI:10.1007/s11172-013-0061-x

Selective synthesis of dimers of cycloolefins C₆-C₈ was carried out in the presence of highly dispersed zeolite catalysts HY, HBeta, and HZSM-12 and granulated zeolite HY-WB, which differ in acidic properties and pore structure. The high selectivity of microporous zeolite HZSM-12 in cyclohexene dimerization (100%) and micromesoporous zeolite HY-WB in cycloheptene and cyclooctene dimerization (90-95%) was established.

Full text of DOI:10.1007/s11172-013-0061-x

Russian Chemical Bulletin, International Edition, Vol. 62, No. 2, pp. 444—449, February, 2013
444
Selective dimerization of higher cycloolefins in the presence
of microꢀ and micromesoporous zeolite catalysts*
N. G. Grigor´eva, S. V. Bubennov, A. N. Khazipova, L. M. Khalilov, and B. I. Kutepov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 231 2750. Еꢀmail: nggꢀink@mail.ru
Selective synthesis of dimers of cycloolefins С6—С8 was carried out in the presence of
highly dispersed zeolite catalysts НY, НBeta, and НZSMꢀ12 and granulated zeolite HYꢀWB,
which differ in acidic properties and pore structure. The high selectivity of microporous zeolite
НZSMꢀ12 in cyclohexene dimerization (100%) and micromesoporous zeolite HYꢀWB in cycloꢀ
heptene and cyclooctene dimerization (90—95%) was established.
Key words: cycloolefins, cyclohexene, cycloheptene, cyclooctene, dimerization, microꢀ
and micromesoporous zeolites.
Cyclic olefins are traditional and accessible raw mateꢀ
Cyclohexene is transformed into cyclohexane, 1ꢀ, 2ꢀ,
rials for organic and petrochemical synthesis. Cyclene
oligomers find diverse practical use as solvents, plasticizꢀ
ers,1 and components of drugs and cosmetic materials.2—4
Oligomerization of the most studied compound, cycloꢀ
hexene, in the presence of homogeneous acidic catalysts
P2O5, BF3, H2SO4, HF, and AlCl3 (see Refs 5—11) afꢀ
fords a mixture of diꢀ, triꢀ, tetraꢀ, and higherꢀmolecularꢀ
weight oligomers. The dimeric fraction, obtained by cycloꢀ
hexene oligomerization in the presence of H2SO4, conꢀ
tains 2ꢀ and 3ꢀmethylcyclopentylcyclohexanes along with
1ꢀ(1´ꢀcyclohexenyl)cyclohexane (1a).8,11 This indicates that
sulfuric acid induces the isomerization of one of the rings.
In the presence of the metathesis catalysts, cyclohexꢀ
ene can transform itself into cyclic unsaturated comꢀ
pounds, viz., dimers and trimers (catalyst WCl6), or into
saturated and aromatic hydrocarbons (catalytic system
WCl6 + ROH + EtAlCl2, where R = Et, Ph, PhCh2).12
It was established13,14 by the study of cyclohexene
transformations in the presence of the heterogeneous catꢀ
alysts that chromium, zirconium, and vanadium oxides,
manganese protoxide, and other catalysts exhibit different
activities in cyclohexene dehydrogenation to benzene.
Such catalysts as SiO2, Al2O3, BeO; mixed silica, alumiꢀ
na, thorium, or zirconia; or aluminosilicates favor the
isomerization of the sixꢀmembred ring into the fiveꢀmemꢀ
bered ring.13—17 In addition to cyclohexene isomerizaꢀ
tion, polymerization and hydrogen redistribution occur.
In this process, hydrogen donors are intermediate comꢀ
pounds leading to coking and hydrocarbons of the polyꢀ
mer fraction.
and 3ꢀmethylcyclopentenes, methylcyclopentane, and
dimers on granulated zeolite Y modified by rareꢀearth metal
(REM) cations.18 The yield of dimers is independent of
the concentration of the REM cation, whereas the yield of
the hydrogen transfer products (cyclohexane and methylꢀ
cyclopentane) increases with an increase in the REM conꢀ
tent from 2.1 to 13.0%. The hydrogen transfer reaction is
favored by the use of dealuminated Y zeolites with the
molar ratio SiO2/Al2O3 (M) > 30.19
The Mobil Oil Corporation patented the method for
the dimerization of cycloolefins С5—С12 on zeolites ZSMꢀ12
(M > 83) in an autoclave at 75—400 С.20 It was shown that
the olefin conversion decreases and the selectivity of dimer
formation increases with an increase in the ring size.
The synthesis of dimers of other higher cyclenes is
poorly studied. The preparations of the cyclooctene dimer,
viz., 1ꢀ(1´ꢀcyclooctenyl)cyclooctane (2a), in the presence
of sulfuric acid21 and of a mixture of two cyclooctene
dimers 2a,b in the presence of nickel acetylacetonate22
(Scheme 1) were described.
Scheme 1
* Dedicated to the Academician of the Russian Academy of
Sciences S. M. Aldoshin on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0445—0450, February, 2013.
1066ꢀ5285/13/6202ꢀ0444 © 2013 Springer Science+Business Media, Inc.

Selective dimerization of cycloolefins
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
445
Table 1. Physicochemical characteristics of the zeolite catalysts
Catalyst
Degree
of crystallinity
(arb.%)
M*
Equilibrium adsorption
capacity at 20 C and
P/Ps = 0.8 for vapors of
Acidic properties
Tmax/С
Concentration of acid sites
/mol g–1
I
II
water
benzene
СI
CII
СI+II
НY
НВeta
НZSMꢀ12
HYꢀWB
100
100
100
85
6.0
18.0
34.0
7.6
0.30
0.26
0.15
0.23
0.30
0.32
0.16
0.27
250
280
300
250
400
450
450
420
622
530
409
515
560
340
260
410
1182
870
669
925
* Molar ratio SiO2/Al2O3.
The purpose of the present work is to develop selective
catalytic methods for synthesis of dimers of cyclohexene,
cycloheptene, and cyclooctene in the presence of zeolite
catalysts with microꢀ (НY, НBeta, НZSMꢀ12) microꢀ
mesoporous (HYꢀWB) structures.
gree of crystallinity close to 100%. For the sample of zeoꢀ
lite YꢀWB, the relative crystallinity is ~85%.
The spectra of zeolite acidity obtained by temperatureꢀ
programmed desorption (TPD) of ammonia contain two
peaks characterizing weak acid sites with the temperature
maximum (Tmax) at 100—350 С and strong acid sites
with Tmax in the range >350 С. The total concentration of
acid sites maximizes in zeolite НY and decreases on
going to zeolite НYꢀWB and further to highꢀsilica zeolites
HBeta and НZSMꢀ12. The strength of acid sites as estiꢀ
mated by the shift of the temperature maximum of the
peak in the TPD spectrum, decreases in the following
order: zeolite НBeta = HZSMꢀ12 > НYꢀWB > НY.
Dimerization of cyclic olefins. The composition of the
oligomerization products of cycloolefins depends on the
chemical structure of the monomer, properties of the zeoꢀ
lite catalysts, and reaction conditions.
In the presence of the zeolite catalysts, cyclohexene is
mainly transformed into dimers (87.9—100%), among
which 1ꢀ(1´ꢀcyclohexenyl)cyclohexane (1а) prevails
(Scheme 2). In addition to compound 1a, other cyclohexꢀ
ene dimers are also observed: unsaturated 1ꢀ(2´ꢀcyclohexꢀ
enyl)ꢀ (1b) and 1ꢀ(3´ꢀcyclohexenyl)cyclohexane (1c) and
saturated bicyclohexane (1d).
Results and Discussion
Characterization of zeolite catalysts. Zeolite catalysts
of various structural types with different acidic properties
and porous structures were used. Zeolites НY, НBeta, and
HZSMꢀ12 have a microporous structure, whereas in zeoꢀ
lite НYꢀWB (without binders) the microporous structure
of individual crystals combines with mesoꢀ and macropores
formed between aggregates of zeolite crystals.23,24 Accordꢀ
ing to the data of mercury porosimetry, the specific surꢀ
face of mesoꢀ and macropores of this zeolite is 8.5 m2 g–1
,
and their volume is 0.32 cm3 g–1. Thus, mesoꢀ and
macropores account for about half a volume of the porous
structure of the granules thus providing efficient diffusion
of molecules of reacting substances to the catalytically
active sites.
The physicochemical properties of the studied zeolites
are given in Table 1. According to the Xꢀray diffraction
data and adsorption characteristics of the zeolites, all samꢀ
ples of microporous zeolites are characterized by the deꢀ
At temperatures higher than 150 С, oligomerization
is complicated by destructive processes leading to methylꢀ
cyclopentenes, methylpentenes, and hexadienes. In the
Scheme 2

446
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
Grigor´eva et al.
Scheme 3
presence of the studied zeolites, these compounds, as the
starting olefins, undergo oligomerization to form a comꢀ
plex mixture of products.
two catalysts and lower steric hindrances for transport of
the monomers and dimers in the zeolite pores. Actually,
the pore size in zeolite HY is 0.75 nm, in zeolite HBeta it
is 0.64—0.75 nm, and the pores of zeolite HZSMꢀ12 are
smaller (0.55—0.67 nm).26
Along with cyclohexene dimers, higherꢀmolecularꢀ
weight oligomers, trimers and tetramers, can be formed
on the zeolite catalysts. According to the data of gas
chromatography coupled with mass spectrometry (GC/MS),
trimers include, together with compounds with the moꢀ
lecular weight (MW) 246, hydrocarbons with MW 242
and 244, formation of which is possible due to the hydride
ion transfer reactions (Scheme 3). The occurence of hyꢀ
drogen redistribution reaction as indicated by the presence
of saturated hydrocarbons (1d) and aromatic compounds
in the reaction mixture is characteristic of olefin converꢀ
sion on the acid zeolites.25
A comparison of the catalytic properties of zeolites of
various structural types (Table 2) shows that the most
active catalyst is zeolite HBeta, in the presence of which the
conversion of cyclohexene attains 65—74% (150—200 С).
The higher activity in the reaction of zeolites HBeta and
HY compared to that of zeolite HZSMꢀ12 is due, most
likely, to the high concentration of acid sites in the former
Dimer 1a is most selectively (up to 100%) formed on
the catalyst HZSMꢀ12 at 100—120 С (10—20 wt.% of
the catalyst). The selectivity of formation of dimer 1a is
lower (76—82 and 94—96%, respectively) on zeolites HY
and HBeta under the same conditions, because the dimerꢀ
ization products also contain compounds 1b—d. The temꢀ
perature increase to 180—200 С leads to a more complex
composition of the dimeric fraction, since it contains,
along with dimers 1a—d, hydrocarbons obtained by the
diꢀ and codimerization of products of cyclohexene deꢀ
struction. The broadest fraction of dimers was obtained on
zeolite HY, in the presence of which isomerization and
destruction of cyclohexene and hydrogen transfer occur
most intensely. A possible explanation is the heterogeneity
of the acid sites of HY zeolite.27
The total yield of the dimers decreases on zeolites HY
and HBeta with the temperature increase to 200 С, but
Table 2. Oligomerization of cyclohexene in the presence of the zeolyte catalysts (nonane, initial monomer
concentration in the solvent [M0] = 1.2 mol L–1, 5 h)
Catalyst
Ccat
(wt.%)
T
/С
X
(%)
Oligomers (%)
Dimers
1b,c 1d
Trimers Tetraꢀ
mers
1a
Other
HY
20
20
20
120
180
200
20.7
50.0
56.3
75.7
55.1
52.4
10.0
19.9
18.6
6.5
9.1
9.6
14.7
16.7
19.8
13.1
19.1
19.4
—
0.1
0.2
HBeta
10
20
20
20
20
120
100
120
150
200
61.4
47.0
61.7
64.9
74.3
95.8
93.8
89.5
80.1
58.7
12.9
13.0
13.0
13.3
16.4
0.1
—
0.5
1.4
1.3
10.8
11.8
14.4
12.9
11.0
10.4
11.4
12.6
12.3
12.1
—
—
—
—
0.5
HZSMꢀ12
10
20*
20
120
100*
150
180
15.0
40.7
14.5
33.2
100.0
100.0
92.4
—
—
16.7
18.9
—
—
0.9
2.9
—
—
—
—
—
—
—
—
—
—
—
20
85.3
12.9
Note. Here and in Tables 3 and 4, Ccat is the amount of the catalyst and X is conversion.
* The experiment was carried out for 16 h.

Selective dimerization of cycloolefins
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
447
Scheme 4
the amount of higherꢀmolecularꢀweight oligomers, trimers
and tetramers, increases (see Table 2). Only cyclohexene
dimers are formed by cyclohexene oligomerization in the
presence of zeolite HZSMꢀ12.
The results of transformations of cycloheptene and
cyclooctene in the presence of the zeolite catalysts are
given in Tables 3 and 4.
A comparison of the conversion of cycloolefins on diꢀ
verse zeolites shows that zeolite HBeta exhibits the highꢀ
est activity.
Cycloheptene forms dimers on all microporous zeoꢀ
lites, but their composition changes substantially dependꢀ
ing on the reaction conditions. At 40—60 С more than
90% of the dimer composition fall on the fraction of two
compounds, 3a,b, formed in a ratio of ~1 : 1 (Scheme 4).
At 120—180 С cycloheptene undergoes structural and
destructive transformations to form cyclic and alicyclic
compounds, namely, methylcyclohexenes and methylꢀ
cyclohexanes, dimethylcyclopentenes, isoheptenes, etc. As
a result, the number of compounds in the dimeric fraction
increases sharply.
the C atoms of the methylene groups in both cycloheptane
moieties appear as three intense signals at  31.42, 28.88,
and 27.97, which exhibit (in HSQC experiment) direct
С—H bonds with the corresponding protons of the CH2
groups at  2.25, 1.57, and 1.52 (see Experimental).
Cyclooctene isomerization on zeolites HY, HBeta, and
HZSMꢀ12 starts already at 40 С and, hence, the reaction
products contain a large amount of hydrocarbons with the
empirical formula С8H14 and dimers, among which comꢀ
pounds 2a,b predominate (their structure is shown in
Scheme 1).
In the 13С NMR spectrum of dimer 3b, the quaternary
carbon atoms at the double bond arranged between two
cycloheptane rings are characterized by a signal in a low
field at  133.28. Due to high symmetry of the molecule,
Table 3. Transformations of cycloheptene in the presence of the zeolyte catalysts ([M0] = 1.2 mol L–1, 5 h)
Catalyst
Ccat
T/C
Solvent
X
Composition (%)
(wt.%)
(%)
Isomers
Dimers 3a,b
Other products
HY
20
20
20
20
20
20
10
60
120
100
150
100
120
40
—
Undecane
Undecane
Undecane
—
4.2
23.6
48.3
62.1
8.9
3.1
16.8
19.5
12.4
1.8
88.1
39.4
48.5
40.2
54.5
36.1
90.2
8.8
43.8
32.0
47.4
43.7
53.8
—
HBeta
HZSMꢀ12
HYꢀWB
—
—
15.4
55.2
10.1
9.8
Table 4. Transformations of cyclooctene in the presence of the zeolyte catalysts ([M0] = 1.2 mol L–1, 5 h)
Catalyst
Ccat
T/C
Solvent
X
Composition (%)
(wt.%)
(%)
Isomers
Dimers 2a,b
Other products
HY
10
10
20
20
50
100
10
20
10
30
10
60
120
120
40
40
40
120
60
120
180
60
Undecane
Undecane
Undecane
6.2
34.1
40.8
15.2
33.2
40.3
83.2
5.1
58.1
48.8
41.3
38.2
24.1
10.4
35.7
71.8
53.4
56.7
5.9
25.1
20.5
20.6
35.9
44.1
40.8
22.9
14.7
16.1
13.2
94.1
16.8
30.7
35.1
25.9
31.8
48.8
41.4
13.5
30.5
30.1
—
HBeta
—
—
—
—
—
—
—
—
HZSMꢀ12
HYꢀWB
68.2
95.9
50.4

448
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
Grigor´eva et al.
respectively. Zeolites NH4ꢀBeta (M = 18) and NH4ꢀZSMꢀ12
(M = 34), produced at the OAO "Angarskii zavod katalizatorov
i organicheskogo sinteza" (Angarsk Plant of Catalysts and Organic
Synthesis, Angarsk, Russia), were transformed into the H form
by calcination at 540 С. Prior to catalytic tests, the zeolite samples
were subjected to the thermal treatment in air for 4 h at 540 С.
The physicochemical characteristics of the zeolite catalysts
were determined using described procedures.24,30
The content of products 2a,b in the dimers does not
exceed ~60% even at 40—50 С. As the temperature increasꢀ
es, the yield of hydrocarbons obtained by the dimerization
and codimerization of compounds, which are products of
the destructive transformations of cyclooctene, increases.
The yield of dimers maximizes on zeolite HBeta and
decreases on zeolites HY and HZSMꢀ12.
It was shown for cyclooctene transformation in the
presence of zeolite HBeta that the conversion of the monoꢀ
mer and the yield of dimers increased with an increase in
catalyst concentration. This dependence is characteristic
of reactions that occur on the external surface of catalysts.
The data obtained indicate that the possibilities of
dimerization of cycloheptene and cyclooctene in the presꢀ
ence of zeolites with microporous structure are constrained
by the molecularꢀsieve properties of the catalysts. The apꢀ
plication of zeolite HYꢀWB with the combined microꢀ
mesoporous structure in the dimerization of the oleꢀ
fins made it possible to synthesize dimers of cyclohepꢀ
tene (3a,b) and cyclooctene (2a,b) with high selectivity
90—94% (see Tables 3 and 4). The amount of isomerizaꢀ
tion products does not exceed 10%.
Thus, the study of the catalytic properties of the zeolite
catalysts with different acidic properties and characterisꢀ
tics of the porous structure made it possible to develop
selective methods for synthesis of dimers of cycloolefins
С6—С8. It was found that zeolites HY and HBeta with the
maximum concentration of strong acid sites exhibit the
highest activity in cyclohexene dimerization. However,
a high acidity of these catalysts favors the intense occurꢀ
rence of isomerization and destruction reactions, which
finally results in a more complex composition of the reacꢀ
tion products. The major product of cyclohexene isomerꢀ
ization is 1ꢀ(1´ꢀcyclohexenyl)cyclohexane, whose selecꢀ
tivity of formation on zeolite HZSMꢀ12 achieves 100%.
The dimerization of cycloolefins С7—С8 with retenꢀ
tion of the ring structure on the microporous zeolite cataꢀ
lysts is impeded because steric hindrances appear when
the bulky molecules of monomers and dimers move inside
the catalyst channels. The dimers of cycloheptene (3a,b)
and cyclooctene (2a,b) were synthesized with a selectivity
of 90—94% in the presence of zeolite HYꢀWB with the
micromesoporous structure.
The conversion of the initial monomers and the composition
of the reaction products were determined by GLC and HPLC as
described previously.31
Dimers of compounds 1—3 were identified using GL/MS
and 1D and 2D NMR spectroscopy. Highꢀresolution mass specꢀ
tra were recorded on a Fisons instrument with chromatograph
equipped with a DBꢀ560 quartz column (50 m); the column was
heated from 50 to 320 С with a rate of 4 С min–1; an electron
impact of 70 eV was applied. 1H and 13С NMR spectra were
recorded on a Bruker AVANCEꢀ400 spectrometer with working
frequencies of 400.13 and 100.62 MHz, respectively, in standard
tubes (5 mm in diameter) for solutions of substances in CDCl3.
2D Homoꢀ (COSY HH) and heteronuclear (HSQC, HMBS)
correlation experiments were performed using pulse field gradiꢀ
ent procedures.
1ꢀ(1´ꢀCyclohexenyl)cyclohexane (1а). Cyclohexene (5 mL,
0.048 mol) and zeolite HZSMꢀ12 (0.8 g) were loaded in a glass
tube. Then the tube was sealed and placed inside a metallic
autoclave, which was continuously rotated in a temperatureꢀ
maintained bond for 5 h at 150 С. After cooling and separating
the catalyst, 3.9 g of the product was obtained. The product had
the following composition (wt.%): cyclohexene, 59.3; isomers,
0.8; 1ꢀ(1´ꢀcyclohexenyl)cyclohexane, 38; other dimers, 1.7; trimers,
0.2. 1ꢀ(1´ꢀCyclohexenyl)cyclohexane (1a) was isolated from the
obtained mixture under reduced pressure. The yield was 38%,
b.p. 60 С (40 Torr). Found (%): C, 87.25; H, 12.75. С12H20. Calꢀ
culated (%): C, 87.73; H, 12.27. 1H NMR, : 1.13 (m, 1 H, C(4)H2);
1.18 (m, 2 H, C(2)H2, C(6)H2); 1.29 (m, 2 H, C(3)H2, C(5)H2);
1.55, 1.59 (both m, 1 H each, C(4´)H2); 1.60 (m, 1 H, C(4)H2);
1.64 (m, 1 H, C(5´)H2); 1.68 (m, 2 H, C(2)H2, C(6)H2); 1.72
(m, 1 H, С(1)H); 1.75 (m, 1 H, C(5´)H2); 1.77 (m, 2 H, C(3)H2,
C(5)H2); 1.78 (m, 1 H, C(3´)H2); 1.94 (m, 1 H, C(6´)H2); 2.00
(m, 1 H, C(3´)H2); 5.39 (s, 1 H, C(2´)H). 13C NMR, : 22.85
(C(5´)); 23.23 (C(4)); 25.27 (C(3´)); 26.50 (C(4)); 26.75 (C(6´));
26.85 (C(3), C(5)); 31.92 (C(2), C(6)); 45.88 (C(1)); 119.34
(C(2´)); 142.34 (C(1´)). MS, m/z: 164. Kovats index: 1329.
1,1´ꢀBicyclohexane (1d). The counter synthesis of bicycloꢀ
hexane was carried out by the hydrogenation of 1ꢀ(1´ꢀcycloꢀ
hexenyl)cyclohexane (1a) on Pd/Al2O3 in an autoclave for 6 h at
150 С. After cooling and separating the catalysts, product 1d
was isolated from the reaction mixture under reduced pressure,
Experimental
b.p. 79.7 С (5 Torr). Found (%): C, 85.91; H, 14.09. С12H22
.
1
Calculated (%): C, 85.67; H, 14.33. H NMR, : 1.02 (m, 4 H,
C(2)H2, C(2´)H2, C(6)H2, C(6´)H2); 1.08 (m, 2 H, С(1)H2,
C(1´)H2); 1.25 (m, 6 H, C(3´)H2, C(4)H2, C(4´)H2, C(5)H2,
C(5´)H2); 1.70 (m, 2 H, C(4)H2, C(4´)H2); 1.71 (m, 4 H,
C(2)H2, C(2´)H2, C(6)H2, C(6´)H2); 1.72 (m, 4 H, C(3)H2,
C(3´)H2, C(5)H2, C(5´)H2). 13C NMR, : 26.93 (C(3), C(3´),
C(4), C(4´), C(5), C(5´)); 30.21 (C(2), C(2´), C(6), C(6´)); 43.52
(С(1), C(1´)). MS, m/z: 166. Kovats index: 1319.
Cycloolefins (cyclohexene, cycloheptene, cyclooctene) purꢀ
chased from Acros were used as received. Prior to experiments
the solvents (nonane, undecane) were purified using standard
procedures.28
Highly dispersed zeolites Y, Beta, and ZSMꢀ12 were studꢀ
ied, as well as granulated zeolite Y without binders (YꢀWB) in
the H form. Zeolites HY with the degree of exchange of Na+
ions by H+ () equal to 96% and НYꢀWB ( = 94%) were obꢀ
tained by the decationation of zeolites NaY (M = 6) and NaYꢀWB
(M = 5), which were synthesized using known procedures,23,29
1ꢀ(1´ꢀCycloheptenyl)cycloheptane (3a) and 1,1´ꢀbicycloꢀ
heptylidene (3b). Dimers 3a,b were synthesized similarly to comꢀ
pound 1a in the presence of zeolite HYꢀWB for 10 h at 110 С.

Selective dimerization of cycloolefins
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
449
The composition of the obtained oligomerizate is the following
(wt.%): cycloheptene, 30; isomers, 10; dimers, 60. Dimers 3a,b
were isolated under reduced pressure. The total yield was 58.3%,
b.p. 145—150 С (4 Torr). 1H NMR of compound 3a (subtracted
from the spectrum of the mixture), : 1.40—1.60 (m, 14 H,
С(3)H2, С(4)H2, C(5)H2, C(6)H2, C(3´)H2, C(4´)H2, C(5´)H2,
C(6´)H2); 1.74 (m, 2 H, C(2´)H2, C(7´)H2); 2.02 (m, 1 H,
C(1´)H); 2.06 (m, 2 H, C(7)H2); 2.09 (m, 2 H, C(3)H2); 5.54
(t, 1 H, C(2)H, J = 6.4 Hz). 13C NMR, : 27.37 (C(3), C(6)); 27.66
(C(6´)); 27.85 (C(5´)); 28.08 (C(4), C(5)); 28.14 (C(4´)); 28.26
(C(7´)); 30.80 (C(3´)); 33.49 (C(2), C(7)); 50.20 (C(1));
123.33 (C(2´)); 151.28 (C(1´)). MS, m/z: 192. Kovats index:
1568.1H NMR of dimer 3b, : 1.52 (m, 8 H, C(4)H2, C(5)H2,
C(4´)H2, C(5´)H2); 1.57 (m, 8 H, C(3)H2, C(6)H2, C(3´)H2,
C(6´)H2); 2.25 (m, 8 H, C(2)H2, C(7)H2, C(2´)H2, C(7´)H2).
13C NMR, : 27.97 (C(4), C(5), C(4´), C(5´)); 28.88 (C(3),
C(6), C(3´), C(6´)); 31.42 (C(2), C(7), C(2´), C(7´)); 133.28
(C(1), C(1´)). MS, m/z: 192.34. Kovats index: 1589.
7. S. Nametkin, L. Abskumowskaja, Ber. Deut. Chem. Ges.,
1933, 66, 358.
8. R. Sperling, J. Chem. Soc., 1949, 1928.
9. H. I. Watterman, J. J. Leendertse, A. C. Ter Poorten, Recl.
Trav. Chim. PaysꢀBas, 1935, 54, 245.
10. M. Nojima, T. Nagai, N. Tokura, J. Org. Catal., 1996,
31, 3966.
11. P. Plesch, Cationic Polymerization, Pergamon Press, Oxford—
London—New York—Paris, 1963.
12. R. Giezynski, A. Korda, J. Mol. Catal., 1980, 7, 349.
13. A. V. Topchiev, G. M. Mamedaliev, M. V. Shishkina, G. N.
Anikina, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1960, 9,
1011 [A. V. Topchiev, G. M. Mamedaliev, M. V. Shishꢀ
kina, G. N. Anikina, Izv. Akad. Nauk SSSR, Ser. Khim.,
1960, 1084].
14. A. V. Frost, Trudy po kinetike i katalizu [The Works on Kinetꢀ
ics and Catalysis], Izd. Akad. Nauk SSSR, Moscow, 1956,
538 pp. (in Russian).
1ꢀ(1´ꢀCyclooctenyl)cyclooctane (2a) and 1,1´ꢀbicyclooctylꢀ
idene (2b). Dimers 2a,b were synthesized similarly to compounds
3a,b. The composition of the oligomerizate is as follows (wt.%):
cyclooctene, 17; isomers, 31.7; dimers, 51.3. Dimer 2b was isoꢀ
lated by crystallization from ethanol from a mixture of dimers
2a,b, which was obtained by vacuum distillation. The crystals
were washed with cold ethanol and dries. The yield of mixture
2a,b was 48.8%, b.p. 140—150 С (5 Torr). 1H NMR of comꢀ
pound 2a, : 0.95—1.71 (m, 26 H, CH2); 2.00 (m, 1 H, C(9)H);
5.34 (m, 1 H, C(2)H, J = 16.0 Hz). 13C NMR, : 26.24 (C(4),
C(6)); 26.64 (C(3), C(7)); 27.04 (C(8´)); 28.55 (C(5´), C(6´));
29.80 (C(4´), C(7´)); 29.85 (C(3´)); 32.07 (C(2), C(8)); 46.50
(C(1)); 121.47 (C(2´)); 147.32 (C(1´)). MS, m/z: 220.39. Kovats
index: 1814. Dimer 2b, cr.p. 30 С. Found (%): C, 86.35;
H, 13.65. С16H30. Calculated (%): C, 86.89; H, 13.11. 1H NMR,
: 1.48 (m, 12 H, C(4)H2—C(6)H2, C(4´)H2—C(6´)H2); 1.64
(m, 8 H, C(3)H2, C(7)H2, C(3´)H2, C(7´)H2); 2.21 (m, 8 H,
C(2)H2, C(8)H2, C(2´)H2, C(8´)H2). 13C NMR, : 26.24
(C(4)—C(6), C(4´)—C(6´)); 27.25 (C(3), C(7), C(3´), C(7´));
31.16 (C(2), C(8), C(2´), C(8´)); 132.97 (C(1), C(1´)). MS, m/z:
220.39. Kovats index: 1823.
15. H. S. Bloch, C. L. Thomas, J. Am. Chem. Soc., 1944, 66, 1586.
16. H. H. Voge, G. M. Good, B. S. Greensfelder, Ind. Eng.
Chem., 1946, 38, 1033.
17. J. M. Campelo, A. Garcia, J. M. Gutierrez, D. Luna, J. M.
Marinas, Can. J. Chem., 1984, 62, 1455.
18. W. C. Cheng, K. Rajagopolan, J. Сatal., 1989, 119, 354.
19. E. Jacquinot, A. Mendes, F. Raatz, C. Marcilly, J. Caeiro,
Appl. Catal., 1990, 60, 101.
20. US Pat. 4255600; http://worldwide.espacenet.com/publicaꢀ
tionDetails/originalDocument?CC=US&NR=4255600A&ꢀ
KC=A&FT=D&ND=3&date=19810310&DB=EPODOC&
locale=en_EP.
21. D. S. Greidinger, D. Ginsburg, J. Org. Chem., 1957, 22, 1406.
22. B. Bogdanovic, B. Henc, H.ꢀG. Karmann, Ind. Eng. Chem.,
1970, 62, 34.
23. Pat. RF 2412903; Byul. Izobr. [Invention Bulletin], 2011, No. 6
(in Russian).
24. A. N. Khazipova, I. N. Pavlova, N. G. Grigor´eva, B. I.
Kutepov, M. L. Pavlov, R. A. Basimova, Khim. Tekhnologiya
[Chemical Technology], 2012, No. 1, 5 (in Russian).
25. J. A. Rabo, Zeolite Chemistry and Catalysis, ACS, Washingꢀ
ton, 1976.
26. Ch. Baerlocher, L. B. McCusker, D. H. Olson, Atlas of Zeolite
Framework Types, 6th ed., Elsevier, Amsterdam, 2007, 392 pp.
27. N. G. Grigor´eva, E. A. Paukshtis, B. I. Kutepov, R. R.
Galyautdinova, U. M. Dzhemilev, Neftekhimiya, 2005, 45,
453 [Petroleum Chemistry (Engl. Transl.), 2005, 45, 419].
28. A. J. Gordon, R. A. Ford, A Chemists Companion: A Handꢀ
book of Practical Data, Techniques, and References, Wiley
Intersci., New York—London—Sydney—Toronto, 1972,
537 pp.
29. Pat. RF 2151739; Byul. Izobret. [Invention Bulletin], 2000,
No. 18 (in Russian).
30. A. N. Khazipova, B. I. Kutepov, M. L. Pavlov, N. G.
Grigor´eva, A. N. Pashkina, E. A. Travkin, Ya. L. Shestopal,
Zh. Prikl. Khim., 2007, 80, 1815 [Russ. J. Appl. Chem. (Engl.
Transl.), 2007, 80].
References
1. I. L. Knunyants, Bol´shoi entsiklopedicheskii slovar´ [The
Large Encyclopedic Dictionary], 2nd ed., Khimiya, Moscow,
1998, 792 pp. (in Russian).
2. G. N. Jenkins, S. M. Roberts, N. J. Turner, Recent Uses of
Oxidoreductase Enzymes, Department of Chemistry, Univerꢀ
sity of Exeter, 1995; http://www.ch.ic.ac.uk/ꢀectoc/papers/
04/4ꢀOxidoreductases.html.
3. H. Geoff Davies, M. J. Dawson, G. C. Lawrence, J. Mayall,
D. Noble, M. R. Stanley, M. K. Turner, W. F. Wall, Tetraꢀ
hedron Lett., 1986, 27, 1089.
4. US Pat. 7572435; http://worldwide.espacenet.com/publicaꢀ
tionDetails/originalDocument?FT=D&date=20090811&
DB=EPODOC&locale=en_EP&CC=US&NR=7572435B2&
KC=B2&ND=4.
31. N. G. Grigor´eva, R. R. Talipova, L. F. Korzhova, A. V.
Vosmerikov, B. I. Kutepov, U. M. Dzhemilev, Russ. Chem.
Bull., Int. Ed., 2009, 58, 59 [Izv. Akad. Nauk, Ser. Khim.,
2009, 59].
5. J. A. Moulijn, B. M. van de Nouland, React. Kinet. Catal.
Lett., 1975, 3, 405.
6. S. M. McElvain, J. W. Langston, J. Am. Chem. Soc., 1944,
66, 1759.
Received January 29, 2013