Benzene Alkylation with Cycloolefins under the Action of [Et3NH]+[Al2Cl7]? Ionic Liquid

Article abstract of DOI:10.1134/S107036321911001X

Benzene alkylation with mono- and bicyclic olefins under the action of an inorganic ionic liquid [Et₃NH]⁺[Al₂Cl₇]^? with the formation of benzene cycloalkyl derivatives in 58–98% yield has been performed for the first time. It has been found that the increase in the olefin cycle size improves the selectivity with respect to monocycloalkyl derivatives.

Full text of DOI:10.1134/S107036321911001X

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 11, pp. 2171–2177. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 11, pp. 1643–1650.
Benzene Alkylation with Cycloolefins under the Action
of [Et3NH]+[Al2Cl7]– Ionic Liquid
R. I. Aminova,*, A. S. Mazitovaa, and R. I. Khusnutdinova
Institute of Petrochemistry and Catalysis of the Russian Academy of Sciences, Ufa, 450075 Russia
*e-mail: inklab4@gmail.com
Received April 19, 2019; revised April 19, 2019; accepted April 25, 2019
Abstract—Benzene alkylation with mono- and bicyclic olefins under the action of an inorganic ionic liquid
[Et3NH]+[Al2Cl7]– with the formation of benzene cycloalkyl derivatives in 58–98% yield has been performed for
the first time. It has been found that the increase in the olefin cycle size improves the selectivity with respect to
monocycloalkyl derivatives.
Keywords: alkylation, catalysis, cycloolefins, benzene, ionic liquids
DOI: 10.1134/S107036321911001X
Alkylation with olefins is among the most important
reactions of aromatic compounds. Anhydrous aluminum
chloride is a conventional alkylation catalyst; in particu-
lar,AlCl3 is used in industrial-scale synthesis of ethyl- and
isopropylbenzenes. For example, alkylation of benzene
with propene in the presence of AlCl3 is performed at
heating to 130–140°С, which favors side reactions of
oligo- and polymerization of the olefin.
of benzene alkylation with monocyclic (cyclopentene,
cyclohexene, cyclooctene, and cyclododecene) as well
as bicyclic (norbornene) olefins yielding mono-, di-, tri-,
or tetracycloalkyl derivatives, depending on the substrate
nature, reaction conditions, and molar ratio between the
reactants and the catalyst.
The general features of benzene alkylation with
cycloolefins under the action of the [Et3NH]+[Al2Cl7]–
inorganic ionic liquid were studied using cyclopentene 1
as the example. The alkylation was performed at 0–40°С
during 0.5–8 h at the [1] : [ionic liquid] : [benzene] molar
ratio of (10–30) : 1 : (30–90). The ratio of the reaction
products [cyclopentylbenzene 2, 1,3-dicyclopentylben-
zene 3, 1,4-dicyclopentylbenzene 4, 1,3,5-tricyclopen-
tylbenzene 5, and 1,2,4,5-tetracyclopentylbenzene 6
(Scheme 1)] depended on the reaction conditions and the
concentrations of the starting compounds.
It has been recently found that AlCl3 can be replaced
by the ionic liquids based on it in the reactions of alkyla-
tion and acylation, since the aluminate ionic liquid is in
fact a Lewis acid immobilized in the ionic liquid phase
[1–9].
Alkylation of benzene with cycloolefins has been
scarcely studied; generally, the reaction is performed us-
ing such catalysts asAlCl3, BF3/H3PO4 [10], Pt–Ag [11],
or Sc(OTf)3 [12] taken in high amount (0.2–0.4 mol with
respect to the substrate).
When the reaction was performed at 0°С during 8 h,
the olefin 1 to the ionic liquid molar ratio being 10 : 1,
the highest yield of cyclopentylbenzene 2 was observed
(93%, cf. Table 1, Exp. 3). The increase in cyclopentene
1 concentration to [1] : [ionic liquid] to (10–100) : 1 led
to the decrease in the yield of cyclopentylbenzene 2 to
13% and the increase in the yield of tetracyclopentyl-
benzene 6. The highest yield of compound 6 (69%) was
observed at the [1] : [ionic liquid] molar ratio of 100 : 1
(Table 1, Exp. 5). It should be underscored that the data
on the synthesis and physico-chemical parameters of
Being the most frequently used catalyst,AlCl3 suffers
from several drawbacks reducing the cycloalylbenzenes
yield, including low solubility in hydrocarbons, olefin tar-
ring, and the complexity of target products isolation due to
the need to decomposition and neutralization of the reac-
tion mass. For example, the yield of cyclopentylbenzene
in the reaction of benzene alkylation with cyclopentene in
the presence of AlCl3 has not exceeded 70% [10].
Herein we demonstrated that the inorganic ionic
liquid, [Et3NH]+[Al2Cl7]–, could act as efficient catalyst
2171

2172
AMINOV et al.
Scheme 1.
[Et3NH]+[Al2Cl7]ꢀ
+
+
+
1
2
3
4
+
+
5
6
1,2,4,5-tetracyclopentylbenzene 6 have been absent in
the literature.
Furtherexperimentsrevealedthatthe[Et3NH]+[Al2Cl7]–
ionic liquid could be an efficient catalyst of benzene al-
kylation with cyclooctene 11 (Scheme 3). That reaction
exhibited high selectivity with respect to the [1+1]-adduct
12. The optimal conditions of benzene alkylation with
cyclooctene 11 were as follows: temperature 20°С, dura-
tion 0.5 h, [11] : [ionic liquid] molar ratio 30 : 1 (Table 3,
Exp. 2); the yield of compound 12 under those conditions
was 82%. The decrease in the [11] : [ionic liquid] ratio to
(10–200) : 1 led to the decrease in the yield of compound
12 to 12%, due to tarring and the side products formation.
We then studied the alkylation of benzene with
cyclohexene 7 under the action of [Et3NH]+[Al2Cl7]–
(Scheme 2). The highest yield of cyclohexylbenzene 8
(58%) was observed when the reaction was performed at
20°С during 8 h, the cyclohexene 7 to ionic liquid molar
ratio being 100 : 1 (Table 2, Exp. 9). Besides cyclohex-
ylbenzene 8, the reaction mixture contained 1,4-dicyclo-
hexylbenzene 9 and 1,3-dicyclohexylbenzene 10, their
total yield being 42%. The high yield of the derivatives
9 and 10 (72%) was observed upon keeping the reaction
mass at 0°С during 30 min (Table 2, Exp. 10).
It should be mentioned that there have been no ex-
amples of the synthesis of cyclooctylbenzene 12 via
Scheme 2.
[Et3NH]+[Al2Cl7]ꢀ
+
+
+
7
8
9
10
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

BENZENE ALKYLATION WITH CYCLOOLEFINS
2173
Table 1. Alkylation of benzene with cyclopentene under the action of [Et3NH]+[Al2Cl7]–
Yield, %а
Exp. no.
[1] : [ionic liquid] ratio
Т, °С
Time, h
2
3 + 4
5
1
6
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
1
2
2 : 1
2 : 1
0
0
0.5
1.0
8.0
0.5
1.0
2.0
8.0
0.5
1.0
2.0
8.0
0.5
1.0
2.0
8.0
0.5
1.0
2.0
8.0
79
95
98
49
52
61
93
46
49
53
56
66
93
98
99
6
20
5
–
3
2 : 1
0
2
–
4
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
10 : 1
100 : 1
100 : 1
100 : 1
100 : 1
0
23
22
19
6
28
26
20
1
5
0
6
0
7
0
8
20
20
20
20
40
40
40
40
0
35
33
32
31
23
7
19
18
15
13
11
–
9
10
11
12
13
14
15
16
17
18
19
2
–
–
1
10
7
23
22
21
13
61
63
64
69
0
8
0
11
13
4
0
5
а As determined by GLC with n-butylbenzene as internal reference.
direct alkylation of benzene with cyclooctene the avail-
able literature.
during 6 h at the [13] : [ionic liquid] molar ratio 20 : 1
(Table 4, Exp. 5). The decrease in the concentration of
the ionic liquid to [ionic liquid] : [13] = 1 : (50–100) led
to the decrease in the yield of compound 14, whereas its
increase to [ionic liquid] : [13] = 1 : 10 led to the increase
in the yield of tar-like products.
Cyclododecene 13 was found to readily react with
benzene in the presence of [Et3NH]+[Al2Cl7]– (Scheme 4).
The reactions were performed at 20–40°С during 6–8 h
at the [13] : [ionic liquid] : [benzene] molar ratio of
(10–30) : 1 : (30–90) (Table 4).
The earlier described synthesis of cyclododecylben-
zene 14 is based on benzene alkylation with cyclododecyl
mesylate prepared in its turn from cyclododecene in three
The highest yield of cyclododecylbenzene 14 (98%)
was observed when the reaction was performed at 40°С
Scheme 3.
[Et3NH]+[Al2Cl7]ꢀ
+
11
12
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

2174
AMINOV et al.
Table 2. Alkylation of benzene with cyclohexene under the
action of [Et3NH]+[Al2Cl7]–
Table 3. Alkylation of benzene with cyclooctene under the
action of [Et3NH]+[Al2Cl7]–
Yield, %а
Exp. [11] : [ionic liquid]
Yield 12,
[7] : [ionic liquid]
Т, °С Time, h
Exp. no.
Т, °С Time, h
no.
ratio
%
ratio
8
9 + 10
66
1
2
10 : 1
30 : 1
20
20
20
20
20
20
0
8.0
0.5
1.0
3.0
6.0
8.0
0.5
1.0
2.0
0.5
1.5
2.0
0.5
1.5
8.0
8.0
2.0
72
82
65
60
57
31
33
38
44
55
48
43
19
21
29
20
12
1
2
10 : 1
10 : 1
30 : 1
30 : 1
30 : 1
30 : 1
30 : 1
30 : 1
100 : 1
100 : 1
100 : 1
100 : 1
100 : 1
20
20
20
20
20
0
3.0
8.0
1.0
2.0
8.0
0.5
1.5
8.0
8.0
0.5
2.0
3.0
8.0
44
47
30
45
56
38
42
45
58
28
45
54
57
53
3
30 : 1
3
70
4
30 : 1
5
30 : 1
4
55
6
30 : 1
5
44
7
50 : 1
6
62
8
50 : 1
0–5
0–5
20
20
20
0
7
0
58
9
50 : 1
8
0
55
10
11
12
13
14
15
16
17
100 : 1
100 : 1
100 : 1
100 : 1
100 : 1
100 : 1
100 : 1
200 : 1
9
20
0
42
10
11
12
13
72
0
55
0
0
46
0
0
43
40
20
a As determined by GLC.
stages (epoxidation, hydrogenation, and methanesulfona-
tion) [13].
of bicyclo[2.2.1]hept-2-ene (norbornene) 15 with benzene
under the action of the [Et3NH]+[Al2Cl7]– inorganic ionic
liquid gave 2-norbornylbenzene 16 (Scheme 5). The
highest yield of compound 16 (78%) was observed when
the reaction was performed at 20°С during 6 h (Table 5).
Hence, it was experimentally demonstrated that the
increase in the size of olefin cycle improved the selectivity
of benzene alkylation in the presence of the ionic liquid
with respect to the monocycloalkyl derivatives, likely
due to steric factors.
We attempted the alkylation of naphthalene, anthra-
cene, and pyridine with cyclopentene under the action of
[Et3NH]+[Al2Cl7]–. However, the alkylation of naphtha-
lene or anthracene at 20–40°C did not occur within 8 h.
We further investigated the behavior of a bicyclic ole-
fin in the same reaction. It was found that the interaction
Scheme 4.
[Et3NH]+[Al2Cl7]ꢀ
+
cis,trans-13
14
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

BENZENE ALKYLATION WITH CYCLOOLEFINS
2175
Table 4. Alkylation of benzene with cyclododecene under the
action of [Et3NH]+[Al2Cl7]–
Table 5. Alkylation of benzene with norbornene under the
action of [Et3NH]+[Al2Cl7]–
Exp. [13] : [ionic liquid]
Yield 14,
Exp. [15] : [ionic liquid]
Yield 16,
Time, h
Т, °С Time, h
Т, °С
no.
ratio
%
no.
ratio
%
1
10 : 1
10 : 1
20 : 1
20 : 1
20 : 1
20 : 1
50 : 1
50 : 1
100 : 1
100 : 1
100 : 1
20
40
20
20
40
40
20
40
20
40
80
8
8
55а
62а
94
95
98
83а
30
25
15
20
22
1
2
10 : 1
10 : 1
10 : 1
10 : 1
50 : 1
50 : 1
50 : 1
50 : 1
100 : 1
100 : 1
100 : 1
20
20
20
40
20
0
0.03
0.50
6.00
8.00
8.00
0.50
1.00
8.00
0.50
1.00
8.00
53а
53а
78а
47а
44а
46
2
3
8
3
4
16
6
4
5
5
6
8
6
7
8
7
0
78
8
8
8
0
49а
55
9
8
9
0
10
8
10
11
0
46
11
8
0
40а
a Resinification.
a Side products formation.
Minor amount of cyclopentylnaphthalene or cyclopentyl-
anthracene (~10%) was observed under harsh conditions
(120°С, 10 h); about 50% of cyclopentene was converted
into dimers, trimers, and higher oligomers, which com-
plicated the isolation of the target cycloalkyl derivatives
of naphthalene and anthracene. The attempt of pyridine
alkylation also failed, due to the formation of its complex
with the catalyst, resulting in deactivation of the latter.
using a Shimadzu GCMS-QP2010Plus instrument (SPB-5
capillary column, 30 m × 0.25 mm, helium as carrier gas,
temperature program: 40 to 300°С at 8 deg/min, evapo-
rator temperature 280°С, ion source temperature 200°С,
ionization energy 70 eV). The reactions progress and the
products purity were determined by means of gas-liquid
chromatography using a Shimadzu GC-9A, GC-2014
device [column 2 m × 3 mm, stationary phase: SE-30
silicone (5%) on Chromaton N-AW-HMDS, temperature
program: 50 to 270°С at 8 deg/min, helium as carrier
gas (47 mL/min)], n-butylbenzene as internal reference.
Elemental analysis was performed using a Carlo Erba
1106 instrument.
In summary, we performed for the first time benzene
alkylation with cyclopentene, cyclohexene, cyclooctene,
cyclododecene, and norbornene under the action of the
[Et3NH]+[Al2Cl7]– inorganic ionic liquid; the cycloalkyl
derivatives were formed in 58–98% yield.
The chloroaluminate ionic liquid was prepared as
described elsewhere [14, 15].
EXPERIMENTAL
Benzene alkylation with cyclic olefins under the
action of [Et3NH]+[Al2Cl7]– (general procedure).
2–100 mmol of a cyclic olefin and 1 mmol of the
[Et3NH]+[Al2Cl7]– inorganic ionic liquid were loaded to
a glass reactor (V = 50 mL) under argon. The reaction was
performed in benzene at constant stirring, temperature
being 0–40°С, during 0.5–8 h. After the reaction was
complete, the mixture was filtered through alumina layer.
The solvent was distilled off, liquid products were isolated
by means of vacuum distillation, and solid products were
isolated via recrystallization.
1H and 13С NMR spectra were recorded using a
Bruker Avance-III 400 Ascend instrument [400 (1Н) and
100 MHz (13С)] in CDCl3. Mass spectra were recorded
Scheme 5.
[Et3NH]+[Al2Cl7]ꢀ
+
15
16
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

2176
AMINOV et al.
Cyclopentylbenzene (2) [16]. Yield 94%, bp 51–52°С
Cyclohexylbenzene (8) [13]. Yield 58%, bp 63–65°С
(1 mmHg). Н NMR spectrum, δ, ppm: 1.42 m (6Н,
1
(1 mmHg). 1Н NMR spectrum, δ, ppm: 1.66–1.79 m (4H,
С3,4H2), 1.87–2.00 m (4Н, С2,5H2), 3.01–3.18 m (1Н,
С1Н), 7.23–7.44 m (5Н, С7–11Н). 13С NMR spectrum,
δС, ppm: 27.72 (С3,4), 32.82 (С2,5), 42.88 (С1), 126.31
(С9), 127.58 (С7,11), 128.41 (С8,10), 145.82 (С6). Mass
spectrum, m/z (Irel, %): 146(55) [M]+, 145 (3), 131 (11),
118 (22), 117 (100), 116 (6), 115 (20), 104 (99), 91 (47),
78 (13).
С2,4,6Н2), 1.86 m (4Н, С3,5Н2), 2.56 m (1Н, С1Н), 7.26
m (5Н, С8–12Н). 13С NMR spectrum, δС, ppm: 26.55
(С4), 27.3 (С3,5), 35.1 (С2,6), 45.2 (С1), 126.1 (С10), 127.3
(С8,12), 128.4 (С9,11), 147.8 (С7), Mass spectrum, m/z (Irel,
%): 160(49) [M]+, 117(59), 115(14), 105(15), 104(100),
103(8), 91(45), 78(8), 77(6), 41(6).
1,4-Dicyclohexylbenzene (9) and 1,3-dicyclohexyl-
1,3-Dicyclopentylbenzene (3) and 1,4-dicyclopen-
benzene (10) [18]. Yield 42%, bp 133–138°С(0.5 mmHg).
tylbenzene (4). Yield 31%, bp 111–116°С (0.8 mmHg).
1
1,4-Dicyclohexylbenzene (9). Н NMR spectrum,
1,3-Dicyclopentylbenzene (3). Н NMR spectrum,
δ, ppm: 1.35 m (4Н, С4,16Н2), 1.57 m (8Н, С2,6,14,18Н2),
1.83 m (8Н, С3,5,15,17Н2), 2.49 m (2Н, С1,3Н), 7.14 m
(4Н, С8,9,11,12Н). 13С NMR spectrum, δС, ppm: 26.3
(С4,16), 27.1 (С3,5,15,17), 34.6 (С2,6,14,18), 44.2 (С1,13),
126.5 (С8,9,11,12), 145.3 (С7,10). Mass spectrum, m/z (Irel,
%): 242(100) [M]+, 243(18), 186(19), 173(13), 160(15),
159(67), 129(13), 105(13), 91(44), 41(14).
1,3-Dicyclohexylbenzene (10). 1Н NMR spectrum, δ,
ppm: 7.15 m (4Н), 2.49 t (2Н, J = 7.2 Hz), 1.87 m (8Н),
1.55 m (8Н), 1.36 m (4Н). 1.36 m (4Н, С4,16Н2), 1.55 m
(8Н, С2,6,14,18Н2), 1.87 m (8Н, С3,5,15,17Н2), 2.49 t (2Н,
С1,13Н, J = 7.6 Hz), 7.15 m (4Н, С8,10–12Н). 13С NMR
spectrum, δС, ppm: 26.77 (С4,16), 27.86 (С3,5,15,17), 35.76
(С2,6,14,18), 43.47 (С1,13), 124.08 (С8), 124.74 (С10,12),
128.69 (С11), 144.44 (С7,9). Mass spectrum, m/z (Irel,
%): 242(100) [M]+, 186(16), 173(9), 159(61), 129(18),
117(63), 91(47), 83(28), 55(26), 41(12).
1
δ, ppm: 1.61–1.69 m (8Н, С3,4,14,15Н2), 1.84–1.88 m
(8Н, С2,5,13,16Н2), 3.10–3.23 m (2Н, С1,12Н), 6.84–7.39
m (4Н, С7,9,10,11Н). 13С NMR spectrum, δС, ppm: 28.27
(С3,4,14,15), 32.43 (С2,5,13,16), 42.37 (С1,12), 124.96 (С7),
125.18 (С9,11), 128.51 (С10), 143.21 (С8,6). Mass spec-
trum, m/z (Irel, %): 214(66) [M]+, 172(9), 159(9), 146(30),
145(100), 129(16), 128(15), 115(21), 69(18), 41(20).
1
1,4-Dicyclopentylbenzene (4). Н NMR spectrum,
δ, ppm: 1.84–1.88 m (8Н, С3,4,14,15Н2), 1.98 m (8Н,
С2,5,13,16Н2), 2.89–2.98 m (2Н, С1,12Н), 6.65–7.48 m
(4Н, С7,8,10,11Н). 13С NMR spectrum, δС, ppm: 27.72
(С3,4,14,15), 33.38 (С2,5,13,16), 47.71 (С1,12), 127.16
(С7,8,10,11), 142.16 (С9,6). Mass spectrum, m/z (Irel, %):
214(52) [M]+, 172(10), 146(23), 145(100), 129(15),
117(53), 115(17), 91(46), 67(9), 41(14). Found, %: C
90.04; H 9.96. C16H22. Calculated, %: C 89.65; H 10.35.
1,3,5-Tricyclopentylbenzene (5) [17]. Yield 13%,
bp 150–156°С (0.5 mmHg). 1Н NMR spectrum, δ, ppm:
1.65–1.79 m (12Н, С3,4,14,15,19,20Н2), 1.87–2.07 m (12Н,
С2,5,13,16,18,21Н2), 2.89–3.01 m (3Н, С1,12,17Н), 6.81
s (3Н, С7,9,11Н). 13С NMR spectrum, δС, ppm: 23.83
(С3,4,14,15,19,20), 32.04 (С2,5,13,16,18,21), 41.86 (С1,12,17),
122.53 (С7,9,11), 142.15 (С6,8,10). Mass spectrum, m/z (Irel,
%): 282(85) [M]+, 227(5), 213(100), 212(6), 214(24),
159(10), 145(39), 91(18), 69(29), 41(20).
Cyclooctylbenzene (12) [19]. Yield 70%, bp 94–96°С
(1 mmHg). Н NMR spectrum, δ, ppm: 1.16 m (4Н,
1
С4,6Н2), 1.23 m (4Н, С3,7Н2), 1.48 m (2Н, С5Н2), 1.93 m
(4Н, С2,8Н2), 2.59 m (1Н, С1Н), 7.20 m (5Н, С10–14Н).
13С NMR spectrum, δС, ppm: 26.49 (С5), 26.83 (С6,4),
26.96 (С3,7), 34.62 (С2,8), 37.92 (С1), 125.45 (С12), 126.96
(С10,14), 128.26 (С11,13), 145.96 (С9). Mass spectrum,
m/z (Irel, %): 188(80) [M]+, 131(31), 118(27), 117(40),
104(100), 92(31), 91(84).
1,2,4,5-Tetracyclopentylbenzene (6). Yield 68%, mp
259–263°С. Н NMR spectrum, δ, ppm: 1.63 m (16Н,
Cyclododecylbenzene (14) [13]. Yield 98%, mp 42–
43°С. 1Н NMR spectrum, δ, ppm: 0.74 m (6Н, С6,7,8Н2),
0.95 m (4Н, С5,9Н2), 1.10–1.12 m (8Н, С3,4,10,11Н2),
1.89 m (4Н, С2,12Н2), 2.55 m (1Н, С1Н), 7.19–7.22 m
(5Н, С14–18Н). 13С NMR spectrum, δС, ppm: 22.75 (С7),
23.22 (С5,9), 23.51 (С6,8), 23.90 (С4,10), 23.97 (С3,11),
31.59 (С2,12), 47.30 (С1), 127.32 (С16), 127.66 (С14,18),
128.08 (С15,17), 144.81 (С13). Mass spectrum, m/z (Irel,
%): 244(80) [M]+, 131(31), 118(27), 117(40), 104(100),
92(31), 91(84).
1
С3,4,14,15,19,20,24,25Н2), 1.86 m (16Н, С2,5,13,16,18,21,23,26Н2),
2.81 m (4Н, С1,12,17,22Н), 6.94 m (2Н, С8,11Н). 13С NMR
spectrum, δС, ppm: 27.48 (С3,4,14,15,19,20,24,25), 33.25
(С2,5,13,16,18,21,23,26), 38.95 (С1,12,17,22), 124.83 (С8,11),
139.80 (С6,7,9,10). Mass spectrum, m/z (Irel, %): 350(100)
[M]+, 321(4), 281(60), 145(17), 129(11), 69(22), 67(12),
41(19). Found, %: C 88.94; H 11.06. C26H38. Calculated,
%: C 89.07; H 10.93.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

BENZENE ALKYLATION WITH CYCLOOLEFINS
2177
7. Boon, J.A., Levisky, J.A., Pflug, J.L., and Wilkes, J.S.,
J. Org. Chem., 1986, vol. 51, p. 480.
2-Norbornylbenzene (16) [19]. Yield 78%, bp 123°С
(10 mmHg). Н NMR spectrum, δ, ppm: 1.21 m (4Н,
1
С3,7Н2), 1.56 m (2Н, С5Н2), 1.78 m (2Н, С6Н2), 2.20
m (2Н, С1,4Н), 2.94 m (1Н, С2Н), 7.09–7.16 m (5Н,
С9–13Н). 13С NMR spectrum, δС, ppm: 28.81 (С6), 29.59
(С7), 34.54 (С3), 36.34 (С4), 39.24 (С5), 40.90 (С2),
41.12 (С1), 126.19 (С11), 127.08 (С9,13), 128.05 (С10,12),
145.77 (С8). Mass spectrum, m/z (Irel, %): 172(38) [M]+,
129(11), 117(12), 115(16), 105(20), 104(100), 92(47),
81(32), 79(10), 67(19).
https://doi.org/10.1021/jo00354a013
8. Adams, C.J., Earle, M.J., and Seddon, K.R., Chem.
Commun., 1998, p. 2097.
https://doi.org/10.1039/a805599h
9. Xin-hua, Y., Min, C., Qi-xun, D., and Xiao-nong, C.,
Chem. Eng. J., 2009, vol. 146, p. 266.
https://doi.org/10.1016/j.cej.2008.09.022
10. Zavgorodnii, S.V., Ovchinnikov, V.G., Ovchinnikova, G.K.,
Mramornova, S.A., and Bass, S.I., Neftekhim., 1972, vol.
12, p. 201.
FUNDING
This study was financially supported by the Russian
Foundation for Basic Research (no. 17-43-020155 r_a)
in the scope of the State Task of the Ministry of Educa-
tion and Science (no. AAAA-А19-119022290009-3) and
the Program for Support of Young Russian Scientists –
Scholarship from the President of Russian Federation (SP-
1601.2018.1). The study of the structure of the synthesized
compounds was performed using the equipment of “Agidel”
Regional Center for Collective Usage (Institute of Petrochem-
istry and Catalysis, Russian Academy of Sciences).
11. Karshtedt, D., Bell, A.T., and Tilley, T.D., Organometallics,
2004, vol. 18, p. 4169.
https://doi.org/10.1021/om0495325
12. Qiao, K. and Yokoyama, C., Chem. Lett., 2004, vol. 33,
p. 472.
https://doi.org/10.1246/cl.2004.472
13. Singh, R.P., Kamble, R.M., Chandra, K.L., Saravanan, P.,
and Singh, V.K., Tetrahedron, 2001, vol. 57, p. 241.
https://doi.org/10.1016/s0040-4020(00)01005-x
14. Fang, M.-H. and Wang, L.-S., Int. J. Mol. Sci., 2007,
vol. 8, p. 470.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
REFERENCES
https://doi.org/10.3390/i8060470
15. Kumara, R., Kumarb, A., and Khannab, A., Catal. Ind.,
2015, vol. 7, p. 188.
1. Koch, V.R., Miller, L.L., and Osteryoung, R.A., J. Am.
Chem. Soc., 1976, vol. 98, p. 5277.
https://doi.org/10.1021/ja00433a037
https://doi.org/10.1134/S2070050415030095
16. Bedford, R.B., Brenner, P.B., Carter, E., Carvell, T.W.,
Cogswel, P.M., Gallagher, T., and Pye, D.R., Chem. – A
Eur. J., 2014, vol. 20, p. 7935.
2. Qiao, K. and Deng, Y., J. Mol. Catal. (A), 2001,
vol. 17, p. 81.
https://doi.org/10.1016/s1381-1169(01)00107-8
3. Wilkes, J.S., Frye, J.S., and Reynolds, G.F., Inorg. Chem.,
1983, vol. 22, p. 3870.
https://doi.org/10.1002/chem.201402174
17. Salvi, L., Davis, N.R., Ali, S.Z., and Buchwald, S.L., Org.
Lett., 2011, vol. 14, p. 170.
https://doi.org/10.1021/ic00168a011
4. Xin, H., Wu, Q., Han, M., Wang, D., and Jin, Y., Appl.
Catal. (A), 2005, vol. 292, p. 354.
https://doi.org/10.1021/ol202955h
https://doi.org/10.1016/j.apcata.2005.06.012
18. Kloppenburg, L., Jones, D., and Bunz, U.H.F., Macromol.,
1999, vol. 32, p. 4194.
5. Sun, X.W. and Thao, S.Q., Pet. Sci., 2011, vol. 8,
p. 495.
https://doi.org/10.1021/ma9900535
https://doi.org/10.1007/s12182-011-0167-4
19. Powell, D.A. and Fu, G.C., J. Am. Chem. Soc., 2004,
vol. 126, p. 7788.
6. Kim, D.S. and Ahn, W.S., Korean J. Chem. Eng., 2003,
vol. 20, p. 39.
https://doi.org/10.1007/bf02697182
https://doi.org/10.1021/ja047433c
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