Alkylation of Aromatic Hydrocarbons with 2-Methyl-2-Vinyl-gem-Dichlorocyclopropane over Zeolite Catalysts

Article abstract of DOI:10.1134/S0965544119060057

Abstract: It has been found as a result of the investigation of the catalytic properties of various microporous zeolites (of FAU, BEA, MOR, and MFI structural types) and a micro–meso–macroporous H-Ymmm zeolite (FAU) in the alkylation reaction of arenes (benzene (II) and toluene (III)) with the unsaturated compound 2-methyl-2-vinyl-gem-dichlorocyclopropane (I) that the reaction proceeds with the formation of chloroalkylarenes [1-(2,2-dichloro-1-methylcyclopropyl)ethyl]benzene (IV) and 1-[1-(2,2-dichloro-1-methylcyclopropyl)ethyl]-4-methylbenzene(V). Compounds IV and V are the most selectively formed over H-Beta (up to 82%) and H-Ymmm (up to 79%) zeolite catalysts with a high conversion of I (from 90% to full). It has been shown that high selectivity for chloroalkylarenes IV and V is achieved at 100°C, an arene : unsaturated compound molar ratio of 8 : 1, a catalyst concentration of 20 wt % of the reaction mass, and a reaction time of 2 h.

Full text of DOI:10.1134/S0965544119060057

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 6, pp. 581–586. © Pleiades Publishing, Ltd., 2019.
Alkylation of Aromatic Hydrocarbons with 2-Methyl-2-Vinyl-gem-
Dichlorocyclopropane over Zeolite Catalysts
A. V. Baiburtlia, G. Z. Raskil’dinaa, *, N. G. Grigor’evaa, b, and S. S. Zlotskiia
aUfa State Petroleum Technological University, Ufa, 450062 Bashkortostan, Russia
bInstitute of Petroleum Chemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences,
Ufa, 450075 Bashkortostan, Russia
*e-mail: graskildina444@mail.ru
Received September 26, 2018; revised February 2, 2019; accepted February 12, 2019
Abstract—It has been found as a result of the investigation of the catalytic properties of various microporous
zeolites (of FAU, BEA, MOR, and MFI structural types) and a micro–meso–macroporous H-Ymmm zeo-
lite (FAU) in the alkylation reaction of arenes (benzene (II) and toluene (III)) with the unsaturated com-
pound 2-methyl-2-vinyl-gem-dichlorocyclopropane (I) that the reaction proceeds with the formation of
chloroalkylarenes [1-(2,2-dichloro-1-methylcyclopropyl)ethyl]benzene (IV) and 1-[1-(2,2-dichloro-1-
methylcyclopropyl)ethyl]-4-methylbenzene(V). Compounds IV and V are the most selectively formed over
H-Beta (up to 82%) and H-Ymmm (up to 79%) zeolite catalysts with a high conversion of I (from 90% to
full). It has been shown that high selectivity for chloroalkylarenes IV and V is achieved at 100°C, an arene :
unsaturated compound molar ratio of 8 : 1, a catalyst concentration of 20 wt % of the reaction mass, and a
reaction time of 2 h.
Keywords: alkylation, arenes, vinyl-gem-dichlorocyclopropane, zeolites
DOI: 10.1134/S0965544119060057
Vinyl-gem-dichlorocyclopropanes, which are of lysts are the most efficient heterogeneous catalyst sys-
significant interest as intermediates for organic syn- tems for the alkylation of aromatic hydrocarbons
thesis, are readily formed in quantitative yields during (HCs) with olefins including the industrial processes
the dichlorocarbenylation of commercially available [7–11].
dienes (divinyl and isoprene) [1–4].
Thus, in this work we studied the reaction of arenes
(benzene and toluene) with 2-methyl-2-vinyl-gem-
dichlorocyclopropane in the presence of various zeo-
lite catalysts, namely, microporous zeolites, such as
H-Y (FAU structural type), H-Beta (BEA), H-MOR
(MOR), and H-ZSM-5 (MFI), and micro–meso–
macroporous H-Ymmm (FAU) catalysts.
The alkylation of aromatic structures with vinyl-
gem-dichlorocyclopropanes can be successfully used
for preparing a wide range of low-production-volume
chemicals containing the gem-dichlorocyclopropane
moiety. The resulting substituted benzenes are of sig-
nificant interest as additives for fuels, oils, and poly-
mers [5].
Acid-catalyzed alkylation of benzene and toluene
with vinyl-gem-dichlorocyclopropanes in the presence
of concentrated sulfuric acid has been studied earlier.
The corresponding alkyl arenes have been obtained in
a low yield (up to 34%). It has been shown that the
ratio of o- and p-isomers in the case of alkylation of
toluene with vinyl-gem-dichlorocyclopropanes is 1 : 4
in favor of the p-isomer [6]. In addition to the low yield
of the desired product, the procedure used is charac-
terized by tarring, need for expensive organic solvents,
and the multistage nature—it includes the reaction
mixture neutralization and washing steps. An alterna-
EXPERIMENTAL
Benzene and toluene of the reagent grade (EKOS-1)
were used in this work. The initial aromatic hydrocar-
bons (HCs) were thoroughly purified and dried
according to a procedure described in [12].
The unsaturated compound 2-methyl-2-vinyl-
gem-dichlorocyclopropane (I) was obtained according
to a procedure given in [4].
The H-Y zeolite (a molar ratio SiO2/Al2O3 = 5 and
a degree of decationation αNa = 0.95) was obtained via
ion exchange in a solution of NH4NO3 at 70°C from
tive method eliminating all the above disadvantages is Na-Y zeolite synthesized at the Institute of Petroleum
catalysis with the use of heterogeneous catalysts. As it Chemistry and Catalysis, Russian Academy of Sci-
has been acknowledged in recent years, zeolite cata- ences, according to a procedure described in [13]. The
581

582
BAIBURTLI et al.
Beta zeolite (SiO2/Al2O3 = 18) manufactured by the of 8°C/min; evaporator temperature, 280°C; ion
source temperature, 200°C; ionization energy, 70 eV).
Angarsk Catalyst and Organic Synthesis Plant in the
13
1H and C NMR spectra and homo- and heteronu-
NH4+
form was converted into the H-form by thermal
clear procedures, such as COSY, HSQC, and HMBC,
were recorded on Bruker Avance-400 instruments
(operating frequencies of 400.13 and 100.62 MHz for
1H and 13C, respectively) using CDCl3 as the solvent.
treatment in air at 540°C for 3 h. The H-ZSM-5 zeo-
lite (SiO2/Al2O3 = 30) was purchased from the Ishim-
bai Specialty Catalyst Plant. The Na-MOR zeolite
(SiO2/Al2O3 = 5.0) was synthesized at the Institute of
Petroleum Chemistry and Catalysis, according to
a procedure described in [14] and converted into the
+
The compounds had the following characteristics:
[1-(2,2-dichloro-1-methylcyclopropyl)ethyl]ben-
zene IV. Colorless liquid. Tb 106°C (2 mmHg).1H
NMR, δ, ppm (CDCl3): 1.31 (d, 3H, CH3(5)), 1.79 (s,
3H, CH3(6)), 2.45–2.65 (m, 2H, CH2(2)), 2.99–3.08
H-form by ion exchange of Na+ for
cations fol-
NH4
lowed by the thermal treatment of the obtained
ammonium form.
(m, H, CH(4)), 7.24 (s, H, CH(10)),7.32 (s, H,
The procedure for preparing the micro–meso–
13
macroporous Ymmm zeolite in the H-form CH(8,12)), 7.34 (s, H, CH(9,11)). C NMR, δ, ppm
(SiO2/Al2O3 = 7.2) is described in [15, 16] and is based (CDCl3): 20.37 (C(5)), 21.17 (C(6)), 38.11 (C(4)),
on the selective crystallization of pellets, made of 38.21 (C(3)), 44.05 (C(2)), 126.36 (C(10)), 126.88
finely divided Na-Y zeolite and amorphous binder (C(8,12)), 128.44 (C(9,11)), 133.96 (C(7)), 146.11
(C(1)). Mass spectrum, m/e (Irel, %): 228 (8) [M+],
201 (8), 199 (13), 165 (16), 163 (46), 157 (10), 129 (10),
115 (10), 105 (100), 103 (9), 91 (17), 77 (16).
(metakaolin), in sodium silicate solutions at 96–98°C.
A sample of H-Ymmm zeolite with αNa = 0.95 was
prepared via ion exchange of the Na-Ymmm zeolite.
Prior to catalyst testing, zeolite samples were sub-
jected to thermal treatment in air at 350°C for 4 h.
The zeolite catalysts were characterized using
X-ray phase (XPA) and X-ray diffraction (XRD) anal-
ysis techniques, adsorption methods, low-tempera-
ture adsorption of nitrogen, mercury porosimetry, and
temperature-programmed adsorption–desorption of
ammonia (NH3-TPD) [17–20].
1-[1-(2,2-dichloro-1-methylcyclopropyl)ethyl]-4-
methylbenzene V. Colorless liquid. Tb 131°C
1
(2 mmHg). H NMR, δ, ppm (CDCl3): 1.28 (d, 3H,
CH3(5)), 1.79 (s, 3H, CH3(6)), 2.36 (s, 3H, CH3(13)),
2.45–2.65 (m, 2H, CH2(2)), 2.96–3.02 (m, H,
CH(4)), 7.06 (s, H, CH(9,11)), 7.28 (s, H, CH(8,12)).
13C NMR, δ, ppm (CDCl3): 20.21 (C(5)), 21.20
(C(6)), 21.28 (C(13)), 37.77 (C(4)), 38.11 (C(3)),
44.06 (C(2)), 126.72 (C(9,11)), 127.08 (C(8,12)),
134.00 (C(10)), 143.77 (C(1)).Mass spectrum, m/e
(Irel, %): 242 (2) [M+], 206 (8), 191 (2), 171 (3), 141
(2), 119 (51), 103 (19), 91 (9), 77 (4).
General Procedure for C-Alkylation of Benzene
and Toluene with 2-Methyl-2-Vinyl-gem-
Dichlorocyclopropane
A calculated amount of zeolite, a reactant aromatic
(benzene (II) or toluene (III)), and the unsaturated
reactant 2-methyl-2-vinyl-gem-dichlorocyclopropane
(I) in a molar ratio of 2 : 1–8 : 1 were charged into a
glass ampoule. After sealing, the ampoule was placed
in a 17-mL “finger-type” metal autoclave which was
heated at a preset temperature with continuous rota-
tion in a thermostated cabinet for a certain time. Then
the reaction mixture was cooled, separated from the
catalyst by filtering, and analyzed by GLC. The reac-
tion products were isolated by vacuum distillation.
Compounds IV and V were obtained according to this
procedure.
RESULTS AND DISCUSSION
Characteristics of Zeolite Catalysts
The catalytic properties of the zeolite catalysts dif-
fering in the crystal lattice structure, acidic properties,
and porosity have been studied. The H-Y, H-Beta,
H-MOR, and H-ZSM-5 zeolites have a microporous
structure, and the H-Ymmm zeolite has a hierarchal
structure formed not only by micro-, but also meso-
and macropores [21, 22].
In the series of microporous zeolites, zeolites Y
(cavities with the entrance window of 0.74 × 0.74 nm)
and Beta (straight channels with a size of 0.66 ×
0.67 nm and tortuous channels with a size of 0.56 ×
0.56 nm) possess the widest pores. Pentasil ZSM-5 is
characterized by narrower pores are (straight channels
of a 0.51 × 0.55 size nm and tortuous channels of a
0.53 × 0.56 nm size). The H-MOR zeolite has a uni-
dimensional channel structure (two types of channels
with sizes of 0.70 × 0.65 and 0.26 × 0.57 nm) [23].
The chromatographic analysis of the products was
performed on a chromatograph equipped with a flame
ionization detector (25 m glass capillary column
coated with SE-30; column temperature, 50–280°C
programmed for a heating rate of 8°C/min; detector
temperature, 250°C; evaporator temperature, 300°C;
carrier gas (helium) flow rate, 30 mL/min). Mass
spectra were obtained on a SHIMADZU GCMS-
QP2010Plus instrument (SPB-5 capillary column
30 m × 0.25 mm; helium as the carrier gas, tempera-
The physicochemical properties of the zeolite cat-
ture programming from 40 to 300°C at a heating rate alysts studied are presented in Table 1.
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ALKYLATION OF AROMATIC HYDROCARBONS
Table 1. Physicochemical characteristics of the zeolites
583
Equilibrium adsorption
capacity
(20°C and P/Ps = 0.8),
cm3/g, for vapor of
Acidic properties*
Crystallinity,
rel. %
Ssp, m2/g
concentration of acid sites, μmol g−1
Catalyst
H2O
C6H6
CI
CII
C
H-Y
H-Beta
H-MOR
H-ZSM-5
H-Ymmm
100
100
100
100
93
0.30
0.26
0.18
0.14
0.25
0.30
0.32
0.16
0.15
0.30
870
470
393
320
741
610
530
651
270
515
520
340
349
190
460
1130
870
1000
460
975
* C , C , and C are the concentrations of “weak” and “strong” acid sites and their total concentration, respectively.
I
II
According to the XPA data and values of the alysts proceeds with the formation of chloroalky-
adsorption characteristics of the zeolites, the degree of larenes IV and V (see Scheme 1). In addition to them,
crystallinity is close to 100% for all the samples of products of transformation of unsaturated reactant I
microporous zeolites. For the H-Ymmm zeolite, the denoted as “light” were identified in the reaction mix-
crystallinity is 93%, which is associated with the ture.
incomplete crystallization of its amorphous compo-
Note that in the case of alkylation of toluene with
nent.
vinylcyclopropane I in the presence of the studied zeo-
According to the data of the low-temperature
adsorption–desorption of nitrogen and mercury poro-
simetry for an H-Ymmm zeolite sample, the “appar-
ent” BET specific surface area of the samples is
741 m2/g, and the specific surface area of the second-
ary porous structure determined using mercury poro-
simetry is 12.1 m2/g. The volumes of micro-, meso-,
and macropores are 0.28, 0.15, and 0.15 cm3/g,
respectively.
The NH3-TPD spectra of the microporous zeolites
exhibit two peaks, the low-temperature peak with a
maximum at 250–300°C and the high-temperature
peak with a maximum in the range of 410–480°C.
Their presence suggests that there are acid sites of two
types in the samples under study, namely, weak sites
characterized by the low-temperature peak and strong
sites characterized by the high-temperature peak [18].
The concentration of strong acid sites, which
are the most important for catalytic transformations,
decreases in the order H-Y > H-MOR ≥ H-Beta > H-
ZSM-5. The total concentration of the acid sites varies
in a similar manner.
lites, only the p-isomer is produced. Due to presence
of two chiral centers in IV and V, two diastereomers
with the (R*,R*)- and (R*,S*)-configurations can be
formed. The presence of the diastereomeric pair in the
products is confirmed by the appearance of a twinned
13
set of signals with a 2 : 3 ratio in the C NMR spec-
trum. Unfortunately, it is difficult to perform direct
identification of the prevalent isomer because com-
pounds IV and V lack functional groups capable of
selective binding of derivatizing shift agents.
R
R
CH3
CH2
+
Cl Cl
CH3
H3C
II, III
I
Cl Cl
IV, V
R = H (II, IV), R = CH3 (III, V)
The acidity spectra of the H-Ymmm zeolite display
two peaks due to weak acid sites with a temperature
maximum Tmax at 250–280°C and strong acid sites
with Tmax in the temperature range of 350–420°C. The
concentration of the strong acid sites in the H-Ymmm
zeolite is lower than that in the H-Y zeolite.
Scheme 1. Scheme of the reaction of benzene and tolu-
ene with 2-methyl-2-vinyl-gem-dichlorocyclopropane.
The alkylation proceeds most selectively in the
presence of the microporous H-Beta zeolite or the
micro–meso–macroporous
H-Ymmm
zeolite
(Table 2). The values of selectivity for alkylarenes IV
and V are close, being 73–82%. The highest conver-
Catalytic Properties of Microporous Zeolites in Synthesis sion of vinylcyclopropane I was observed over the
of Alkylarenes
same catalysts (H-Beta and H-Ymmm).
The alkylation of arenes II and III with unsaturated
The high catalytic activity and selectivity of the H-
compound I in the presence of the studied zeolite cat- Beta and H-Ymmm zeolites is apparently determined
PETROLEUM CHEMISTRY Vol. 59 No. 6 2019

584
BAIBURTLI et al.
Table 2. Synthesis of [1-(2,2-dichloro-1-methylcyclopropyl)ethyl]benzene IV and 1-[1-(2,2-dichloro-1-methylcyclopro-
pyl)ethyl]-4-methylbenzene V in the presence of zeolite catalysts. Synthesis conditions: 20 wt % catalyst, T = 100°C, molar
ratio arene : I = 8 : 1, 2 h
Selectivity, %
Catalyst
Arene
Conversion of I, %
IV and V
light
H-Y
H-MOR
H-Beta
H-ZSM-5
H-Ymmm
H-Y
H-MOR
H-Beta
Benzene
70
35
100
0
90
86
15
97
0
39
57
82
0
79
29
52
81
0
61
43
18
0
21
71
48
19
0
Toluene
H-ZSM-5
H-Ymmm
96
73
27
by their porous structure characteristics providing low nor high acidity is desirable because the catalyst is
good accessibility of catalyst active sites for the react- inactive in the former case and predominantly cata-
ing molecules and not creating diffusion limitations lyzes the transformations of vinylcyclopropane I in the
for the transport of the reactant and product mole- latter case.
cules. The lower values of the selectivity of the H-
The influence of the reaction parameters (tem-
Ymmm zeolite for alkylarenes in comparison with the
perature, molar ratio of the reactants, catalyst concen-
H-Beta zeolite (73 versus 81%, respectively, in reac-
tration, reaction time) on the conversion of vinylcy-
tion with toluene) can be explained by a higher acidity
clopropane I and the product composition has been
of the H-Ymmm zeolite, which leads to the intensifi-
studied in the presence of H-Beta, the most active of
cation of the reactions of transformation of vinylcyclo-
the zeolite catalysts.
propane I, resulting in an increase in concentration of
It has been shown that a high conversion of vinyl-
the “light” compounds in the products.
cyclopropane I (from 90% to complete) is achieved at
The same factor, a high concentration of acid sites,
70–150°C (Fig. 1). The maximum selectivity for alky-
also explains the results obtained over H-Y and
larene V is observed at 100°C, a further increase in
H-MOR zeolites. The reaction mixture obtained in
temperature leads to an increase in the yield of the side
the presence of these catalysts contained a significant
products.
amount of the “light” compounds, because of which
Increasing the concentration of toluene in the ini-
tial reaction mixture from 2 : 1 to 8 : 1 leads to an
increase in selectivity for desired product V (Fig. 2). At
the minimum concentration of toluene in the reaction
mixture, the alkylarene selectivity is low because of the
predominant occurrence of side reactions of transfor-
mation of vinylcyclopropane I. The high alkylarene
selectivity with an almost complete conversion of
vinylcyclopropane I is achieved at a toluene : I molar
ratio of 8 : 1.
The conversion of vinylcyclopropane I and the
selectivity for alkylarene V are also affected by the con-
centration of the zeolite catalyst (Fig. 3). The alkyla-
tion proceeds most selectively and with a high conver-
sion of vinylcyclopropane I in the presence of the cat-
alyst in an amount of 20% of the mass of the reactants.
the selectivity for alkyl arenes IV and V is lower than
over the H-Beta zeolite. At the same time, the signifi-
cant difference in the values of the vinylcyclopropane
I conversion observed over the H-Y and H-MOR
samples is apparently due to particular features of the
crystal lattice structure of these zeolites. The three-
dimensional wide-pore structure of the H-Y zeolite
provides better accessibility of active sites for the reac-
tants than does the unidimensional porous structure
of H-MOR; therefore, the conversion of vinylcyclo-
propane I over the H-Y zeolite is two- to fivefold
higher tan that on the H-MOR zeolite.
The H-ZSM-5 zeolite was inactive in the reaction.
It can be supposed that the lack of activity is due to the
low concentration of acid sites in it or spatial hin-
drances created by the narrow channels of H-ZSM-5
zeolite to the reactants and the products.
Figure 4 illustrates the influence of the reaction
The obtained results show that in order to obtain time on the degree of conversion of unsaturated com-
alkylarenes IV and V with a high yield, it is necessary pound I and the selectivity for 1-[1-(2,2-dichloro-1-
that a zeolite catalyst have both a wide-pore structure methylcyclopropyl)ethyl]-4-methylbenzene V. The
and an optimum concentration of acid sites. Neither maximum conversion of the unsaturated compound
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ALKYLATION OF AROMATIC HYDROCARBONS
585
1—conversion of unsaturated compound I, %
1—conversion of unsaturated compound I, %
2—selectivity for alkylarene V, %
3—selectivity for “light” products
2—selectivity for alkylarene V, %
3—selectivity for “light” products
1
1
1
100
90
80
70
60
50
40
30
20
10
0
100
80
60
40
20
0
1
1
2
1
3
2
2
2
2
2
3
3
3
3
3
2
1
3
2 : 1
5 : 1
Toluene : unsaturated compound molar ratio
40
70
Temperature, °C
100
8 : 1
150
Fig. 1. The influence of temperature on the conversion of
I and the selectivity for 1-[1-(2,2-dichloro-1-methylcy-
clopropyl)ethyl]-4-methylbenzene V. Synthesis condi-
tions: a molar ratio of toluene : I = 5 : 1, 20 wt % catalyst,
2 h.
Fig. 2. The influence of the molar ratio of the reactants on
the conversion of I and the selectivity for 1-[1-(2,2-
dichloro-1-methylcyclopropyl)ethyl]-4-methylbenzene V.
Synthesis conditions: 100°C, 20 wt % catalyst, autoclave,
2 h.
1—conversion of unsaturated compound I, %
2—selectivity for alkylarene V, %
1—conversion of unsaturated compound I, %
2—selectivity for alkylarene V, %
3—selectivity for “light” products
1
100
90
80
70
60
50
40
30
20
10
0
3—selectivity for “light” products
1
1
1
100
90
80
70
60
50
40
30
20
10
0
2
2
1
2
3
2
2
3
2
3
1
3
3
3
5
1
10
2
20
3
Concentration of H-Beta, %
Reaction time, h
Fig. 3. The influence of the concentration of the catalyst
on the conversion of unsaturated compound I and the
selectivity for 1-[1-(2,2-dichloro-1-methylcyclopro-
pyl)ethyl]-4-methylbenzene V. Synthesis conditions:
100°C, a molar ratio of arene : I = 8 : 1, autoclave, 2 h.
Fig. 4. The influence of the reaction time on the conver-
sion of unsaturated compound I and the selectivity for
1-[1-(2,2-dichloro-1-methylcyclopropyl)ethyl]-4-methyl-
benzene V. Synthesis conditions: 100°C, a molar ratio of
arene : I = 8 : 1, 20 wt % catalyst.
and selectivity for the desired product are achieved selective catalysts for the synthesis of alkylarenes. The
after 2 h. Further running the synthesis leads to a
selectivity for [1-(2,2-dichloro-1-methylcyclopro-
pyl)ethyl]benzene IV and 1-[1-(2,2-dichloro-1-meth-
ylcyclopropyl)ethyl]-4-methylbenzene V over these
catalysts reaches 82% at a conversion of vinylcyclopro-
pane I of 90–100%.
decrease in selectivity for V.
In summary, it has been found as a result of the
investigation of the catalytic properties of various zeo-
lites in the alkylation reaction of benzene and toluene
with 2-methyl-2-vinyl-gem-dichlorocyclopropane,
that zeolites H-Beta (microporous) and H-Ymmm
It has been shown that the maximum yield of alky-
(micro–meso–macroporous) are the most active and larenes is achieved at a molar ratio of arene : I = 8 : 1
PETROLEUM CHEMISTRY Vol. 59 No. 6 2019

586
BAIBURTLI et al.
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12. L. F. Tietze und T. Eicher, Reaktionen und Synthesen im
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PETROLEUM CHEMISTRY
Vol. 59
No. 6
2019