Sulfated Zirconia-catalyzed Alkylation of Phenol with Camphene and Isomerization of n-butane

Article abstract of DOI:10.1016/j.mencom.2014.03.011

Sulfated zirconia modified with polyvalent cations is capable of catalyzing alkylation of phenol with camphene and isomerization of utane into isobutane.

Full text of DOI:10.1016/j.mencom.2014.03.011

Mendeleev
Communications
Mendeleev Commun., 2014, 24, 98–99
Sulfated zirconia-catalyzed alkylation of phenol
with camphene and isomerization of n-butane
a
a
a
Svetlana A. Popova, Irina Yu. Chukicheva, Alexander V. Kutchin,
b
b,c
Andrei L. Tarasov and Leonid M. Kustov*
a
b
c
Institute of Chemistry, Komi Scientific Centre, Ural Branch of the Russian Academy of Sciences, 167982 Syktyvkar,
Komi, Russian Federation. Fax: +7 8212 21 8477; e-mail: chukicheva-iy@chemi.komisc.ru
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 499 135 5328; e-mail: lmk@ioc.ac.ru
Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation
DOI: 10.1016/j.mencom.2014.03.011
Sulfated zirconia modified with polyvalent cations is capable of catalyzing alkylation of phenol with camphene and isomerization of
n-butane into isobutane.
Development of catalysts and processes for alkylation of phenols
is an important problem since such products find use in medicine
and other areas. Terpenophenols are among the most demanded
1,2
compounds for their antioxidant and pharmacological activity.
Synthesis of terpenophenols is based on catalytic alkylation using
1
acid catalysts, such as mineral or organic acids, metal halides,
1
0%
cation-exchange resins, solid oxides etc.3–8 Some aluminum-
3
2
950
containing organoelement compounds providing high selectivity
2
of ortho-alkylation of phenols can be used as homogeneous
3150
2
765
3
,6,9
catalysts.
3350
Sulfated oxides are known10,11 to exhibit strong acidic pro-
perties exceeding the acidity of zeolites. For instance, sulfated
3640
12
4000
3500
3000
2500
zirconium dioxide is sometimes classified as a solid superacid.
The strength of acid sites in such systems increases in the range
Al O < TiO < ZrO . Some multivalent metal ions (Fe, Mn, Ga,
n/cm–1
2
3
2
2
Figure 1 IR spectra of 5%SO 42 –/ZrO calcined in air at (1) 650, (1) 750
2
Zn, Co) are capable of enhancing the acidic properties of these
and (3) 850°C.
1
3–15
solid acids,
which is usually accounted for the inductive
effect of the multivalent cation on the Brønsted acid sites, i.e.,
OH groups bonded to the introduced sulfate moieties.
IR spectra of the samples of sulfated zirconia in the region of
–
1
OH group stretching vibrations (4000–3500 cm ) are presented
in Figure 1. The spectra represent a superposition of the narrow
Sulfated oxides possess certain additional benefits compared
to zeolites. As a rule, the range of the catalytic applications of
zeolites is limited by the diameter of zeolite entrances (< 0.65 nm)
and cavities (< 1.3 nm), which would restrict the size of the
interacting molecules, typically below 1 nm. For the sulfated
oxides based on rather wide-pore carriers (ZrO , TiO , Al O ),
–
1
absorption bands with maxima at 3730 and 3640 cm attributed
to terminal and bridging ZrOH groups, respectively.
In addition to the narrow lines, a broad absorption band of
the main stretching OH vibrations at 3350–3150 cm–1 is also
observed with its maximum and intensity being dependent upon
the pretreatment temperature in the range of 650–850°C. Earlier9
this band was ascribed to the delocalized protons emerged from
H SO . These protons can also be shared with oxygen atoms of the
2
2
2
3
such limitations are absent. Furthemore, the sulfated systems are
characterized by the enhanced thermal stability, as far as they
are typically prepared by calcinations at temperatures higher than
2
4
2
–
6
50°C.
This work is focused on the study of the alkylation of phenol
zirconia framework (Figure 2). The IR spectra of the SO /ZrO
4 2
catalysts additionally modified with metal ions are very similar
2
–
with camphene in the presence of sulfated catalysts based on
to the spectrum of the unmodified SO /ZrO sample.
4 2
†
zirconium dioxide, including the systems modified with cations
Isobornyl phenyl ether 3a was found to be the main product
of the alkylation of phenol 1 with camphene 2 (Scheme 1).‡
C-Alkylated phenols, namely 2-isobornylphenol 4a and 2-iso-
camphylphenol 4b were formed in minor quantities (Table 1). The
of gallium, iron, cerium and vanadium. These catalysts were
also tested in isomerization of n-butane, a reaction requiring the
presence of very strong Brønsted acid sites.
†
2
–1
VO2+ nitrates with further drying at 120°C for 6 h and calcinations in
a flow of dry air at 650°C for 2 h. The loading of the modifying metal
was 2 wt%.
ZrO2 was prepared by calcination of Zr(OH)4 (Ssurf = 150 m g ,
Magnesium Electron Co., grade XZO632/03) at 500°C for 2 h in a flow
2–
2–
of air. In order to prepare SO /ZrO , SO anions were introduced from
4
2
4
a 1 m aqueous solution of H SO ; the concentration of sulfate groups in
Prior to spectral studies, the samples were calcined at 300–650°C in
2
4
the samples was 5 wt%. The samples were dried at 120°C for 6 h and
calcined in a flow of dry air at 650°C for 2 h. Modification with metal
cations was carried out by incipient wetness impregnation of the calcined
a vacuum for 2 h in a quartz IR-ampule supplied with a CaF window.
2
Diffuse-reflectance IR spectra were measured with a Nicolet Impact 410
FTIR spectrometer and processed using the Kubelka–Munk function (the
OMNIC program).
3+
3+
3+
3+
sulfated sample with 0.3 m aqueous solutions of Fe , Ga , Co , Ce ,
©
2014 Mendeleev Communications. All rights reserved.
– 98 –

Mendeleev Commun., 2014, 24, 98–99
O
S
2
–
H
O
30
SO /ZrO
4 2
O
O
Zr
O
Zr
2
1
0
0
0
O
Zr
Zr
Figure 2 Delocalized protons in sulfated zirconia.
Ga
Co
Fe
Table 1 Sulfated zirconia-catalyzed alkylation of phenol with camphene.
8
0
100 120 140 160 180 200 220 240 260
Phenol
Product composition (%)
T/°C
Catalyst
T/°C t/h conver-
sion (%) 3a
3b
4a + 4b
Figure 3 Yield of isobutane in the course of n-butane isomerization on
Fe3+/5SO /ZrO
2–
sulfated zirconia and that modified with metal cations (190°C, liquid hourly
speed velocity is 1 h ).
2
2
2
2
60
100
100
110
3
3
5
3
76
84
70
0
71
92
79
—
11
5
18
3
4
2
–1
Ga3+/5SO /ZrO
2–
4
2
Ce3+/5SO /ZrO
2–
9
12
—
4
2
commercial catalyst for isomerization of n-butane, is active at
lower temperatures (140–160°C) than those found for the sulfated
zirconia (~190°C). Sulfated oxides are also promising for other
acid-catalyzed chemical processes.
V5+/5SO /ZrO
2–
—
4
2
OH
OR
OH
R
Me
catalyst
+
Me
CH2
+
This work was supported by the Program of Fundamental
Research of Ural Branch of the Russian Academy of Sciences
(project no. 12-C-3-1013) and by the Ministry of Education and
Science of the Russian Federation (project nos. 8441 and 8431).
1
2
3a,b
4a,b
Me
Me
Me
Me
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a R =
b R =
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Scheme 1
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3
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2
>
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§
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3
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‡
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3
(
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H
1
3
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–
1
1
00–240°C, heating rate 6 K min ).
§
Isomerization of n-butane was studied in a flow reactor at 190°C,
pressure of 1 atm, butane liquid hourly space velocity 1 h . Products were
analyzed by GC.
–1
Received: 1st August 2013; Com. 13/4182
–
99 –