H-β-zeolite-catalysed hydroarylation of styrenes

Article abstract of DOI:10.1002/ejoc.201200283

The hydroarylation of styrenes with various arene(heteroarene) compounds using H-β-zeolite as a green and recyclable heterogeneous catalyst under mild reaction conditions has been developed. The catalyst showed versatility and high selectivity (up to 100a€‰%) of desired 1,1-diarylalkanes in cyclohexane as solvent under the conditions studied. The catalyst could be reactivated by simple treatment with mineral acid at room temperature for better catalytic activity. Hydroarylation of styrenes with variousarene(heteroarene) compounds using H-β-zeolite as a green, heterogeneous and reusable catalyst under mild conditions is reported.

Full text of DOI:10.1002/ejoc.201200283

FULL PAPER
DOI: 10.1002/ejoc.201200283
H-β-Zeolite-Catalysed Hydroarylation of Styrenes
Darapaneni Chandra Mohan,[a] Rajendra D. Patil,[a] and Subbarayappa Adimurthy*[a]
Keywords: Synthetic methods / Green chemistry / Heterogeneous catalysis / Zeolites / Arenes / Arylation
The hydroarylation of styrenes with various arene(heteroar-
ene) compounds using H-β-zeolite as a green and recyclable
heterogeneous catalyst under mild reaction conditions has
been developed. The catalyst showed versatility and high
selectivity (up to 100%) of desired 1,1-diarylalkanes in cyclo-
hexane as solvent under the conditions studied. The catalyst
could be reactivated by simple treatment with mineral acid
at room temperature for better catalytic activity.
In a continuation of our program on the development of
green and efficient methods,[20] herein, we wish to report an
efficient, facile and reusable heterogeneous catalytic system
for the C–H functionalization of various arenes/heteroar-
enes (Scheme 1). The procedures reported herein have the
following significant advantages over previously reported
procedures for the hydroarylation of styrenes: (i) atom effi-
ciency and no byproduct formation, (ii) it is easily handled
(open atmosphere), (iii) a variety of arenes can be used as
starting substrates (the use of a range of anisoles, phenols,
naphthols and heteroarene is also possible); (iv) separation
of the catalyst and product is very easy, (v) H-β-zeolite cata-
lyst is inexpensive in comparison to metal-based catalysts,
and (vi) H-β-zeolite can be reused many times without ap-
preciable loss of its high catalytic activity.
Introduction
The majority of known fine chemicals, pharmaceuticals,
agrochemicals, dyes and relevant target molecules contain
aromatic/heteroaromatic backbones.[1] In the recent past,
most aromatic C–H functionalization has been achieved
through well-known classic transformations such as Frie-
del–Crafts alkylation, Friedel–Crafts acylation, nitration
and halogenations reactions. Recently, promising metal-cat-
alyzed C–H activation of arenes and heteroarenes have been
reported,[2–4] including precious metals such as ruthe-
nium,[5] palladium[6,7] and platinum[8] catalysts. Other
[11]
prominent systems, including FeCl3,[9] BiCl3,[10] Bi(OTf)3
and iodine,[12] have been used to catalyse the hydroarylation
of styrenes for the synthesis of a variety of 1,1-diaryl alk-
anes in good yields. Although these methods work reliably
with a variety of substrates, they are often associated with
major drawbacks such as the need for drastic reaction con-
ditions (high temperature, strong acidic conditions), low re-
gioselectivity, moisture sensitivity and generation of stoi-
chiometric amounts of byproducts (typically salts). Due to
increased interest in this class of compounds, efforts have
been made to develop cleaner and more environmentally
friendly processes using, for example, zeolites,[13] ion ex-
change resin,[14] and iron-containing mesoporous alumino-
silicate[15] as heterogeneous catalytic systems. H-β-Zeolite is
known to have Brønsted acid sites in the micropores and
active Lewis acid sites on the external surface.[16] The com-
bination of active Lewis acid site along with the available
Brønsted acid site in the H-β-zeolite has enabled this mate-
rial to be used as an acid catalyst in organic chemical trans-
formations such as alkylation[17] and acylation.[18] Although
H-β-zeolite has been employed as a heterogeneous cata-
lyst,[19] its use has not been explored in hydroarylation reac-
tions for synthetic chemistry.
Scheme 1.
Results and Discussion
Initially, the H-β-zeolite catalytic system was applied for
C–H functionalization of anisole 1 with styrene 2 as model
substrates; the results are presented in Table 1. It was ob-
served that the reaction has considerable dependence on
solvent, temperature and amount of catalyst. The reactions
were assessed in various solvent media and a range of cata-
lytic systems were examined. As can be seen from the data
presented in Table 1, the best yield of the desired product
was obtained with 20% (w/w) H-β-zeolite catalyst and cy-
clohexane as solvent at 80 °C for a period of 6 h. These
parameters were set as optimum for the subsequent synthe-
sis of diaryl alkanes.
[a] Analytical Science Division, Central Salt & Marine Chemicals
Research Institute (CSIR), G. B. Marg,
Bhavnagar 364021, India
Fax: +91-278-2567562
E-mail: adimurthy@csmcri.org
3520
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H-β-Zeolite-Catalysed Hydroarylation of Styrenes
Table 1. Optimization of conditions for hydroarylation of styrene
Table 2. Reactions of anisole (1) with styrenes.[a]
(2) with anisole (1).[a]
[a] Reagents and conditions (unless otherwise stated):
1
[a] Reagents and conditions (unless otherwise stated):
1
(19.2 mmol), styrene (4.8 mmol), H-β-zeolite (20 wt.-% with re-
spect to styrene), cyclohexane (3 mL), 80 °C. In all entries, the con-
versions were 100% with reference to styrene. [b] GC yield of aryl-
ated product (yield in parenthesis refers to isolated yields). [c] Main
product to the alternative isomer. [d] Produced together with the
homocoupled product.
(19.2 mmol), 2 (4.8 mmol), catalyst, 80 °C. [b] Conversion with the
reference to styrene. n.r. = no reaction. [c] GC yield of arylated
products. [d] Main product 3 to the alternative isomer. [e] Styrene
to anisole molar ratio was 1:1, 1:2 and 1:3 in entries 2, 3 and 4,
respectively. [f] Reaction temperature 60 °C. [g] Room temperature.
Encouraged by the results obtained for the reaction of
To explore the scope of the present system under the op- anisole with styrenes, we extended this methodology for the
timum conditions (Table 1, entry 5), anisole 1 was treated functionalization of other arenes (Table 3). The reaction of
with a range of styrenes; the results are presented in Table 2. substituted phenols with various styrene derivatives pro-
The desired product 3 was isolated in 96% yield from styr- ceeded smoothly and provided good yields of diarylethanes
ene (2) (Table 2, entry 1). Styrenes having either electron- (Table 3, entries 1–4). Similar to phenols, 2-naphthol also
donating or -withdrawing substituents were well-tolerated reacted smoothly with styrenes with either electron-donat-
in this system and resulted in excellent yields of the corre- ing or electron-withdrawing substituents and provided ex-
sponding diarylethanes (Table 2, entries 2–6). Reaction of cellent yields of the corresponding products with high re-
anisole with compounds containing an internal olefin, such gioselectivity (98–100%; Table 3, entries 5–9). It may be
as indene, also provided good (76%) isolated yield of de- noted that functionalization of 2-naphthols with styrenes
sired product (Table 2, entry 7). However, α-methyl styrene provided excellent yield and selectivity of the desired prod-
gave low yield of desired product and was accompanied by ucts compared to literature methods.[9,14] The reaction of 1-
the formation of the homocoupled product (Table 2, en- naphthol with styrene also provided 96% GC yield of diary-
try 8). Aliphatic alkene substrates did not react and re- lethanes (Table 3, entry 10). The present methodology is
mained unaffected (Table 2, entry 9). The presence of cata- also applicable for the direct alkylation of aryl ethers with
lytic sites located within the rigid pores of the zeolite matrix good yield and selectivity (Table 3, entry 11). Thus, the high
imposes additional constraints on reacting partners, thereby yield and regioselectivity of products in Table 3 indicate the
favouring the formation of only one regioisomer, usually catalytic efficiency of H-β-zeolite for hydroarylation of vari-
the most linear para-isomer.[19]
ous styrenes under simple reaction conditions.
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D. C. Mohan, R. D. Patil, S. Adimurthy
FULL PAPER
Table 3. Reaction of arenes with styrenes.[a]
[a] Reagents and conditions: styrene (4.8 mmol), arene (4.8–19.2 mmol), H-β-zeolite (20 wt.-% with respect to styrenes), cyclohexane
(3 mL), 80 °C. In all entries, the conversions were 100% with reference to styrene. [b] Styrene to arene molar ratios were 1:4 in entries 1–
4, and 11, and 1:1 in entries 5–10; only 5 wt.-% catalyst used in entries 5–10. [c] GC yield of arylated product (yield in parenthesis refers
to isolated yield). [d] Main product to the alternative isomer. [e] Produced together with the homocoupled product of styrene.
To further evaluate the scope of the present methodology compatible with the present system and these compounds
for arene functionalization, a series of heteroarenes were ex- failed to undergo the reaction (data not shown).
amined with different styrenes (Table 4). The reaction of
As evident from the recyclability study (Table 5), the cat-
various thiophenes with styrenes resulted in a good to high alyst could be easily recovered and reused[21,22] up to three
yield of heteroalkylated products (Table 4, entries 1–6). How- consecutive cycles without compromising conversion or
ever, electron-withdrawing 2-acetoxythiophene (Table 4, en- selectivity.
try 7) remained unaffected under the reaction conditions.
The unactivated catalyst required longer reaction time
Due to the high acidity of the catalyst, the use of acid-sensi- than activated catalyst. This may be due to its acidic charac-
tive heteroarenes such as N-phenyl pyrrole or indoles is in- ter. As the catalyst is reused, its acidic property slightly de-
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Eur. J. Org. Chem. 2012, 3520–3525

H-β-Zeolite-Catalysed Hydroarylation of Styrenes
Table 4. Reactions of heteroarenes with styrenes.[a]
same morphology for the fresh and recovered catalyst (Fig-
ure 1). The acidity of the H-β-zeolite was also investigated
by using the Temperature Programmed Desorption of am-
monia (TPD-NH3) technique (see the Supporting Infor-
mation); two desorption peaks were observed at 185.2 and
388 °C on the H-β-zeolite, corresponding to its weak and
strong acidic sites, respectively.
Figure 1. SEM image of H-β-zeolite (a) before and (b) after the re-
action.
Conclusions
We have developed a simple and versatile protocol for
the hydroarylation of styrenes with arenes/heteroarenes
using H-β-zeolite as a green and heterogeneous catalyst un-
der mild reaction conditions. The catalyst is commercially
available, regioselective, inexpensive, easily recoverable, re-
usable, and its applicability for a wide range of arene and
styrene substrates favours the scope of the present protocol
for C–C bond forming reactions.
[a] Reagents and conditions: styrene (4.8 mmol), heteroarene
(19.2 mmol), H-β-zeolite (20 wt.-% with respect to styrenes), cyclo-
hexane (3 mL), 80 °C. [b] Isolated yield. [c] Selectivity based on 1H
NMR spectroscopic analysis (main product to alternative arylated
product).
Table 5. Recyclability study of the catalyst.[a]
Experimental Section
The H-β-zeolite (SiO2/Al2O3 = 24) was procured from Zeochem,
Switzerland.
General Procedure for the Synthesis of 1,1-Diarylethane (3): To a
stirred solution of anisole 1 (2.07 g, 19.2 mmol) and styrene 2
(0.50 g, 4.8 mmol) in cyclohexane (3 mL), was added H-β-zeolite
(100 mg, 20 wt.-%). The mixture was heated to reflux at 80 °C for
6 h and the progress of the reaction was monitored by TLC. The
reaction mixture was then allowed to attain room temperature and
filtered to remove H-β-zeolite catalyst. The H-β-zeolite was washed
with diethyl ether (10 mL) and a sample was drawn for GC-MS
analysis, which showed 100% hydroarylated products. The filtrate
was concentrated in vacuo and the residue was subjected to column
chromatography on silica gel (ethyl acetate/hexane). The pure hy-
droarylated product 3 (0.98 g, 4.6 mmol) was obtained in 96% yield
as a colourless liquid. All reactions were carried out in air without
any special precautions.
[a] Reagents and conditions as described in Table 2. [b] Recovered
catalyst is activated and reused.[22] [c] Recovered catalyst is used as
such. [d] GC yield of arylated products. [e] Main product 3 to the
alternative isomer.
creases, presumably due to leaching of H+ ions. Hence, a
slight decrease in the catalytic activity was observed. How-
ever, the catalytic activity can be restored by simple treat-
ment of the catalyst with mineral acid (H+) at room tem-
perature.[22] The H-β-zeolite catalyst utilised in the present
study is commercially available.
The catalyst (fresh and reused) has been characterized by
using XRD and FTIR analysis.[23] The XRD analysis of
reused catalyst matched well with the fresh catalyst, thus
suggesting that crystallinity and phase purity of the reused
catalyst are comparable to the original material (see the
1-tert-Butyl-4-[1-(4-Methoxyphenyl)ethyl]benzene: Table 2, entry 2.
1
White solid; m.p. 53 °C. H NMR (200 MHz, CDCl3): δ = 1.32 (s,
9 H), 1.63 (d, J = 6.8 Hz, 3 H), 3.71 (s, 3 H), 4.11 (q, J = 7 Hz, 1
H), 6.84 (d, J = 7 Hz, 2 H), 7.18 (d, J = 7.8 Hz, 4 H), 7.33 (d, J =
6 Hz, 2 H) ppm. 13C NMR (50 MHz, CDCl3): δ = 22.3, 31.6, 34.5,
43.7, 55.2, 113.9, 125.4, 127.3, 128.7, 138.9, 143.9, 148.7, 158 ppm.
IR (neat): ν
= 3433, 2906, 2874, 1611, 1509, 1461, 1451, 1365,
˜
max
1260, 1118, 1113, 1044, 1020, 883, 819, 611, 557, 469 cm–1.
C19H24O (268.40): calcd. C 85.03, H 9.01; found C 85.36, H 9.09.
1-Phenoxy-4-(1-phenylethyl)benzene: Table 3, entry 11. White solid;
1
Supporting Information). SEM images also confirm the m.p. 60 °C. H NMR (500 MHz, CDCl3): δ = 1.63 (d, J = 9 Hz, 3
Eur. J. Org. Chem. 2012, 3520–3525
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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3523

D. C. Mohan, R. D. Patil, S. Adimurthy
FULL PAPER
H), 4.13 (q, J = 7 Hz, 1 H), 6.92 (d, J = 8.5 Hz, 2 H), 6.99 (d, J =
8.5 Hz, 2 H), 7.07 (t, J = 7 Hz, 1 H), 7.17 (d, J = 8.5 Hz, 3 H),
7.21 (m, 2 H), 7.29 (m, 4 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 22.7, 44.8, 119.4, 119.5, 123.7, 126.8, 128.3, 129.1, 129.5, 134,
[1]
K. Weissermel, H. J. Arpe, Industrielle Organische Chemie, 5th
ed., Wiley-VCH, Weinheim, Germany, 1988, p. 167.
[2] a) G. Dyker, Angew. Chem. 1999, 111, 1808; Angew. Chem. Int.
Ed. 1999, 38, 1698–1712; b) G. Dyker, E. Muth, A. S. K.
Hashmi, L. Ding, Adv. Synth. Catal. 2003, 345, 1247–1252; c)
B. Sezen, D. Sames, J. Am. Chem. Soc. 2003, 125, 10580–10585;
d) B. Sezen, D. Sames, J. Am. Chem. Soc. 2003, 125, 5274–
5275; e) F. Muhlthau, O. Schuster, T. J. Bach, J. Am. Chem.
Soc. 2005, 127, 9348–9349; f) J. Liu, E. Muth, U. Florke, G.
Henkel, K. Merz, J. Sauvageau, E. Schwalke, G. Dyker, Adv.
Synth. Catal. 2006, 348, 456–462.
[3] Y. Nakao, K. S. Kanyiva, S. Oda, T. Hiyama, J. Am. Chem.
Soc. 2006, 128, 8146–8147.
[4] M. Yasuda, T. Somyo, A. Baba, Angew. Chem. 2006, 118, 807;
Angew. Chem. Int. Ed. 2006, 45, 793–796.
142, 147.1, 156, 158.1 ppm. IR (neat): ν
= 3029, 2966, 2929,
˜
max
1536, 1490, 1415, 1392, 1291, 1227, 1136, 1110, 1073, 1016, 1012,
860, 802, 756, 694, 604, 537 cm–1. C20H18O (274.36): calcd. C 87.56,
H 6.61; found C 87.80, H 6.93.
3-Methyl-2-(1-phenylethyl)thiophene: Table 4, entry 2. Colourless li-
quid. 1H NMR (500 MHz, CDCl3): δ = 1.64 (d, J = 7 Hz, 3 H),
2.03 (s, 3 H), 4.34 (q, J = 7 Hz, 1 H), 6.74 (d, J = 5 Hz, 1 H), 7.00
(d, J = 5 Hz, 1 H), 7.13–7.25 (m, 5 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 14, 23.4, 39, 118.8, 121.4, 126.3, 127.3, 128.6, 130.3,
132.6, 137.2, 146.1 ppm. IR (neat): ν
= 3433, 3062, 3027, 2969,
˜
max
2927, 2871, 1602, 1492, 1451, 1378, 1168, 1026, 913, 836, 805, 762,
701, 670, cm–1. HRMS: calcd. for C13H15S 203.0894; found
203.0904.
[5] a) F. Kakiuchi, S. Murai, Acc. Chem. Res. 2002, 35, 826–834;
b) Y. Guari, A. Castellanos, S. Sabo-Etienne, B. Chaudret, J.
Mol. Catal. A 2004, 212, 77–82; c) C. H. Jun, J. B. Hong, Y. H.
Kim, K. Y. Chung, Angew. Chem. 2000, 112, 3582; Angew.
Chem. Int. Ed. 2000, 39, 3440–3442; d) S. W. Youn, S. J. Pas-
tine, D. Sames, Org. Lett. 2004, 6, 581–584.
2-[1-(4-tert-Butylphenyl)ethyl]-3-methylthiophene: Table 4, entry 3.
1
Colourless liquid. H NMR (500 MHz, CDCl3): δ = 1.36 (s, 9 H),
[6] a) S. Cacchi, G. Fabrizi, Chem. Rev. 2005, 105, 2873–2920; b)
N. P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J. Gaunt,
Angew. Chem. 2005, 117, 3185; Angew. Chem. Int. Ed. 2005,
44, 3125–3129; c) M. Kimura, M. Futamata, R. Mukai, Y. J.
Tamaru, J. Am. Chem. Soc. 2005, 127, 4592–4593; d) M. Band-
ini, A. Melloni, F. Piccinelli, R. Sinisi, S. Tommasi, A. Umani-
Ronchi, J. Am. Chem. Soc. 2006, 128, 1424–1425; e) B. M.
Trost, J. Quancard, J. Am. Chem. Soc. 2006, 128, 6314–6315;
f) C. Liu, R. A. Widenhoefer, Chem. Eur. J. 2006, 12, 2371–
2382; g) D. R. Stuart, K. Fagnou, Science 2007, 316, 1172–
1175.
[7] Y. Iwai, K. M. Gligorich, M. S. Sigman, Angew. Chem. 2008,
120, 3263; Angew. Chem. Int. Ed. 2008, 47, 3219–3222.
[8] a) C. Liu, X. Han, X. Wang, R. A. Widenhoefer, J. Am. Chem.
Soc. 2004, 126, 3700–3701; b) X. Han, R. A. Widenhoefer, Org.
Lett. 2006, 8, 3801–3804; c) Z. Zhang, X. Wang, R. A. Wid-
enhoefer, Chem. Commun. 2006, 3717–3719.
1.72 (d, J = 7 Hz, 3 H), 2.17 (s, 3 H), 4.43 (q, J = 7 Hz, 1 H), 6.84
(d, J = 5 Hz, 1 H), 7.11 (d, J = 5 Hz, 1 H), 7.26 (m, 2 H), 7.38 (m,
2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 13.9, 23.3, 31.4, 34.4,
38.6, 118.5, 121.2, 125.3, 126.8, 130.1, 132.4, 137.1, 142.7,
148.9 ppm. IR (neat): ν
= 3434, 2963, 2871, 1657, 1579, 1510,
˜
max
1455, 1405, 1269, 1169, 1111, 1022, 918, 899, 839, 709, 573 cm–1.
HRMS: calcd. for C17H23S 259.1520; found 259.1591. C17H22S
(258.42): calcd. C 78.67, H 9.22, S 11.96; found C 79.01, H 8.58, S
12.41.
2-[1-(4-Bromophenyl)ethyl]-3-methylthiophene: Table 4, entry 4.
Colourless liquid. 1H NMR (500 MHz, CDCl3): δ = 1.61 (d, J =
7 Hz, 3 H), 2.02 (s, 3 H), 4.29 (q, J = 7.5 Hz, 1 H), 6.78 (d, J =
5 Hz, 1 H), 7.02 (d, J = 5 Hz, 1 H), 7.08 (m, 2 H), 7.35 (m, 2
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 13.9, 23.1, 38.3, 118.9,
121.5, 126.3, 129, 131.5, 132.8, 137.2, 142.4, 145 ppm. IR (neat):
[9] J. Kischel, I. Jovel, K. Mertins, A. Zapf, M. Beller, Org. Lett.
2006, 8, 19–22.
ν
max = 3434, 2968, 2927, 2870, 1649, 1573, 1485, 1452, 1403, 1291,
˜
1169, 1072, 1035, 1013, 916, 823, 710, 590, 533 cm–1. HRMS: calcd.
for C13H14SBr 281.0000; found 280.9969.
[10] H. B. Sun, B. Li, R. Hua, Y. Yin, Eur. J. Org. Chem. 2006,
4231–4236.
[11]
[12]
[13]
M. Rueping, B. J. Nachtsheim, T. Scheidt, Org. Lett. 2006, 8,
3717–3719.
C. M. Chu, W. J. Huang, J. T. Liu, C. F. Yao, Tetrahedron Lett.
2007, 48, 6881–6885.
a) S. E. Sen, S. M. Smith, K. A. Sullivan, Tetrahedron 1999, 55,
12657–12698; b) S. Samanta, N. K. Mal, P. Kumar, A. Bhau-
mik, J. Mol. Catal. A 2004, 215, 169–175.
B. Das, M. Krishnaiah, K. Laxminarayana, K. Damodar,
D. N. Kumar, Chem. Lett. 2009, 38, 42–43.
S. Haldar, S. Koner, J. Org. Chem. 2010, 75, 6005–6008.
J. C. Jansen, E. J. Creyghton, S. L. Njo, S. H. van Koningsveld,
H. van Bekkum, Catal. Today 1997, 38, 205–212.
I. Ferino, R. Monaci, E. Rombi, V. Solinas, P. Magnoux, M.
Guisnet, Appl. Catal. A 1999, 183, 303–316.
2-Methyl-5-(1-p-tolylethyl)thiophene: Table 4, entry 6. Colourless li-
quid. 1H NMR (500 MHz, CDCl3): δ = 1.62 (d, J = 7 Hz, 3 H),
2.3 (s, 3 H), 2.38 (s, 3 H), 4.21 (q, J = 7.5 Hz, 1 H), 6.53 (d, J =
3.5 Hz, 1 H), 6.56 (d, J = 3.5 Hz, 1 H), 7.1 (d, J = 8 Hz, 2 H), 7.15
(d, J = 8 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 15.3,
21.1, 23.2, 30.5, 123.1, 124.4, 127.1, 129.2, 136.0, 137.9, 143.3,
148.7 ppm. IR (neat): ν
= 3431, 2967, 2926, 2871, 2735, 1633,
˜
max
[14]
1580, 1511, 1450, 1375, 1228, 1167, 1117, 1029, 950, 805, 702,
653 cm–1. HRMS: calcd. for C14H15S 215.0894; found 215.0880.
[15]
[16]
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of the H NMR, 13C NMR and GC–MS spectra.
[17]
[18]
[19]
[20]
P. M. Bhaskar, D. Loganathan, Synlett 1999, 129–131.
K. Smith, G. A. El-Hiti, Green Chem. 2011, 13, 1579–1608.
a) S. Adimurthy, G. Ramachandraiah, A. V. Bedekar, S. Ghosh,
B. C. Ranu, P. K. Ghosh, Green Chem. 2006, 8, 916–922; b) S.
Adimurthy, S. Ghosh, P. U. Patoliya, G. Ramachandraiah, M.
Agrawal, M. R. Gandhi, S. C. Upadhyay, P. K. Ghosh, B. C.
Ranu, Green Chem. 2008, 10, 232–237; c) R. D. Patil, G. Joshi,
S. Adimurthy, B. C. Ranu, Tetrahedron Lett. 2009, 50, 2529–
2532; d) M. K. Agarwal, S. Adimurthy, B. Ganguly, P. K.
Ghosh, Tetrahedron 2009, 65, 2791–2797; e) G. Joshi, S.
Bhadra, S. Ghosh, M. K. Agrawal, B. Ganguly, S. Adimurthy,
P. K. Ghosh, B. C. Ranu, Ind. Eng. Chem. Res. 2010, 49, 1236–
1241; f) R. D. Patil, G. Joshi, S. Adimurthy, Ind. Eng. Chem.
Acknowledgments
We thank Mr. Hitesh, Mr. H. Bramhabhatt, Mr. A. Das and Mr.
Jayesh at the Analytical Division of this institute for supporting
NMR, GC–MS, LC–MS and SEM analyses, respectively. We would
like to thank Mr. Agrawal, Ms. Pragnya Bhatt and Munnuswamy
for FT-IR, XRD, and TPD analysis respectively. D. C. M. and
R. D. P. are thankful to the University Grants Commission (UGC)
and the Council of Scientific and Industrial Research (CSIR), New
Delhi, India for the awards of JRF and SRF, respectively. S. A. also
thanks the CSIR/CSMCRI for internal grants.
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Eur. J. Org. Chem. 2012, 3520–3525

H-β-Zeolite-Catalysed Hydroarylation of Styrenes
Res. 2010, 49, 8100–8105; g) K. C. Chunavala, G. Joshi, E. Su-
resh, S. Adimurthy, Synthesis 2011, 635–641; h) S. Adimurthy,
C. C. Malakar, U. Beifuss, J. Org. Chem. 2009, 74, 5648–5651;
i) R. D. Patil, S. Adimurthy, Adv. Synth. Catal. 2011, 353,
1695–1700; j) R. D. Patil, G. Joshi, S. Adimurthy, Monatsh.
Chem. 2010, 141, 1093–1099.
[22] For the regeneration and reuse of H-β-zeolite, see: S. Adimur-
thy, G. Ramachandraiah, A. V. Bedekar, Tetrahedron Lett.
2003, 44, 6391–6392.
[23] a) P. Botella, A. Corma, J. M. López-Nieto, S. Valencia, R.
Jacquot, J. Catal. 2000, 195, 161–168; b) A. Corma, H. Garcia,
Top. Catal. 1998, 6, 127–140.
[21] The recovered catalyst activated with mineral acid[22] delivered
the same selectivities as fresh catalyst (Table 5).
Received: March 7, 2012
Published Online: May 16, 2012
Eur. J. Org. Chem. 2012, 3520–3525
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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