One-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols over Snβ zeolite

Article abstract of DOI:10.1016/j.catcom.2016.11.026

An environmentally benign catalytic protocol has been successfully developed for the one-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols via dehydration of 1-arylethanols followed by head-to-tail dimerization of vinylarenes over heterogeneous c

Full text of DOI:10.1016/j.catcom.2016.11.026

Accepted Manuscript
One-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols
over Snβ zeolite
Naresh Mameda, Krishna Sai Gajula, Swamy Peraka, Srujana
Kodumuri, Durgaiah Chevella, Rammurthy Banothu, Vasu
Amrutham, Narender Nama
PII:
DOI:
Reference:
S1566-7367(16)30443-5
doi: 10.1016/j.catcom.2016.11.026
CATCOM 4867
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Catalysis Communications
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Accepted date:
16 August 2016
28 November 2016
29 November 2016
Please cite this article as: Naresh Mameda, Krishna Sai Gajula, Swamy Peraka, Srujana
Kodumuri, Durgaiah Chevella, Rammurthy Banothu, Vasu Amrutham, Narender Nama
, One-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols over Snβ zeolite. The
address for the corresponding author was captured as affiliation for all authors. Please
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ACCEPTED MANUSCRIPT
One-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols over Snβ
zeolite
Naresh Mameda,ab Krishna Sai Gajula,ab Swamy Peraka,ab Srujana Kodumuri,a Durgaiah Chevella,a
Rammurthy Banothu,ab Vasu Amruthama and Narender Nama*ab
a Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad
500007, India.
b Academy of Scientific and Innovative Research, CSIR-Indian Institute of Chemical Technology, Hyderabad
500007, India.
*
Corresponding author. Tel.: +91–40-27191703; Fax: +91-40-27160387/27160757. E-mail address: narendern33@yahoo.co.in;
nama@iict.res.in; (N. Narender)
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ABSTRACT
An environmentally benign catalytic protocol has been successfully developed for the one-
pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols via dehydration of 1-arylethanols
followed by head-to-tail dimerization of vinylarenes over heterogeneous catalyst (Snβ
zeolite). The scope of the reaction was explored for various 1-arylethanols and afforded the
corresponding dimers in good to excellent yields with high regio- and stereoselectivity.
Moreover, Snβ zeolite could be easily recovered and reused without significant loss in its
catalytic activity.
Keywords: Alcohols; Alkenes; Dimerization; Heterogeneous catalysts; Zeolites
1. Introduction
Great efforts have been made in the field of green chemistry to adopt methods that are step
economic, produce fewer by-products and use less energy and less toxic chemicals [1]. In
particularly, tandem reactions have become powerful tools that combine multiple reaction
steps into a single synthetic operation and the efficiency of a process can be drastically
improved by avoiding isolation, purification and analysis of intermediate products, as well as
catalyst separation and recycle [2-5]. Moreover, tandem approaches can minimize the
generation of waste, save time and energy when compared to the corresponding stepwise
sequences of reactions. Consequently, the design and implementation of tandem reaction is of
significant importance for optimizing processes that involve consecutive steps to acquire the
target product in good yield and purity.
The development of catalytic C-H bond activation followed by C-C bond formation might
be very attractive since it would be atom-efficient and their significant impact on the both
academic and industrial research [6-8]. In particular, the catalytic dimerization of alkenes is a
100% atom-economical reaction and an industrially important process for preparing higher
alkenes from simple and small alkenes. Moreover, it finds extensive applications as industrial
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intermediates, as a source of new kind of polymers, lubricants, detergents and many other
useful chemicals [9]. Conventionally, this reaction has been performed in the presence of
late-transition metals as catalysts or Brønsted acids [10-12]. The regioselectivity of the
reaction follows three different pathways, such as head-to-head, head-to-tail and tail-to-tail
[13-15]. Especially, the head-to-tail dimerization of alkenes has been considered more
attractive transformation since a new allylic carbon stereogenic center can be formed. In
addition, several compounds contain a diarylmethane motif, which is an important part of
various valuable biologically active compounds and pharmaceuticals, such as oral
anticoagulants warfarin and phenprocoumone, antihyperlipidemic nafenopin and antiallergic
agent dimentindene [16].
In past decades, many catalytic systems have successfully been developed for the head to-
tail dimerization of styrenes [17-20]. However, most of the existing methods suffer from one
or more drawbacks such as inadequate yields, harsh reaction conditions, use of
expensive/toxic homogenous catalysts, critical product isolation procedure and requires
relatively costly phosphorus ligands and additives, which limit their use under the aspect of
environmentally benign process. Synthesis of dimers from alcohols instead of olefins in a
single step is a challenging task and only one method using TfOH/MeNO2
(trifluoromethanesulfonic acid/nitromethane) [21] is reported in the literature. However, this
homogeneous catalytic system has disadvantages related to the recovery and reuse of catalyst.
Thus, there is a strong demand for development of heterogeneous catalytic system for the
synthesis of 1,3-diaryl but-1-enes from 1-aylalcohols under mild conditions.
Over the past decades, catalysis by zeolites and related materials has become an attractive
research area in the heterogeneous catalysis and green chemistry [22-23]. As an important
type of solid acids, they have been extensively used as replacement for highly toxic and
corrosive mineral acids or inorganic Lewis acids in synthesis of fine chemicals [24-25]. This
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is mainly due to the fact that zeolites have well defined porous structures with large amount
of acid sites (both Bronsted and Lewis type) present on the inner surface of the pores. One of
the most important properties of zeolites is the great variety of topologies and pore
architectures, together with the possibility to adjust their acidity (type, concentration and
strength of acid sites). As a result, the catalytic activity of zeolites could be tailored for
special chemical transformations. Additionally, their environmentally benign nature, high
surface area and adsorption capacity, as well as outstanding chemical and thermal stability,
make them ideal candidates for heterogeneous catalysis. Especially, Sn containing
microporous and mesoporous materials have attracted much attention due to their surface
acidity and catalytic activity in a variety of reactions (hydroxylation of phenols [26], Baeyer–
Villiger oxidations [27], Meerwein-Ponndorf–Verley reductions [28], sugar isomerization
[29], epimerization [30], oxidative dehydrogenation of cyclohexane [31] and Cannizzaro-type
reactions [32]). Therefore, numerous efforts have been made to prepare and investigate the
catalytic properties of Sn-incorporated microporous and mesoporous materials. In
continuation of our efforts toward the development of novel and eco-friendly synthetic
protocols using zeolites [33-37], we herein report the Snβ zeolite catalyzed one-pot synthesis
of 1,3-diaryl but-1-ene derivatives directly from alcohols.
2. Experimental
2.1. General information
Zeolite β in ammonia form (NH4β) with SiO2/Al2O3 = 38 was purchased from Alfa Aesar.
1-Arylethanols and metal precursors were purchased from Sigma-Aldrich. All the samples
were systematically characterized by different spectroscopic techniques. The XRD patterns of
the samples was obtained on a Regaku miniflux X-ray diffractometer using Ni filtered CuK-
alpha radiation at 2θ = 2-80° with a scanning rate of 2° min-1 and the beam voltage and
currents of 30 kV and 15 mA, respectively. FT-IR (Cary 600, Agilent) spectra were obtained
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in the range of 1300-1700 cm-1 with a resolution of 4 cm-1 and 64 scans. The experiments
were performed in situ using a purpose-made IR cell connected to a conventional vacuum-
adsorption apparatus. The sample powders were pressed into self-supporting wafers (density-
40 mg cm-3) under a pressure of 105 Pa. After that, the samples were introduced in the IR
cell. Firstly, the samples were pre-treated by heating them in dynamic vacuum at a rate of 10
°C min-1 up to 400 °C and maintained at the same temperature for 1 h. After cooling down to
150 °C the spectrum was collected in the DRIFT mode. Then the samples were exposed to
pyridine until surface saturation and the spectrum was recorded. The DRIFT spectra after
pyridine treatment were subtracted from the spectra of the untreated catalyst to obtain the
peaks only due to pyridine-acid interaction. Finally, the spectra were quantified with the
Kubelka-Munk function. The temperature programmed desorption (TPD) of ammonia of Hβ
and Snβ zeolite samples were measured using an Auto Chem 2910 (Micromeritics, USA). In
a typical method about 0.1 g of calcined sample was degassed at 200 °C for 3 h in helium at a
flow rate of 30 mL min-1. After degassing the sample was saturated with 10% NH3 (balance
helium) at 60 °C, at a flow rate of 50 mL min-1 and subsequently flushed with helium gas at
60 °C for 1 h. The TPD measurements were carried out from 60 °C to 700 °C at a ramping
rate of 10 °C min-1. The amount of desorbed NH3 was calculated using GRAMS/32 software.
The reaction products were identified by NMR spectra using a Bruker VX NMR FT-300 or
Varian Unity 500 spectrometers instrument in CDCl3. Chemical shifts (δ) are reported in
parts per million (ppm) down field from TMS.
2.2. Preparation of catalyst
The NH4β zeolite (commercially available) was calcined at 500 °C for 10 h to obtain Hβ
zeolite. Metal modified zeolite Hβ was prepared by wet impregnation using the metal
precursors (Fe(NO3)3.9H2O, Cu(NO3)2.3H2O, (NH4)6Mo7O24.4H2O, Ni(NO3)2.6H2O,
Co(NO3)2.6H2O, (NH4)6H2W12O40.XH2O, Cr(NO3)3.9H2O and SnCl4.5H2O) with 10 weight
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percentage (The amount of 10 wt.% corresponds to the metal). Zeolite Hβ was added to the
aqueous solution of corresponding metal salt (the ratio of weight of the zeolite to the volume
of distilled water used to dissolve the metal salt was 1:3), which was then placed on a hot
plate with stirring at 80 °C to remove the excess water. Finally, the resulting solid was dried
in an air oven at 100 °C and calcined at 450 °C for 6 h in the presence of static air flow
before using it for the reaction.
2.3. General procedure for the one-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols
A 15 mL sealed tube was charged with 1-arylethanol (2 mmol), 10% Snβ zeolite (0.1 g)
and 1,2-dichloroethane (DCE) (1 mL). The reaction mixture was allowed to stir at 100 °C and
monitored by TLC (thin layer chromatography). Upon completion, the reaction mixture was
cooled to room temperature and diluted with DCM (dichloromethane). The catalyst was
separated by filtration and the solvent was removed under vacuum. The residue was purified
by column chromatography on silica gel using n-hexane/ethyl acetate as eluent to afford the
desired 1,3-diaryl but-1-enes. All the products were identified on the basis of 1H and 13C
NMR spectral data.
3. Results and discussion
3.1. Optimization of reaction conditions
Using the conversion of 1-arylethanol (1a) to 1,3-diaryl but-1-ene (3a) as a model reaction,
we initiated our work by testing the catalytic activity of various zeolites at 80 °C for 15 h in
1,2-dichloroethane (DCE) (Table 1, entries, 1-5). Among the catalysts examined, Hβ zeolite
exhibited better catalytic activity and gave the corresponding dimer 3a in 67% yield due to its
higher concentration of acid sites and special three-dimensional large size porous structure
[38] (Table 1, entry 5). The substrate 1a was inert in the absence of catalyst, thus confirming
the role of catalyst in the reaction (Table 1, entry 6). Once Hβ catalyst was found as the best
catalyst for this reaction, further increase of reaction temperature (80-100°C) and catalyst
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amount (100-200 mg) (see the ESI Table S1 and Table S2), could not improve the yield of 3a
due to Hβ zeolite having less number of week acid sites and lower Lewis acidity (Table 3) .
Next, in an attempt to improve the yield of 3a, we studied this transformation over various
metal modified zeolite β catalysts under similar reaction conditions (Table 1, entries 7-13). It
is well acknowledged that the metal modification in zeolites manipulates the total acidity,
acid site strength and nature of acid sites [39]. The various salts of these metal ions are
widely used as Lewis acid catalyst in numerous acid-promoted organic transformations. To
our delight, Snβ zeolite exhibited best catalytic performance in this transformation compared
to others (Table 1, entry 7). After extensive screening, we have observed that 100 mg of 10%
Snβ was optimum for 2 mmol of 1-arylethanol to obtain the maximum yield of the desired
product in 1,2-dichloroethane (DCE) (1 mL) at 80 °C (Table 1, entry 7).
Table 1
Optimization study for the synthesis of 1,3-diphenyl-1-butene (3a).a
Entry
Catalyst
Conversation Selectivity Yield of 3a
of 1a (%)b
of 3a (%)b
(%)c
1
2
3
4
5
6
7
8
9
NaY
H-Y
HZSM (40)
H-Mordenite
Hβ
22
35
41
40
68
00
92
71
70
79
73
82
99
98
99
98
99
00
98
99
99
98
99
98
22
34
40
39
67
00
Absence of catalyst
10% Snβ
10% Feβ
90 (10.68)d
70 (3.91)d
69 (4.07)d
77 (4.00)d
72 (4.23)d
80 (7.68)d
10% Coβ
10% Crβ
10% Niβ
10
11
12
a
10% Moβ
Reaction conditions: 1-arylethanol (2 mmol), catalyst (100 mg), 1,2-dichloroethane
(DCE) (1 mL), 80 oC, 15 h, sealed tube. b Conversion and selectivity based on GC.
c Isolated yields. d TON
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3.2. Synthesis of 1,3-diarylbut-1-ene derivatives 3 from 1-arylethanols 1 over Snβ zeolite
With the optimized conditions in hand, the scope and limitations of this reaction were
investigated with a variety of 1-arylethanol derivatives under present reaction conditions and
results are summarized in Table 2. To determine the influence of substitution on the aromatic
ring of 1-arylethanol with this reagent system, we have carried out the reaction with different
substituted 1-arylethanols. Highly activating or moderately activating groups present on
aromatic ring of 1-arylethanol 1b-1e afforded good to excellent yields of the respective 1,3
diarylbut-1-enes 2b-2e (Table 2, entries 2-5), whereas highly deactivating group present on
aromatic ring of 1-arylethanol 1i failed to react under present reaction conditions (Table 2,
entry 9). However, the meta substituted 1-arylethanol 1d gave relatively lower yield with
respect to the corresponding para isomer 1c probably due to some steric hindrance (Table 2,
entries 3 and 4). Halo substituted 1-phenylethanols such as 1-(4-fluorophenyl)ethanol (1f), 1-
(4-chlorophenyl)ethanol (1g) and 1-(4-bromophenyl)ethanol (1h) could be transformed into
Table 2
Formation of 1,3-diarylbut-1-ene derivatives 3 from 1-arylethanols 1 over Snβ zeolite.a
Entry Alcohol
R
Ph
Product Time (h) Yield (%)b
1
15
12
16
18
24
10
15
20
24
24
90 (10.68)e
97c (11.51)e
89c (10.56)e
62c (7.36)e
76c (9.02)e
93 (11.04)e
95 (11.28)e
90 (10.68)e
-
1a
3a
3b
3c
3d
3e
3f
3g
3h
3i
2
4-MeOPh
4-MePh
3-MePh
4-tertButyl
4-FPh
4-ClPh
4-BrPh
3-NO2Ph
n-C8H16
1b
3
1c
4
1d
5
1e
6
1f
7
1g
8
1h
1i
1j
9d
10d
-
3j
a
Reaction conditions: alcohol (2 mmol), 10% Snβ (100 mg), 1,2-
dichloroethane (DCE) (1 mL), 80 oC. Isolated yields. 65 C. No
b
c
o
d
conversion of substrate was observed. e TON.
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the corresponding trans-1,3-diaryl-1-butenes 3f-3h with excellent yields (Table 2, entries 6-
8). Unfortunately, aliphatic olefin i.e. 2-octene (1j) was failed to react under present reaction
conditions and only starting material was recovered (Table 2, entry 10).
Attempting to elucidate the peculiar catalytic activity of Snβ zeolite on this reaction,
the structure and acidic properties of the parent Hβ zeolite and Snβ zeolite were compared
using classic methods, including X-ray diffraction (XRD), temperature programmed
desorption (NH3-TPD) and PyFT-IR spectroscopy. The XRD patterns of Hβ and Snβ
indicated that similar patterns occurred after Sn+4 metal modification (see Supplementary
Information, Fig. S1), except a prominent peak at 2θ = 51.7° which is attributed to SnO2
phase (ICDD# 88-0287) and according to previous reports, these SnO2 crystals formed during
calcinations [39]. We assumed that these SnO2 particles produced new catalytic sites on the
surface of zeolite, and play a certain role in this transformation. The TPD-NH3 profiles of Hβ
and 10% Snβ catalysts are given in Fig.1 and the respective results of total acidity are shown
in Table 3. The total acidity and acid site strength are enhanced upon modification of Hβ with
Sn metal ion (Table 3). The presence of more number of weak acid sites on Snβ are
responsible for high yield of 3a, whereas parent Hβ zeolite gave less yield of 3a due to less
number of weak acid sites (Table 3).
The pyridine adsorbed Hβ and Snβ samples were analyzed by FT-IR spectroscopy to
distinguish the Bronsted and Lewis acid sites present on the catalyst surface (Fig. 2). The
interaction of pyridine with the Bronsted and Lewis acid sites gives rise to bending vibrations
at 1540 and 1450 cm-1, respectively and a vibrational band at 1490.4 cm-1 is attributed to
pyridine adsorbed on both Bronsted and Lewis acid sites. The relative ratio of peak intensities
corresponding to Bronsted and Lewis acid sites is measured and the results are reported in
Table 3. It is evident from Table 3 that the Snβ with relatively higher Lewis acidity (B/L = 0.
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20) gave the highest yield of 3a (90%) than parent Hβ. Based on above results, the excellent
catalytic ability of Snβ on this transformation could be attributed to the effect of the newly
generated Lewis acid sites by SnO2 particles.
Fig.1. NH3-TPD profiles of (a) Hβ (b) Snβ
Fig.2. Pyridine FT-IR spectra of (a) Hβ (b) Snβ
Table 3
Acidity of Hβ and Snβ zeolites.
b
Catalyst
Aciditya
Acidityb
Acidic sites distribution
(B/L ratio)
(mmol/g)
LT-peakc MT-peakc
HT-Peakc
Hβ
10% Snβ
1.13
0.20
0.47
1.04
25.4
55.4
74.6
41.6
-
3.1
a Relative ratio of Bronsted to Lewis acidity measured by pyridine adsorbed FT-IR spectra. b Total
acidity amount determined by NH3-TPD. b The NH3-TPD (%) distribution of acidic sites. c LT-peak
represents weak acid sites (150-250 °C), MT-peak represents medium acid sites (250-550 °C) and HT-
peak represents strong acid sites (550- 650 °C).
3.3. Reusability of catalyst
We also tested the potential recycling ability of Snβ by performing the reaction with 1-
arylethanol under standard reaction conditions, catalyst (Snβ) recovered by simple filtration
and maintained its catalytic activity. No obvious loss of the catalytic activity was observed
even after five cycles (Table 4). The catalyst was highly crystalline before and after the
reaction, which was confirmed by XRD (See supporting information Figure S1). There was
no leaching of aluminium or silicon from zeolite (Hβ) and confirmed by elemental analysis.
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Table 4
The synthesis of 1,3-diphenyl-1-butene from 1-arylethanol over Snβ zeolite-reusability of the
catalysta
Entry
Cycle
First
Second
Third
Fourth
Fifth
3a Yield (%)b
1
2
3
4
5
90
91
90
89
88
a Reaction conditions: 1-arylethanol (2 mmol),
catalyst (100 mg), 1,2-dichloroethane (DCE) (1
mL), 80 oC, 15 h, sealed tube. b Isolated yields.
3.4. Reaction mechanism
Scheme 1. Plausible reaction mechanism.
A plausible reaction mechanism is illustrated in Scheme 1. It is assumed that the Lewis
acidic sites of Snβ zeolite brings the 1-arylethanol molecules closer by coordinating with an
unshared pair of electrons on the oxygen atom. Once the 1-arylethanol molecules are
adsorbed and coordinated to acidic sites (both Lewis and Bronsted) of Snβ zeolite, led to the
formation of vinylarenes via dehydration of alcohol. Then the resulting olefin in presence of
acidic sites of zeolite generating an electrophilic center by polarization of the C-C bond,
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which subsequently reacts with another olefin to give the corresponding dimer 3 via
intermediate (A).
4. Conclusion
In summary, we have successfully developed a heterogeneous catalytic system for the
one-pot synthesis of 1,3-diaryl but-1-enes from 1-arylethanols via dehydration of 1-
arylethanol followed by head-to-tail dimerization of vinylarenes under mild conditions. The
scope and limitations of this process are demonstrated with various 1-arylethanols. The
heterogeneous catalyst Snβ could be conveniently recovered and reused without obvious loss
of the catalytic activity.
Acknowledgements
We thank the CSIR Network project CSC-0123 for financial support. M. N., G. K. S. and
C. D. acknowledge the financial support from CSIR, India in the form of fellowships. P. S.,
K. S. and B. R. acknowledge the financial support from UGC, India in the form of
fellowship.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version, at
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Graphical abstract
Naresh Mameda, Krishna Sai Gajula, Swamy Peraka, Srujana Kodumuri, Durgaiah Chevella,
Rammurthy Banothu, Vasu Amrutham and Narender Nama*
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ACCEPTED MANUSCRIPT
Highlights
 Snβ exhibits best catalytic activity towards the synthesis of 1,3-diaryl but-1-enes.
 Variety of 1-arylalcohols gave the respective dimers in moderate to excellent yields.
 The catalyst can be reused without significant loss in their catalytic activity.
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