A solvent free method for preparation of β-amino alcohols by ring opening of epoxides with amines using MCM-22 as a catalyst

Article abstract of DOI:10.1016/j.apcata.2016.05.029

β-amino alcohols were synthesized at room temperature employing microporous MCM-22 zeolite as catalyst in an eco-friendly manner without using solvent. The zeolite MCM-22 showed promising activity for the conversion of primary and secondary amines into β-amino alcohols under mild reaction conditions. The catalytic activity remains intact for three recycles.

Full text of DOI:10.1016/j.apcata.2016.05.029

Accepted Manuscript
Title: A solvent free method for preparation of ␤-amino
alcohols by ring opening of epoxides with amines using
MCM-22 as a catalyst
Author: Thangaraj Baskaran Akanksha Joshi Gunda
Kamalakar Ayyamperumal Sakthivel
PII:
S0926-860X(16)30309-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.apcata.2016.05.029
APCATA 15893
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Applied Catalysis A: General
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Revised date:
Accepted date:
15-3-2016
28-5-2016
30-5-2016
Please cite this article as: Thangaraj Baskaran, Akanksha Joshi, Gunda Kamalakar,
Ayyamperumal Sakthivel, A solvent free method for preparation of ␤-amino alcohols
by ring opening of epoxides with amines using MCM-22 as a catalyst, Applied Catalysis
A, General http://dx.doi.org/10.1016/j.apcata.2016.05.029
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A solvent free method for preparation of β-amino alcohols by ring
opening of epoxides with amines using MCM-22 as a catalyst
Thangaraj Baskaran,a Akanksha Joshi,a Gunda Kamalakar,b and Ayyamperumal Sakthivela, c*
a Department of Chemistry, Inorganic Materials and Catalysis Laboratory,
University of Delhi, Delhi-110007, India.
bSABIC Technology and Innovation Center, PO BOX 42503,Riyadh 11551, Saudi Arabia.
c
Department of Chemistry, Riverside Transit Campus, Central University of Kerala,
Padnekkad, Nileshwar, Kerala - 671 314, India.
*E-mail:sakthiveldu@gmail.com / asakthivel@chemistry.du.ac.in
1

Graphical abstract
Layered MCM-22 zeolite is identified as potential catalyst for the preparation of β-amino
alcohols by ring opening of epoxides in the presence of amines under solvent free conditions.
Research highlights
 Layered MCM-22 zeolite was utilized for the preparation of β-amino alcohols.
 Ring opening of epoxide using amine by MCM-22 catalyst in absence of solvent.
 The Catalyst exhibits excellent selectivity towards the mono alkylated product.
 . Catalyst found to be promising for variety of epoxides and amines.
 Catalytic activity is remains constant even after three repeated cycles.
2

ABSTRACT: β-amino alcohols were synthesized at room temperature employing microporous
MCM-22 zeolite as catalyst in an eco-friendly manner without using solvent. The zeolite MCM-
22 showed promising activity for the conversion of primary and secondary amines into β-amino
alcohols under mild reaction conditions. The catalytic activity remains intact for three recycles.
KEY WORDS: MCM-22, β-amino alcohols,epoxide ring opening, zeolite, heterogeneous catalyst.
Introduction
Heterogeneous catalysts, such as zeolites, zeolite-like molecular sieve materials, mesoporous
molecular sieves and hydrotalcite-derived materials play a major role in the development of eco-
friendly catalysts for the synthesis of various fine chemicals and petrochemical processes, as well
as for the synthesis of organic intermediates [1-17]. In particular, microporous zeolite materials
have been extensively used as catalysts, adsorbents, drug delivery systems and bio-sensors [18-
23]. Among the range of zeolites, MCM-22, with a medium pore opening, has been extensively
used in Friedel-Craft alkylation, disproportionation and isomerisation. MCM-22 is a layered
anionic framework zeolite, composed of two non-intersecting pore systems with a large amount
of super-cages in the external pocket [24-31]. These pockets present in the external surface of
MCM-22 plays an important role in the catalytic activity of various processes and are referred in
literature as surface pocket catalysis [24-26]. Different materials are derived from MCM-22
precursors such as MCM-36, MCM-56, ITQ-2, etc., by various post-synthetic
modifications/treatments such as pillaring, swelling, calcination and silylation. The materials
3

thus prepared exhibited immense catalytic activity for various organic transformations and
petrochemical processes [24-26]. The textural and surface properties of MCM-22 and it’s
modified forms are extensively employed for various organic transformations. These
modifications include; incorporation of various transition, alkali and rare earth metal ions [32-
34]. For example, Zeolite beta and MWW exhibited similar performance as ITQ-2 in
dimethylacetal formation and tetrahydropyranylation of alcohols and phenols. Ti-ITQ-6 is more
active than Ti-FER or Ti-BEA in hexene and norbornene epoxidation. Incorporation of Titanium
into lamellar zeolites is beneficial in the case of epoxidation reactions of bulky substrates. Ti-
ITQ-2 exhibited high activity and selectivity in epoxidation of olefins with organic
hydroperoxides. Synthesis of cumene and cymene were investigated over MWW zeolites with
different Si/Al ratios. It is clear from the above literatures MWW based zeolite possessing
external pocket yield superior catalytic activity than relevant microporous zeolites for several
organic transformations.
Epoxides are extremely important organic intermediates in the synthesis of various organic
compounds. Ethylene oxide ranks one of the top 10 industrially important chemicals produced in
the world. Ethylene oxide is strained heterocyclic compound that can easily undergo ring
opening with various nucleophile yielding bi-functional group compounds. The ring opening of
epoxides with nucleophiles, such as amines, is an important organic reaction for the preparation
of β-amino alcohols, the products which act as key intermediates in a range of various
biologically active compounds and the preparation of amino acids, oxazolines, β-blockers, in
addition to usage in pharmaceuticals industries [35-43]. Only few reports are available on the
epoxide ring opening using heterogonous catalysts such as functionalized SBA-15 [35],
amberlyst-15 [36], Heteropoly acid [37], zeolites & hydrotalcite [38], NaY-zeolite [39], BiCl3
4

[40], montmorillonite K10 [41], diaminosilane functionalized SAPO-37 [42] and silica
nanoparticles [43].
Heterogeneous catalysts and catalytic supports (eg. silica, zeolites, carbon based materials, clay,
Heteropoly acids) are important catalysts in various chemical transformations due to their eco-
friendly nature and recyclability. In general, many of the catalyst systems use relatively high
temperatures, sensitive catalysts and hazardous organic solvents [35-43]. Hence, it is essential to
develop an efficient heterogeneous catalyst, which can work in environmentally friendly
conditions, for the preparation of amino alcohols. It will be interesting to utilize zeolite based
catalyst, in particular, MCM-22 zeolite possessing non-connected 10 and 12 membered ring
opening with 12 member external pocket which may play an important role on the chosen
reactions, by effective utilization of active sites present on both internal and external surface of
the zeolite molecular sieves. Thus, here we report epoxide ring opening with amines to yield β-
amino alcohols using heterogeneous MCM-22 as the catalyst under solvent free conditions at
room temperature.
Experimental Section
Preparation of MCM-22
MCM-22 was prepared by hydrothermal method using the molar gel composition of 1 SiO2: 0.3
NaOH: 0.033 Al2O3: 0.5 HMI: 40 H2O according to procedure described in literature [27, 28].
The typical procedure involve by addition of known quantity of hexamethyleneimine (HMI) into
an aqueous solution containing sodium aluminate (NaAlO2) and sodium hydroxide (NaOH). The
resultant mixture was allowed to stir to become homogeneous. The silica source (40 wt. %
colloidal silica) was added to the above homogeneous mixture with constant stirring at room
5

temperature. The final synthesis gel was transferred into an autoclave (Teflon lined) and allowed
to crystallization for 5 days at 150 °C. The as-synthesized MCM-22 was filtered and washed
with distilled water. The structure directing agent was removed by calcining the as-prepared
o
materials at 550 C in an atmospheric air using muffle furnace and final material is represented
as Na-MCM-22.
Preparation of Zeolites Y, β-zeolite and ZSM-5
For comparison, various zeolites such as, zeolite-β, ZSM-5 and zeolite Y explored for the
epoxide ring opening using amines. These zeolites were prepared according to the procedures
described in literature and the detailed procedures are presented in the supplementary
o
information [3, 8, 44]. The as synthesized zeolite materials were calcined at 550 C to remove
the organic template. The resultant materials are in the Na-form of corresponding zeolites.
Characterization methodology
Powder X-ray diffraction patterns were recorded by using a Bruker D8 diffractometer with Cu-K
α radiation (λ = 1.54184 Å). The X-ray diffraction patterns were recorded in the 2θ range of 3–
70°, with a scan speed and step size of 0.5°/min and 0.02 ° respectively. The structural
framework features of MCM-22 material were analyzed by FT-IR Spectrometer BRUKER,
TENSOR 27 in the range 400–4000 cm-1 using KBr pellet method. The textural properties of
synthesized materials (surface area (BET method), pore volume) were derived from N2 sorption
measurements carried out at −196 °C using an automatic micropore physisorption analyser
(Micromeritics ASAP 2020, USA) after the samples were degassed at 300 °C for 12h under 10-3
Torr pressure prior to the analysis. The morphology of the MCM-22 material was obtained using
Scanning electron microscopy (Jeol) by operating at 18–20 kV. The acidity of NaMCM-22
6

material was determined by pyridine vapour adsorption using Perkin Elmer GX
spectrophotometer with Diffuse Reflectance FT-IR (DRIFT) accessory (Graseby Specac, P/N
19,900) and a temperature controller (Graseby Specac, P/N 20,130). The MCM-22 material was
exposed to ex-situ pyridine vapor under vacuum for 1 h followed by evacuation to remove
physisorbed pyridine for 15 min. The spectra were collected in the temperature range of 150–450
°C after allowing it to equilibrate at that temperature condition for 10 min. The acidity of the
prepared materials were analyzed by temperature programmed desorption of ammonia method
equipped with a TCD detector (NH3-TPD; in-house assembled). Approximately 200 mg of solid
sample was loaded in quartz reactor and activated at 550 ºC for 6 h in the flow of nitrogen. The
reactor temperature was brought down to 100 ºC followed by ammonia gas adsorption in pulses
along with a helium carrier gas. The saturation of the catalyst with adsorbing ammonia was
confirmed by the constant TCD signal. The catalyst material adsorbed with ammonia was
maintained at 100 ºC for an hour to permit the physisorbed ammonia to be flushed out along with
carrier gas. The desorption of ammonia was carried out by ramping the temperature at a rate of 5
ºC/min till the reactor temperature reaches to 700 ºC. The quantity of desorbed ammonia was
computed with help of TCD (thermal conducting detector) signal as a response for ammonia.
Catalytic studies on epoxide ring opening using MCM-22 material
The epoxide ring opening using amine was carried out using NaMCM-22 as catalyst for the
preparation of β- amino alcohol. Prior to each catalytic run the samples were pre-heated at 150 oC
for 3 h in an air convection oven. The typical procedure involves the addition of 10.7 mmol of
aniline to 16.0 mmol of propylene oxide (Aniline: Propylene oxide ratio; 1:1.5) in a round bottom
flask with 100 mg of Na-MCM-22 catalyst. The resulting mixture was stirred for 6h at 35 ºC.
7

After completion of the reactions, the reaction mixture was analyzed by gas chromatography
(Agilent 7890 A, GC) equipped with a FID. The conversion was calculated based on the
consumption of amines by gas chromatography.
Results and discussion
FT-IR spectra of the as-synthesised and calcined MCM-22 are depicted in Figure 1. The spectra
of the MCM-22 materials show vibrational bands at around 600 and 555 cm-1, which are
characteristic of the framework double ring of MWW zeolite structures [29, 30]. The observed
bands at around 790 and 1240 cm-1 correspond to the symmetric and asymmetric stretching of
the tetrahedral Si-O-Si linkage present in MCM-22 framework materials. Furthermore, the alkyl
group present in the template was confirmed by the corresponding vibrational bands at around
2900 cm-1 in the MCM-22 preparation [29, 30].
The powder XRD patterns of the as-synthesised MCM-22 precursor and calcined MCM-22
materials are shown in Figure 2. The samples are free from any impurity phases and are
agreement with the reported elsewhere [6, 24-28, 32, 34, 45]. The samples show relatively sharp
and well defined peaks corresponding to the characteristic (002) (100), (101) and (102) planes of
the MWW structure [28-34, 45]. The observed reflection at 2 of 6.54 characteristic of (002)
plane of as-synthesized layered MCM-22(P) material disappeared and merged with the sharp
peak of (1 0 0) plane evident at 2 of 7.11 on calcined MCM-22 [28-34, 45]. The above fact
support that as-synthesized MCM-22(P) is a two dimensional layered structure which is
converted in to three dimensional MWW framework topology by condensation of hydroxyl
group in c-direction [45]. The XRD patterns are in good agreement with the MWW type layered
MCM-22 structure. The nitrogen adsorption and desorption isotherms of the MCM-22 and other
zeolite materials are displayed in Figure 3. All the zeolite materials showed a sharp uptake below
8

0.1 relative pressure (p/po), which is attributed to the microporous framework derived from the
microporous channel. The MCM-22, ZSM-5 and zeolite beta materials exhibit H4 type
hysteresis. The textural properties of the various zeolite materials are summarised in Table 1.
The surface area (480-680 m2/g) and pore volume (0.4 cm3/g), evident on the zeolites, are well in
the range of microporous zeolite materials.
The local morphologies of MCM-22 were obtained using a scanning electron microscope and the
images are displayed in Figure 4. The SEM images clearly show the closed packing of the
platelet morphology of the MWW zeolites, which are arranged in spherical species similar to a
doughnut-like structure. A uniform spherical particle was observed in the diameter range of 8-10
µm, in agreement with reported literature values (5-15 µm) [31]. The acidity of calcined MCM-
22 was studied using pyridine adsorption technique and spectra were monitored using FT-IR
spectroscopy (Fig. S1). The MCM-22 material showed broad absorption band around 1445 cm-1
which is characteristic of Lewis acidic sites [12, 30]. The Brønsted acidic sites were evident from
the typical band around 1550 cm-1 in the material. Further, band around 1490 cm-1 evident of
both Brønsted and Lewis acidic sites in the MCM-22 material. The disappearance of above band
at degassing temperature of 450 oC indicates the material possesses moderate acidity. The above
fact is further in agreement with ammonia TPD (Fig. S2), where ZSM-5 and MCM-22 showed
moderate-acidity, zeolite-Y possesses weak acidity and zeolite-β shows relatively strong acidic
sites.
Catalytic activity
The intrinsic properties of the synthesised NaMCM-22 material were evaluated for epoxide ring
opening with amines in a liquid phase medium under solvent free conditions (Scheme 1). In all
9

the reactions, mono-alkylated (I) and di-alkylated (II) products was observed as the major and
minor products, respectively. The reaction was studied with different parameters, such as
temperature, reaction duration, epoxide molar ratio, the effect of amines, the effect of epoxides
and different zeolite materials under optimum reaction conditions. After the reactions, the
catalysts were activated and studied for recyclability under identical reaction conditions.
Figure 5 represents the effect of reaction temperature by keeping the aniline to propylene oxide
molar ratio to 1:1.5. The conversion is increased with an increase in temperature and reaches the
maximum aniline conversion of 83% at 35 ºC for 6 h with selectivity of product (I) of 89 %.
With a further increase in reaction temperature, there is no appreciable change in conversion and
propylene oxide started to decompose. Irrespective of the reaction temperature, the product
distributions remain intact. Hence, for subsequent studies, the reaction temperature was
maintained at 35 ºC.
Figure 6 shows the effect of reaction duration on propylene oxide ring opening with aniline at 35
ºC over NaMCM-22. The aniline conversion increased steadily with time and reached a
maximum at 6 h. Subsequently, the effect of the aniline: propylene oxide ratio was studied and
the results are shown in Figure 7. The aniline conversion increased linearly with an increasing
molar ratio of propylene oxide. The maximum conversion was observed at around 93%, using a
1:2 (aniline: propylene oxide) molar ratio with the mono-alkylated product selectivity of (83 %).
However, at higher molar concentrations, a considerable decrease in mono-alkylated product
selectivity occurred and the corresponding di-alkylated product increased. For the selective
formation of β-amino alcohol, the optimised aniline: propylene oxide molar ratio was found to be
1:1.5.
10

After optimisation of the reaction parameters, the catalytic activity of NaMCM-22 was also
explored using several epoxides and amines, and the results are summarised in Table 2.
NaMCM-22 was found to be an efficient catalyst for the preparation of amino alcohol using both
aliphatic and aromatic substituted epoxides. The catalyst was found to be effective for both
cyclic and acyclic epoxides. The use of an aliphatic long chain substituted epoxide showed
relatively lower conversion due to steric hindrance. Furthermore, the MCM-22 catalyst was
found to be effective for various substituted amines and cyclic amines. The use of a heterocyclic
amine yielded relatively lower conversion. However, for all cases, the mono-alkylated product
was obtained as the major component.
The epoxide ring opening of aniline was also compared with various other zeolites, such as
medium pore ZSM-5, large pore zeolite-Y and zeolite-β, the results are summarised in Table 3.
In the absence of a catalyst, the reaction showed only 1% aniline conversion (Table 3, entry 1).
The three dimensional medium pore ZSM-5 and zeolite-Y showed comparable conversion
compared to NaMCM-22 owing medium pore opening and weak acidity of ZSM-5 and Zeolite-
Y respectively. Alternatively, although zeolite-β facilities similar conversion due to presence of
strong acidity, the large pore channel results in a decrease in product selectivity. The presence of
a 12 member external pocket of MCM-22 with moderate acidity might facilitate the observed
better conversion. Furthermore, the reusability of the NaMCM-22 catalyst was studied after the
reaction, the catalyst was washed with ethanol and subsequently studied under identical reaction
conditions. The catalytic activity remained intact for several runs.
Conclusion
In summary, MCM-22 was prepared and characterised, systematically, by various analytical and
spectroscopic techniques. NaMCM-22 was found to be an efficient catalyst for the epoxide ring
11

opening to produce β-amino alcohol at room temperature without the need for a solvent. The
catalytic activity remains intact for several runs. Furthermore, NaMCM-22 was found to be an
efficient catalyst for various aliphatic, aromatic epoxide ring openings using various amines.
Acknowledgement
Authors thank DST-SERB (EMR/2014/001214), New Delhi and University of Delhi for the
financial support. TB and AJ grateful to DST and CSIR for the grant of SRF and JRF fellowship.
12

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Figure Captions
Fig. 1 FT-IR spectra of as-synthesized and calcined MCM-22 material (a-as-synthesized and c-
calcined).
Fig. 2 XRD patterns of as-synthesized and calcined MCM-22 material (a-as-synthesized and c-
calcined).
Fig. 3 Nitrogen sorption isotherms of MCM-22 and other zeolites materials.
Fig. 4 SEM images of MCM-22 material.
Fig. 5 Effect of reaction temperature on epoxide ring opening with amines using MCM-22
material (A-Aniline conversion, I-monoalkylated, II-dialkylated products).
Fig. 6 Effect of reaction time on epoxide ring opening with amines using MCM-22 material (A-
Aniline conversion, I-monoalkylated, II-dialkylated products).
Scheme 1. General representation of epoxide ring opening with amines for synthesis β-amino
alcohols.
16

Fig. 1 Baskaran et.al
17

Fig. 2 Baskaran et.al
18

Fig. 3 Baskaran et.al
19

Fig. 4 Baskaran et.al
20

Fig. 5 Baskaran et.al
21

Fig. 6 Baskaran et.al
22

Fig. 7 Baskaran et.al
23

Scheme 1
24

Table 1. Textural properties of various zeolite materials.
Pore Volume (cm3.g-1)
S.
BET
area (m2.g-1)
Catalysts
Si/Al ratio
No
Total
0.36
1.24
0.18
Micro pore
1
2
3
Na-MCM-22
Na-Zeolite Beta
Na-ZSM-5
30
25
67
487
686
348
0.20
0.26
0.11
25

Table 2. Effect of epoxides and amines on β-amino alcohol synthesis using MCM-22 material.
Amines
Conversion
(%)
Selectivity (%) Yield I
S.
Epoxides
No
I
II
(%)
1
83
89
11
74
2
3
4
97
82
31
100
--
--
97
82
100
99
1.0
31
5
6
7
8
9
31
75
100
100
--
--
31
75
73
59
87
100
100
100
--
--
--
73
59
87
[a] Reaction conditions: Amine: epoxide molar ratio: 1:1.5, catalyst: 100 mg, Temperature: 35oC,
Time: 6 h.
26

Table 3. Effect of various catalysts on the epoxide ring opining with aniline.[a]
Selectivity (%)
Yield
(%)
I
S.
Conversion
(%)
Catalysts
No
I
II
1
No catalyst
01
83
91
59
70
96
100
89
86
91
88
75
--
100
74
78
54
62
72
2
Na-MCM-22
Na-MCM-22
Na-ZSM-5
11
14
9
3#
4
5
Na-Zeolite Y
Na-Zeolite-β
12
25
6
[a]
Reaction conditions: Aniline: Propylene oxide molar ratio: 1:1.5,catalyst: 100 mg,
Temperature: 35 oC, Time: 6 h, #After 3rd recycle.
27