Synthesis of nanoporous aluminosilicate materials and their application as highly selective heterogeneous catalysts for the synthesis of β-amino alcohols

Article abstract of DOI:10.1016/j.molcata.2010.06.018

The ability of nanoporous aluminosilicate materials, synthesized using an evaporation-induced self-assembly (EISA) approach, to function as catalysts for the formation of β-amino alcohols from aromatic amines and epoxides was assessed. Materials containing high aluminium loadings displayed catalytic activity, giving the desired β-amino alcohols in high yield and with high selectivity for the Markovnikov addition product. These materials exhibited nanoporous pores, typically 1.34-1.49 nm, with a narrow pore size distribution and the expected large surface areas.

Full text of DOI:10.1016/j.molcata.2010.06.018

Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
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Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Synthesis of nanoporous aluminosilicate materials and their application as highly
selective heterogeneous catalysts for the synthesis of ␤-amino alcohols
Mathew W.C. Robinsona, A. Matthew Daviesb, Ian Mabbetta, Thomas E. Daviesb, David C. Apperleyc,
Stuart H. Taylorb, Andrew E. Grahama,∗
a Sustainable Environment Research Centre, Department of Science and Sport, University of Glamorgan, CF37 4AT, UK
b Cardiff Catalyst Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK
c EPSRC Solid-State NMR Service, Department of Chemistry, Durham University, DH1 3LE, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 April 2010
Received in revised form 14 June 2010
Accepted 16 June 2010
Available online 23 June 2010
The ability of nanoporous aluminosilicate materials, synthesized using an evaporation-induced self-
assembly (EISA) approach, to function as catalysts for the formation of ␤-amino alcohols from aromatic
amines and epoxides was assessed. Materials containing high aluminium loadings displayed catalytic
activity, giving the desired ␤-amino alcohols in high yield and with high selectivity for the Markovnikov
addition product. These materials exhibited nanoporous pores, typically 1.34–1.49 nm, with a narrow
pore size distribution and the expected large surface areas.
Keywords:
© 2010 Elsevier B.V. All rights reserved.
Nanoporous aluminosilicates
Evaporation-induced self-assembly
Lewis acid catalysts
Epoxides
␤-Amino alcohols
1. Introduction
[4,8]. Although excellent progress has been made in this area, the
current synthetic methods have several inherent drawbacks such
Since the initial disclosure of synthetic routes to ordered
mesostructured silicate materials, surfactant directed self-
assembly has developed into one of the most versatile and widely
applied approaches for the synthesis of inorganic materials with
controlled composition, structure and function [1,2]. Numerous
studies have detailed the use of a range of templates which have
been employed under a diverse range of reaction conditions for
the synthesis of silicate materials in particular, providing access to
materials with well-defined pore sizes and mesostructures [3–7].
One of the limitations, however, that is yet to be fully addressed
in the continuing development of this field is the preparation of
materials possessing regular pores in the 1.2–2.0 nm range, that is,
materials with the pore size between the upper limit of zeolites and
the lower end of mesoporous materials. Synthetic routes to silicas
with pore sizes in this range are of considerable interest as, while
numerous approaches to mesoporous materials with large pore
sizes have been reported, the formation of ordered pores between
1.2 and 2.0 nm remains a significant challenge since there is only
a limited number of template surfactants which can be employed
as the requirement for hydrothermal conditions, poor control of
the properties or poor reproducibility of the syntheses [8,9–12].
As part of our ongoing studies into the application of sil-
icate materials as highly efficient and selective heterogeneous
catalysts, we reported a simple and flexible route for the synthe-
sis of nanoporous silicate and aluminosilicate materials using an
evaporation-induced self-assembly (EISA) approach [13–15]. The
EISA processes has proved to be one of the most straightforward
methods for the preparation of highly ordered silicates, and offers
a ready access point for the production of materials with a wide
range of potential uses [16–18]. It has found application for the
formation of thin films of surfactant-templated silicas, and has sub-
sequently been employed for the synthesis of a variety of products
including fibres and hollow spheres [5,19,20]. It is surprising that
the use of EISA approaches for the synthesis of bulk silicate and
aluminosilicate materials for catalytic applications has received rel-
atively little attention, given the simplicity of this approach. Our
interest in this approach was stimulated by the work of Nagamine
et al. who demonstrated that thin films of mesoporous silicates
were produced using an EISA approach employing ethanol as the
solvent [21]. Excellent control of the physical properties of the films
was achieved by changing the ratios of the templating agent and
inorganic precursor, or by controlling the rate of gelation by vary-
ing the ratio of acid to inorganic precursor. Thus, this approach
∗
Corresponding author. Tel.: +44 1448342468.
E-mail addresses: AEGraham@Glamorgan.ac.uk, GrahamAE@Cardiff.ac.uk
(A.E. Graham).
1381-1169/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2010.06.018

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M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
Table 1
Physical characteristics of the nanoporous catalysts.
b
c
Catalyst
Si/Al (gel composition)
Si/Al (EDX)a
BET surface area (m2 g−1
)
Pore volume (cm3 g−1
)
Pore width (nm)d
S-1
–
102
72
29
23
–
111
88
44
30
704
927
789
699
580
588
0.277
0.375
0.298
0.315
0.266
0.168
1.49
1.48
1.35
1.35
1.34
1.37
AS-(111)
AS-(88)
AS-(44)
AS-(30)
AS-(14)
13
14
a
Determined by EDX analysis.
b
c
Surface areas were obtained by the BET method.
Pore volumes determined by the DH method.
Pore width determined by the BJH method.
d
offers a potentially highly flexible, inexpensive, operationally sim-
ple and extremely versatile route to structured silicate materials.
Importantly, it also addresses some of the limitations of previous
methodologies for nanoporous silicate and aluminosilicate synthe-
sis. In this paper we outline our recent progress in the synthesis
of nanoporous aluminosilicate materials produced by the EISA
approach, and their use as highly effective and selective hetero-
geneous catalysts for the addition reactions of aromatic amines to
epoxides.
through a Celite plug which was washed with dichloromethane (2×
5 ml). The combined solvents were removed under reduced pres-
sure to give and oil that was purified by column chromatography
(hexane → 20% ethyl acetate–hexane) to give the product a 19:1
mixture of 2-phenylamino-2-phenylethanol and 2-phenylamino-1-
phenylethanol (150 mg, 70%) as a colourless oil; ꢀmax (film)/cm−1
(neat) = 3394, 3026, 1600, 1499, 1315, 1064, 1026, 908, 748 and
691; 1H NMR (CDCl3, 400 MHz) ı = 7.47–7.11 (m, 6H), 6.74 (t, 2H,
J = 8 Hz), 6.61 (d, 2H, J = 9 Hz), 4.53 (dd, 1H, J = 4 and 7 Hz), 3.96 (dd,
1H, J = 4 and 11 Hz), 3.77 (dd, 1H, J = 7 and 11 Hz), 2.03 (br s, 2H); 13
C
NMR (CDCl3, 100 MHz) ı = 147.7, 140.6, 129.7, 129.6, 128.5, 127.2,
118.3, 114.3, 67.8, 60.3; MS (EI) m/z 213 (M)+; exact mass (ES) cal-
culated for C14H16NO (M+H)+, 214.1226, found (M+H)+ 214.1225.
2. Experimental
2.1. Materials
All chemicals employed were purchased from the Aldrich
Chemical Company and were used as received without further
purification.
3. Results and discussion
3.1. Catalyst preparation and characterisation
The silica and aluminosilicate materials used in this study were
produced using our previously reported procedure and were char-
acterised using a range of standard techniques [13–15,22]. The
nitrogen adsorption–desorption isotherms of all the materials dis-
played a reversible isotherm with no noticeable hysteresis (Fig. 1).
The isotherms displayed a well-defined capillary condensation step
atvery lowrelativepressure(P/P0 = 0.10–0.20), indicativeof thefor-
mation of small pores less than 2.0 nm. The absence of any further
adsorption and the lack of hysteresis at higher relative pressure
regions indicate the absence of large macropores in the sample
[23]. This was confirmed from the pore-size data (Fig. 2) calculated
using the Barrett–Joyner–Halenda (BJH) method, which revealed
a narrow pore size distribution for the aluminosilicate materials
ranging between 1.34 and 1.49 nm (Table 1). While the reliability
of this model has been the subject of some debate, the position of
2.2. Catalyst preparation and characterisation
Five nanoporous aluminosilicates (AS-(111), AS-(88), AS-(44),
AS-(33) and AS-(14)), in addition to the unmodified silica material
(S-1), were synthesized and characterised using a range of stan-
dard techniques (Table 1) as described previously [22]. A typical
preparation for the synthesis of the aluminosilicate AS-(14) catalyst
is as follows: cetyltrimethylammonium bromide (4.0 g, 11 mmol)
was dissolved in a solution of hydrochloric acid (2.5 ml, 0.1 M) and
ethanol (17.5 ml). Tetraethyl orthosilicate (25 ml, 112 mmol) was
then added and the mixture stirred for 10 min at 40 ◦C. The solution
was cooled to room temperature and aluminium nitrate nonahy-
drate (3.35 g, 8.95 mmol) was added in one portion. The mixture
was stirred for 20 min and then left to age at room temperature for
1 week. The resultant orange solid was crushed into a fine powder,
dried overnight at 90 ◦C and then calcined in air at 550 ◦C for 12 h
to remove the organic template to give a fine white powder.
2.3. Catalyst testing and product analysis
All reactions were carried out in a stirred batch reactor. The cat-
alyst was removed from the sample by filtration through a Celite
plug, which was washed with dichloromethane (2× 5 ml) and the
combined solvents were removed under reduced pressure. Product
mixtures were analysed using 1H NMR, GC or GC–MS techniques
and percentage conversions of reactions were determined by inte-
gration of the relevant signals from crude 1H NMR spectra.
2.4. General procedure for the aminolysis of epoxides
The aluminosilicate catalyst AS-(14) (120 mg) was added to a
mixture of styrene oxide (118 mg, 0.98 mmol) and aniline (102 mg,
1.10 mmol) in dichloromethane (5 ml) which was stirred at room
temperature. After 6 h the catalyst was removed by filtration
Fig. 1. Representative BET isotherm data.

M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
59
Table 2
Comparison of aluminosilicate materials for the addition of aniline to styrene oxide.
.
Entry
Catalyst
Conversion (%)a,b
Selectivity (1:2)c
1
2
3
4
5
6
S-1
0
28
37
30
26
37
–
AS-(111)
AS-(88)
AS-(44)
AS-(30)
AS-(14)
95:5
93:7
95:5
95:5
95:5d
a
Reactions employ 1 mmol of styrene oxide and 1 mmol of aniline in 5 ml CH2Cl2.
Conversion determined from 1H NMR analysis of crude reaction mixtures.
b
c
Regioisomeric ratio determined from 1H NMR analysis of crude reaction mixtures.
Regioisomeric ratio determined from 1H NMR and GC–MS analysis of crude reaction mixtures.
d
the condensation step observed in our samples is a clear indication
that the pore diameters in these materials are smaller than typical
mesostructured silicates and so would appear to be generally valid
in the size range under consideration [23–25].
These observations are in good agreement with data originally
reported by Nagamine et al. for thin silicate films synthesized using
this approach [21]. The smaller pore sizes produced in this study are
explained by the minor deviations in the reaction conditions, par-
ticularly the increased quantity of acid employed. The reduction in
pore size and surface area for the high aluminium containing mate-
rials synthesized in this study is consistent with previous literature
reports [26].
The formation of ␤-amino alcohols from epoxides and amines is
an important reaction in medicinal and organic chemistry as they
are useful synthetic intermediates for the preparation of ␤-amino
acids, in natural product synthesis and as chiral auxiliaries [30–32].
Typically, this transformation has been carried out using an excess
of the amine nucleophile at elevated temperatures, however, these
conditions are far from ideal as they are not tolerated by a number
of functional groups, and the requirement to use an excess of the
amine nucleophile impacts on the efficiency of the reaction [33].
Therefore, new methods which employ Lewis acid promoters, and
which work at low temperatures employing near-stoichiometric
amounts of amine, have continued to be of interest [34–38]. These
approaches, however, also suffer from disadvantages, such as the
toxicity of the Lewis acid catalyst employed, the extended reac-
tion times or the requirement for protracted work-up procedures.
Subsequent developments have focussed on the application of
heterogeneous catalysts, and while these processes have greatly
improved the overall atom efficiency of the process, they suffer
3.2. Catalytic activity and selectivity of nanoporous
aluminosilicate materials
Epoxides are highly versatile synthetic intermediates and
undergo a range of addition and rearrangement reactions [27–29].
Table 3
Optimisation of conditions for the addition of aniline to styrene oxide.
.
Entry
Catalyst (mg/mmol epoxide)
Aniline (equiv.)
Conversiona,b (%)
Selectivity (1:2)b
1
2
3
4
5
6
7
8
9
50
50
50
50
50
50
50
50
50
1.1
1.1
1.1
1.4
1.8
2.1
1.1
1.1
1.1
1.1
1.1
1.1
37
28c
53d
33
29
30
95:5
95:5
95:5
95:5
95:5
95:5
26e
33f
66g,h
33i
53
88:12
90:10
80:20
82:18
95:5
10
11
12
50
100
120
70
95:5j
a
Reactions employ 1 mmol of styrene oxide in 5 ml of CH2Cl2.
Determined from 1H NMR analysis of crude reaction mixture.
Reaction at 40 ◦C.
Conversion after 24 h at room temperature.
Reaction in hexane.
b
c
d
e
f
Reaction in acetone.
Reaction in ethanol.
g
h
i
Product contains 20% of 2-ethoxy-2-phenylethanol.
Reaction in water over 2 h.
j
Determined by 1H NMR and GC–MS analysis of crude reaction mixture.

60
M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
Table 4
Aminolysis of aromatic epoxides using aluminosilicate catalyst AS-(14).
.
Entry
Epoxide
Aniline
HNEt2
Time (h)
Product
Yield (%)a,b
1
2
10c,d
2
3
4
24
68e,f
6
6
70f
65f
5
6
6
38f,g
6
8
79f
7
80h
a
Isolated yield after column chromatography.
b
c
d
e
f
Reactions employ 120 mg of catalyst/mmol of epoxide and 1.1 equiv. of aniline in 5 ml of CH2Cl2.
Conversion from 1H NMR analysis of crude reaction mixture.
Reaction at 40 ◦C using 50 mg of catalyst/mmol of epoxide in 5 ml of NHEt2.
Reaction using 50 mg of catalyst/mmol of epoxide.
Product isolated as a 95:5 ratio of regioisomers. Major isomer shown.
g
h
Reaction at 40 ◦C.
Product is an 85:15 ratio of regioisomers. Major isomer shown.
from limitations of their own [39–45]. We recently reported that
nanoporous aluminosilicate materials function as highly efficient
and selective heterogeneous catalysts for the preparation of ␤-
alkoxy alcohols from epoxides and alcohols [13,46]. These reactions
proceed rapidly under very mild reaction conditions and display
excellent selectivity for the Markovnikov addition product. Given
the obvious similarities in these transformations and the catalytic
efficiency previously displayed by our nanoporous materials, we
were interested in extending our initial studies to realise a new
procedure for the preparation of ␤-amino alcohols from amines
and epoxides under nanoporous aluminosilicate catalysis. We ini-
tially investigated the ability of five nanoporous aluminosilicate
materials synthesized using the EISA approach, in addition to the
plain silica material (Table 1), to catalyse the addition of aniline to
styrene oxide (Table 2).
In line with our own and previous literature observations,
the unmodified silica S-1 demonstrated no catalytic activity and
the epoxide starting material was recovered unchanged (Table 2,
entry 1) [46–48]. The incorporation of aluminium into the silica
structure resulted in the production of effective catalysts for the
addition reaction, and all of the aluminosilicate materials displayed
activity to catalyse the addition reaction under the conditions
employed. Importantly, all catalysts displayed high selectivity (typ-
ically 95:5) for the formation of the Markovnikov addition product
2-phenylamino-2-phenylethanol (1), over the anti-Markovnikov
product 1-phenyl-2-(phenylamino)ethanol (2). Interestingly, and
in contrast to our previous experience with addition reactions of
alcohols to epoxides catalysed by these materials, no phenylac-
Table 5
Optimisation of the conditions for the addition of aniline to cyclohexene oxide.
.
Entry
Catalyst (mg/mmol epoxide)
Time (h)
Conversiona,b (%)
1
2
3
4
5
6
50
50
50
50
50
6
9
3
6
9
6
62c
85
68d
84d
71d
93
120
a
Reactions employ 1 mmol of epoxide and 1 mmol of aniline in 5 ml CH2Cl2.
Determined from 1H NMR analysis of crude reaction mixture.
Determined from 1H NMR and GC–MS analysis of crude reaction mixture.
Reaction at 40 ◦C.
b
c
d

M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
61
Table 6
Aminolysis of cyclohexene oxide using aluminosilicate catalyst AS-(14).
.
Entry
Epoxide
Aniline
Time (h)
Product
Yielda,b (%)
1
2
12
65c,d
6
6
85
65
3
4
5
18
12
61d
69
6
7
6
53d,e
12
57
8
9
12
24
6
61b,d
61c,d
10
81
a
Isolated yield after column chromatography.
b
c
Reactions using 120 mg of catalyst/mmol of epoxide and 1.1 equiv. of aniline in 5 ml of CH2Cl2.
Reaction at room temperature using 50 mg of catalyst/mmol of epoxide in 5 ml of CH2Cl2.
Conversion determined by 1H NMR analysis of the crude reaction mixture.
d
e
Reaction at 40 ◦C using 50 mg of catalyst/mmol of epoxide in 5 ml of CH2Cl2.

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M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
quantity of catalyst to 120 mg/mmol of epoxide provided high
isolated yields of the addition product which was obtained with
excellent selectivity for the Markovnikov addition product (entry
12). With successful conditions established, the scope of the alumi-
nosilicate catalysed addition was demonstrated with both a range
of epoxides and amine nucleophiles (Table 4). All reactions pro-
ceeded to give the Markovnikov addition product with good to
excellent selectivity, except in the case of the addition of aniline
to 1,2-epoxy-3-phenyoxypropane (entry 7) which gave the anti-
Markovnikov product, derived from addition to the least hindered
carbon of the epoxide, in accordance with literature reports [46].
We next studied the additional reactions of aniline to cyclo-
hexene oxide. We have previously reported that for the addition
of alcohols, these transformations proceed more rapidly than the
corresponding reactions involving styrene oxide [13,46]. There-
fore, a short additional optimisation study was completed which
encompassed the effect of temperature, reaction time and cata-
lyst quantity (Table 5). In line with our previous observations with
this substrate, acceptable conversions were achieved using a lower
quantity of catalyst (Table 5, entry 1), which were improved on
extending reaction times (entry 2) or by carrying out the reac-
tions at elevated temperatures (entry 3). It proved most expedient,
however, to increase the quantity of catalyst to 120 mg/mmol of
epoxide (entry 6), and under these conditions, the AS-(14) mate-
rial again proved to be a highly effective catalyst for the addition
of a diverse range of aromatic amine nucleophiles giving good to
excellent isolated yields of ␤-amino alcohol products (Table 6).
Fig. 2. Pore-size distribution of aluminosilicate catalysts.
etaldehyde was observed in the crude reaction mixture of these
reactions. We have previously observed this product, formed by
a competing Meinwald rearrangement reaction, in reactions in
which the addition of the nucleophile is slow due either to its poor
nucleophilicity or by competing steric factors [29,46,49].
3.3. Reaction optimisation and scope
4. Conclusions
We next optimised the reaction conditions using the addition
of aniline to styrene oxide as a model reaction employing the AS-
(14) material, and all subsequent reactions were undertaken with
this catalyst. Reactions carried out with no catalysts present gave
no addition products and the starting materials were recovered
unchanged in these cases. Our initial reaction conditions replicated
those we employed in our previous studies for the addition of alco-
hols to styrene oxide, and were carried out in dichloromethane at
room temperature using 50 mg of catalyst/mmol of epoxide over
2 h (Table 3, entry 1).
In conclusion, we have demonstrated that both silica and alu-
minosilicates displaying pore sizes in the nano range, typically
1.3–1.5 nm, are easily and efficiently synthesized using a templated
EISA approach. The process is operationally simple, requires no
specialist equipment and gives materials with a narrow pore-size
distribution and with the expected large surface areas. Synthetic
routes to materials with pore sizes in this range are of considerable
interest as, while numerous approaches to mesoporous materials
with large pore sizes have been reported, the synthesis of mate-
rials with pore sizes between the upper limit of zeolites and the
lower end of mesoporous materials remains a significant chal-
lenge. Our materials are highly flexible and well characterised
heterogeneous solid acid catalysts, which efficiently catalyse the
regioselective addition of aromatic amines to epoxides to pro-
duce ␤-amino alcohols in high yields and with excellent selectivity
for the Markovnikov addition product. These silicate catalysts are
highly stable, crystalline materials which are easy to handle, and
the operationally simple protocol requires no special precautions,
such as the exclusion of moisture or specialist equipment. Indeed,
the reaction of styrene oxide with aniline carried out in water
gives moderate conversion to the corresponding ␤-amino alco-
hol product with good selectivity. The addition reactions typically
proceed at room temperature with near-stoichiometric quanti-
ties of the amine nucleophile to give good to excellent yields of
the Markovnikov addition products from a range of epoxides and
amines. The facile synthesis of these materials, their benign nature,
their ease of handling, their high catalytic activity and the simplified
reaction and isolation procedures make them a highly attractive
alternative to current methodologies.
These conditions, however, provided only moderate conver-
sions to (1) even after extended reaction times (entries 1 and 3),
albeit with high selectivity for the expected Markovnikov prod-
uct. We envisage that the observed decrease in the conversion of
epoxide to ␤-amino alcohol reflects the increased affinity of the
amine for acidic sites in the aluminosilicate [50]. With this in mind,
we next investigated reactions carried out at elevated tempera-
tures, in different solvents or with increased quantities of aniline
to assess whether these simple expedients would lead to improved
conversions. Disappointingly, none of these measures provided
an acceptable solution to resolve the limited reactivity observed
(Table 3, entries 2 and 4–10). It was of interest, however, to observe
that the reaction performed in water as the reaction medium (entry
10) gave conversions with selectivities that were comparable to
reactions carried out in organic solvents. Indeed, only trace quanti-
ties of corresponding diol hydrolysis product were detected by 1
H
NMR analysis of the crude reaction mixture. There has been consid-
erable recent interest in the ring-opening reactions of epoxides in
aqueous media, particularly those reactions involving amine nucle-
ophiles [51–55]. Therefore, it is somewhat surprising that there
appear to be no previous reports of similar protocols carried out
using porous silicate catalysts.
We next studied reactions with increased quantities of cata-
lyst, and under these conditions, we were gratified to observe that
acceptable conversions of styrene oxide to aminolysis products
were realised using near-stoichiometric quantities of the nucle-
ophile at room temperature (entry 11). Further increasing the
Acknowledgements
The authors thank the Engineering and Physical Sciences
Research Council (EPSRC) and Cardiff University for financial sup-
port, the EPSRC National Mass Spectrometry service, Swansea

M.W.C. Robinson et al. / Journal of Molecular Catalysis A: Chemical 329 (2010) 57–63
63
University and Mr Peter Davies (School of Engineering, Swansea
University) for his assistance in obtaining EDX data. The authors
are indebted to Dr N.C.O. Tomkinson (Cardiff University) and Dr S.D.
Kean (University of Glamorgan) for continued support, encourage-
ment and inspiration.
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