MCM-41 catalyzed efficient regioselective synthesis of β-aminoalcohol under solvent-free conditions

Article abstract of DOI:10.1002/cjoc.201090065

β-Aminoalcohols were synthesized in high yields by reaction of epoxides with amines in the presence of MCM-41 as a green and reusable catalyst under solvent-free conditions.

Full text of DOI:10.1002/cjoc.201090065

FULL PAPER
MCM-41 Catalyzed Efficient Regioselective Synthesis of
β-Aminoalcohol under Solvent-free Conditions
Heravi, Majid M.*,a
Bakhtiari, Khadijeh*,a
Alinejhad, Hamideha
Saeedi, Minaa
Malakooti, Reihaneb
a Department of Chemistry, School of Science, Azzahra University, Vanak, Tehran, Iran
b Nanochemistry Research Laboratory, Department of Chemistry, University of Birjand, Birjand, Iran
β-Aminoalcohols were synthesized in high yields by reaction of epoxides with amines in the presence of
MCM-41 as a green and reusable catalyst under solvent-free conditions.
Keywords β-aminoalcohol, solvent-free condition, MCM-41, aromatic amine, aliphatic amine
Introduction
compounds under solvent-free conditions,26 herein, we
wish to report a simple, environmentally friendly and
proficient method for the preparation of β-aminoalcohol
in the presence of a catalytic amount of MCM-41 as a
green reusable and efficient catalyst (Scheme 1).
β-Aminoalcohols are flexible intermediates in the
synthesis of a broad range of biologically active natural
and synthetic products and used as building blocks for
the synthesis of pharmaceuticals.1 Also they are present
in unnatural amino acids, chiral auxiliaries, as chiral
catalysts in asymmetric synthesis.2 Thus, developing
various methodologies for their synthesis always is de-
manding. These compounds are conventionally synthe-
sized by reaction of epoxides with excessive amounts of
amines at elevated temperatures.3 Classical methodolo-
gies suffer from one or more disadvantages such as long
reaction time, elevated temperature, high pressure,
moderate yields and poor regioselectivities.4 Up till now,
different protocols have been reported for the synthesis
of β-aminoalcohols including practical methods like
utilizing microwave5 and ultrasound6 as well as efficient
catalysts such as sulfamic acid,7 amberlyst-15,8 metal
triflates,9 metal alkoxides,10 metal halides,11,12 transition
metal salts,13,14 heteropolymolybdate or tungstate,15
monodispersed silica nanoparticles,16 zeolites,17 mont-
Scheme 1
In order to obtain the standard conditions, 2,3-ep-
oxypropyl phenyl ether (1 mmol) was treated with
aniline (1 mmol) under solvent-free conditions in the
presence of MCM-41 at various temperatures and their
effect on the yield and rate of the reaction was investi-
gated (Table 1). The desired product was attained at 120
℃ and 0.03 g of catalyst in 75% yield. Increasing tem-
perature did not result in higher yield and shorter reac-
tion time. Various aromatic and aliphatic amines were
treated with cyclohexene epoxide or 2,3-epoxypropyl
phenyl ether and their corresponding results are summa-
rized in Table 2. To examine the recyclability of the
morillonite,18 ionic liquids,19 sulfated zirconia and
SZ/MCM-41,20 Er(OTf)3,21 Y(NO3)3
and ZnO.23
22
MCM-41 is a mesoporous inorganic solid with pore
diameters of 2—50 Å, which has attracted much atten-
tion because of its large internal surface, regular arrays
of uniform channels, long range ordered framework
with uniform mesopores and sharply distributed pore
dimensions. Since MCM-41 was synthesized by Kre-
sege et al.,24 its role as catalyst and support in organic
reactions has been established.25 In this work, in view of
great catalytic effect of MCM-41 in literature, it was
selected for synthesis of β-aminoalcohols.
Table 1 Effect of catalyst and temperature on the reaction of
2,3-epoxypropyl phenyl ether with aniline
Entry
Temperature/℃
Time/h
Yielda/%
1
2
3
4
5
Room temperature
12
12
1
40
40
65
75
65
50
110
120
130
0.55
1
Results and discussion
a Yields refer to isolated products.
In continuation of our interest in synthesis of organic
*
E-mail: mmh1331@yahoo.com; khb1352@yahoo.com; Tel.: 0098-21-88044051; Fax: 0098-21-88041344
Received August 9, 2009; revised September 24, 2009; accepted October 19, 2009.
Chin. J. Chem. 2010, 28, 269— 272
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
269

Heravi et al.
Table 2 MCM-41 catalyzed synthesis of β-aminoalcohols through regioselective opening of epoxide by aromatic and aliphatic amines
FULL PAPER
Entry
1
Epoxide
Amine
Product
Time/min
Yielda/%
1a
60
85
2
3
1b
1c
50
45
80
82
4
5
6
7
1d
1e
1f
55
45
75
66
68
70
45
1g
100
8
9
1h
1i
90
75
75
75
CH3CH2CH2CH2NH2
a Yields refer to isolated products.
catalyst, after completion of the reaction, hot ethanol
was added to the mixture and the catalyst was filtered,
washed with diethyl ether, dried at 120 ℃ for 1 h and
reused in subsequent two reactions. The results are
summarized in Table 3. It is worthwhile to mention that
desired regioselective transformation of epoxides to
corresponding β-aminoalcohols in high yields was
achieved by MCM-41 and product 2 was not observed
(Scheme 1).
Table 3 Reusability of catalyst in reaction of aniline and
2,3-epoxypropyl phenyl ether
Entry
Number of recycle
Time/min
Yielda/%
1
2
3
4
Fresh
55
55
55
55
75
75
70
70
1
2
3
a Yields refer to isolated products.
Working on the model reaction, 2,3-epoxypropyl ph-
enyl ether (1 mmol) and aniline (1 mmol) in the absence
of catalyst gave poor yield (30%) and side reactions.
1
paratus and are uncorrected. H NMR spectra were re-
corded on a Bruker AQS-AVANCE spectrometer at 500
MHz, using TMS as an internal standard (CDCl3 solu-
tion). FTIR spectra were recorded from KBr disks on
FT-IR Bruker Tensor 27 instrument. GC/Mass analysis
was performed using an Agilent 6890 GC system of
Hp-5 capillary 30 m×530 µm×1.5 µm. The reactions
Chin. J. Chem. 2010, 28, 269— 272
Experimental
Melting points were measured by using a capillary
tube method with a Bamstead Electrothermal 9200 ap-
270
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MCM-41 Catalyzed Synthesis of β-Aminoalcohol
were monitored by TLC. All solvents and reagents were
purchased from Aldrich and Merck with high-grade
quality, and used without any purification. Known
products were characterized by their spectral and
physical data.
short time and excellent regioselectivity.
Acknowledgment
We gratefully acknowledged for partial financial
support from the Azzahra University.
General procedure
MCM-41 was prepared according to the procedure
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Chin. J. Chem. 2010, 28, 269— 272