Al(HSO4)3 as an efficient catalyst for the acetylation of alcohols in solution and under solvent free conditions

Article abstract of DOI:10.1007/s00706-003-0083-4

Alcohols are acetylated in a mild, clean, and efficient reaction with acetic anhydride in the presence of a catalytic amount of Al(HSO ₄)₃ in solution and under solvent free conditions. All reactions were performed at room temperature in good to high yields. Springer-Verlag 2003.

Full text of DOI:10.1007/s00706-003-0083-4

Monatshefte f€ur Chemie 135, 279–282 (2004)
DOI 10.1007/s00706-003-0083-4
Al(HSO4)3 as an Efficient Catalyst
for the Acetylation of Alcohols
in Solution and Under Solvent
Free Conditions
Farhad Shirini1;ꢀ, Mohammad A. Zolfigol2, and Masoumeh Abedini1
1
Department of Chemistry, Faculty of Science, Guilan University, Rasht, Iran
2
Department of Chemistry, College of Science, Bu-Ali Sina University, Hamadan, Iran
Received May 12, 2003; accepted (revised) June 4, 2003
Published online January 27, 2004 # Springer-Verlag 2003
Summary. Alcohols are acetylated in a mild, clean, and efficient reaction with acetic anhydride in the
presence of a catalytic amount of Al(HSO4)3 in solution and under solvent free conditions. All
reactions were performed at room temperature in good to high yields.
Keywords. Acetylation; Acetic anhydride; Al(HSO4)3; Alcohols; Solvent free conditions.
Introduction
The conversion of alcohols to esters is an important synthetic transformation that
has received considerable attention [1]. Conversion of an alcohol to the corre-
sponding acetate is typically carried out using acetic anhydride or acetyl chloride in
the presence of triethyl amine or pyridine as a catalyst [2]. 4-(Dimethylamino)pyr-
idine (DMAP) is known to cause a remarkable rate acceleration in this reaction [3].
In addition to catalysis by tertiary amines, protic or Lewis acids have also been
reported to catalyze the acetylation of alcohols. Examples include TMSCl [4],
magnesium bromide [5], Sc(AcO)3-(CF3SO2)2NH [6], TiCl4 þ AgClO4 [7], CoCl2
[8], NBS [9], Sn(OTf)2 [10], Cu(OTf)2 [11], In(OTf)3 [12], Bi(OTf)3 [13, 14],
Sc(OTf)3 [15], p-toluenesulfonic acid [16], and sulfamic acid [17]. However, most
of the reported methods suffer from one or more of the following disadvantages:
long rection time, vigorous reaction conditions, the occurrance of side reactions,
use of expensive or unavailable reagents, and poor yields of the desired product.
Thus, there is still a demand to develop new and mild methods for the acetylation
of alcohols in the presence of inexpensive and bench top reagents.
ꢀ
Corresponding author. E-mail: shirini@guilan.ac.ir

280
F. Shirini et al.
Scheme 1
In continuation of our studies on the applications of inorganic acidic salts
[18–20], we wish to report a new method for the acetylation of alcohols with acetic
anhydride in the presence of a catalytic amount of Al(HSO4)3 in solution and under
solvent free conditions (Scheme 1).
Results and Discussion
Acetylation of different types of alcohols including primary, allylic, benzylic, sec-
ondary, and sterically hindered tertiary alcohols, using Ac2O in the presence of
Al(HSO4)3 with and without a solvent were performed (Scheme 1, Table 1). In a
simple procedure, a mixture of reactants was stirred at room temperature for the
a
Table 1. Acetylation of alcohols catalyzed by Al(HSO4)3
Entry
Substrate
Product
Acetylation in the
absence of solvent
Acetylation in
solution
Time=min
Yield=%b
Time=min
Yield=%b
1
2
C6H5CH2OH
C6H5CH2OAc
1
1
1
1
1
1
1
3
1
1
1
1
8
4
4
4
4
10
8
8
2
95
85
90
92
95
92
85
90
90
86
82
90
60
85
90
87
85
90
95
86
70
2
1
87
84
90
86
89
85
85
85
86
85
85
80
60
85
85
85
80
80
82
85
80c, d
2-BrC6H4CH2OH
2-ClC6H4CH2OH
2-MeC6H4CH2OH
4-ClC6H4CH2OH
4-(Me)3CC6H4CH2OH
3-NO2C6H4CH2OH
C6H5CH(OH)C6H5
C6H5CH2CH(OH)CH3
C6H5CH(CH3)CH2OH
C6H5CH2CH2CH2OH
C6H5CH2CH2OH
C6H5CH¼CHCH2OH
Cyclohexanol
2-BrC6H4CH2OAc
3
2-ClC6H4CH2OAc
1
4
2-MeC6H4CH2OAc
4-ClC6H4CH2OAc
1
5
1
6
4-(Me)3CC6H4CH2OAc
3-NO2C6H4CH2OAc
C6H5CH(OAc)C6H5
C6H5CH2CH(OAc)CH3
C6H5CH(CH3)CH2OAc
C6H5CH2CH2CH2OAc
C6H5CH2CH2OAc
2
7
1
8
3
9
1
10
11
12
13
14
15
16
17
18
19
20
21
3
1
1
C6H5CH¼CHCH2OAc
Cyclohexyl acetate
1-Octyl acetate
10
3
1-Octanol
5
(ꢁ)-Menthol
(ꢁ)-Menthyl acetate
1-Methylcyclohexyl acetate
tert-Butyl acetate
4
1-Methylcyclohexanol
tert-Butyl alcohol
1-Adamantanol
4
10
8
1-Adamantanyl acetate
2-Adamantanyl acetate
C6H5CH(OAc)CH2OAc
2-Adamantanol
8
C6H5CH(OH)CH2OH
3
a
Products were characterized by their physical constants, comparison with authentic samples, and IR and NMR spectroscopy;
b
c
Isolated yield; Yield refers to isolated pure diacetate; 2.5 mmol of acetic anhydride were used
d

Al(HSO4)3 as an Efficient Catalyst
281
appropriate time (Table 1). Alcohols reacted efficiently and the corresponding
acetates were isolated in good to high yields.
In order to compare the obtained results with those obtained in solution, we
studied the acetylation reaction in n-hexane. As shown in Table 1, there are only
small differences between the results obtained in solution and those under solvent
free conditions. However, by ommiting the solvent, in addition to an easy work-up
procedure, the need for a solvent is avoided. In the case of allylic alcohols, in
addition to the desired acetate, two unidentified products were also produced
(Table 1, Entry 13).
In conclusion, we have shown that Al(HSO4)3 is a very efficient and versatile
catalyst for the acetylation of alcohols. The advantage of the method is that even
hindered substrates can be acetylated in good to high yields under mild reaction
conditions. Investigations on further applications of Al(HSO4)3 are ongoing in our
laboratory.
Experimental
Preparation of Al(HSO4)3
A 500 cm3 suction flask was equipped with a constant- pressure dropping funnel. A gas outlet was
connected to a vacuum system through an absorbing solution (H2O) and an alkali trap. The flask was
charged with 66.7g of anhydrous AlCl3 (0.5mol) and 147.1 g of conc. H2SO4 (1.5mol) was added
dropwise over a period of 40 min at room temperature. HCl gas evolved immediately. After completion
of the addition of H2SO4, the mixture was shaken for 30min, meanwhile, the residual HCl was
exhausted by suction. A white solid material (158.5g) was obtained.
General Procedure for Acetylation of Alcohols in n-Hexane
A mixture of 1 mmol of alcohol, 1.5mmol of acetic anhydride, and 0.05mmol of Al(HSO4)3 in
5 cm3 of n-hexane was stirred at room temperature. The progress of the reaction was monitored by
TLC or GC. After completion of the reaction, the solvent was evaporated and 10cm3 of H2O were
added. The mixture was extracted with 2ꢂ10cm3 of CH2Cl2. The organic layer was separated,
washed with 2ꢂ10cm3 of saturated NaHCO3 solution and 5 cm3 of H2O, and dried over anhydrous
MgSO4. Evaporation of the solvent followed by column chromatography on silica gel afforded the
pure acetate.
General Procedure for Acetylation of Alcohols Under Solvent Free Conditions
A mixture of 1 mmol of alcohol, 1.5 mmol of acetic anhydride, and 0.05 mmol of Al(HSO4)3 was
agitated at room temperature. The progress of the reaction was monitored by TLC or GC. After
completion of the reaction, 10 cm3 of H2O were added and the mixture was extracted with
2ꢂ10 cm3 of CH2Cl2. The organic layer was seperated, washed with 2ꢂ10cm3 of saturated NaHCO3
solution and 5 cm3 of H2O, and dried over anhydrous MgSO4. Evaporation of the solvent followed by
column chromatography on silica gel afforded the pure acetate.
Acknowledgement
Partial support of this work by the Guilan University Research Council is acknowledged.

282
F. Shirini et al.: Al(HSO4)3 as an Efficient Catalyst
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