A novel and efficient conversion of aldehydes to 1,1-diacetates catalyzed with FeCl3/SiO2 under microwave irradiation

Article abstract of DOI:10.1081/SCC-120014779

1,1-Diacetates (3) are effectively synthesized in few minutes by acylation reaction of aldehydes with acetic anhydride in the presence of FeCl₃/SiO₂ under microwave irradiation.

Full text of DOI:10.1081/SCC-120014779

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A NOVEL AND EFFICIENT CONVERSION OF ALDEHYDES
TO 1,1-DIACETATES CATALYZED WITH FeCl3/SiO2 UNDER
MICROWAVE IRRADIATION
Cunde Wang a & Minghua Li a
a Department of Chemistry, Yangzhou University, Yangzhou, 225002, P.R. China
Published online: 22 May 2009.
To cite this article: Cunde Wang & Minghua Li (2002) A NOVEL AND EFFICIENT CONVERSION OF ALDEHYDES TO 1,1-DIACETATES
CATALYZED WITH FeCl3/SiO2 UNDER MICROWAVE IRRADIATION, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:22, 3469-3473, DOI: 10.1081/SCC-120014779
To link to this article: http://dx.doi.org/10.1081/SCC-120014779
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MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHETIC COMMUNICATIONS
Vol. 32, No. 22, pp. 3469–3473, 2002
A NOVEL AND EFFICIENT CONVERSION
OF ALDEHYDES TO 1,1-DIACETATES
CATALYZED WITH FeCl3/SiO2 UNDER
MICROWAVE IRRADIATION
*
Cunde Wang and Minghua Li
Department of Chemistry, Yangzhou University,
Yangzhou 225002, P.R. China
ABSTRACT
1,1-Diacetates (3) are effectively synthesized in few minutes by
acylation reaction of aldehydes with acetic anhydride in the
presence of FeCl3/SiO2 under microwave irradiation.
1,1-Diacetates(acylals), which are stable in neutral and basic media,
are useful protective group for aldehydes.[1–3] 1,1-Diacetates are syn-
thetically important precursors for the preparation of 1-acetoxydienes for
Diels-Alder reactions.[4] Also some industrial uses of these compounds,
which have been applied as crosslinking reagents for cellulose in cotton[5]
and activators in the composition of bleaching mixtures for wine-stained
fabrics,[6] have been reported.
Usually, 1,1-diacetates are prepared from aldehydes and acetic
anhydride in the presence of strong protic acids such as H2SO4,[7] H3PO4
*Corresponding author. E-mail: wcd640918@163.com
3469
DOI: 10.1081/SCC-120014779
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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3470
WANG AND LI
and CH3SO3H,[8] or Lewis acids such as FeCl3,[3] ZnCl2,[9] PCl3,[10] I2,[11]
Sc(OTf )3,[12] Cu(OTf )2.[13]
Other catalysts such as Nafion–H,[14] zeolites,[15] NBS,[16] etc. are also
known for the same transformation. But the preparation of 1,1-diacetates
from aldehydes and aecticanhydride using protonicor Lewis aicds as
catalysts have been known for either a reaction long time or a low yield
of product. Therefore, the development of new methods with more efficiency
and better yield is of interest.
In recent years, the method of rapidly heating by microwave oven has
been applied in organicsynthesis, and organicsynthesis on solid supported
reagents coupled with microwave (in dry media) is currently a matter of
increasing interest due to its greater selectivity, enhanced reaction rates,
cleaner reaction products and operational simplicity.[17] Additionally,
microwave assisted reactions are novel, more efficient, convenient and
provide solvent free conditions. In continuation of our work,[18,19] we
currently working in synthesis of some 1,1-diacetates 3 by the reaction of
aldehydes 1 including aromatic and aliphatic and a,b-unsaturated ones and
acetic anhydride 2 using iron trichloride/silica gel without solvent under
microwave irradiation (Sch. 1).
Effects of incident power as well as those of reaction times are checked.
The optimum conditions for the reaction and yields are given in Table 1.
We report here a mild reaction condition procedure using a commer-
cially available Lewis acid FeCl3/SiO2 which, in general, proceeds in short
time ranging between 3 and 5 min. All the reactions were run at lower
microwave power, and high yields of 1,1-diacetates were obtained (Table 1).
The use of inexpensive catalyst and non-solvent reaction conditions makes
this procedure more economic and ecofriendly.
Scheme 1.

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ALDEHYDE CONVERSION WITH FeCl3/SiO2
Table 1. Preparation of Compounds 3
3471
Microwave Power
(W)
Irradiation Time
(min)
Yielda
(%)
Compound
Formula
3a
3b
3c
3d
3e
3f
3g
3h
3i
C8H14O4
C7H10O4
200
200
225
225
225
300
300
300
300
225
200
200
3
3
4
4
4
3
3
4
4
5
4
4
78
83
95
93
91
92
90
93
90
88
80
83
C11H12O4
C12H15O4
C12H14O5
C11H11NO6
C11H11NO6
C11H11ClO4
C15H14O4
C13H14O4
C9H10O5
3j
3k
3l
C9H10SO4
aIsolated yield.
EXPERIMENTAL
Melting points were uncorrected, IR spectra were measured with a
model 408 infrared spectrometer, 1H-NMR spectra were recorded on a
JNM-90Q spectrometer by using TMS as an internal standard (CDCl3
solutions).
General Procedure for the Preparation of 1,1-Diacetates
A mixture of aldehyde (5 mmol), acetic anhydride (15 mmol) and
FeCl3 (0.5 g, 0.3 mmol)/SiO2 (5 g) were introduced into a Galanz WP
750A domestic microwave oven in an 25 mL beaker. Microwave irradiation
was carried out for the appropriate time and at the power indicated (see
Table 1). The mixture was cooled to ambient temperature, the product was
obtained directly by silica gel column chromatography. The structures of all
products are identified on the base of literature description. IR and
1H-NMR data are given.
1
Compound 3a: Oil, H NMR ꢀ (ppm): 0.94 (t, 3H, J ¼ 3.5 Hz, CH3),
1.42–1.45 (m, 2H, CH2), 1.77–1.79 (m, 2H, CH2), 2.06 (s, 6H, 2COCH3),
6.81 (t, 1H, J ¼ 5.5 Hz, CH); IR (KBr) ꢁ (cmꢀ1): 2960, 2880, 1760, 1250,
1220, 1080.