An efficient and practical procedure for synthesis of 1,1-diacetates from aldehydes catalyzed by zirconium sulfate tetrahydrate-silica gel

Article abstract of DOI:10.1081/SCC-120030752

A facile and efficient procedure for synthesis of 1,1-diacetates from aldehydes with acetic anhydride was described using zirconium sulfate tetrahydrate-silica gel as catalyst in excellent yields under mild reaction conditions.

Full text of DOI:10.1081/SCC-120030752

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An Efficient and Practical Procedure for Synthesis
of 1,1‐Diacetates from Aldehydes Catalyzed by
Zirconium Sulfate Tetrahydrate–Silica Gel
a
a
a
a
Tongshou Jin , Guoliang Feng , Mina Yang & Tongshuang Li
a
Department of Chemistry, College of Chemistry and Environmental Science , Hebei
University , Baoding, 071002, Hebei Province, P.R. China
Published online: 16 Aug 2006.
To cite this article: Tongshou Jin , Guoliang Feng , Mina Yang & Tongshuang Li (2004) An Efficient and Practical Procedure
for Synthesis of 1,1‐Diacetates from Aldehydes Catalyzed by Zirconium Sulfate Tetrahydrate–Silica Gel, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 34:9, 1645-1651, DOI:
10.1081/SCC-120030752
To link to this article: http://dx.doi.org/10.1081/SCC-120030752
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SYNTHETIC COMMUNICATIONS
Vol. 34, No. 9, pp. 1645–1651, 2004
An Efficient and Practical Procedure for
Synthesis of 1,1-Diacetates from Aldehydes
Catalyzed by Zirconium Sulfate
Tetrahydrate–Silica Gel
*
Tongshou Jin, Guoliang Feng, Mina Yang,
and Tongshuang Li
Department of Chemistry, College of Chemistry and Environmental
Science, Hebei University, Baoding, Hebei Province, P.R. China
ABSTRACT
A facile and efficient procedure for synthesis of 1,1-diacetates from
aldehydes with acetic anhydride was described using zirconium sulfate
tetrahydrate–silica gel as catalyst in excellent yields under mild reaction
conditions.
Key Words: Synthesis; 1,1-Diacetates; Aldehydes; Zirconium sulfate
tetrahydrate–silica gel.
*
Correspondence: Tongshou Jin, Department of Chemistry, College of Chemistry and
Environmental Science, Hebei University, Baoding 071002, Hebei Province,
P.R. China; Fax: þ86-312-507-9628; E-mail: orgsyn@mail.hbu.edu.cn.
1
645
DOI: 10.1081/SCC-120030752
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Jin et al.
INTRODUCTION
,1-Diacetates are synthetically useful as protecting groups for aldehydes
1
because they are stable and easy conversion into parent aldehydes
[
1–5]
and
Gener-
[
6,7]
they are used as substrates in nucleophilic substitution reactions.
ally, 1,1-diacetates are prepared from aldehydes and acetic anhydride using
[
8,9]
[10–12]
[13–16]
strong proton acids,
Lewis acids,
and other catalysts.
Some
of these methods have not been entirely satisfactory owing to such drawbacks
as long reaction times, expensive and hazardous reagents, cumbersome
experimental and non-recoverable catalysts. So, it is necessary to find new
catalysts for the synthesis of 1,1-diacetates from aldehydes under mild and
environment friendly conditions.
Zirconium sulfate tetrahydrate is a kind of layered compound and the
crystal water of zirconium sulfate tetrahydrate can produce sites of Brønsted
[17,18]
acid with moderate strength. For the reactions of syntheses of acetate,
zirconium sulfate tetrahydrate has a high catalytic activity and selectivity
owing to its layered structure and interlayer acidic sites. Herein we wish to
report a fast and efficient procedure for the synthesis of 1,1-diacetates from
aldehydes with acid anhydrides catalyzed by zirconium sulfate tetra-
hydrate–silica gel at room temperature (Sch. 1).
Representative results of this study are summarized in Table 1. As shown
in Table 1, both aromatic and aliphatic aldehydes gave excellent yield of the
corresponding 1,1-diacetates in a short reaction time at room temperature
except for 4-dimethylaminobenzaldehyde (1q, no reaction). These reactions,
however, did not proceed in the absence of zirconium sulfate tetrahydrate–
silica gel. We also observed that aromatic aldehydes containing electron-
withdrawing groups or donor groups (1d–1m and 1o), benzaldehyde (1c), and
cinnamaldehyde (1n) gave the corresponding 1,1-diacetaes in near quantita-
tive yields in shorter times using zirconium sulfate–silica gel catalyst.
Mention must be made here that phenol groups were also protected as
acetals in hydroxyl containing aromatic aldehydes (11 and 1m) under these
conditions. It is also worth nothing that ketones, such as acyclohexanone,
acetophenone, and 3-pentanone, did not give any 1,1-diacetates under the
same reaction conditions. The ketone group remains unaffected with alde-
hydes converted into 1,1-diacetates, this indicates that the procedure offers
Scheme 1.

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Synthesis of 1,1-Diacetates from Aldehydes
1647

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1
648
Jin et al.
good selectivity for protection of aldehydes in the presence of ketones. In con-
trast to earlier reports, the solid aldehydes (1b, 1g, 1i, 1j, and 1o), which can
resolve into the acid anhydrides under stirring, are absence of CH Cl in the
2
2
reaction in order to reduce the environmental pollution. Additionally,
-dimethylaminobenzaldehyde (1q) failed to give the corresponding 1,1-di-
4
acetate and the starting materials were quantitatively recovered under the
same conditions. The explanation for this result may be due to the strong elec-
tron donating dimethylamino group in (1q) which will reduce the reactivity. A
degree of tautomeisation may occur in (1q) with formation of quinoid struc-
ture and thus decreased reactivity of the aldehyde group. Finally, the catalyst
provides convenience of workup, lower the environmental hazards and after
six times of repeated use the activity of catalyst do not decrease.
In conclusion, our results confirm that zirconium sulfate tetrahydrate–
silica gel can offer definite advantages over traditional catalysts in terms of
activity, ease of separation, high yields, short reaction time, non-corrosive,
and non-pollutive aspects for the chemoselective conversion of aldehydes
into 1,1-diacetates. Moreover, they can be regenerated and reused. The
method will be better than many other existing ones.
EXPERIMENTAL
1
Melting and boiling points are uncorrected. H NMR spectra were deter-
minded on a Varian VXP-300s spectrometer using CDCl as solvent and
3
tetramethylsilane (TMS) as internal reference. The products were also charac-
terized by comparison of their melting point with literature values. The cata-
.
lyst was prepared as follows. A mixture of Zr(SO4)2 4H O (5 g), Et O
2
2
(
20 mL), silica gel (5 g) was stirred at room temperature for 30 min. After
the mixture was evaporated under reduced pressure, they are dried at 1008C
for 2 hr, finally stored in a desiccator until use.
General Procedure for the Preparation of 1,1-Diacetates
A mixture of the aldehyde (5.00 mmol), freshly distilled acetic anhydride
10.0 mmol), and catalyst (100 mg) was stirred at room temperature for the
(
length of time indicated in Table 1, for the reactions with solvent CH Cl
2
2
(5 mL) was also added. After completion, as indicated by TLC, Et O (5 mL)
2
was added to the reaction mixture and the catalyst was filtered off. The catalyst
was washed with Et O (2 ꢀ 5 mL) and then the organic layer was washed with
2
5
% HCl (10 mL), 5%NaHCO (15 mL), and brine (2 ꢀ 10 mL) successively
3
and dried over anhydrous MgSO . The solvent was evaporated under reduced
4

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Synthesis of 1,1-Diacetates from Aldehydes
1649
pressure to provide crude product and the crude product was chromatographed
on silica gel (light petroleum ether as eluent) to give the pure product 3.
1
H NMR data of some of the products are given below:
3a. dH 1.00 [1H, t, CH (CH ) CH(OAc) ], 1.90–1.30 [2H, brm,
CH CH CH CH(OAc) ,], 2.40–2.00 [2H, brm, CH CH CH CH(OAc) ],
3 2 2 2
3
2
2
2
3
2
2
2
2.00 [6H, s, RCH(O CCH ) ], 6.50 [lH, m, RCH(OAc)2].
2 3 2
3e. d 2.10 [6H, s, ArCH(O CCH ) ], 3.80 [3H, s, Ar-OCH ], 6.75 [2H,
H 2 3 2 3
d, J ¼ 9 Hz, 3,5-Ar-H], 7.35 [2H, d, J ¼ 9 Hz, 2,6-Ar-H], 7.40 [lH, d,
ArCH(OAc) ].
2
3g. d 2.10 [6H, s, ArCH(O CCH ) ], 7.30 [4H, s, C H ], 7.50 [1H, s,
H 2 3 2 6 4
ArCH(OAc)2].
h. d 2.15 [6H, s, ArCH(O CCH ) ], 7.28–7.53 (3H, m, C H ), 7.93
3
H
2
3 2
6
3
[
1H, s, ArCH(OAc)2].
k. d 2.10 [6H, s, ArCH(O CCH ) ], 7.45 [1H, s, ArCH(OAc) ], 7.47
3
H
2
3 2
2
[
2H, d, J ¼ 9 Hz, 2,6-Ar-H], 8.05 [2H, d, J ¼ 9 Hz, 3,5-Ar-H].
3
l. d 2.09 [6H, s, ArCH(O CCH ) ], 2.33 (3H, s, 2-O CCH ),
2
H
2
3 2
3
7.05–7.69 (4H, m, C H ), 7.89 [1 H, s, ArCH(OAc) ].
6 4 2
3m. d 2.11 [6H, s, ArCH(O CCH ) ], 2.29 (3 H, s, 4-O CCH ), 3.85
H 2 3 2 2 3
(
3H, s, OCH ), 7.00–7.10 (3H, m, C H ), 7.65 [lH, s, ArCH(OAc) ].
3 6 3 2
3
n. d 2.15 [6H, s, ArCH 55 CHCH(O CCH ) ], 5.95 [1H, dd, J ¼ 16.5
H
2
3 2
and 7.2 Hz ArCH 55 CHCH(OAc) ], 6.85 [1H, d, J ¼ 16.5 Hz,
2
ArCH 55 CHCH(OAc) ], 7.20–7.45 [6H, m, C H CH].
2
6
5
3o. d 2.02 [6H, s, ArCH(O CCH ) ], 5.87 (2H, s, OCH O), 6.65–6.93
H 2 3 2 2
(
3H, m, C H ), 7.51 [1H, s, ArCH(OAc) ].
6
3
2
ACKNOWLEDGMENT
The project was supported by National Natural Science Foundation of
China (29872011 and 29572039), Educational Ministry of China, Educational
Department of Hebei Province (990104), Science and Technology Commis-
sion of Hebei Province.
REFERENCES
1
2
. Narayana, C.; Padmanabhan, S.; Kabalka, G.W. Cleavage of ethers
and diacetates using the boron triiodide-N,N-diethylaniline complex.
Tetrahedron Lett. 1990, 31, 6977–6978.
. Varma, R.S.; Chatterjee, A.K.; Varma, M. Alumina-mediated deacetylation
of beuzaldehyde diacetates. A simple deprotection method. Tetrahedron
Lett. 1993, 34, 3207–3210.

ORDER
REPRINTS
1
650
Jin et al.
3
4
. Sudhakar, R.G.; Radhika, R.; Parvathi, N.; Iyengar, D.S. A mild and
.
efficient method for deprotection of 1,1-diacetates by CeCl3 7H O–
2
NaI system. Indian J. Chem. 2002, 41B, 863–864.
. Reddy, M.A.; Reddy, L.R.; Bhanumathi, N.; Rao, R.K. An efficient bio-
mimetic cleavage of gem-diacetates to aldehydes by b-cyclodextrin under
neutral conditions in aqueous medium. Synth. Commun. 2002, 32,
273–277.
5. Jin, T.S.; Sun, X.; Li, T.S. A facile and efficient catalyst for deprotection
of 1,1-diacetates. J. Chem. Res. (s). 2000, 128–129.
6
. Sanderg, M.; Sydnes, L.K. The chemistry of acylals. Part II. Formation of
nitriles by treatment of acylals with trimethylsilyl azide in the presence of
a Lewis acid. Tetrahedron Lett. 1998, 39, 6361–6364.
7
. Yadav, J.S.; Subba Reddy, B.V.; Kiran Kumar Reddy, G.S. Indium-
mediated allylation of gem-diacetates to homoallyic acetates in aqueous
media. Tetrahedron Lett. 2000, 41, 2695–2697.
8
9
. Freeman, F.; Karchefski, E.M. Preparation of spectral properties of ben-
zylidene diacetates. J. Chem. Eng. Data. 1997, 22, 355–357.
. Jin, T.S.; Sun, G.; Li, Y.W.; Li, T.S. An efficient and convenient pro-
cedure for the preparation of 1,1-diacetals from aldehydes catalyzed by
H NSO H. Green Chem. 2002, 4, 255–258.
2
3
1
1
0. Sampath Kumar, H.M.; Subba Reddy, B.V.; Thirupathi Reddy, P.;
Yadav, J.S. Efficient and selective protection of aldehydes as geminal di-
acetates using LiBr. J. Chem. Research(s) 2000 (2), 86–87.
1. Aggarwal, V.K.; Fonquerna, S.; Vennall, G.P. Sc(oTf) , an efficient cat-
3
alyst for formation and deprotection of geminal diacetates; chemoselec-
tive protetion of aldehydes in presence of ketones. Synlett. 1998 (8),
849–850.
1
1
1
2. Yadav, J.S.; Reddy, B.V.S.; Venugopal, C.; Ramalingam, T. LiBF4-
mediated conversion of aldehydes to gem-diacetates. Synlett. 2002 (4),
604–606.
3. Kumar, P.; Hegda, V.R.; Kumar, T.P. An efficient synthesis of diacetates
from aldehydes using beta zeolite. Tetrahedron Lett. 1995, 36 (4),
601–602.
4. Jin, T.S.; Ma, Y.R.; Du, G.Y.; Zhang, Z.H.; Li, T.S. An efficient and
convenient procedure for preparation of 1,1 -diacetates from aldehydes
catalysed by expansive graphite. Synth. Commun. 1997, 27,
2261–2266.
1
5. Deka, N.; Borah, R.; Kalita, D.J.; Sarma, J.C. Synthesis of 1,1-diacetates
from aldehydes using trimethylchlorosilane and sodium Lodide as catalyst.
J. Chem. Research(s) 1998 (2), 94–95.

ORDER
REPRINTS
Synthesis of 1,1-Diacetates from Aldehydes
1651
1
6. Jin, T.S.; Ma, Y.R.; Sun, X.; Liang, D.; Li, T.S. Facile preparation of 1,1-
2
2
diacetates from aldehydes with acetic anhydride catalysed by TiO /SO
2
4
solid superacid. J. Chem. Res.(s) 2000, 96–97.
17. Lin, J. Study on the synthesis of isoamyl butyrate catalyzed by zirconium
sulfate. Chemical Reagents (in Chinese) 2001, 23, 171–172.
1
8. Zhao, H.P.; Zhao, B.Y.; Lu, Q.T. Catalytic performance of Zr(SO ) and
4
2
2
2
SO /ZrO in methacrylic acid esterification with higher alcohol. Petro-
4
2
chemical Technology (in Chinese) 2000, 29, 98–101.
Received in the UK May 7, 2003

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