Montmorillonite Clay Catalysis. Part 4.11 An Efficient and Convenient Procedure for Preparation of 1,1-Diacetates from Aldehydes

Article abstract of DOI:10.1039/a608318h

An easy preparation of 1,1-diacetates from aldehydes with montmorillonite clays as catalysts has been carried out in excellent yield.

Full text of DOI:10.1039/a608318h

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174 J. CHEM. RESEARCH (S), 1997
Montmorillonite Clay Catalysis. Part 4.1 An Efficient and
Convenient Procedure for Preparation of 1,1-Diacetates
from Aldehydes†
J. Chem. Research (S),
1997, 174–175†
Zhan-Hui Zhang, Tong-Shuang Li* and Cheng-Guang Fu
Department of Chemistry, Hebei University, Baoding 071002, Hebei Province, P.R. China
An easy preparation of 1,1-diacetates from aldehydes with montmorillonite clays as catalysts has been carried out in
excellent yield.
1,1-Diacetates have attracted considerable attention owing to
their moderate stability and easy conversion into parent alde-
hydes.2–7 They are an alternative protecting group to acetals
for protecting aldehydes and can be used as starting materials
for the synthesis of valuable intermediates for Diels–Alder
cycloaddition reactions.8 Usually, the syntheses of 1,1-di-
acetates are carried out under the catalysis of strong proton
acids, such as sulfuric acid,9,10 phosphoric or methanesulfonic
acid,10 and Lewis acids, such as zinc chloride.11 These
methods have not been entirely satisfactory, owing to such
drawbacks as low yields, long reaction times, corrosivity, diffi-
cult work-up and effluent pollution. In recent years, several
catalysts have been employed for this reaction to improve
yields, to decrease reaction time and to eliminate the men-
tioned unfavourable effects. Phosphorus trichloride was used
as a catalyst resulting in good yields with most aldehydes, but
the yields were poor for aromatic aldehydes containing elec-
tron-withdrawing groups.12 Kochlar et al.2 developed a fast
reaction (less than 30 min), catalysed by iron(III) chloride,
even for a,b-unsaturated aldehydes and aromatic aldehydes
having electron-withdrawing groups. Nafion-H,13 Y-zeolite,14
b-zeolite,15 sulfated zirconia16 and HZSM-517 have been rela-
tively successfully used as catalysts for the conversion of alde-
hydes into 1,1-diacetates.
Montmorillonite clays have been used as efficient catalysts
for a number of organic reactions and offer several advant-
ages over classic acids: strong acidity, non-corrosivity, cheap-
ness, mild reaction conditions, high yield and selectivity, and
ease of set-up and work-up.18 Here we report an easy and
efficient procedure for the synthesis of 1,1-diacetates from
aldehydes catalysed by montmorillonite clays (Scheme 1).
As shown in Table 1, a series of 1,1-diacetates 2 were
synthesized using montmorillonite K-10 or KSF as a catalyst
at room temperature. K-10 and KSF gave similar results in
terms of reaction time and yield. Both aromatic and aliphatic
aldehydes gave high, although unmaximized, yields of the
corresponding 1,1-diacetates. For example, furfural gave
2-furylmethanediyl diacetate (2j) in 74% yield and chloral
diacetate (2b) was obtained in 53% yield after distillation.
4-Nitrobenzaldehyde (1h) required a relatively longer reac-
K-10 or KSF
Ac2O, room temperature, 0.2–6 h
RCHO
RCH(OAc)2
0–98%
1
2
Scheme 1
Table 1 Conversion of aldehydes into 1,1-diacetates in the presence of montmorillonite clays
Mp (T/°C) [bp (T/°C)/Torr]
Aldehyde 1
R
Diacetate 2
R
Catalyst/Solvent
Time (t/h)
Yield (%)
Found
Reported
Et (1a)
Cl3CCH(OH)2 (1b)
Ph (1c)
Et (2a)
Cl3C (2b)
Ph (2c)
K-10/none/0.8
K-10/none/4
K-10/none/0.2
KSF/none/0.2
K-10/none/0.5
K-10/none/0.5
K-10/CCl4/1
87
53
98
98
98
98b
96
95
94b
96
90
96
94
94
74
97b
93b
92b
98b
96
[105–109/35]
[145–148/32]
44–45
115–118/82
98–99/619
44–454
4-MeC6H4 (1d)
4-MeOC6H4 (1e)
4-ClC6H4 (1f)
4-MeC6H4 (2d)
4-MeOCH6H4 (2e)
4-ClC6H4 (2f)
80.5–81.5
64–65
81–82
81–824
64–654
80–814
KSF/CCl4/0.6
K-10/none/1
KSF/none 0.6
K-10/CCl4/6
3-ClC6H4 (1g)
4-O2NC6H4 (1h)
3-O2NC6H4 (1i)
3-ClC6H4 (2g)
4-O2NC6H4 (2h)
3-O2NC6H4 (2i)
65–66
65–6610
123–12512
64–662
125.5–126.5
64–66
KSF/CCl4/6
K-10/none/4
KSF/none/4
K-10/none/2
K-10/none/0.5
K-10/none/1
2-furyl (1j)
PhCHtCH (1k)
2-HOC6H4 (1l)
2-furyl (2j)
PhCHtCH (2k)
2-AcOC6H4 (2l)
50.5–51.5
83.5–84.5
103–104
90–91
50–5110
84–8712
104–10520
79–8010
75–7610
3-MeO-4-HOC6H3 (1m) 3-MeO-4-AcOC6H3 (2m) K-10/none/1
3,4-(OCH2O)C6H3 (1n)
4-HOC6H4 (1o)
4-Me2NC6H4 (1p)
Me2N (1q)
3,4-(OCH2O)C6H3 (2n)
K-10/none/0.5
KSF/none/0.5
K-10/none/48
KSF/none/48
K-10/none/48
KSF/none/48
K-10/none/48
KSF/none/48
78–79
c
no reaction
—
c
—
c
no reaction
—
c
—
—
c
no reaction
c
—
aIsolated yield. bSatisfactory elemental analysis obtained: C<0.20, H<0.19%. c100% aldehyde was recovered.
tion time (6 h), possibly owing to the strong electron-with-
*To receive any correspondence.
drawing nitro substituent. Interestingly, the a,b-unsaturated
aldehyde 1k gave a better yield in a shorter reaction time than
the previously mentioned methods.2,12,16
†This is a Short Paper as defined in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1997, Issue 1]; there is there-
fore no corresponding material in J. Chem. Research (M).

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J. CHEM. RESEARCH (S), 1997 175
tored by TLC. Upon completion, Et2O (10 mL) was added to the
reaction mixture and the catalyst was filtered off. The catalyst was
washed with Et2O (2Å10 mL) and then the filtrate was washed
with 10% HCl (20 mL) and brine (2Å20 mL) and then dried
(MgSO4). The solvent was removed under reduced pressure and
the residue was purified by distillation or crystallization from cyclo-
hexane to give 1,1-diacetates 2 in 0–98% yields.
It is worth noting that the hydroxy groups in 2-hydroxy-
and 3-methoxy-4-hydroxy-benzaldehyde (1l and 1m) were
also acetylised to afford the corresponding triacetates 2l and
2m under these conditions.
The scope and limitation of this method were investigated.
N,N-Dimethylformamide (1q) was not acetylised with acetic
anhydride even under reflux for 3 h in the presence of K-10
or KSF. Ketones, such as cyclohexanone and acetophenone,
were not converted into the corresponding 1,1-diacetates at
room temperature. Therefore the present procedure is a
selective preparation of the 1,1-diacetates 2 of aldehydes in
the presence of ketones. We also attempted the reaction of
maleic anhydride, phthalic anhydride and succinic anhydride
with benzaldehyde (1c) with K-10 or KSF as catalyst. How-
ever, none of these reagents gave the expected cyclic diesters
even when the reaction mixtures were stirred either at room
temperature for 2 d or under reflux for 2 h. The starting
materials were quantitatively recovered. It is worth noting
that when 4-hydroxybenzaldehyde (1o) and 4-(dimethyl-
amino)benzaldehyde (1p) were treated with acetic anhydride
with K-10 or KSF as catalyst, to our surprise, none of the
reactions gave the corresponding products even when the
reaction mixtures were stirred at room temperature for 2 d.
The starting materials were quantitatively recovered. We
propose, as an explanation for this result, that selective
adsorption of the phenolic and amino compounds (1o and
1p) at the hydroxy and dimethylamino groups of the catalyst
occurs. This might keep the aldehyde away from the active
site thus stopping the reaction and blocking the sites. Com-
pound 1l would adsorb favourably for the reaction. The
hydrogen bond and the bulk of the methoxy group in 1m
might be enough to discourage adsorption in the ‘wrong’
manner.
This project was supported by the National Natural
Science Foundation of China, the Education Commission of
Hebei Province and the Science and Technology Commis-
sion of Hebei Province.
Received, 10th December 1996; Accepted, 10th February 1997
Paper E/6/08318H
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In conclusion, we have provided an alternative preparation
of 1,1-diacetates from aldehydes, with the advantages of
selectivity, operational simplicity, high yields, short reaction
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Experimental
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Boiling points and melting points are uncorrected. K-10 and
KSF were purchased from Fluka and employed directly for the
reactions. The products were characterized by their melting or
1
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boiling points and/or IR, H NMR and mass spectra.
General Procedure for the Preparation of 1,1-Diacetates 2.sA
mixture of the aldehyde 1 (10 mmol), acetic anhydride (30 mmol)
and K-10 (or KSF) montmorillonite (200 mg) was stirred at room
temperature for the time indicated in Table 1. For the reactions
with solvent, CCl4 (5 mL) was also added. The reaction was moni-
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