Synthesis of 1,1-diacetates catalyzed by cellulose sulfonic acid from aldehydes and acetic anhydride

Article abstract of DOI:10.14233/ajchem.2015.17926

1,1-Diacetates have been synthesized in good to excellent yields via a reaction of corresponding aldehydes and acetic anhydride in the presence of cellulose sulfonic acid as a heterogeneous catalyst at room temperature. The protection of aldehydes generated an anhydrodimer as single product under similar reaction conditions. The catalysis is equally applicable for the deprotection of acylal in acetonitrile.

Full text of DOI:10.14233/ajchem.2015.17926

Asian Journal of Chemistry; Vol. 27, No. 1 (2015), 340-342
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2015.17926
Synthesis of 1,1-Diacetates Catalyzed by Cellulose Sulfonic Acid from Aldehydes and Acetic Anhydride
*
SONGSONG DING, JIMING ZHANG , WEI SHI and JIANHUA ZHOU
School of Chemistry and Pharmaceutical Engineering, Qilu University of Technology, Jinan 250353, P.R. China
*Corresponding author: E-mail: zhangjiming@gmail.com, slzshiwei@163.com
Received: 30 April 2014; Accepted: 10 July 2014;
Published online: 26 December 2014;
AJC-16567
1
,1-Diacetates have been synthesized in good to excellent yields via a reaction of corresponding aldehydes and acetic anhydride in the
presence of cellulose sulfonic acid as a heterogeneous catalyst at room temperature. The protection of aldehydes generated an anhydro-
dimer as single product under similar reaction conditions. The catalysis is equally applicable for the deprotection of acylal in acetonitrile.
Keywords: 1,1-Diacetates, Cellulose sulfonic acid, Reusable catalyst, Protection, Deprotection.
INTRODUCTION
EXPERIMENTAL
Selective protection and deprotection of carbonyl groups
have been a subject of great interest to research workers in
All reagents and solvents were purchased from commer-
cial sources, unless otherwise noted and were used without
purification. Melting points were determined on a SGW X-4
melting-point apparatus with microscope and were uncorrec-
ted. Infrared spectra were recorded on an IR Prestige-21 FTIR
1
modern organic chemistry . The use of protecting groups is
-5
of great importance in organic synthesis, being often a valuable
6,7
intermediate in various organic syntheses . About the protec-
tion of the carbonyl group, the preparation of 1,1-diacetates
from aldehydes and acetic anhydride is the most common
route. 1,1-Diacetates are stable in neutral and basic media and
1
spectrophotometer (KBr). H NMR spectra were recorded on
a Bruker Advance-II spectrometer at 400 MHz with TMS and
3
referenced to CDCl ; δ values are reported in ppm and J values
8
-10
.
easy to convert to corresponding aldehydes
So far, several improved methods have been reported using
in Hz.
Catalyst preparation: To a magnetically stirred mixture
of cellulose (3 g, DEAE for column chromatography) in CHCl
1
1
12
a variety of catalysts such as Al(HSO
14
4
)
3
, zinc metal ,
3
1
3
15
, SbCl
3
16
, KHSO
4
20 21
3 4
, TiCl (OTf) , InBr , HBF
17
22
CuSO
4
·5H O , P
2
O /Al O
2 5 2 3
, HClO -SiO
4
2
2
,
,
(
20 mL), chlorosulfonic acid (0.60 g) was added dropwise at
°C during 1 h.After addition was complete, the mixture was
1
0
18
, LiBr , In(OTf)
19
FeCl
3
3
3
-SiO
0
2
-
23
/SnO
2
24
and LiBF
4
SO
4
under different kinds of conditions.
stirred for 1 h until HCl was removed from reaction vessel.
Then, the mixture was filtered and washed with ice water
However, most of these methods require expensive or waste-
ful reagents, long reaction times, tedious work-up procedure
and give unsatisfied yields. So, a simple, efficient, environ-
mental and economical catalyst is in great demand.
(30 mL) and dried at room temperature to obtain cellulose
sulfuric acid as white powder.
General procedure for the preparation of 1,1-diacetates:
To a mixture of aldehyde (2 mmol) and acetic anhydride (1 mL)
was added cellulose sulfonic acid (0.05 g), the reaction mixture
was mixed well and stirred at room temperature.After comple-
tion of the reaction, as indicated by TLC, dichloromethane
As a solid acid catalyst, cellulose sulfonic acid is efficient
and easy to handle. In addition, cellulose has several unique
properties, which make it attractive alternative for the support
for catalytic applications. Cellulose is the most abundant natural
material on earth and it has been widely studied recently. Hereby,
we wish to report an efficient and reusable catalyst called
cellulose sulfonic acid to these reactions (Scheme-I).
(20 mL) was added and the catalyst was separated by filtration.
The organic substance was washed with 10 % NaHCO
3
solution. The organic layer was dried over anhydrous Na SO
2
4
and evaporated. The isolated crude product was purified by
preparative TLC to provide the corresponding 1,1-diacetates.
General procedure for the deprotection of 1,1-diacetates:
The cellulose sulfonic acid (0.05 g) was added to a stirred
solution of 1,1-diacetate (2 mmol) in acetonitrile (10 mL) at
O
cellulose sulfonic acid, CH Cl2 / r.t.
2
OAc
OAc
Ac O
2
R
R
H
cellulose sulfonic acid, CH CN/50°C
3
1
2
3
R = aromatic or aliphatic group
Scheme-I: Protection-deprotection reactions of aldehydes

Vol. 27, No. 1 (2015)
Synthesis of 1,1-Diacetates Catalyzed by Cellulose Sulfonic Acid from Aldehydes and Acetic Anhydride 341
-
1
5
0 °C in a round-bottom flask with a reflux condenser. After
IR (KBr, νmax, cm ) = 3045, 3015, 1760, 1615, 1521, 1375,
1240, 1205, 995, 930.
completion of the reaction (monitored by TLC), the reaction
mixture was filtered to separated the catalyst which is reusable.
The filtrate was extracted with dichloromethane and dried over
1
1,1-Diacetoxy-1-(2-nitrophenyl)methane (entry 5): H
NMR (CDCl
3
, 400 MHz): δ = 2.15 (s, 6H), 7.54-7.66 (m, 1H),
2 4
anhydrous Na SO . The dichloromethane solution was evapo-
7.70-7.73 (m, 2H), 8.05-8.08 (m, 1H), 8.21 (s, 1H); IR (KBr,
-1
rated under reduced pressure to provide the crude product.
Then the isolated crude product was purified by TLC to provide
the corresponding aldehydes in pure form.
ν
max, cm ): 3019, 1763, 1534, 1374, 1216, 757, 669.
1,1-Diacetate-1-(3-nitrophenyl)methane (entry 6): H
NMR (CDCl , 400 MHz): δ = 8.39 (s, 1H), 8.28-8.24 (dd, J =
8.2, 1.2 Hz, 1H),7.83 (d, J = 7.7 Hz, 1H), 7.72 (s, 1H), 7.61-
1
3
1
1
,1-Diacetoxy-1-phenyl-methane (entry 1): H NMR
-1
(
CDCl , 400 MHz): δ = 2.02 (s, 6H), 7.35-7.43 (m, 3H), 7.52-
3
7.57 (t, J = 8.0 Hz, 1H), 2.14 (s, 6H); IR (KBr, νmax, cm ):
2963, 1760, 1533, 1358, 1255, 1203, 1091, 1016, 809, 685.
-1
7
.55 (s, 2H), 7.72 (s, 1H); IR (KBr, νmax, cm ): 3060, 1752,
1
1,1-Diacetoxybutane (entry 7): H NMR (CDCl
1
602, 1470, 1378, 1245, 1210, 1065, 1015, 758, 702.
1
,1-Diacetoxy-1-(4-chlorophenyl)methane (entry 2): H
3
, 400
MHz): δ = 0.94 (t, J = 3.5 Hz, 3H), 1.42-1.45 (m, 2H), 1.77-
1.79 (m, 2H), 2.06 (s, 6H), 6.80 (t, J = 5.5 Hz, 1H); IR (KBr,
1
NMR (CDCl , 400 MHz): δ = 2.18 (s, 6H), 7.38 (d, J = 6.4
3
-1
Hz, 2H), 7.46 (d, J = 6.4 Hz, 2H), 7.63 (s, 1H); IR (KBr, νmax,
cm ): 3014, 2913, 1764, 1749, 1609, 1477, 1370, 1237, 1201,
ν
max, cm ): 2956, 2880, 1755, 1250, 1225, 1080.
1,1-Diacetoxy-1-(cinnamyl)methane (entry 8): H NMR
(CDCl , 400 MHz): δ = 2.11 (s, 6H), 6.15 (dd, J = 15.0 Hz, 6
-1
1
1
037, 795, 675.
,1-Diacetoxy-1-(2-methoxyphenyl)methane (entry 3):
H NMR (CDCl , 400 MHz): δ = 2.11 (s, 6H), 3.85 (s, 3H),
3
1
Hz, 1H), 6.82 (d, J = 15.0 Hz, 1H), 7.28-7.34 (m, 5H), 7.38 (d,
-1
J = 6.0 Hz, 1H); IR (KBr, νmax, cm ): 3020, 2971, 2876, 1759,
1
3
6
.91 (dd, J = 8.1, 1.5 Hz, 1H), 6.99 (td, J = 7.6, 1.8 Hz, 1H),
.37 (td, J = 8.1 Hz, 1H), 7.48 (dd, J = 7.6, 1.8 Hz, 1H), 8.02
1601, 1472, 1216, 1011, 759, 669.
7
-1
RESULTS AND DISCUSSION
(
s, 1H); IR (KBr, νmax, cm ): 1760, 1244, 1203, 1000, 760.
,1-Diacetoxy-1-(4-methoxyphenyl)methane (entry 4):
H NMR (CDCl , 400 MHz): δ = 2.11 (s, 6H), 3.81 (s, 3H),
.75 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 9.0 Hz, 2H), 7.42 (s, 1H);
1
As shown in Table-1, both aromatic and aliphatic
aldehydes reacted smoothly with acetic anhydride to afford
the corresponding geminal diacetates in good to excellent
1
3
6
TABLE-1
PROTECTION REACTION OF ALDEHYDE CARBONYL CATALYZED BY CELLULOSE SULFONIC ACID
m.p. (°C)
Reported
a
Yield (%)
Entry
1
Substrate
CHO
Product
CH(OAc)2
Time (min)
3
Found
41-42
1
0
98
44-45
CHO
CH(OAc)2
b
92 ,95,95
c
25
2
3
4
3
3
3
82-83
81-83
69-70
65-67
Cl
Cl
CHO
CH(OAc)2
2
6
6
88
95
68-70
65-66
OCH3
OCH3
CHO
CH(OAc)2
2
H CO
3
H3CO
O2N
CHO
NO2
CH(OAc)2
1
6
5
3
92
88
86
NO2
O2N
CHO
CH(OAc)2
2
6
6
7
3
3
96
95
65-66
65
O
CH(OAc)2
CH(OAc)2
27
Oil
Oil
H
CHO
2
7
8
9
3
93
0
86
85-87
-
O
-
180
-
O
1
0
-
180
0
-
-
a
b
Yields refer to the isolated pure products. 0.045 g cellulose sulfonic acid, 0.055 g cellulose sulfonic acid was used
c

342 Ding et al.
Asian J. Chem.
yields. Optimization of the reaction condition was studied with
different quality of the catalyst. When 2 mmol of water parti-
cipate in the reaction, 0.05 g of catalyst was the most appro-
priate condition (Table-1, Entry-2).
Conclusion
In summary, at room temperature, synthesis of 1,1-
diacetates catalyzed by cellulose sulfonic acid can be achieved
from aldehydes and acetic anhydride efficiently. The advan-
tages of this protocol are mild reaction conditions, short
reaction times and good yields. In addition, the catalystis
equally applicable for the deprotection of acylal availably.
However, when cyclohexanone and acetophenone were
used in this reaction, no corresponding product was obtained
(Table-1, Entry 9, 10). In the case of substrates bearing aldehyde
and ketone functionalities, only aldehyde was converted into
1
,1-diacetate (Scheme-II).
ACKNOWLEDGEMENTS
This work was supported by the International Cooperation
Promotion Funding for TalentedYoung Faculties in Shandong
Province.
O
AcO OAc
CHO
OAc
OAc
cellulose sulfonic acid (0.05g)
r.t.
2
Ac O
98%
0
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a
b
Yields refer to the isolated pure products; Heating at room
temperature