Preparation of silica-bonded propyl-diethylene-triamine-N-sulfamic acid as a recyclable catalyst for chemoselective synthesis of 1,1-diacetates

Article abstract of DOI:10.1002/cjoc.201180403

A simple and efficient procedure for the preparation of silica-bonded propyl-diethylene-triamine-N-sulfamic acid (SPDTSA) by reaction of 3-diethylenetriamine-propylsilica (DTPS) and chlorosulfonic acid in chloroform is described. Silica-bonded propyl-diethylene-triamine-N-sulfamic acid is employed as a recyclable catalyst for the synthesis of 1,1-diacetates from aromatic aldehydes and acetic anhydride under mild and solvent-free conditions at room temperature. Catalyst could be recycled for several times without any additional treatment.

Full text of DOI:10.1002/cjoc.201180403

FULL PAPER
Preparation of Silica-bonded Propyl-diethylene-triamine-N-
sulfamic Acid as a Recyclable Catalyst for Chemoselective
Synthesis of 1,1-Diacetates
Nouri Sefat, Maryam
Deris, Abdolah
Niknam, Khodabakhsh*
Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr, 75169, Iran
A simple and efficient procedure for the preparation of silica-bonded propyl-diethylene-triamine-N-sulfamic
acid (SPDTSA) by reaction of 3-diethylenetriamine-propylsilica (DTPS) and chlorosulfonic acid in chloroform is
described. Silica-bonded propyl-diethylene-triamine-N-sulfamic acid is employed as a recyclable catalyst for the
synthesis of 1,1-diacetates from aromatic aldehydes and acetic anhydride under mild and solvent-free conditions at
room temperature. Catalyst could be recycled for several times without any additional treatment.
Keywords silica-bonded propyl-diethylene-triamine-N-sulfamic acid, 1,1-diacetates, aromatic aldehydes, catalyst,
solvent-free
Introduction
methansulfonate,26 cobalt(II) bromide,27 and SO3H-
functionalized ionic liquids,28 were reported for the
synthesis of 1,1-diacetates.
Selective protection and deprotection of carbonyl
groups are essential steps in modern organic chemistry.1
The protection of aldehydes as acetals, acylals,
oxathioacetals, or dithioacetals is common practice for
manipulation of other functional groups during
multi-step syntheses. Protection of aldehydes as acylals
is often preferred due to their ease of preparation and
their stability towards basic and neutral conditions.1,2 In
addition, the preparation of 1,1-diacetates from the cor-
responding aldehydes can be achieved very easily in the
presence of ketones. Moreover, they also serve as valu-
able precursors for asymmetric allylic alkylation3 and
natural product synthesis4 as well as for the synthesis of
1-acetoxydienes and 2,2-dichlorovinylacetates for Di-
els-Alder reactions.5,6 Acylals have also been used as
cross-linking agents for cellulose in cotton7 and are
useful intermediates in industry.5 Moreover, the acylal
functionality can be converted into other functional
groups by reaction with appropriate nucleophiles.8,9
Generally, they are synthesized from acetic anhydride
and aldehydes using strong protonic acids,6,10,11 Lewis
acids,2,12-14 heterogeneous catalysts,15,16 and supported
reagents.17,18 Other catalysts, such as iodine,19 copper
p-toluene-sulfonate/HOAc,20 and 1,3-dibromo-5,5-di-
methylhydantoin,21 have also been used for this trans-
formation, but these procedures are often accompanied
by longer reaction times, poor product yields, stringent
conditions, good catalyst loading; require the use of
toxic solvents; and so on. More recently, supported
catalysts,22,23 silica-bonded S-sulfonic acid,24 poly(N,N'-
dibromo-N-ethylbenzene-1,3-disulfonamide),25 ferrous
Heterogenization of homogeneous catalysts has been
an interesting area of research from the industrial point
of view; this combines the advantages of homogeneous
catalysts (high activity and selectivity, etc.) with the
engineering advantages of heterogeneous catalysts (easy
catalyst separation, long catalytic life, easy catalyst re-
generability, thermal stability and recyclability).29
Several types of solid sulfonic acid functionalized
silica (both amorphous and ordered) have been synthe-
sized and applied as an alternative to traditional sulfonic
acid resins and homogeneous acids in catalyzing
chemical transformations.30-36 In continuation of our
studies on the design and application of solid acid cata-
lysts in organic transformations,31-36 herein, we describe
the preparation and application of silica-bonded propyl-
diethylene-triamine-N-sulfamic acid (SPDTSA) as a
new and recyclable catalyst for the synthesis of
1,1-diacetates (Scheme 1).
Results and discussion
Silica-bonded propyl-diethylene-triamine-N-sul-
famic acid (SPDTSA) was prepared by reaction of
3-diethylenetriamine-propylsilica (DTPS) and chloro-
sulfonic acid in chloroform. The BET surface area
analysis using nitrogen adsorption isotherms at the
temperature of liquid nitrogen gave the results of as,BET
－1
－1
762 m2•g and the total pore volume 0.1342 cm3•g
(see supplementary material). The elemental analysis
gave the results: C, H, N, and S content to be 10.3%,
*
E-mail: khniknam@gmail.com, niknam@pgu.ac.ir; Fax: (＋98) 771-4545188
Received March 3, 2011; revised June 23, 2011; accepted July 19, 2011.
Chin. J. Chem. 2011, 29, 2361— 2367
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2361

Nouri Sefat, Deris & Niknam
FULL PAPER
Scheme 1
2.7%, 3.1%, and 3.17% respectively. Accor＋ding to S
content typically a loading of 0.99 mmol/g H was ob-
tained. The thermal stability of the catalyst was an im-
portant property for the catalyst. TG curve for the cata-
lyst was shown in Figure1. The decrease in gravity be-
gan at about 120 ℃ which indicated the decomposition
of the catalyst. The covalent chemical bonds connection
made the catalyst own high thermal stability.
Table 1 Conversion of 4-chlorobenzaldehyde to the corre-
sponding diacetate (1b) with different amounts of acetic anhy-
dride in the presence of different amounts of SPDTSA under sol-
vent-free conditions at room temperature
Entry Catalyst loading/g
Ac2O/mmol Time/min Yielda/%
1
2
3
4
5
6
7
8
9
10
No catalyst
0.005
0.01
15
15
15
1
12 h
10
5
0
90
95
70
70
75
82
87
95
95
0.01
5
0.01
2
5
0.01
4
5
0.01
10
12
15
15
5
0.01
5
0.015
0.03
5
5
a Isolated yield.
Table 2 The reaction of 4-chlorobenzaldehyde (1 mmol) with
different amount of Ac2O in various solvents in the presence of
SPDTSA (0.01 g) into the corresponding diacetate (1b)
Figure 1 TGA of the SPDTSA.
Entry Solventa
Ac2O/mmol
Time/min
Yieldb/%
1
2
3
4
5
6
7
8
9
10
EtOH
1
45
45
5
15
To study the effect of catalyst loading on the protec-
tion of aromatic aldehydes as the corresponding
1,1-diacetates, the reaction of 4-chlorobenzaldehyde
with acetic anhydride was chosen as a model reaction
(Table 1). The results show clearly SPDTSA are effec-
tive catalyst for this transformation and in the absence of
SPDTSA the reaction did not take place, even after 12 h.
Although lower catalyst loading 0.005 g of SPDTSA
accomplished this protection, however, 0.01 g of
SPDTSA per 1 mmol of aldehyde was optimum in terms
of reaction time and isolated yield. Also, as shown in
Table 1, the best result in the case of time and isolated
yield was obtained by using 15 mmol of acetic anhy-
dride.
H2O
1
30
CH2Cl2
1
89
n-hexane
MeCN
1
30
5
84
1
84
MeCOOH
MeCOOH
MeCOOH
MeCOOH
1
10
10
10
10
5
70
2
70
4
75
10
80
solvent-free 15
95
a The reaction was carried out in 5 mL of solvent at r.t. b Isolated
yield.
The model reaction was also examined in various
solvents as well as under solvent-free conditions in the
presence of 0.01 g of SPDTSA with different amounts
of acetic anhydride (Table 2).
The yield of the reaction under solvent-free condi-
tions was the highest and the reaction time was shorter.
In protic solvents such as water and ethanol this pro-
tection reaction proceeded in longer reaction times and
with very poor yields, which may be related to the
instability of acetic anhydride in protic solvents. Acetic
acid was used as solvent and the reaction was accom-
plished with longer reaction time and lower yield (En-
tries 6—9). Therefore, we employed the optimized
－1
conditions (0.01 g•mmol of SPDTSA, 15 mmol of
Ac2O, and solvent-free conditions) for the conversion of
various aldehydes into the corresponding acylals
(Scheme 2).
2362
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Chin. J. Chem. 2011, 29, 2361— 2367

Preparation of Silica-bonded Propyl-diethylene-triamine-N-sulfamic Acid
Scheme 2
The results of the solvent-free preparation of acylals
from aromatic aldehydes in the presence of SPDTSA at
room temperature are shown in Table 3. 1,1-Diacetate
1a was obtained in high yield in 4 min by the reaction of
benzaldehyde with acetic anhydride. Benzaldehydes
with electron-withdrawing or electron-donating groups,
for example, 3-nitro- and 4-nitrobenzaldehyde, or
4-methyl- and 2-methylbenzaldehyde, 2-methoxy- and
3,4,5-trimethoxybenzaldehyde were converted into the
corresponding acylals 1e— 1j in high yields after very
short reaction times (Table 3, Enties 5—10). The
acid-sensitive substrate thiophene-2-carbaldehyde gave
the expected acylal 1n in 81% yield (Table 3, Entry 14).
We also investigated the reactions of 4-hydroxy-
benzaldehyde and 2-hydroxy-5-bromobenzaldehyde
under the above-mentioned conditions and observed that
both carbonyl and phenolic groups were acylated (Table
3, Entries 12 and 13). Additionally, 4-N,N-dimethyl-
aminobenzaldehyde failed to give the corresponding
1,1-diacetate and the starting material was quantitatively
recovered under the same conditions. The explanation
for this result may be due to the strong electron donating
dimethylamino group which will reduce the reactivity.
A degree of tautomerisation may occur in 4-N,N-
dimethylaminobenzaldehyde with formation of a quini-
noid structure and thus decrease the reactivity of the
aldehyde group (Table 3, Entry 17). 2-Oxo-2-phenyl-
acetaldehyde substrate was exposed to the reaction con-
ditions that only aldehyde group was protected and car-
bonyl group remained unchanged (Table 3, Entry 18).
Table 3 Reaction of aldehydes with acetic anhydride using SPDTSA as catalyst under solvent-free conditions at room temperaturea
Entry Ar
Product
Time/min
Yieldb/%
M.p./℃
CH(OAc)2
44—45
1
2
C6H5-
4
95
Lit.18 45
1a
Cl
CH(OAc)2
81—83
4-Cl-C6H4-
2-Cl-C6H4-
4-Br-C6H4-
3-O2N-C6H4-
5
95
90
80
92
Lit.18 80
1b
Cl
58—60
CH(OAc)2
3
4
5
50
15
20
Lit.22 59
1c
Br
CH(OAc)2
90—92
Lit.16 92—95
1d
O2N
64—65
CH(OAc)2
Lit.24 65—66
1e
O2N
Me
CH(OAc)2
CH(OAc)2
126—128
6
7
4-O2N-C6H4-
4-Me-C6H4-
4
4
94
90
Lit.18 125
1f
79—81
Lit.20 80—82
1g
Me
63—65
CH(OAc)2
8
2-Me-C6H4-
75
90
Lit.21 75—77
1h
Chin. J. Chem. 2011, 29, 2361— 2367
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2363

Nouri Sefat, Deris & Niknam
FULL PAPER
Continued
Entry Ar
Product
Time/min
5
Yieldb/%
60
M.p./℃
OMe
78—80
CH(OAc)2
9
2-MeO-C6H4-
Lit.20 72—74
1i
MeO
MeO
MeO
CH(OAc)2
117—119
10
3,4,5,-(MeO)3-C6H2-
4
90
Lit.18 114—116
1j
1k
1l
MeS
CH(OAc)2
CH(OAc)2
59—61
11
12
4-MeS-C6H4-
4-HO-C6H4-
90
4
90
60
Lit.24
AcO
94—96
Lit.20 90—91
CH(OAc)2
OAc
Br
13
14
2-HO,5-Br-C6H3-
2-Thienyl-
13
25
92
81
94—97
1m
S
CH(OAc)2
67—68
Lit.21 65—67
1n
CH(OAc)2
172—174
15
4-OHC-C6H4-
5
90
(AcO)2HC
(AcO)2HC
Lit.18 174—175
1o
CH(OAc)2
CH(OAc)2
108—110
16
17
3-OHC-C6H4-
3
92
Lit.24 108—110
1p
1q
Me2N
4-(Me)2N-C6H4-
24 h
NR
—
O
50—52
CH(OAc)2
18
C6H5-CO-
30
94
Lit.18 50—51
1r
H
b.p. 127—129
Lit.2 b.p. 128—129
(2 mmHg)
OAc
OAc
19
20
21
Me(CH2)4-
5
68
1s
OAc
OAc
Acetophenone
2h
2h
NR
NR
—
—
Me
1t
OAc
OAc
Br
4-Bromoaceto-phenone
Me
1u
The aliphatic aldehyde such as hexanal was converted
into corresponding acylal in lower yield (Table 3, Entry
2364
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Chin. J. Chem. 2011, 29, 2361— 2367

Preparation of Silica-bonded Propyl-diethylene-triamine-N-sulfamic Acid
19). The protocol was then extended towards the protec-
tion of ketones but the reaction did not yield corre-
sponding acylals (Table 3, Entries 20, 21). This
prompted us to check and extend the present protocol
for chemoselective synthesis of acylals of an aldehyde
over ketone. An equimolar (1 mmol each) mixture of
benzaldehyde and acetophenone was allowed to react
with acetic anhydride (15 mmol) in presence of
SPDTSA (0.01 g). However, even after stirring for 7
min at ambient temperature, only benzaldehyde got
converted into corresponding acylal leaving acetophe-
none practically unaffected (Scheme 3).
dried in air and the catalyst reused in the next reaction.
The recycled catalyst could be reused six times in the
presence of SPDTSA without any additional treatment.
No observation of any appreciable loss in the catalytic
activity of SPDTSA was observed (Figure 2).
Scheme 3
Figure 2 Recyclability of SPDTSA (0.01 g) in the reaction of
4-chlorobenzaldehyde (1 mmol) and acetic anhydride (15 mmol)
at room temperature. Reaction time＝5 min.
In conclusion, we have shown that silica-bonded
propyl-diethylene-triamine-N-sufamic acid (SPDTSA),
which can be prepared from commercially available and
cheap starting materials, catalyzed efficiently the syn-
thesis of aromatic 1,1-diacetates from aryl aldehydes.
The mild reaction conditions, simplicity of the proce-
dure and reusability of catalyst offer improvements over
many existing methods.
Finally, a comparative study of SPDTSA with other
recently reported catalysts for acetylation of
4-chlorobenzaldehyde, as a model compound was made
which revealed that SPDTSA is an equally efficient but
much cheaper and reusable catalyst (Table 4).
Table 4 Comparison of the efficiency of SPDTSA with some of
the reported procedure on the reaction of 4-chlorobenzaldelyde
with acetic anhydride
Experimental section
General
Catalyst
load/mmol
0.4
Catalyst
Time/minYielda/%
Ref.
Chemicals were purchased from Fluka, Merck and
Aldrich Chemical Companies. All the products were
H2NSO3H
10
2
92
98
92
11
18
20
1
characterized by comparison of their IR, H NMR and
13C NMR spectroscopic data and their melting points
with the reported values.16-29 Chloropropyl silica was
prepared by a known procedure as previously reported.37
HClO4/SiO2
0.005
b
CPTS-HOAc
H3PW12O40-
supported
—
150
0.3 g
240
91
22
(20 wt%)
Preparation of silica propyl chloride
MCM-41
Silica was first immersed in hydrochloric acid for 24
h and then washed with deionized water and dried under
vacuum at 120 ℃ for 8 h. The activated silica (25.0 g)
was suspended in 300 mL of dry toluene and then an
excess of 3-chloropropyltrimethoxysilane (25.0 mL)
was added, followed by 2.5 mL of triethylamine (added
as a catalyst). The suspension was mechanically stirred
and refluxed for 48 h. After refluxing, the reaction was
stopped and the modified silica was cooled to room
temperature, transferred to a vacuum glass filter, and
washed with toluene, ethanol-water mixture, deionized
water in turn and finally with methanol. Chloropropyl
silica was dried under vacuum at 60 ℃ for 4 h and
28.45 g was obtained.
PEG-SO3H
0.1
30
94
92
23
26
Fe(CH3SO3)2•4H2O0.45
360
CoBr2
0.1
25
93
27
SPDTSA
0.009
5
95
present work
a Isolated yield. b 0.045 mmol of CPTS and 12 mmol of HOAC
were used.
The possibility of recycling the catalyst was exam-
ined using the reaction of 4-chlorobenzaldehyde and
acetic anhydride under the optimized conditions. Upon
completion, the reaction mixture was filtered and the
remaining solid was washed with dichloromethane,
Chin. J. Chem. 2011, 29, 2361— 2367
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2365

Nouri Sefat, Deris & Niknam
FULL PAPER
Preparation of 3-diethylenetriamine-propylsilica
(DTPS)
Acknowledgment
Financial support for this work by the Research
Council of Persian Gulf University, Bushehr, Iran, is
gratefully acknowledged. Also, we are thankful to Dr
Mohammad Mahdi Doroodmand for helpful comments.
To a mixture of chloropropyl silica (25 g) in anhy-
drous xylene (250 mL) an excess of diethylenetriamine
(25 mL) was added and the mixture was refluxed with
stirring for 24 h. After refluxing, the reaction was
stopped and the modified silica was cooled to room
temperature, transferred to a vacuum glass filter, and
washed with xylene and large excess of ethanol in turn.
The silica chemically bonded with propyl-diethylene-
triamine was dried under vacuum overnight at 80 ℃
and 26.23 g was obtained.
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Preparation of silica-bonded propyl-diethylene-
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To a magnetically stirred mixture of 3-diethylene-
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plete, the mixture was stirred for 2 h until all HCl was
removed from reaction vessel. The mixture was then
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room temperature to give the silica-bonded propyl-
diethylenetriamine-N-sulfamic acid (SPDTSA) as a
white powder (5.39 g). IR, BET, and TGA were running
for characterization of SPDTSA (see supplementary
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General procedure for the synthesis of 1,1-diacetates
To a mixture of aromatic aldehyde (1 mmol) and
acetic anhydride (15 mmol) was added SPDTSA cata-
lyst (0.01 g) and the mixture was stirred at room tem-
perature. When the reaction was complete as judged by
TLC, CH2Cl2 (5 mL) was added and the reaction mix-
ture was filtered and the remaining solid was washed
with CH2Cl2 (5 mL×3) in order to separate the catalyst.
The CH2Cl2 layer was washed with water (10 mL×2)
and dried over anhydrous MgSO4. After removal of the
solvent in vacuo, the obtained residue was recrystallized
from ethanol.
Compound 1m (Table 3, Entry 13) 1H NMR
(CDCl3, 500 MHz) δ: 2.13 (s, 6H), 2.35 (s, 3H), 7.04 (d,
J＝8.6 Hz, 1H), 7.55 (dd, J＝8.6, 1.2 Hz, 1H), 7.78 (d, J
＝2.4 Hz, 1H), 7.87 (s, 1H); 13C NMR (CDCl3, 125
MHz) δ: 21.12, 21.23, 84.77, 119.71, 125.40, 130.25,
131.24, 134.12, 147.61, 168.67, 169.45; IR (KBr) ν:
3060, 3015, 2360, 1760, 1490, 1370, 1200, 1120, 1085,
－
1
1060, 1000, 970, 945, 840, 745 cm . Anal calcd for
C13H13BrO6: C 45.24, H 3.80, Br 23.15; found C 45.06,
H 3.88.
Compound 1r (Table 3, Entry 18) 1H NMR
(CDCl3, 500 MHz) δ: 2.19 (s, 6H), 7.51 (t, J＝7.6 Hz,
2H), 7.63—7.66 (m, 2 H), 7.95 (d, J＝7.7 Hz, 2H); 13C
NMR (CDCl3, 125 MHz) δ: 21.01, 86.70, 129.32,
133.62, 134.69, 169.10, 189.23; IR (KBr) ν: 3060, 2955,
1765, 1725, 1710, 1600, 1450, 1380, 1230, 1200, 1050,
－
1
1015, 955, 900, 775, 695 cm .
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 2361— 2367

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