1
42
Y.-X. Zong et al. / Chinese Chemical Letters 24 (2013) 140–142
[
2] B.M. Trost, C.B. Lee, gem-Diacetates as carbonyl surrogates for asymmetric
synthesis. Total syntheses of sphingofungins E and F, J. Am. Chem. Soc. 123
2001) 12191–12201.
1
00
(
[
[
[
[
[
3] M. Sandberg, L.K. Sydnes, The Chemistry of acylals. 3. Cyanohydrin esters from
acylals with cyanide reagents, Org. Lett. 2 (2000) 687–689.
4] H. Held, A. Rengstle, A. Mayer, in: W. Gerhartz (Ed.), 5th ed., Ullman’s Encyclo-
pedia of Industrial Chemistry, vol. 1, Wiley-VCH, New York, 1985.
5] F. Freeman, E.M. Karcherski, Preparation and spectral properties of benzylidene
diacetates, J. Chem. Eng. Data 22 (1977) 355–357.
6] J.G. Frick Jr., R.J. Harper Jr., Crosslinking cotton cellulose with aldehydes, J. Appl.
Polym. Sci. 29 (1984) 1433–1447.
7] M. Tomita, T. Kikuchi, K. Bessho, T. Hori, Y. Inubushi, Study on piocereine and
related compounds. III. Synthesis of 2,2’,3- trimethoxydiphenyl ether-4’,5- and -
8
6
4
2
0
0
0
0
4’, 6-dicarboxalaehyde, Chem. Pharm. Bull. 11 (1963) 1484–1490.
[
8] J.A. Marshall, P.G.M. Wuts, Stereoselective synthesis of racemic occidentalol and
related cis-fused hexahydronaphthalenes from m-toluic acid, J. Org. Chem. 42
(1977) 1794–1798.
[9] A. Khazaei, A.A. Manesh, A. Rostami, H.A. Alavi-Nik, Z.T. Roosta, Conversion of
aldehydes to acylals using acetic anhydride in presence of catalytic amount of
Fe(NO
3 3.9 2
) H O under solvent-free conditions at room temperature, Asian J. Chem.
0
23 (2011) 614–616.
1
2
3
4
5
6
7
8
[10] M.M. Heravi, S. Taheri, K. Bakhtiari, H.A. Oscooie, Cupric sulfate pentahydrate: a
mild and efficient catalyst for the chemoselective synthesis of 1,1-diacetates from
aldehydes in a solvent-free system, Monatsh Chem. 137 (2006) 1075–1078.
Run times
[
[
[
11] R. Ghosh, S. Maiti, A. Chakraborty, R. Halder, Indium triflate: a reusable catalyst for
expeditious chemoselective conversion of aldehydes to acylals, J. Mol. Catal. A
Chem. 215 (2004) 49–53.
Fig. 2. The reuse of the catalyst.
the above conditions, both carbonyl and phenolic OH groups were
acylated (Table 2, entry I). The reaction of ketone with acetic
anhydride was also examined. However, the yield was very low
trace) (Table 2, entry K).
Finally, we were interested in studying the reusability of the
2 5 2 3
12] A.R. Hajipour, A. Zarei, A.E. Ruoho, P O /Al O as an efficient heterogeneous
catalyst for chemoselective synthesis of 1,1-diacetates under solvent-free con-
ditions, Tetrahedron Lett. 48 (2007) 2881–2884.
13] B. Karimi, J. Maleki, Lithium trifluoromethanesulfonate (LiOTf) as a recyclable
catalyst for highly efficient acetylation of alcohols and diacetylation of aldehydes
under mild and neutral reaction conditions, J. Org. Chem. 68 (2003) 4951–4954.
(
catalysts for economic and environmental reasons. The reaction of
-nitro-benzaldehyde and acetic anhydride was chosen as a model
reaction using PEG–SO H under solvent-free conditions. At the end
of each run, the catalyst was recovered from the reaction mixture
by addition of Et O followed by a simple filtration. The recovered
catalyst was dried under vacuum condition at 40 8C and reused.
The yields remained unchanged even after the catalyst had been
recycled eight times (Fig. 2). Compared with the fresh catalyst, the
IR of the catalyst after being recycled eight times had no obvious
changes (Fig. S3 see supporting information).
[14] D.H. Aggen, J.N. Arnold, P.D. Hayes, N.J. Smoter, R.S. Mohan, Bismuth compounds
in organic synthesis. Bismuth nitrate catalyzed chemoselective synthesis of
acylals from aromatic aldehydes, Tetrahedron 60 (2004) 3675–3679.
4
3
[15] B.F. Mirjalili, M.A. Zolfigol, A. Bamoniri, M.A. Amrollahi, N. Sheikhan, Chemose-
lective synthesis of 1,1-diacetates from aldehydes in the presence of Al(HSO
under mild solvent-free conditions, Russ. J. Org. Chem. 43 (2007) 852–854.
4 3
)
2
[
16] D. Angeles-Beltran, G. Negron-Silva, L. Lomas-Romero, M.A. Iglesias-Arteaga, F.J.C.
Santos-Aires, Titanium-modified MCM-41 prepared by ultrasound and by hydro-
thermal treatment, catalysts for acetylation reactions, J. Mex. Chem. Soc. 52
(
2008) 175–180.
17] G. Romanelli, P. Dimitroff, P. Vazquez, J.C. Autino, Chemoselective preparation of
,1-diacetates from aldehydes, mediated by a Keggin heteropolyacid under
solvent free conditions at room temperature, Eur. J. Chem. 4 (2007) 83–89.
18] K. Niknam, D. Saberi, Preparation of sulfuric acid ([3-(3-silicapropyl)sulfanyl]pro-
pyl)ester: a new and recyclable catalyst for the formylation and acetylation of
alcohols under heterogeneous conditions, Appl. Catal. A Gen. 366 (2009) 220–225.
19] (a) K. Niknam, D. Saberi, Silica-bonded N-propyl sulfamic acid as an efficient
catalyst for the formylation and acetylation of alcohols and amines under
heterogeneous conditions, Tetrahedron Lett. 50 (2009) 5210–5214;
[
[
[
1
4
. Conclusion
The reactions to synthesize 1,1-diacetates from aldehydes and
acetic anhydride were efficiently catalyzed by PEG–SO
solvent-free conditions. The catalyst can be recovered and reused at
least eight times without apparent loss of activity. It should be noted
3
H under
(b) N.S. Maryam, D. Abdolah, N. Khodabakhsh, Preparation of silica-bonded
propyl-diethylene-triamine-N-sulfamic acid as a recyclable catalyst for chemo-
selective synthesis of 1,1-diacetates, Chin. J. Chem. 29 (2011) 2361–2367.
20] H.J. Yoon, S.M. Lee, J.H. Kim, H.J. Cho, J.W. Choi, S.H. Lee, et al., Polymer-supported
gadolinium triflate as a convenient and efficient Lewis acid catalyst for acetyla-
tion of alcohols and phenols, Tetrahedron Lett. 49 (2008) 3165–3171.
[
[
that PEG–SO
PEG–SO H is sufficient to catalyze the reaction in most cases. These
results not only provide a new aspect of catalytic organic reactions,
but also extend the utility of PEG–SO H in organic synthesis that
3
H has high catalytic activity, and that only 5 mol% of
3
21] K. Niknam, D. Saberi, M.N. Sefat, Silica-bonded S-sulfonic acid as a recyclable
catalyst for chemoselective synthesis of 1,1-diacetate, Tetrahedron Lett. 50
3
(2009) 4058–4062.
might lead to environmentally benign processes.
[22] A.R. Massah, R.J. Kalbasi, A. Shafiei, ZSM-5-SO H as a novel, efficient, and reusable
3
catalyst for the chemoselective synthesis and deprotection of 1,1-diacetates
under eco-friendly conditions, Monatsh. Chem. 143 (2012) 643–652.
[23] V.L.C. Goncalves, B.P. Pinto, J.C. Silva, C.J.A. Mota, Acetylation of glycerol catalyzed
by different solid acids, Catal. Today 133 (2008) 673–677.
Acknowledgments
[
[
[
[
[
[
24] H. Wu, Y. Shen, L. Fan, Y. Wan, D. Shai, Solid silica sulfuric acid (SSA) as a novel and
efficient catalyst for acetylation of aldehydes and sugars, Tetrahedron 62 (2006),
7995-7995.
25] S.P. Borikar, T. Daniel, A convenient and efficient protocol for the synthesis of
acylals catalyzed by Brønsted acidic ionic liquids under ultrasonic irradiation,
Ultrason. Sonochem. 18 (2011) 928–931.
This work was financially supported by Key Laboratory of Hexi
Corridor Resources Utilization of Gansu Universities (No. XZ1011),
the President’s Funds of Hexi University (No. XZ-2009-9) and the
National Natural Science Foundation of China (No. 21262010).
26] X.C. Wang, Z.J. Quan, F. Wang, M.G. Wang, Z. Zhang, Z. Li, PEG–SO
,4-dihydropyrimidones via biginelli reaction under microwave and solvent-free
conditions, Synth. Commun. 36 (2006) 451–456.
27] C.B. Reddy, K.S. Kumar, M.A. Kumar, M.V.N. Reddy, B.S. Krishna, M. Naveen, et al.,
PEG–SO H catalyzed synthesis and cytotoxicity of a-aminophosphonates, Eur. J.
3
H as catalyst for
3
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.cclet.2013.01.007.
3
Med. Chem. 47 (2012) 553–559.
28] R.S. Shou, Y.W. Qiu, D. Yan, L.L. Xiao, Z.C. Ming, Synthesis of bis(indolyl)methanes
using recyclable PEG-supported sulfonic acid as catalyst, Catal. Lett. 128 (2009)
4
18–422.
29] Z.J. Quan, Y.X. Da, Z. Zhang, X.C. Wang, PS–PEG–SO
dihydropyrimidonesvia Biginelli reaction, Catal. Commun. 10 (2009) 1146–1148.
References
3
H as an efficient catalyst for 3,4-
[
1] H.W. Pinnick, K.S. Kochhar, R.P. Deshpande, S.N. Rajadhyak-sha, Protecting groups
in organic synthesis. Part 8. Conversion of aldehydes into geminal diacetates, J.
Org. Chem. 48 (1983) 1765–1767.
[30] Y.X. Zong, Y. Zhao, W.C. Luo, et al., Highly efficient synthesis of 2,3-dihydroqui-
nazolin-4(1H)-ones catalyzed by heteropoly acids in water, Chin. Chem. Lett. 21
(2010) 778–781.