4730
M. W. C. Robinson, A. E. Graham / Tetrahedron Letters 48 (2007) 4727–4731
bined solvents removed under reduced pressure. Purifi-
cation by column chromatography (ethyl acetate/hexane
1:3) gave the product benzaldehyde dimethyl acetal
(132 mg, 87%) as a colourless oil.
vice, University of Wales, Swansea, UK, and the EPSRC
Solid-State NMR Service, University of Durham, UK.
We also wish to thank Mr Peter Davies (School of Engi-
neering, University of Wales Swansea) for his assistance
in obtaining EDX data and Dr. S. H. Taylor (Cardiff
University) for his continued interest in this work.
Typical experimental procedure for the synthesis of cyclic
acetals: Benzaldehyde (112 mg, 1.06 mmol) and 2,2-di-
methylpropane-1,3-diol (212 mg, 2.03 mmol) were
dissolved in dichloromethane (10 mL) at room tempera-
ture. The catalyst (50 mg) was added and the reaction
mixture stirred at 45 ꢁC for 6 h. After this time, the reac-
tion mixture was cooled to room temperature and the
catalyst was removed by filtration through a Celite plug,
which was washed with dichloromethane (2 · 5 mL),
and the combined solvents removed under reduced pres-
sure. Purification by column chromatography (ethyl ace-
tate:hexane 1:4) gave the product 5,5-dimethyl-2-phenyl-
[1,3]-dioxane (160 mg, 80%) as a colourless oil; 1H
NMR (400 MHz; CDCl3) d = 7.45–7.40 (m, 2H), 7.32–
7.23 (m, 3H), 5.30 (s, 1H), 3.67 (d, 2H, J = 11 Hz),
3.56 (d, 2H, J = 11 Hz), 1.22 (s, 3H), 0.71 (s, 3H); 13C
NMR (100 MHz; CDCl3) d = 130.1, 129.3, 128.5,
126.6, 102.2, 78.1, 23.5, 22.3; MS (EI) m/z 192 (M+);
HRMS (EI) calculated for C12H17O2 (M+H+),
193.1223, found (M+H+) 193.1223.
References and notes
1. (a) Satori, G.; Ballini, R.; Bigi, G.; Bosica, G.; Maggi, R.;
Righi, P. Chem. Rev. 2004, 104, 199–250; (b) Kocienski, P.
J. Protecting Groups; Thieme: New York, 2003.
2. (a) Wenkert, E.; Goodwin, T. E. Synth. Commun. 1977, 7,
409–415; (b) Torok, D. S.; Figueroa, J. J.; Scott, W. J. J.
Org. Chem. 1993, 58, 7274–7276; (c) Yu, M.; Pagenkopf,
B. L. Tetrahedron 2003, 59, 2765–2771.
3. (a) Gemal, A. L.; Luche, J. H. J. Org. Chem. 1979, 44,
4187–4189; (b) Ishihara, K.; Karumi, Y.; Kubota, M.;
Yamamoto, H. Synlett 1996, 839–841; (c) Clerici, A.;
Pastori, N.; Porta, O. Tetrahedron 1998, 54, 15679–15690;
(d) Firouzabadi, H.; Iranpoor, N.; Karimi, B. Synlett
1999, 321–323; (e) Leonard, N. M.; Oswald, M. C.;
Freiberg, D. A.; Nattier, B. A.; Smith, R. C.; Mohan, R.
S. J. Org. Chem. 2002, 67, 5202–5207; (f) Kumar, R.;
Chakraborti, A. K. Tetrahedron Lett. 2005, 46, 8319–8323;
(g) Khan, A. T.; Mondal, E.; Ghosh, S.; Islam, S. Eur. J.
Org. Chem. 2004, 9, 2002–2009; (h) Wu, H.; Yang, F.; Cui,
P.; Hang, J.; He, M. Tetrahedron Lett. 2004, 45, 4963–
4965; (i) Smith, B. S.; Graham, A. E. Tetrahedron Lett.
2006, 47, 9317–9319.
4. (a) Sato, S.; Sagara, K.; Furuta, H.; Nozaki, F. J. Mol.
Catal. A: Chem. 1996, 114, 209–216; (b) Ballini, R.;
Bosica, G.; Frullanti, B.; Maggi, R.; Sartori, G.; Schror,
F. Tetrahedron Lett. 1998, 39, 1615–1618; (c) Kawabata,
T.; Misogamist, T.; Beltane, K.; Knead, K. Tetrahedron
Lett. 2001, 42, 8329–8332; (d) Shimizu, K.-I.; Hayashi, E.;
Hatamachi, T.; Kodama, T.; Kitayama, Y. Tetrahedron
Lett. 2004, 45, 5135–5138.
Typical experimental procedure for the synthesis of [1,3]-
dioxolanes: 1-Phenylethane-1,2-diol (135 mg, 0.98
mmol) was dissolved in acetone (5 mL). The catalyst
(50 mg) was added and the reaction mixture stirred at
55 ꢁC for 6 h. After this time, the reaction mixture was
cooled to room temperature. The catalyst was
removed by filtration through a Celite plug, which was
washed with dichloromethane (2 · 5 mL), and the
combined solvents removed under reduced pressure to
give the product 2,2-dimethyl-4-phenyl-[1,3]-dioxolane
1
(166 mg, 97%) as a colourless oil; H NMR (400 MHz;
5. Corma, A. Chem. Rev. 1997, 97, 2373–2419.
6. Tanaka, Y.; Saumur, N.; Iwanmoto, M. Tetrahedron Lett.
1998, 39, 9457–9460.
CDCl3) d = 7.44–7.31 (m, 5H), 5.10 (dd, 1H, J = 6
and 2 Hz), 4.33 (dd, 1H, J = 6 and 2 Hz), 3.74 (t, 1H,
J = 8 Hz), 1.20 (s, 3H), 0.77 (s, 3H); 13C NMR
(100 MHz; CDCl3) d = 129.2, 128.9, 126.3, 110.2, 77.8,
72.3, 27.0, 26.7; MS (CI–NH3) m/z 197 (M+NH4þ);
HRMS (EI) calculated for C11H15O2 (M+H+),
179.1067, found (M+H+) 179.1068.
´
7. (a) Rodriguez, I.; Climent, M. J.; Iborra, S.; Fornes, V.;
Corma, A. J. Catal. 2000, 192, 441–447; (b) Jermy, B. R.;
Pandurangan, A. J. Mol. Catal. A: Chem. 2006, 256, 184–
192.
8. Catalyst preparation (Si/Al = 14): The cetyltrimethylam-
monium bromide template (4.0 g, 11 mmol) was dissolved
in a solution of hydrochloric acid (2.5 mL, 0.1 M) and
ethanol (17.5 mL). Tetraethylorthosilicate (25 mL,
112 mmol) was then added and the mixture stirred for
10 min at 40 ꢁC. The solution was cooled to room
temperature and aluminium nitrate nonahydrate (3.35 g,
8.95 mmol) was added in one portion. The mixture was
stirred for 20 min and then left to age at room temperature
for 1 week. The resultant orange solid was crushed into a
fine powder, dried overnight at 90 ꢁC and then calcined in
air at 550 ꢁC for 12 h to remove the organic template. The
resulting white aluminosilicate catalyst was characterized
by EDX, MAS-NMR (27Al and 29Si) and XRD. Surface
area measurements and pore size distribution were
obtained from BET experiments.
Typical procedure for the hydrolysis of acetals: Benzalde-
hyde dimethyl acetal (152 mg, 1 mmol) and water
(42 mg, 2.3 mmol) were dissolved in acetone (5 mL) at
room temperature. The catalyst (25 mg) was added
and the reaction mixture stirred at 55 ꢁC for 30 min.
After this time, the reaction mixture was cooled to room
temperature. The catalyst was removed by filtration
through a Celite plug, which was washed with dichloro-
methane (2 · 5 mL). The combined solvents were
removed under reduced pressure to yield the product
benzaldehyde (93 mg, 87%) as a colourless oil.
9. Zhao, X. S.; Lu, G. Q.; Hu, X. Colloids Surf. A:
Physicochem. Eng. Aspects 2001, 179, 261–269.
Acknowledgements
10. (a) Deslonchamps, P.; Dory, Y. L.; Li, S. Tetrahedron
2000, 56, 3533–3537; (b) Sato, K.; Kishimoto, T.; Mor-
imoto, M.; Saimoto, H.; Shigemasa, Y. Tetrahedron Lett.
2003, 44, 8623–8625; (c) Lee, S. H.; Lee, J. H.; Yoon, C.
The authors thank the Engineering and Physical Sciences
Research Council (EPSRC) for financial support
(MWCR), the EPSRC National Mass Spectrometry ser-