Heterogeneous Catalysis
FULL PAPER
was checked. After stirring for 72 h at room temperature in the various
solvents, no differences were noticed in the X-ray diffractograms. Before
reaction, a freshly prepared catalyst sample was dried overnight at 383 K.
[9] M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. OꢁKeeffe,
O. Yaghi, Science 2002, 295, 469–472.
[10] U. Müller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J.
PastrØ, J. Mater. Chem. 2006, 16, 626–636.
3
The reference Lewis acid catalysts and H BTC were stirred in the appro-
priate solvent over a 72 h period to ensure maximum solubility. Depend-
ing on the solubility of these reference catalysts, reactions were partly or
totally homogeneous or heterogeneous. The ion exchange resins were
dried overnight at 333 K before reaction. For the reactions with a-pinene
oxide, 0.1 g was added to 0.1 g catalyst with 5 mL of solvent. Reactions
were carried out at 298 K. For the reactions with citronellal, 0.5 g was
added to 0.1 g catalyst with 5 mL of solvent. Reactions were carried out
at 383 K. For the filtration tests, part of the reaction suspension was with-
drawn at a certain conversion at reaction temperature, the catalyst was
separated, and the supernatant was allowed to react further in a separate
vial. Regeneration tests were identical to the normal reactions; after re-
action, the catalyst was quickly washed three times in the same solvent as
used in the reaction, dried at 333 K and subsequently overnight at 383 K
before the next run. Hereafter, as a second regeneration procedure, a
number of samples was successively washed in ethanol, ethanol/water
and twice in water and finally dried in two steps. For the reactions with
the ethylene acetal of 2-bromopropiophenone, two literature procedures
were followed with chlorobenzene or 1,2-dichlorobenzene as reflux sol-
[11] H. Dathe, E. Peringer, V. Roberts, A. Jentys, J. Lercher, C. R. Chim.
2005, 8, 753–763.
[12] B. Gómez-Lor, E. GuttiØrez-Puebla, M. Iglesias, M. Monge, C.
Ruiz-Valero, N. Snejko, Chem. Mater. 2005, 17, 2568–2573.
[13] K. Schlichte, T. Kratzke, S. Kaskel, Microporous Mesoporous Mater.
2004, 73, 81–88.
[14] C. Wu, A. Hu, L. Zhang, W. Lin, J. Am. Chem. Soc. 2005, 127,
8940–8941.
[15] L. Huang, H. Wang, J. Chen, Z. Wang, J. Sun, D. Zhao, Y. Yan, Mi-
croporous Mesoporous Mater. 2003, 58, 105–114.
[16] C. Lin, S. Chui, S. Lo, F. Shek, M. Wu, K. Suwinska, J. Lipkowski, I.
Williams, Chem. Commun. 2002, 1642–1643.
[17] T. Reineke, M. Eddaoudi, M. OꢁKeeffe, O. Yaghi, Angew. Chem.
1999, 111, 2712–2716; Angew. Chem. Int. Ed. 1999, 38, 2590–2594.
[18] M. Rosseinsky, Microporous Mesoporous Mater. 2004, 73, 15–30.
[19] O. Yaghi, C. Davis, G. , Li, H. Li, J. Am. Chem. Soc. 1997, 119,
2861–2868.
[20] L. Yang, H. Naruke, T. Yamase, Inorg. Chem. Commun. 2003, 6,
1020–1024.
[21] A. Corma, H. García, Chem. Rev. 2003, 103, 4307–4365.
[22] K. Wilson, A. RØnson, J. Clark, Catal. Lett. 1999, 61, 51–55.
[23] J. Kaminska, M. Schwegler, A. Hoefnagel, H. van Bekkum, Recl.
Trav. Chim. Pays-Bas 1992, 111, 432–437.
[
30,31]
vents.
GC-MS data for 7 were m/z (%): 258 (3) [M
50 (2), 133 (1), 105 (100), 79 (7), 77 (10), 51 (4); for 8: 214 (1) [M
The samples were immediately analyzed with GC or GC-MS.
+
81
+
79
ACHTREUNG
A
H
R
U
G
( Br)],
+
1
3
7
+ 35
ACHTREUNG
A
C
H
T
R
E
U
N
G
( Cl)], 212 (3) [M ( Cl)], 150 (1), 133 (3), 105 (100), 79 (7), 77 (9), 51
+
(
4); for 9: 176 (33) [M ], 115 (5), 105 (100), 77 (38), 51 (10).
[
[
[
24] P. Kunkeler, J. van der Waal, J. Bremmer, B. Zuurdeeg, R. Downing,
H. van Bekkum, Catal. Lett. 1998, 53, 135–138.
25] C. Milone, C. Gangemi, G. Neri, A. Pistone, S. Galvagno, Appl.
Catal. A 2000, 199, 239–244.
Acknowledgement
26] C. Milone, A. Perri, A. Pistone, G. Neri, S. Galvagno, Appl. Catal. A
2
002, 233, 151–157.
The authors are grateful to H. Leeman for SEM measurements and to G.
Vanbutsele for nitrogen physisorption measurements. LA wishes to thank
F.W.O. (Research Foundation Flanders) for financial support. DDV is
grateful to F.W.O. for grant G.0323.04. This work was performed in the
frame of the Belgian Interuniversity Poles of Attraction (IUAP V-3).
[27] P. Kropp, W. Breton, S. Craif, S. Crawford, W. Durland, J. Jones, J.
Raleigh, J. Org. Chem. 1995, 60, 4146–4152.
[28] G. Castaldi, A. Belli, F. Uggeri, C. Giordano, J. Org. Chem. 1983,
48, 4658–4661.
[29] M. Baldoví, A. Corma, V. FornØs, H. García, A. Martínez, J. Primo,
J. Chem. Soc. Chem. Commun. 1992, 949–951.
[
30] F. Algarra, A. Corma, V. FornØs, H. García, A. Martínez, J. Primo,
[
[
[
[
1] H. Li, M. Eddaoudi, M. OꢁKeeffe, O. Yaghi, Nature 1999, 402, 276–
79.
2] S. Chui, S. Lo, J. Charmant, A. Orpen, I. Williams, Science 1999,
83, 1148–1150.
3] J. Rowsell, O. Yaghi, Microporous Mesoporous Mater. 2004, 73, 3–
4.
4] S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. 2004, 116, 2388–
430; Angew. Chem. Int. Ed. 2004, 43, 2334–2375.
Stud. Surf. Sci. Catal. 1993, 78, 653–660.
[31] A. Corma, H. García, A. Primo, A. Domenech, New J. Chem. 2004,
28, 361–365.
[32] A. Vimont, J. Goupil, J. Lavalley, M. Daturi, S. SurblØ, C. Serre, G.
Ferey, J. Am. Chem. Soc. 2006, 128, 3218–3227.
[33] K. Hadjiivanov, G. , Vayssilov, Adv. Catal. 2002, 47, 307–511.
[34] K. Hadjiivanov, H. Knçzinger, A. Milushev, Catal. Commun. 2002,
3, 37–44.
2
2
1
2
[
[
[
5] C. Janiak, Dalton Trans. 2003, 2781–2804.
[35] P. Mꢂki-Arvela, N. Kumar, V. Nieminen, S. Sjçholm, T. Salmi, D.
Murzin, J. Catal. 2004, 225, 155–169.
[36] P. Smeets, M. Groothaert, R. Schoonheydt, Catal. Today 2005, 110,
303–309.
6] J. Lee, J. Li, J. , Jagiello, J. Solid State Chem. 2005, 178, 2527–2532.
7] Q. Wang, D. Shen, M. Bülow, M. Lau, S. Deng, F. Fitch, N. Lemcoff,
J. Semanscin, Microporous Mesoporous Mater. 2002, 55, 217–230.
8] J. Rowsell, A. Millward, K. Park, O. Yaghi, J. Am. Chem. Soc. 2004,
[
Received: February 16, 2006
1
26, 5666–5667.
Published online: July 31, 2006
Chem. Eur. J. 2006, 12, 7353 – 7363
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
7363