Professional Documents
Culture Documents
020 httpsdoi-org10-1016S0926-860X-01-00961-9 Hydroxyapatite As A New Solid Support For The Knoevenagel PDF
020 httpsdoi-org10-1016S0926-860X-01-00961-9 Hydroxyapatite As A New Solid Support For The Knoevenagel PDF
Abstract
The Knoevenagel condensation is easily carried out without a solvent at room temperature using hydroxyapatite (HAP).
Activation by water and benzyltriethylammonium chloride (BTEAC) has also been investigated. When used with water and
ammonium salt, hydroxyapatite is an excellent solid support for the Knoevenagel condensation, leading to excellent yields
in a few minutes. Taking into account environmental and economical considerations, the handling of hydroxyapatite used
here presents many advantages such as easier separation and recovery from the reaction mixture and thus, enhanced recycling
possibilities, which are now well established in fine organic synthesis. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydroxyapatite; Activation by ammonium; Activation by water; Solid support; Heterogeneous catalysis; Knoevenagel reaction
0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 9 6 1 - 9
156 S. Sebti et al. / Applied Catalysis A: General 228 (2002) 155–159
Table 1
Synthesis of alkenes 3 by Knoevenagel condensation with HAP, HAP/water, HAP/BTEAC and HAP/BTEAC/water
Alkenes Yield in percent (time) (min)a,b
94 (7)
97 (10)
3g Ph– CO2 Et 10 (30) 20 (30) 44 (20) 66 (20)
90 (60)c
observed in phase transfer catalyst (PTC) with very [8] M. Lasperas, T. Llorett, L. Chaves, I. Rodriguez, A. Cauvel,
large concentrations of surfactant [32,33] or in sup- D. Brunel, Stud. Surf. Sci. Catal. 108 (1997) 75.
[9] M. Lakshmi Kantam, B.M. Choudary, C.V. Reddy, K.
ported aqueous phase (SAP) catalysis used for hydro-
Koteswara Rao, F. Figueras, Chem. Commun. (1998) 1033.
formylation [34,35], hydrogenation [36] and allylic [10] D.J. Macquarrie, J.H. Clark, D.B. Jackson, A. Lambert, J.E.G.
alkylation [37]. That suggests an great assistance effect Mdoe, A. Priest, Spec. Publ.: R. Soc. Chem. 216 (1998) 174.
provided by ammonium cation contained in the water [11] D.J. Macquarrie, J.H. Clark, A. Lambert, J.E.G. Mdoe, A.
film, to activate the carbonyl group of the aldehyde. Priest, React. Funct. Polym. 35 (1997) 153.
[12] K. Borszeky, T. Mallat, A. Baiker, Tetrahedron: Asymmetry
In the synthesis of alkene 3a, the yield (time)
8 (1997) 3745.
obtained with HAP/BTEAC/water are equivalent [13] P. De la Cruz, E. Diez-Barra, A. Loupy, F. Langa, Tetrahedron
to that of natural phosphate [19] (90 (7)), fluorap- Lett. 37 (1996) 1113.
atite/BTEAC/water [20] (98 (4)), MgO [4] (94 (5)), [14] J.A. Cabello, J.M. Campelo, A. Garcia, D. Luna, J.M.
Al2 O3 [1] (96 (3)) or Na2 CO3 /zeolite [18] (98 (15)) Marinas, J. Org. Chem. 49 (1984) 5195.
[15] T.I. Reddy, R.S. Varma, Tetrahedron Lett. 38 (1997) 1721.
and greater to that of KF/Al2 O3 [2] (86 (150)),
[16] I. Rodriguez, S. Iborna, A. Corma, F. Rey, J.L. Jorda, Chem.
AlPO4 /Al2 O3 [14] (80 (15)), resin [5] (92 (300)) and Commun. (1999) 593.
zeolite [15] (78 (720)). [17] H.M. Wiame, C.M. Cellier, P. Grange, J. Phys. Chem. B 104
In summary, the activity of hydroxyapatite has been (2000) 591.
improved by the addition of water or BTEAC. The [18] B. Siebenhaar, B. Casagrande, M. Studer, H.-U. Blaser, Can.
J. Chem. 79 (2001) 566.
good conditions to promote the Knoevenagel conden-
[19] S. Sebti, A. Saber, A. Rhihil, Tetrahedron Lett. 35 (1994)
sation are obtained by simultaneous addition of water 9399.
and BTEAC. The yields obtained are very high. The [20] S. Sebti, R. Nazih, R. Tahir, L. Salhi, A. Saber, Appl. Catal.
hydroxyapatite is a new solid support of the Knoeve- A 197 (2000) L 187.
nagel condensation in heterogeneous media without [21] S. Sebti, A. Rhihil, A. Saber, N. Hanafi, Tetrahedron Lett.
37 (1996) 6555.
solvent, which can contribute to the development of
[22] S. Sebti, A. Rhihil, A. Saber, M. Laghrissi, S. Boulaajaj,
cleaner catalytic processes. Tetrahedron Lett. 37 (1996) 3999.
[23] S. Sebti, R. Tahir, R. Nazih, S. Boulaajaj, Appl. Catal. A 218
(2001) 25.
Acknowledgements [24] J.A.S. Bett, L.G. Christner, W.K. Hall, J. Am. Chem. Soc.
89 (1967) 5535.
[25] M.E. Fleet, X. Liu, J. Solid State Chem. 149 (2000) 391.
Financial assistance of the Ministry of Education, [26] K. Kandori, A. Fudo, T. Ishikawa, Phys. Chem. Chem. Phys.
Government of Morocco (PROTARS, P2T3/59) is 2 (2000) 2015.
gratefully acknowledged. We thank also the “Office [27] S. Sugiyama, T. Minami, T. Moriga, H. Hayashi, K. Koto,
Chérifien des Phosphates (OCP)” and the “Cen- M. Tamka, J.B. Moffat, J. Mater. Chem. 6 (1996) 459.
[28] S. Sugiyama, K. Abe, H. Hayashi, Y. Matsumura, J.B. Moffat,
tre d’Etudes et de Recherches sur les Phosphates
J. Mol. Catal. A: Chem. 144 (1999) 347.
Minéraux (CERPHOS)” for their support. [29] T.S.B. Narasaraju, D.E. Phebe, J. Mater. Sci. 31 (1996) 1 and
references cited therein.
[30] K. Ishikawa, M. Kon, S. Tenshin, N. Kuwayama, Dent. Mater.
References J. 9 (1990) 58.
[31] S. Sebti, A. Saber, A. Rhihil, R. Nazih, R. Tahir, Appl. Catal.
[1] F. Texier-Boullet, A. Foucaud, Tetrahedron Lett. 23 (1982) A 206 (2001) 217.
4927. [32] D.H. Wang, H.S. Weng, Chem. Eng. Sci. 43 (1988) 2019.
[2] J. Yamawaki, T. Kawate, T. Ando, T. Hanafusa, Bull. Chem. [33] D. Mason, S. Magdassi, Y. Sasson, J. Org. Chem. 56 (1991)
Soc., Jpn. 56 (1983) 1885. 7229.
[3] E. Angeletti, C. Canepa, G. Martinetti, P. Venturello, [34] J.P. Arhancet, M.E. Davis, J.S. Merola, B.E. Hanson, J. Catal.
Tetrahedron Lett. 29 (1988) 2261. 121 (1990) 327.
[4] H. Moison, F. Texier-Boullet, A. Foucaud, Tetrahedron 43 [35] G. Fremy, E. Monflier, J.F. Carpentier, Y. Castanet, A.
(1987) 537. Mortreux, Angew. Chem. Ind. Ed. Engl. 34 (1995) 1474.
[5] T. Saito, H. Goto, K. Honda, T. Fujii, Tetrahedron Lett. 33
[36] E. Fache, C. Mercier, N. Pagnier, B. Despeyroux, P. Panster,
(1992) 7535.
J. Mol. Catal. 79 (1993) 117.
[6] E. Kim, D.L. Gin, Polym. Mater. Sci. Eng. 79 (1998) 64.
[37] S. dos Santos, Y. Tong, F. Quignard, A. Choplin, D. Sinou,
[7] I. Rodriguez, H. Cambon, D. Brunel, M. Lasperas, J. Mol.
J.P. Dutasta, Organometallics 17 (1998) 78.
Catal. A: Chem. 130 (1998) 195.