Synthesis, Characterization and Catalytic Application of MCM 41 Supported Phenanthrolinium…
and N analyses were performed with a Vario EL III ele-
mental. Thermo gravimetric analysis (TGA) was per-
formed using a Rheometric Scientific model STA-1500
analyzer. Fourier transform infrared spectroscopy (FT-IR)
spectra were recorded using a Bruker vector 22 spec-
trometer using KBr pellets. Small-angle X-ray diffraction
(XRD) patterns were recorded in the 2h range of 0.8–10
using a X’Pert Pro MPDX-ray diffractometer using CuKa
radiation. Nitrogen (N2) adsorption/desorption isotherms
were measured using a NOVA 2200e analyzer. The sam-
ples were out-gassed for 14 h at 60 °C under vacuum
before measurement. Energy Dispersive X ray (EDAX)
pattern was performed using a Rontec analyzer. Scanning
electron microscopy (SEM) was performed using a KYKY-
EM3200 analyzer. Transmission electron microscopy
(TEM) experiments were conducted on a Philips EM 208
electron microscope.
(1702 cm-1), –CONH– (1650, 1546 cm-1), Si–O–Si
(1088 cm-1).
4.1.4 Synthesis of Phenanthrolinium Dibromide
Immobilized on MCM-41(phen-MCM-Br2)
To 5 g of phen-MCM-41 was added 15 g 1,2-dibro-
moethane in 30 mL anhydrous acetonitrile; the mixture
was stirred at 80 °C for 24 h. The resulting brown solid
was collected by filtration and washed with acetonitrile.
This material was then transferred to a soxhlet tube in
argon. The excess 1,2-dibromoethane was removed by
soxhlet extraction with acetonitrile for 24 h. The resulting
solid was denoted as phen-MCM-Br2. The loading of
phenanthrolinium dibromide on MCM-41 was quantified
by CHN and found to be 0.56 mmol g-1 based on nitrogen
content determination. IR (KBr, cm-1): C=O (1702 cm-1),
–CONH– (1653, 1545 cm-1), Si–O–Si (1088 cm-1).
4.1 General Procedure
4.1.5 General Procedure for the Aza-Michael Addition
of Aromatic Amines to a,b-Unsaturated Nitriles
and Nitro Compounds
4.1.1 Synthesis of Mesoporous MCM-41
MCM-41 was prepared according to reported procedure
[55]. Typically, 0.6 g of CTAB was dissolved in 23 g of
demineralized water and stirred for 15 min at a rate of
140 rpm. Then 3 g of sodium silicate was added and stirred
for 30 min. The pH of the mixture was adjusted to 9 by
gradual addition of 2 mol L-1 of sulfuric acid. After stir-
ring the resulting solution for 4 h, the resulting gel was
filtered, washed thoroughly with demineralized water,
dried at 40 °C for 24 h and calcined at 540 °C for 6 h.
Phen-MCM-Br2 catalyst (0.070 g, 4.0 mol %) was added to
a flask containing of aromatic amines (1 mmol) and acry-
lonitrile or nitro-olefin (1.2 mmol) in water (3 mL) and the
mixture was stirred at room temperature until completion of
the reaction as monitored by TLC. Ethyl acetate was then
added and the mixture was stirred for 15 min to ensure
product removal from the catalyst. The catalyst was filtered
off, washed with water and the product was separated by
extraction with ethyl acetate. The organic layer was evapo-
rated under vacuum in a rotary evaporator to obtain the crude
product. Further purification was achieved by column
chromatography using an ethyl acetate/n-hexane gradient.
Structural assignments of the products were based on their
1H and 13C NMR data and their melting points.
4.1.2 Synthesis of 5-(N,N-Bis-3-(triethoxysilyl) propyl)
ureyl-1,10-phenanthroline (Phen-Si)
The starting reagent 5-amino-1,10-phenanthroline (phen-
NH2) and the modified phen group (phen-Si) were prepared
1
according to the procedure described previously [56]. H
NMR (400 Hz, CDCl3): d 0.50–0.60 (m, 4H), 1.15 (t, 18H,
J = 6.8 Hz), 1.56–1.63 (m, 4H), 3.21–3.26 (m, 4H), 3.71
(q, 12H, J = 6.8 Hz), 7.17 (bs, 2H), 7.69–7.72 (m, 2H),
7.89 (s, 1H), 8.24–8.29 (m, 2H), 9.24–9.28 (m, 2H).
Acknowledgments Financial support of this work from the
Research Council of the University of Mazandaran is gratefully
acknowledged.
References
4.1.3 Modification of MCM-41 with phen-Si (phen-MCM-
41)
1. Perlmutter P (1992) Conjugate addition reactions in organic
synthesis. Pergamon, Oxford, p 114
2. Frackenpohl J, Arridson PI, Screiber JV, Seebach D (2001)
ChemBioChem 2:445–455
3. Bull SD, Davies SG, Delgado-Ballester S, Fenton G, Kelly PM,
Smith AD (2000) Synlett 9:1257–1260
4. Abrouki Y, Zahouily M, Rayadh A, Bahlaouan B, Sebti S (2002)
Tetrahedron Lett 43:8951–8953
0.500 g of MCM-41 was slurried in about 80 mL of anhy-
drous toluene. Phen-Si (0.5 mmol; 0.344 g) was dissolved in
8 mL of anhydrous CHCl3 and added to the previous mix-
ture. The reaction mixture was stirred for 24 h under argon at
reflux temperature. The reaction mixture was filtered and the
collected solid was washed several times with toluene and
dried overnight under vacuum. IR (KBr, cm-1): C=O
5. Bandini M, Cozzi PG, Giacomini M, Melchiorre P, Selva S,
Umani-Ronchi A (2002) J Org Chem 67:3700–3704
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