B. Tamami, H. Mahdavi / Tetrahedron 59 (2003) 821–826
825
4
. Experimental
The polymer sample was filtered, washed with distilled
water, ether and dried at 508C under reduced pressure.
4
.1. Materials and technique
4.4. Typical procedure for reduction of carbonyl
compounds
Acrylamide was purchased from Fluka and was recrystal-
lized from chloroform. DVB (55%) was also purchased
from Fluka and was washed with sodium hydroxide solution
A solution of a carbonyl compound (1 mmol) and NaBH4
(0.5 mmol) in wet THF (20 ml) was added to the poly[N-(2-
aminoethyl)acrylamido]trimethyl ammonium halide resin
(,0.1 g) with stirring. Progress of the reaction was
monitored by TLC and/or GC. After completion of the
reaction, the resin was removed by filtration. A small
amount of NaBH4 which dissolved in wet THF was
removed using a short silica-gel column. The organic
solvent was dried with anhydrous Na SO . The correspond-
(
1%, 10 ml£2) and water (20 ml£3), to remove the
inhibitor. Other reagents and solvents were used without
further purification. Gas chromatography was recorded on a
Shimadzu GC 14-A. IR spectra were run on a Perkin–Elmer
IR-157-G Spectrophotometer. NMR spectra were recorded
on a Bruker Avance DPX instrument (250 MHz). All
products were characterized by comparison of their IR and
NMR spectra and physical data with those of the authentic
samples. All yields refer to the isolated products.
2
4
ing pure product was obtained upon evaporation of solvent.
1
The characterization of the product was performed with H
NMR, and IR techniques.
4
.2. Preparation of poly[N-(2-aminoethyl)acrylamide]
DVB (3.9 g, 0.03 mol) and acrylamide (60.4 g, 0.85 mol)
were dissolved in ethanol (250 ml). Benzoyl peroxide
Acknowledgements
(
350 mg, 1.4 mmol) was added and the mixture was heated
while stirring at 70–758C, for 5 h. The polymer formed was
collected by filtration, washed several times with water,
ethanol, benzene, and tetrahydrofuran, and dried at 608C
under reduced pressure. The IR spectrum of the polymer
showed the characteristic absorption of amide (N–H) at
We are thankful to Professor H. Firouzabadi for his valuable
comments and suggestions, and to Shiraz University
Research Council and Ministry of Science, Research and
Technology of Iran.
200 and 3300 cm2 , and carbonyl groups at 1660 cm
1
21
.
3
Polyacrylamide (10 g) was equilibrated with excess ethy-
lenediamine (100 ml) for 12 h, and then the mixture was
heated at 1008C for 12 h with stirring. The reaction mixture
was poured into cold water (1 l). The resin was filtered and
washed with NaCl solution (0.1 M) until the filtrate was free
from ethylenediamine, as indicated by the absence of blue
coloration with ninhydrin reagent. The gel was washed with
water, methanol and then dried at 608C under reduced
pressure. The IR spectrum of the amino functionalized
polyacrylamide showed the characteristic absorption of
References
1. Starks, C. M.; Liotta, C. L.; Halperm, M. Phase Transfer
Catalysis, Chapman & Hall: New York, 1994.
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R. Pure Appl. Chem. 1988, 60, 415, and the references cited
therein.
3. Keller, W. E. Phase Transfer Reaction, Georg Thieme:
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(b) Tomoi, M.; Ford, W. T. In Synthesis and Separation Using
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Wiley: New York, 1988; pp 181–207.
2
1
amino (N–H) group at 3500 cm . The amino group
content was determined by back titration and was found to
be equal to 3.72 mmol/g.
5
. (a) George, B. K.; Pillai, V. N. R. Polymer 1989, 30, 178. (b)
Aiswaryakumari, K.; Sreekumar, K. J. Appl. Polym. Sci. 1996,
59, 2039.
4.3. Preparation of poly[N-(2-aminoethyl)acrylamido]-
trimethyl ammonium iodide resin
6
. (a) Atherton, E.; Harkiss, F. D.; Sheppard, R. C. J. Chem. Soc.,
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Poly[N-(2-aminoethyl)acrylamide] (5 g) was equilibrated in
DMF (100 ml) for 12 h. Methyl iodide (20 ml, 320 mmol)
and NaOH (1 g, 25 mmol) was added and the reaction
mixture stirred at room temperature for 48 h. The quater-
nized polymer was collected by filtration, washed several
times with water and methanol until the filtrate was free
7. Tamami, B.; Mahdavi, H. Tetrahedron Lett. 2001, 42, 8721.
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69, 50630, and the references cited therein. (b) Hudlicky, M.
Reduction in Organic Chemistry, Ellis Horwood: Chichester,
1984.
from CH I, as indicated by absence of formation of AgI with
3
AgNO . Finally the polymer was washed with ether and
3
dried at 508C under reduced pressure to afford the desired
compound in a yield of 8.23 g. The capacity of quaternized
resin was determined both gravimetrically and by titration.
This was found to be 3.21 and 3.06 mmol/g of resin,
respectively.
11. (a) Gibson, H. W.; Baily, F. C. J. Chem. Soc., Chem. Commun.
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1
2. Spackman, D. H.; Stein, W. H.; Moore, S. Anal. Chem. 1958,
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For the conversion of the iodide resin to other resin halides,
the resin (5 g) was added to the metal halide aqueous
solution (2 M, 100 ml), and the mixture was stirred for 12 h.
13. (a) Johnson, M. R.; Rickborn, B. J. Org. Chem. 1970, 35,
1041. (b) Wilson, K. E.; Seinder, R. T.; Masamune, S. J. Chem.