Synthesis, Characterization, and Gas Permeation Properties

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1.66 (brs, 1.1H, NHCH(CH2CH)CO), 3.22–4.49 (m, 19.83H, OCHCH3, OCH, OCH2,
and 1.1H, NHCHCO), 4.88 (brs, 1H, OCHCH3); IR (ATR, cm -1 ): 3441, 2969, 2877,
1752, 1708, 1521, 1456, 1367, 1328, 1271, 1161, 1114, 1047, 842; [α]D = –37.8° (c =
0.10 g/dL in CH3OH); anal. calcd for (C31.93H58.56N1.1O12.91)n (664.4862)n: C, 57.71; H,
8.88; N, 2.32; O, 31.09, found: C 57.74; H, 8.50; N, 1.99; O, 31.77.
N-α-t-Butoxycarbonyl-L-asparagine Ester of Hydroxypropyl Cellulose (2d).
The reaction of hydroxypropyl cellulose, 1, (1.35 g, 3.13 mmol) with
N-α-t-butoxycarbonyl-L-asparagine (6.54 g, 28.17 mmol) and the purification of the
product were carried out in the same way as that for the synthesis of 2a. Yield 90%,
white solid, 1 H NMR (400 MHz, d6-DMSO, 80 ºC, ppm): 1.04–1.18 (m, 13.83H,
OCHCH3), 1.40 (s, 9.0H, OCOC(CH3)3), 2.88–2.96 (m, 2.0H, NHCH(CH2CO)CO),
3.21–4.45 (m, 19.83H, OCHCH3, OCH, OCH2, and 1.0H, NHCHCO), 4.91 (brs, 1H,
OCHCH3); IR (ATR, cm -1 ): 3441, 2972, 2926, 2884, 1751, 1713, 1514, 1456, 1370,
1285, 1158, 1116, 1052, 887, 851, 790, 769, 668; [α]D = –25.8° (c = 0.10 g/dL in
CH3OH); anal. calcd for (C28.83H51.66N2.00O13.61)n (644.1039)n: C, 53.76; H, 8.08; N,
4.35; O, 33.81, found: C, 53.32; H, 8.37; N, 4.01; O, 34.30.
N-α-t-Butoxycarbonyl-L-glutamine Ester of Hydroxypropyl Cellulose (2e).
It was synthesized by adopting the same procedure as for 2a using
N-α-t-butoxycarbonyl-L-glutamine (6.94 g, 28.17 mmol) instead of
N-α-t-butoxycarbonyl-L-glycine. Yield 93%, white solid, 1 H NMR (400 MHz,
d6-DMSO, 80 ºC, ppm): 1.04–1.17 (m, 13.83H, OCHCH3), 1.40 (s, 15.3H,
OCOC(CH3)3), 1.93 (brs, 3.4H, NHCH(CH2CH2CO)CO), 2.65 (brs, 3.4H,
NHCH(CH2CH2CO)CO), 3.21–4.50 (m, 19.13H, OCHCH3, OCH, OCH2, and 1.7H,
NHCHCO), 4.93 (brs, 1.7H, OCHCH3); IR (ATR, cm -1 ): 3332, 2977, 2921, 1750, 1706,
1670, 1621, 1511, 1452, 1365, 1161, 1120, 1068, 1049, 834, 690; [α]D = –25.7° (c =
0.10 g/dL in CH3OH); anal. calcd for (C36.83H64.86N3.4O16.41)n (817.9020)n: C, 54.08; H,
7.99; N, 5.82; O, 32.11, found: C, 54.49; H, 7.67; N, 5.45; O, 32.39.
N-α-,N-ε-di-t-Butoxycarbonyl-L-lysine Ester of Hydroxypropyl Cellulose
(2f). The synthesis of 2f was accomplished in the same way as that of 2a by making