X. Yang et al. / Carbohydrate Research 337 (2002) 1309–1312
1311
mum amount of water. The solution was applied to a
column of CM-22 [H+] ion-exchange resin. The column
was washed with distilled water until there was no
b-CD in the fractions as assayed by TLC, then the
product was eluted out with 0.1 M aq NaCl. The
fractions, including those of the product, were com-
bined and concentrated, then desalted on a G-15
column eluted with distilled water. The product was
precipitated from the aqueous solution by using ace-
tone to give a white powder (1.2 g, 65%): TLC (A) Rf
0.33; IR (KBr): 3350, 2921, 1630, 1460, 1400, 1371,
1326, 1292, 1202, 1153, 1075, 1025, 936, 838, 750, 702,
mixture was added to the solution of b-CD-6-I (7) (1.0
g, 0.8 mmol) in DMF (50 mL). The reaction was
carried out at 60 °C for 40 h under stirring, followed by
evaporating the DMF. The brown residue was ground
with acetone (50 mL). The solid was filtered and ace-
tone was again added. This procedure was repeated
twice. The resulting primrose powder was dissolved in
water and precipitated by adding acetone. The white
powder thus obtained was dried in vacuum to give the
product (0.8 g, 78%): TLC (B) Rf 0.34; IR (KBr) 3381,
2928, 1707, 1637, 1410, 1365, 1332, 1299, 1236, 1153,
1078, 1028, 943, 857, 754, 705, 638, 605, 578, 526, 486,
603, 578, 530 cm−1 13C NMR (D2O): l 103.7, 103.4,
;
440 cm−1 13C NMR (D2O): l 164.1, 138.5, 133.4,
;
92.2, 82.8, 82.2, 79.4, 74.9, 74.6, 74.1, 73.7, 62.2, 61.8,
55.7, 50.1, 44.5. Anal. Calcd for C44H76N2O34·2 H2O:
C, 43.56; H, 6.65; N, 2.31. Found: C, 43.69; H, 6.51; N,
2.40.
130.6, 129.4, 128.8, 127.2, 103.3, 102.7, 98.3, 84.6, 83.7,
82.8, 75.6, 74.7, 74.1, 73.7, 62.1, 61.9. Anal. Calcd for
C49H73NO35Se·2 H2O: C, 43.56; H, 5.74; N, 1.04.
Found: C, 43.72; H, 5.61; N, 0.87.
6-[(2-Aminopropyl)amino]-6-deoxy-i-CD
(6b).—
6-[[2-(3-Oxo-1,2-benzoisoselenazole-3(2H)-propionyl-
amino)ethyl]amino]-6-deoxy-i-CD (9a).—To a solution
of compound 6a (1.0 g, 0.825 mmol) in DMF (50 mL),
compound 2 (0.47 g, 1.65 mmol) was added. The
reaction was carried out at 80 °C for 40 h with stirring.
Then the solvent was distilled. The brown residue was
dissolved in water and then filtered. The brown–red
filtrate was decolorized with activated carbon. The col-
orless aqueous solution thus obtained was concentrated
to a small volume, then applied to a CM-22 ion-ex-
change column ([H+]) and eluted with a gradient of
0–0.15 M aq NaCl. The fractions were collected and
assayed by TLC. The combined fractions that gave
only one spot (Rf 0.62, solvent A) were concentrated.
The residue was further desalted on a G-15 column
eluted with distilled water and freeze-dried to give a
white powder (0.33 g, 27%): TLC (A) Rf 0.62; IR (KBr)
3349, 2927, 2791, 2665, 2137, 1660, 1637, 1525, 1404,
1365, 1298, 1234, 1154, 1078, 1028, 942, 851, 753, 705,
Compound 6b 1.3 g (yield 71%) was prepared from
compound 5 (2.0 g, 1.5 mmol) and propanediamine (20
mL) as generally described above, but differently in
that the reaction time was 10 h: TLC (A) Rf 0.35; IR
(KBr) 3348, 2924, 1635, 1572, 1461, 1402, 1315, 1288,
1154, 1073, 1028, 992, 940, 744, 606, 527 cm−1 13C
;
NMR (D2O): l 103.6, 103.2, 98.1, 83.1, 82.9, 75.2, 74.5,
74.1, 62.1, 56.4, 49.6, 40.8, 27.3. Anal. Calcd for
C45H78N2O34·2 H2O: C, 44.05; H, 6.74; N, 2.28. Found:
C, 43.86; H, 6.57; N, 2.41.
6-[(2-Aminobutyl)amino]-6-deoxy-i-CD (6c).—Com-
pound 6c 1.4 g (yield 75%) was prepared from com-
pound 5 (2.0 g, 1.5 mmol) and butanediamine (20 mL)
as generally described above, but differently in that the
reaction time was 10 h and the temperature of the
reaction was 80 °C: TLC (A) Rf 0.34; IR (KBr) 3350,
2924, 1632, 1465, 1402, 1324, 1292, 1154, 1074, 1022,
942, 748, 604, 580 cm−1 13C NMR (D2O): l 104.4,
;
104.1, 84.1, 83.9, 75.1, 74.6, 73.9, 62.2, 52.3, 51.2, 43.6,
31.1, 29.4. Anal. Calcd for C46H80N2O34·3 H2O: C,
43.88; H, 6.88; N, 2.22. Found: C, 43.61; H, 6.78; N,
2.07.
646, 608, 575, 526, 438 cm−1 13C NMR (D2O): l
;
171.2, 166.1, 139.2, 132.4, 130.2, 129.1, 126.3, 124.5,
103.7, 103.1, 97.8, 84.2, 83.8, 82.6, 75.4, 75.1, 74.8, 73.6,
61.3, 59.2, 56.2, 51.4, 47.8, 42.1, 36.3. Anal. Calcd for
C54H83N3O36Se·2 H2O: C, 44.27; H, 5.98; N, 2.87.
Found: C, 44.15; H, 5.84; N, 2.69.
6-[(2-Aminohexyl)amino]-6-deoxy-i-CD
(6d).—
Compound 6d 1.3 g (yield 67%) was prepared from
compound 5 (2.0 g, 1.5 mmol) and hexanediamine (20
mL) as generally described above, but differently in
that the reaction time was 6 h and the temperature of
reaction was 80 °C: TLC (A) Rf 0.37; IR (KBr) 3350,
2930, 1634, 1462, 1400, 1324, 1285, 1152, 1072, 1024,
6-[[2-(3-Oxo-1,2-benzoisoselenazole-3(2H)-propionyl-
amino)propyl]amino]-6-deoxy-i-CD (9b).—Compound
9b 0.37 g (yield 31%) was prepared from compound 6b
(1.0 g, 0.815 mmol) as generally described above: TLC
(A) Rf 0.64; IR (KBr) 3353, 2928, 1682, 1654, 1579,
1407, 1364, 1328, 1233, 1203, 1153, 1079, 1030, 942,
997, 938, 745, 702, 604, 580 cm−1 13C NMR (D2O): l
;
103.7, 103.2, 84.3, 83.2, 75.8, 75.1, 74.2, 62.3, 50.2, 49.7,
41.4, 30.6, 28.1, 27.3, 26.7. Anal. Calcd for
C48H84N2O34·2 H2O: C, 45.42; H, 6.99; N, 2.21. Found:
C, 45.61; H, 6.82; N, 2.09.
845, 753, 704, 681, 647, 606, 576, 527, 486, 444 cm−1
;
13C NMR (D2O): l 172.1, 166.0, 139.2, 136.2, 133.8,
130.7, 129.5, 127.2, 103.3, 102.7, 99.2, 84.6, 82.2, 74.1,
73.6, 72.9, 70.4, 61.2, 59.3, 50.4, 47.6, 38.8, 37.2, 31.3.
Anal. Calcd for C55H85N3O36Se·2 H2O: C, 44.66; H,
6.06; N, 2.84. Found: C, 44.48; H, 5.94; N, 2.67.
6-(1,2-Benzoisoselenazol-3(2H)-one)-i-CD
(8).—
Compound 3 (0.48 g, 2.4 mmol) was dissolved in DMF
(20 mL) in an ice bath, then 50% aq KOH (0.14 g, 2.4
mmol) was added with stirring for a moment. This