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C6′H2), 5.70 br.s (14H, С2OН, С3OН), 8.08 t (2H, Hβ),
8.59 t (1H, Hγ), 8.98 d (2H, Hα). 13C NMR spectrum
(DMSO-d6), δ, ppm: 53.9 (C6'), 60.4 (C6), 72.6 (C5),
72.9 (C2), 73.6 (C3), 82.0 (C4), 102.5 (C1), 128.4 (Cβ),
141.8 (Cα), 146.7 (Cγ). Found, %: C 44.32; H 5.79; N
1.18. C47H74BrNO34. Calculated, %: C 44.21; H 5.84;
N 1.10.
Mono-{6-[2-(4-hydroxyphenyl)ethan-1-ami-
nium]-6-deoxy}-β-cyclodextrin iodide (21) was ob-
tained from 1.00 g (0.80 mmol) iodo derivative 2 and
1.10 g (8.00 mmol) of 4-(2-aminoethyl)phenol 12.
Yield 0.85 g (77%), mp 173–175°С (decomp.), Rf
1
0.73. Н NMR spectrum (DMSO-d6), δ, ppm: 2.54 t
(2H, СН2Ph), 3.03–3.75 m (44Н, Н2–5, С6Н2,
CH2N+H2), 4.51 br.s (6Н, С6OН), 4.79 s (7H, С1Н),
5.92 br.s (16H, С2OН, С3OН, N+H2), 6.62 d (2Н, Hm),
6.93 d (2Н, Ho), 9.06 s (1H, OH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 34.7 (СН2Ph), 39.6 (CH2N+H2),
43.5 (C6′), 60.4 (C6), 72.5 (C5), 72.9 (C2), 73.6 (C3),
82.0 (C4), 102.4 (C1), 115.7 (Cm), 129.5 (CiCH2),
130.0 (Co), 156.5 (Cp). Found, % C 43.53; H 5.76; N
0.95. C50H80INO35. Calculated, %: C 43.45; H 5.83; N
1.01.
Mono[6-deoxy-6-(pyridin-1-ium)]-β-cyclodextrin
iodide (18) was obtained similarly to compound 17
from 1.00 g (0.80 mmol) of iodo derivative 2 and 0.63 g
(8.00 mmol) of pyridine. Yield 0.83 g (78%), mp 268–
270°С (decomp.), Rf 0.77. 1Н NMR spectrum (DMSO-
d6), δ, ppm: 3.29–3.68 m (40Н, Н2–5, С6Н2), 4.43 br.s
(6Н, С6OН), 4.79 s (7H, С1Н), 5.26 m (2H, C6'H2),
5.69 br.s (14H, С2OН, С3OН), 8.08 t (2H, Hβ),
8.59 t (1H, Hγ), 8.98 d (2H, Hα). 13C NMR spectrum
(DMSO-d6), δ, ppm: 53.9 (C6'), 60.4 (C6), 72.6 (C5),
72.9 (C2), 73.6 (C3), 82.0 (C4), 102.5 (C1), 128.4 (Cβ),
141.8 (Cα), 146.7 (Cγ). Found, %: C 42.49; H 5.55; N
0.91. C47H74INO34. Calculated, %: C 42.64; H 5.63; N
1.06.
Mono[6-(hexan-1-aminium)-6-deoxy]-β-cyclodex-
trin chloride (22). To a solution of 0.50 g (0.39 mmol)
of monotosylate 3 in 20 mL of DMF was added at
stirring 0.034 g of sodium hydrogen carbonate, 0.04 g
(0.39 mmol) of hexan-1-amine 6, and the reaction
mixture was stirred for 28 h at 70°C. The solution was
concentrated to a volume of 2 mL, filtered, diluted
with 10 mL of acetone, the separated precipitate was
filtered off, washed successively with chloroform (2 ×
5 mL), ethanol (2 × 5 mL), acetone (2 × 5 mL), ethyl
ether (2 × 5 mL), and dried in a vacuum (1 mm Hg) for
4 h at 80°C. Yield 0.38 g (82%), mp 248–250°С
Mono[6-deoxy-6-(cyclohexylaminium)]-β-cyclo-
dextrin iodide (19) was obtained from 1.00 g (0.80 mmol)
of iodo derivative 2 and 0.79 g (8.0 mmol) of cyclo-
hexylamine 10. Yield 0.79 g (73%), mp 248–250°С
1
(decomp.), Rf 0.74. Н NMR spectrum (DMSO-d6), δ,
ppm: 0.98–1.27 m (6Н, Н3–5), 1.54–1.79 m (4Н, С2Н2,
С6Н2), 3.03–3.72 m (43Н, Н2–5, С6Н2, С1Н), 4.45 br.s
(6Н, С6OН), 4.78 s (7H, С1Н), 5.63 br.s (16H, С2OН,
С3OН, N+H2). 13C NMR spectrum (DMSO-d6), δ, ppm:
24.9 (С3, С5), 25.1 (С4), 32.8 (С2, С6), 46.6 (C6'), 60.4
(C6), 60.7 (С1), 72.6 (C5), 72.9 (C2), 73.6 (C3),
82.0 (C4), 102.5 (C1). Found, %: C 42.76; H 6.07; N
0.96. C48H82INO34. Calculated, %: C 42.89; H 6.15; N
1.04.
1
(decomp.), Rf 0.74. Н NMR spectrum (DMSO-d6), δ,
ppm: 0.84 t (3H, CH3), 1.18–1.29 m [6H, (CH2)3СH3],
1.34 m (2H, NCH2CH2), 3.01 t (2H, NCH2), 3.29–3.72
m (42Н, Н2–5, С6Н2), 4.11 br.s (6Н, С6OН), 4.81 s (7H,
С1Н), 5.37 br.s (15H, С2OН, С3OН, NH). 1Н (D2O), δ,
ppm: 0.78 t (3H, CH3), 1.13–1.23 m [6H, (CH2)3СH3],
1.34 m (2H, NCH2CH2), 2.97 t (2H, NCH2), 3.45–3.79
1
m (42Н, Н2–5, С6Н2), 4.88 br.c (7H, С1Н). Н NMR
Mono[6-deoxy-6-(2-phenylethan-1-aminium)]-β-
cyclodextrin iodide (20) was obtained from 1.00 g
(0.80 mmol) of iodo derivative 2 and 0.97 g (8.00 mmol)
of 2-phenylethan-1-amine 11. Yield 0.84 g (76%), mp
spectrum (D2O, pH 2), δ, ppm: 0.76 t (3H, CH3), 1.11–
1.18 m [6H, (CH2)3СH3], 1.51 m (2H, NCH2CH2), 2.93
t (2H, NCH2), 3.15–3.82 m (42Н, Н2–5, С6Н2), 4.87 br.s
(7H, С1Н). 13C NMR spectrum (DMSO-d6), δ, ppm:
14.5 (CH3), 22.6 (CH2CH3), 27.0 [CH2(CH2)2CH3],
31.8 (CH2CH2N), 49.9 (CH2N), 54.6 (C6'), 60.4 (C6),
72.5 (C5), 72.9 (C2), 73.6 (C3), 82.0 (C4), 102.4 (C1).
13C NMR spectrum (D2O), δ, ppm: 13.4 (CH3), 20.5
(CH2CH3), 25.5 [CH2(CH2)2CH3], 30.5 (CH2CH2N),
47.2 (CH2N), 54.6 (C6'), 60.1 (C6), 70.7 (C5), 72.0 (C2),
73.2 (C3), 81.1 (C4), 101.9 (C1). 13C NMR spectrum (D2O,
pH 2), δ, ppm: 13.2 (CH3), 20.6 (CH2CH3), 25.0 [CH2·
(CH2)2CH3], 30.2 (CH2CH2N), 46.2 (CH2N), 54.6 (C6'),
60.2 (C6), 71.9 (C5), 72.2 (C2), 73.2 (C3), 81.1 (C4), 101.9
1
174–176°С (decomp.), Rf 0.76. Н NMR spectrum
(DMSO-d6), δ, ppm: 3.17–3.78 m (46Н, Н2–5, С6Н2,
СН2СН2Ph), 4.44 br.s (6Н, С6OН), 4.79 s (7H, С1Н),
5.57 br.s (16H, С2OН, С3OН, N+H2), 7.05–7.31 m
(5Н, Ph). 13C NMR spectrum (DMSO-d6), δ, ppm:
35.5 (СН2Ph), 39.6 (CH2N+H2), 42.9 (C6'), 60.4 (C6),
72.6 (C5), 72.9 (C2), 73.6 (C3), 82.1 (C4), 102.5 (C1),
126.7 (Cp), 128.9 (Co), 129.1 (Cm), 139.8 (CiCH2).
Found, %: C 43.85; H 6.01; N 0.95. C50H80INO34.
Calculated, %: C 43.96; H 5.90; N 1.03.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017