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KUROCHKINA et al.
spectrum (CDCl3), δ, ppm: –3.7 and –3.6 (SiCH3),
20.5, 20.9, 21.1 [C(O)CH3], 61.6 (C6), 63.1 (C6'), 69.8
(C5'), 73.7, 73.9, 74.8 (C2, C3, C5), 83.4 (C4), 101.2
(C1), 127.2–135.8 (C6H5), 168.2, 169.8, 170.5 [C=O].
Found, %: C52.62; H 5.51. C95H122O55Si. Calculated,
%: C 52.53; H 5.66.
b. Obtained like compound IX (method b) from
0.40 g of compound XVII in 4 ml of pyridine and 0.21
g of silyl chloride XII. Yield 0.44 g (85%), mp 149–
1
150°C (decomp.), Rf 0.63 (B). H and 29Si NMR
spectra are identical to those of compound obtained by
the method a.
per-6-O-(Trimethylsilyl)-β-cyclodextrin (XI) was
obtained similarly to compound III by the method a
from 3.00 g of β-cyclodextrin I in 40 ml of pyridine
and 2.44 g of trimethylsilyl chloride XII solution in
20 ml of pyridine. Yield 2.13 g (49%), mp 253–255°C
per-2,3-O-acetyl-β-cyclodextrin (XVII). To
a
solution of 2.00 g of compound XVI in 50 ml of
methanol was added 0.60 g of ammonium fluoride.
The mixture was refluxed at 70°C for 24 h,
concentrated to 4 ml, and poured into 40 ml of ice
water. The precipitate formed was filtered off, washed
with water (2×10 ml), and dried in a vacuum (1 mm
Hg) for 3 h at 80°C. Yield 1.21 g (86%), mp 185–186°C
1
(decomp.), Rf 0.27 (B). H NMR spectrum (CDCl3), δ,
ppm: 0.21 and 0.24 s (63H, SiCH3), 3.34–3.93 m (42H,
C2–5H, C6H2), 4.80–5.05 m (7H, C1H), 5.20– 6.52 br.s
(14H, C2,3OH). 13C NMR spectrum (CDCl3), δ, ppm:
0.2 and 0.4 (SiCH3), 61.7 (C6), 70.5–73.5 (C2, C3, C5),
81.5 (C4), 102.1 (C1). The NMR spectrum of 29Si, δ,
ppm: 17.2–17.5 br.s. Mass spectrum, m/z: 1678.54
[M + K]. Calculated for C63H126KO35Si7: 1678.61.
Found, %: C46.01; H 7.85. C63H126O35Si7. Calculated,
%: C 46.13; H 7.74.
1
(published data: 184–188°C [14]), Rf 0.67 (D). H
NMR spectrum (C5D5N), δ, ppm: 1.80–2.25 br.s [42H,
CH3C(O)OC2,3], 3.95–4.72 m (42H, C2–5H, C6H2),
5.45–5.55 m (7H, C1H), 5.60–6.40 br.s (6H, C6OH).
Found, %: C 48.61; H 5.77. C70H98O49. Calculated, %:
C 48.78; H 5.73.
per-2,3,6-O-(trimethylsilyl)-β-cyclodextrin (XIII).
To a solution of 0.5 g of β-cyclodextrin I in 6 ml of
pyridine while stirring at 20°C was added a solution of
0.15 g of silyl chloride XII in 3 ml of pyridine. The
mixture was stirred for 5 h at 60°C, the solution was
poured into 50 ml of ice-cold water, the precipitate
formed was washed with water (5 ml), filtered off,
washed with water again (3×10 ml) and dried in a
vacuum (1 mm Hg) for 3 h at 80°C. Yield 0.95 g
(81%), mp 148–150°C (decomp.) (published data:
REFERENCES
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1
145–155°C [13]), Rf 0.84 (B). H NMR spectrum
(CDCl3), δ, ppm: 0.19–0.27 br.s (189H, SiCH3), 3.33–
3.96 m (42H, C2–5H, C6H2), 4.80–5.07 m (7H, C1H).
The 29Si NMR spectrum, δ, ppm: 17.2–17.5 and 22.1–
22.4 br.s. Mass spectrum, m/z: 2688.10 [M + K].
Calculated for C105H238KO35Si21: 2688.17. Found, %:
C 47.47; H 9.19. C105H238O35Si21. Calculated, %: C
47.58; H 9.05.
5. Grachev, M.K., Edunov ,A.V., Kurochkina, G.I., Levi-
na, I.I., and Nifant’ev, E.E., Zh. Obshch. Khim., 2011,
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Grachev, M.K., Kudryavtseva, N.A., Kurochkina, G.I.,
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per-6-O-(trimethylsilyl)-per-(2,3-O-acetyl)-β-cyclo-
dextrin (XIV). a. It was obtained like compound IX
(method a) from 0.50 g of compound XI and 0.42 g of
pyridine in 5 ml of DMF and 0.38 g of acetyl chloride.
Yield 0.60 g (88%), mp 149–150°C (decomp.), Rf 0.63
(B). 1H NMR spectrum (CDCl3), δ, ppm: 0.21 and 0.24
s (63H, SiCH3), 1.85–2.30 br.s [42H, CH3C(O)OC2,3],
3.34–3.93 m (42H, C2–5H, C6H2), 4.79–5.05 m (7H,
C1H). The 29Si NMR spectrum, δ, ppm: 17.2–17.5 br.s.
Found, %: C49.15; H 6.89. C91H154O49Si7. Calculated,
%: C 49.04; H 6.96.
7. Kurochkina, G.I., Senyushkina, I.A., Grachev, M.K.,
Vasyanina,L.K., and Nifant’ev, E.E., Zh. Obshch.
Khim., 2008, vol. 78, no. 1, p. 64.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 2 2013