ACETYLATION OF SECONDARY HYDROXY GROUPS
327
kept for 24 h at 20°C, the solvent was distilled off, and
the residue was ground with 5 ml of water, the
precipitate formed was dried, dissolved in 1 ml of
acetone, and poured in 10 ml of water. The mixture
obtained was stirred for some time, the precipitate
formed was filtered off, washed with water (3×10 ml),
and dried in a vacuum (1 mm Hg) for 4 h at 60°C.
solution of 0.27 g of acetyl chloride in 2 ml of DMF.
Yield 0.36 g (73%), mp 154–156°C, Rf 0.62 (A). H
1
NMR spectrum (CDCl3), δ, ppm: 0.04 s [36H, Si(CH3)2],
0.89 s [54H, C(CH3)3], 2.06 s [9H, CH3C(O)OC3], 2.16
s [18H, CH3C(O)OC2], 3.32–4.45 m (36H, C2H–C5H,
C6H2). 4.76–5.10 m (6H, C1H), 5.15–5.65 m (3H,
C2,3OH). Found, %: C 53.09, H 8.05. C90H162O39Si6.
Calculated, %: C 53.07, H 8.02.
1
Yield 0.29 g (50%), mp 156–158°C, Rf 0.69 (A). H
NMR spectrum (CDCl3), δ, ppm: 0.03 s [36H, Si(CH3)3],
0.89 s [54H, C(CH3)3], 2.05 s [13.5H, CH3C(O)OC3],
2.14 s [13.5 H, CH3C(O)OC2], 3.30–4.40 m (36H,
C2H–C5H, C6H2), 4.80–5.15 m (5H, C1H), 5.20–5.70
m (3H, C2,3OH). 13C NMR spectrum (CDCl3), δc, ppm:
–4.7 and –5.9 [Si(CH3)2], 18.4 [C(CH3)3], 20.8 and
20.9 [C(O)CH3], 25.9 [C(CH3)3], 61.9 (C6), 70.5–72.1
(C2, C3, C5), 80.5 (C4), 101.5 (C1), 169.4 and 170.5
(C=O). Found, %: C 53.05, H 8.01. C90H162O39Si6.
Calculated, %: C 53.06, H 8.02.
Compound VI. This compound was prepared
analogously to III from 0.40 g of cyclodextrine
derivative I in 4 ml of pyridine and a solution of 0.27 g
of acetyl chloride in 2 ml of pyridine. Yield 0.28 g
(61%), mp 152–154°C, Rf 0.66 (A). 1H NMR spectrum
(CDCl3), δ, ppm: 0.05 s [36H, Si(CH3)2], 0.89 s [54H,
C(CH3)3], 2.06 s [6H, CH3C(O)OC3], 2.16 s [9H,
CH3C(O)OC2], 3.30–4.43 m (36H, C2H–C5H, C6H2),
4.75–5.20 m (6H, C1H), 5.30–5.80 m (6H, C2,3OH).
Found, %: C 52.78, H 8.20. C84H156O36Si6. Calculated,
%: C 52.80, H 8.23.
b. The sample was obtained analogously to a from
0.40 g of α-cyclodextrine derivative I, 0.45 g of N,N-
dimethylaniline in 4 ml of benzene, and a solution of
0.27 g of acetyl chloride in 2 ml of benzene. Yield
0.36 g (73%), mp 156–158°C, Rf 0.69 (A).
Compound VII. This compound was prepared
analogously to compound Va (method a) from o.40 g
of β-cyclodextrine derivative II, 0.37 g of triethyl-
amine in 4 ml of benzene, and a solution of 0.26 g of
acetyl chloride in 2 ml of benzene. Yield 0.34 g (70%),
c. The sample was obtained analogously to III from
0.40 g of α-cyclodextrine derivative I, 0.38 g of
triethylamine in 4 ml of DMF, and a solution of 0.27 g
of acetyl chloride in 2 ml of DMF. Yield 0.34 g (69%),
mp 156–158°C, Rf 0.69 (A).
1H and 13C NMR spectra in both cases were
identical to that of compound Va obtained according to
the procedure a.
1
mp 142-144°C, Rf 0.67 g (B). H NMR spectrum
(CDCl3), δ, ppm: 0.03 s [42H, Si(CH3)2], 0.89 s [63H,
C(CH3)3], 2.06 s [15H, CH3C(O)OC3], 2.16 s [15H,
CH3C(O)OC2], 3.30–4.35 m (42H, C2H–C5H, C6H2),
4.60–5.05 m (7H, C1H), 5.10–5.75 m (4H, C2,3OH).
Found, %: C 53.07, H 8.09. C104H188O45Si7. Cal-
culated, %: C 53.04, H 8.05.
Compound VIII. It was prepared analogously to
compound Va (method a) from 0.40 g of β-
cyclodextrine derivative II, 0.29 g of pyridine in 4 ml
of benzene, and a solution of 0.26 g of acetyl chloride
in 2 ml of benzene. Yield 0.39 g (77%), mp 144–146°C,
Rf 0.68 (B). 1H NMR spectrum (CDCl3), δ, ppm: 0.03 s
[42H, Si(CH3)2], 0.89 s [63H, C(CH3)3], 2.06 s [24H,
CH3C(O)OC3], 2.16 s [12H, CH3C(O)C2], 3.30–4.35 m
(42H, C2H–C5H, C6H2), 4.55–4.95 m (7H, C1H), 5.05–
5.55 m (2H, C2,3OH). Found, %: C 53.20, H 7.90.
C108H192O47Si7. Calculated, %: C 53.18, H 7.93.
Compound Vb. This compound was obtained
analogously to Va (method a) from 0.40 g of α-
cyclodextrine derivative I, 0.29 g of pyridine in 4 ml of
benzene, and a solution of 0.27 g of acetyl chloride in
2 ml of benzene. Yield 0.40 g (82%), mp 158–160°C,
Rf 0.64 (A). 1H NMR spectrum (CDCl3), δ, ppm: 0.03 s
[36H, Si(CH3)3], 0.87 s [54H, C(CH3)3], 2.06 s [16H,
CH3C(O)OC3], 2.15 s [9H, CH3C(O)OC2], 3.30–4.40
m (36H, C2H–C5H, C6H2), 4.60–5.20 m (6H, C1H),
5.20–5.70 m (3H, C2,3OH). 13C NMR spectrum
(CDCl3), δC, ppm: –4.8 and –5.0 [Si(CH3)2], 18.4
[C(CH3)3], 20.8 and 20.9 [C(O)CH3], 25.9 [C(CH3)3],
61.9 (C6), 70.5–72.1 (C2, C3, C5), 80.5 (C4), 101.9 (C1),
169.6 and 170.5 (C=O). Found, %: C 53.07, H 8.01.
C90H162O39Si8. Calculated, %: C 53.07, H 8.02.
Compound IXa. It was prepared analogously to
compound Va (method a) from 0.40 g of β-cyclo-
dextrine derivative II, 0.44 g of N,N-dimethylaniline in
4 ml of benzene, and a solution of 0.26 g of acetyl
chloride in 2 ml of benzene. Yield 0.59 g (85%), mp
Compound Vc. This compound was prepared
analogously to III from 0.40 g of α-cyclodextrine
derivative I, 0.29 g of pyridine in 4 ml of DMF, and a
1
138–140°C, Rf 0.63 (B). H NMR spectrum, δ, ppm:
0.03 s [42H, Si(CH3)3], 0.87 s [63H, C(CH3)3], 2.05 s
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011