Synthesis of 6-bromo-6-dezoxy-β-cyclodextrin from its silyl and tosyl derivatives [1]

Full text of DOI:10.1134/S1070363206120231

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 12, pp. 1958 1959.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 2047 2048.
S.V. Sipin, M.K. Grachev, L.K. Vasyanina, E.E. Nifant’ev, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 12,
LETTERS
TO THE EDITOR
Synthesis of 6-Bromo-6-dezoxy- -cyclodextrin from Its Silyl
and Tosyl Derivatives
S. V. Sipin, M. K. Grachev, L. K. Vasyanina, and E. E. Nifant’ev
Moscow State Pedagogical University,
Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: chemdept@mtu-net.ru
Received October 13, 2006
DOI: 10.1134/S1070363206120231
6
-Bromo-6-dezoxy derivatives of -cyclodextrin
dextrin because of the significant inculsion of the
named reagents and the products of their conversion
into the cyclodextrin cavity (for example, of triphenyl-
phosphine oxide). Continuing our research in the field
of the synthesis of bromodezoxy derivatives [6] we
found that easily available per-6-O-(tert-butyldime-
thylsilyl)- -cyclodextrin (I) and per-6-O-tosyl- -cyclo-
dextrin (II) containing free secondary hydroxyl groups,
under the treatment with 10 mol equivalent of di-
bromotriphenylphosphorane readily undergo desilyla-
tion (method a) or detosylation (method b) with the
formation of per-6-bromo-6-dezoxy- -cyclodexrtrin
(III).
attract a permanent interest owing to their high alkyl-
ating properties toward N-containing organic nucleo-
philes because they allow to prepare numerous alkyl-
ammonium derivatives of cyclodextrins that signifi-
cantly extends the possibility of cyclodextrins prac-
tical usage, for example for the synthesis of -cyclo-
dextrin cationic derivatives [1 3]. Bromodezoxy de-
rivatives of cyclodextrins are usually prepared by the
reaction of spare cyclodextrins with Riden [4] and
Wilsmier Haack [5] reagents. These methods being
widely practiced in carbohydrate chemistry, give not
reproductive results in the reactions with free cyclo-
Br7
R7
a. 10Ph PBr /CH Cl ;
3
2
2
2
b. 10Ph PBr /CH Cl /Py
3
2
2
2
(
OH
OH)7
(
OH
OH)7
I, II
III
I: R = OSiMe t-Bu; II: R = OTs.
2
Note that this synthetic route to compound III has
been described, but only for the silylated derivative I
containing completely methylated secondary hydroxyl
groups, without description of detailed experimental
procedures for the desilylation [7]. In the case of our
reaction, isolation of the product III is carried out by
its precipitation by chloroform from DMF allowing us
to obtain the target compound not contaminated with
triphenylphosphine oxide, which often is necessary for
further functionalization of bromodezoxycyclodextrin
Per-6-bromo-6-dezoxy- -cyclodextrin (III). a. To
1 g (0.516 mmol) of silyl derivative I in 5 ml of me-
thylene chloride, 2.62 g (6.202 mmol) of dibromotri-
phenylphosphorane was added. Then the reaction mix-
ture was stirred for 24 h, and centrifuged. The solu-
tion was decanted, and the obtained precipitate was
dissolved in 2 ml of DMF. Then 8 10 ml of chloro-
form was added to this solution, the solution was
stirred for 24 h and then centrifuged. The precipitate
formed was washed with chloroform, and dried in a
vacuum (1.5 mm Hg) for 8 h at 60 C to yield 0.524 g
[3].
1958

SYNTHESIS OF 6-BROMO-6-DEZOXY- -CYCLODEXTRIN
1959
(
62%) of compound III, mp 220 223 C (decomp.).
33083a) and Grant of President of Russian Federation
for supporting the leading scientific schools (no. NSH-
5515.2006.3).
1
H NMR spectrum (DMSO-d ), , ppm, (J, Hz):
6
6
3
2
3
.34 d.d (7H, H , J
5
6
9.86, J
6
6
14.26), 3.41 d
H H
H H
2
3
6
3
(
7H, H , J
1
2
4.02), 3.66 d.d (7H, H , J
5
6
9.87,
H H
H H
REFERENCES
2
4
3
3
J
6
6
14.26), 3.71 d.d (7H, H , J
4
5
9.14, J
H H
3 4
H H
H H
5
3
3
1
0.23), 3.85 m (7H, H , J
4
5
9.14, J
5
6
9.87,
9.87), 4.98 d (7H,
H H
1. Khan, A.R., Forgo, P., Stine, K.J., and D’Souza, V.T.,
H H
3 3
3 4
H H
3
Chem. Rev., 1998, vol. 98, no. 5, p. 1977.
J
5
6
9.86), 3.99 d (7H, H , J
H H
1
3
2
H , J
1
2
4.02), 5.89 d (7H, C OH), 6.03 d (7H,
H H
2. Grachev, M.K., Mustafin, I.G., and Nifant’ev, E.E., Zh.
Obshch. Khim., 1998, vol. 68, no. 9, p. 1519.
3
C OH). Found, %: C 32.53; H 4.01; Br 35.00.
C H Br O . Calculated, %: C 32.02; H 4.03; Br
4
2
63
7
28
3
. Grachev, M.K., Sipin, S.V., Kurochkina, G.I., and Ni-
fant’ev, E.E., Zh. Obshch. Khim., 2006, vol. 76, no. 6,
p. 1048.
3
5.51.
b. To a solution of 1 g (0.457 mmol) of tosyl
derivative II in 5 ml of methylene chloride and 2 ml
of pyridine, 1.93 g (4.570 mmol) of dibromotriphe-
nylphosphorane was added. Then the reaction mixture
workup was similar to the described in method a.
4
5
. Gadelle, A., and Defaye, J., Angew. Chem., 1991,
vol. 103, no. 1, p. 94.
. Gorin, B.I., Riopelle, R.J., and Thatcher G.R.J., Tetra-
hedron Lett., 1996, vol. 37, no. 27, p. 4647; Chmur-
ski, K., and Defaye, J., Tetrahedron Lett., 1997, vol. 38,
no. 42, p. 7365; Visitiu, D., Walkinshaw, C.S., Go-
rin, B.I., and Thatcher, G.R.J., J. Org. Chem., 1997,
vol. 62, no. 25, p. 8760.
Yield of compound III is 0.418 g (58%), mp 220
1
2
23 C (decomp.). The H NMR spectrum in DMSO-
d6 is identical to the listed in method a. Found, %:
C 32.58; H 4.010; Br 35.29. C H Br O . Calcu-
4
2
63
7
28
lated, %: C 32.02; H 4.03; Br 35.51.
1
The H NMR spectra were recorded on a Bruker
WP-250 spectrometer (external reference TMS).
6
. Kurochkina, G.I., Trushkin, M.K., Grachev, M.K., and
Nifant’ev, E.E., Zh. Obshch. Khim., 2004, vol. 74,
no. 10, p. 1743.
ACKNOWLEDGMENTS
This work was financially supported by Russian
Foundation for Basic Research (project no. 05-03-
7. Alker, D., Ashton, P.R., Harding, V.D., and Koniger, R.,
Tetrahedron Lett., 1994, vol. 35, no. 48, p. 9091.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 12 2006