1,6-Anhydro-1-thio-β-D-glucopyranose
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th e Cam bridge Crystallograph ic Data Cen tre, 12, Un ion Road, Cam bridge, CB2 1EZ, UK; fax:
+44 1223 336033; or deposit@ccdc.cam .ac.uk).
2,3,4-Tri-O-acetyl-1,6-an h ydro-1-th io-β-D-glucopyran ose (S)-S-Oxide (7b)
Sulfoxide 7a (0.3 g, 1.6 m m ol) was dissolved in dry pyridin e (30 m l) an d acetic an h ydride
(1.5 m l) was added. After 12 h th e crystallin e product was filtered off to obtain 7b (0.2 g, 40%);
th e secon d crop of 7b (0.275 g, 55%) was obtain ed from th e m oth er liquors. After crystalli-
zation from eth an ol–dieth yl eth er–petroleum eth er, com poun d 7b h ad m .p. 117–119 °C
(decom p.), [α]D –61 (c 0.55, CHCl3); ref.12 gives m .p. 122–123.5 °C, [α]D –75 (CHCl3). For
C
12H16O8S (320.3) calculated: 44.99% C, 5.03% H, 10.01% S; foun d: 45.22% C, 5.07% H,
9.79% S.
2,3,4-Tri-O-acetyl-1,6-an h ydro-1-th io-β-D-glucopyran ose (R)-S-Oxide (8b)
Sulfoxide 8a (0.09 g) in pyridin e (5 m l) was treated dropwise with acetic an h ydride (1.5 m l)
an d th e reaction m ixture was left stan din g at 0 °C overn igh t. Th en ice water was added an d
th e reaction m ixture was extracted with dich lorom eth an e, th e organ ic layer was wash ed
with dilute h ydroch loric acid, sodium h ydrogen carbon ate an d water, an d dried over an h y-
drous MgSO4. After evaporation of th e solven t, th e solid residue was crystallized from eth yl
acetate–petroleum eth er to give 8b (80 m g, 54%), m .p. 114–116 °C, [α]D –133 (c 0.74,
CHCl3); ref.12 gives m .p. 119–120 °C, [α]D –149 (CHCl3). FAB MS, m/z: 321 [M + H+].
1,6-An h ydro-1-th io-β-D-glucopyran ose S-Dioxide (9a)
A solution of th iolevoglucosan (2a; 0.1 g, 0.56 m m ol) in acetic acid (0.2 m l) was treated
with 30% H2O2 (0.31 g, 2.74 m m ol) an d th e reaction was m on itored by TLC. After 5 days,
th e secon d portion of 30% H2O2 (0.31 g) was added an d th e reaction tim e was prolon ged
for an oth er 5 days. Durin g th e course of oxidation th e product 9a con tin uously precipitated
from th e reaction m ixture. Crystals were filtered off, wash ed with eth an ol an d dried to give
9a (0.023 g, 20%), m .p. ~ 200 °C (decom p.), [α]D –32 (c 0.8, water), RF 0.46, RF (7a) 0.12
(eth yl acetate–m eth an ol 9:1); ref.12 gives m .p. 208–209 °C, [α]D –40.6 (water). For C6H10O6S
(210.2) calculated: 34.28% C, 4.79% H, 15.25% S; foun d: 34.34% C, 4.82% H, 14.65% S.
Crystal structure analysis of compound 9a. A colorless crystal of dim en sion s 0.45 × 0.45 ×
0.2 m m is orth orh om bic, space group P212121, C6H10O6S, M = 210.20, a = 6.9660(2) Å, b =
10.4660(2) Å, c = 10.8700(3) Å, V = 792.49(4) Å3, Z = 4, Dx = 1.762 Mg m –3. Diffraction ex-
perim en t was carried on a Non ius KappaCCD diffractom eter usin g m on och rom atized MoKα
radiation (λ = 0.71069 Å) at room tem perature. Absorption correction was n eglected (µ =
0.405 m m –1). A total of 12390 m easured reflection s in th e ran ge h = –9 to 8, k = –13 to 13,
l = –14 to 14 (θm ax = 27.5°) out of wh ich 1813 were un ique (Rin t = 0.024) an d 1758 observed
41
accordin g to th e I > 2σ(I) criterion . Th e structure was solved by direct m eth ods (SIR92
)
an d refin ed by full-m atrix least squares on F2 (SHELXL97 42). All n on -h ydrogen atom s were
refin ed an isotropically. Th e h ydrogen atom s on carbon s were calculated in to idealized posi-
tion s an d con strain ed durin g refin em en t (ridin g m odel) with assign ed displacem en t param e-
ter Hiso(H) = 1.2Ueq(pivot atom ). Th e h ydrogen atom s of h ydroxyls were foun d on differen ce
m ap an d refin ed isotropically. Th e refin em en t con verged (∆/σm ax = 0.000) to R = 0.024 for
observed reflection s; wR = 0.064, GOF = 1.080 for 131 param eters an d all 1813 reflection s.
Th e fin al differen ce m ap displayed n o peaks of ch em ical sign ifican ce (∆ρm ax = 0.183, ∆ρm in
=
Collect. Czech. Chem. Commun. 2006, Vol. 71, No. 3, pp. 311–336