R. Elek et al. / Carbohydrate Research 340 (2005) 1397–1402
1401
92 mg (93%), white crystals from water, mp 188–
189 ꢁC (Rf 0.60, 7:3 CHCl3–MeOH); [a]D +10
(c 1, Me2SO). Anal. Calcd for C13H17NO6S (315.34):
C, 49.52; H, 5.43; N, 4.44; O, 30.44; S, 10.17.
Found: C, 49.61; H, 5.31; N, 4.58; O, 30.25; S,
10.25.
crystals from EtOH–hexane, mp 93–95 ꢁC (Rf 0.28, 1:2
EtOAc–hexane 2·); [a]D +33 (c 0.5, CHCl3). Anal.
Calcd for C25H27NO10S (533.55): C, 56.28; H, 5.10; N,
2.63; O, 29.99; S, 6.01. Found: C, 56.35; H, 5.16; N,
2.30; O, 30.14; S, 6.05.
1.12. 1-S-(Z)-(2-Naphthhydroximoyl)-1-thio-b-D-galacto-
pyranose (5b)
1.7. 2,3,4,6-Tetra-O-acetyl-1-S-(Z)-4-methoxybenzhydr-
oximoyl-1-thio-b-D-galactopyranose (3a)
According to General method III from 5a (560 mg,
1.05 mmol), reaction time 3 days. Yield: 347 mg (90%),
white crystals from water, mp 121–123 ꢁC (Rf 0.63, 7:3
CHCl3–MeOH); [a]D +23 (c 1, Me2SO). Anal. Calcd
for C17H19NO6S (365.40): C, 55.88; H, 5.24; N, 3.83;
O, 26.27; S, 8.77. Found: C, 56.05; H, 5.26; N, 3.82;
O, 26.21; S, 8.69.
According to General method I from 1 (2.51 g,
6.90 mmol), reaction time 1 h. Yield: 2.88 g
(82%), foam (Rf 0.17, 1:1 EtOAc–hexane); [a]D +29
(c 1, CHCl3). Anal. Calcd for C22H27NO11S
(513.52): C, 51.46; H, 5.30; N, 2.73; O, 34.27; S,
6.24. Found C 51.51; H, 5.21; N, 2.57; O, 34.41; S,
6.30.
1.13. (1S)-2,3,4,6-Tetra-O-acetyl-1,5-anhydro-D-galacti-
tol-spiro[1.5]-3-phenyl-1,4,2-oxathiazole (6a)
1.8. 1-S-(Z)-4-Methoxybenzhydroximoyl-1-thio-b-D-
galactopyranose (3b)
According to General method II from 2a (767 mg,
1.59 mmol), reaction time 60 min. Yield: 61%, syrup
(Rf 0.56, 1:1 EtOAc–hexane); other data identical to
lit.10 except for the erroneously reported d H-1 value
(5.58 ppm) to be changed to 5.86 ppm.
According to General method III from 3a (1.00 g,
1.95 mmol), reaction time 1 day. Yield: 561 mg (83%),
brownish crystals from water, mp 99–101 ꢁC (Rf 0.47,
7:3 CHCl3–MeOH); [a]D +11 (c 1, Me2SO). Anal. Calcd
for C14H19NO7S (345.37): C, 48.69; H, 5.55; N, 4.06; O,
32.43; S, 9.28. Found: C, 48.73; H, 5.61; N, 4.12; O,
32.51; S, 9.18.
1.14. (1S)-1,5-Anhydro-D-galactitol-spiro[1.5]-3-phenyl-
1,4,2-oxathiazole (6b)
According to General method III from 6a (300 mg,
0.62 mmol), reaction time 15 min. Yield: 186 mg
(96%), brownish crystals from water, mp 115–117 ꢁC
(Rf 0.63, 1:1 CHCl3–MeOH); [a]D ꢁ2.7 (c 0.19 MeOH).
Anal. Calcd for C13H15NO6S (313.33): C, 49.83; H, 4.83;
N, 4.47; O, 30.64; S, 10.23. Found: C, 50.01; H, 4.85; N,
4.44; O, 30.50; S, 10.20.
1.9. 2,3,4,6-Tetra-O-acetyl-1-S-(Z)-4-bromobenzhydrox-
imoyl-1-thio-b-D-galactopyranose (4a)
According to General method I from 1 (3.63 g,
10.0 mmol), reaction time 1.5 h. Yield: 4.5 g (80%), foam
(Rf 0.30, 1:2 EtOAc–hexane); [a]D +30 (c 1, CHCl3).
Anal. Calcd for C21H24BrNO10S (562.39): C, 44.85; H,
4.30, Br 14.21; N, 2.49; O, 28.45; S, 5.70. Found: C,
45.34; H, 4.67, Br 14.28; N, 2.02; O, 29.41; S, 5.72.
1.15. (1S)-2,3,4,6-Tetra-O-acetyl-1,5-anhydro-D-galacti-
tol-spiro[1.5]-3-para-methoxyphenyl-1,4,2-oxathiazole
(7a)
1.10. 1-S-(Z)-4-Bromobenzhydroximoyl-1-thio-b-D-
galactopyranose (4b)
According to General method II from 3a (800 mg,
1.56 mmol), reaction time 80 min. Yield: 352 mg
(44%), foam (Rf 0.47, 1:1 EtOAc–hexane); [a]D +84 (c
1, CHCl3). Anal. Calcd for C22H25NO11S (511.50): C,
51.65; H, 4.93; N, 2.74; O, 34.42; S, 6.26. Found: C,
51.61; H, 5.01; N, 2.67; O, 34.41; S, 6.30.
According to General method III from 4a (1.00 g,
1.80 mmol), reaction time 2 days. Yield: 624 mg (88%),
white crystals from water, mp 151–153 ꢁC (Rf 0.44, 7:3
CHCl3–MeOH); [a]D +20 (c 1, Me2SO). Anal. Calcd
for C13H16BrNO6S (394.24): C, 39.61; H, 4.09, Br
20.27; N, 3.55; O, 24.35; S, 8.13. Found: C, 37.90; H,
4.25, Br 20.88; N, 3.57; O, 25.21; S, 8.25.
1.16. (1S)-1,5-Anhydro-D-galactitol-spiro[1.5]-3-para-
methoxyphenyl-1,4,2-oxathiazole (7b)
1.11. 2,3,4,6-Tetra-O-acetyl-1-S-(Z)-(2-naphthhydroxi-
moyl)-1-thio-b-D-galactopyranose (5a)
According to General method III from 7a (152 mg,
0.3 mmol), reaction time 20 min. Yield: 60 mg (58%),
brownish crystals from water, mp 188–190 ꢁC (Rf 0.63,
7:3 CHCl3–MeOH); [a]D +98 (c 0.25, Me2SO). Anal.
Calcd for C14H17NO7S (343.35): C, 48.97; H, 4.99; N,
According to General method I from 1 (1.00 g,
2.75 mmol), reaction time 1 h. Yield: 1.34 g (91%), white