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10.0 Hz, H-5), 4.39 (dd, 1 H, J6a,6b 10.0 Hz,
H-6a), 3.77 (br s, 1 H, H-2), 3.75 (apt t, 1 H,
H-6b), 3.66 (dd, 1 H, H-4); 13C NMR (300
MHz, CDCl3) l 162.3, 142.4 (each s, each
aromatic C) 138.5, 128.9, 128.2, 126.7, 125.8,
116.8 (each d, each aromatic CH), 101.7, 99.6,
78.9, 71.1 (each d), 69.6 (t, C-6), 68.8, 63.6
(each d); IR (KBr): 3491, 1593, 1511, 1346,
1247, 1081, 971 cm−1. Anal. Calcd for
C19H19O8N: C, 58.61; H, 4.92; N, 3.60. Found:
C, 58.45; H, 4.78; N, 3.83.
tive); mp 155–157 °C (water); [h]D −40° (c
1
0.4, CHCl3); H NMR (300 MHz, CDCl3): l
7.52–7.04 (ms, 10 H, aromatic H), 5.60 (s, 1
H, CHPh), 5.35 (d, 1 H, J1,2 8.0 Hz, H-1), 4.49
(apt t, 1 H, J2,3 2.5, J3,4 2.5 Hz, H-3), 4.43 (dd,
1 H, J5,6a 5.5, J6a,6b 10.0 Hz, H-6), 4.15 (dt, 1
H, J4,5 10.0, J5,6b 10.0 Hz, H-5), 3.80 (overlap-
ping signals, 2 H, H-2, H-6b) 3.70 (dd, 1 H,
H-4), 2.72 (br s, 1 H, OH), 2.54 (br s, 1 H,
OH); 13C NMR (270 MHz, CDCl3): l 157.0,
136.9 (each s, each aromatic C), 129.6, 129.4,
128.4, 126.3, 122.9, 116.7 (each d, each aro-
matic CH), 102.0 (d, CHPh), 99.3 (d, C-1),
78.5, 70.9 (each d), 69.0 (t, C-6), 69.0, 63.2
(each d); IR (KBr): 3415, 2919, 1597, 1491,
1391, 1228, 1076, 1011, 761 cm−1. Anal.
Calcd for C19H20O6: C, 66.27; H, 5.85. Found:
C, 65.97; H, 5.55.
Octyl 4,6-O-benzylidene-i- -allopyranoside
D
(5d).—Treatment of 4d (0.46 g, 1.56 mmol) as
described for 4b gave 5d (0.54 g, quantitative);
mp 112–114 °C (water); [h]D −42° (c 0.2,
CHCl3); 1H NMR (300 MHz, CDCl3): l
7.52–7.32 (ms, 5 H, aromatic H), 5.56 (s, 1 H,
CHPh), 4.69 (d, 1 H, J1,2 8.0 Hz, H-1), 4.39
(br s, 1 H, H-3), 4.38 (dd, 1 H, J5,6a 5.5, J6a,6b
10.0 Hz, H-6a) 3.96 (apt dt, 1 H, J5,6b 10.0, J4,5
10.0 Hz, H-5), 3.89 (m, 1 H, OCH(H)CH2),
3.75 (apt t, 1 H, H-6b), 3.58 (dd, 1 H, J3,4 2.5
Hz, H-4), 3.51 (m, 2 H, H-2, OCH(H)CH2),
2.57 (2 H, br s, OH), 1.65 (m, 2 H, octyl-CH2),
1.28 (10 H, m, octyl-CH2), 0.88 (3 H, t, J 6.5
Hz, CH3); 13C NMR (300 MHz, CDCl3): l
137.3 (s, aromatic C), 129.5, 128.6, 126.5 (each
d, each aromatic H), 102.2, 101.5, 79.1, 71.6
(each d), 70.8, 69.4 (each t), 69.2, 63.5 (each
d), 32.0, 29.9, 29.6, 29.5, 26.2, 22.9 (each t,
octyl-CH2), 14.3 (q, CH3); IR (KBr): 3501,
3206, 2924, 2853, 1450, 1376, 1085, 1001, 747,
698 cm.−1 Anal. Calcd for C21H32O6: C, 66.31;
H, 8.48. Found: C, 66.08; H, 8.31. ESHRMS:
Found 403.2079, required 403.2097 [M+
Na]+.
Methyl
4,6-O-benzylidene-i- -allopyran-
D
oside (5a).—Treatment of 4a (0.25 g, 1 mmol)
as described for 4b gave 5b (0.26 g, 92% yield);
mp 157–158 °C (water); [h]D −63° (c 0.88,
CHCl3) (lit.:26 [h]D −45.1° (c 0.48, CHCl3));
1H NMR (300 MHz, 1:10 Me2SO-d6-CDCl3):
l 7.53–7.32 (ms, 5 H, aromatic H), 5.55 (s, 1
H, CHPh), 4.58 (d, 1 H, J1,2 7.5 Hz, H-1), 4.38
(dd, 1 H, J5,6a 5.0, J6a,6b 10.5 Hz, H-6), 4.31 (br
s, 1 H, H-3), 4.11 (br s, 1 H, OH), 4.00 (m, 1
H, H-5), 3.83 (br d, 1 H, J 6.0 Hz, OH), 3.74
(apt t, 1 H, J5,6b 10.5 Hz, H-6b), 3.56 (s, 3 H,
OCH3), 3.54 (dd, 1 H, J3,4 2.5, J4,5 9.5 Hz,
H-4), 3.46 (br s, 1 H, H-2); 13C NMR (270
MHz, CDCl3): l 137.4 (s, aromatic C), 129.1,
128.2, 126.4 (each d, each aromatic CH),
102.6, 101.8, 79.1, 71.1 (each d), 69.2 (t, C-6),
68.9, 62.9 (each d), 57.3 (OCH3); IR (KBr):
3490, 3403, 2923, 2862, 1451, 1385, 1209,
1109, 1014, 757, 701 cm−1; Anal. Calcd for
C14H18O6: C, 59.57; H, 6.43. Found: C, 59.32;
H, 6.46.
Methyl (4,6-O-benzylidene-i-
osyl)-(12)-3-O-benzyl-4,6-O-benzylidene-i-
-glucopyranoside (5e).—Treatment of 4e (90
D
-allopyran-
D
mg, 0.15 mmol) as described for 4b gave 5e
(30 mg, 32%); mp 194–196 °C (EtOAc); [h]D
4-Nitrophenyl
4,6-O-benzylidene-i- -
D
1
allopyranoside (5c).—Treatment of 4c (0.15 g,
0.42 mmol) as described for 4b gave 5c (0.13
g, 79%); mp 203–205 °C (water); [h]D −294°
(c 0.02, CHCl3); 1H NMR (300 MHz,
CDCl3:Me2SO-d6, 10:1): l 8.25–8.21 (d, 2 H,
J 9.0 Hz, aromatic H), 7.98–7.29 (ms, 5 H,
aromatic H), 7.18 (d, 2 H, J 9.0 Hz, aromatic
H), 5.67 (s, 1 H, CHPh), 5.52 (d, 1 H, J1,2 8.0
Hz, H-1), 4.42 (apt t, 1 H, J2,3 2.5, J3,4 2.5 Hz,
H-3), 4.21 (apt dt, 1 H, J4,5 10.0, J5,6a 5.0, J5,6b
−50.4° (c 0.25, CHCl3); H NMR (300 MHz,
CDCl3) l 7.50–7.25 (ms, 15 H, aromatic H),
5.57 and 5.54 (each s, each 1 H, each CHPh),
4.79 and 4.99 (AB d, 2 H, OCH2Ph, J 11.0
Hz), 4.93 (d, 1 H, J1,2 7.5 Hz, H-1), 4.41 (d, 1
H, J1%,2% 7.5 Hz, H-1%), 4.39–4.32 (overlapping
signals, 3 H, H-3,6,6%), 4.05 (apt d, 1 H, J5,6a
5.0, J6a,6b 9.5 Hz, H-5), 3.88–3.70 (overlapping
signals, 4 H, H-3%,4%,6%,6), 3.63 (apt t, 1 H, J2,3
7.5 Hz, H-2), 3.57 (dd, 1 H, J3%,4% 2.5, J4%5% 9.5