Synthesis of Per- and Poly-Substituted Trehalose Derivatives
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1H NMR (250 MHz, CDCl3): δ: 2.00 (s, 3H, Me), 2.02 (s, 3H, Me), 2.10 (s, 3H,
Me), 2.35–2.85 (m, 4H, O2CCH2CH2CO2), 3.74 (dd, 1H, J = 1.8 & 11.9 Hz,
H-6ꢀ), 4.04 (ddd, 1H, J = 1.8, 8.9, & 9.7 Hz, H-5), 4.68 (dd, 1H, J = 8.9 &
11.9 Hz, H-6), 4.92 (t, 1H, J = 9.7 Hz, H-4) 5.01 (dd, 1H, J = 3.4 & 9.7 Hz,
H-2), 5.27 (d, 1H, J = 3.4 Hz, H=1), 5.48 (t, 1H, J = 9.7 Hz, H-3).
13C NMR (63 MHz, CDCl3): δ: 15.3, 20.6, 20.7, 28.4, 29.1, 43.5, 61.6, 65.9, 68.0,
69.7, 69.8, 90.9, 169.7, 170.0, 172.1, 179.4.
IR (KBr): ν: 3612-3347, 2964, 1761, 1740, 1718, 1436, 1371, 1245, 1168, 1042,
984, 956.
MS (ES+): 817.1 (100%, M + Na), 833.1 (10%, M + K).
Anal. Calcd for C32H42O23: C, 48.31; H, 5.33. Found: C, 48.51; H, 5.42.
2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-acetyl-6,6ꢀ-bis-(1,2,3,4-tetra-O-acetyl-6-O-succinyl-β-D-
glucopyranuronyl)-α,α-trehalose, 17
2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-acetyl-6,6ꢀ-di-O-succinyl-α,α-trehalose, 19 (1.00 g, 1.3
mmol), 1,2,3,4-tetra-O-acetyl-β-D-glucopyranose (0.99 g, 2.7 mmol), and p-
(dimethylamino)pyridine (4 mg, 0.03 mmol) were dissolved in acetonitrile (10
mL). To this mixture was slowly added a solution of DCC (0.55 g, 2.6 mmol) in
acetonitrile (10 mL) with stirring. After 18 h the solution was filtered to remove
the 1,3-dicyclohexylcarbodiimide adduct and the filtrate reduced. An impure
sample of the title compound, contaminated with one other compound, was
obtained on crystallization of the residue from aqueous methanol. Further pu-
rification was achieved by column chromatography using ethyl acetate:petrol
ether (40–60◦C) (2:1) as eluent. The title compound was the more mobile of the
two components in the mixture; yield 200 mg (11%); m.p. 113–115◦C.
1H NMR (250 MHz, CDCl3): δ: 1.99 (s, 3H, Me), 2.02 (s, 9H, 3 × Me), 2.03 (s,
3H, Me), 2.08 (s, 3H, Me), 2.11 (s, 3H, Me), 2.65 (br.s, 4H, O2CCH2CH2CO2),
3.85 (m, 1H, H-5 [G]), 4.03 (d, 1h, J = 12.8Hz, H-6ꢀ [T]), 4.17 (m, 1H, H-5
[T]), 4.17 (d(d), 1H, H-6ꢀ [G]), 4.24 (m, 2H, H-6 [G], H-6 [T]), 5.03 (m, 2H,
H-2, 4 [T]), 5.12 (t, 2H, J = 8.2 Hz, H-2, 4 [G]), 5.22 (t, 1H, J = 9.2 Hz, H-3
[G]), 5.29 (d, 1H, J = 3.7 Hz, H-1 [T]), 5.48 (dd, 1H, J = 8.24 & 10.1 Hz, H-3
[T]), 5.70 (d, 1H, J = 8.2 Hz, H-1 [G]).
13C NMR (63 MHz, CDCl3): δ: 20.4, 20.6, 20.8, 28.6, 28.7, 61.8 (C-6, [T]+[G]),
67.8 (C-4, [G]), 68.2 (C-5, [T]), 68.6 (C-4, [T]), 69.8 (C-2, [T]), 70.0 (C-3, [T]),
70.3 (C-2, [G]), 72.7 (C-5, [G]), 72.8 (C-3, [G]), 91.7 (C-1, [G]), 92.1 (C-1, [T]),
169.0, 169.2, 169.4, 169.6, 169.7, 170.0, 170.1, 171.8, 171.9.
MS (FAB): 269.1 (100%), 229.1 (52%), 209.0 (46%), 557.1 (34%), 335.1 (30%),
719.1 (25%), 431.1 (20%), 845.1 (16%), 1477.4 (15%, M + Na).
Anal. Calcd for C60H70O41: C, 49.55; H, 4.85. Found: C, 49.74; H, 4.77.