Chloroform → HCID 69732337, compound

Participants

Reaction Steps

[litt=P. Jarglis, Thesis, Darmstadt-Eberstadt 1980] 3,4,6-Tri-O-acetyl-1,5-anhydro-D-fructose oxime (2) (5.00 g, 16.5 mmol) was dissolved in dioxane (100 mL) and NH4OAc (13.0 g, 169 mmol) was added. The mixture was cooled on ice, 15% TiCl3 (44 mL, 54 mmol) was added and the reaction mixture was stirred at rt for 3 h. The mixture was extracted with CHCl3 (5×30 mL) and the combined organic phase was washed with saturated aqueous NaHCO3 (70+50 mL). The combined aqueous phase was extracted with CHCl3 (30 mL) and the combined organic phase was washed with H2O (30 mL). The organic phase was dried (MgSO4) and evaporated to a syrup of 3 (3.54 g, 75%). Upon addition of Et2O, the product crystallises (1.29 g, mp 81-85° C.). Two recrystallisation from Et2O afforded an analytical sample: mp 93-95° C.; [α]D−7.2 (c 1.5. CHCl3) [Lit. mp 86-88° C., [α]D−10 (c 0.5, CHCl3)]. 1 H NMR (CDCl3 at 727, 300 MHz) δ 2.08 (s, 3H, OCOCH3) 2.10 (s, 3H, OCOCH3), 2.16 (s, 3H, OCOCH3), 3.99 (ddd, J=2.5, 5.0 and 9.0, 1H, H-5), 4.10 (d, J=15.5, 1H, H-1), 4.23 (dd, J=2.5 and 12.5, 1H, H-6), 4.27 (d, J=15.5. 1H, H-1′), 4.32 (dd, J=5.0 and 12.5, 1H, H-6′), 5.34 (t, J=9.5, 1H, H-4), 5.42 (d, J=10.0, 1H, H-3). 13C NMR (CDCl3 at 77.0. 75.5 MHz) δ 20.4, 20.7 (3×OCOCH3), 62.1 (C-6), 69.4 (C-4), 72.9 (C-1), 76.5 (C-5), 76.8 (C-3), 169.1, 169.8, 170.5 (3×OCOCH3), 196.3 (C-2).

Provenance & Evidence