Chloroform → HCID 69732337, compound

HRID 1760890Notes

Reaction equation

HRID 1760890 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[O:8][CH2:7][C:6]1=NO)(=[O:3])[CH3:2].C(Cl)(Cl)Cl.[O:26]1CCOCC1>>[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[O:8][CH2:7][C:6]1=[O:26])(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 6212Chloroform2×HCID 312751,4-DioxaneHCID 86585087HCID 86585087, compound

Product 1

HCID 69732337HCID 69732337, compound

Procedure

[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).

Workup

  1. additionwas added
  2. extractionThe mixture was extracted with CHCl3 (5×30 mL)
  3. washthe combined organic phase was washed with saturated aqueous NaHCO3 (70+50 mL)
  4. extractionThe combined aqueous phase was extracted with CHCl3 (30 mL)
  5. washthe combined organic phase was washed with H2O (30 mL)
  6. dry with materialThe organic phase was dried (MgSO4)
  7. customevaporated to a syrup of 3 (3.54 g, 75%)
  8. additionUpon addition of Et2O
  9. customthe product crystallises (1.29 g, mp 81-85° C.)
  10. customTwo recrystallisation from Et2O
  11. customafforded an analytical sample

Sources & evidence

ORD record
ord-68a1606649e0464091ee9c70bc2a4074
Source dataset
uspto-grants-2005_01
Patent number
US06846505B2

Reaction notes

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