Acetic Acid → 1-(5-O-Acetyl-beta-D-ribofuranosyl)-2,5,6-trichlorobenzimidazole

HRID 2289464Notes

Reaction equation

HRID 2289464 reaction equation
[Cl:1][C:2]1[N:6]([C@@H:7]2[O:19][C@H:18]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[C@@H:13]([O:14]C(=O)C)[C@H:8]2[O:9]C(=O)C)[C:5]2[CH:25]=[C:26]([Cl:30])[C:27]([Cl:29])=[CH:28][C:4]=2[N:3]=1.CC([O-])=O.[K+].CC(O)=O>CO.O>[C:22]([O:21][CH2:20][C@H:18]1[O:19][C@@H:7]([N:6]2[C:5]3[CH:25]=[C:26]([Cl:30])[C:27]([Cl:29])=[CH:28][C:4]=3[N:3]=[C:2]2[Cl:1])[C@H:8]([OH:9])[C@@H:13]1[OH:14])(=[O:24])[CH3:23]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 466019[(2R,3R,4R,5R)-3,4-diacetoxy-5-(2,5,6-trichlorobenzimidazol-1-yl)tetrahydrofuran-2-yl]methyl acetateHCID 517044Potassium Acetate

Product 1

HCID 228765571-(5-O-Acetyl-beta-D-ribofuranosyl)-2,5,6-trichlorobenzimidazole

Reagents, catalysts & solvents 1

HCID 22242641Methanol--water (1/1)Solvent

Procedure

A mixture of 42 (0.48 g, 1.0 mmol) and KOAc (0.49 g, 5.0 mmol) in MeOH/H2O (20 mL/2 mL) was stirred at room temperature for 24 h. AcOH (0.286 mL, 5.0 mmol) was added and stirring was continued at room temperature for 15 min. The reaction mixture was evaporated and the residue was partitioned between H2O/CHCl3 (50 mL/50 mL). The CHCl3 layer was washed with sat. NaCl solution (50 mL), dried (Na2SO4), and evaporated. The residue was chromatographed on a silica column (1.9×20 cm, eluted with CHCl3, 1%, 2%, 4% MeOH/CHCl3). Evaporation of fractions 42-51 (15 mL per fraction) and recrystallization from MeOH gave 0.178 g (2 crops, 45%) of 42a as white crystals. MP: 82-87° C. MS: (EI) m/e 393.9875 (20%, M+ =393.9890). 1H NMR (DMSO-d6): d 8.00, 7.96 (2×s, 2, 7-H and 4-H), 5.91 (d, 1, 1-H, J1'-2' =7.5 Hz), 5.59 (d, 1, 2-OH, J2'-2'OH =6.0 Hz), 5.45 (d, 1, 3-OH, J3'-3'OH =4.5 Hz), 4.44 (dd, 1, 5-H, J5'-4' =4.5 Hz, J5'-5" =12.5 Hz), 4.42 (m, 1, 2'-H, J2'-3' =6.0 Hz), 4.25 (dd, 1, 5"-H, J5'-4" =2.5 Hz), 4.17 (m, 1, 4'-H, J3'-4' =3.5 Hz), 4.11 (m, 1, 3'-H), 2.14 (s, 3, 5'-OAc). 13C NMR (DMSO-d6): d 169.95 (COCH3), 142.03 (C2), 140.92 (C3a), 132.30 (C7a), 125.96, 125.86 (C5 and C6), 120.28 (C4), 113.47 (C7), 89.32 (C1'), 82.63 (C4'), 71.41 (C2'), 69.03 (C3'), 63.35 (C5'). 20.56 (COCH3). Anal. Calcd. for C14H13Cl3N2O5 : C, 42.50; H, 3.31; N, 7.08. Found: C, 42.45; H, 3.20; N, 6.97.

Workup

  1. stirringstirring
  2. waitwas continued at room temperature for 15 min
  3. customThe reaction mixture was evaporated
  4. customthe residue was partitioned between H2O/CHCl3 (50 mL/50 mL)
  5. washThe CHCl3 layer was washed with sat. NaCl solution (50 mL)
  6. dry with materialdried (Na2SO4)
  7. customevaporated
  8. customThe residue was chromatographed on a silica column (1.9×20 cm, eluted with CHCl3, 1%, 2%, 4% MeOH/CHCl3)
  9. customEvaporation of fractions 42-51 (15 mL per fraction) and recrystallization from MeOH

Sources & evidence

ORD record
ord-d4a3e5bd43534d3cb5d5cd710e0e1cc3
Source dataset
uspto-grants-2000_07
Patent number
US06093698

Reaction notes

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