Methanol → 2-Chloro-5,6-dinitro-1-beta-D-ribofuranosylbenzimidazole

HRID 724845

Reaction equation

HRID 724845 reaction equation
[Cl:1][C:2]1[N:6]([C@@H:7]2[O:27][C@H:26]([CH2:28][O:29]CC3C=CC=CC=3)[C@@H:17]([O:18]CC3C=CC=CC=3)[C@H:8]2[O:9]CC2C=CC=CC=2)[C:5]2[CH:37]=[C:38]([N+:44]([O-:46])=[O:45])[C:39]([N+:41]([O-:43])=[O:42])=[CH:40][C:4]=2[N:3]=1.B(Cl)(Cl)Cl.CO>C(Cl)Cl.CCOC(C)=O>[Cl:1][C:2]1[N:6]([C@@H:7]2[O:27][C@H:26]([CH2:28][OH:29])[C@@H:17]([OH:18])[C@H:8]2[OH:9])[C:5]2[CH:37]=[C:38]([N+:44]([O-:46])=[O:45])[C:39]([N+:41]([O-:43])=[O:42])=[CH:40][C:4]=2[N:3]=1

Participants

6

Reactant 3

HCID 887MethanolHCID 25135Boron TrichlorideHCID 540450672-Chloro-5,6-dinitro-1-(2,3,5-tri-O-benzyl-beta-D-ribofuranosyl)benzimidazole

Product 1

HCID 228814602-Chloro-5,6-dinitro-1-beta-D-ribofuranosylbenzimidazoleYield 77.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 0.464 g (0.719 mmol) of 60 in 12 mL of CH2Cl2, was added dropwise 8.4 mL of 1M BCl3 at -78° C. The reaction mixture was stirred at -78° C. for 2 hr and then at -40° C. for 2 hr. MeOH (5 mL) was added and stirring was continued at -40° C. for 10 min. The reaction mixture was diluted with EtOAc (75 mL). The EtOAc solution was washed with cold H2O (50 mL), sat. NaHCO3 solution (50 mL), sat. NaCl solution (50 mL), dried (Na2SO4), and evaporated. The residue was coevaporated with MeOH (3×) and then suspended in a small amount of CHCl3 for a few hours. The solid product was filtered to give 0.209 g of 61. This sample was contaminated by a small amount of 2-chloro-5,6-dinitrobenzimidazole. A part of the sample (0.18 g) was purified on a silica column (2.4×10 cm, eluted with pure EtOAc). Evaporation of the appropriate fractions and crystallization by addition of CHCl3 gave 0.084 g of 61 as a white Solid. MP: 132°-135° C. MS: (El) m/e 374.0276 (1%, M+ =374.0265). 1H NMR (DMSO-d6): δ 9.18 (s, 1, 7-H), 8.60 (s, 1, 4-H), 6.00 (d, 1, 1'-H, J1'-2' =7.5 Hz), 5.59 (d, 1, 2'-OH, J2'-2'OH =6.0 Hz), 5.52 (t, 1, 5'-OH, J5'-5'OH =4.5 Hz), 5.38 (d, 1, 3'-OH, J3'-3'OH =4.5 Hz), 4.01 (m 1, 2'-H, J2'-3' =5.5 Hz), 4.16 (m, 1, 3'-H, J3'-4' =2.0 Hz), 4.07 (m, 1, 4'-H, J4'-5' =J4'-5" =2.5 Hz), 3.73 (m, 2, 5'-H and 5"-H, J5'-5" =12.0 Hz). 13C NMR (DMSO-d6): δ 146.55 (C2), 142.63 (C3a), 138.90, 138.60 (C5 and C6), 134.12 (C7a), 116.67 (C4), 111.62 (C7), 89.98 (C1'), 86.91 (C4'), 72.86 (C2'). 69.84 (C3'), 60.85 (C5'). Anal Calcd. for C12H11ClN4O8 : C, 38.47; H, 2.96; N, 14.95. Found: C, 38.46; H, 2.98; N, 14.62.

Workup

  1. waitat -40° C. for 2 hr
  2. stirringstirring
  3. waitwas continued at -40° C. for 10 min
  4. washThe EtOAc solution was washed with cold H2O (50 mL), sat. NaHCO3 solution (50 mL), sat. NaCl solution (50 mL)
  5. dry with materialdried (Na2SO4)
  6. customevaporated
  7. waitsuspended in a small amount of CHCl3 for a few hours
  8. filtrationThe solid product was filtered

Sources & evidence

ORD record
ord-53b36fcbf4a84f5aa9edd320fa1089e0
Source dataset
uspto-grants-1998_01
Patent number
US05705490

Linked notes

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