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

HRID 6347

反応式

HRID 6347 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

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 h and then at -40° C. for 2 h. 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 x) 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): δ9.18 (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): δ146.55 (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.

後処理

  1. waitat -40° C. for 2 h
  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

出典と根拠

ORDレコード
ord-888777079fb14ca3a86b3b24b2f9e593
出典データセット
uspto-grants-1993_09
特許番号
US05248672

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