Ethanol → HCID 54190709, compound

HRID 2379063Notes

Reaction equation

HRID 2379063 reaction equation
[Cl:1][C:2]1[N:6]([C@@H:7]2[O:19][C@H:18]([CH2:20][O:21]C(=O)C)[C@@H:13]([O:14]C(=O)C)[C@H:8]2[O:9]C(=O)C)[C:5]2[CH:25]=[C:26]([Br:31])[C:27]([Br:30])=[C:28]([Br:29])[C:4]=2[N:3]=1.[C-]#N.[K+].CCO>CCOC(C)=O>[Cl:1][C:2]1[N:6]([C@@H:7]2[O:19][C@H:18]([CH2:20][OH:21])[C@@H:13]([OH:14])[C@H:8]2[OH:9])[C:5]2[CH:25]=[C:26]([Br:31])[C:27]([Br:30])=[C:28]([Br:29])[C:4]=2[N:3]=1

Participants

5

Reactant 3

HCID 702EthanolHCID 9032Potassium CyanideHCID 53812447HCID 53812447, compound

Product 1

HCID 54190709HCID 54190709, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 0.430 g (0.664 mmol) of the blocked nucleoside (102) and 0.216 g (3.317 mmol) of KCN in 13 of mL of 70% EtOH was stirred at room temperature for 6 hr. The reaction mixture was diluted with 75 mL of EtOAc. The EtOAc solution was washed with H2O (50 mL), sat. NaCl solution (50 mL), dried (Na2SO4), and evaporated. The residue was chromatographed on a silica column (1.9×15 cm, eluted successively with CHCl3, 1%, 2%, 3% MeOH/CHCl3). Evaporation of fractions 43-60 (10 mL per fraction) and recrystallization from MeOH/MeCN gave 0.157 g (2 crops, 44%) of 103 as white crystals. MP: 168°-170° C. MS: (FAB) m/e 518.7947 (28%, MH+ =518.7957). 1H NMR (DMSO-d6): d 8.76 (s, 1, 7-H), 5.87 (d, 1, 1'-H, J1'-2' =8.0 Hz), 5.51 d, 1, 2'-OH, J2'-2'OH =6.0 Hz), 5.42 (t, 1, 5'-OH, J5'-5'OH =4.5 Hz), 5.30 (d, 1, 3'-OH, J3'-3'OH =4.5 Hz), 4.37 (m, 1, 2'-H, J2'-3' =5.5 Hz), 4.14 (m, 1, 3'-H, J3'-4' =2.0 Hz), 4.02 (m, 1, 4'-H, J4'-5' =J4'-5" =2.5 Hz), 3.71 (m, 2, 5'-H and 5"-H, J5'-5" =12.0 Ha). 13C NMR (DMSO-d6): d 142.32 (C2), 140.92 (C3a), 132.50 (C7a), 120.62 (C5), 118.44 (C6), 117.10 (C7), 115.34 (C4), 89.58 (C1'), 86.50 (C4'), 71.93 (C2'), 69.63 (C3'), 60.89 (C5'). Anal. Calcd. for C12H10Br3ClN2O4 0.3 MeCN: C, 28.36; H, 2.06; N, 6.04. Found: C, 28.25; H, 1.84; N, 5.90. (the Content of 0.3 MeCN was also indicated by 1H NMR.)

Workup

  1. washThe EtOAc solution was washed with H2O (50 mL), sat. NaCl solution (50 mL)
  2. dry with materialdried (Na2SO4)
  3. customevaporated
  4. customThe residue was chromatographed on a silica column (1.9×15 cm
  5. washeluted successively with CHCl3, 1%, 2%, 3% MeOH/CHCl3)
  6. customEvaporation of fractions 43-60 (10 mL per fraction) and recrystallization from MeOH/MeCN

Sources & evidence

ORD record
ord-b58175b10fea45a4b1ffb7942e115431
Source dataset
uspto-grants-1994_11
Patent number
US05360795

Reaction notes

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