Réaction #1951022

Équation de réaction

MeOH H2O

2,5,6-trichloro-3-formyl-1-(β-D-ribofuranosyl)indole

2,5,6-Trichloro-3-formyl-1-(β-D-ribofuranosyl)indole

methoxylamine hydrochloride

sodium bicarbonate

→

4.29

Rendement 70.0%

2,5,6-Trichloro-3-(N-hydroxyiminomethylidene)-1-(β-D-ribofuranosyl)indole

Rendement 70.0%

Solvants

sodium thiosulfate

MeOH

water

Conditions de réaction

Traitement

1. 1
   Autrethe solvent was evaporated
2. 2
   Autreto provide a pale yellow residue
3. 3
   Extractionextracted with EtOAc (2×50 mL)
4. 4
   LavageThe combined organic extracts were washed with brine (25 mL)
5. 5
   Séchagedried over MgSO4
6. 6
   Filtrationfiltered
7. 7
   Autreevaporated
8. 8
   Autreto yield a pink residue
9. 9
   Autreevaporated

Mode opératoire

To a solution of 2,5,6-trichloro-3-formyl-1-(β-D-ribofuranosyl)indole (4.3, 170 mg, 0.45 mmol) in MeOH (10 mL) was added a solution of methoxylamine hydrochloride (39 mg, 0.56 mmol) and sodium bicarbonate (49 mg, 0.48 mmol) in water (2.0 mL). The resulting mixture was stirred at room temperature for 16 h, then the solvent was evaporated to provide a pale yellow residue. The residue was suspended in 20 mL of 5% aqueous sodium thiosulfate and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (25 mL), dried over MgSO4, filtered and evaporated to yield a pink residue. The residue was subjected to column chromatography (40×350 mm) on C18 reverse-phase silica gel with 75% MeOH/H2O. The appropriate UV-active fractions were pooled and evaporated to yield 124 mg (70%) of 4.29 as a white powder. A portion was recrystallized from Et2O/hexane to yield a white crystalline solid: mp 208-209 C; Rf0.2 (10% MeOH/CHCl3); 1H NMR (500 MHz, DMSO-d6) δ 11.31 (s, 1H), 8.54 (s, 1H), 8.22 (s, 1H), 8.19 (s, 1H), 5.93 (d, 1H), 5.37 (m, 2H, D2O exch.), 5.25 (m, 1H, D2O exch.), 4.43 (m, 1H), 4.16 (m, 1H), 3.99 (m, 1H), 3.73 (m, 2H). 13C NMR (125 MHz, DMSO-d6) δ 141.30, 133.03, 128.48, 125.85, 124.73, 124.05, 121.76, 115.31, 106.70, 88.81, 86.02, 71.39, 69.65, 61.11. HRMS (EI) m/z calcd. for C14H13Cl3N2O5 393.9890, found 393.9892. Anal calcd for C14H13Cl3N2O5.½Et2O: C, 44.41; H, 4.19; N, 6.47. Found: C, 44.16; H, 4.18; N, 6.48.

Source