反応 #56629

反応方程式

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

→

4.30

収率 41.0%

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

収率 41.0%

溶媒

sodium thiosulfate

MeOH

water

反応条件

後処理

1. 1
   その他the solvent was evaporated
2. 2
   その他to provide a pale yellow residue
3. 3
   抽出extracted with EtOAc (2×25 mL)
4. 4
   洗浄The combined organic extracts were washed with brine (10 mL)
5. 5
   乾燥dried over MgSO4
6. 6
   ろ過filtered
7. 7
   その他evaporated
8. 8
   その他to yield a yellow residue
9. 9
   その他evaporated
10. 10
    その他to yield a white powder
11. 11
    その他The powder was recrystallized from Et2O

実験手順

To a solution of 2,5,6-trichloro-3-formyl-1-(β-D-ribofuranosyl)indole (4.3, 103 mg, 0.27 mmol) in MeOH (5 mL) was added a solution of methoxylamine hydrochloride (27 mg, 0.32 mmol) and sodium bicarbonate (22 mg, 0.26 mmol) in water (1.0 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 10 mL of 5% aqueous sodium thiosulfate and extracted with EtOAc (2×25 mL). The combined organic extracts were washed with brine (10 mL), dried over MgSO4, filtered and evaporated to yield a yellow residue. The residue was subjected to column chromatography (40×350 mm) on C18 reverse-phase silica gel with 80% MeOH/H2O. The appropriate UV-active fractions were pooled and evaporated to yield a white powder. The powder was recrystallized from Et2O to yield 45 mg (41%) of 4.30 as a white crystalline solid: mp 197-198 C; Rf 0.4 (10% MeOH/CHCl3); 1H NMR (500 MHz, DMSO-d6) δ 8.57 (s, 1H), 8.27 (s, 1H), 8.17 (s, 1H), 5.93 (d, 1H), 5.42 (d, 1H, D2O exch.), 5.40 (t, 1H, D2O exch.), 5.27 (d, 1H, D2O exch.), 4.42 (q, 1H), 4.14 (m, 1H), 4.00 (d, 1H), 3.96 (s, 3H), 3.71 (m, 2H). 13C NMR (125 MHz, DMSO-d6) δ 141.84, 133.04, 129.74, 126.09, 125.03, 123.82, 121.70, 115.46, 105.59, 88.85, 86.13, 71.43, 69.65, 61.84, 61.09. HRMS (EI) m/z calcd. for C15H15Cl3N2O5 408.0047, found 408.0047. Anal calcd for C15H15Cl3N2O5: C, 43.98; H, 3.69; N, 6.84. Found: C, 43.79; H, 3.68; N, 6.61.

出典