반응 #1951022

ord-65211f8994b246b8adda48f661267ba3

반응 방정식

CO.O
MeOH H2O
O=Cc1c(Cl)n([C@@H]2O[C@H](CO)[C@@H](O)[C@H]2O)c2cc(Cl)c(Cl)cc12
2,5,6-trichloro-3-formyl-1-(β-D-ribofuranosyl)indole
O=Cc1c(Cl)n([C@@H]2O[C@H](CO)[C@@H](O)[C@H]2O)c2cc(Cl)c(Cl)cc12
2,5,6-Trichloro-3-formyl-1-(β-D-ribofuranosyl)indole
CON.Cl
methoxylamine hydrochloride
O=C([O-])O.[Na+]
sodium bicarbonate
OC[C@H]1O[C@@H](N2c3cc(Cl)c(Cl)cc3C(=C=NO)C2Cl)[C@H](O)[C@@H]1O
4.29
수율 70.0%
OC[C@H]1O[C@@H](N2c3cc(Cl)c(Cl)cc3C(=C=NO)C2Cl)[C@H](O)[C@@H]1O
2,5,6-Trichloro-3-(N-hydroxyiminomethylidene)-1-(β-D-ribofuranosyl)indole
수율 70.0%

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타the solvent was evaporated
  2. 2
    기타to provide a pale yellow residue
  3. 3
    추출extracted with EtOAc (2×50 mL)
  4. 4
    세척The combined organic extracts were washed with brine (25 mL)
  5. 5
    건조dried over MgSO4
  6. 6
    여과filtered
  7. 7
    기타evaporated
  8. 8
    기타to yield a pink residue
  9. 9
    기타evaporated

실험 절차

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.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US07625871B2uspto-grants-2009_12