Sodium Bicarbonate → 2,5,6-Trichloro-3-(N-hydroxyiminomethylidene)-1-(beta-D-ribofuranosyl)indole

HRID 28350

반응식

HRID 28350 반응식
[Cl:1][C:2]1[N:3]([C@@H:15]2[O:21][C@H:20]([CH2:22][OH:23])[C@@H:18]([OH:19])[C@H:16]2[OH:17])[C:4]2[C:9]([C:10]=1[CH:11]=O)=[CH:8][C:7]([Cl:13])=[C:6]([Cl:14])[CH:5]=2.Cl.[O:25]([NH2:27])C.C(=O)(O)[O-].[Na+].CO.O>CO.O.S([O-])([O-])(=O)=S.[Na+].[Na+]>[Cl:1][CH:2]1[C:10](=[C:11]=[N:27][OH:25])[C:9]2[C:4](=[CH:5][C:6]([Cl:14])=[C:7]([Cl:13])[CH:8]=2)[N:3]1[C@@H:15]1[O:21][C@H:20]([CH2:22][OH:23])[C@@H:18]([OH:19])[C@H:16]1[OH:17]

참가 물질

8

반응물 4

HCID 516892Sodium BicarbonateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 3011610FtcriHCID 22242641Methanol--water (1/1)

생성물 1

HCID 865989682,5,6-Trichloro-3-(N-hydroxyiminomethylidene)-1-(beta-D-ribofuranosyl)indole수율 70%

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 24477Sodium Thiosulfate용매

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; Rf 0.2 (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.

후처리

  1. customthe solvent was evaporated
  2. customto provide a pale yellow residue
  3. extractionextracted with EtOAc (2×50 mL)
  4. washThe combined organic extracts were washed with brine (25 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. customto yield a pink residue
  9. customevaporated

출처 및 근거

ORD 기록
ord-770da38fa8834008a9fa6f1e782aad9f
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07419963B2

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