Stannous Chloride → 6-amino-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole

HRID 1816814노트

반응식

HRID 1816814 반응식
[Sn](Cl)Cl.[N+:4]([C:7]1[CH:15]=[C:14]2[C:10]([C:11]([C:24]3[N:28]([CH2:29][O:30][CH2:31][CH2:32][Si:33]([CH3:36])([CH3:35])[CH3:34])[C:27]4[CH:37]=[CH:38][CH:39]=[CH:40][C:26]=4[N:25]=3)=[N:12][N:13]2[CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])=[CH:9][CH:8]=1)([O-])=O.C(=O)(O)[O-].[Na+]>CN(C=O)C.O>[NH2:4][C:7]1[CH:15]=[C:14]2[C:10]([C:11]([C:24]3[N:28]([CH2:29][O:30][CH2:31][CH2:32][Si:33]([CH3:35])([CH3:34])[CH3:36])[C:27]4[CH:37]=[CH:38][CH:39]=[CH:40][C:26]=4[N:25]=3)=[N:12][N:13]2[CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])=[CH:9][CH:8]=1

참가 물질

5

반응물 3

HCID 24479Stannous ChlorideHCID 516892Sodium BicarbonateHCID 229806876-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole

생성물 1

HCID 229806486-amino-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole수율 89.2%

시약·촉매·용매 1

HCID 21962138N,N-Dimethylformamide--water (1/1)용매

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온도
50 °C

실험 절차

Tin(II) chloride (12.0 g, 63.3 mmol) was added to a solution of 6-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole (7.18 g, 13.3 mmol) in DMF/H2O (160 mL/10 mL), and the reaction stirred at 50° C. for 2.5 h. The reaction was cooled to 0° C., and saturated sodium bicarbonate was added slowly, with mixing, until all frothing from quenching had subsided. The material was concentrated in vacuo and taken up in ether (100 mL). Insoluble material was removed by filtration and rinsed with ether (50 mL). The filtrate was washed with brine (50 mL), dried (Na2SO4), and concentrated in vacuo. Purification by silica gel chromatography (25% ethyl acetate/hexane) gave 6.05 g (89%) of 6-amino-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole as a faintly yellow waxy solid. 1H NMR (300 MHz, CDCl3) δ 8.40 (d, 1H, J=9.0 Hz), 7.89-7.86 (m, 1H), 7.63-7.60 (m, 1H), 7.35-7.31 (m, 2H), 6.78 (dd, 1H, J=8.7, 1.8 Hz), 6.75 (s, 1H), 6.25 (s, 2H), 5.69 (s, 2H), 3.93 (br s, 2H), 3.65-355 (m, 4H), 0.93 (t, 2H, J=8.1 Hz), 0.85 (t, 2H, J=8.1 Hz), −0.04 (s, 9H), −0.15 (s, 9H). Anal. (C26H39N5O2Si2) C, H, N. Calculated: C, 61.26; H, 7.71; N. 13.74. Found: C, 61.18; H, 7.65; N, 13.82.

후처리

  1. temperatureThe reaction was cooled to 0° C.
  2. additionwith mixing, until all frothing
  3. customfrom quenching
  4. concentrationThe material was concentrated in vacuo
  5. customInsoluble material was removed by filtration
  6. washrinsed with ether (50 mL)
  7. washThe filtrate was washed with brine (50 mL)
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated in vacuo
  10. customPurification by silica gel chromatography (25% ethyl acetate/hexane)

출처 및 근거

ORD 기록
ord-f47b0e3f574047b1be2c36cecf3500aa
출처 데이터셋
uspto-grants-2005_04
특허 번호
US06884890B2

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