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

HRID 724398Notes

Reaction equation

HRID 724398 reaction equation
[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

Participants

5

Reactant 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

Product 1

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

Reagents, catalysts & solvents 1

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

Conditions

Temperature
50 °C

Procedure

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, 1 H, J=9.0 Hz), 7.89–7.86 (m, 1 H), 7.63–7.60 (m, 1 H), 7.35–7.31 (m, 2 H), 6.78 (dd, 1 H, J=8.7, 1.8 Hz), 6.75 (s, 1 H), 6.25 (s, 2 H), 5.69 (s, 2 H), 3.93 (br s, 2 H), 3.65–3.55 (m, 4 H), 0.93 (t, 2 H, J=8.1 Hz), 0.85 (t, 2 H, J=8.1 Hz), −0.04 (s, 9 H), −0.15 (s, 9 H). 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.

Workup

  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)

Sources & evidence

ORD record
ord-7b415874af8b441c81227c2c4d5f4103
Source dataset
uspto-grants-2006_11
Patent number
US07141587B2

Reaction notes

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