N-(5-fluoro-3-nitropyridin-2-yl)-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)formamide → 6-((6-fluoro-3H-imidazo[4,5-b]pyridin-3-yl)methyl)-2-(methylthio)benzo[d]thiazole

HRID 1848190Notes

Reaction equation

HRID 1848190 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:23]([O-])=O)[C:5]([N:8]([CH2:11][C:12]2[CH:22]=[CH:21][C:15]3[N:16]=[C:17]([S:19][CH3:20])[S:18][C:14]=3[CH:13]=2)[CH:9]=O)=[N:6][CH:7]=1>CCO.CC(O)=O.[Fe]>[F:1][C:2]1[CH:3]=[C:4]2[N:23]=[CH:9][N:8]([CH2:11][C:12]3[CH:22]=[CH:21][C:15]4[N:16]=[C:17]([S:19][CH3:20])[S:18][C:14]=4[CH:13]=3)[C:5]2=[N:6][CH:7]=1

Participants

5

Reactant 1

HCID 86681158N-(5-fluoro-3-nitropyridin-2-yl)-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)formamide

Product 1

HCID 866810516-((6-fluoro-3H-imidazo[4,5-b]pyridin-3-yl)methyl)-2-(methylthio)benzo[d]thiazoleYield 28%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolvent

Procedure

A stirred mixture of N-(5-fluoro-3-nitropyridin-2-yl)-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)formamide and iron powder (6 g, 108 mmol) in EtOH (70 mL) and HOAc (30 mL) was heated at reflux for 2 h. The mixture was cooled to rt, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel flash chromatography, eluting with a gradient of 100% hexanes to 100% EtOAc, to afford 6-((6-fluoro-3H-imidazo[4,5-b]pyridin-3-yl)methyl)-2-(methylthio)benzo[d]thiazole (1 g, 28%) as a white foam. 1H NMR (500 MHz, DMSO-d6) δ 8.72 (s, 1H), 8.40 (t, J=2.0 Hz, 1H), 8.09 (dd, J=2.6, 9.5 Hz, 1H), 7.99 (s, 1H), 7.80 (d, J=8.4 Hz, 1H), 7.45 (dd, J=1.5, 8.4 Hz, 1H), 5.61 (s, 2H), 2.76 (s, 3H); LCMS (ESI) m/z 331 (M+H)+.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 2 h
  3. filtrationfiltered
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by silica gel flash chromatography
  6. washeluting with a gradient of 100% hexanes to 100% EtOAc

Sources & evidence

ORD record
ord-06940adfa5a94f2dac3bb7f7e803d336
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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