Tetrabutylammonium Fluoride → 1-ethyl-3-(4-hydroxyphenyl)-7-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide

HRID 1044309Notes

Reaction equation

HRID 1044309 reaction equation
[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[CH2:19]([N:21]1[C:29]2[C:24](=[N+:25]([O-:31])[CH:26]=[CH:27][C:28]=2[CH3:30])[N:23]([C:32]2[CH:37]=[CH:36][C:35]([O:38][Si](C(C)C)(C(C)C)C(C)C)=[CH:34][CH:33]=2)[C:22]1=[O:49])[CH3:20].[Cl-].[Cl-].[Ca+2]>C1COCC1>[CH2:19]([N:21]1[C:29]2[C:24](=[N+:25]([O-:31])[CH:26]=[CH:27][C:28]=2[CH3:30])[N:23]([C:32]2[CH:33]=[CH:34][C:35]([OH:38])=[CH:36][CH:37]=2)[C:22]1=[O:49])[CH3:20]

Participants

5

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 5284359Calcium ChlorideHCID 585774851-ethyl-7-methyl-3-(4-{[tris(1-methylethyl)silyl]oxy}phenyl)-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide

Product 1

HCID 679932051-ethyl-3-(4-hydroxyphenyl)-7-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxideYield 105.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Tetrabutylammonium fluoride (0.566 mL) was added to a solution of 1-ethyl-7-methyl-3-(4-{[tris(1-methylethyl)silyl]oxy}phenyl)-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide (250 mg) in THF (5 mL) at room temperature. The mixture was stirred at room temperature under a dry atmosphere (CaCl2 tube) for 30 min. The reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (silica gel, eluted with 0%-100% EtOAc in hexane) to give 1-ethyl-3-(4-hydroxyphenyl)-7-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide (170 mg) as a colorless solid. 3-Methyl-2-(methylsulfonyl)-3H-imidazo[4,5-b]pyridine (126 mg) was added to a solution of 1-ethyl-3-(4-hydroxyphenyl)-7-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide (170 mg) and NaH (23.83 mg) in DMA (1 mL) at room temperature. The mixture was stirred at 150° C. under a dry atmosphere (CaCl2 tube) for 30 min. The reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (NH silica gel, eluted with 50%-100% EtOAc in hexane) to give 1-ethyl-7-methyl-3-{4-[(3-methyl-3H-imidazo[4,5-b]pyridin-2-yl)oxy]phenyl}-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one 4-oxide as colorless crystals.

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. customThe residue was purified by column chromatography (silica gel, eluted with 0%-100% EtOAc in hexane)

Sources & evidence

ORD record
ord-1eacc584fc1246fd958a6d7a3595b4c8
Source dataset
uspto-grants-2013_10
Patent number
US08563575B2

Reaction notes

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