Water → HCID 18472450, compound

HRID 2228308Notes

Reaction equation

HRID 2228308 reaction equation
[Br:1][C:2]1[CH:19]=[CH:18][C:5]([N:6]([CH2:8][CH2:9][CH2:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH3:7])=[C:4]([CH:20]=O)[CH:3]=1.C(O[K])(C)(C)C.O>C(O)(C)(C)C>[Br:1][C:2]1[CH:19]=[CH:18][C:5]2[N:6]([CH3:7])[CH2:8][CH2:9][C:10]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[CH:20][C:4]=2[CH:3]=1.[Br:1][C:2]1[CH:19]=[CH:18][C:5]2[N:6]([CH3:7])[CH2:8][CH2:9][C:10]([C:11]([OH:13])=[O:12])=[CH:20][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 962WaterHCID 18472651tert-butyl 4-(4-bromo-2-formyl-N-methylanilino)butyrateHCID 178418922HCID 178418922, compound

Product 2

HCID 184722637-bromo-1-methyl-2,3-dihydro-1H-1-benzoazepine-4-carboxylic acidYield 17%HCID 18472450HCID 18472450, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

In tert-butanol (250 ml) was dissolved tert-butyl 4-(4-bromo-2-formyl-N-methylanilino)butyrate (4.54 g) and tert-butoxy potassium (1.43 g), and the mixture was refluxed for 1 hour and cooled. To the mixture was added water (500 ml), and the mixture was extracted with ethyl acetate (500 ml×2). The aqueous layer was made weakly acidic with 1N hydrochloric acid (about 12.5 ml), and the mixture was extracted with ethyl acetate (500 ml). Both of these organic layer was washed with saturated brine (250 ml) and dried with anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified with silica gel column chromatography (200 g, hexane:ethyl acetate=10:1→1:1) to give tert-butyl 7-bromo-1-methyl-2,3-dihydro-1-benzoazepine-4-carboxylate (3.33 g, 77%) and 7-bromo-1-methyl-2,3-dihydro-1H-1-benzoazepine-4-carboxylic acid (0.60 g, 17%). tert-butyl 7-bromo-1-methyl-2,3-dihydro-1-benzoazepine-4-carboxylate;

Workup

  1. temperaturethe mixture was refluxed for 1 hour
  2. temperaturecooled
  3. extractionthe mixture was extracted with ethyl acetate (500 ml×2)
  4. extractionthe mixture was extracted with ethyl acetate (500 ml)
  5. washBoth of these organic layer was washed with saturated brine (250 ml)
  6. dry with materialdried with anhydrous magnesium sulfate
  7. customThe solvent was evaporated under reduced pressure
  8. customthe residue was purified with silica gel column chromatography (200 g, hexane:ethyl acetate=10:1→1:1)

Sources & evidence

ORD record
ord-74d775024ead4897a68591ed17655caa
Source dataset
uspto-grants-2002_07
Patent number
US06413947B1

Reaction notes

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