Hydrochloric Acid → Ethyl 7-bromo-1-formyl-2,3-dihydro-1-benzazepine-4-carboxylate

HRID 566143Notes

Reaction equation

HRID 566143 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]([N:6]([CH2:9][CH2:10][CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:7]=[O:8])=[C:4]([CH:19]=O)[CH:3]=1.CC(C)([O-])C.[K+].O.Cl>C(O)(C)(C)C>[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[N:6]([CH:7]=[O:8])[CH2:9][CH2:10][C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:19][C:4]=2[CH:3]=1.[Br:1][C:2]1[CH:18]=[CH:17][C:5]2[N:6]([CH:7]=[O:8])[CH2:9][CH2:10][C:11]([C:12]([OH:14])=[O:13])=[CH:19][C:4]=2[CH:3]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 21715711ethyl 4-(4-bromo-2,N-diformylanilino)butyrateHCID 23665647Potassium tert-butoxide

Product 2

HCID 18472216Ethyl 7-bromo-1-formyl-2,3-dihydro-1-benzazepine-4-carboxylateYield 22%HCID 184725177-Bromo-1-formyl-2,3-dihydro-1-benzazepine-4-carboxylic acidYield 10%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

In t-butanol (500 ml) were dissolved ethyl 4-(4-bromo-2,N-diformylanilino)butyrate (15.32 g) and potassium t-butoxide (5.53 g), and the mixture was refluxed for 30 minutes. To the mixture were added water (500 ml) and 1N hydrochloric acid (50 ml), and the mixture was extracted with ethyl acetate (1000 ml). The organic layer was washed with saturated brine (200 ml) and dried with magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified with silica gel column chromatography (300 g, hexane:ethyl acetate=4:1→1:1) to give ethyl 7-bromo-1-formyl-2,3-dihydro-1-benzazepine-4-carboxylate (3.13 g, 22%) and 7-bromo-1-formyl-2,3-dihydro-1-benzazepine-4-carboxylic acid (1.39 g, 10%).

Workup

  1. temperaturethe mixture was refluxed for 30 minutes
  2. extractionthe mixture was extracted with ethyl acetate (1000 ml)
  3. washThe organic layer was washed with saturated brine (200 ml)
  4. dry with materialdried with magnesium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customthe residue was purified with silica gel column chromatography (300 g, hexane:ethyl acetate=4:1→1:1)

Sources & evidence

ORD record
ord-bf374e104b1346d0a6c29df6dccf8ee2
Source dataset
uspto-grants-2001_01
Patent number
US06172061B2

Reaction notes

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