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

HRID 1277317Notes

Reaction equation

HRID 1277317 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 ref luxed 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). Theorganiclayerwaswashedwithsaturatedbrine (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. extractionthe mixture was extracted with ethyl acetate (1000 ml)
  2. dry with materialTheorganiclayerwaswashedwithsaturatedbrine (200 ml) and dried with magnesium sulfate
  3. customThe solvent was evaporated under reduced pressure
  4. customthe residue was purified with silica gel column chromatography (300 g, hexane:ethyl acetate=4:1→1:1)

Sources & evidence

ORD record
ord-736d4569bdeb4b27a0646c1e45fe27f9
Source dataset
uspto-grants-2000_12
Patent number
US06166006

Reaction notes

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