Water → 6-Bromo-1,4,4-trimethyl-3,4-dihydroquinolin-2(1H)-one

HRID 395094Notes

Reaction equation

HRID 395094 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]([CH3:15])[C:9](=[O:14])[CH:10]=[C:11]([CH3:13])[CH3:12])=[CH:4][CH:3]=1.[Cl-].[Al+3].[Cl-].[Cl-].O>CCCCCC.ClCCl>[Br:1][C:2]1[CH:3]=[C:4]2[C:5](=[CH:6][CH:7]=1)[N:8]([CH3:15])[C:9](=[O:14])[CH2:10][C:11]2([CH3:12])[CH3:13]

Participants

5

Reactant 3

HCID 962WaterHCID 6451240Aluminum(III) ChlorideHCID 22568913N-(4-Bromophenyl)-N-methyl-3-methyl-2-butenamide2×

Product 1

HCID 225690036-Bromo-1,4,4-trimethyl-3,4-dihydroquinolin-2(1H)-oneYield 26.4%

Reagents, catalysts & solvents 1

HCID 21226440Methylenechloride HexaneSolvent

Procedure

N-(4-bromophenyl)-N-methyl-3-methyl-2-butenamide (Intermediate 54, 6.42 g, 24 mmol) was heated to 130° C. and aluminum chloride (5 g, 37.4 mmol) was added in portions over 0.5 h. The reaction mixture was stirred for 1 hour at the same temperature and then cooled to room temperature. Ice was added cautiously to the solid, followed by 200 mL of iced water. The reaction mixture was then extracted with ether (×2) and dichloromethane (×1) and the combined organic phase was dried over anhydrous magnesium sulfate and evaporated in vacuo to yield a brown solid. The solid was treated with hexane-dichloromethane and filtered to afford 1.7g of product. The mother liquor was evaporated and purified by flash column chromatography on silica gel (230-400 mesh) to afford 2.9g of the title compound as a solid (total 72%).

Workup

  1. additionIce was added cautiously to the solid
  2. extractionThe reaction mixture was then extracted with ether (×2) and dichloromethane (×1)
  3. dry with materialthe combined organic phase was dried over anhydrous magnesium sulfate
  4. customevaporated in vacuo
  5. customto yield a brown solid
  6. filtrationfiltered

Sources & evidence

ORD record
ord-fec723d6b14948adb9af9f2eb5c93956
Source dataset
uspto-grants-2003_08
Patent number
US06603019B2

Reaction notes

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