Aluminum(III) Chloride → 7-Bromo-4,4,6-trimethyl-3,4-dihydro-1H-quinoline-2-one

HRID 915185ノート

反応式

HRID 915185 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([NH:9][C:10](=[O:15])[CH:11]=[C:12]([CH3:14])[CH3:13])[CH:5]=[CH:6][C:7]=1[CH3:8].[Cl-].[Al+3].[Cl-].[Cl-]>>[Br:1][C:2]1[CH:3]=[C:4]2[C:5]([C:12]([CH3:13])([CH3:14])[CH2:11][C:10](=[O:15])[NH:9]2)=[CH:6][C:7]=1[CH3:8]

参加物

3

反応物 2

HCID 6451240Aluminum(III) ChlorideHCID 60729710N-(3-Bromo-4-methylphenyl)-3-methyl-2-butenamide

生成物 1

HCID 219664237-Bromo-4,4,6-trimethyl-3,4-dihydro-1H-quinoline-2-one収率 65.7%

反応条件

温度
115 °C

実験手順

To a solution of 3-methyl-but-2-enoic acid (3-bromo-4-methyl-phenyl)-amide (70.0 g, 261 mmol, Example d) at 90° C. was added portion wise, under argon, with vigorous stirring aluminum chloride (52.3 g, 391 mmol) over 1.5 hr. The reaction mixture was stirred for 2 hours at 110-120° C. The reaction mixture was cooled to room temperature and ice-water was carefully added. The solution was extracted with dichloromethane and the organic washed with 2N HCl, water, saturated aqueous NaHCO3, water and brine, dried (Mg2SO4), filtered and evaporated. The residue was crystallized from dichloromethane/hexane to give 46 g of 7-bromo-4,4,6-trimethyl-3,4-dihydro-1H-quinoline-2-one. The mother liquor was further chromatographed on silica gel(20% ethyl acetate in hexane) to give 6.2 g more of product. (75%). 1H NMR (300 MHz; CDCl3): 1.30 (s, 6 H), 2.33 (s, 3 H), 2.46 (s, 2 H), 7.07 (s, 1 H), 7.10 (s, 1 H), 9.87 (br s, 1 H).

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionThe solution was extracted with dichloromethane
  3. washthe organic washed with 2N HCl, water, saturated aqueous NaHCO3, water and brine
  4. dry with materialdried (Mg2SO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was crystallized from dichloromethane/hexane

出典と根拠

ORDレコード
ord-8a86a5a67dc54d78a78f4f0e41046c4d
出典データセット
uspto-grants-2007_09
特許番号
US07265139B2

反応ノート

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