Water → (S)-6-chloro-2-(alpha-methylbenzyl) 3,4-dihydronaphthalene

HRID 726695

反応式

HRID 726695 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH2:8][C:7](=O)[CH2:6][CH2:5]2.[CH3:13][C@H:14](N)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.O>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([C@H:14]([CH3:13])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:6][CH2:5]2

参加物

5

反応物 3

HCID 962WaterHCID 758181-Phenethylamine, (-)-HCID 44561396-Chloro-2-tetralone

生成物 1

HCID 53932928(S)-6-chloro-2-(alpha-methylbenzyl) 3,4-dihydronaphthalene

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

To a stirred solution of 6-chloro-2-tetralone (1.0 equiv., 100.0 mmol., 18.06 g) in toluene (300 ml) was added (S)-(-)-α-methylbenzylamine (1.0 equiv., 100.0 mmol., 12.9 ml). The mixture was heated at reflux for 3 hrs with the azeotropic removal of water (Dean-Stark). The cooled reaction mixture was concentrated in vacuo to give the enamine, (S)-6-chloro-2-(α-methylbenzyl)-3,4-dihydronaphthalene, as a purple oil. The oil was taken up in chloroform (150 ml) and saturated aqueous sodium bicarbonate was added (150 ml). The vigorously stirred mixture was treated with acryloyl chloride (1.05 equiv., 105.0 mmol., 8.5 ml) dropwise over 5 min. The reaction mixture was allowed to stir at ambient temperature for 20 min., then diluted with chloroform and the layers separated. The aqueous layer was extracted with chloroform (1×). The combined organics were washed with brine (1×), dried (Na2 SO4), and concentrated in vacuo to give 37.9 g of a black oil. The crude oil was subjected to HPLC on silica gel (gradient elution with hexanes increasing to 25% ethyl acetate/hexanes) to give 19.03 g of a purple oil which was further purified by flash chromatography on silica gel (elution with 20% ethyl acetate/hexanes) to give 17.96 g, 53% yield of the title compound as a brown glass which was homogeneous by HPLC analysis (reverse phase, C18, mobile phase: 60% acetonitrile/0.5% aqueous ammonium acetate buffer), thin layer chromatography (Silica gel, Rf =~0.5, developed with 40% ethyl acetate/hexanes), and 300 MHz 1H NMR analysis. FDMS: m/e=337. α[D]589 =-24.75 (c=1.0, CHCl3).

後処理

  1. temperatureThe mixture was heated
  2. customThe cooled reaction mixture
  3. concentrationwas concentrated in vacuo

出典と根拠

ORDレコード
ord-dc07ecb4273a4f5ebc767a7d97fcc4a7
出典データセット
uspto-grants-1998_01
特許番号
US05710163

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