beta-Cyclocitral → Isoquinolin-7-yl(2,6,6-trimethylcyclohex-1-enyl)methanol

HRID 530234ノート

反応式

HRID 530234 の反応式
Br[C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][N:8]=[CH:9]2)=[CH:4][CH:3]=1.C([Li])CCC.[CH3:17][C:18]1[CH2:23][CH2:22][CH2:21][C:20]([CH3:25])([CH3:24])[C:19]=1[CH:26]=[O:27]>O1CCCC1>[CH:9]1[C:10]2[C:5](=[CH:4][CH:3]=[C:2]([CH:26]([C:19]3[C:20]([CH3:25])([CH3:24])[CH2:21][CH2:22][CH2:23][C:18]=3[CH3:17])[OH:27])[CH:11]=2)[CH:6]=[CH:7][N:8]=1

参加物

5

反応物 3

HCID 9895beta-CyclocitralHCID 122574417-BromoisoquinolineHCID 178418339Butyllithium

生成物 1

HCID 89602863Isoquinolin-7-yl(2,6,6-trimethylcyclohex-1-enyl)methanol収率 122.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of 7-bromoisoquinoline (958 mg, 4.6 mmol) in tetrahydrofuran (15 mL) was added dropwise into n-butyl lithium (1.6 M in hexane, 2.87 mL, 4.6 mmol) at −78° C. and stirred at −78° C. for 30 minutes. Then 2,6,6-trimethylcyclohex-1-enecarbaldehyde (350 mg, 2.3 mmol) in tetrahydrofuran (2 mL) was added and the reaction was stirred at −78° C. for 1 hour and then allowed to warm to room temperature. The reaction was quenched with saturated aqueous ammonium chloride and the organics were extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give the title compound (794 mg, Yield: 100%). Rf 0.5 (2:1 petroleum ether/ethyl acetate); 1H NMR (400 MHz, CDCl3) δ 9.24 (s, 1H), 8.49 (d, J=5.6 Hz, 1H), 8.04 (s, 1H), 7.78 (s, 2H), 7.64 (d, J=5.6 Hz, 1H), 5.56 (s, 1H), 2.05-2.00 (m, 2H), 1.70-1.56 (m, 4H), 1.35 (s, 3H), 1.24 (s, 3H), 1.16 (s, 3H) ppm; Mass spectrum (ESI +ve) m/z 282 (M+H+).

後処理

  1. stirringthe reaction was stirred at −78° C. for 1 hour
  2. temperatureto warm to room temperature
  3. customThe reaction was quenched with saturated aqueous ammonium chloride
  4. extractionthe organics were extracted with ethyl acetate
  5. washThe organic phase was washed with saturated aqueous sodium bicarbonate and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-3529ede6973243d5b5e40f138e3825fb
出典データセット
uspto-grants-2016_05
特許番号
US09353063B2

反応ノート

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