Ethylene Glycol → (1-Allylcyclohexyl)benzene

HRID 71245ノート

反応式

HRID 71245 の反応式
[CH2:1]([C:4]1([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:9][CH2:8][CH2:7][CH2:6][C:5]1=O)[CH:2]=[CH2:3].C(O)CO.NN.[OH-].[K+]>>[CH2:1]([C:4]1([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:9][CH2:8][CH2:7][CH2:6][CH2:5]1)[CH:2]=[CH2:3]

参加物

5

反応物 4

HCID 174Ethylene GlycolHCID 9321HydrazineHCID 14797Potassium HydroxideHCID 130232142-Allyl-2-phenylcyclohexanone

生成物 1

HCID 86688202(1-Allylcyclohexyl)benzene収率 44.8%

反応条件

温度
100 °C

実験手順

To a solution of 2-allyl-2-phenylcyclohexanone (1.97 g, 9.19 mmol) in ethylene glycol (8 mL, 143 mmol) were added hydrazine (0.8 mL, 25.5 mmol) and potassium hydroxide (1.547 g, 27.6 mmol), and the mixture was stirred at 100° C. for 1 hr and refluxed in a 180° C. oil bath for 2.5 hrs. TLC showed that the hydrazone formation nearly complete. Then the excess hydrazine and water were distilled out in a 200° C. oil bath, and it was continued to heat at the same temperature for 4 hrs. After cooling to room temp it was added to ether and washed with water and brine. The combined aqueous layers were back-extracted with ether (2×) and combined. Dried over Na2SO4 and evaporated to give an oily residue. It was purified by Combiflash (80 g silica gel) eluting with hexane followed by 5:95 EtOAc-hexane to give product (825 mg). 1H NMR (400 MHz, CCl3D) δ ppm 7.31 (4H, d, J=4.39 Hz), 7.17 (1H, dq, J=4.39, 4.25 Hz), 5.32-5.45 (1H, m), 4.89 (1H, s), 4.83-4.87 (1H, m), 2.26 (2H, d, J=7.47 Hz), 2.07 (2H, dd, J=13.84, 6.59 Hz), 1.33-1.63 (8H, m).

後処理

  1. temperaturerefluxed in a 180° C. oil bath for 2.5 hrs
  2. distillationThen the excess hydrazine and water were distilled out in a 200° C. oil bath
  3. temperatureto heat at the same temperature for 4 hrs
  4. temperatureAfter cooling to room temp it
  5. additionwas added to ether
  6. washwashed with water and brine
  7. extractionThe combined aqueous layers were back-extracted with ether (2×)
  8. dry with materialDried over Na2SO4
  9. customevaporated
  10. customto give an oily residue
  11. customIt was purified by Combiflash (80 g silica gel)
  12. washeluting with hexane

出典と根拠

ORDレコード
ord-37cd9b4ce07a45d9aa86f3854b8f6044
出典データセット
uspto-grants-2014_09
特許番号
US08822510B2

反応ノート

読み込み中…