Potassium Hydroxide → 1-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

HRID 1015504ノート

反応式

HRID 1015504 の反応式
[CH3:1][C:2]1([OH:18])[CH:9]2[CH2:10][CH:5]3[CH2:6][C:7]([C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=4)([CH2:11][CH:3]1[CH2:4]3)[CH2:8]2.[O-]Cl.[Na+].[OH-].[K+]>CC(O)=O.C1COCC1.[N+](CCCC)(CCCC)(CCCC)CCCC.[I-]>[C:12]1([C:7]23[CH2:6][CH:5]4[CH2:10][CH:9]([CH2:8]2)[C:3]([C:2](=[O:18])[CH3:1])([CH2:4]4)[CH2:11]3)[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

参加物

7

反応物 3

HCID 14797Potassium HydroxideHCID 120380532-Methyl-5-phenyladamantan-2-olHCID 23665760Sodium Hypochlorite

生成物 1

HCID 593749561-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone収率 251.9%

試薬・触媒・溶媒 3

HCID 67553Tetrabutylammonium Iodide触媒HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

2-Methyl-5-phenyl-adamantan-2-ol (20 g, 82.6 mmol) obtained in step III, (86 g, 355.4 mmol), dissolved in a mixture of AcOH (76.3 mL) and THF (360 mL) was added dropwise via an addition funnel to the ice bath cooled NaOCl (4%, 3.5 L) solution over a period of 15 minutes. Solid n-Bu4NI (13.1 g, 35.6 mmol) was added and the reaction mixture was stirred for 1.5 h. The two layers were separated, the aqueous layer was extracted with diisopropylether and the combined organic layer was washed with water and brine, dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was dissolved in methanol (165 mL), KOH (39.8 g, 300 mmol) was added, and the mixture was refluxed for 1 h. The solvent was evaporated under reduced pressure and the crude product was purified by column chromatography to yield compound 1-(1-phenyltricyclo[3.3.1.03,7]non-3-yl)ethanone (50.0 g) in 59% yield as viscous liquid. m/z (M+1) 241; IR (cm−1): 2924, 2867, 1697, 1445, 1356, 1223, 757, 699. 1H NMR (CDCl3) 300 MHz δ 7.38-7.19 (m, 5H), 2.86-2.80 (m, 1H), 2.59-2.50 (m, 1H), 2.32-2.25 (m, 1H), 2.23 (s, 3H), 2.10-1.99 (m, 4H), 1.90-1.79 (m, 4H), 1.78-1.71 (m, 1H). 13C NMR (CDCl3) 75 MHz δ, 211.7, 146.7, 128.2 (2C), 125.7 (2C), 124.7, 61.9, 50.2, 49.0, 47.9, 45.7, 42.4, 42.3, 37.6, 26.4.

後処理

  1. customThe two layers were separated
  2. extractionthe aqueous layer was extracted with diisopropylether
  3. washthe combined organic layer was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. customthe solvent was removed under reduced pressure
  6. dissolutionThe residue was dissolved in methanol (165 mL)
  7. temperaturethe mixture was refluxed for 1 h
  8. customThe solvent was evaporated under reduced pressure
  9. customthe crude product was purified by column chromatography

出典と根拠

ORDレコード
ord-9b72e08ef2a041c299b52221c36e857e
出典データセット
uspto-grants-2011_07
特許番号
US07985759B2

反応ノート

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