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

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.

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

ORD record

ord-9b72e08ef2a041c299b52221c36e857e

Source dataset

uspto-grants-2011_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07985759B2