反应详情

Under a N2 atmosphere was added 26.17 ml (0.20 ml) of diethylaminosulfur trifluoride (DAST) to 24 ml. of dry dichloromethane which was cooled to -78° C. To this solution was added drop-wise a dichloromethane solution (10 ml) of methyl 3-hydroxyadamantane-1-carboxylate (42.0 g, 0.20 mol). The suspension was allowed to warm to ambient temperature and stirred for 1 hour. To the resultant solution was added water (500 ml). The organic layer was separated, washed with brine, dried over magnesium sulfate, filtered and concentrated in vacuo to afford 41.6 g (98%) of crude product, mp <34° C, which slowly crystallized. 1H NMR (CDCl3) 1.70-1.80 (m-6H), 2.20-2.35(m-3H), 2.50-2.60 (m-6H), 7.00-7.70 (m-5H) 13C NMR (CDCl3) 30.84 (10.11), 34.79 (0.91), 37.56, 41.81 (17.73), 43.70 (20.15), 44.86 (10.16), 51.86, 92.13 (184.14). Under a N2 atmosphere was added to crude ester (41.6 g, 0.196 mol), 100 ml of methanol, 75 ml of tetrahydrofuran (THF), 50 ml of water followed by 16.0 g (0.40 mol) of NaOH pellets. The solution was allowed to stir overnight. The organic solvents were removed under reduced pressure, water (200 ml) was added and the solution was acidified to a pH of 1.0 with 6N HCl. The resultant solids were filtered, washed with water and air dried to afford 37.0 g (95%) of 3-fluoroadamantane-1-carboxylic acid (mp 154-156° C). An analytical sample of the title compound was obtained following an EtOAc/hexane recrystallization. Crystals from the recrystallization were suitable for X-ray analysis. Anal. Calc'd for C11H15O2F: C, 66.65; H, 7.63; F, 9.58; Found: C, 66.44; H, 7.72; F, 9.22.

1. customThe organic layer was separated
2. washwashed with brine
3. dry with materialdried over magnesium sulfate
4. filtrationfiltered
5. concentrationconcentrated in vacuo
6. customto afford 41.6 g (98%) of crude product, mp <34° C, which
7. customslowly crystallized
8. stirringto stir overnight
9. customThe organic solvents were removed under reduced pressure, water (200 ml)
10. additionwas added
11. filtrationThe resultant solids were filtered
12. washwashed with water and air
13. customdried