反应详情

[(3-Hydroxyphenyl)methoxymethylene]adamantane (1a) was prepared as described in my previous application Ser. No. 224,681, filed Jul. 27, 1988. A 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel, and nitrogen line. The apparatus was dried by means of a hot air gun and nitrogen purging. Dry THF (40 mL) was added and the flask cooled in an ice bath. TiCl3 (1.5 g, 10 mmol) was added rapidly followed by LAH (0.19 g, 5 mmol) in portions with stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (0.7 mL, 5 mmol) was added to the stirred suspension and refluxed for 15 min. After this period, a solution of methyl 3-hydroxybenzoate (152 mg, 1 mmol) and 2-adamantanone (300 mg, 2 mmol) in 20 mL of dry THF was added dropwise to the refluxing mixture over 15 min. Refluxing was continued for an additional 15 min after which the reaction was cooled to room temperature and diluted with 100 mL of distilled water. The aqueous solution was extracted with 3×50 mL portions of ethyl acetate. The combined organic layer was washed with water, dried over MgSO4, and concentrated. Chromatography over silica with 15 % ethyl acetate/hexane gave 240 mg (89%) of la as a white solid: mp 133°-4° C.; 1H NMR (CDCl3) δ 1.64-1.96 (m, 12H), 2.65 (s, 1H), 3.24 (s, 1H), 3.32 (s, 3H), 5.25 (s, 1H, OH exchange with D2O), 6.70-7.30 (m, 4H); 13C NMR (CDCl3) δ 28.45, 30.36, 32.36, 37.30, 39.18, 39.33, 57.82, 114.60, 116.16, 122.19, 129.24, 137.24, 155.62; MS m/e (rel intensity)271 (20. M+1), 270 (100, M), 253 (7.3), 213 (35.1), 121 (41.7), 93 (9.4); Exact mass calcd 270.1619, found 270.1616. ##STR22##

1. customA 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel
2. customThe apparatus was dried by means of a hot air gun and nitrogen purging
3. additionDry THF (40 mL) was added
4. temperaturethe flask cooled in an ice bath
5. customThe cooling bath was removed
6. temperaturerefluxed for 15 min
7. waitAfter this period
8. temperatureRefluxing
9. temperatureafter which the reaction was cooled to room temperature
10. extractionThe aqueous solution was extracted with 3×50 mL portions of ethyl acetate
11. washThe combined organic layer was washed with water
12. dry with materialdried over MgSO4
13. concentrationconcentrated
14. customChromatography over silica with 15 % ethyl acetate/hexane gave 240 mg (89%) of la as a white solid