Reaktion #81035

Reaktionsgleichung

methyl 3-hydroxybenzoate

2-adamantanone

Triethylamine

LAH

→

[(3-Hydroxyphenyl)methoxymethylene]adamantane

Lösungsmittel

water

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeA 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel
2. 2
   SonstigeThe apparatus was dried by means of a hot air gun and nitrogen purging
3. 3
   workup.ADDITIONDry THF (40 mL) was added
4. 4
   Temperaturthe flask cooled in an ice bath
5. 5
   SonstigeThe cooling bath was removed
6. 6
   Temperaturrefluxed for 15 min
7. 7
   workup.WAITAfter this period
8. 8
   TemperaturRefluxing
9. 9
   Temperaturafter which the reaction was cooled to room temperature
10. 10
    ExtraktionThe aqueous solution was extracted with 3×50 mL portions of ethyl acetate
11. 11
    WaschenThe combined organic layer was washed with water
12. 12
    Trocknendried over MgSO4
13. 13
    Einengenconcentrated
14. 14
    SonstigeChromatography over silica with 15 % ethyl acetate/hexane gave 240 mg (89%) of la as a white solid

Vorschrift

[(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##

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