Triethylamine → [(3-Hydroxyphenyl)methoxymethylene]adamantane

HRID 52757

Reaktionsgleichung

Reaktionsgleichung von HRID 52757
[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N(CC)CC)C.[OH:14][C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][CH:24]=1)[C:18]([O:20][CH3:21])=O.[CH:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[C:26]1=O)[CH2:32]2>C1COCC1.O>[OH:14][C:15]1[CH:16]=[C:17]([CH2:18][O:20][CH:21]=[C:26]2[CH:27]3[CH2:33][CH:31]4[CH2:30][CH:29]([CH2:34][CH:25]2[CH2:32]4)[CH2:28]3)[CH:22]=[CH:23][CH:24]=1

Komponenten

7

Edukt 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 88068Methyl 3-HydroxybenzoateHCID 21226445Aluminium lithium hydride

Produkt 1

HCID 53971236[(3-Hydroxyphenyl)methoxymethylene]adamantane

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

[(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##

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-789c59a50330475e8db6c922b48c1aa0
Quelldatensatz
uspto-grants-1997_04
Patentnummer
US05616729

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