Adamantanone → HCID 15158793, Verbindung

HRID 964821Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 964821
[Al].[Li].[Si:3]([O:10][C:11]1[CH:12]=[C:13]([CH:20]=[CH:21][CH:22]=1)[C:14]([O:16][CH2:17][CH2:18][Cl:19])=O)([C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:5])[CH3:4].[CH:23]12[CH2:32][CH:27]3[CH2:28][CH:29]([CH2:31][CH:25]([CH2:26]3)[C:24]1=O)[CH2:30]2>[Cl-].[Cl-].[Cl-].[Ti+3].C(OCC)(=O)C.CCCCCC>[Si:3]([O:10][C:11]1[CH:12]=[C:13]([C:14](=[C:24]2[CH:25]3[CH2:31][CH:29]4[CH2:28][CH:27]([CH2:32][CH:23]2[CH2:30]4)[CH2:26]3)[O:16][CH2:17][CH2:18][Cl:19])[CH:20]=[CH:21][CH:22]=1)([C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:5])[CH3:4]

Komponenten

6

Edukt 3

HCID 64151AdamantanoneHCID 151587922-Chloroethyl 3-t-butyldimethylsilyloxybenzoateHCID 16211445Aluminum;lithium

Produkt 1

HCID 15158793HCID 15158793, VerbindungAusbeute 77 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 10313229titanium(III) trichlorideKatalysatorHCID 21226206Ethyl acetate hexaneLösungsmittel

Versuchsvorschrift

##STR34## A 100 mL three-necked flask fitted with a reflux condenser, was dried by means of a hot air gun and nitrogen purging. This was charged with dry THF 200 mL and cooled in an ice-bath. Titanium trichloride (24.5 g, 0.16 mol) followed by lithium aluminum hyride (3.0 g, 0.08 mol) was added in small portions with vigorous stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (15 mL) was added dropwise and the reaction mixture was refluxed for 1 hour. A solution of 2-chloroethyl 3-(tert-butyldimethylsilyloxy)benzoate (5.0 g, 0.015 mol) and adamantanone (7.1 g, 0.05 mol) was added dropwise to the refluxing mixture over a 1 hour period. TLC analysis (ethyl acetate/hexane, 10:90) after 1 hour of refluxing showed conversion to a new material. The reaction mixture was cooled, extracted with hexane. After the evaporation of solvent, the crude material was chromatographed using (ethyl acetate/hexane, 3:97) to give 5.0 g (74%) of alkene 7 as a white oil: 1H NMR (CDCl3) δ 0.194 (s, 6H), 0.982 (s, 9H), 1.78-1.98 (m, 12H), 2.65 (bs, 1H), 3.34 (bs, 1H), 3.55 (t, 2H, J=5.7 Hz), 3.66 (t, 2H, J=5.7 Hz), 6.85-7.29 (m, 4H); 13C NMR (CDCp3) δ -4.46, 18.21, 25.66, 28.28, 30.20, 32.39, 38.94, 39.20, 42.61, 68.95, 119.62, 121.04, 122.50, 129.09, 132.78, 136.40, 141.11, 155.49; MS m/e (rel. intensity) 432 (100) 331 (22), 235 (13), 199 (10), 151 (19), 105 (17), 73 (44), 57 (14); MS exact mass: calcd. 432.2251, found 432.2247.

Aufarbeitung

  1. custom##STR34## A 100 mL three-necked flask fitted with a reflux condenser
  2. customwas dried by means of a hot air gun and nitrogen purging
  3. additionThis was charged with dry THF 200 mL
  4. temperaturecooled in an ice-bath
  5. additionwas added in small portions with vigorous stirring
  6. customThe cooling bath was removed
  7. additionTriethylamine (15 mL) was added dropwise
  8. temperaturethe reaction mixture was refluxed for 1 hour
  9. temperatureThe reaction mixture was cooled
  10. extractionextracted with hexane
  11. customAfter the evaporation of solvent
  12. customthe crude material was chromatographed

Quellen und Nachweise

ORD-Eintrag
ord-47b55a1866554ba19decda18ac997d4b
Quelldatensatz
uspto-grants-1998_06
Patentnummer
US05770743

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