Hydrochloric Acid → 3-(3-{Hydroxy-[3-(3-hydroxy-2,2-dimethylpropyl)-phenyl]-methyl}-phenyl)-2,2-dimethylpropan-1-ol

HRID 455784

Reaktionsgleichung

Reaktionsgleichung von HRID 455784
[H-].[H-].[H-].[H-].[Li+].[Al+3].C([O:9][C:10](=O)[C:11]([CH3:37])([CH3:36])[CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([C:19](=[O:35])[C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([CH2:26][C:27]([C:30](OCC)=[O:31])([CH3:29])[CH3:28])[CH:21]=2)[CH:14]=1)C.C(OCC)(=O)C.Cl>CC(OC)(C)C>[OH:35][CH:19]([C:15]1[CH:16]=[CH:17][CH:18]=[C:13]([CH2:12][C:11]([CH3:37])([CH3:36])[CH2:10][OH:9])[CH:14]=1)[C:20]1[CH:21]=[C:22]([CH2:26][C:27]([CH3:29])([CH3:28])[CH2:30][OH:31])[CH:23]=[CH:24][CH:25]=1

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 112591923-{3-[3-(2-Ethoxycarbonyl-2-methylpropyl)-benzoyl]phenyl}-2,2-dimethylpropionic acid ethyl esterHCID 21226445Aluminium lithium hydride

Produkt 1

HCID 666171083-(3-{Hydroxy-[3-(3-hydroxy-2,2-dimethylpropyl)-phenyl]-methyl}-phenyl)-2,2-dimethylpropan-1-olAusbeute 90,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 15413tert-Butyl methyl etherLösungsmittel2×

Versuchsvorschrift

Under Ar atmosphere, to a suspension of LiAlH4 (7.90 g, 208 mmol) in MTBE (200 mL) was added dropwise a solution of 3-{3-[3-(2-ethoxycarbonyl-2-methylpropyl)-benzoyl]phenyl}-2,2-dimethylpropionic acid ethyl ester (25.9 g, 59 mmol) in MTBE (150 mL). The reaction mixture was stirred at room temperature for 16 h and heated to reflux for 3 h. Ethyl acetate (100 mL) was added and the reaction mixture was heated to reflux for 1 h and cooled to room temperature. The reaction mixture was poured into ice (500 g) and acidified with hydrochloric acid solution (2 N, 800 mL). The aqueous solution was extracted with MTBE (4×200 mL). The combined organic layers were washed with saturated NaHCO3 solution (200 mL) and saturated NaCl solution (200 mL), dried over MgSO4, and concentrated under vacuum. The residue (22.6 g) was subjected to column chromatography on silica gel using hexanes/ethyl acetate (3:2) as eluent to afford 3-(3-{hydroxy-[3-(3-hydroxy-2,2-dimethylpropyl)-phenyl]-methyl}-phenyl)-2,2-dimethylpropan-1-ol (19.0 g, 90%) as a white solid. Mp 98-99° C. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 7.26-7.19 (m, 6H), 7.06-7.03 (m, 2H), 5.80 (d, 1H, J=3.4 Hz), 3.23 (s, 4H), 3.05 (d, 1H, J=3.4 Hz), 2.56 (s, 4H), 2.07 (br d, 2H, J=4.4 Hz), 0.85 (s, 12H). 13C NMR (75 MHz, CD3OD=49.15 ppm): δ (ppm): 145.5, 140.2, 130.5, 130.1, 128.7, 125.4, 77.1, 71.5, 45.6, 37.4, 24.6, 24.5. HRMS (FAB, gly): Calcd for C23H33O3 (M+H): 357.2430. found: 357.2388. HPLC: 99.8% pure.

Aufarbeitung

  1. temperatureheated
  2. temperatureto reflux for 3 h
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 1 h
  5. temperaturecooled to room temperature
  6. extractionThe aqueous solution was extracted with MTBE (4×200 mL)
  7. washThe combined organic layers were washed with saturated NaHCO3 solution (200 mL) and saturated NaCl solution (200 mL)
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-97448f97a82f4619a0a9e54a297c32a3
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08497301B2

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