Hydrochloric Acid → 4-[[2'-(Hydroxymethyl)-4-biphenylyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

HRID 229307

Reaktionsgleichung

Reaktionsgleichung von HRID 229307
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:25]2[CH2:30][C:29]([CH3:32])([CH3:31])[CH2:28][C:27]([CH3:34])([CH3:33])[CH2:26]2)[C:9]2[CH:14]=[CH:13][C:12]([C:15]3[C:16]([C:21](OC)=[O:22])=[CH:17][CH:18]=[CH:19][CH:20]=3)=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].CCOC(C)=O.Cl>C1COCC1>[OH:22][CH2:21][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[C:12]1[CH:13]=[CH:14][C:9]([C:8](=[C:25]2[CH2:26][C:27]([CH3:34])([CH3:33])[CH2:28][C:29]([CH3:32])([CH3:31])[CH2:30]2)[C:5]2[CH:4]=[CH:3][C:2]([OH:1])=[CH:7][CH:6]=2)=[CH:10][CH:11]=1

Komponenten

6

Edukt 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 21226445Aluminium lithium hydrideHCID 68654495Methyl 4'-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-biphenylcarboxylate

Produkt 1

HCID 577572234-[[2'-(Hydroxymethyl)-4-biphenylyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenolAusbeute 87 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of methyl 4′-[(4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-biphenylcarboxylate (248) (0.102 g, 0.23 mmol) in THF (8 mL) at 0° C. was added lithium aluminum hydride (1 M in THF, 0.56 mL, 0.56 mmol) dropwise. The reaction mixture was stirred at 0° C. for 1 h. EtOAc (5 mL) was added, and stirring continued for 10 minutes. The mixture was then acidified to pH=2 with an aqueous solution of 1 N HCl, extracted with EtOAc (2×50 mL). The combined organic extract was washed with water, brine and dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as light yellow oil. The crude product was purified by flash chromatography over SiO2 eluted with a gradient from hexanes to 40% EtOAc in hexanes to give 83 mg (87%) of the title compound (250) as a white solid. mp 171-172° C. 1H NMR (400 MHz, DMSO-d6): δ 0.88 (s, 6H), 0.90 (s, 6H), 1.25 (s, 2H), 1.91 (s, 2H), 1.92 (s, 2H), 4.36 (d, J=5.1 Hz, 2H), 5.10 (t, J=5.3 Hz, 1H), 6.67 (d, J=8.2 Hz, 2H), 6.96 (d, J=8.2 Hz, 2H), 7.12-7.23 (m, 3H), 7.24-7.36 (m, 4H), 7.53 (d, J=7.5 Hz, 1H), 9.27 (s, 1H). LCMS (ESI): m/z 425 (M−H)−.

Aufarbeitung

  1. stirringstirring
  2. waitcontinued for 10 minutes
  3. extractionextracted with EtOAc (2×50 mL)
  4. extractionThe combined organic extract
  5. washwas washed with water, brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationthe filtrate was concentrated
  9. customto give the crude product as light yellow oil
  10. customThe crude product was purified by flash chromatography over SiO2
  11. washeluted with a gradient from hexanes to 40% EtOAc in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-695d356de5d24176ad7625af6e4dc854
Quelldatensatz
uspto-grants-2009_07
Patentnummer
US07560589B2

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