Cyclohexanone → 4-[(4-Bromo-3-methylphenyl)(cyclohexylidene)methyl]phenol

HRID 2100075Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2100075
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=O)=[CH:4][C:3]=1[CH3:17].[C:18]1(=O)[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1>C1COCC1.[Ti](Cl)(Cl)(Cl)Cl.[Zn]>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:18]2[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]2)[C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=[CH:4][C:3]=1[CH3:17]

Komponenten

6

Edukt 2

HCID 7967CyclohexanoneHCID 68654843(4-Bromo-3-methylphenyl)(4-hydroxyphenyl)methanone

Produkt 1

HCID 686545224-[(4-Bromo-3-methylphenyl)(cyclohexylidene)methyl]phenolAusbeute 85 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23994ZincKatalysatorHCID 24193Titanium TetrachlorideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

Titanium tetrachloride (2.70 mL, 24.5 mmol) was added dropwise to a suspension of zinc powder (3.24 g, 49.5 mmol) in anhydrous THF (60 mL) at RT. After refluxing for 1 h, a mixture of 66 (1.78 g, 6.11 mmol) and cyclohexanone (1.80 g, 18.3 mmol) dissolved in THF (20 mL) was added dropwise. Refluxing was continued for 30 min. The reaction mixture was cooled to RT and filtered through Celite. Water (250 mL) was added and the mixture was extracted with Et2O (3×100 mL). The combined ethereal extracts were washed with water (200 mL), brine (200 mL), and dried over MgSO4. Concentration followed by flash chromatography (20:1 to 5:1 hexanes:EtOAc) afforded 1.85 g (85%) of 67 as an orange solid. 1H NMR (400 MHz, CDCl3): δ 1.58 (m, 6H), 2.20 (m, 4H), 2.32 (s, 3H), 5.95 (br s, 1H), 6.73 (d, J=8.4 Hz, 2H), 6.79 (dd, J=8.1 Hz, 2.0 Hz, 1H), 6.95 (m, 3H), 7.40 (d, J=8.1 Hz, 1H).

Aufarbeitung

  1. temperatureAfter refluxing for 1 h
  2. additionwas added dropwise
  3. temperatureRefluxing
  4. filtrationfiltered through Celite
  5. additionWater (250 mL) was added
  6. extractionthe mixture was extracted with Et2O (3×100 mL)
  7. washThe combined ethereal extracts were washed with water (200 mL), brine (200 mL)
  8. dry with materialdried over MgSO4
  9. concentrationConcentration

Quellen und Nachweise

ORD-Eintrag
ord-71a37db37d244b8ca481fdfac5f2b3fb
Quelldatensatz
uspto-grants-2009_08
Patentnummer
US07569601B2

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