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

HRID 1716029Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1716029
[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-82d2d9857e994d24b344b10cbbf5eab4
Quelldatensatz
uspto-grants-2010_09
Patentnummer
US07799828B2

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