3,3,5,5-Tetramethylcyclohexanone → 4-[(4-Fluorophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

HRID 229290

Reaktionsgleichung

Reaktionsgleichung von HRID 229290
[F: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][CH:3]=1.[CH3:17][C:18]1([CH3:27])[CH2:23][C:22]([CH3:25])([CH3:24])[CH2:21][C:20](=O)[CH2:19]1>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:20]2[CH2:21][C:22]([CH3:25])([CH3:24])[CH2:23][C:18]([CH3:27])([CH3:17])[CH2:19]2)[C:10]2[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1

Komponenten

6

Edukt 2

HCID 843993,3,5,5-TetramethylcyclohexanoneHCID 1176664-Fluoro-4'-hydroxybenzophenone

Produkt 1

HCID 111635614-[(4-Fluorophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenolAusbeute 80,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23994ZincKatalysatorHCID 24193Titanium TetrachlorideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

The general McMurry coupling procedure described for 14 was followed. To a stirred suspension of zinc powder (13.0 g, 0.2 mol) in THF (400 mL) was slowly added TiCl4 (11 mL, 0.10 mol) via a syringe at room temperature under a nitrogen atmosphere. The reaction mixture was heated at reflux for 1 h. A solution of (4-fluorophenyl)(4-hydroxyphenyl)methanone (4.32 g, 0.02 mol) and 3,3,5,5-tetramethylcyclohexanone (9.26 g, 0.06 mol) in THF (100 mL) was added to the reaction mixture. The reaction mixture was heated at reflux for an additional 2 h. Standar work-up followed by purification gave 5.450 g (80%) of compound 231 as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.14 (d, J=5.7 Hz, 1H), 7.12 (d, J=5.7 Hz, 1H), 7.04 (d, J=8.7 Hz, 2H), 6.97 (dd, J=8.7 Hz, 2H), 6.76 (d, J=8.7 Hz, 2H), 4.68 (s, 1H), 1.99 (s, 2H), 1.96 (s, 2H), 1.31 (s, 2H), 0.95 (s, 6H), 0.94 (s, 6H).

Aufarbeitung

  1. customat room temperature
  2. temperatureThe reaction mixture was heated
  3. temperatureat reflux for 1 h
  4. temperatureThe reaction mixture was heated
  5. temperatureat reflux for an additional 2 h
  6. customfollowed by purification

Quellen und Nachweise

ORD-Eintrag
ord-24d8297e978041619db9a70652535c87
Quelldatensatz
uspto-grants-2009_07
Patentnummer
US07560589B2

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