2-Methylresorcinol → 8-Methyl-2-phenylchroman-7-ol

HRID 1811020

Reaktionsgleichung

Reaktionsgleichung von HRID 1811020
C1(/C=C/CO)C=CC=CC=1.CC1C(O)=CC=CC=1O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH2:32]([C:41]1[CH:46]=[CH:45][C:44]([OH:47])=[C:43]([CH3:48])[C:42]=1[OH:49])[CH:33]=[CH:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.C(C1C=C(CC=CC2C=CC=CC=2)C(O)=C(C)C=1O)C=CC1C=CC=CC=1>ClCCCl.C1(C)C=CC=CC=1.CCOC(C)=O>[CH3:48][C:43]1[C:44]([OH:47])=[CH:45][CH:46]=[C:41]2[C:42]=1[O:49][CH:34]([C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)[CH2:33][CH2:32]2

Komponenten

9

Edukt 5

HCID 118432-MethylresorcinolHCID 521998p-Toluenesulfonic acid monohydrate2×HCID 5315892Cinnamyl AlcoholHCID 66606284HCID 66606284, VerbindungHCID 86663002HCID 86663002, Verbindung

Produkt 1

HCID 142248968-Methyl-2-phenylchroman-7-ol

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 111,2-DichloroethaneLösungsmittelHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

Step 1 A suspension of (E)-3-phenylprop-2-en-1-ol (2.22 g, 16.51 mmol) and 2-methylbenzene-1,3-diol (2.05 g, 16.51 mmol) in 1,2-dichloroethane (100 mL) was treated with p-toluenesulfonic acid monohydrate (0.157 g, 0.826 mmol) and the mixture was heated at reflux for 1 h. The mixture was cooled to rt and concentrated, and the residue was subjected to column chromatography (eluting with a gradient from 90:10 to 75:25 hexane-EtOAc) provided a mixture of 4-cinnamyl-2-methylbenzene-1,3-diol and 4,6-dicinnamyl-2-methylbenzene-1,3-diol (2:1, 1.97 g). This material (1.89 g) was dissolved in toluene (60 mL) and treated with p-toluenesulfonic acid monohydrate (299 mg, 1.57 mmol) and heated at reflux for 6 h. The mixture was cooled to rt, diluted with EtOAc (100 mL), washed with NaHCO3 (aq) (2×30 mL), water (30 mL) and brine (30 mL), dried and concentrated. Column chromatography (eluting with a gradient from 95:5 to 70:30 hexane-EtOAc) provided 8-methyl-2-phenylchroman-7-ol as a brown liquid (ca. 85% purity, 672 mg, 17%) used without further purification. 1H NMR (400 MHz, chloroform-d) δ 7.35-7.50 (4 H, m), 7.27-7.35 (1 H, m), 6.79 (1 H, d, J=8.36 Hz), 6.38 (1 H, d, J=8.14 Hz), 5.07 (1 H, dd, J=10.12, 2.42 Hz), 4.64 (1 H, s), 2.83-3.02 (1 H, m), 2.71 (1 H, ddd, J=16.01, 4.90, 3.74 Hz), 2.16-2.27 (1 H, m), 2.14 (3 H, s), 1.86-2.04 (1 H, m). Mass spectrum m/z 241.0 (M+H)+.

Aufarbeitung

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 1 h
  3. concentrationconcentrated
  4. washeluting with a gradient from 90:10 to 75:25 hexane-EtOAc)
  5. customprovided
  6. temperatureheated
  7. temperatureat reflux for 6 h
  8. temperatureThe mixture was cooled to rt
  9. washwashed with NaHCO3 (aq) (2×30 mL), water (30 mL) and brine (30 mL)
  10. customdried
  11. concentrationconcentrated
  12. washColumn chromatography (eluting with a gradient from 95:5 to 70:30 hexane-EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-6195d32797824c0a9df5e4f0ba2fe72c
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08362065B2

Verknüpfte Notizen

Wird geladen…