Monobenzone → (S)-p-Benzyloxy-(1-methylheptyloxy)benzene

HRID 1077386

Reaktionsgleichung

Reaktionsgleichung von HRID 1077386
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:35][C@@H:36](O)[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42].N(C(OCC)=O)=NC(OCC)=O>ClCCl.O>[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]([O:15][C@@H:36]([CH3:35])[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])=[CH:13][CH:14]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

7

Edukt 4

HCID 7638MonobenzoneHCID 11776TriphenylphosphineHCID 80080(R)-2-OctanolHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Produkt 1

HCID 53745214(S)-p-Benzyloxy-(1-methylheptyloxy)benzeneAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterKatalysatorHCID 6344DichloromethaneLösungsmittel3×

Versuchsvorschrift

To an argon-flushed flask containing a solution of 3.01 g (15 mmol) of p-benzyloxy-phenol and 1.25 eq of triphenylphosphine in 220 ml in dry dichloromethane, was added a solution of 4.91 g (15.14 mmol) of (R)-2-octanol in 30 ml of dry dichloromethane via syringe. Then 1.20 eq of diethyl azodicarboxylate dissolved in 60 ml of dry dichloromethane was added dropwise for 30 min. The reaction mixture was stirred at room temperature for 19 h, Then 5 drops of water were added and the mixture was stirred for 1 h. The solvent was then evaporated and the residual crude product was triturated in a mixture of hexanes/ethyl acetate [70/30] for 1 h and filtered through a short silica gel pad. The filtrate was evaporated and the product was purified by flash chromatography on silica gel using dichloromethane/hexanes [10/90 ] as eluent, affording 3.32 g (71%) of (S)-p-Benzyloxy-(1-methylheptyloxy)benzene (Compound 18, Scheme III, R2 =(S)-OCH(CH3) C6H13) as a colorless liquid: Rf [dichloromethane/hexanes 10/90]: 0.13; 1H NMR (300 MHz, CDCl3): δ0.87(t, 3H, J=6.6 Hz), 1.20-1.60(m, 12H), 1.70(m, 1H), 4.21(m, 1H), 5.00(s, 2H), Distorted AA'BB' System [6.82(d, 2H) 6.88(d, 2H)], 7.30-7.46(m, 5H); 13C NMR (300 MHz, CDCl3): δ14.02, 19.77, 22.55, 25.52, 29.26, 31.77, 36.51, 70.63, 74.95, 115.77, 117.35, 127.49, 127.87, 128.55, 137.39, 152.53, 153.01; IR (CHCl3): 3010, 2940, 2850, 1600, 1500, 1475, 1450, 1375; 1230, 1200, 1125, 1025, 925, 825 cm-1 ; Mass spectrum, m/z (rel. Intensity): 312(M+ 7), 212(15), 91(100), 71(5), 57(8), 43(10).

Aufarbeitung

  1. customTo an argon-flushed flask
  2. additionwas added dropwise for 30 min
  3. stirringthe mixture was stirred for 1 h
  4. customThe solvent was then evaporated
  5. customthe residual crude product was triturated in a mixture of hexanes/ethyl acetate [70/30] for 1 h
  6. filtrationfiltered through a short silica gel pad
  7. customThe filtrate was evaporated
  8. customthe product was purified by flash chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-b36a4e63cdba4205bafb41704be9ad1b
Quelldatensatz
uspto-grants-1996_08
Patentnummer
US05543078

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