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

HRID 1683135

반응식

HRID 1683135 반응식
[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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water촉매HCID 6344Dichloromethane용매3회

실험 절차

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): δ 0.87(t, 3 H, J=6.6 Hz), 1.20-1.60(m, 12 H), 1.70(m, 1 H), 4.21(m, 1 H), 5.00(s, 2 H), Distorted AA'BB' System [6.82(d, 2 H) 6.88(d, 2 H)], 7.30-7.46(m, 5 H); 13C NMR (300 MHz, CDCl3): δ 14.02, 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).

후처리

  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

출처 및 근거

ORD 기록
ord-d5d55b3bf4014618810cb0cafb718c4a
출처 데이터셋
uspto-grants-1997_06
특허 번호
US05637256

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