6-(5-Ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexanoic acid ethyl ester → 6-(6-Hydroxy-5-methyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexan-1-ol

HRID 48315노트

반응식

HRID 48315 반응식
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:9][C:10](=O)[C:11]([CH3:40])([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH2:12][CH2:13][CH2:14][CH2:15][S:16][CH2:17][CH2:18][CH2:19][CH2:20][C:21]([C:29](OCC)=[O:30])([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[CH3:22])C>C(OCC)C>[OH:9][CH2:10][C:11]([CH3:40])([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH2:12][CH2:13][CH2:14][CH2:15][S:16][CH2:17][CH2:18][CH2:19][CH2:20][C:21]([CH3:22])([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[CH2:29][OH:30]

참가 물질

4

반응물 2

HCID 116418176-(5-Ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexanoic acid ethyl esterHCID 21226445Aluminium lithium hydride

생성물 1

HCID 102018946-(6-Hydroxy-5-methyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexan-1-ol수율 71.8%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매2회

실험 절차

Under nitrogen atmosphere, to a solution of lithium aluminum hydride (1.0 M solution in diethyl ether, 60 mL, 60 mmol) in diethyl ether (150 mL) was added a solution of 6-(5-ethoxycarbonyl-5-phenylhexylsulfanyl)-2-methyl-2-phenyl-hexanoic acid ethyl ester (9.45 g, 18 mmol) in anhydrous diethyl ether (50 mL). The reaction mixture was heated to reflux for 3 h and was stirred at rt overnight. The excess of lithium aluminum hydride was carefully quenched by addition of ethyl acetate (20 mL) and the precipitate was completely dissolved with 6 N HCl (10 mL) and water (100 mL). The mixture was extracted with diethyl ether (4′ 60 mL). The combined organic layers were washed with saturated NH4Cl solution (20 mL), dried over MgSO4, and concentrated in vacuo to give a crude product (6.9 g). Purification by column chromatography on silica gel (hexanes/ethyl acetate=10/1) yielded 6-(6-hydroxy-5-methyl-5-phenylhexylsulfanyl)-2-methyl-2-phenylhexan-1-ol (5.36 g, 69%) as a yellow oil. 1H NMR (300 MHz, CDCl3/TMS): d (ppm): 7.40-7.13 (m, 10H), 3.69 (d, J=11.0 Hz, 2H), 3.53 (d, J=11.0 Hz, 2H), 2.38 (t, J=7.3 Hz, 4H), 1.85-1.63 (m, 2H), 1.60 (br., 2H), 1.58-1.40 (m, 6H), 1.40-1.20 (m, 2H), 1.34 (s, 6H), 1.15-0.93 (m, 2H). 13C NMR (75 MHz, CDCl3/TMS): d (ppm): 144.63, 128.43, 126.62, 126.14, 72.42, 43.34, 37.91, 31.85, 30.31, 23.16, 21.53. HRMS (HR, LSIMS, gly): Calcd. for C26H39O2S, (MH+): 415.2671, found: 415.2670. HPLC: 97.3% purity.

후처리

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 3 h
  3. customThe excess of lithium aluminum hydride was carefully quenched by addition of ethyl acetate (20 mL)
  4. dissolutionthe precipitate was completely dissolved with 6 N HCl (10 mL) and water (100 mL)
  5. extractionThe mixture was extracted with diethyl ether (4′ 60 mL)
  6. washThe combined organic layers were washed with saturated NH4Cl solution (20 mL)
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customto give a crude product (6.9 g)
  10. customPurification by column chromatography on silica gel (hexanes/ethyl acetate=10/1)

출처 및 근거

ORD 기록
ord-c2d9f5b7104e41bfb5ae4db4c896d154
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06703422B2

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