Iodine → 4-({3,5-Bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene

HRID 495223노트

반응식

HRID 495223 반응식
[O-]CC.[Li+].[C:5]([C:9]1[CH:10]=[C:11]([CH:19]=[CH:20][C:21]2[CH:22]=[C:23]([CH:26]=[C:27]([CH:29]=[CH:30][C:31]3[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:34]=[C:33]([C:41]([CH3:44])([CH3:43])[CH3:42])[CH:32]=3)[CH:28]=2)[CH:24]=O)[CH:12]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:14]=1)([CH3:8])([CH3:7])[CH3:6].[Cl-].[CH3:46][C:47]1[CH:54]=[CH:53][C:50]([CH2:51][PH3+])=[CH:49][CH:48]=1.II>C(OCC)C.C1(C)C=CC=CC=1>[C:5]([C:9]1[CH:10]=[C:11]([CH:19]=[CH:20][C:21]2[CH:22]=[C:23]([CH:24]=[CH:46][C:47]3[CH:54]=[CH:53][C:50]([CH3:51])=[CH:49][CH:48]=3)[CH:26]=[C:27]([CH:29]=[CH:30][C:31]3[CH:36]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:34]=[C:33]([C:41]([CH3:44])([CH3:43])[CH3:42])[CH:32]=3)[CH:28]=2)[CH:12]=[C:13]([C:15]([CH3:18])([CH3:17])[CH3:16])[CH:14]=1)([CH3:8])([CH3:7])[CH3:6]

참가 물질

7

반응물 4

HCID 807IodineHCID 179813694-Methylbenzylphosphonium chlorideHCID 23661847Lithium ethoxideHCID 540286873,5-Bis[2-(3,5-di-tert-butylphenyl)ethenyl]benzaldehyde

생성물 1

HCID 865927514-({3,5-Bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene수율 64.4%

시약·촉매·용매 2

HCID 1140Toluene용매HCID 3283Diethyl Ether용매

실험 절차

Lithium ethoxide (1.0 M in ethanol, 15.0.mL, 15 mmol) was added to a stirred suspension of 3,5-bis[(3,5-di-tert-butylphenyl)vinyl]benzaldehyde (A) (WO99/9921935) (4.00 g, 7.48 mmol) and 4-methylbenzylphosphoniumchloride (8) (3.62 g, 8.98 mmol) in diethyl ether (40 mL), giving a clear orange solution which was stirred at room temperature for 2 h. The solution was washed with water (3×40 mL) and brine (40 mL), dried over anhydrous magnesium sulphate, filtered and the solvent removed, This residue was passed through a plug of silica with dichloromethane—light petroleum (1:4) as eluent to give a white solid, which was found by 1H NMR to be mainly cis isomer. The solid was heated with iodine (210 mg) and toluene (100 mL) at 100° C. under argon for 6 h and allowed to cool. The solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL) and the solvent removed. The residue was recrystallised from a dichloromethane—hexanes mixture to leave 4-({3,5-bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene (9) (3.00 g, 64%) as a white solid. δH(400 MHz, CDCl3) 1.40 (36 H, s, t-butyl), 2.39 (3 H, s, CH3), 7.13 and 7.22 (2 H, d, J 16, core vinyl H), 7.17 and 7.28 (4 H, d, J 16, branch vinyl H), 7.21 and 7.48 (4 H, AA′BB′, core phenyl H), 7.39 (2 H, dd, J 1.5, sp H), 7.43 (4 H, d, J 1.5, sp H), 7.59 (2 H, d, J 1, bp H) and 7.62 (1 H s, bp H).

후처리

  1. customgiving a clear orange solution which
  2. washThe solution was washed with water (3×40 mL) and brine (40 mL)
  3. dry with materialdried over anhydrous magnesium sulphate
  4. filtrationfiltered
  5. customthe solvent removed
  6. customto give a white solid, which
  7. temperatureto cool
  8. washThe solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL)
  9. customthe solvent removed
  10. customThe residue was recrystallised from a dichloromethane—hexanes mixture

출처 및 근거

ORD 기록
ord-e5b234f572924e66bf347b897c6d3f1b
출처 데이터셋
uspto-grants-2009_05
특허 번호
US07537842B2

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