Reaktion #6678

ord-042ea76dc6784c55b2a71fe62bfbe739

Reaktionsgleichung

CC(C)(C)c1cc(C=Cc2cc(C=Cc3cc(C=Cc4cc(C=O)cc(C=Cc5cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)c5)c4)cc(C=Cc4cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)c4)c3)cc(C=Cc3cc(C(C)(C)C)cc(C(C)(C)C)c3)c2)cc(C(C)(C)C)c1
3,5-bis{3′,5′-bis[3″,5″-bis(3′″,5′″-di-tert-butylstyryl)styryl]styryl}benzaldehyde
[BH4-].[Na+]
sodium borohydride
→
CC(C)(C)c1cc(C=Cc2cc(C=Cc3cc(C=Cc4cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)c4)cc(C=Cc4cc(C=Cc5cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)c5)cc(CO)c4)c3)cc(C=Cc3cc(C(C)(C)C)cc(C(C)(C)C)c3)c2)cc(C(C)(C)C)c1
3,5-bis{3′,5′-bis[3″,5″-bis(3′″,5′″-di-tert-butylstyryl)styryl]styryl}benzyl alcohol
Ausbeute 80.0%

Edukte

CC(C)(C)c1cc(C=Cc2cc(C=Cc3cc(C=Cc4cc(C=O)cc(C=Cc5cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)cc(C=Cc6cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)cc(C=Cc7cc(C(C)(C)C)cc(C(C)(C)C)c7)c6)c5)c4)cc(C=Cc4cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)cc(C=Cc5cc(C(C)(C)C)cc(C(C)(C)C)c5)c4)c3)cc(C=Cc3cc(C(C)(C)C)cc(C(C)(C)C)c3)c2)cc(C(C)(C)C)c1
3,5-bis{3′,5′-bis[3″,5″-bis(3′″,5′″-di-tert-butylstyryl)styryl]styryl}benzaldehyde
[BH4-].[Na+]
sodium borohydride

Reagenzien

Keine

Lösungsmittel

C1CCOC1
tetrahydrofuran

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Temperaturheated
  2. 2
    Temperaturat reflux for 135 min
  3. 3
    SonstigeThe solvent was removed
  4. 4
    workup.ADDITIONDichloromethane (50 cm3) was added
  5. 5
    Waschenthe solution washed with water (50 cm3) and brine (50 cm3)
  6. 6
    Trocknendried over sodium sulphate
  7. 7
    Filtrationfiltered
  8. 8
    Sonstigethe solvent removed
  9. 9
    Sonstigeto leave a yellow foam
  10. 10
    SonstigeThe product was purified by column chromatography over silica
  11. 11
    Wascheneluting with dichloromethane-light petroleum (2:3)
  12. 12
    SonstigeRecrystallisation from a dichloromethane-methanol mixture

Vorschrift

A solution of 3,5-bis{3′,5′-bis[3″,5″-bis(3′″,5′″-di-tert-butylstyryl)styryl]styryl}benzaldehyde (3.853 g, 1.585 mmol) in tetrahydrofuran (50 cm3) was treated with sodium borohydride (121 mg, 3.20 mmol) and heated at reflux for 135 min. The solvent was removed. Dichloromethane (50 cm3) was added and the solution washed with water (50 cm3) and brine (50 cm3), dried over sodium sulphate, filtered and the solvent removed to leave a yellow foam. The product was purified by column chromatography over silica, eluting with dichloromethane-light petroleum (2:3). Recrystallisation from a dichloromethane-methanol mixture gave 3,5-bis{3′,5′-bis[3″,5″-bis(3′″,5′″-di-tert-butylstyryl)styryl]styryl}benzyl alcohol (3.07 g, 80%) as a yellow powder, mp 248° C. (Found: C, 89.89; H, 8.89. C183H220O requires C, 90.24; H, 9.10%); vmax(KBr)/cm−1 3568 (OH), 1594 (C═C) and 959 (C═C—H trans); λmax(CH2Cl2)/nm (log ε) 323 (5.59) and 334sh (5.52); δH(400 MHz, CDCl3) 1.39 (144H, s, t-Bu), 1.80 (1H, t, OH), 4.85 (2H, d, CH2OH), 7.19 and 7.31 (16H, ABq, J 16, 7′″, 8′″-H), 7.32(4H, s, 7′, 8′-H), 7.34(8H, s, 7″, 8″-H), 7.38 (8H, dd, J 1.5, 4′″-H), 7.44 (16H, d, J 1.5, 2′″, 6′″-H), 7.57(2H, br s, 4′-H), 7.67 (12H, br s, 2″, 4″, 6″-H), 7.67 (4H, br s, 2′, 6′-H), 7.70 (1H, br s, 4-H) and 7.74 (2H, br s, 2, 6-H); m/z (MALDI) 2434.94 (M+, 100%).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US07083862B2uspto-grants-2006_08