Reaction #6678

ord-042ea76dc6784c55b2a71fe62bfbe739

Reaction equation

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
Yield 80.0%

Reactants

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

Reagents

None

Solvents

C1CCOC1
tetrahydrofuran

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Temperatureheated
  2. 2
    Temperatureat reflux for 135 min
  3. 3
    OtherThe solvent was removed
  4. 4
    workup.ADDITIONDichloromethane (50 cm3) was added
  5. 5
    Washthe solution washed with water (50 cm3) and brine (50 cm3)
  6. 6
    Dryingdried over sodium sulphate
  7. 7
    Filtrationfiltered
  8. 8
    Otherthe solvent removed
  9. 9
    Otherto leave a yellow foam
  10. 10
    OtherThe product was purified by column chromatography over silica
  11. 11
    Washeluting with dichloromethane-light petroleum (2:3)
  12. 12
    OtherRecrystallisation from a dichloromethane-methanol mixture

Procedure

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%).

Source

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