Reacción #6678

ord-042ea76dc6784c55b2a71fe62bfbe739

Ecuación de reacción

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
Rendimiento 80.0%

Reactantes

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

Reactivos

Ninguno

Disolventes

C1CCOC1
tetrahydrofuran

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Tratamiento posterior

  1. 1
    Temperaturaheated
  2. 2
    Temperaturaat reflux for 135 min
  3. 3
    OtroThe solvent was removed
  4. 4
    workup.ADDITIONDichloromethane (50 cm3) was added
  5. 5
    Lavadothe solution washed with water (50 cm3) and brine (50 cm3)
  6. 6
    Secadodried over sodium sulphate
  7. 7
    Filtraciónfiltered
  8. 8
    Otrothe solvent removed
  9. 9
    Otroto leave a yellow foam
  10. 10
    OtroThe product was purified by column chromatography over silica
  11. 11
    Lavadoeluting with dichloromethane-light petroleum (2:3)
  12. 12
    OtroRecrystallisation from a dichloromethane-methanol mixture

Procedimiento

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%).

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US07083862B2uspto-grants-2006_08