반응 #1253205

반응 방정식

HI

n-BuLi

Compound 2

2,6-bis(t-Butyldimethylsilyloxy)anthraquinone

THF

Compound 1

1-Bromo-4-heptylbenzene

THF

→

light yellow brown solid

수율 51.0%

9,10-bis(4-Heptyl)phenyl-2,6-dihydroxyanthracene

수율 51.0%

반응 조건

후처리

1. 1
   온도to maintain the temperature below −60° C
2. 2
   workup.ADDITIONAfter addition
3. 3
   workup.ADDITIONadded dropwise to the above cooled solution
4. 4
   온도The reaction was slowly warmed up to room temperature
5. 5
   workup.STIRRINGstirred at room temperature overnight
6. 6
   기타The deep brown reaction
7. 7
   온도was heated
8. 8
   온도to reflux for 10 min. and most of the solvent
9. 9
   기타was removed under reduced pressure
10. 10
    추출The reaction mixture was then extracted with methylene chloride three times
11. 11
    세척The combined organic phase was washed with saturated sodium metabisulfate solution, water, and brine
12. 12
    건조dried over MgSO4
13. 13
    기타The crude product was obtained as brown viscous oil
14. 14
    기타was purified by column chromatography on silica gel with 10/90 ether/hexane as an eluent

실험 절차

Compound 2 (37 g, 0.079 mol) was dissolved in 200 mL of anhydrous THF and cooled to −78° C. To this solution was added n-BuLi (2.5 M in hexane, 94 mL, 0.24 mol) slowly to maintain the temperature below −60° C. After addition, the orange-yellow solution was stirred at −78° C. for an hour. Compound 1 (60.2 g, 0.24 mol) was dissolved in 100 mL of anhydrous THF and added dropwise to the above cooled solution. The reaction was slowly warmed up to room temperature and stirred at room temperature overnight. The reaction was quenched with HI aqueous solution (47% in water, 143 mL, 0.79 mol) and TBDMS group was also de-protected. The deep brown reaction was heated to reflux for 10 min. and most of the solvent was removed under reduced pressure. The reaction mixture was then extracted with methylene chloride three times. The combined organic phase was washed with saturated sodium metabisulfate solution, water, and brine, and dried over MgSO4. The crude product was obtained as brown viscous oil and was purified by column chromatography on silica gel with 10/90 ether/hexane as an eluent. The pure product was obtained as 22.4 g light yellow brown solid at 51% yield. 1H NMR (CDCl3) δ (ppm): 0.91 (t, J=7.0 Hz, 6H), 1.26-1.43 (m, 8H), 1.71-1.81 (m, 2H), 2.73 (t, J=7.8 Hz, 2H), 5.21 (s, br, 2H, OH), 6.89 (d, J=2.3 Hz, 2H), 6.96 (dd, J1=9.5 Hz, J2=2.5 Hz, 2H), 7.32 (d, J=8.6 Hz, 4H, phenyl), 7.35 (d, J=8.6 Hz, 4H, phenyl), 7.57 (d, J=9.4 Hz, 2H). 13C NMR (CDCl3): 14.16, 22.72, 29.26, 29.52, 31.60, 31.86, 35.90, 106.84, 118.58, 127.07, 128.46, 128.98, 129.64, 131.04, 134.94, 136.30, 142.10, 151.69. Mp 162-164° C. FD-MS: m/z 558 (M+).

출처