반응 #54306

반응 방정식

3-ethynylphenyl(p-toluenesulfonate)

potassium hydroxide

sodium hydroxide

4-nitrobenzil

→

4-(3-ethynylphenoxy)benzil

수율 65.0%

용매

methanol

methanol

—

ice water

dimethylsulfoxide

dimethylsulfoxide

반응 조건

후처리

1. 1
   온도The mixture was heated
2. 2
   온도to reflux under a nitrogen atmosphere
3. 3
   온도maintained
4. 4
   온도at reflux for 4 hours
5. 5
   workup.DISTILLATIONwas distilled from the flask until the residue
6. 6
   workup.ADDITIONThen, 400 ml of anhydrous benzene was added
7. 7
   workup.DISTILLATIONdistillation
8. 8
   기타was removed
9. 9
   기타dried under reduced pressure
10. 10
    기타leaving a dry, white powder
11. 11
    기타transferred to an addition funnel under nitrogen
12. 12
    workup.ADDITIONWhen addition
13. 13
    workup.STIRRINGthe reaction mixture was stirred overnight at 23° C.
14. 14
    추출Extraction with toluene (3 × 50 ml)

실험 절차

To 100 ml of anhydrous methanol was added 20 g (0.073 mole) of 3-ethynylphenyl(p-toluenesulfonate) and 8.19 g (0.146 mole) of potassium hydroxide. The mixture was heated to reflux under a nitrogen atmosphere and maintained at reflux for 4 hours. A distillation apparatus was attached to the flask, and methanol was distilled from the flask until the residue approached dryness. Then, 400 ml of anhydrous benzene was added, and distillation was continued until 200 ml of benzene was removed. The reaction mixture was freeze dried under reduced pressure, leaving a dry, white powder. The white powder was dissolved in 150 ml of dimethylsulfoxide and transferred to an addition funnel under nitrogen. The solution was added over a 60 minute period to a solution of 4-nitrobenzil (18.6 g, 0.073 mole) in dimethylsulfoxide (300 ml) and stirred at 90° C. under nitrogen. When addition was completed, the reaction mixture was stirred overnight at 23° C. and poured into a solution of sodium hydroxide (50 g) in ice water (1 liter). Extraction with toluene (3 × 50 ml) followed by chromatography on silica gel with benzene as eluent gave 15.4 g (65% yield) of 4-(3-ethynylphenoxy)benzil as a yellow oil which solidified upon standing overnight at 23° C. into a pale yellow solid (m.p. 79°-81° C.).

출처