반응 #3050

반응 방정식

phenol

N-methylformanilide

phosphoryl chloride

Ortho-tertbutylphenol

→

3-(1,1-dimethylethyl)-4-hydroxybenzaldehyde

용매

—

hexanes

toluene

반응 조건

후처리

1. 1
   온도with cooling
2. 2
   기타the resulting reaction mixture
3. 3
   workup.STIRRINGwas stirred for an additional 30 minutes at room temperature
4. 4
   온도heated to approximately 60° C.
5. 5
   workup.STIRRINGstirred for five hours at that temperature
6. 6
   workup.ADDITIONThe reaction mixture was poured into a volume of crushed ice
7. 7
   추출extracted with chloroform
8. 8
   기타The aqueous layer was separated
9. 9
   세척washed again with chloroform
10. 10
    추출extracted with 2000 ml of a 5% potassium hydroxide solution
11. 11
    추출The aqueous potassium hydroxide extract
12. 12
    workup.ADDITIONwas then added to 1000 ml of chloroform
13. 13
    기타The mixture's layers were separated
14. 14
    추출the aqueous layer was again extracted with chloroform
15. 15
    추출The organic layer from the two-phase mixture and the chloroform extract
16. 16
    세척washed with water
17. 17
    건조dried over sodium sulfate
18. 18
    기타The volatile components of the solution were removed under reduced pressure
19. 19
    기타to provide a residue
20. 20
    온도The solution was slowly cooled to room temperature while a precipitate
21. 21
    기타formed
22. 22
    여과This precipitate was recovered by filtration
23. 23
    세척washed with hexanes
24. 24
    기타dried under vacuum
25. 25
    기타to provide 20.0 g of the

실험 절차

Into 184.4 ml (1,494 mol) of N-methylformanilide were added dropwise, with cooling, 130.9 ml (1,404 mol) of phosphoryl chloride over a period of 20 minutes. The mixture was allowed to warm to room temperature and stirred for one hour. Ortho-tertbutylphenol (138.2 ml; 0.9 mol) was then added dropwise to the reaction solution over a period of 25 minutes. After phenol addition was complete, the resulting reaction mixture was stirred for an additional 30 minutes at room temperature and then heated to approximately 60° C. and stirred for five hours at that temperature. The reaction mixture was poured into a volume of crushed ice and extracted with chloroform. The aqueous layer was separated and washed again with chloroform. The chloroform layers were combined and extracted with 2000 ml of a 5% potassium hydroxide solution. The aqueous potassium hydroxide extract was then added to 1000 ml of chloroform. The pH of the resulting two-phase mixture was adjusted to approximately pH 2.0 with concentrated hydrochloric acid. The mixture's layers were separated and the aqueous layer was again extracted with chloroform. The organic layer from the two-phase mixture and the chloroform extract were combined, washed with water and then dried over sodium sulfate. The volatile components of the solution were removed under reduced pressure to provide a residue. This residue was dissolved in 100 ml of hot toluene and the resulting solution was diluted with 100 ml of hexanes. The solution was slowly cooled to room temperature while a precipitate formed. This precipitate was recovered by filtration, washed with hexanes and then dried under vacuum to provide 20.0 g of the desired substituted intermediate.

출처