반응 #155415

반응 방정식

3-(methylthio)benzenethiol

sodium metabisulfite

4-fluorobenzaldehyde

→

title compound

수율 55.0%

Sodium hydroxy(4-{[3-(methylthio)phenyl]thio}phenyl)methanesulfonate

수율 55.0%

용매

acetonitrile

acetonitrile

acetonitrile

water

반응 조건

후처리

1. 1
   기타was sparged with nitrogen for 1 hour
2. 2
   세척wash)
3. 3
   세척wash) and
4. 4
   온도to cool to ambient temperature
5. 5
   workup.ADDITIONdiluted with ethyl acetate (3 L)
6. 6
   세척washed with hydrochloric acid (2M aqueous solution, 1.5 L) and sodium bicarbonate (1 M aqueous solution, 3 L) and brine (half saturated, 1.5 L)
7. 7
   농축The resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L
8. 8
   workup.ADDITIONdiluted with acetonitrile (3 L)
9. 9
   농축the resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L
10. 10
    workup.ADDITIONdiluted with acetonitrile (3 L)
11. 11
    농축concentrated by distillation at atmospheric pressure to a final volume of 3 L
12. 12
    온도The resulting solution was cooled to ambient temperature
13. 13
    여과was filtered
14. 14
    기타the solid collected
15. 15
    세척was washed with water (2-fold 2.5 L) and acetonitrile (2-fold 2.5 L)
16. 16
    workup.STIRRINGstirred at ambient temperature for 18 hours after which time the suspension
17. 17
    여과was filtered
18. 18
    세척the solid was washed with acetonitrile (2-fold 1 L)
19. 19
    기타dried in vacuo at 50° C.

실험 절차

A solution of 3-(methylthio)benzenethiol as prepared in Preparation 8 (290 g, 1.856 mol) in acetonitrile (3 L) was sparged with nitrogen for 1 hour and then treated with 4-fluorobenzaldehyde (196 mL, 1.856 mol) followed by acetonitrile (150 mL, used as a line wash). The resulting solution was treated with 1,1′,3,3′-tetramethylguanidine (256 mL, 2.04 mol) followed by acetonitrile (150 mL used as a line wash) and heated to 50° C. under nitrogen for 16 hours. The resulting solution was allowed to cool to ambient temperature and diluted with ethyl acetate (3 L) and washed with hydrochloric acid (2M aqueous solution, 1.5 L) and sodium bicarbonate (1 M aqueous solution, 3 L) and brine (half saturated, 1.5 L). The resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L and diluted with acetonitrile (3 L). the resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L and diluted with acetonitrile (3 L) and concentrated by distillation at atmospheric pressure to a final volume of 3 L. The resulting solution was cooled to ambient temperature and treated with a solution of sodium metabisulfite (377 g, 1.982 mol) in water (3 L). After stirring at ambient temperature for 48 hours the resulting suspension was filtered and the solid collected was washed with water (2-fold 2.5 L) and acetonitrile (2-fold 2.5 L). The solid was suspended in acetonitrile (2 L) and stirred at ambient temperature for 18 hours after which time the suspension was filtered and the solid was washed with acetonitrile (2-fold 1 L) and dried in vacuo at 50° C. to give the title compound as a white solid, 55% yield, 368.7 g.

출처