반응 #48460

반응 방정식

fumaric acid

benzylmagnesium chloride

ether

Carbon disulfide

→

title compound ( 21 )

수율 33.0%

2-[(2-phenylethanethioyl)sulfanyl]succinic Acid

수율 33.0%

용매

tetrahydrofuran

반응 조건

후처리

1. 1
   기타the ether was mostly removed by distillation
2. 2
   workup.ADDITIONMore tetrahydrofuran (100 mL) was added
3. 3
   온도the solution was heated
4. 4
   온도under reflux for 14 h
5. 5
   온도The reaction was cooled
6. 6
   workup.ADDITIONpoured into ether (1 L)
7. 7
   추출extracted with water (3×100 mL)
8. 8
   추출extracted with ether (2×100 mL)
9. 9
   추출extracted with ethyl acetate (3×200 mL)
10. 10
    세척The combined organic layers were washed with water (200 mL) and saturated sodium chloride (100 mL)
11. 11
    기타evaporated
12. 12
    기타The crude mixture was crystallized by trituration with 50:50 ether/light petroleum (100 mL)
13. 13
    기타The solid was collected
14. 14
    기타placed in water (150 mL) at 65°
15. 15
    workup.DISSOLUTIONdissolved
16. 16
    온도The mixture was then quickly cooled in an ice bath
17. 17
    기타the resulting crystals were collected
18. 18
    세척washed with cold water (3×33 mL)
19. 19
    workup.DISSOLUTIONThe solid was then dissolved in a mixture of water (150 mL), ethyl acetate (600 mL) and tetrahydrofuran (50 mL)
20. 20
    기타The water was removed
21. 21
    세척the organic phase was washed with water (3×100 mL), saturated sodium chloride (100 mL)
22. 22
    건조dried over magnesium sulfate
23. 23
    기타evaporated

실험 절차

A solution of benzylmagnesium chloride in ether (1.0 M, 200 mL, 0.20 mol) was added to dry tetrahydrofuran (200 mL) under nitrogen. Carbon disulfide (20 mL, 25 g, 0.33 mol) was then added slowly with stirring. After 15 min, fumaric acid (23.2 g, 0.20 mol) was added and the ether was mostly removed by distillation. More tetrahydrofuran (100 mL) was added, and the solution was heated under reflux for 14 h. The reaction was cooled and poured into ether (1 L), then extracted with water (3×100 mL) followed by saturated sodium bicarbonate (5×200 mL). The bicarbonate extracts were combined and extracted with ether (2×100 mL), then acidified slowly to pH<1 with concentrated hydrochloric acid, and extracted with ethyl acetate (3×200 mL). The combined organic layers were washed with water (200 mL) and saturated sodium chloride (100 mL), and then evaporated. The crude mixture was crystallized by trituration with 50:50 ether/light petroleum (100 mL). The solid was collected and placed in water (150 mL) at 65° whereupon most of the solid dissolved. The mixture was then quickly cooled in an ice bath and the resulting crystals were collected and washed with cold water (3×33 mL). The solid was then dissolved in a mixture of water (150 mL), ethyl acetate (600 mL) and tetrahydrofuran (50 mL). The water was removed and the organic phase was washed with water (3×100 mL), saturated sodium chloride (100 mL), dried over magnesium sulfate, and evaporated to give the title compound (21) as a yellow solid (18.4 g, 33%).

출처