반응 #1848635

반응 방정식

acrylonitrile

5-aminomethyl-6-methoxypyridine-2-carboxylic acid

triethanolamine

bromine

triethanolamine

sodium

→

desired compound

5-[(2-Cyano-1-aziridinyl)-methyl]-6-methoxypyridine-2-carboxylic acid

용매

methanol

methanol

water

ethanol

methanol

ethanol

diethyl ether

methanol

반응 조건

후처리

1. 1
   기타illuminating
2. 2
   온도The mixture is occasionally cooled in order
3. 3
   기타does not exceed 40° C
4. 4
   workup.ADDITIONthe reaction mixture is diluted with 60 ml
5. 5
   workup.WAITAfter a further hour
6. 6
   workup.ADDITIONthere are simultaneously added dropwise
7. 7
   workup.WAITThe solution is left
8. 8
   workup.WAITto stand for 24 hours
9. 9
   기타evaporated substantially on a rotary evaporator
10. 10
    추출by extracting continuously for 2 days with methylene chloride
11. 11
    건조The methylene chloride phase is then dried
12. 12
    기타evaporated
13. 13
    기타to give 4.8 g
14. 14
    workup.DISSOLUTIONof an oil which is dissolved in 50 ml
15. 15
    온도While cooling
16. 16
    workup.ADDITIONthe solution is mixed with a solution of 440 mg
17. 17
    기타The sodium salt of 5-[(2-cyano-1-aziridinyl)-methyl]-6-methoxypyridine-2-carboxylic acid precipitates out
18. 18
    workup.ADDITIONafter the addition of 100 ml
19. 19
    여과isopropanol, it is filtered off with suction
20. 20
    기타dried
21. 21
    세척washed with diethyl ether
22. 22
    기타to give 3.7 g

실험 절차

2.33 g. (44 mmol) acrylonitrile are diluted with 1 ml. diethyl ether and, while stirring and illuminating, 7.05 g. (44 mmol) bromine are added dropwise thereto. The mixture is occasionally cooled in order to ensure that the internal temperature does not exceed 40° C. Stirring is continued for a further 5 minutes, the reaction mixture is diluted with 60 ml. methanol and a solution of 6.55 g. (44 mmol) triethanolamine in 60 ml. methanol is added dropwise thereto. After a further hour, there are simultaneously added dropwise thereto a solution of 6.55 g. (44 mmol) triethanolamine in 60 ml. methanol and a solution of 8 g. (44 mmol) 5-aminomethyl-6-methoxypyridine-2-carboxylic acid (m.p. 269°-270° C. (decomp.)) in 1 liter methanol/200 ml. water. The solution is left to stand for 24 hours, then evaporated substantially on a rotary evaporator and the aqueous solution adjusted with 2N hydrochloric acid to a pH of 4.5, followed by extracting continuously for 2 days with methylene chloride. The methylene chloride phase is then dried and evaporated to give 4.8 g. of an oil which is dissolved in 50 ml. ethanol. While cooling, the solution is mixed with a solution of 440 mg. sodium in 15 ml. ethanol. The sodium salt of 5-[(2-cyano-1-aziridinyl)-methyl]-6-methoxypyridine-2-carboxylic acid precipitates out and, after the addition of 100 ml. isopropanol, it is filtered off with suction, dried and washed with diethyl ether to give 3.7 g. (33% of theory) of the desired compound; m.p. 230°-232° C.

출처