反応 #461584

反応方程式

ethanol

Glucosamine hydrochloride

sodium nitrite

acryloyl chloride

→

2-Acrylamido-2-deoxy-D-glucose

溶媒

potassium carbonate

反応条件

後処理

1. 1
   その他was kept below 5° C
2. 2
   その他to come to room temperature
3. 3
   workup.WAITFinally, it was left at room temperature for 14 h
4. 4
   workup.ADDITIONstrongly mixed
5. 5
   ろ過The resulting suspension was filtered by suction
6. 6
   洗浄the cake was washed three times with 250 ml of 95% ethanol
7. 7
   workup.ADDITIONTo the combined filtrates and washings 1 l of ether was added
8. 8
   workup.WAITthe solution was kept at 0° C. for 24 h
9. 9
   その他The desired product crystallized as white cubes, while the yellowish needles that
10. 10
    その他It could be separated
11. 11
    workup.STIRRINGby stirring up the whole mixture
12. 12
    その他decanting the liquid with the floating needles while the product
13. 13
    workup.ADDITIONBy addition of 1 l of ether to the mother liquid a second crop
14. 14
    その他could be isolated
15. 15
    その他The product was recrystallized two times from water/ethanol/ether

実験手順

Glucosamine hydrochloride (0.1 mol; 21.56 g) and sodium nitrite (0.2 g) as inhibitor were dissolved under nitrogen atmosphere in 100 ml of a 0.3 M potassium carbonate solution, and the mixture was cooled to 0° C. Under vigorous stirring, acryloyl chloride (0.2 mol; 18.1 g) was added while the temperature was kept below 5° C. Stirring was continued for 3 h at 0°-5° C. and further 2 h while the mixture was allowed to come to room temperature. Finally, it was left at room temperature for 14 h. The solution was poured into 1 l of dry ethanol and strongly mixed. The resulting suspension was filtered by suction, and the cake was washed three times with 250 ml of 95% ethanol. To the combined filtrates and washings 1 l of ether was added and the solution was kept at 0° C. for 24 h. The desired product crystallized as white cubes, while the yellowish needles that might appear were a by-product. It could be separated by stirring up the whole mixture and decanting the liquid with the floating needles while the product remained on the ground of the reaction flask. By addition of 1 l of ether to the mother liquid a second crop could be isolated. The product was recrystallized two times from water/ethanol/ether. Yield 8.1-10.5 g (35-45%), m.p.:124°-125° C.

出典