反应详情

温度

10 °C

A 5 L 4-neck round bottle flask was equipped with mechanical stirrer, a thermometer, a condenser, a nitrogen inlet and an additional funnel. Prepare 47% of sodium hydroxide solution from 855 g of sodium hydroxide was dissolved in 972 mL of water. Charge 1800 g of [1-(mercaptomethyl)cyclopropyl]acetate, 1540 mL of methanol to the reaction flask. 1540 g of 47% sodium hydroxide aqueous solution was slowly added to the reaction mixture. After the addition, the reaction mixture was heated to 70˜80° C. and was aged for a period of about 2 hours until completion of reaction as check by TLC (mobile phase: EA/hx=1/2(V/V)). When the reaction was complete, the temperature was lowered below 40° C. The resulting resolution was acidified to pH=3.0˜4.0 with about 1800 mL of 32% HCl aqueous solution. After the reaction mixture was filtered, 2700 g of ethylacetate was added to the filtrate with vigorous stirring over 30 min. The layers were separated; cake and 1000 g of water were added to the aqueous layer and back extracted with 2700 g of ethylacetate. Combined the organic layers and concentrated by rotatory evaporator. Temperature was controlled at 3018 40° C. and pressure was controlled below 100 torr. Distillation was continued to collect about 4000˜5000 mL of distillate. 2000 mL of heptanes was added and the distillation was continued to collect about 1000˜2000 mL at 30˜40° C./<100 torr. After the addition of 2100 g of heptanes, the reaction mixture was cooled to at 10° C. for about 4˜5 hours. A large amount of white solid was obtained by filtration. Cake was washed with 1000 g of heptanes. 1468 g of pure [1-(mercaptomethyl)cyclopropyl]acetic acid was obtained by vacuum dried. (purity by GC: >99%, m.p.=42˜45° C.), H1-NMR(CDCl3): 0.55 ppm (CH2, t), 0.58 ppm (CH2,t), 1.34 ppm (SH, t), 2.50 ppm (CH2, s), 2.60 ppm (CH2, d)

1. customA 5 L 4-neck round bottle flask was equipped with mechanical stirrer
2. additionAfter the addition
3. temperaturethe reaction mixture was heated to 70˜80° C.
4. customwas lowered below 40° C
5. filtrationAfter the reaction mixture was filtered
6. addition2700 g of ethylacetate was added to the filtrate
7. customThe layers were separated
8. additioncake and 1000 g of water were added to the aqueous layer
9. extractionback extracted with 2700 g of ethylacetate
10. concentrationconcentrated by rotatory evaporator
11. customwas controlled at 3018 40° C. and pressure
12. distillationDistillation
13. distillationto collect about 4000˜5000 mL of distillate
14. addition2000 mL of heptanes was added
15. distillationthe distillation
16. customto collect about 1000˜2000 mL at 30˜40° C./<100 torr
17. additionAfter the addition of 2100 g of heptanes
18. customA large amount of white solid was obtained by filtration
19. washCake was washed with 1000 g of heptanes