反応 #55092

ord-3193c8a1af014ccb9c4786376fc8f99c

反応方程式

O=C(O)CCl
chloroacetic acid
[Na+].[OH-]
sodium hydroxide
OCc1ccc2c(c1)OCO2
piperonyl alcohol
NC(=[NH2+])S
thiouronium
Cl
HCl
NC(N)=S
thiourea
Br
hydrobromic acid
CC(C)OC(C)C
diisopropyl ether
O=C([O-])O
bicarbonate
OC(=S)CCc1ccc2c(c1)OCO2
said acid
収率 52.8%
OC(=S)CCc1ccc2c(c1)OCO2
3,4-Methylenedioxybenzylthio-acetic acid
収率 52.8%

反応条件

温度
60°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他equipped with a magnetic stirrer and a condenser
  2. 2
    温度The temperature is raised to 95° C.
  3. 3
    温度to cool
  4. 4
    ろ過these are filtered off
  5. 5
    その他The precipitate thus obtained
  6. 6
    温度The mixture is heated to 70° C.
  7. 7
    温度The whole is then heated
  8. 8
    温度under reflux for half an hour
  9. 9
    温度after which it is cooled
  10. 10
    その他the precipitate obtained
  11. 11
    workup.DISSOLUTIONis redissolved in
  12. 12
    洗浄the solution is washed with methylene chloride
  13. 13
    ろ過filtered over charcoal
  14. 14
    その他to precipitate 3,4-methylenedioxybenzylthio-acetic acid, which
  15. 15
    ろ過is filtered off
  16. 16
    その他After recrystallisation

実験手順

A solution of 18.24 g (0.24 mol) of thiourea in 104 ml of 48% strength hydrobromic acid and 20 ml of water is introduced into a one liter three-necked flask equipped with a magnetic stirrer and a condenser. The mixture is heated to 60° C. and 30.4 g (0.2 mol) of piperonyl alcohol are introduced. The temperature is raised to 95° C. and the mixture is allowed to cool. Crystals of thiouronium salt appear; these are filtered off and suction-drained. The precipitate thus obtained is introduced into a 500 ml three-necked flask together with 60 ml of sodium hydroxide solution. The mixture is heated to 70° C. and 15.6 g (0.164 mol) of chloroacetic acid in 30 ml of water are added dropwise. The whole is then heated under reflux for half an hour, after which it is cooled. The mixture is acidified with 3 N HCl, the precipitate obtained is redissolved in a dilute (sodium) bicarbonate solution, and the solution is washed with methylene chloride, filtered over charcoal and again acidified with 3 N HCl so as to precipitate 3,4-methylenedioxybenzylthio-acetic acid, which is filtered off. After recrystallisation from a 1:1 (volume/volume) mixture of diisopropyl ether and petroleum ether, 18.2 g (40% yield) of the said acid (instantaneous melting point=87° C.) are collected.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US04151300uspto-grants-1979_04