반응 #55092

ord-3193c8a1af014ccb9c4786376fc8f99c

반응 방정식

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
수율 52.8%
OC(=S)CCc1ccc2c(c1)OCO2
3,4-Methylenedioxybenzylthio-acetic acid
수율 52.8%

반응 조건

온도
60°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타equipped with a magnetic stirrer and a condenser
  2. 2
    온도The temperature is raised to 95° C.
  3. 3
    온도to cool
  4. 4
    여과these are filtered off
  5. 5
    기타The precipitate thus obtained
  6. 6
    온도The mixture is heated to 70° C.
  7. 7
    온도The whole is then heated
  8. 8
    온도under reflux for half an hour
  9. 9
    온도after which it is cooled
  10. 10
    기타the precipitate obtained
  11. 11
    workup.DISSOLUTIONis redissolved in
  12. 12
    세척the solution is washed with methylene chloride
  13. 13
    여과filtered over charcoal
  14. 14
    기타to precipitate 3,4-methylenedioxybenzylthio-acetic acid, which
  15. 15
    여과is filtered off
  16. 16
    기타After recrystallisation

실험 절차

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.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US04151300uspto-grants-1979_04