Hydrogen Bromide → 3,4-Methylenedioxybenzylthio-acetic acid

HRID 28183

Reaktionsgleichung

Reaktionsgleichung von HRID 28183
NC(N)=[S:3].Br.[CH2:6](O)[C:7]1[CH:15]=[CH:14][C:13]2[O:12][CH2:11][O:10][C:9]=2[CH:8]=1.[NH2+]=C(N)S.[OH-].[Na+].Cl[CH2:24][C:25]([OH:27])=O.Cl.C(=O)(O)[O-].C(OC(C)C)(C)C>O>[CH2:11]1[O:12][C:13]2[CH:14]=[CH:15][C:7]([CH2:6][CH2:24][C:25]([OH:27])=[S:3])=[CH:8][C:9]=2[O:10]1

Komponenten

11

Edukt 9

HCID 260Hydrogen BromideHCID 300Chloroacetic AcidHCID 313Hydrochloric AcidHCID 769Bicarbonate IonHCID 7914Diisopropyl EtherHCID 10322Piperonyl alcoholHCID 14798Sodium HydroxideHCID 2723790ThioureaHCID 178512448HCID 178512448, Verbindung

Produkt 1

HCID 1785261673,4-Methylenedioxybenzylthio-acetic acidAusbeute 52,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel2×

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

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 3N 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 3N 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.

Aufarbeitung

  1. customequipped with a magnetic stirrer and a condenser
  2. temperatureThe temperature is raised to 95° C.
  3. temperatureto cool
  4. filtrationthese are filtered off
  5. customThe precipitate thus obtained
  6. temperatureThe mixture is heated to 70° C.
  7. temperatureThe whole is then heated
  8. temperatureunder reflux for half an hour
  9. temperatureafter which it is cooled
  10. customthe precipitate obtained
  11. dissolutionis redissolved in
  12. washthe solution is washed with methylene chloride
  13. filtrationfiltered over charcoal
  14. customto precipitate 3,4-methylenedioxybenzylthio-acetic acid, which
  15. filtrationis filtered off
  16. customAfter recrystallisation

Quellen und Nachweise

ORD-Eintrag
ord-b39752b53b1947aa81e876ffdc1c2b70
Quelldatensatz
uspto-grants-1980_09
Patentnummer
US04225617

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