Reaktion #617792

Reaktionsgleichung

[2-amino-1-(3-methoxy-phenyl)-ethylsulfanyl]-acetic acid methyl ester

methyl 2-bromo-2-(3-methoxyphenyl)acetate

2-aminoethanethiol

potassium carbonate

→

2-(3-methoxyphenyl)thiomorpholin-3-one

Ausbeute 83.0%

Lösungsmittel

H2O

ethanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigeto give a light yellow suspension
2. 2
   TemperaturThe mixture was further heated
3. 3
   Temperaturat reflux for an additional 4.5 h
4. 4
   SonstigeReaction mixture
5. 5
   Extraktionextracted with EtOAc (3×300 mL)
6. 6
   WaschenThe combined organic layers were washed with brine
7. 7
   Trocknendried over MgSO4
8. 8
   Einengenconcentrated in vacuo
9. 9
   SonstigeThe resulting pale yellow solid was triturated with cold ether
10. 10
    Sonstigedried under vacuum

Vorschrift

In a 500 mL round-bottomed flask, methyl 2-bromo-2-(3-methoxyphenyl)acetate (5.2 g, 20.1 mmol), 2-aminoethanethiol (1.55 g, 20.1 mmol) and potassium carbonate (5.55 g, 40.1 mmol) were combined with ethanol (150 ml) to give a light yellow suspension. The resultant mixture was stirred at 85° C. (bath temp.) for 2.5 h. No starting material remained. The intermediate, [2-amino-1-(3-methoxy-phenyl)-ethylsulfanyl]-acetic acid methyl ester, was the major product with 25% of the cyclized product. The mixture was further heated at reflux for an additional 4.5 h. Complete by LCMS. Reaction mixture was allowed to cool to room temperature and sit overnight. The reaction mixture was poured into 500 mL H2O and extracted with EtOAc (3×300 mL). The combined organic layers were washed with brine, dried over MgSO4 and concentrated in vacuo. The resulting pale yellow solid was triturated with cold ether and dried under vacuum to afford 2-(3-methoxyphenyl)thiomorpholin-3-one (3.7 g, 83%) as a yellow solid. (M+H)+=224 m/e. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.88 (td, J=5.81, 2.78 Hz, 2H) 3.67 (td, J=5.81, 3.54 Hz, 2H) 3.82 (s, 3H) 4.63 (s, 1H) 6.42 (br. s., 1H) 6.85 (ddd, J=8.34, 2.53, 0.76 Hz, 1H) 7.00 (t, J=2.15 Hz, 1H) 7.01-7.05 (m, 1H) 7.29 (t, J=7.93, 1H).

Quelle