Реакция #617792

Уравнение реакции

[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

Выход 83.0%

Растворители

H2O

ethanol

Условия реакции

Обработка

1. 1
   Другоеto give a light yellow suspension
2. 2
   ТемператураThe mixture was further heated
3. 3
   Температураat reflux for an additional 4.5 h
4. 4
   ДругоеReaction mixture
5. 5
   Экстракцияextracted with EtOAc (3×300 mL)
6. 6
   ПромывкаThe combined organic layers were washed with brine
7. 7
   Сушкаdried over MgSO4
8. 8
   Концентрированиеconcentrated in vacuo
9. 9
   ДругоеThe resulting pale yellow solid was triturated with cold ether
10. 10
    Другоеdried under vacuum

Методика

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).

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