Reaktion #81854

Reaktionsgleichung

2-hydroxybenzenecarbothioamide

2-Hydroxybenzenecarbothioamide

ethyl 4-chloroacetoacetate

NaHCO3

CO2

NaHCO3

→

4a

Ausbeute 93.0%

2-(2-Hydroxyphenyl)-4-thiazoleacetic Acid Ethyl Ester

Ausbeute 93.0%

Lösungsmittel

EtOAc

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturto reflux under nitrogen for 2.5 days
2. 2
   SonstigeThe organic layer was separated
3. 3
   Waschenwashed with brine (40 mL×2)
4. 4
   Trocknendried over MgSO4
5. 5
   Filtrationfiltered
6. 6
   EinengenAfter concentration in vacuo
7. 7
   Sonstigethe oily residue was chromatographed on silica gel gradient EtOAc/CH2Cl2

Vorschrift

A stirred solution of 2-hydroxybenzenecarbothioamide 3a (5.36 g, 35.0 mmol), ethyl 4-chloroacetoacetate (6.34 g, 38.5 mmol) in dry THF (70 mL) was heated to reflux under nitrogen for 2.5 days. At ambient temperature, the mixture was diluted with EtOAc (200 mL), then cautiously treated with saturated aq. NaHCO3 (40 mL), and followed by adding solid NaHCO3 in small portions until CO2 evolution ceased. The organic layer was separated, washed with brine (40 mL×2), dried over MgSO4, and filtered. After concentration in vacuo, the oily residue was chromatographed on silica gel gradient EtOAc/CH2Cl2 :0-4%) to provide 4a (8.53 g, 93%) as a white solid, which was recrystallized from toluene/hexane at -30° C. mp 35.5-36.5° C.; IR (neat) 3120, 1740, 480, 1225 cm-1 ; 1H NMR (DMSO-d6) δ1.15 (3H, t, J=7.1 Hz, CH3), 3.84 (2H, t, CH2), 4.07 (2H, q, J=7.1 Hz, CH2), 6.89 (1H, S, J=7.8 Hz, Ar), 6.97 (1H, d, J=7.8 Hz, Ar), 7.26 (1H, t, J=7.8 Hz, Ar), 7.48 (1H, s, 7.93 (1H, d, J=7.8 Hz, Ar, 11.29 (1H, s, OH); FABMS m/z 263 (M30 ), 264 (M+ +1); Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.16; H, 4.97; N, 5.50.

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