Carbon Dioxide → 2-(2-Hydroxyphenyl)-4-thiazoleacetic Acid Ethyl Ester

HRID 53576

反応式

HRID 53576 の反応式
[OH:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[S:10])[NH2:9].Cl[CH2:12][C:13](=O)[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16].C([O-])(O)=O.[Na+].C(=O)=O>C1COCC1.CCOC(C)=O>[CH2:18]([O:17][C:15](=[O:16])[CH2:14][C:13]1[N:9]=[C:8]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[OH:1])[S:10][CH:12]=1)[CH3:19]

参加物

7

反応物 4

HCID 280Carbon DioxideHCID 69484Ethyl 4-chloroacetoacetateHCID 516892Sodium Bicarbonate2 回HCID 27593422-Hydroxybenzenecarbothioamide

生成物 1

HCID 1360263402-(2-Hydroxyphenyl)-4-thiazoleacetic Acid Ethyl Ester収率 93%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

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.

後処理

  1. temperatureto reflux under nitrogen for 2.5 days
  2. customThe organic layer was separated
  3. washwashed with brine (40 mL×2)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationAfter concentration in vacuo
  7. customthe oily residue was chromatographed on silica gel gradient EtOAc/CH2Cl2

出典と根拠

ORDレコード
ord-03254211a67c4917a77af42c0cf5b043
出典データセット
uspto-grants-1997_04
特許番号
US05620968

関連ノート

読み込み中…