3-(2-Nitrophenyl)-2-oxopropanoic acid → 2-[[4-(3,4-Dichlorophenyl)-1,3-thiazol-2-yl]hydrazinylidene]-3-(2-nitrophenyl)propanoic acid

HRID 2380753

Reaktionsgleichung

Reaktionsgleichung von HRID 2380753
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][C:11](=O)[C:12]([OH:14])=[O:13])([O-:3])=[O:2].[Cl:16][C:17]1[CH:18]=[C:19]([C:24]2[N:25]=[C:26]([NH:29][NH2:30])[S:27][CH:28]=2)[CH:20]=[CH:21][C:22]=1[Cl:23]>C(O)(=O)C.C(O)C>[Cl:16][C:17]1[CH:18]=[C:19]([C:24]2[N:25]=[C:26]([NH:29][N:30]=[C:11]([CH2:10][C:5]3[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=3[N+:1]([O-:3])=[O:2])[C:12]([OH:14])=[O:13])[S:27][CH:28]=2)[CH:20]=[CH:21][C:22]=1[Cl:23]

Komponenten

5

Edukt 2

HCID 795833-(2-Nitrophenyl)-2-oxopropanoic acidHCID 71740714-(3,4-Dichlorophenyl)-2-hydrazinylthiazole

Produkt 1

HCID 28310242-[[4-(3,4-Dichlorophenyl)-1,3-thiazol-2-yl]hydrazinylidene]-3-(2-nitrophenyl)propanoic acidAusbeute 133 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 176Acetic AcidLösungsmittelHCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

3-(2-Nitro-phenyl)-2-oxo-propionic acid (1.0 mmol, 209 mg) in 5% acetic acid (2 mL) was added in to solution of 4-(3,4-dichloro-phenyl)-thiazol-2-yl-hydrazine (1.0 mmol, 259 mg) in ethanol (4 mL). The reaction mixture was stirred at 90° C. for 1 h and cooled to 0° C.; the orange solid was precipitated out, filtered and washed by water. Recrystallization from MeOH—H2O afford the final product as a yellow powder (600 mg, 66.7%). mp ; Z/E isomer was further separated by HPLC-MS, using gradient eluting solvents: 0.05% HOAc in acetonitrile 50%: 0.05% HOAc in water 50% to 0.05% HOAc in acetonitrile 75%: 0.05% HOAc in water 25% in 20 min. 1H NMR (400 MHz) δ 12.85 (br, 1H), 12.10 (br, 1H), 8.06 (d, J=8.4 Hz, 1H), 8.03(s, 1H), 7.78 (d, J=8.4 Hz, 1H), 7.64 (d, J=6.0 Hz , 2H), 7.61(s, 1H), 7.50 (t, J=7.6 Hz, 1H), 7.06 (d, J=7.6 Hz, 1H), 4.28 (s, 2H). 13C NMR (125.78 MHz) δ 166.097, 164.759, 149.785, 134.607, 134.281, 133.663, 132.596, 132.182, 131.543, 130.680, 129.559, 128.927, 127.854, 126.318, 125.795, 125.299, 108.552, 36.896. Z-isomer: 1H NMR (400 MHz) δ 12.35 (br, 1H), 12.10 (br, 1H), 8.06 (dd, J=8.4 Hz, 1H), 8.03(s, 1H), 7.78 (d, J=8.4 Hz, 1H), 7.64 (d, J=6.0 Hz, 2H), 7.61(s, 1H), 7.50 (t, J=7.6 Hz, 1H), 7.06 (d, J=7.6 Hz, 1H), 4.12 (s, 2H).

Aufarbeitung

  1. temperaturecooled to 0° C.
  2. customthe orange solid was precipitated out
  3. filtrationfiltered
  4. washwashed by water
  5. customRecrystallization from MeOH—H2O

Quellen und Nachweise

ORD-Eintrag
ord-adbb4edbbf694dfab01c80408a903b2e
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08257931B2

Verknüpfte Notizen

Wird geladen…