2-Thiophenecarboxaldehyde → HCID 54465784, Verbindung

HRID 259942Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 259942
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH:6]=O.[Br:8][C:9]1[C:10]([OH:20])=[C:11]([NH2:19])[C:12](=[C:16]([Br:18])[CH:17]=1)[C:13]([OH:15])=[O:14].[O-]S([O-])(=O)=O.[Na+].[Na+].C([BH3-])#N.[Na+]>CO.C(O)(=O)C>[Br:8][C:9]1[C:10]([OH:20])=[C:11]([NH:19][CH2:6][C:2]2[S:1][CH:5]=[CH:4][CH:3]=2)[C:12](=[C:16]([Br:18])[CH:17]=1)[C:13]([OH:15])=[O:14]

Komponenten

7

Edukt 4

HCID 73642-ThiophenecarboxaldehydeHCID 24436Sodium SulfateHCID 5003444Sodium cyanoborohydrideHCID 99048002-Amino-4,6-dibromo-3-hydroxybenzoic acid

Produkt 1

HCID 54465784HCID 54465784, VerbindungAusbeute 12,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 176Acetic AcidLösungsmittelHCID 887MethanolLösungsmittel2×

Versuchsvorschrift

A solution of 2-thiophenecarboxaldehyde (38 mg, 0.34 mmol) in dry methanol (0.8 mL) was added to a mixture of 4,6-dibromo-3-hydroxyanthranilic acid (105 mg, 0.34 mmol) and Na2SO4 (240 mg, 1.7 mmol) in methanol (2 mL). The reaction mixture was stirred overnight at room temperature. Sodium cyanoborohydride (32 mg, 0.51 mmol) was added, and the mixture was stirred for 2 days at room temperature. Conc. acetic acid (1 mL) was added, and the solvent was removed in vacuo. The residue was partitioned between brine and EtOAc (20 mL). The layers were separated and the aqueous layer was extracted with EtOAc (20 mL). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure. The obtained material was purified by column chromatography (SiO2, CH2Cl2 -hexane-EtOAc-conc. HOAc 30:30:20:3). Preparative HPLC (H2O-acetonitrile-conc. HOAc 50:50:1) yielded the title compound as a yellowish solid (17 mg): 1H NMR (CD 3 OD-d4) 7.26 (dd, J=5 Hz, 1 Hz), 7.20 (s, 1H), 6.99 (m, 1H), 6.92 (dd, J=5 Hz, J=5 Hz, 1H), 4.54 (s, 2H); MS (TSP): m/z (rel. int.) 410/408/406 (M+1, 5/12/7), 234/232 (31/28), 154 (100).

Aufarbeitung

  1. stirringthe mixture was stirred for 2 days at room temperature
  2. customthe solvent was removed in vacuo
  3. customThe residue was partitioned between brine and EtOAc (20 mL)
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc (20 mL)
  6. dry with materialThe combined organic layers were dried (MgSO4)
  7. concentrationconcentrated under reduced pressure
  8. customThe obtained material was purified by column chromatography (SiO2, CH2Cl2 -hexane-EtOAc-conc. HOAc 30:30:20:3)

Quellen und Nachweise

ORD-Eintrag
ord-3a77d6383bb14043bab6881b3611d49c
Quelldatensatz
uspto-grants-1996_06
Patentnummer
US05523475

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