2-Thiophenecarboxaldehyde → HCID 54465784, compound

HRID 259942Notes

Reaction equation

HRID 259942 reaction equation
[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]

Participants

7

Reactant 4

HCID 73642-ThiophenecarboxaldehydeHCID 24436Sodium SulfateHCID 5003444Sodium cyanoborohydrideHCID 99048004,6-Dibromo-3-hydroxyanthranilic acid

Product 1

HCID 54465784HCID 54465784, compoundYield 12.3%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent2×

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-3a77d6383bb14043bab6881b3611d49c
Source dataset
uspto-grants-1996_06
Patent number
US05523475

Reaction notes

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