Ethyl Acetate → HCID 69586621, compound

HRID 723271Notes

Reaction equation

HRID 723271 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([S:30][CH3:31])=[C:8]([S:10]([C:13]2[CH:18]=[C:17]([N+:19]([O-])=O)[C:16]([NH:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[C:15]([Br:29])[CH:14]=2)(=[O:12])=[O:11])[CH:9]=1)=[O:4].[CH3:32]COC(C)=O>CCO.CC(O)=O.[Fe]>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([S:30][CH3:31])=[C:8]([S:10]([C:13]2[CH:14]=[C:15]([Br:29])[C:16]3[N:22]([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[CH:32]=[N:19][C:17]=3[CH:18]=2)(=[O:12])=[O:11])[CH:9]=1)=[O:4]

Participants

6

Reactant 2

HCID 8857Ethyl AcetateHCID 69586673HCID 69586673, compound

Product 1

HCID 69586621HCID 69586621, compound

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

Iron powder (110 mg, 2 mmol) was added to a solution of 4-(3-bromo-5-nitro-4-phenylamino-benzenesulfonyl)-5-methylsulfanyl-thiophene-2-carboxylic acid methyl ester (Example 318: step d) in EtOH (4 mL) and 50% aqueous AcOH (1 mL). The reaction was stirred for 30 min at 60° C. during which a new lower spot became evident by TLC analysis. EtOAc (10 mL) was added and the mixture was filtered through a 0.22 μm polypropylene syringe filter. Additional EtOAc (30 mL) was added and the solution was extracted with aq NaHCO3 (3×10 mL) and brine (20 mL). The solution was dried and concentrated in vacuo. One-half of the residue (26 mg) was suspended in formic acid (3 mL) and was heated at 95° C. for 4 h. The formic acid was removed in vacuo and the residue was purified by chromatography to yield the product (23 mg). 1H-NMR (CDCl3): δ 8.56 (d, 1H, J=1.6 Hz), 8.13 (s, 1H), 8.07 (d, 1H, J=1.6 Hz), 8.04 (s, 1H), 7.55 (m, 3H, 7.41 (m, 2H), 3.87 (s, 3H), 2.61 (s, 3H).

Workup

  1. filtrationthe mixture was filtered through a 0.22 μm polypropylene syringe
  2. filtrationfilter
  3. additionAdditional EtOAc (30 mL) was added
  4. extractionthe solution was extracted with aq NaHCO3 (3×10 mL) and brine (20 mL)
  5. customThe solution was dried
  6. concentrationconcentrated in vacuo
  7. temperaturewas heated at 95° C. for 4 h
  8. customThe formic acid was removed in vacuo
  9. customthe residue was purified by chromatography

Sources & evidence

ORD record
ord-9a49dbc9298a404280af4e5588569b49
Source dataset
uspto-grants-2006_11
Patent number
US07138530B2

Reaction notes

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