Dimethylformamide → 4-Nitroaniline

HRID 1398271Notes

Reaction equation

HRID 1398271 reaction equation
I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].C(NCC)C.CN(C)C=O>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C(OCC)(=O)C>[N+:9]([C:7]1[CH:8]=[CH:2][C:3]([NH2:4])=[CH:5][CH:6]=1)([O-:11])=[O:10]

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 8021DiethylamineHCID 2226292-Iodo-4-nitroaniline

Product 1

HCID 74754-Nitroaniline

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Into a 300 mL four-necked flask, 2-iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis(triphenylphosphine)palladium dichloride (1.20 g, 1.71 mmol), and copper iodide (0.651 g, 3.42 mmol) were charged, and nitrogen substitution was carried out, and then diethylamine (43.7 g, 598 mmol) and N,N-dimethylformamide (128 mL) were added thereto, followed by addition of the above-described t-butyl N-propargylamino-N-t-butoxycarbonyl acetate while stirring with ice-cooling, and further stirring at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added thereto, and then washing with 150 mL of a 1 mol/L ammonium chloride aqueous solution was carried out three times and washing with 150 mL of a saturated sodium chloride aqueous solution was carried out once, followed by drying by magnesium sulfate. Thereafter, the solvent was removed by evaporation under reduced pressure to precipitate a solid material, and then the solid material was dissolved in 200 mL of ethyl acetate, followed by addition of 1 L of hexane to carry out recrystallization. The solid material was collected by filtration and dried under reduced pressure, thereby to obtain a yellow solid material of 2-{3-(N-t-butoxycarbonyl-N-t-botxycarbonylmethylamino)-1-propynyl)}-4-nitroaniline (compound (A7)). The total amount of yield was 23.0 g, and the yield rate was 66%.

Workup

  1. temperaturecooling
  2. stirringfurther stirring at room temperature for 20 hours
  3. additionwas added
  4. washwashing with 150 mL of a 1 mol/L ammonium chloride aqueous solution
  5. washwashing with 150 mL of a saturated sodium chloride aqueous solution
  6. dry with materialby drying by magnesium sulfate
  7. customThereafter, the solvent was removed by evaporation under reduced pressure
  8. customto precipitate a solid material
  9. dissolutionthe solid material was dissolved in 200 mL of ethyl acetate
  10. additionfollowed by addition of 1 L of hexane
  11. customrecrystallization
  12. filtrationThe solid material was collected by filtration
  13. customdried under reduced pressure

Sources & evidence

ORD record
ord-06a6323182f746fc862004fb7521be21
Source dataset
uspto-grants-2014_12
Patent number
US08901353B2

Reaction notes

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