Dimethylformamide → 2,4-Dicyanoaniline

HRID 1170022Notes

Reaction equation

HRID 1170022 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:3]=1[C:4]#[N:5].[CH3:11][N:12](C=O)C>[C-]#N.[Zn+2].[C-]#N>[NH2:1][C:2]1[CH:9]=[CH:8][C:7]([C:11]#[N:12])=[CH:6][C:3]=1[C:4]#[N:5]

Participants

4

Reactant 2

HCID 6228DimethylformamideHCID 4297402-Amino-5-bromobenzonitrile

Product 1

HCID 881692,4-Dicyanoaniline

Reagents, catalysts & solvents 1

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst

Conditions

Temperature
90 °C

Procedure

Using a literature procedure described in the following literature reference which is herein incorporated by reference in its entirety for all purposes as if fully set forth herein, a dry round bottom flask was charged with 2-amino-5-bromo benzonitrile (1 equivalent) and zinc cyanide (2 equivalents), and DMF was added: J. Med. Chem. 2000, 43, 4063. Nitrogen was bubbled through the solution for 5 minutes, and Pd[P(Ph)3]4 was added in one portion. The reaction mixture was stirred at 90° C. overnight. After cooling to room temperature, saturated NaHCO3 was added, and the mixture was extracted with EtOAc. The organic extracts were collected and dried (Na2SO4). Evaporation of the solvent under reduced pressure and purification by column chromatography on silicagel (2% methanol in methylene chloride) afforded the desired 4-aminobenzene-1,3-dicarbonitrile as a white solid. GC/MS m/z: 143 (M+, 100%), Rt 14.7 minutes.

Workup

  1. additionwas added
  2. customNitrogen was bubbled through the solution for 5 minutes
  3. additionPd[P(Ph)3]4 was added in one portion
  4. temperatureAfter cooling to room temperature
  5. additionsaturated NaHCO3 was added
  6. extractionthe mixture was extracted with EtOAc
  7. customThe organic extracts were collected
  8. dry with materialdried (Na2SO4)
  9. customEvaporation of the solvent
  10. customunder reduced pressure and purification by column chromatography on silicagel (2% methanol in methylene chloride)

Sources & evidence

ORD record
ord-33b70271ceb44c449aa31128570a01e4
Source dataset
uspto-grants-2010_11
Patent number
US07825132B2

Reaction notes

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