Dimethylformamide → 2-Methyl-4-nitrobenzonitrile

HRID 1428758Notes

Reaction equation

HRID 1428758 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[CH3:11].[CH3:12][N:13](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[C:12]#[N:13]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 792252-Iodo-5-nitrotoluene

Product 1

HCID 43463672-Methyl-4-nitrobenzonitrileYield 81%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To a stirred solution of 1-iodo-2-methyl-4-nitrobenzene (812 mg, 3.087 mmol) in dimethylformamide were added zinc cyanide (544 mg, 4.63 mmol) and tetrakis(triphenylphosphine) palladium (713 mg, 0.6174 mmol). The reaction mixture was stirred for 24 h at 120° C., then cooled to room temperature and diluted with ethyl acetate. The mixture was filtered using celite pad. The filtrate dissolved in ethyl acetate and extracted with NaHCO3. The organic layer was dried over magnesium sulfate and filtered. The filtrate removed in vacuo. The crude was purified by column chromatography to give 2-methyl-4-nitrobenzonitrile (407 mg, 81%).

Workup

  1. temperaturecooled to room temperature
  2. filtrationThe mixture was filtered
  3. dissolutionThe filtrate dissolved in ethyl acetate
  4. extractionextracted with NaHCO3
  5. dry with materialThe organic layer was dried over magnesium sulfate
  6. filtrationfiltered
  7. customThe filtrate removed in vacuo
  8. customThe crude was purified by column chromatography

Sources & evidence

ORD record
ord-ee0a2580042248988548ae9d4e11666f
Source dataset
uspto-grants-2015_01
Patent number
US08937092B2

Reaction notes

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