Dimethylformamide → 4-(1-Cyano-1-methylethyl)benzonitrile

HRID 603139Notes

Reaction equation

HRID 603139 reaction equation
[CH3:1][C:2]([C:6]1[CH:11]=[CH:10][C:9]([CH3:12])=[CH:8][CH:7]=1)([CH3:5])[C:3]#[N:4].C[N:14](C=O)C>O.[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:3]([C:2]([C:6]1[CH:7]=[CH:8][C:9]([C:12]#[N:14])=[CH:10][CH:11]=1)([CH3:1])[CH3:5])#[N:4]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 123690832-Methyl-2-(4-methylphenyl)propanenitrile

Product 1

HCID 101763144-(1-Cyano-1-methylethyl)benzonitrileYield 85%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

2-methyl-2-(4-methylphenyl)propanenitrile (3.51 g, 15.7 mmol) is dissolved in dry DMF (10 mL). Zn(CN)2 (2.02 g, 17.2 mmol) and Pd(PPh3)4 (906 mg, 5 mol %) are added and the mixture heated at 100° C. for 3 hours. The reaction mixture is diluted with water and the solid recovered by filtration. The solid residue is dissolved in methanol, filtered to remove insoluble impurities, concentrated under vacuo and purified by normal phase MPLC (SiO2, hexane to EtOAc), giving 4-(1-cyano-1-methylethyl)benzonitrile (2.28 g, 13.4 mmol, 85%) as a white solid. 1H NMR (400 MHz, DMSO-D6) δ ppm 1.70 (s, 6H) 7.73 (dt, J=8.64, 2.03 Hz, 2H) 7.92 (dt, J=8.69, 2.00 Hz, 2H).

Workup

  1. filtrationthe solid recovered by filtration
  2. dissolutionThe solid residue is dissolved in methanol
  3. filtrationfiltered
  4. customto remove insoluble impurities
  5. concentrationconcentrated under vacuo
  6. custompurified by normal phase MPLC (SiO2, hexane to EtOAc)

Sources & evidence

ORD record
ord-17235208c33a46dcaa7e41e12a4fece2
Source dataset
uspto-grants-2011_03
Patent number
US07906654B2

Reaction notes

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