Dimethylformamide → 4-[2-(Dimethylamino)ethenyl]-3-nitrobenzonitrile

HRID 1836646Notes

Reaction equation

HRID 1836646 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH3:12])[CH:7]=[CH:8][C:9]=1[C:10]#N)([O-:3])=[O:2].[CH3:13][N:14]([CH:16]=O)[CH3:15].C[NH:19]C.CN(C)C=O>O>[CH3:13][N:14]([CH3:16])[CH:15]=[CH:10][C:9]1[CH:8]=[CH:7][C:6]([C:12]#[N:19])=[CH:5][C:4]=1[N+:1]([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 962352-Nitro-4-toluonitrileHCID 86587686HCID 86587686, compound

Product 1

HCID 8941414-[2-(Dimethylamino)ethenyl]-3-nitrobenzonitrileYield 74%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 3-nitro-p-tolunitrile (30.0 g, 185 mmol), DMF (100 mL), and dimethylformamide dimethylamine (24.3 g, 204 mmol) was heated to 110° C. for 16 h. The deep red solution was poured into H2O (1L) and extracted with EtOAc (4×250 mL). The organic layers were washed with H2O, brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The solid residue was triturated with hexanes to give 4-(2-dimethylamino-vinyl)-3-nitro-benzonitrile (28.5 g, 74%) after filtration. 1H NMR (400 MHz, DMSO-d6) 8.22 (1H, s), 7.83 (2H, m), 7.65 (1H, m), 5.67 (1H, d, J=13 Hz), 2.98 (6H, s); MS m/e 219 (M+H)+. Anal calcd. for C11H11N3O2: C, 60.82; H, 5.10; N, 19.34. Found: C, 60.54; H, 4.99; N, 19.40.

Workup

  1. extractionextracted with EtOAc (4×250 mL)
  2. washThe organic layers were washed with H2O, brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe solid residue was triturated with hexanes

Sources & evidence

ORD record
ord-6cdabc9331554c629165c593af381238
Source dataset
uspto-grants-2004_08
Patent number
US06777437B2

Reaction notes

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