Dimethylformamide → 2-n-Hexyloxy-5-nitrobenzonitrile

HRID 1744520Notes

Reaction equation

HRID 1744520 reaction equation
CN(C)C=O.Cl[C:7]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:8]=1[C:9]#[N:10].[CH2:18]([OH:24])[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23].[H-].[Na+]>O>[CH2:18]([O:24][C:7]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:8]=1[C:9]#[N:10])[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 81031-HexanolHCID 24758Sodium hydrideHCID 855042-Chloro-5-nitrobenzonitrile

Product 1

HCID 222278912-n-Hexyloxy-5-nitrobenzonitrileYield 65.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To dimethylformamide solution (91 ml) containing 2-chloro-5-nitrobenzonitrile (18.2 g) and n-hexanol (11.2 g) was added sodium hydride (60% content, 4.8 g) under ice-cooling and the mixture was stirred for 1 h. The reaction mixture was added to water and extracted with toluene. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, after which the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (mobile phase: chloroform) to give 2-n-hexyloxy-5-nitrobenzonitrile (16.2 g). Then, ammonium chloride (0.2 g) and iron powder (1.6 g) were added to a mixed solvent of water (6.3 ml) and ethanol (17 ml), and the mixture was heated to 65° C. Then, the obtained ethanol solution (4 ml) containing 5-nitro-2-n-hexyloxybenzonitrile (16.2 g) was added dropwise thereto, and the mixture was stirred at a refluxing temperature for 30 min. The reaction mixture was ice-cooled and filtrated and the solvent was evaporated under reduced pressure. To the residue was added aqueous sodium hydroxide solution and the mixture was extracted with toluene. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, after which the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (mobile phase: chloroform) to give the title compound (6.0 g).

Workup

  1. temperaturecooling
  2. extractionextracted with toluene
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customafter which the solvent was evaporated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (mobile phase: chloroform)

Sources & evidence

ORD record
ord-9ffbbaf8cc1a40e2bea5f44342a68eae
Source dataset
uspto-grants-2006_03
Patent number
US07015218B1

Reaction notes

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