Isoamyl Nitrite → 3-Methyl-4-(trifluoromethyl)benzonitrile
Reaction equation
N[C:2]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[C:7]([CH3:14])=[CH:6][C:3]=1[C:4]#[N:5].N(OCCC(C)C)=O>C1COCC1.CC(OC)(C)C>[CH3:14][C:7]1[CH:6]=[C:3]([CH:2]=[CH:9][C:8]=1[C:10]([F:11])([F:12])[F:13])[C:4]#[N:5]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 23 °C
Procedure
To a solution of 2-amino-5-methyl-4-trifluoromethyl-benzonitrile from step 4 (23.34 g, 117 mmol) in dry THF (350 mL) was added isoamyl nitrite (34.3 mL, 257 mmol) and the mixture was refluxed for 20 h. Additional isoamyl nitrite (16.6 mL, 129 mmol) was added and the mixture was refluxed for further 20 h. The mixture was cooled to 23° C. and diluted with TBME, the organic layer was washed with 1 N HCl, sat. NaHCO3-sol. and brine, dried over Na2SO4. Removal of the solvent in vacuum left a brown oil (25.82 g), which was purified by bulb to bulb distillation to give a yellow liquid (20.11 g), which was finally purified by distillation to give the title compound as a yellow liquid (17.10 g, 79%; bp 38-42° C. at 0.8 mbar). MS (EI) 185.1 [M].
Workup
- temperaturethe mixture was refluxed for 20 h
- temperaturethe mixture was refluxed for further 20 h
- washthe organic layer was washed with 1 N HCl, sat. NaHCO3-sol
- dry with materialand brine, dried over Na2SO4
- customRemoval of the solvent in vacuum
- waitleft a brown oil (25.82 g), which
- distillationwas purified by bulb to bulb distillation
Sources & evidence
- ORD record
- ord-2dad9ca12f0a4cdebbe56d3a67afacc9
- Source dataset
- uspto-grants-2009_03
- Patent number
- US07504404B2
Reaction notes
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