Ammonia → 3-Bromo-4-methylbenzonitrile

HRID 1678493Notes

Reaction equation

HRID 1678493 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[CH3:11])[C:5](O)=O.C(Cl)(=O)C(Cl)=O.C[N:19]1CCOCC1.N>C1(C)C=CC=CC=1.CN(C=O)C.C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[CH3:11])[C:5]#[N:19]

Participants

8

Reactant 4

HCID 222AmmoniaHCID 79724-MethylmorpholineHCID 65578Oxalyl chlorideHCID 821303-Bromo-4-methylbenzoic acid

Product 1

HCID 140048403-Bromo-4-methylbenzonitrile

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

3-Bromo-4-methyl-benzoic acid (3 g) in toluene (75 ml) was treated with oxalyl chloride (10 ml) and DMF (4 drops). The mixture was then stirred at 20 C for 3 h. and then the solvent evaporated giving a yellow solid. This in turn was dissolved in THF (30 ml) containing N-methyl-morpholine (1.5 ml). Aqueous ammonia (0.880, 40 ml) was then added and the mixture stirred for 18 h. The THF was then evaporated and the resulting amide intermediate collected by filtration as a colourless solid (2.9 g). This material was then suspended in thionyl chloride (35 ml) and was heated to 85 C for 6 h. The excess reagent was then evaporated and the residue purified on silica gel. Elution with 5-50% ethyl acetate in hexane gave the title compound as a white solid (1.4 g)

Workup

  1. customthe solvent evaporated
  2. customgiving a yellow solid
  3. stirringthe mixture stirred for 18 h
  4. customThe THF was then evaporated
  5. filtrationthe resulting amide intermediate collected by filtration as a colourless solid (2.9 g)
  6. temperaturewas heated to 85 C for 6 h
  7. customThe excess reagent was then evaporated
  8. customthe residue purified on silica gel
  9. washElution with 5-50% ethyl acetate in hexane

Sources & evidence

ORD record
ord-ed6c8c3175ab483889166bec990e4761
Source dataset
uspto-grants-2011_08
Patent number
US08008303B2

Reaction notes

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