N-bromobutanimide → 3-Bromo-4-(bromomethyl)benzonitrile

HRID 1804461Notes

Reaction equation

HRID 1804461 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[C:5]#[N:6].[Br:11]N1C(=O)CCC1=O>C(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH2:10][Br:11])[C:5]#[N:6]

Participants

5

Reactant 2

HCID 67184N-bromobutanimide2×HCID 140048403-Bromo-4-methylbenzonitrile

Product 1

HCID 2884363-Bromo-4-(bromomethyl)benzonitrileYield 56.5%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalyst4×HCID 6212ChloroformSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 3-bromo-4-methylbenzonitrile (1 g, 5.10 mmol) in chloroform (20 mL) was heated to 40-50° C. and N-bromosuccinimide (0.953 g, 5.36 mmol) was added in one portion followed by AIBN (8.38 mg, 0.051 mmol). After 1.5 hr. additional AIBN (20 mg) was added and the reaction was allowed to stir at 50° C. overnight. Additional AIBN (20 mg) and N-bromosuccinimide (1.1 g) were added, a reflux condenser was attached and the solution was heated to reflux. After several hours, additional AIBN (20 mg) was added and the reaction was allowed to stir at reflux overnight. The reaction was quenched by the addition of water and sat. aq. sodium bicarbonate. The organic phase was separated, concentrated in vacuo and purified by flash column chromatography (120 g silica, eluting with 0%-20% Ethyl Acetate in hexanes) to afford 3-bromo-4-(bromomethyl)benzonitrile as a pale yellow solid (800 mg, 2.88 mmol). 1H NMR (500 MHz, MeOD) δ ppm 4.70 (s, 2H), 7.71 (d, J=8.0 Hz, 1H), 7.73 (d, J=8.0 Hz, 1H), 8.04 (s, 1H).

Workup

  1. customa reflux condenser was attached
  2. temperaturethe solution was heated to reflux
  3. waitAfter several hours
  4. stirringto stir
  5. temperatureat reflux overnight
  6. customThe reaction was quenched by the addition of water and sat. aq. sodium bicarbonate
  7. customThe organic phase was separated
  8. concentrationconcentrated in vacuo
  9. custompurified by flash column chromatography (120 g silica, eluting with 0%-20% Ethyl Acetate in hexanes)

Sources & evidence

ORD record
ord-e0aaeb6a9cff40248cda805d09f3537d
Source dataset
uspto-grants-2013_01
Patent number
US08354398B2

Reaction notes

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