4-Aminobenzonitrile → 4-Amino-3-chlorobenzonitrile

HRID 1847972Notes

Reaction equation

HRID 1847972 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[Cl:10]N1C(=O)CCC1=O>CC#N>[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[Cl:10]

Participants

4

Reactant 2

HCID 133964-AminobenzonitrileHCID 31398Chlorosuccinimide2×

Product 1

HCID 5198964-Amino-3-chlorobenzonitrileYield 95%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

To a stirred solution of 4-aminobenzonitrile (10.0 g, 84.7 mmol) in MeCN (100 mL) at 90° C. was slowly added N-chlorosuccinimide (12.4 g, 93 mmol). After the addition of N-chlorosuccinimide, the reaction mixture was stirred at 90° C. for 2 h. The reaction mixture was then cooled to rt and concentrated under reduced pressure. The residue was dissolved in 500 mL of CH2Cl2 and washed with 5% aq NaOH. The organic layer was dried over MgSO4 and concentrated under reduced pressure to give 4-amino-3-chlorobenzonitrile as a tan solid (12.2 g, 95%). 1H NMR (300 MHz, CDCl3) δ 7.54 (d, J=1.7 Hz, 1H), 7.35 (dd, J=1.8, 8.4 Hz, 1H), 6.77 (d, J=8.5 Hz, 1H), 4.63 (br s, 2H).

Workup

  1. customat 90° C.
  2. temperatureThe reaction mixture was then cooled to rt
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residue was dissolved in 500 mL of CH2Cl2
  5. washwashed with 5% aq NaOH
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-90f4f1ad8be64655936d3acf9db5bd47
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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