Chlorosuccinimide → 2-Amino-5-chlorobenzonitrile

HRID 2210227Notes

Reaction equation

HRID 2210227 reaction equation
[C:1](#[N:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[NH2:4].[Cl:10]N1C(=O)CCC1=O>C(#N)C>[Cl:10][C:7]1[CH:6]=[CH:5][C:3]([NH2:4])=[C:2]([C:1]#[N:9])[CH:8]=1

Participants

4

Reactant 2

HCID 31398ChlorosuccinimideHCID 729132-Aminobenzonitrile

Product 1

HCID 800192-Amino-5-chlorobenzonitrileYield 94%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
50 °C

Procedure

A 2 L round bottom flask was charged with 138 g (1.168 mol) of anthranilonitrile (Aldrich) and 1.05 L of acetonitrile. The flask was heated to 50° C. and 172.5 g (1.29 mol) of N-chlorosuccinimide (Aldrich) was added in one portion. The reaction was heated at reflux for 2.0 h (HPLC monitoring), cooled to approx. 35° C., and the solvent is removed by rotovap at reduced pressure. The residue was partitioned between 1.5 L ethyl acetate and 1 L cold water. The aqueous layer was extracted with ethyl acetate and the combined organic layers washed with 3 portions of cold water, brine, dried over MgSO4 and treated with activated carbon. The solvent was removed by rotovap at reduced pressure to give a pale orange solid which was crystallized from 430 mL of hot 1-chlorobutane and allowed to cool to room temp. overnight. After filtration, the resulting crystals were washed with cold butylchloride and air dried to give 82.5 g of off-white crystals (94% pure by HPLC). This material was recrystallized from 140 mL of s chlorobutane and 125 mL hexane to give 73 g (41%) of the title compound as a colorless solid. An additional 18.8 g (10.5%) was obtained from two recrystallizations of material from the mother liquors.

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 2.0 h (HPLC monitoring)
  3. temperaturecooled to approx. 35° C.
  4. customthe solvent is removed by rotovap at reduced pressure
  5. customThe residue was partitioned between 1.5 L ethyl acetate and 1 L cold water
  6. extractionThe aqueous layer was extracted with ethyl acetate
  7. washthe combined organic layers washed with 3 portions of cold water, brine
  8. dry with materialdried over MgSO4
  9. additiontreated with activated carbon
  10. customThe solvent was removed by rotovap at reduced pressure
  11. customto give a pale orange solid which
  12. customwas crystallized from 430 mL of hot 1-chlorobutane
  13. temperatureto cool to room temp. overnight
  14. filtrationAfter filtration
  15. washthe resulting crystals were washed with cold butylchloride and air
  16. customdried

Sources & evidence

ORD record
ord-facf5d514ef945f59a8b480beaa20edb
Source dataset
uspto-grants-1995_10
Patent number
US05457201

Reaction notes

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