Oxalyl chloride → 2-Chloronicotinoyl chloride

HRID 2414289Notes

Reaction equation

HRID 2414289 reaction equation
[Cl:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4](O)=[O:5].C(Cl)(=O)C([Cl:14])=O>C(Cl)Cl.CN(C=O)C>[Cl:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([Cl:14])=[O:5]

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 762582-Chloronicotinic acid

Product 1

HCID 27745412-Chloronicotinoyl chlorideYield 99%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 2-chloronicotinic acid (37.8 g, 0.240 mol) in dry DCM (150 mL) and DMF (0.1 mL) cooled in an ice-bath was added oxalyl chloride (22.9 mL, 0.264 mol) dropwise over a period of 15 min. After stirring for 1 h at 0° C., the reaction mixture was heated to reflux for 6 h (the mixture became a clear brownish solution). The solvent and the excess oxalyl chloride was evaporated under reduced pressure. Toluene (100 mL) was added to the residue and the mixture was evaporated. The obtaining residue was purified by vacuum distillation to give 2-chloronicotinoyl chloride (41.7 g, 99%); bp 98-100° C./2 mmHg, mp 38-39° C. (from Lancaster catalog). Caution: Distillation may need a special care due to the high melting point of the product.

Workup

  1. temperaturecooled in an ice-bath
  2. temperaturethe reaction mixture was heated
  3. temperatureto reflux for 6 h (the mixture
  4. customThe solvent and the excess oxalyl chloride was evaporated under reduced pressure
  5. additionToluene (100 mL) was added to the residue
  6. customthe mixture was evaporated
  7. distillationThe obtaining residue was purified by vacuum distillation

Sources & evidence

ORD record
ord-8dd649ef69b94cc48eebd7701a680742
Source dataset
uspto-grants-2004_11
Patent number
US06812238B1

Reaction notes

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