Water → 5-Chloro-2-cyanopyridine

HRID 1581809Notes

Reaction equation

HRID 1581809 reaction equation
[C:1]([Cl:6])(=O)[C:2](Cl)=O.[CH3:7][N:8](C)C=O.[N:12]1[CH:17]=[CH:16][CH:15]=CC=1.O>C(OCC)(=O)C>[C:17]([C:16]1[CH:15]=[CH:2][C:1]([Cl:6])=[CH:7][N:8]=1)#[N:12]

Participants

6

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 6228DimethylformamideHCID 65578Oxalyl chloride

Product 1

HCID 38339425-Chloro-2-cyanopyridineYield 92%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-25 °C

Procedure

Oxalyl chloride (18.1 ml, 207 mmol) is added slowly to dimethylformamide cooled to −25° C. The resulting mixture is cooled to −45° C. and 2-carboxamido-5-chloropyridine (25 g, 160 mmol) is added portionwise. The reaction stirred for 30 minutes and pyridine (14.2 ml, 176 mmol) is added. The reaction stirred for 5 hours, 20 minutes and is poured into 1.5 L of water and 1 L of ethyl acetate is added. The phases are separated and the aqueous layer is extracted with 100 ml of ethyl acetate. The combined organics are washed with water (850 ml and 350 ml), saturated aqueous sodium chloride (100 ml), dried over sodium sulfate, filtered and concentrated in vacuo to give 19.95 g (92%) of 2-cyano-5-chloropyridine which is used without further purification.

Workup

  1. temperatureThe resulting mixture is cooled to −45° C.
  2. stirringThe reaction stirred for 5 hours, 20 minutes
  3. additionis added
  4. customThe phases are separated
  5. extractionthe aqueous layer is extracted with 100 ml of ethyl acetate
  6. washThe combined organics are washed with water (850 ml and 350 ml), saturated aqueous sodium chloride (100 ml)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a9b5e0a1c46d4282b4a5f1e76a3b2f83
Source dataset
uspto-grants-2004_05
Patent number
US06730792B2

Reaction notes

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