Pyridine → N-(5-chloropyridin-2-yl)-5-methyl-2-nitrobenzamide

HRID 988699Notes

Reaction equation

HRID 988699 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([N+:11]([O-:13])=[O:12])=[C:6]([CH:10]=1)[C:7]([OH:9])=O.C(Cl)(=O)C(Cl)=O.[NH2:20][C:21]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][N:22]=1.N1C=CC=CC=1>ClCCl.CN(C)C=O.O>[Cl:27][C:24]1[CH:25]=[CH:26][C:21]([NH:20][C:7](=[O:9])[C:6]2[CH:10]=[C:2]([CH3:1])[CH:3]=[CH:4][C:5]=2[N+:11]([O-:13])=[O:12])=[N:22][CH:23]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 183715-Methyl-2-nitrobenzoic acidHCID 65578Oxalyl chlorideHCID 661742-Amino-5-chloropyridine

Product 1

HCID 3562519N-(5-chloropyridin-2-yl)-5-methyl-2-nitrobenzamideYield 70.7%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirring suspension of 5-methyl-2-nitrobenzoic acid (23.36 g, 129 mmol) in dichloromethane (100 mL) was added a couple of drops of N,N-dimethylformamide followed by oxalyl chloride (12.36 mL, 142 mmol). The reaction was stirred at room temperature overnight and the residue transferred slowly to an ice cold solution of 2-amino-5-chloropyridine (16 g, 126 mmol) and pyridine (30 mL) in dichloromethane (200 mL). The reaction was stirred overnight, treated with water (100 mL), and concentrated. The resulting mixture was treated with ethyl acetate (2 L), washed consecutively with aqueous citric acid, saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude product was purified by recrystallization from toluene to give 26 g (69%) of a white solid.

Workup

  1. stirringThe reaction was stirred overnight
  2. concentrationconcentrated
  3. additionThe resulting mixture was treated with ethyl acetate (2 L)
  4. washwashed consecutively with aqueous citric acid, saturated aqueous sodium bicarbonate
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified by recrystallization from toluene

Sources & evidence

ORD record
ord-cb43d0aa31b84efe92a93c8927142845
Source dataset
uspto-grants-2003_10
Patent number
US06635657B1

Reaction notes

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