2-Chloro-3-nitrobenzoic acid → N-methyl-N-hydroxy-2-chloro-3-nitrobenzamide

HRID 1421848

Reaction equation

HRID 1421848 reaction equation
[Cl:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4](O)=[O:5].S(Cl)(Cl)=O.Cl.[CH3:19][NH:20][OH:21].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.O.CCOCC>[CH3:19][N:20]([OH:21])[C:4](=[O:5])[C:3]1[CH:7]=[CH:8][CH:9]=[C:10]([N+:11]([O-:13])=[O:12])[C:2]=1[Cl:1]

Participants

8

Reactant 4

HCID 198702-Chloro-3-nitrobenzoic acidHCID 24386Thionyl ChlorideHCID 77906N-methylhydroxylamine hydrochlorideHCID 516892Sodium Bicarbonate

Product 1

HCID 18706122N-methyl-N-hydroxy-2-chloro-3-nitrobenzamideYield 89.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

To a stirred solution of 2-chloro-3-nitrobenzoic acid (6.0 grams, 0.031 mole) in toluene (100 mL) was added thionyl chloride (6.8 mL, 0.092 mole). Upon completion of addition, the reaction mixture was heated to reflux where it stirred for four hours. After this time, the reaction mixture was filtered and concentrated. The concentrate was taken up in ether and added dropwise to an ice-cold solution of N-methylhydroxylamine hydrochloride (2.6 g, 0.031 mole), sodium bicarbonate (5.5 g, 0.065 mole), water (20 mL), and ether (160 mL). Upon completion of addition, the reaction mixture was stirred for one hour. After this time, the reaction mixture was diluted with water and the ether layer was separated. The aqueous layer was extracted twice with ether. The combined ether layer and extracts were dried over magnesium sulfate and concentrated to provide 6.4 grams of N-methyl-N-hydroxy-2-chloro-3-nitrobenzamide. The NMR spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. temperaturethe reaction mixture was heated
  3. temperatureto reflux where it
  4. filtrationAfter this time, the reaction mixture was filtered
  5. concentrationconcentrated
  6. additionUpon completion of addition
  7. stirringthe reaction mixture was stirred for one hour
  8. customthe ether layer was separated
  9. extractionThe aqueous layer was extracted twice with ether
  10. dry with materialThe combined ether layer and extracts were dried over magnesium sulfate
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-508616ff3d344431965cb4b8d09d056a
Source dataset
uspto-grants-2000_06
Patent number
US06080702

Linked notes

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