Aniline → 4-Methyl-3-nitro-N-phenylbenzene-1-carboximidic acid

HRID 1859644Notes

Reaction equation

HRID 1859644 reaction equation
C(Cl)(=O)C(Cl)=O.[N+:7]([C:10]1[CH:11]=[C:12]([CH:16]=[CH:17][C:18]=1[CH3:19])[C:13]([OH:15])=O)([O-:9])=[O:8].ClCCl.[NH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>O1CCCC1.CN(C)C=O>[CH3:19][C:18]1[CH:17]=[CH:16][C:12]([C:13]([NH:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[O:15])=[CH:11][C:10]=1[N+:7]([O-:9])=[O:8]

Participants

7

Reactant 4

HCID 6115AnilineHCID 6344DichloromethaneHCID 73194-Methyl-3-nitrobenzoic acidHCID 65578Oxalyl chloride

Product 1

HCID 7964134-Methyl-3-nitro-N-phenylbenzene-1-carboximidic acidYield 94.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Oxalyl chloride (3 mL, 35 mmol) was added dropwise to a stirred solution of 3-nitro-4-methylbenzoic acid (5.0 g, 28 mmol) in a mixture of tetrahydro-furan or dichloromethane (125 mL) and dimethylformamide (½ mL) under N2 at ice bath temperature. The mixture was allowed to warm to room temperature. After 1 hour, the solvent was removed by rotary evaporator under reduced pressure. The residue was redissolved in fresh tetrahydro-furan (100 mL) and recooled to ice bath temperature under N2, while a solution of aniline (5.2 g, 56 mmol) in tetrahydro-furan (25 mL) was added dropwise. After 16 hours of stirring at room temperature, the mixture was concentrated to half-volume by rotary evaporator and the residue stirred in water (200 mL). After several hours, the precipitate was filtered off, rinsed three times with water, and dried to afford the product (6.8 g); m.p. 147-148° C.

Workup

  1. customthe solvent was removed by rotary evaporator under reduced pressure
  2. dissolutionThe residue was redissolved in fresh tetrahydro-furan (100 mL)
  3. customrecooled to ice bath
  4. concentrationthe mixture was concentrated to half-volume by rotary evaporator
  5. stirringthe residue stirred in water (200 mL)
  6. waitAfter several hours
  7. filtrationthe precipitate was filtered off
  8. washrinsed three times with water
  9. customdried

Sources & evidence

ORD record
ord-fa1c3f4b108f4dc2b5d8d6444cde804e
Source dataset
uspto-grants-2003_03
Patent number
US06528528B2

Reaction notes

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