4-Nitrobenzoic Acid → 4-Nitrobenzanilide

HRID 717333Notes

Reaction equation

HRID 717333 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].ClC(C(Cl)=O)=O.[C:19]1([NH2:25])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(N(CC)CC)C>ClCCl.CN(C)C=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([C:8]([NH:25][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[O:10])=[CH:11][CH:12]=1)([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 6115AnilineHCID 8471TriethylamineHCID 65578Oxalyl chloride

Product 1

HCID 770034-Nitrobenzanilide

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

Into a 1-L 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 4-nitrobenzoic acid (167 g, 999.29 mmol, 1.00 equiv) in dichloromethane (400 mL) and ClCOCOCl (317.5 g, 2.50 equiv). This was followed by the addition of N,N-dimethylformamide (1 mL) dropwise with stirring. The resulting solution was stirred for 4 h at room temperature. The mixture was concentrated under vacuum. To the residue was added a solution of PhNH2 (93 g, 1.00 equiv) in dichloromethane (400 mL), triethylamine (415 mL, 3.00 equiv) dropwise with stirring at 0° C. The resulting solution was stirred overnight at room temperature. The resulting mixture was washed with 2×500 mL of HCl (10%) and 1×500 mL of brine. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was diluted with 500 mL of petroleum ether/ethyl acetate=5:1. The solids were collected by filtration. This resulted in 205 g (85%) of 4-nitro-N-phenylbenzamide as light yellow solid. 1H NMR (300 MHz, DMSO-d6) δ 7.12-7.17 (m, 1H), 7.32-7.41 (m, 2H), 7.78-7.81 (m, 2H), 8.16-8.21 (m, 2H), 8.36-8.42 (m, 2H), 10.58 (s, 1H); MS (ESI) m/z 243 ([M+H]+).

Workup

  1. customInto a 1-L 3-necked round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. stirringThe resulting solution was stirred for 4 h at room temperature
  4. concentrationThe mixture was concentrated under vacuum
  5. stirringwith stirring at 0° C
  6. stirringThe resulting solution was stirred overnight at room temperature
  7. washThe resulting mixture was washed with 2×500 mL of HCl (10%) and 1×500 mL of brine
  8. dry with materialThe mixture was dried over anhydrous sodium sulfate
  9. concentrationconcentrated under vacuum
  10. additionThe residue was diluted with 500 mL of petroleum ether/ethyl acetate=5:1
  11. filtrationThe solids were collected by filtration
  12. customThis resulted in 205 g (85%) of 4-nitro-N-phenylbenzamide as light yellow solid

Sources & evidence

ORD record
ord-83776d9b304d48e496f5a6ad6ebfc87a
Source dataset
uspto-grants-2015_11
Patent number
US09193707B2

Reaction notes

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