3-Nitroaniline → 1-Carboxymethyl-6,7-dibromo-5-nitro-1,4-dihydro-2,3-quinoxalinedione

HRID 439472Notes

Reaction equation

HRID 439472 reaction equation
[C:1]([CH2:4][N:5]1[C:14]2[C:9](=[CH:10][C:11]([Br:16])=[C:12]([Br:15])[CH:13]=2)[NH:8][C:7](=[O:17])[C:6]1=[O:18])([OH:3])=[O:2].[N+:19](C1C=C(C=CC=1)N)([O-:21])=[O:20].C1CCC(N=C=NC2CCCCC2)CC1>CN(C=O)C>[C:1]([CH2:4][N:5]1[C:14]2[C:9](=[C:10]([N+:19]([O-:21])=[O:20])[C:11]([Br:16])=[C:12]([Br:15])[CH:13]=2)[NH:8][C:7](=[O:17])[C:6]1=[O:18])([OH:3])=[O:2]

Participants

5

Reactant 3

HCID 74233-NitroanilineHCID 10868DicyclohexylcarbodiimideHCID 199585561-Carboxymethyl-6,7-dibromo-1,4-dihydroquinoxaline-2,3-dione

Product 1

HCID 199585981-Carboxymethyl-6,7-dibromo-5-nitro-1,4-dihydro-2,3-quinoxalinedione

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
28 °C

Procedure

To a stirred solution of N-carboxymethyl-6,7-dibromo-1,4-dihydroquinoxaline-2,3-dione (100 mg, 0.260 mmol) and m-nitroaniline (40 mg, 0.29 mmol) in dry DMF (2 mL) under N2 at 28° C., DCC (60 mg, 0.29 mmol) was added in one portion. The solution was stirred for 4 h at 28° C. The insoluble solid was filtered and washed with DMF (1 mL). The clear filtrate was then poured into water (30 mL). The precipitated solid was filtered and dried under vacuum (water aspirator) to obtain 65 mg crude product as a yellow powder. The product was purified by Soxhlet extraction in boiling ethanol (20 mL), keeping the oil bath temperature at 120° C., for 4 h. The insoluble material (in the thimble) was dried under vacuum to obtain 30 mg pure (1H NMR) N-(N'-(m-nitrophenyl)carboxamidyl)-methyl-6,7-dibromo-1,4-dihydroquinox-aline-2,3-dione as a white solid (some of the product also ends up being extracted by hot ethanol which accounts for the low yield of pure product). M.p.>300° C. (decomposes). 1H NMR: δ4.98 (s, 1H), 7.45 (s, 1H), 7.61 (d of d seen as a t, J=8.1 Hz) 7.79 (s, 1H), 7.86 (d, 1H, J=9 Hz), 7.91 (d, 1H, J=8.4 Hz), 8.54 (s, 1H), 10.76 (s, 1H), 12.28 (s, 1H). IR (KBr, cm-1): 3444, 3289, 1707, 1686, 1672, 1602. HRMS: Calculated for C16H10BF2N4O5, 495.9018; Observed, 495.9008.

Workup

  1. filtrationThe insoluble solid was filtered
  2. washwashed with DMF (1 mL)
  3. additionThe clear filtrate was then poured into water (30 mL)
  4. filtrationThe precipitated solid was filtered
  5. dry with materialdried under vacuum (water aspirator)
  6. customto obtain 65 mg crude product as a yellow powder
  7. customThe product was purified by Soxhlet extraction
  8. customat 120° C.
  9. waitfor 4 h
  10. customThe insoluble material (in the thimble) was dried under vacuum

Sources & evidence

ORD record
ord-4201ab31878d4d56bab4d956eae8706a
Source dataset
uspto-grants-1996_05
Patent number
US05514680

Reaction notes

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