Aniline → 1-[[(o-Tolylamino)carbonyl]amino]-1,4-dihydro-2,3-quinoxalinedione

HRID 53753Notes

Reaction equation

HRID 53753 reaction equation
C(C[N:5]1[C:14]2[C:9](=[CH:10][C:11](Br)=[C:12](Br)[CH:13]=2)[NH:8][C:7](=[O:17])[C:6]1=[O:18])(O)=O.[NH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.[CH2:26]1CCC(N=C=NC2CCCCC2)CC1.C[N:42]([CH:44]=[O:45])C>>[C:21]1([CH3:26])[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=1[NH:19][C:44]([NH:42][N:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[NH:8][C:7](=[O:17])[C:6]1=[O:18])=[O:45]

Participants

5

Reactant 4

HCID 6115AnilineHCID 6228DimethylformamideHCID 10868DicyclohexylcarbodiimideHCID 199585561-Carboxymethyl-6,7-dibromo-1,4-dihydroquinoxaline-2,3-dione

Product 1

HCID 199585841-[[(o-Tolylamino)carbonyl]amino]-1,4-dihydro-2,3-quinoxalinedione

Conditions

Temperature
28 °C

Procedure

To a stirred solution of N-carboxymethyl-6,7-dibromo-1,4-dihydroquinoxaline-2,3-dione (100 mg, 0.250 mmol) and aniline (25 mg, 0.25 mmol) in dry DMF (1.5 mL) under N2 at 28° C., DCC (55 mg, 0.25 mmol) was added in one portion. The solution was stirred at 28° C. for 18 h. The insoluble white solid was filtered and the clear filtrate was poured into water (6 mL). The precipitated solid was filtered and air dried to obtain 113 mg crude product as a grey powder. The crude product was then purified by Soxhlet extraction in boiling ethanol (20 mL), keeping the oil bath temperature at 120° C., for 5 h. The residue (in the thimble) was dried in the oven (approx. 70°-80° C.) overnight to furnish 35 mg pure (1H NMR) N-(N'-phenylcarboxamidyl)methyl-6,7-dibromo-1,4-dihydroquinox-aline-2,3-dione as a light grey powder; m.p. >300° C. (decomposes). 1H NMR: δ 4.97 (s, 1H), 6.99-7.11 (m, 1H), 7.23-7.37 (m, 2H), 7.44 (s, 1H), 7.52 (d, 2H, J=8.4 Hz), 7.73 (s, 1H), 10.25 (s, 1H), 12.25 (s, 1H). IR (KBr, cm-1): 3620, 3468, 1714, 1694, 1595, 1542. HRMS: Calculated for C16H11Br2N3O3, 450.9168; Observed, 450.9177.

Workup

  1. filtrationThe insoluble white solid was filtered
  2. additionthe clear filtrate was poured into water (6 mL)
  3. filtrationThe precipitated solid was filtered
  4. customair dried
  5. customto obtain 113 mg crude product as a grey powder
  6. customThe crude product was then purified by Soxhlet extraction
  7. customat 120° C.
  8. waitfor 5 h
  9. customThe residue (in the thimble) was dried in the oven (approx. 70°-80° C.) overnight

Sources & evidence

ORD record
ord-f353e0c4d077491b84d0174268e2ebf0
Source dataset
uspto-grants-1997_04
Patent number
US05620979

Reaction notes

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