Diethyl Oxalate → 2,3-Dioxo-1,2,3,4-tetrahydroquinoxaline-6-carbonitrile

HRID 439440Notes

Reaction equation

HRID 439440 reaction equation
[C:1]([O:8]CC)(=O)[C:2]([O:4]CC)=O.[NH2:11][C:12]1[CH:13]=[C:14]([CH:17]=[CH:18][C:19]=1[NH2:20])[C:15]#[N:16]>C(O)(=O)C>[C:15]([C:14]1[CH:13]=[C:12]2[C:19](=[CH:18][CH:17]=1)[NH:20][C:1](=[O:8])[C:2](=[O:4])[NH:11]2)#[N:16]

Participants

4

Reactant 2

HCID 7268Diethyl OxalateHCID 7372853,4-Diaminobenzonitrile

Product 1

HCID 51006912,3-Dioxo-1,2,3,4-tetrahydroquinoxaline-6-carbonitrile

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

The title compound was prepared using an adaptation of the method of Cheeseman. (Cheeseman, G. W. H. J. Chem. Soc. 1171 (1962)). A mixture of diethyl oxalate (3.90 g, 27.6 mmol) and 3,4-diaminobenzonitrile (275 mg, 2.06 mmol) was heated to reflux under N2 for 2 h. The reaction was allowed to cool to room temperature and the solid collected by vacuum filtration and rinsed with EtOH. The yellow brown solid was air dried to yield 156.6 mg (40.8%) which was >98% pure by 1H NMR. An analytically pure sample was prepared by recrystallization of 100 mg in 10 mL glacial acetic acid to give 21.2 mg of fine white crystals. 1H NMR (d6 -DMSO) δ7.20 (d, J=8.1, 1H, ArH), 7.39 (d, J=1.2, 1H, ArH), 7.50 (dd, J=1.2, J=8.4, 1H, ArH), 12.09 (s, 1H, NH), 12.22 (s, 1H, NH). EIMS m/z 187(87, M+), 159 (100, bp), 131(83), 104 (77), 77 (65), 53 (43), 28 (30). EIHRMS calc. for C9H5N3O2 187.0381, found 187.0377.

Workup

  1. temperaturewas heated
  2. temperatureto reflux under N2 for 2 h
  3. filtrationthe solid collected by vacuum filtration
  4. washrinsed with EtOH
  5. customdried
  6. customto yield 156.6 mg (40.8%) which

Sources & evidence

ORD record
ord-ebfc7095f4a5492cbc9aae68f34e5b56
Source dataset
uspto-grants-1996_05
Patent number
US05514680

Reaction notes

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