Methane → 5-Bromo-6,7-difluoro-1,4-dihydro-2,3-quinoxalinedione

HRID 53706ノート

反応式

HRID 53706 の反応式
[C:1]([O:8]CC)(=O)[C:2]([O:4]CC)=O.[Br:11][C:12]1[C:13]([NH2:21])=[C:14]([NH2:20])[CH:15]=[C:16]([F:19])[C:17]=1[F:18].C>[OH-].[Na+]>[Br:11][C:12]1[C:17]([F:18])=[C:16]([F:19])[CH:15]=[C:14]2[C:13]=1[NH:21][C:2](=[O:4])[C:1](=[O:8])[NH:20]2

参加物

5

反応物 3

HCID 297MethaneHCID 7268Diethyl OxalateHCID 199585973-Bromo-4,5-difluorobenzene-1,2-diamine

生成物 1

HCID 199585655-Bromo-6,7-difluoro-1,4-dihydro-2,3-quinoxalinedione

試薬・触媒・溶媒 1

HCID 14798Sodium Hydroxide溶媒

実験手順

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 (2.70 g, 18.5 mmol) and 3-bromo-4,5-difluoro-1,2-diaminobenzene (410 mg, 1.85 mmol) was heated to reflux under N2 for 15 h. The reaction was allowed to cool to room temperature and the dark-brown solid collected by vacuum filtration and rinsed with EtOH (20 mL) and air dried to give 215 mg (42%). A portion of this solid (150 mg) was taken and dissolved in 20 mL 1N NaOH with heating. The solution was treated with activated charcoal and filtered through a pad of Celite. The resulting solution was carefully acidified with 1N HCl (pH=1). Pale yellow needles slowly formed in the solution and were collected by vacuum filtration, rinsed with 20 mL of H2O and dried under vacuum (0.1 torr, 78° C.) to yield 67.8 mg of powdery pale yellow crystals, mp 306°-310° C. (dec). 1H NMR (d6 -DMSO) δ 7.09 (dd, 1H, J=7.5, H-8), 11.3 (br s, 1H, NH), 12.1 (br s, 1H, NH). EIMS m/z 278 (M+2, 75), 276 (M+, 77), 250 (56), 248 (57), 14 1 (bp). EIHRMS calc. for C8H4BrF2N2O2 275.9346, found 275.9331.

後処理

  1. temperaturewas heated
  2. temperatureto reflux under N2 for 15 h
  3. filtrationthe dark-brown solid collected by vacuum filtration
  4. washrinsed with EtOH (20 mL) and air
  5. customdried
  6. customto give 215 mg (42%)
  7. temperaturewith heating
  8. filtrationfiltered through a pad of Celite
  9. customPale yellow needles slowly formed in the solution
  10. filtrationwere collected by vacuum filtration
  11. washrinsed with 20 mL of H2O
  12. customdried under vacuum (0.1 torr, 78° C.)

出典と根拠

ORDレコード
ord-1a5ee532bd0d449ba863916bff88d655
出典データセット
uspto-grants-1997_04
特許番号
US05620979

反応ノート

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