Methyldiphenylamine → 6-[p-(Methylphenylamino)phenyl]-2,3,5-pyrazinetricarbonitrile

HRID 1658236

反応式

HRID 1658236 の反応式
[C:1]([C:3]1[N:8]=[C:7]([C:9]#[N:10])[C:6]([C:11]#[N:12])=[N:5][C:4]=1[C:13]#[N:14])#N.[CH3:15][N:16]([C:23]1[CH:28]=[CH:27]C=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>CS(C)=O>[CH3:15][N:16]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)[C:23]1[CH:24]=[CH:25][C:1]([C:3]2[N:8]=[C:7]([C:9]#[N:10])[C:6]([C:11]#[N:12])=[N:5][C:4]=2[C:13]#[N:14])=[CH:27][CH:28]=1

参加物

4

反応物 2

HCID 11098MethyldiphenylamineHCID 300186Pyrazinetetracarbonitrile

生成物 1

HCID 537977206-[p-(Methylphenylamino)phenyl]-2,3,5-pyrazinetricarbonitrile収率 9%

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
100 °C

実験手順

A mixture of 18 g of tetracyanopyrazine and 18.3 g of N-methyl-N-phenylaniline in 200 ml of dimethylsulfoxide was heated at 100°C for 21 hours, the solution was cooled and poured onto 6 liters of ice water to give a sticky precipitate. The mixture was extracted with ethyl acetate. The ethyl acetate solution was back-extracted with water, dried over sodium sulfate and concentrated to give a dark brown solid. Unreacted tetracyanopyrazine was removed by recrystallization of the solid from toluene, from which TCP was the first to crystallize. The toluene solution was concentrated and the residue was rinsed with hexane to partially remove unreacted N-methyl-N-phenylaniline. The residue was dissolved in aqueous tetrahydrofuran (THF) (75% tetrahydrofuran) at 50°C, the THF removed by distillation, and the residual solid washed with water to remove water-soluble by-products. The remaining product was chromatographed on a column of neutral silicic acid using hexane/benzene/ acetonitrile eluents. Red fractions were combined, concentrated, and the product recrystallized from heptane-toluene to give 3.02 g of red-purple 6-[p-(methylphenylamino)phenyl]-2,3,5-pyrazinetricarbonitrile, mp 187.3°- 1.88.8°C after drying at 111°C (0.1 mm). Another 1.93 g of this product was recovered from mother liquors. Silica paper chromatography revealed only one colored product.

後処理

  1. temperaturethe solution was cooled
  2. customto give a sticky precipitate
  3. extractionThe mixture was extracted with ethyl acetate
  4. extractionThe ethyl acetate solution was back-extracted with water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customto give a dark brown solid
  8. customUnreacted tetracyanopyrazine was removed by recrystallization of the solid from toluene, from which TCP
  9. customto crystallize
  10. concentrationThe toluene solution was concentrated
  11. washthe residue was rinsed with hexane to partially remove unreacted N-methyl-N-phenylaniline
  12. dissolutionThe residue was dissolved in aqueous tetrahydrofuran (THF) (75% tetrahydrofuran) at 50°C
  13. customthe THF removed by distillation
  14. washthe residual solid washed with water
  15. customto remove water-soluble by-products
  16. customThe remaining product was chromatographed on a column of neutral silicic acid
  17. concentrationconcentrated
  18. customthe product recrystallized from heptane-toluene

出典と根拠

ORDレコード
ord-919430f7f947404eaacd071761c15bc6
出典データセット
uspto-grants-1976_06
特許番号
US03963715

関連ノート

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