Hydrogen Bromide → 2,3,5,6,7,8-Hexahydroisoquinoline-3,8-dione

HRID 596819ノート

反応式

HRID 596819 の反応式
[O:1]=[C:2]1[C:11](C#N)=[C:10]2[C:5]([C:6](=[O:14])[CH2:7][CH2:8][CH2:9]2)=[CH:4][NH:3]1.Br.C(=O)(O)[O-].[Na+]>>[CH:4]1[NH:3][C:2](=[O:1])[CH:11]=[C:10]2[C:5]=1[C:6](=[O:14])[CH2:7][CH2:8][CH2:9]2

参加物

4

反応物 3

HCID 260Hydrogen BromideHCID 516892Sodium BicarbonateHCID 222665143,8-Dioxo-2,3,5,6,7,8-hexahydroisoquinoline-4-carbonitrile

生成物 1

HCID 125594472,3,5,6,7,8-Hexahydroisoquinoline-3,8-dione

実験手順

A solution of 28.4 parts of 2,3,5,6,7,8hexahydro-3,8-dioxo-4-isoquinolinecarbonitrile in 500 parts by volume of 48% hydrobromic acid is heated at the reflux temperature in the absence of light for about 7 hours, following which time the solvent is removed by distillation under reduced pressure. The resulting residue is partitioned between chloroform and aqueous sodium chloride and the layers are separated. The aqueous phase is extracted several times with chloroform, then combined with the original chloroform layer. That organic solution is washed with aqueous sodium chloride, then dried over anhydrous sodium sulfate and stripped of solvent under reduced pressure to afford the crude product. The original aqueous layer is neutralized by the addition of sodium bicarbonate, then is extracted with chloroform. Evaporation of that chloroform extract to dryness affords additional product. The combined crude product is purified by recrystallization from aqueous acetone, thus affording pure 2,3,5,6,7,8-hexahydro-3,8isoquinolinedione, melting at about 246°-248° with decomposition. Ultraviolet absorption maxima are observed in methanol at 279 and 221 mμ with molecular extinction coefficients of about 16,700 and 13,500, respectively. In deuteropyridine, nuclear magnetic resonance peaks are displayed at about 1.96, 2.57, 2.92, 5.50 and 8.71 parts per million.

後処理

  1. customis removed by distillation under reduced pressure
  2. customThe resulting residue is partitioned between chloroform and aqueous sodium chloride
  3. customthe layers are separated
  4. extractionThe aqueous phase is extracted several times with chloroform
  5. washThat organic solution is washed with aqueous sodium chloride
  6. dry with materialdried over anhydrous sodium sulfate
  7. customto afford the crude product
  8. extractionis extracted with chloroform
  9. customEvaporation of that chloroform
  10. extractionextract to dryness
  11. customaffords additional product
  12. customis purified by recrystallization from aqueous acetone

出典と根拠

ORDレコード
ord-2c0d4333996548e9afea8b92c03bee0d
出典データセット
uspto-grants-1977_03
特許番号
US04012391

反応ノート

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