Hexamethylenetetramine → Benzo(b)thiophene-5-carboxaldehyde

HRID 979588ノート

反応式

HRID 979588 の反応式
[CH2:1]1[C:6](=O)N(Br)[C:3](=[O:4])[CH2:2]1.CC1C=C[C:13]2[S:14][CH:15]=[CH:16][C:12]=2[CH:11]=1.C1N2CN3CN(C2)CN1C3>C(Cl)(Cl)(Cl)Cl.C(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH:3]([C:2]1[CH:1]=[CH:6][C:13]2[S:14][CH:15]=[CH:16][C:12]=2[CH:11]=1)=[O:4]

参加物

7

反応物 3

HCID 4101HexamethylenetetramineHCID 67184N-bromobutanimide2 回HCID 843465-Methylbenzo(b)thiophene

生成物 1

HCID 139097Benzo(b)thiophene-5-carboxaldehyde収率 297.4%

試薬・触媒・溶媒 3

HCID 7187Benzoyl Peroxide触媒HCID 5943Carbon Tetrachloride溶媒HCID 6212Chloroform溶媒

実験手順

Under N2, NBS (6 g, 0.034 mol) was added to a solution of 5-methylbenzo[b]thiophene (30.8 g, 0.21 mol), benzoylperoxide (1.6 g) in CCl4 (300 ml) and was heated at reflux. After 15 minutes, the remainder of the NBS (35 g, 0.2 mol) was added over a period of 5 minutes and heated at reflux for 1.5 hours. The reaction mixture was then cooled, filtered and the filtrate washed with H2O (2x), dried, filtered and concentrated to dryness. The residue was dissolved in CHCl3 (130 ml) and added to a solution of hexamethylenetetramine (33.6 g, 0.24 mol) in CHCl3 (60 ml). After 0.5 hour, the reaction mixture was cooled, filtered and the solid washed with hexane. After drying, the solid was dissolved in acetic acid-H2O (275 ml) and heated at reflux for 2 hours. Then concentrated HCl (55 ml) was added and the mixture refluxed an additional 5 minutes. After cooling, the solution was extracted with ether (3×), and the organic extracts were backwashed with saturated Na2CO3 (2×), dried, filtered, and concentrated to dryness to yield 16.4 g (48%) of product

後処理

  1. temperaturewas heated
  2. temperatureat reflux
  3. temperatureheated
  4. temperatureat reflux for 1.5 hours
  5. temperatureThe reaction mixture was then cooled
  6. filtrationfiltered
  7. washthe filtrate washed with H2O (2x)
  8. customdried
  9. filtrationfiltered
  10. concentrationconcentrated to dryness
  11. dissolutionThe residue was dissolved in CHCl3 (130 ml)
  12. waitAfter 0.5 hour
  13. temperaturethe reaction mixture was cooled
  14. filtrationfiltered
  15. washthe solid washed with hexane
  16. customAfter drying
  17. dissolutionthe solid was dissolved in acetic acid-H2O (275 ml)
  18. temperatureheated
  19. temperatureat reflux for 2 hours
  20. additionThen concentrated HCl (55 ml) was added
  21. temperaturethe mixture refluxed an additional 5 minutes
  22. temperatureAfter cooling
  23. extractionthe solution was extracted with ether (3×)
  24. customdried
  25. filtrationfiltered
  26. concentrationconcentrated to dryness

出典と根拠

ORDレコード
ord-dbb990442d21427194cccc45d6fce2bb
出典データセット
uspto-grants-1987_05
特許番号
US04668697

反応ノート

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