p-Aminoacetophenone → HCID 22501575, compound

HRID 488032Notes

Reaction equation

HRID 488032 reaction equation
N[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.[S-:11][C:12]#[N:13].[NH4+:14].BrBr>C(O)(=O)C.O>[NH2:13][C:12]1[S:11][C:2]2[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][C:3]=2[N:14]=1

Participants

6

Reactant 3

HCID 7468p-AminoacetophenoneHCID 15666Ammonium thiocyanateHCID 24408Bromine

Product 1

HCID 22501575HCID 22501575, compoundYield 82.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

13.5 g of p-aminoacetophenone and 31.70 g of ammonium thiocyanate were dispersed in a mixture of 800 ml of glacial acetic acid and 40 ml of water, and a solution of 20 g of bromine dissolved in 100 ml of glacial acetic acid was dropwise added thereto at 7° to 10° C. over about 1 hour while stirring. After stirring at 10° C. for 2 hours, the solution was heated and stirred at 70° C. for 5 hours. The reacted mixture was filtered at 50° C. or more, and the obtained filtrate was added to 1000 ml of a hot water of about 70° C. To this mixture, crystals of anhydrous sodium carbonate were added while leaving it to cool and stirring until the pH became 5. Fresh pale yellow crystals were filtered and dried to obtain 15.83 g of 2-amino-5-acetylbenzothiazole of the following structural formula: ##STR158## Then, 2.00 g of (0.0105 mol) of 2-amino-5-acetylbenzothiazole obtained above, 0.69 g (0.0105 mol) of malononitrile and 0.4 g of ammonium acetate were added to a mixture of 10 ml of glacial acetic acid and 5 ml of toluene, heated while stirring, and refluxed for 2 hours while evaporating toluene and water. The resulting product was left to cool, and then added to 100 ml of water. The obtained fresh yellow crystals were filtered and dried to obtain 2.47 g of 5-(2',2-dicyano-1'-methyleteno)-2-aminobenzotiazole of the following structural formula. The molecular weight of this compound was confirmed with a mass spectrum. ##STR159##

Workup

  1. additionwas dropwise added
  2. stirringAfter stirring at 10° C. for 2 hours
  3. temperaturethe solution was heated
  4. stirringstirred at 70° C. for 5 hours
  5. filtrationThe reacted mixture was filtered at 50° C. or more
  6. additionthe obtained filtrate was added to 1000 ml of a hot water of about 70° C
  7. additionTo this mixture, crystals of anhydrous sodium carbonate were added
  8. customwhile leaving it
  9. temperatureto cool
  10. stirringstirring until the pH
  11. filtrationFresh pale yellow crystals were filtered
  12. customdried

Sources & evidence

ORD record
ord-d11d82f2432c4cc092ff7f88a152864d
Source dataset
uspto-grants-1994_03
Patent number
US05298608

Reaction notes

Loading…