Allylamine → 6-(trifluoromethyl)-3,4-dihydro-N-(2-propenyl)-2H-1,4-benzoxazine-2-carboxamide

HRID 261190Notes

Reaction equation

HRID 261190 reaction equation
[F:1][C:2]([F:17])([F:16])[C:3]1[CH:4]=[CH:5][C:6]2[O:11][CH:10]([C:12]([OH:14])=O)[CH2:9][NH:8][C:7]=2[CH:15]=1.[CH2:18]([NH2:21])[CH:19]=[CH2:20]>C(O)C>[F:16][C:2]([F:1])([F:17])[C:3]1[CH:4]=[CH:5][C:6]2[O:11][CH:10]([C:12]([NH:21][CH2:18][CH:19]=[CH2:20])=[O:14])[CH2:9][NH:8][C:7]=2[CH:15]=1

Participants

4

Reactant 2

HCID 7853AllylamineHCID 203952756-Trifluoromethyl-3,4-dihydro-2H-benzo[1,4]oxazine-2-carboxylic acid

Product 1

HCID 203952736-(trifluoromethyl)-3,4-dihydro-N-(2-propenyl)-2H-1,4-benzoxazine-2-carboxamide

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 20.6 g of 6C, 25.7 g of 2-propenamine and 34 ml of ethanol was stirred at room temperature for 36 hours. The excess amine and solvent were evaporated under reduced pressure. The solid residue was mixed with 150 ml of ether and the remaining solid material was filtered. The filtrate was added to petroleum ether and cooled; the resulting viscous material was filtered. The filtrate was stripped and the residue was triturated with petroleum ether to give an off-white powder which was purified by dry-column chromatography (silica gel), using ether as eluent. The higher Rf band was collected and extracted with ether, the solvent was stripped and the solid residue was recrystallized from ether/hexane (4/5 v/v). Thin-layer chromatography indicated that two components were present. The product was purified by wet-column chromatography (silica gel) using petroleum ether/ethyl ether (1:4 v/v) as eluent. The solvent was stripped and the residue was recrystallized from ether/hexane (75:100 v/v) to give 6, as a solid, mp: 95°-97° C.

Workup

  1. customThe excess amine and solvent were evaporated under reduced pressure
  2. additionThe solid residue was mixed with 150 ml of ether
  3. filtrationthe remaining solid material was filtered
  4. additionThe filtrate was added to petroleum ether
  5. temperaturecooled
  6. filtrationthe resulting viscous material was filtered
  7. customthe residue was triturated with petroleum ether
  8. customto give an off-white powder which
  9. customwas purified by dry-column chromatography (silica gel)
  10. customThe higher Rf band was collected
  11. extractionextracted with ether
  12. customthe solid residue was recrystallized from ether/hexane (4/5 v/v)
  13. customThe product was purified by wet-column chromatography (silica gel)
  14. customthe residue was recrystallized from ether/hexane (75:100 v/v)
  15. customto give 6

Sources & evidence

ORD record
ord-e91b3cbcfadc4565abcd17b9a6c9cb2b
Source dataset
uspto-grants-1979_08
Patent number
US04164576

Reaction notes

Loading…