Hydrochloric Acid → 68285-16-5

HRID 1389514Notes

Reaction equation

HRID 1389514 reaction equation
[CH2:1]([O:3][C:4]([NH:6][C:7]1[C:12]([F:13])=[CH:11][C:10]([C:14](=[O:16])[CH3:15])=[CH:9][C:8]=1[Cl:17])=[O:5])[CH3:2].[Se](=O)=O.[C:21]([NH2:25])([CH3:24])([CH3:23])[CH3:22].Cl>O1CCOCC1.O.C(O)C.CCOCC>[ClH:17].[CH2:1]([O:3][C:4]([NH:6][C:7]1[C:12]([F:13])=[CH:11][C:10]([CH:14]([OH:16])[CH2:15][NH:25][C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:9][C:8]=1[Cl:17])=[O:5])[CH3:2]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 6385Tert-ButylamineHCID 24007Selenium DioxideHCID 20296718HCID 20296718, compound

Product 1

HCID 305198368285-16-5

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

8.7 gm of 4'-ethoxycarbonylamino-3'-chloro-5'-fluoro-acetophenone were added in portions to a solution of 3.7 gm of selenium dioxide in 30 ml of dioxane and 1 ml of water at 60° C. while stirring. The mixture obtained was refluxed for 4 hours and, after cooling, 4.1 ml of tert. butylamine were added dropwise to the solution of 4'-ethoxycarbonylamino-3'-chloro-5'-fluoro-phenylglyoxal thus obtained while cooling with ice. The resulting mixture was diluted with 350 ml of ethanol and filtered. 5 gm of sodium borohydride were added in portions to the filtrate containing crude 4'-ethoxy-carbonylamino-3'-chloro-5'-fluoro-phenyl-glyoxylidene-tert.-butylamine, while stirring and cooling with ice. After allowing the mixture thus obtained to stand overnight at room temperature, the excess sodium borohydride was destroyed with acetone. The resulting mixture was admixed with water and extracted with chloroform. The chloroform extract was washed with water, dried over sodium sulfate and, after the addition of activated charcoal and rapidly heated to the boiling point filtered, and evaporated in vacuo. The solid residue consisting of 1-(4-ethoxy-carbonylamino-3-chloro-5-fluoro-phenyl)-2-tert. butylamino-ethanol was admixed with isopropanol, and the mixture obtained was acidified with ethereal hydrochloric acid to pH 4. After addition of ether, the precipitated crystals were suction-filtered off and washed with ether.

Workup

  1. customThe mixture obtained
  2. temperaturewas refluxed for 4 hours
  3. temperatureafter cooling
  4. customthus obtained
  5. temperaturewhile cooling with ice
  6. filtrationfiltered
  7. addition5 gm of sodium borohydride were added in portions to the filtrate
  8. additioncontaining crude 4'-ethoxy-carbonylamino-3'-chloro-5'-fluoro-phenyl-glyoxylidene-tert.-butylamine
  9. stirringwhile stirring
  10. temperaturecooling with ice
  11. customthus obtained
  12. customthe excess sodium borohydride was destroyed with acetone
  13. extractionextracted with chloroform
  14. extractionThe chloroform extract
  15. washwas washed with water
  16. dry with materialdried over sodium sulfate
  17. additionafter the addition of activated charcoal
  18. temperaturerapidly heated to the boiling point
  19. filtrationfiltered
  20. customevaporated in vacuo
  21. customthe mixture obtained
  22. filtrationthe precipitated crystals were suction-filtered off
  23. washwashed with ether

Sources & evidence

ORD record
ord-6341c134253645bbaf7f997419849c04
Source dataset
uspto-grants-1981_01
Patent number
US04244967

Reaction notes

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