Hydroxyamine hydrochloride → HCID 13343677, compound

HRID 1154585Notes

Reaction equation

HRID 1154585 reaction equation
Cl.[NH2:2][OH:3].[C:4]([C:12]1[C:13](Cl)=[C:14]([Cl:24])[C:15]2[O:19][CH:18]([C:20]([OH:22])=[O:21])[CH2:17][C:16]=2[CH:23]=1)(=O)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>N1C=CC=CC=1>[Cl:24][C:14]1[C:13]2[O:3][N:2]=[C:4]([C:5]3[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=3)[C:12]=2[CH:23]=[C:16]2[CH2:17][CH:18]([C:20]([OH:22])=[O:21])[O:19][C:15]=12

Participants

4

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 12747895HCID 12747895, compound

Product 1

HCID 13343677HCID 13343677, compoundYield 32.3%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Hydroxylamine hydrochloride (15.19 g, 0.2186 mol.) and (3a) (10.84 g., 0.0322 mol.) were heated at reflux in 75 ml. of dry pyridine for 5 hours. On cooling, the pyridine was removed on a rotary evaporator and chased with ethanol. The residue, a yellow gum, was taken up in ethyl acetate and washed with dilute aqueous hydrochloric acid and brine, then dried over anhydrous magnesium sulfate and evaporated to a gum containing both E and Z isomers of the oxime. Without further purification, the gum was taken up in 20 ml. of absolute ethanol and treated with 120 ml. of 1M alcoholic potassium hydroxide at reflux on a steam bath for 3 hours then refrigerated at 0°-5° C. for 48 hours. The resulting precipitate was collected by filtration, washed with hexane, dried, and dissolved in 300 ml. warm distilled water. Acidification to pH 2.0 by addition of 4.0 M aqueous hydrochloric acid gave a gelatinous precipitate which was extracted into ethyl acetate, dried with anhydrous magnesium sulfate, decolorized with Darco, and evaporated. Recrystallization from ethyl acetate with hexane afforded the furobenzisoxazole (4a) in 32.3% yield, m.p. 214°-215° C. Analysis (C16H10ClNO4) C,H,N,Cl.

Workup

  1. temperatureat reflux in 75 ml
  2. temperatureOn cooling
  3. customthe pyridine was removed on a rotary evaporator and chased with ethanol
  4. washwashed with dilute aqueous hydrochloric acid and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customevaporated to a gum
  7. additioncontaining both E and Z isomers of the oxime
  8. customWithout further purification
  9. additionof absolute ethanol and treated with 120 ml
  10. temperatureof 1M alcoholic potassium hydroxide at reflux on a steam bath for 3 hours
  11. filtrationThe resulting precipitate was collected by filtration
  12. washwashed with hexane
  13. customdried
  14. dissolutiondissolved in 300 ml
  15. temperaturewarm
  16. distillationdistilled water
  17. additionAcidification to pH 2.0 by addition of 4.0 M aqueous hydrochloric acid
  18. customgave a gelatinous precipitate which
  19. extractionwas extracted into ethyl acetate
  20. dry with materialdried with anhydrous magnesium sulfate
  21. customevaporated
  22. customRecrystallization from ethyl acetate with hexane

Sources & evidence

ORD record
ord-2fa49e0de4c741d5aa13a3b5fdb506f6
Source dataset
uspto-grants-1984_12
Patent number
US04490384

Reaction notes

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