Hydrochloric Acid → 3-Isoxazolamine, 5-(1,1-dimethylethyl)-

HRID 128433Notes

Reaction equation

HRID 128433 reaction equation
[C:1]([CH2:7][C:8]#[N:9])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[OH-].[Na+].Cl.[NH2:13]O.Cl>C(O)C.O>[NH2:9][C:8]1[CH:7]=[C:1]([C:2]([CH3:5])([CH3:4])[CH3:3])[O:6][N:13]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 443297Hydroxyamine hydrochloride

Product 1

HCID 1714733-Isoxazolamine, 5-(1,1-dimethylethyl)-

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

In a 1 l. round bottom 3-neck flask there was placed 30 g. of pivalyl acetonitrile, 12.8 g. of sodium hydroxide, 394 ml. of water, and 281 ml. of ethanol. This mixture was heated to refluxing and there was added thereto over a period of about 10 minutes an aqueous solution of 22.2 g. of hydroxylamine hydrochloride. The pH of the reaction mixture after addition was complete was about 6.4. After 30 minutes the pH was determined to be about 6.5. After 11/2 hours the pH was about 6.8, and after 2 hours the pH was about 7.0. The pH was adjusted to about 6.2 using concentrated aqueous hydrochloric acid. After another 3 hours the pH was about 6.6. The reaction mixture was refluxed overnight and at the end of 22 hours of reaction time the pH was about 7.3. The reaction mixture was cooled and ethanol removed in vacuo. The solid which separated was filtered off and dried. It weighed 18.9 g., had a melting point of about 103°-105° C., and was determined by vpc to contain 91.2% of 3-amino-5-(t-butyl)isoxazole and 5.2% of 5-amino-3-(t-butyl)isoxazole. Yield: 56% of desired isomer.

Workup

  1. customround bottom 3-neck flask there was placed
  2. temperatureThis mixture was heated
  3. temperatureto refluxing
  4. additionthere was added
  5. additionThe pH of the reaction mixture after addition
  6. waitAfter 30 minutes the pH was determined
  7. waitAfter 11/2 hours the pH was about 6.8, and after 2 hours the pH was about 7.0
  8. waitAfter another 3 hours the pH was about 6.6
  9. temperatureThe reaction mixture was refluxed overnight and at the end of 22 hours of reaction time the pH was about 7.3
  10. temperatureThe reaction mixture was cooled
  11. customethanol removed in vacuo
  12. customThe solid which separated
  13. filtrationwas filtered off
  14. customdried

Sources & evidence

ORD record
ord-66c7fce790954e00ab7146ed9e3f4fa5
Source dataset
uspto-grants-1981_03
Patent number
US04259501

Reaction notes

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