Sodium Azide → 4-Aminosampangine

HRID 483839Notes

Reaction equation

HRID 483839 reaction equation
[CH:1]1[CH:6]=[C:5]2[C:7]3[C:12]4[C:13]([C:18](=[O:19])[C:4]2=[CH:3][CH:2]=1)=[N:14][CH:15]=[C:16](Br)[C:11]=4[CH:10]=[CH:9][N:8]=3.[N-:20]=[N+]=[N-].[Na+]>CC(C)=O.O>[CH:1]1[CH:6]=[C:5]2[C:7]3[C:12]4[C:13]([C:18](=[O:19])[C:4]2=[CH:3][CH:2]=1)=[N:14][CH:15]=[C:16]([NH2:20])[C:11]=4[CH:10]=[CH:9][N:8]=3

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 99048014-Bromosampangine

Product 1

HCID 117767144-AminosampangineYield 91%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
10 °C

Procedure

A mixture of 4-bromosampangine (622 mg, 2.0 mmol) in acetone (40 mL) and sodium azide (1.30 g, 20.0 mmol) in H2O (10 mL) was heated at reflux for 1 h. The acetone was then removed by evaporation, MeOH (40 mL) added, and the mixture transferred to a three necked flask and cooled to 10° C. Piperidine (2 drops) was added and a stream of hydrogen sulfide bubbled through the reaction. After 30 min, the temperature was allowed to rise to 23° C. and the reaction continued for an additional 30 min. The solvent was then removed evaporated and the residue chromatographed as above to give 4-aminosampangine (23) (450 mg, 91%).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 h
  3. customThe acetone was then removed by evaporation, MeOH (40 mL)
  4. additionadded
  5. additionPiperidine (2 drops) was added
  6. customa stream of hydrogen sulfide bubbled through the reaction
  7. customto rise to 23° C.
  8. waitthe reaction continued for an additional 30 min
  9. customThe solvent was then removed
  10. customevaporated
  11. customthe residue chromatographed as above

Sources & evidence

ORD record
ord-5aaeb16a297043e0af1a31cdca21d72f
Source dataset
uspto-grants-1993_07
Patent number
US05227383

Reaction notes

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