Hydrazine hydrate (1:1) → 3-Amino-2-hydroxy-N,N-dimethylbenzamide

HRID 1927574Notes

Reaction equation

HRID 1927574 reaction equation
[OH:1][C:2]1[C:12]([N+:13]([O-])=O)=[CH:11][CH:10]=[CH:9][C:3]=1[C:4]([N:6]([CH3:8])[CH3:7])=[O:5].O.NN>CCO.CC(O)=O.O.CCOC(C)=O>[NH2:13][C:12]1[C:2]([OH:1])=[C:3]([CH:9]=[CH:10][CH:11]=1)[C:4]([N:6]([CH3:8])[CH3:7])=[O:5]

Participants

6

Reactant 2

HCID 24654Hydrazine hydrate (1:1)2×HCID 113678032-hydroxy-N,N-dimethyl-3-nitrobenzamide

Product 1

HCID 160984833-Amino-2-hydroxy-N,N-dimethylbenzamide

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 18476134Acetic acid ethanolSolvent

Procedure

67.5 g of 2-Hydroxy-N,N-dimethyl-3-nitro-benzamide are dissolved in 1000 ml of EtOH/AcOH 9/1 and degassed 4× by evacuating and purging with argon. 7.5 g of Ru/C are added and the mixture obtained is degassed 4× by evacuating and purging with argon. A reaction mixture obtained is heated to reflux and 25 ml of hydrazine hydrate are added slowly. At 1 hour intervals 3 further portions of 25 ml of hydrazine hydrate are added. A reaction mixture obtained is cooled to rt, filtered and washed with EtOH. Solvent from the filtrate obtained is evaporated. Toluene is added 4× to the residue obtained and solvent is evaporated. A residue obtained is taken up in 1 l of H2O and 1 l of EtOAc. An aqueous layer obtained is extracted 3× with EtOAc. The organic layers obtained are washed 2× with brine, dried, filtered and solvent is evaporated. A residue obtained is purified by column chromatography over 500 g of silica using EtOAc/heptane 1/1 as the eluant to give 3-amino-2-hydroxy-N,N-dimethyl-benzamide.

Workup

  1. customdegassed 4×
  2. customby evacuating
  3. custompurging with argon
  4. addition7.5 g of Ru/C are added
  5. customthe mixture obtained
  6. customis degassed 4×
  7. customby evacuating
  8. custompurging with argon
  9. customA reaction mixture obtained
  10. temperatureis heated
  11. temperatureto reflux
  12. customA reaction mixture obtained
  13. filtrationfiltered
  14. washwashed with EtOH
  15. customSolvent from the filtrate obtained
  16. customis evaporated
  17. additionToluene is added 4× to the residue
  18. customobtained
  19. customsolvent is evaporated
  20. customA residue obtained
  21. customAn aqueous layer obtained
  22. extractionis extracted 3× with EtOAc
  23. customThe organic layers obtained
  24. washare washed 2× with brine
  25. customdried
  26. filtrationfiltered
  27. customsolvent is evaporated
  28. customA residue obtained
  29. customis purified by column chromatography over 500 g of silica

Sources & evidence

ORD record
ord-1c2e42a6b8084ed3a90f004a53a93ce0
Source dataset
uspto-grants-2012_05
Patent number
US08183281B2

Reaction notes

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