Trifluoroacetic acid → 3,4-Dimethoxy-6-methylphenanthren-9-amine

HRID 746002Notes

Reaction equation

HRID 746002 reaction equation
FC(F)(F)C(OC(=O)C(F)(F)F)=O.FC(F)(F)C(O)=O.[CH3:21][O:22][C:23]1[CH:24]=[CH:25][C:26]2[CH:27]=[C:28](C(O)=O)[C:29]3[C:34]([C:35]=2[C:36]=1[O:37][CH3:38])=[CH:33][C:32]([CH3:39])=[CH:31][CH:30]=3.[N-:43]=[N+]=[N-].[Na+].[OH-].[Na+]>C(O)C>[NH2:43][C:28]1[C:29]2[C:34]([C:35]3[C:36]([O:37][CH3:38])=[C:23]([O:22][CH3:21])[CH:24]=[CH:25][C:26]=3[CH:27]=1)=[CH:33][C:32]([CH3:39])=[CH:31][CH:30]=2

Participants

7

Reactant 5

HCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 14798Sodium HydroxideHCID 33557Sodium AzideHCID 137729813,4-Dimethoxy-6-methylphenanthrene-9-carboxylic acid

Product 1

HCID 137729823,4-Dimethoxy-6-methylphenanthren-9-amine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 400 ml (2.87M) of trifluoroacetic anhydride and 400 ml (5.22M) of trifluoroacetic acid is added at room temperature under a nitrogen atmosphere to 61.1 g (0.206M) of 3,4-dimethoxy-6-methyl-phenanthrene-9-carboxylic acid and the mixture is stirred for 10 minutes. After the mixture has been cooled to -5°, 16.08 g (0.247M) sodium azide are carefully added in solid form. The mixture is stirred for 2 hours at 0°, poured onto ice, extracted three times with methylene chloride and washed with a solution 1N of sodium hydroxide. The aqueous phases are extracted twice with methylene chloride 2-propanol 8:2. The organic phases are combined, dried and evaporated, to give white crystals. 86 g of the resultant mixted anhydride are warmed for 2 hours under reflux in 800 ml of a solution 2N of sodium hydroxide and 800 ml ethanol and the mixture is evaporated. The residue is washed with water/ice and extracted three times with methylene chloride. The organic phases are combined, dried and evaporated to give the title compound as an oil.

Workup

  1. temperatureAfter the mixture has been cooled to -5°
  2. stirringThe mixture is stirred for 2 hours at 0°
  3. additionpoured onto ice
  4. extractionextracted three times with methylene chloride
  5. washwashed with a solution 1N of sodium hydroxide
  6. extractionThe aqueous phases are extracted twice with methylene chloride 2-propanol 8:2
  7. customdried
  8. customevaporated
  9. customto give white crystals
  10. customthe mixture is evaporated
  11. washThe residue is washed with water/ice
  12. extractionextracted three times with methylene chloride
  13. customdried
  14. customevaporated

Sources & evidence

ORD record
ord-34cfd9305b404366befbd0b08335e82c
Source dataset
uspto-grants-1986_07
Patent number
US04602032

Reaction notes

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