Sulfuric Acid → Bis[3-(dibutylamino)propyl]5,6-dihydro-6-oxophenanthridine-3,8-dicarboxylate dihydrochloride

HRID 1580800Notes

Reaction equation

HRID 1580800 reaction equation
[ClH:1].Cl.[CH2:3]([N:7]([CH2:43][CH2:44][CH2:45][CH3:46])[CH2:8][CH2:9][CH2:10][O:11][C:12]([C:14]1[CH:26]=[CH:25][C:24]2[C:23]3[C:18](=[CH:19][C:20]([C:27]([O:29][CH2:30][CH2:31][CH2:32][N:33]([CH2:38][CH2:39][CH2:40][CH3:41])[CH2:34][CH2:35][CH2:36][CH3:37])=[O:28])=[CH:21][CH:22]=3)[C:17](=[O:42])[C:16]=2[CH:15]=1)=[O:13])[CH2:4][CH2:5][CH3:6].S(=O)(=O)(O)O.[N-:52]=[N+]=[N-].[Na+]>FC(F)(F)C(O)=O>[ClH:1].[ClH:1].[CH2:38]([N:33]([CH2:34][CH2:35][CH2:36][CH3:37])[CH2:32][CH2:31][CH2:30][O:29][C:27]([C:20]1[CH:21]=[CH:22][C:23]2[C:24]3[C:16]([C:17](=[O:42])[NH:52][C:18]=2[CH:19]=1)=[CH:15][C:14]([C:12]([O:11][CH2:10][CH2:9][CH2:8][N:7]([CH2:3][CH2:4][CH2:5][CH3:6])[CH2:43][CH2:44][CH2:45][CH3:46])=[O:13])=[CH:26][CH:25]=3)=[O:28])[CH2:39][CH2:40][CH3:41]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 68140824Bis[3-(dibutylamino)propyl] 9-oxo-9H-fluorene-2,7-dicarboxylate--hydrogen chloride (1/2)

Product 1

HCID 21543599Bis[3-(dibutylamino)propyl]5,6-dihydro-6-oxophenanthridine-3,8-dicarboxylate dihydrochloride

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 20.4 g (0.03 mole) of bis[3-(dibutylamino)propyl]9-oxo-fluorene-2,7-dicarboxylate dihydrochloride and 13 ml of concentrated sulfuric acid contained in 150 ml of trifluoroacetic acid, which has been cooled to 0°C., is slowly added 2.6 g (0.04 mole) of sodium azide with stirring. Stirring is continued for 30 minutes whereupon most of the trifluoroacetic acid is removed in vacuo. Cracked ice is added and the residue is made alkaline with a 50% sodium hydroxide solution. The reaction mixture is extracted with methylene chloride, the extracts are combined, dried over magnesium sulfate, filtered and the filtrate treated with a slight excess of ethereal hydrogen chloride. The solution is concentrated to approximately 300 ml in vacuo, and approximately 500 ml of warm butanone is added. The mixture is permitted to cool slowly whereupon the desired bis[3-(dibutylamino)propyl]5,6-dihydro-6-oxophenanthridine-3,8-dicarboxylate crystallizes as the dihydrochloride salt. The product when recrystallized from a methylene chloride-ethyl acetate mixture has a m.p. 204.5°-6.5°C., and a N.E. of 349.4.

Workup

  1. stirringStirring
  2. customwhereupon most of the trifluoroacetic acid is removed in vacuo
  3. additionCracked ice is added
  4. extractionThe reaction mixture is extracted with methylene chloride
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. additionthe filtrate treated with a slight excess of ethereal hydrogen chloride
  8. concentrationThe solution is concentrated to approximately 300 ml in vacuo, and approximately 500 ml of warm butanone
  9. additionis added
  10. temperatureto cool slowly whereupon the desired bis[3-(dibutylamino)propyl]5,6-dihydro-6-oxophenanthridine-3,8-dicarboxylate
  11. customcrystallizes as the dihydrochloride salt
  12. customThe product when recrystallized from a methylene chloride-ethyl acetate mixture

Sources & evidence

ORD record
ord-e91d0faa10174ac385cacfe54870b94c
Source dataset
uspto-grants-1976_01
Patent number
US03933893

Reaction notes

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