3-[2,4-Bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide → 3-[2,4-Bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-aminophthalide

HRID 1660271Notes

Reaction equation

HRID 1660271 reaction equation
[CH3:1][N:2]([CH3:37])[C:3]1[CH:8]=[C:7]([N:9]([CH3:11])[CH3:10])[CH:6]=[CH:5][C:4]=1[C:12]1([C:25]2[C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[N:27]([CH2:34][CH3:35])[C:26]=2[CH3:36])[C:21]2[C:16](=[CH:17][C:18]([N+:22]([O-])=O)=[CH:19][CH:20]=2)[C:14](=[O:15])[O:13]1>Cl>[CH3:1][N:2]([CH3:37])[C:3]1[CH:8]=[C:7]([N:9]([CH3:10])[CH3:11])[CH:6]=[CH:5][C:4]=1[C:12]1([C:25]2[C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[N:27]([CH2:34][CH3:35])[C:26]=2[CH3:36])[C:21]2[C:16](=[CH:17][C:18]([NH2:22])=[CH:19][CH:20]=2)[C:14](=[O:15])[O:13]1

Participants

3

Reactant 1

HCID 205235443-[2,4-Bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide

Product 1

HCID 205235763-[2,4-Bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-aminophthalideYield 11.5%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 25.0 g (0.054 mole) of 3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide, prepared as described in part B above, in 285 ml of concentrated hydrochloric acid was heated to 60° C. at which temperature 31.25 g (0.142 mole) of stannous chloride dihydrate was added at such a rate as to maintain the temperature of 60° C. After the addition was complete, the solution was heated to 70° C. and held there for a period of one hour and then allowed to cool to 25° C. The green-colored solid which separated was collected by filtration and was slurried in five percent aqueous sodium hydroxide solution. The resulting suspension was extracted with 500 ml of toluene at room temperature and the toluene extract was filtered, decolorized, and dried over sodium sulfate. On standing, a cream solid separated from the toluene solution. The solid was filtered off and dried to obtain 2.9 g of 3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-aminophthalide (Formula III: Ro =R1 =R3 =Y1 =H; R2 =NH2 ; R=R5 =CH3 ; R4 =N(CH3)2 ; R6 =CH2CH3) having a melting point of 206°-209° C. Infrared analysis showed a maximum at 1727 cm-1 (C=O; s). The nuclear magnetic resonance spectrum was concordant with the assigned structure. A toluene solution of the above compound developed an intense grape-black color when spotted on a paper coated with phenolic resin.

Workup

  1. additionwas added at such a rate as
  2. additionAfter the addition
  3. temperaturethe solution was heated to 70° C.
  4. temperatureto cool to 25° C
  5. customThe green-colored solid which separated
  6. filtrationwas collected by filtration
  7. extractionThe resulting suspension was extracted with 500 ml of toluene at room temperature
  8. extractionthe toluene extract
  9. filtrationwas filtered
  10. dry with materialdried over sodium sulfate
  11. customa cream solid separated from the toluene solution
  12. filtrationThe solid was filtered off
  13. customdried

Sources & evidence

ORD record
ord-4d2b87ba8c404f23af7ba3ecfdf084e9
Source dataset
uspto-grants-1981_12
Patent number
US04307018

Reaction notes

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