Methanol → 5,12-Dihydro-2,9-dimethylquino(2,3-b)acridine-7,14-dione

HRID 1439822Notes

Reaction equation

HRID 1439822 reaction equation
[CH3:1][C:2]1[CH:28]=[CH:27][C:5]([NH:6][C:7]2[CH:15]=[C:14]([C:16]([OH:18])=O)[C:13]([NH:19][C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)=[CH:12][C:8]=2[C:9](O)=[O:10])=[CH:4][CH:3]=1.CO>O.S([O-])([O-])(=O)=O.[Na+].[Na+]>[CH3:1][C:2]1[CH:28]=[CH:27][C:5]2[NH:6][C:7]3[C:8]([C:9](=[O:10])[C:4]=2[CH:3]=1)=[CH:12][C:13]1[NH:19][C:20]2[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][C:21]=2[C:16](=[O:18])[C:14]=1[CH:15]=3

Participants

5

Reactant 2

HCID 887MethanolHCID 825242,5-Di-p-toluidinoterephthalic acid

Product 1

HCID 704235,12-Dihydro-2,9-dimethylquino(2,3-b)acridine-7,14-dione

Reagents, catalysts & solvents 2

HCID 24436Sodium SulfateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
60 °C

Procedure

To 320 g of polyphosphoric acid (111.8% phosphoric acid) heated at 80°-95° C. was added 0.72 g (5.1 mmole) of sodium sulfate followed by 72 g (0.1915 mole) of essentially salt-free 2,5-di(4-methylanilino)terephthalic acid. The mixture was heated at 120°-125° C. for two hours. The viscous solution was cooled to 90°-95° C. and then slowly poured into a mixture of 468 g of methanol and 52 g of water (i.e., 90% aqueous methanol) at 40° C. The temperature of the resultant slurry was allowed to rise during the addition to about 64° C., with the temperature being controlled during addition by external cooling and adjustment of melt addition rate. The slurry was heated at reflux for one hour, cooled to 60° C., and diluted with 600 g of water. After the slurry was stirred at 60° C. for 30 minutes, the solid component was collected by filtration and washed with water until acid-free. The resultant presscake was reslurried in 800 g of aqueous sodium hydroxide, then heated at about 90°-95° C. The slurry was cooled, filtered, and washed with water until free of alkali, then reslurried in water. The resultant slurry was heated at 140°-145° C. in a closed system (e.g., a pressure reactor), cooled, acidified to pH 3.5 with phosphoric acid, treated with an aqueous emulsion of sodium dioctyl sulfosuccinate and VM&P Naphtha (available from Unocal Chemicals), and stirred. The solid component was collected by filtration and washed with water. The wet cake can be oven dried or used as is for specific applications. Here, the wet cake was dried in an oven at 60° C. to give about 60 g of 2,9-dimethylquinacridone as a brilliant magenta solid.

Workup

  1. temperatureThe mixture was heated at 120°-125° C. for two hours
  2. temperatureThe viscous solution was cooled to 90°-95° C.
  3. additionto rise during the addition to about 64° C., with the temperature
  4. additionbeing controlled during addition
  5. temperatureby external cooling
  6. additionadjustment of melt addition rate
  7. temperatureThe slurry was heated
  8. temperatureat reflux for one hour
  9. filtrationthe solid component was collected by filtration
  10. washwashed with water until acid-free
  11. temperatureheated at about 90°-95° C
  12. temperatureThe slurry was cooled
  13. filtrationfiltered
  14. washwashed with water until free of alkali,
  15. temperatureThe resultant slurry was heated at 140°-145° C. in a closed system (e.g., a pressure reactor)
  16. temperaturecooled
  17. additiontreated with an aqueous emulsion of sodium dioctyl sulfosuccinate and VM&P Naphtha (available from Unocal Chemicals)
  18. stirringstirred
  19. filtrationThe solid component was collected by filtration
  20. washwashed with water
  21. customdried
  22. customHere, the wet cake was dried in an oven at 60° C.

Sources & evidence

ORD record
ord-87926f4bff4c48aba3096cc7208f488e
Source dataset
uspto-grants-1996_03
Patent number
US05496405

Reaction notes

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