Diphenylamine-2,2'-dicarboxylic acid → 4-Carboxy-9-acridanone

HRID 1662928Notes

Reaction equation

HRID 1662928 reaction equation
[NH:1]([C:11]1[CH:19]=[CH:18][CH:17]=[CH:16][C:12]=1[C:13]([OH:15])=O)[C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5]>P(Cl)(Cl)(Cl)=O>[C:4]([C:3]1[C:2]2[NH:1][C:11]3[C:12](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:13](=[O:15])[C:10]=2[CH:9]=[CH:8][CH:7]=1)([OH:6])=[O:5]

Participants

3

Reactant 1

HCID 11371Diphenylamine-2,2'-dicarboxylic acid

Product 1

HCID 35607584-Carboxy-9-acridanoneYield 94%

Reagents, catalysts & solvents 1

HCID 24813Phosphorus oxychlorideSolvent

Procedure

2,2′-Iminodibenzoic acid (5.27 g, 20.5 mmol) was mixed with phosphorus oxychloride (20 ml). The resulting pale yellow slurry was heated to boiling. The slurry turned initially bright yellow, then dissolved to give a deep red solution which was intensely yellow at the meniscus. After 2 hrs at reflux, excess solvent was evaporated under vacuum to give a dark oil. This was quenched with ice, then diluted with 2.0M aqueous HCl (25 ml) and the resulting dark solution re-heated to boiling. After 20 mins a solid precipitated and the mixture became very thick; another 20 mls of water was then added to allow effective stirring. After 1.5 hrs, the mixture was allowed to cool to ambient temperature. The yellow solid was collected by vacuum filtration, washed well with water, then acetone, and dried under vacuum to give 4-carboxyacridone (4.61 g, 94%). λmax (EtOH)=408, 390, 256 nm. δH (300 MHz, DMSO-d6) 7.24-7.33 (2H, m), 7.67-7.76 (2H, m), 8.17 (1H, d), 8.38 (1H, dd), 8.47 (1H, dd) and 11.9 (broad s, partially exch). Mass spectrum: (ES+) 240 (M+H), 262 (M+Na). Melting Point>300° C.

Workup

  1. temperatureThe resulting pale yellow slurry was heated to boiling
  2. dissolutiondissolved
  3. customto give a deep red solution which
  4. temperatureAfter 2 hrs at reflux
  5. customexcess solvent was evaporated under vacuum
  6. customto give a dark oil
  7. customThis was quenched with ice
  8. additiondiluted with 2.0M aqueous HCl (25 ml)
  9. temperaturethe resulting dark solution re-heated to boiling
  10. customAfter 20 mins a solid precipitated
  11. additionanother 20 mls of water was then added
  12. filtrationThe yellow solid was collected by vacuum filtration
  13. washwashed well with water
  14. dry with materialacetone, and dried under vacuum

Sources & evidence

ORD record
ord-0c9fef10ff3a404981ec26dbda5ae129
Source dataset
uspto-grants-2011_10
Patent number
US08034558B2

Reaction notes

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