Aniline → HCID 54043359, compound

HRID 2396064Notes

Reaction equation

HRID 2396064 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH2:10][C:9](O[Si](C)(C)C)=[C:8](O[Si](C)(C)C)[CH2:7][C:6]=1[C:21]([O:23][CH3:24])=[O:22])=[O:4].C(O)(=O)C(C)(C)C.[CH3:32][O:33][C:34]1[CH:40]=[C:39]([O:41][CH3:42])[CH:38]=[CH:37][C:35]=1[NH2:36].[NH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1>CN(C=O)C.O.C(O)C>[CH3:1][O:2][C:3](=[O:4])[C:5]1[C:6](=[CH:7][C:8]([NH:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)=[C:9]([NH:36][C:35]2[CH:37]=[CH:38][C:39]([O:41][CH3:42])=[CH:40][C:34]=2[O:33][CH3:32])[CH:10]=1)[C:21]([O:23][CH3:24])=[O:22]

Participants

8

Reactant 4

HCID 6115AnilineHCID 6417Pivalic acid2×HCID 176522,4-DimethoxyanilineHCID 10022190HCID 10022190, compound

Product 1

HCID 54043359HCID 54043359, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 1.31 g (3 mmol) 4,5-Bis(trimethylsilyloxy)-cyclohexa-1,4-diene-1,2-dicarboxylic acid dimethyl ester (Example 1a), 306 mg (3 mmol) pivalic acid and 1 ml of DMF is heated under argon to 120° and a solution of 460 mg (3 mmol) 2,4-dimethoxy-anilin in 1 ml of DMF is added within 5 minutes. The reaction mixture is heated at 120° for 10 minutes, cooled, diluted with water and extracted with ethyl acetate. The organic phase is washed in succession with 1N HCl, water, saturated Na2CO3, water and brine, dried with magnesium sulfate and concentrated by evaporation. The evaporation residue, a brown oil, 402 mg (3.9 mmol) pivalic acid and 2 ml of ethanol are heated to reflux and a solution of 358 μl (3.9 mmol) of aniline in 3 ml of ethanol is added dropwise. The reaction mixture is heated to reflux for 15 hours, cooled, diluted with water and extracted with ethyl acetate. The organic phase is washed in succession with 1N HCl,water, saturated Na2CO3, water and brine, dried with magnesium sulfate and concentrated by evaporation. The evaporation residue is chromatographed on silica gel with ethyl acetate/hexane 1:2 and the product fractions are concentrated by evaporation. This way, in the first product fractions 4-anilino-5-(2,4-dimethoxy-anilino)-phthalic acid dimethyl ester is obtained in the form of a yellow oil: FAB-MS: 437 [M+ +H]. The evaporation residue of the product fractions following thereafter is recrystallized, and 4,5-bis-(2,4-dimethoxy-anilino)-phthalicacid dimethyl ester is obtained in the form of a yellow foam: FAB-MS: 497 [M+ +H].

Workup

  1. temperatureThe reaction mixture is heated at 120° for 10 minutes
  2. temperaturecooled
  3. extractionextracted with ethyl acetate
  4. washThe organic phase is washed in succession with 1N HCl, water, saturated Na2CO3, water and brine
  5. dry with materialdried with magnesium sulfate
  6. concentrationconcentrated by evaporation
  7. temperatureto reflux
  8. temperatureThe reaction mixture is heated
  9. temperatureto reflux for 15 hours
  10. temperaturecooled
  11. extractionextracted with ethyl acetate
  12. washThe organic phase is washed in succession with 1N HCl,water, saturated Na2CO3, water and brine
  13. dry with materialdried with magnesium sulfate
  14. concentrationconcentrated by evaporation
  15. customThe evaporation residue is chromatographed on silica gel with ethyl acetate/hexane 1:2
  16. concentrationthe product fractions are concentrated by evaporation

Sources & evidence

ORD record
ord-c0df8029e81946c0acba072ea3cb3556
Source dataset
uspto-grants-1996_02
Patent number
US05491144

Reaction notes

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