Aniline → Itaconic acid

HRID 1741811Notes

Reaction equation

HRID 1741811 reaction equation
[CH3:1][CH:2]([CH2:6][C:7]([OH:9])=[O:8])[C:3]([OH:5])=[O:4].C1(N=C=NC2CCCCC2)CCCCC1.NC1C=CC=CC=1>C1COCC1.C(#N)C.CN(C)C1C=CN=CC=1>[C:3]([OH:5])(=[O:4])[C:2]([CH2:6][C:7]([OH:9])=[O:8])=[CH2:1]

Participants

7

Reactant 3

HCID 6115AnilineHCID 10349Methylsuccinic acidHCID 10868Dicyclohexylcarbodiimide

Product 1

HCID 811Itaconic acid

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

The enantiomer excess (hereinafter referred to as "e.e.") of the resulting methylsuccinic acid was determined as follows. A part (1.32 mg, 0.1 mmole) of the crude product was dissolved in 2 ml of THF and 2 ml of acetonitrile, and 45.4 mg (0.22 mmole) of N,N'-dicyclohexylcarbodiimide, 2.4 mg (0.02 mmole) of 4-dimethylaminopyridine, and 0.01 ml (0.11 mmole) of aniline were added to the solution, followed by stirring at room temperature overnight. The solvent was removed from the reaction mixture by distillation under reduced pressure. The residue was dissolved in chloroform, washed three times with a 5M hydrochloric acid aqueous solution and then once with a saturated sodium hydrogencarbonate aqueous solution in a successive manner, and dried over magnesium sulfate. The solvent was removed, and the crude dianilide was purified by silica gel column chromatography using diethyl ether as an eluent. The purified dianilide was subjected to high performance liquid chromatography (HPLC) using a chromatograph equipped with CHIRALCEL-OD® (manufactured by Daicel Chemical Industries, Ltd.) (eluent: isopropyl alcohol/hexane=10/90 by volume; detection: UV 254 nm; flow rate: 1 ml/min) to determine the e.e.

Workup

  1. customThe solvent was removed from the reaction mixture by distillation under reduced pressure
  2. dissolutionThe residue was dissolved in chloroform
  3. washwashed three times with a 5M hydrochloric acid aqueous solution
  4. dry with materialonce with a saturated sodium hydrogencarbonate aqueous solution in a successive manner, and dried over magnesium sulfate
  5. customThe solvent was removed
  6. customthe crude dianilide was purified by silica gel column chromatography
  7. customequipped with CHIRALCEL-OD® (manufactured by Daicel Chemical Industries, Ltd.) (eluent: isopropyl alcohol/hexane=10/90 by volume; detection: UV 254 nm; flow rate: 1 ml/min)

Sources & evidence

ORD record
ord-c816918279b4438eb3824c7bb3b52382
Source dataset
uspto-grants-1994_08
Patent number
US05334758

Reaction notes

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