Diethyl Oxalate → 4-[3-(2,4-Dichlorophenyl)-1,9-dimethyl-2-oxo-2,9-dihydro-1H-pyrido[2,3-b]indol-6-yl]-2,4-dioxobutyric acid ethyl ester

HRID 559157Notes

Reaction equation

HRID 559157 reaction equation
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2]([O:4]CC)=O.[H-].[Na+].Br[CH2:14][C:15]([C:17]1[CH:18]=[C:19]2[C:23](=[CH:24][CH:25]=1)[N:22]([CH3:26])[C:21]1[N:27]([CH3:40])[C:28](=[O:39])[C:29]([C:31]3[CH:36]=[CH:35][C:34]([Cl:37])=[CH:33][C:32]=3[Cl:38])=[CH:30][C:20]2=1)=[O:16].C1OCCOC2C(=CC=CC=2)OCCOCCOC2C(=CC=CC=2)OC1>C1COCC1.CCO.CCOC(C)=O>[CH2:9]([O:8][C:1](=[O:7])[C:2](=[O:4])[CH2:14][C:15]([C:17]1[CH:18]=[C:19]2[C:23](=[CH:24][CH:25]=1)[N:22]([CH3:26])[C:21]1[N:27]([CH3:40])[C:28](=[O:39])[C:29]([C:31]3[CH:36]=[CH:35][C:34]([Cl:37])=[CH:33][C:32]=3[Cl:38])=[CH:30][C:20]2=1)=[O:16])[CH3:10]

Participants

8

Reactant 4

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 26541Dibenzo-18-crown-6HCID 866239506-(bromoacetyl)-3-(2,4-dichlorophenyl)-1,9-dimethyl-1,9-dihydro-2H-pyrido[2,3-b]indol-2-one

Product 1

HCID 669974574-[3-(2,4-Dichlorophenyl)-1,9-dimethyl-2-oxo-2,9-dihydro-1H-pyrido[2,3-b]indol-6-yl]-2,4-dioxobutyric acid ethyl ester

Reagents, catalysts & solvents 3

HCID 702EthanolCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

940 mg (6.4 mmol) of diethyl oxalate are dissolved in 5 ml of anhydrous THF. 273 mg (6.8 mmol) of 60% NaH are added and the mixture is stirred at ambient temperature for 10 minutes. A solution of 1.3 g (3.2 mmol) of compound 6-(bromoacetyl)-3-(2,4-dichlorophenyl)-1,9-dimethyl-1,9-dihydro-2H-pyrido[2,3-b]indol-2-one from preparation 1.2 above and 18 mg (0.052 mmol) of dibenzo-18-crown-6 dissolved in 20 ml of anhydrous THF is added, as are a few drops of anhydrous EtOH. The mixture is heated at 70° C. under argon for 3 hours. The mixture is allowed to return to ambient temperature. EtOAc is added to the reaction medium and the organic phase is washed with a 1N HCl solution. The organic phase is evaporated to dryness and the product obtained is triturated in water and filtered. The product is taken up in EtOH and evaporated to dryness.

Workup

  1. additionis added
  2. temperatureThe mixture is heated at 70° C. under argon for 3 hours
  3. customto return to ambient temperature
  4. washthe organic phase is washed with a 1N HCl solution
  5. customThe organic phase is evaporated to dryness
  6. customthe product obtained
  7. customis triturated in water
  8. filtrationfiltered
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-292f18976b824882804e22661ad9f903
Source dataset
uspto-grants-2011_11
Patent number
US08063061B2

Reaction notes

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