Hydrochloric Acid → HCID 70429717, compound

HRID 364803Notes

Reaction equation

HRID 364803 reaction equation
[Cl:1][C:2]1[C:10]([Cl:11])=[C:9]2[C:5]([CH2:6][C:7]([CH2:14][CH:15]3[CH2:19][CH2:18][CH2:17][CH2:16]3)([CH3:13])[C:8]2=[O:12])=[CH:4][C:3]=1[CH2:20][C:21]([NH2:23])=[O:22].[C:24](OCC)(=[O:30])[C:25](OCC)=[O:26].CC(C)([O-])C.[K+].Cl>CN(C)C=O>[Cl:1][C:2]1[C:10]([Cl:11])=[C:9]2[C:5]([CH2:6][C:7]([CH2:14][CH:15]3[CH2:19][CH2:18][CH2:17][CH2:16]3)([CH3:13])[C:8]2=[O:12])=[CH:4][C:3]=1[C:20]1[C:21](=[O:22])[NH:23][C:25](=[O:26])[C:24]=1[OH:30]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 20193585HCID 20193585, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 70429717HCID 70429717, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

(6,7-Dichloro-2-cyclopentylmethyl-2,3-dihydro-2-methyl-1-oxo-1H-inden-5-yl)acetamide (5 g., 0.0141 mole) and diethyl oxalate (2.19 g., 0.015 mole) are dissolved in dry dimethylformamide (30 ml.) and stirred in an ice bath under nitrogen for 20 minutes. Potassium t-butoxide (3.53 g., 0.0315 mole) is then added in two portions 15 minutes apart. The mixture is stirred while cooling in the ice bath for another 45 minutes, then stirred at room temperature for 18 hours and poured into ice water (500 ml). The mixture is acidified with hydrochloric acid and extracted with ether (4×125 ml.). The combined organic extracts are washed with water and then repeatedly extracted with dilute sodium carbonate. The combined aqueous extracts are acidified with hydrochloric acid, extracted with methylene chloride and then with ether. The combined organic extracts are washed with water, dried over magnesium sulfate and concentrated under vacuum. The residue is chromatographed on silica (175 g.) with a mixture of toluene, dioxane and acetic acid (50:5:1). The appropriate product fractions are concentrated under vacuum and the residue is dissolved in ether and extracted with dilute sodium bicarbonate. The aqueous extracts are acidified with hydrochloric acid and extracted with methylene chloride and then with ether. The combined organic extracts are washed with water, dried over magnesium sulfate and concentrated under vacuum to obtain the 3-(6,7-Dichloro-2-cyclopentylmethyl-2,3-dihydro- 2-methyl-1-oxo-1H-inden-5-yl)-4-hydroxy-1H-pyrrole-2,5-dione as a foam which was then dried under high vacuum at 90° C. for 2 hours to give 3.6 g. (63%).

Workup

  1. stirringThe mixture is stirred
  2. stirringstirred at room temperature for 18 hours
  3. extractionextracted with ether (4×125 ml.)
  4. washThe combined organic extracts are washed with water
  5. extractionrepeatedly extracted with dilute sodium carbonate
  6. extractionextracted with methylene chloride
  7. washThe combined organic extracts are washed with water
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated under vacuum
  10. customThe residue is chromatographed on silica (175 g.) with a mixture of toluene, dioxane and acetic acid (50:5:1)
  11. concentrationThe appropriate product fractions are concentrated under vacuum
  12. dissolutionthe residue is dissolved in ether
  13. extractionextracted with dilute sodium bicarbonate
  14. extractionextracted with methylene chloride
  15. washThe combined organic extracts are washed with water
  16. dry with materialdried over magnesium sulfate
  17. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-f36ca24b50794734b0308b6d36244668
Source dataset
uspto-grants-1986_08
Patent number
US04605663

Reaction notes

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