Hydrochloric Acid → 4-Propionylspiro[cyclohexane-1,1'-indan]-3,5-dione

HRID 236245Notes

Reaction equation

HRID 236245 reaction equation
[CH2:1]([CH:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:7]=[CH:6]1)[C:2]([CH3:4])=[O:3].C[C:15]([CH3:22])([C:19]([O-:21])=O)C([O-])=O.[Na+].[Na+].[C:25](OC(=O)CC)(=[O:28])[CH2:26]C.Cl>CO>[C:19]([CH:4]1[C:2](=[O:3])[CH2:1][C:5]2([C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[CH2:7][CH2:6]2)[CH2:26][C:25]1=[O:28])(=[O:21])[CH2:15][CH3:22]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 31263Propionic anhydrideHCID 14348598HCID 14348598, compoundHCID 15452843HCID 15452843, compound

Product 1

HCID 143486004-Propionylspiro[cyclohexane-1,1'-indan]-3,5-dione

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

1-Acetonylindene (2.4 g) was added to a solution of sodium dimethylmalonate (5.3 equiv) in anhydrous methanol (80 ml) and the mixture was stirred and heated at reflux for 12 hr. The solvent was evaporated and the residue was azeotroped with toluene. The dry residue was dissolved in anhydrous dimethylformamide (80 ml) at 60° C. Propionic anhydride (5.3 equiv) was added and the mixture was stirred and heated at reflux for 0.5 hr. The cooled mixture was poured into a dilute aqueous hydrochloric acid solution which was then extracted with diethyl ether. The organic fraction was evaporated and the residue was heated at reflux with potassium hydroxide (5 g) in water (80 ml) for 4 hr. The cooled mixture was extracted with diethyl ether. The aqueous fraction was heated to 60° C. and was acidified by dropwise addition of a dilute aqueous hydrochloric acid solution. The cooled mixture was extracted with diethyl ether. The dried (MgSO4) organic fraction was evaporated and the residue was purified by column chromatography over silica with dichloromethane elution to give 4-propionylspiro[cyclohexane-1,1'-indan]-3,5-dione as a pale yellow oil. Pmr spectrum (CDCl3 ; δ in ppm): 1.17 (3H, t); 2.03 (2H, t); 2.64-3.24 (8H, m); 7.21-7.25 (4H, m); 18.27 (1H, s). 4-Butyrylspiro[cyclohexane-1,1'-indan]-3,5-dione was similarly prepared from 1-acetonylideneindane, sodium dimethyl malonate and n-butyric anhydride and was obtained as a pale yellow oil. Pmr spectrum (CDCl3 ; δ in ppm): 1.00 (3H, t); 1.70 (2H, m); 2.02 (2H, t); 2.62-3.14 (8H, m); 7.20-7.25 (4H, m); 18.33 (1H, s).

Workup

  1. temperatureheated
  2. temperatureat reflux for 12 hr
  3. customThe solvent was evaporated
  4. customthe residue was azeotroped with toluene
  5. dissolutionThe dry residue was dissolved in anhydrous dimethylformamide (80 ml) at 60° C
  6. stirringthe mixture was stirred
  7. temperatureheated
  8. temperatureat reflux for 0.5 hr
  9. extractionwas then extracted with diethyl ether
  10. customThe organic fraction was evaporated
  11. temperaturethe residue was heated
  12. temperatureat reflux with potassium hydroxide (5 g) in water (80 ml) for 4 hr
  13. extractionThe cooled mixture was extracted with diethyl ether
  14. additionwas acidified by dropwise addition of a dilute aqueous hydrochloric acid solution
  15. extractionThe cooled mixture was extracted with diethyl ether
  16. dry with materialThe dried (MgSO4) organic fraction
  17. customwas evaporated
  18. customthe residue was purified by column chromatography over silica with dichloromethane elution

Sources & evidence

ORD record
ord-8f89d93eb265425e8ee2f8e5e06232e0
Source dataset
uspto-grants-1987_02
Patent number
US04643763

Reaction notes

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