Sulfuric Acid → HCID 12832713, compound

HRID 2059061Notes

Reaction equation

HRID 2059061 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:11][CH2:10][C:9](=[C:12]2[C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14](=[O:21])[CH2:13]2)[CH2:8][CH2:7]1)=[O:5])[CH3:2].S(=O)(=O)(O)[OH:23]>>[C:4]([N:6]1[CH2:7][CH2:8][C:9]2([O:21][C:14](=[O:23])[CH2:13][CH:12]2[C:20]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH2:10][CH2:11]1)([O:3][CH2:1][CH3:2])=[O:5]

Participants

3

Reactant 2

HCID 1118Sulfuric AcidHCID 12832714HCID 12832714, compound

Product 1

HCID 12832713HCID 12832713, compound

Procedure

1-Carboxy-β-phenyl-4-piperidinehydracrylic acid diethyl ester (60 g, 0.17 mol; mp 73°-75° C.), prepared by the general procedures described in Example 1, is added portionwise to a stirred mixture of 600 ml of concentrated sulfuric acid, and stirring at room temperature is continued for 4 hours. The solution is poured onto ice, and the mixture is extracted with a copious volume of diethyl ether. The ether extract is washed with water, dried and evaporated; the residue is collected as a solid (34 g) with the aid of a small volume of ether. This product mixture is purified by partition chromatography on a Celite® diatomaceous earth column developed with a hexane-methanol solvent system. The two main fractions separated on the partition column are each, in methylene chloride solution, passed through a short column of alumina (Woelm, Activity II) and the columns are eluted with methylene chloride and then with ethylacetate. Evaporation of the eluates gives the two products described above. The more polar product is the saturated spirolactone product of the example (17 g); mp. 112° -114° C. Recrystallization from acetone-hexane gives analytically pure material, mp. 121°-122° C. The second product, present in lesser amount, is the less polar 4-(3-oxo-1-indanylidene)-1-piperidinecarboxylic acid ethyl ester described above, mp. 118°-122°; recrystallization from aqueous methanol gives the analytical sample, mp. 114°-116° C.

Workup

  1. additionThe solution is poured onto ice
  2. extractionthe mixture is extracted with a copious volume of diethyl ether
  3. extractionThe ether extract
  4. washis washed with water
  5. customdried
  6. customevaporated
  7. customthe residue is collected as a solid (34 g) with the aid of a small volume of ether
  8. customThis product mixture is purified
  9. customby partition chromatography on a Celite® diatomaceous earth column
  10. customThe two main fractions separated on the partition column
  11. washthe columns are eluted with methylene chloride
  12. customEvaporation of the eluates
  13. customgives the two products
  14. customRecrystallization from acetone-hexane
  15. customgives analytically pure material, mp. 121°-122° C
  16. customrecrystallization from aqueous methanol
  17. customgives the analytical sample, mp. 114°-116° C.

Sources & evidence

ORD record
ord-81a9263652a546ffa66e98be96b01672
Source dataset
uspto-grants-1982_03
Patent number
US04321379

Reaction notes

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