Formate → 1,5-Dimethylbicyclo[3.2.1]octan-8-one

HRID 904997Notes

Reaction equation

HRID 904997 reaction equation
OS(O)(=O)=O.C([O-])=O.[CH3:9][C:10]12[CH:17]([OH:18])[C:14]([CH3:19])([CH2:15][CH2:16]1)[CH2:13][CH2:12][CH2:11]2>O.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(C)=O>[CH3:19][C:14]12[C:17](=[O:18])[C:10]([CH3:9])([CH2:16][CH2:15]1)[CH2:11][CH2:12][CH2:13]2

Participants

7

Reactant 3

HCID 283FormateHCID 1118Sulfuric AcidHCID 1084411,5-Dimethylbicyclo[3.2.1]octan-8-ol

Product 1

HCID 895551,5-Dimethylbicyclo[3.2.1]octan-8-one

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

A quantity of 56 ml of 98% H2SO4 was added dropwise with stirring and cooling to a solution of 67 g of CrO3 (0.67 mol) in 100 ml of ice water. The mixture was diluted with water to a total volume of 200 ml. The solution obtained was added with stirring to a solution of 54.6 g (0.32 mol) of the formate of 1,5-dimethylbicyclo [3,2,1] octan-8-ol and 0.5 g of tetrabutylammonium chloride in 120 ml of acetone at such a rate that the temperature of the reaction mixture was 35°-40° C. The mixture was stirred for a further 2 hours at 35° C. and subsequently, the acetone solution was separated from the bottom layer. The latter was extracted a few times with acetone and the extracts were added to the acetone solution. The mixture was washed with a saturated K2CO3 solution and subsequently dried on K2CO3. The acetone was distilled off and the residue was vacuum-distilled. The distillate was dissolved in 100 ml of pentane and refluxed for 10 minutes after the addition of 50 ml of a 25% KOH solution in methanol. The pentane solution was washed with water and dried on Na2SO4. After the pentane had been distilled off, the residue was vacuum-distilled after the addition of 1 g of sodium. A quantity of 41 g of 1,5-dimethylbicyclo [3,2,1] octan-8-one was obtained having a boiling point of 104° C. at a pressure of 22 mm Hg.

Workup

  1. customThe solution obtained
  2. additionwas added
  3. customwas 35°-40° C
  4. stirringThe mixture was stirred for a further 2 hours at 35° C.
  5. customsubsequently, the acetone solution was separated from the bottom layer
  6. extractionThe latter was extracted a few times with acetone
  7. additionthe extracts were added to the acetone solution
  8. washThe mixture was washed with a saturated K2CO3 solution
  9. customsubsequently dried on K2CO3
  10. distillationThe acetone was distilled off
  11. distillationthe residue was vacuum-distilled
  12. dissolutionThe distillate was dissolved in 100 ml of pentane
  13. temperaturerefluxed for 10 minutes
  14. additionafter the addition of 50 ml of a 25% KOH solution in methanol
  15. washThe pentane solution was washed with water
  16. customdried on Na2SO4
  17. distillationAfter the pentane had been distilled off
  18. distillationthe residue was vacuum-distilled
  19. additionafter the addition of 1 g of sodium

Sources & evidence

ORD record
ord-a1ca64d71d6d44d4ad3edbf8be513f12
Source dataset
uspto-grants-1983_12
Patent number
US04421689

Reaction notes

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