Formic Acid → 2-(4-Chlorophenyl)cyclopentan-1-one

HRID 2370154Notes

Reaction equation

HRID 2370154 reaction equation
[CH:1]([OH:3])=O.OO.[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2C[CH2:16][CH2:15][CH:14]=2)=[CH:9][CH:8]=1>>[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([CH:13]2[CH2:14][CH2:15][CH2:16][C:1]2=[O:3])=[CH:9][CH:8]=1

Participants

4

Reactant 3

HCID 284Formic AcidHCID 784Hydrogen PeroxideHCID 125920571-Chloro-4-(cyclopent-1-en-1-yl)benzene

Product 1

HCID 130238062-(4-Chlorophenyl)cyclopentan-1-oneYield 34.9%

Conditions

Temperature
40 °C

Procedure

A mixture of formic acid (60 mL, 84 mmol) and hydrogen peroxide (15 mL, 84 mmol) was warmed at 40° C. for 10 min. The resulting solution was carefully added to 1-chloro-4-cyclopentenylbenzene (15 g, 84 mmol) under stirring. The two-phase system was initially stirred at room temperature. After a certain period of time, a spontaneous exothermic reaction took place, and the temperature rose to about 50° C. The reaction mixture was stirred at room temperature for 1 h. The LC/MS analysis of the reaction mixture shows the disappearance of the starting material and the formation of the product. The reaction mixture was quenched by careful addition of a saturated sodium bicarbonate solution. Ether was added and the reaction mixture was vigorously shaken. The organic layer was separated and the aqueous layer was extracted with ether. The combined organic extracts were dried over anhydrous magnesium sulfate and filtered. The solvent was removed in vacuum and the residue was purified by column chromatography on silica gel to give 2-(4-chlorophenyl)cyclopentanone (5.7 g, 29.3 mmol, 34.9% yield) as a colorless oil. LC-MS (M+H)+=195.2. 1H NMR (500 MHz, CDCl3) δ ppm 7.21-7.37 (2H, m), 7.11 (2H, d, J=8.5 Hz), 3.25 (1H, dd, J=11.6, 8.5 Hz), 2.44 (2H, d, J=6.1 Hz), 2.15-2.31 (1H, m), 1.96-2.15 (3H, m), 1.78-1.95 (1H, m).

Workup

  1. stirringThe two-phase system was initially stirred at room temperature
  2. waitAfter a certain period of time
  3. customa spontaneous exothermic reaction
  4. customrose to about 50° C
  5. stirringThe reaction mixture was stirred at room temperature for 1 h
  6. customThe reaction mixture was quenched by careful addition of a saturated sodium bicarbonate solution
  7. additionEther was added
  8. stirringthe reaction mixture was vigorously shaken
  9. customThe organic layer was separated
  10. extractionthe aqueous layer was extracted with ether
  11. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  12. filtrationfiltered
  13. customThe solvent was removed in vacuum
  14. customthe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-05b46027c7a9474a8493b99d7eff1860
Source dataset
uspto-grants-2014_04
Patent number
US08710061B2

Reaction notes

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