Hydrochloric Acid → 1-Chloro-3-propyl-2-hexanone

HRID 902213Notes

Reaction equation

HRID 902213 reaction equation
[CH2:1]([CH:4]([CH2:8][CH2:9][CH3:10])[C:5]([OH:7])=O)[CH2:2][CH3:3].C(Cl)(=O)[C:12]([Cl:14])=O.[N+](=C)=[N-].Cl.O1CCOCC1>ClCCl.CN(C=O)C>[Cl:14][CH2:12][C:5](=[O:7])[CH:4]([CH2:1][CH2:2][CH3:3])[CH2:8][CH2:9][CH3:10]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 3121Valproic AcidHCID 9550DiazomethaneHCID 312751,4-DioxaneHCID 65578Oxalyl chloride

Product 1

HCID 107973771-Chloro-3-propyl-2-hexanone

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To 2-propylpentanoic acid (156.6 μl, 1.00 mmol) dissolved in anhydrous dichloromethane (2 mL) was added DMF (3 μL, 4 mole %), and the solution was cooled to 0° C. under a nitrogen atmosphere. To the solution was added oxalyl chloride (94.3 μL, 1.08 mmol) dropwise over a few minutes. The reaction was stirred 18 hours while warming to ambient temperature. The mixture was cooled to 0° C. and excess ˜0.3 M ethereal diazomethane solution was added. The reaction mixture was stirred 18 hours while warming to ambient temperature. The reaction mixture was washed with 1 M aqueous sodium carbonate solution (30 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in ether (2 mL) and cooled to 0° C. under a nitrogen atmosphere. Hydrogen chloride as a 4 N solution in dioxane (275 μL, 1.10 mmol) was added dropwise over a few minutes. The reaction was stirred 18 hours while warming to ambient temperature. The reaction mixture was concentrated under reduced pressure and the residual oil was used in the next step without further purification.

Workup

  1. temperaturewhile warming to ambient temperature
  2. temperatureThe mixture was cooled to 0° C.
  3. stirringThe reaction mixture was stirred 18 hours
  4. temperaturewhile warming to ambient temperature
  5. washThe reaction mixture was washed with 1 M aqueous sodium carbonate solution (30 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe residue was dissolved in ether (2 mL)
  10. temperaturecooled to 0° C. under a nitrogen atmosphere
  11. stirringThe reaction was stirred 18 hours
  12. temperaturewhile warming to ambient temperature
  13. concentrationThe reaction mixture was concentrated under reduced pressure
  14. customthe residual oil was used in the next step without further purification

Sources & evidence

ORD record
ord-49120cc3e8414434ba1c0e203d2a0cf6
Source dataset
uspto-grants-2008_04
Patent number
US07365093B2

Reaction notes

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