Hydrochloric Acid → Carvone, (-)-

HRID 1942941

Reaction equation

HRID 1942941 reaction equation
[CH3:1][C:2]1[CH2:7][CH2:6][C@@H:5]([C:8]([CH3:10])=[CH2:9])[CH2:4][CH:3]=1.Cl.CC1CC[C@@H](C(C)=C)CC=1.N(Cl)=[O:23].CN(C)C=O>C(O)(C)C.N([O-])=O.[Na+]>[CH3:1][C:2]1[C:7](=[O:23])[CH2:6][C@H:5]([C:8]([CH3:10])=[CH2:9])[CH2:4][CH:3]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 440917(+)-Limonene3×HCID 131730184Limonene nitrosochloride2×

Product 1

HCID 439570Carvone, (-)-

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolvent3×HCID 23668193Sodium NitriteSolvent

Procedure

Synthesis of the exemplary Formula VI terpene compound L-Carvone (2-cyclohexen-1-one, 2-methyl-5-(1-methylethenyl)-(R); Millenium Chemicals) from D-limonene is described in Ikan, Natural Products—A Laboratory Guide pp. 151-155 (Academic Press, 1969), incorporated herein by reference. Briefly, a solution of D-limonene in isopropanol is cooled to below 10° C. Solutions of HCl in isopropanol and concentrated aqueous sodium nitrite are added dropwise to the D-limonene solution to generate limonene nitrosochloride. The limonene nitrosochloride and dimethylformamide is refluxed with isopropanol. After cooling, crystallization is induced and the precipitate filtered and washed with water. The resulting L-carvoxime is refluxed with 0.5 M oxalic acid and the mixture is steam distilled. The distillate is extracted with ether, dried over anhydrous magnesium sulfate, and the excess ether evaporated to leave L-carvone.

Workup

  1. temperatureAfter cooling
  2. customcrystallization
  3. filtrationthe precipitate filtered
  4. washwashed with water
  5. temperatureThe resulting L-carvoxime is refluxed with 0.5 M oxalic acid
  6. distillationdistilled
  7. extractionThe distillate is extracted with ether
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customthe excess ether evaporated

Sources & evidence

ORD record
ord-ae746b11e20d4265a9a14da0316eb47f
Source dataset
uspto-grants-2013_03
Patent number
US08389730B2

Linked notes

Loading…