Acetic Acid → 3-Acetoxy-2-cyclohexen-1-one

HRID 982857Notes

Reaction equation

HRID 982857 reaction equation
[OH:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[CH:3]=1.C(Cl)Cl.[C:12](O)(=[O:14])[CH3:13].C1(N=C=NC2CCCCC2)CCCCC1>CN(C)C1C=CN=CC=1.CCCCCC.C(OCC)(=O)C.C(Cl)Cl.CC(C)=O>[O:8]=[C:4]1[CH2:5][CH2:6][CH2:7][C:2]([O:1][C:12](=[O:14])[CH3:13])=[CH:3]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6344Dichloromethane2×HCID 10868DicyclohexylcarbodiimideHCID 5357793-Hydroxycyclohex-2-enone

Product 1

HCID 27554433-Acetoxy-2-cyclohexen-1-one

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 19841213hexane EtOAc CH2Cl2 acetoneSolvent

Procedure

3-Hydroxy-cyclohex-2-enone (1.08 g, 9.64 mmol) was combined with methylene chloride (10 mL) in a 250 mL flask and acetic acid (1.4 eq, 13.75 mmol, 0.78 mL) was added to the mixture. The mixture was cooled in an ice bath and dicyclohexylcarbodiimide (1.3 eq, 12 mmol, 2.5 g) was added portionwise, followed by the addition of 4-(dimethylamino)pyridine (0.05 eq, 0.45 mmol, 50 mg). A sufficient amount of methylene chloride was added to ensure easy stirring and the reaction was monitored by TLC (silica gel, hexane-ethyl acetate-methylene chloride-acetone (3:3:3:1 v/v)), HPLC and LCMS and the intermediate acetic acid 3-oxo-cyclohex-1-enyl ester was formed. The mixture was stirred overnight at room temperature and then toluene (20 mL) was added. The mixture heated to 60° C. and after 72 hours the mixture was filtered, concentrated and purified by flash column chromatography to provide 2-acetyl-3-hydroxy-cyclohex-2-enone (1.19 g, 80%) as a colorless liquid. LCMS: MH+ 154.8.

Workup

  1. temperatureThe mixture was cooled in an ice bath

Sources & evidence

ORD record
ord-95d84dee111c4b9abc2959d2e3c934f7
Source dataset
uspto-grants-2005_03
Patent number
US06861419B2

Reaction notes

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