Acetic Acid → 2-Cyclohexene-1,4-diyl Diacetate

HRID 1636141Notes

Reaction equation

HRID 1636141 reaction equation
[C:1]([O-:4])(=[O:3])[CH3:2].[Li+].[C:6]1(=O)[CH:11]=[CH:10][C:9](=[O:12])[CH:8]=[CH:7]1.C1CCC=CC=1.[C:20](O)(=[O:22])[CH3:21]>CCCCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[O-2].[O-2].[Mn+4]>[C:1]([O:4][CH:6]1[CH2:7][CH2:8][CH:9]([O:12][C:20](=[O:22])[CH3:21])[CH:10]=[CH:11]1)(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 4650QuinoneHCID 116051,3-CyclohexadieneHCID 3474584Lithium acetate

Product 1

HCID 126964352-Cyclohexene-1,4-diyl DiacetateYield 33%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 178418406HCID 178418406, compoundCatalystHCID 8003PentaneSolvent

Procedure

Lit., J. Org. Chem., 49:4619 (1984). To a stirred solution of 2.8 g (12.5 mmol) palladium acetate, 27.2 g (267 mmol) lithium acetate, and 7.64 g (70.7 mmol) benzoquinone in 200 ml acetic acid at room temperature were added 26.1 g (300 mmol) manganese dioxide and a solution of 23.8 ml (250 mmol) 1,-3-cyclohexadiene in 400 ml pentane, and stirring continued for 16 h. The twophase reaction mixture was separated and the acetic acid phase extracted twice with pentane. The combined organic extracts were washed successively with saturated brine, water, and 2 M sodium hydroxide solution, then the organic phases were dried over sodium sulphate and concentrated in vacuo. Recrystallisation from pentane afforded 16.1 g (33%) of the title compound as an off-white crystalline solid. MS m/e (%): 138 ([M−AcOH]+, 8), 96 ([M−AcOH−COCH2]+, 100), 43 (40).

Workup

  1. customThe twophase reaction mixture
  2. customwas separated
  3. extractionthe acetic acid phase extracted twice with pentane
  4. washThe combined organic extracts were washed successively with saturated brine, water, and 2 M sodium hydroxide solution
  5. dry with materialthe organic phases were dried over sodium sulphate
  6. concentrationconcentrated in vacuo
  7. customRecrystallisation from pentane

Sources & evidence

ORD record
ord-a748d6e8a101411db18eb25a92d811a6
Source dataset
uspto-grants-2003_01
Patent number
US06512001B1

Reaction notes

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