Hydroquinone → 1-Methylbicyclo[2.2.2]oct-5-en-2-one

HRID 1462843Notes

Reaction equation

HRID 1462843 reaction equation
[CH3:1][C:2]1[CH2:7][CH:6]=[CH:5][CH2:4][CH:3]=1.Cl[C:9](=[CH2:12])[C:10]#N.[C:13]1([CH:20]=[CH:19][C:17]([OH:18])=[CH:16][CH:15]=1)[OH:14]>>[CH3:1][C:2]12[CH2:12][CH2:9][CH:5]([CH:6]=[CH:7]1)[C:4](=[O:14])[CH2:3]2.[CH3:1][C:19]12[CH2:10][CH2:9][CH:15]([CH:13]=[CH:20]1)[CH2:16][C:17]2=[O:18]

Participants

5

Reactant 3

HCID 785HydroquinoneHCID 701982-ChloroacrylonitrileHCID 780061-Methyl-1,4-cyclohexadiene

Product 2

HCID 126783551-Methylbicyclo[2.2.2]oct-5-en-2-oneHCID 13572561HCID 13572561, compound

Procedure

A mixture of 1-methyl-1,4-cyclohexadiene and 2-chloroacrylonitrile was heated for 14 hours at 110° C. in the presence of hydroquinone as polymerization inhibitor. The raw product was distilled at 60° to 65° C./0.13 millibars and the distillate was hydrolyzed in an aqueous solution of potassium hydroxide in dimethyl sulfoxide for 30 minutes at 120° C. The mixture was hereafter poured on ice. Extraction with pentane and separation by chromatography on a silica gel column resulted in a 5:1 mixture of 4-methyl-bicyclo[2.2.2]oct-5-en-2-one and 1-methyl-bicyclo[2.2.2]oct-5-en-2-one in a yield of 50 to 55%.

Workup

  1. distillationThe raw product was distilled at 60° to 65° C./0.13 millibars
  2. additionThe mixture was hereafter poured on ice
  3. extractionExtraction
  4. customwith pentane and separation by chromatography on a silica gel column

Sources & evidence

ORD record
ord-d8d164b424224a3fa84cf67c82490095
Source dataset
uspto-grants-1984_07
Patent number
US04461687

Reaction notes

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