Tetrahydrofuran → 1,7,7-Trimethyltricyclo[6.2.2.03,8]dodec-9-en-4-one

HRID 1833942Notes

Reaction equation

HRID 1833942 reaction equation
[H-].[Li+].[CH3:3][C:4]([C:11]1[CH2:16][CH2:15][C:14]([CH3:17])=[CH:13][CH:12]=1)([CH3:10])[CH2:5][CH2:6]C(O)=O.[CH:18]([Li])=C.C1COCC1.[CH2:26]([CH2:29][O:30]C)OC>>[CH3:18][C:14]12[CH2:13][CH2:12][C:11]3([CH:16]=[CH:15]1)[CH:26]([C:29](=[O:30])[CH2:6][CH2:5][C:4]3([CH3:3])[CH3:10])[CH2:17]2

Participants

6

Reactant 5

HCID 8028TetrahydrofuranHCID 80711,2-DimethoxyethaneHCID 62714Lithium hydrideHCID 21388144HCID 21388144, compoundHCID 178506890HCID 178506890, compound

Product 1

HCID 536563041,7,7-Trimethyltricyclo[6.2.2.03,8]dodec-9-en-4-oneYield 40%

Conditions

Temperature
5 °C

Procedure

A mixture of freshly distilled dimethoxyethane (250 ml), lithium hydride (880 mg, 110 mmol) and 4-methyl-4(4-methyl-1,3-cyclohexadien-1-yl)pentanoic acid was refluxed under Argon for 2.5 hours. The mixture was then cooled to 5° C and vinyl lithium in THF (111 g, 130 ml, 208 mmol) was added over a ten minute period. After stirring for an additional 5 minutes, the mixture was quenched by siphoning into a vigorously stirring solution of 28 ml of conc. HCl in 400 ml ice water. The aqueous layer was saturated with sodium chloride, and extracted with methylene chloride. The methylene chloride solution was washed (5% NaOH, 10% NaCl) and then concentrated. The product was crystallized from hexane to yield 7.5 g (40%) of the 1,7,7-trimethyltricyclo[6.2.2.03,8 ]dodec-9-en-4-one (8). Analysis by gas liquid chromatography and thin layer chromatography showed this to be a mixture of two isomers.

Workup

  1. temperaturewas refluxed under Argon for 2.5 hours
  2. customthe mixture was quenched
  3. extractionextracted with methylene chloride
  4. washThe methylene chloride solution was washed (5% NaOH, 10% NaCl)
  5. concentrationconcentrated
  6. customThe product was crystallized from hexane

Sources & evidence

ORD record
ord-e4721679473047018f8ab36591ffe7e0
Source dataset
uspto-grants-1978_01
Patent number
US04067906

Reaction notes

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