Methyl iodide → 2,4,8-Trimethylspiro[5.5]undeca-1,4,8-trien-3-one

HRID 1633409Notes

Reaction equation

HRID 1633409 reaction equation
CN([CH2:4][C:5]1[CH:10]=[C:9]([CH3:11])[C:8]([OH:12])=[C:7]([CH3:13])[CH:6]=1)C.[CH3:14]I.[CH3:16][C:17]([CH:19]=[CH2:20])=[CH2:18]>C(OCC)(=O)C>[CH3:13][C:7]1[C:8](=[O:12])[C:9]([CH3:11])=[CH:10][C:5]2([CH2:20][CH2:19][CH:17]=[C:18]([CH3:14])[CH2:4]2)[CH:6]=1.[CH3:13][C:7]1[C:8](=[O:12])[C:9]([CH3:11])=[CH:10][C:5]2([CH2:20][CH2:19][C:17]([CH3:18])=[CH:16][CH2:4]2)[CH:6]=1

Participants

6

Reactant 3

HCID 6328Methyl iodideHCID 6557IsopreneHCID 39355Phenol, 4-[(dimethylamino)methyl]-2,6-dimethyl-

Product 2

HCID 204410692,4,9-Trimethylspiro[5.5]undeca-1,4,8-trien-3-oneYield 33%HCID 204410982,4,8-Trimethylspiro[5.5]undeca-1,4,8-trien-3-oneYield 54.4%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
135 °C

Procedure

To a 250 mL glass reaction vessel containing an ethyl acetate (70 mLs) solution of N,N-dimethyl,2,6-dimethyl-4-aminomethylphenol (3.58 g; 20 mmols), there was added methyl iodide (20 mmols) to give a colorless slurry. The vessel was sealed and 2-methyl-1,3-butadiene (100 mmols) was introduced into the system. The reaction mixture was heated to 135° C. and the pressure was increased from atmospheric to 75 psig. The reaction mixture was maintained at these conditions for approximately 4 hours. The reaction vessel was then allowed to cool to room temperature. After cooling the black reaction mixture was filtered to remove ammonium iodide salt by-product. The filtrate was concentrated to afford a viscous oil which was purified by column chromatography (silica gel eluted with heptane) to give 1.1 g of 2,4,8-trimethylspiro[5.5]undeca-1,4,8-trien-3-one and 2,4,9-trimethylspiro[5.5]undeca-1,4,8-trien-3-one (33% yield based on N,N-dimethyl,2,6-dimethyl-4-aminomethylphenol starting reactant).

Workup

  1. customto give a colorless slurry
  2. customThe vessel was sealed
  3. temperaturethe pressure was increased from atmospheric to 75 psig
  4. temperatureThe reaction mixture was maintained at these conditions for approximately 4 hours
  5. temperatureto cool to room temperature
  6. temperatureAfter cooling the black reaction mixture
  7. filtrationwas filtered
  8. customto remove ammonium iodide salt by-product
  9. concentrationThe filtrate was concentrated
  10. customto afford a viscous oil which
  11. customwas purified by column chromatography (silica gel eluted with heptane)

Sources & evidence

ORD record
ord-78c6591234db41e5a26303c15d02851b
Source dataset
uspto-grants-1984_10
Patent number
US04480133

Reaction notes

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