Methyl iodide → Spiro[5.5]undeca-1,4,8-trien-3-one, 2,4-bis(1,1-dimethylethyl)-

HRID 1633408Notes

Reaction equation

HRID 1633408 reaction equation
CN([CH2:4][C:5]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[C:8]([OH:15])=[C:7]([C:16]([CH3:19])([CH3:18])[CH3:17])[CH:6]=1)C.CI.[CH2:22]=[CH:23][CH:24]=[CH2:25]>C(OCC)(=O)C>[C:16]([C:7]1[C:8](=[O:15])[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:10][C:5]2([CH2:25][CH2:24][CH:23]=[CH:22][CH2:4]2)[CH:6]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 78451,3-ButadieneHCID 66609Phenol, 4-[(dimethylamino)methyl]-2,6-bis(1,1-dimethylethyl)-

Product 1

HCID 10730920Spiro[5.5]undeca-1,4,8-trien-3-one, 2,4-bis(1,1-dimethylethyl)-Yield 98.4%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a 250 mL glass reaction vessel containing an ethyl acetate (50 mLs) solution of N,N-dimethyl,2,6-di-t-butyl-4-aminomethylphenol (1.32 g; 5 mmols), there was added methyl iodide (0.31 mLs; 5 mmols) to give a colorless slurry. The vessel was sealed and 1,3-butadiene (20 mmols) was introduced into the system. The reaction mixture was heated to 100° C. and the pressure was increased from atmospheric to 45 psig. The reaction mixture was maintained at these conditions for approximately 30 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 crystallized from ethanol:water (80:20) to give 1.34 g of 2,4-di-t-butylspiro[5.5]undeca-1,4,8-trien-3-one (49% yield based on the N,N-dimethyl,2,6-di-t-butyl-4-aminomethylphenol starting reactant) as colorless crystals.

Workup

  1. customto give a colorless slurry
  2. customThe vessel was sealed
  3. temperaturethe pressure was increased from atmospheric to 45 psig
  4. temperatureThe reaction mixture was maintained at these conditions for approximately 30 hours
  5. temperatureto cool to room temperature
  6. temperatureAfter cooling
  7. filtrationthe black reaction mixture was filtered
  8. customto remove ammonium iodide salt by-product
  9. concentrationThe filtrate was concentrated
  10. customto afford a viscous oil which
  11. customwas crystallized from ethanol:water (80:20)

Sources & evidence

ORD record
ord-caf8a6f122c64e78867c4db2db01b9b0
Source dataset
uspto-grants-1984_10
Patent number
US04480133

Reaction notes

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