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

HRID 1633412Notes

Reaction equation

HRID 1633412 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.[CH2:20]=[CH:21][CH:22]=[CH2:23]>CN(C)C=O>[C:16]([C:7]1[C:8](=[O:15])[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])=[CH:10][C:5]2([CH2:23][CH2:22][CH:21]=[CH:20][CH2:4]2)[CH:6]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

4

Reactant 2

HCID 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 49%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

To a 250 mL glass reaction vessel there was added a dimethylformamide (10 mLs) solution of N,N-dimethyl,2,6-di-t-butyl-4-aminomethylphenol (2.63 g; 10 mmols). The vessel was sealed and 1,3-butadiene (40 mmols) was introduced into the system. The reaction mixture was then heated to 110° C. and the pressure was increased from atmospheric up to approximately 50 psig. The reaction was maintained at these conditions for approximately 48 hours. The reaction vessel was then cooled to room temperature. After cooling, the reaction mixture was filtered to remove ammonium iodide salt by-product. The filtrate was concentrated to afford a viscous oil crystallized with ethanol:water (60:40) to give 0.11 g of 2,4-di-t-butylspiro[5.5]undeca-1,4,8-trien-3-one (49% yield based on N,N-dimethyl,2,6-di-t-butyl-4-aminomethylphenol starting reactant).

Workup

  1. customThe vessel was sealed
  2. temperaturethe pressure was increased from atmospheric up to approximately 50 psig
  3. temperatureThe reaction was maintained at these conditions for approximately 48 hours
  4. temperatureThe reaction vessel was then cooled to room temperature
  5. temperatureAfter cooling
  6. filtrationthe reaction mixture was filtered
  7. customto remove ammonium iodide salt by-product
  8. concentrationThe filtrate was concentrated
  9. customto afford a viscous oil
  10. customcrystallized with ethanol:water (60:40)

Sources & evidence

ORD record
ord-4d2cb8785c284229b0a44cd2d167a417
Source dataset
uspto-grants-1984_10
Patent number
US04480133

Reaction notes

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