P-Cresol → 4-Methyl-2-t-octylphenol

HRID 2389233Notes

Reaction equation

HRID 2389233 reaction equation
[CH:1]1[C:6]([OH:7])=[CH:5][CH:4]=[C:3]([CH3:8])[CH:2]=1.[CH3:9][C:10]([CH2:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[CH2:11].B(F)(F)F.CCOCC>>[CH3:8][C:3]1[CH:4]=[CH:5][C:6]([OH:7])=[C:1]([C:10]([CH3:11])([CH3:9])[CH2:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH:2]=1

Participants

4

Reactant 3

HCID 2879P-CresolHCID 78682,4,4-Trimethyl-1-penteneHCID 8000Boron trifluoride etherate

Product 1

HCID 5212634-Methyl-2-t-octylphenol

Conditions

Temperature
0 °C

Procedure

Preparation was modified from the method of Kitchen, L. J., J. Am. Chem. Soc. 1948, 70, 1290. In a round-bottom flask to which were attached two addition funnels, a mixture of p-cresol (33.12 g, 306 mmol) and 33 mL 2,4,4-trimethyl-1-pentene was purged with nitrogen. The flask was cooled to 0° C., and 162 mL additional olefin (total amount of 2,4,4-trimethyl-1-pentene=1.23 mol, 4.0 eq.) was added dropwise, while a mixture of boron trifluoride etherate (5 mL, 40 mmol) and 30 mL nitrogen-sparged hexanes was added at the same time. The addition of olefin proceeded for 160 min, and subsequently the flask was allowed to warm to room temperature, and then was heated to 45° C. with stirring under nitrogen for 16 h. After cooling back to room temperature, the reaction was quenched by the addition of 121 g of 30% NaOH/H2O and 10 mL hexanes. After separation, the organic fraction was washed with water, and the combined aqueous fractions were washed with hexanes. The combined organic fractions were again washed with water and then distilled. The fraction distilling at 141° C. and 9-10 Torr was saved and analyzed. Yield: 30.56 g waxy white solid (45%). M.P.=42-5° C. 1H NMR was in accordance with literature (PCT Int. Appl. WO 2006120178 A1, inventors Olesen, Preben. H.; Hansen, H. C.; Christiansen, L. B.; Nielsen, F. E.; Petersen, A. K., to Novo Nordisk A/S).

Workup

  1. customPreparation
  2. customIn a round-bottom flask to which were attached
  3. additiontwo addition funnels
  4. customwas purged with nitrogen
  5. customsparged hexanes
  6. additionwas added at the same time
  7. additionThe addition of olefin
  8. temperatureto warm to room temperature
  9. temperaturewas heated to 45° C.
  10. temperatureAfter cooling back to room temperature
  11. customthe reaction was quenched by the addition of 121 g of 30% NaOH/H2O and 10 mL hexanes
  12. customAfter separation
  13. washthe organic fraction was washed with water
  14. washthe combined aqueous fractions were washed with hexanes
  15. washThe combined organic fractions were again washed with water
  16. distillationdistilled
  17. distillationThe fraction distilling at 141° C.

Sources & evidence

ORD record
ord-368a3099758d4e639a75f9e7834b70c8
Source dataset
uspto-grants-2012_09
Patent number
US08273678B2

Reaction notes

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