Aluminum → 2,4-Di-tert-butyl-6-(trifluoromethyl)phenol

HRID 231325Notes

Reaction equation

HRID 231325 reaction equation
[Al].[C:2]([C:6]1[CH:11]=[C:10]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:9](=[O:16])[C:8](O[Si](CC)(CC)CC)([C:17]([F:20])([F:19])[F:18])[CH:7]=1)([CH3:5])([CH3:4])[CH3:3]>O>[C:12]([C:10]1[CH:11]=[C:6]([C:2]([CH3:3])([CH3:4])[CH3:5])[CH:7]=[C:8]([C:17]([F:19])([F:20])[F:18])[C:9]=1[OH:16])([CH3:13])([CH3:14])[CH3:15]

Participants

4

Reactant 2

HCID 5359268AluminumHCID 14343498HCID 14343498, compound

Product 1

HCID 143435082,4-Di-tert-butyl-6-(trifluoromethyl)phenolYield 83.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
70 °C

Procedure

A strip of aluminum foil weighing 267 mg (9.9 mmol) was amalgmated by immersion in a solution of 2% mercuric chloride in water for 15 seconds, washed with absolute ethanol followed by diethyl ether, cut into small pieces, and added to a solution of 400 mg (0.99 mmol) of 4,6-di-tert-butyl-2-triethylsiloxy-2-trifluoromethyl-3,5-cyclohexadien-1-one in 25 mL of 10% water - 90% tetrahydrofuran. The resulting mixture was heated at 70° C. for 1.5 hours, allowed to cool to room temperature, and filtered. The filter cake was washed with 10 mL of tetrahydrofuran. Concentration of the combined filtrates gave a residue which was poured into 25 mL of water. The aqueous mixture was extracted with three 10 mL portions of dichloromethane. Combination, drying and concentration of the organic layers gave a residue which was purified by PTLC (one 2 mm silica gel plate eluted with petroleum ether), affording 226 mg (83% yield) of 2,4-di-tert-butyl-6-trifluoromethylphenol as a colorless liquid: 1H NMR (CDCl3) δ 1.31 (s, 9H), 1.45 (s, 9H), 5.56 (q, 1H, JHF =4 Hz), 7.39 (d, 1H, J=2 Hz), 7.54 (d, 1H, J=2 Hz); IR (neat) 3624, 2959, 2906, 2868, 1481, 1458, 1448, 1363, 1340, 1263, 1251, 1170, 1126, 1097, 887, 694 cm-1 ; mass spectrum (70 eV) m/z (relative intensity) 274 (20, M+), 259 (100), 239 (68), 98 (20), 57 (22), 41 (34).

Workup

  1. washwashed with absolute ethanol
  2. temperatureto cool to room temperature
  3. filtrationfiltered
  4. washThe filter cake was washed with 10 mL of tetrahydrofuran
  5. customConcentration of the combined filtrates gave a residue which
  6. extractionThe aqueous mixture was extracted with three 10 mL portions of dichloromethane
  7. customCombination, drying
  8. customconcentration of the organic layers gave a residue which
  9. customwas purified by PTLC (one 2 mm silica gel plate eluted with petroleum ether)

Sources & evidence

ORD record
ord-cb63d6b6c2584c62b604ecc4b0b065a8
Source dataset
uspto-grants-1989_07
Patent number
US04845258

Reaction notes

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