Acetic Acid → 4-Cyclopropyl-2,6-dimethylphenol

HRID 1805847Notes

Reaction equation

HRID 1805847 reaction equation
C([Si]([O:8][C:9]1[C:14]([CH3:15])=[CH:13][C:12]([CH:16]2[CH2:18][CH2:17]2)=[CH:11][C:10]=1[CH3:19])(C)C)(C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C(O)(=O)C>C1COCC1>[CH:16]1([C:12]2[CH:11]=[C:10]([CH3:19])[C:9]([OH:8])=[C:14]([CH3:15])[CH:13]=2)[CH2:18][CH2:17]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 2724141Tetrabutylammonium FluorideHCID 67132176Tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane

Product 1

HCID 576935554-Cyclopropyl-2,6-dimethylphenolYield 93%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of (4-bromo-2,6-dimethylphenoxy) tert-butyldimethylsilane (668 mg, 2.12 mmol) and tetrakis(triphenylphosphine)palladium (122 mg, 0.11 mmol) in THF (20 mL) was added cyclopropyl zinc chloride (28.0 mL, 11.2 mmol). The mixture was heated at 80° C. for 24 h and cooled to room temperature. The reaction was passed through a short pad of SiO2 to remove the catalyst and the solution was concentrated to oil. The resulting oil was diluted in EtOAc (100 mL), washed with brine (100 mL), dried with Na2SO4, and concentrated to dryness. Silica gel chromatography (Hexanes:EtOAc=90:10) yielded 370 mg (63%) of tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane. To tert-butyl(4-cyclopropyl-2,6-dimethylphenoxy)dimethylsilane (320 mg, 1.16 mmol) in THF (10 mL) was added a solution of tetrabutylammonium fluoride (5.0 mL, 1 M in THF, 5.0 mmol) and acetic acid (0.40 mL). The reaction was stirred at room temperature for 3 h and concentrated to dryness. Silica gel chromatography (Hexanes:EtOAc=85:15) yielded 175 mg (93%) of 4-cyclopropyl-2,6-dimethylphenol as a light yellow oil.

Workup

  1. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-db40fcdc0d1c42edba06140ceaa6fae9
Source dataset
uspto-grants-2013_01
Patent number
US08354532B2

Reaction notes

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