PMGB

chemical reaction procedures

Phenol

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To a suspension of compound containing an acetyl (-COCH3) group (0.01 mol) in 50 mL of dichloromethane was added m-chloroperbenzoic acid (0.03 mL) in three small portions at room temperature. The resulting mixture was stirred at room temperature for 24 h. The reaction mixture was diluted with 50 mL dichloromethane and washed successively with 2% aqueous sodium thiosulfate (50 mL), saturated aqueous NaHCO3 solution (2 × 50 mL) and brine (50 mL), dried over MgSO4 and evaporated to give the corresponding Baeyer-Villager oxidation product (-OCOCH3) which was purified by triturating with ether. White solid (60%).

Reference: Baeyer-Villager Oxidation

Sosnowski, J. J.; Danaher, E. B.; Murray, R. K. J. Org. Chem. 1985, 50, 2759-2763.

To a suspension of the acetate obtained in the previous step (0.0024 mol) in 4 mL ethanol was added 2 mL 2N aq. NaOH solution. The resulting mixture was stirred at room temperature for 1 h. The reaction mixture was concentrated on rotavapor under reduced pressure and the residue was cooled in ice bath. A few pieces of crushed ice were introduced into the flask and then acidified with 1N HCl solution. The precipitate formed was filtered and washed with water and air dried to give the corresponding phenol. Brown solid (73%).

 

Written by pmgb

June 7, 2008 at 9:06 pm

Posted in acetate, acetyl, phenols

2 Responses

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  1. this particular case of baeyer-villiger reaction is called dakin reaction

    petr

    June 15, 2008 at 12:43 pm

  2. Thanks. I found the following defination for Dakin reaction.

    The Dakin Reaction allows the preparation of phenols from aryl aldehydes or aryl ketones via oxidation with hydrogen peroxide in the presence of base. The aryl formate or alkanoate formed as an intermediate is subsequently saponified to yield the substituted phenol product.

    One can use urea-H2O2 complex for the first step (The Urea-Hydrogen Peroxide Complex: Solid-State Oxidative Protocols for Hydroxylated Aldehydes and Ketones (Dakin Reaction), Nitriles, Sulfides, and Nitrogen Heterocycles
    R. S. Varma, K. P. Naicker, Org. Lett., 1999, 1, 189-191.). However, I got a lower yield although the reaction is cleaner than using mCPBA.

    pmgb

    June 19, 2008 at 6:15 am


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