Chromate ester

Chromate esters, which are mainly of academic interest, are few and often labile. They can be isolated with bulky organic substituents such as tert-butyl or triphenylmethyl. Key is the absence of an alpha C-H bond. Suitable sources of chromium are chromium trioxide (CrO3), chromyl chloride (CrO2Cl2), and similar Cr(VI) reagents. For example, the treatment of chromium trioxide with trityl chloride gives two chromate esters: : (Ph = C6H5) : Diesters Usually chromate ester refers to monoesters, which are transient intermediates in the oxidation of alcohols by chromium(VI) oxides. Dialkychromates have the formula . When R lacks an alpha hydrogen, these diesters are isolable. One chromate diester has attracted significant attention: ((CH3)3CO)2CrO2. It is not an intermediate, rather a reagent. For example, it converts cyclohexene to 2-cyclohexenone. ==Mechanistic significance==

Chromate esters tend to react via redox reactions to liberate chromium(IV). This conversion is rapid when an alpha C-H bond is present (primary and secondary alcohols). Idealized equations for the oxidation of an alcohol are: :formation of the chromate esterr: :fragmentation of the chromate ester: In this way, chromate esters are reactive intermediates in the Jones oxidation, the mechanistically related oxidations using pyridinium dichromate and pyridinium chlorochromate. Chromate esters of allyl alcohols may isomerize via formal Sigmatropic reaction|[3,3]-sigmatropic shift to give rearranged enone products. == References ==