Oxidation reactions using chromium based reagents

Because of the toxicity of chromium-based reagents, other methods for the oxidation of alcohols have been developed. One of the most widely employed methods, called the Swem oxidation, uses dimethyl sulfoxide [(CH3)2SO], oxalyl chloride [(COCl)2], and triethylamine. Since the reaction is not carried out in an... 

An interesting alternative to the use of chromium(VI) oxidants for the conversion of 1 to 2 involves the use of a low-valent iron reagent prepared in situ by the action of hydrogen peroxide on an iron(II) complex of 1 (73). Vinblastine (as the free base) is treated with 2 equiv of perchloric acid in acetonitrile at -20°C. Ferrous perchlorate is then added, followed by the addition of excess 30% hydrogen peroxide. Work-up of the reaction mixture with a saturated solution of ammonium hydroxide gives 2 in yields of 35-50% after chromatography. 

Most of the metallic oxidants which have been used for the oxidation of ethers have been based on oxides of the transition metals chromium, manganese and ruthenium, the latter being of greatest synthetic importance. The first reported example of the application of ruthoiium tetroxide in the oxidation of ethers tqipeared over 30 years ago in 1958, although an indication of its reactivity towards ethers had been obt ed some years before. In a systematic study which revealed the powerful oxidizing properties of the reagent, Berkowitz and Rylander demonstrated the quantitative conversion of tetrahydrofuran and R-butyl ether into y-butyrolactone and butyl butyrate, respectively. Significantly, no overoxidation was observed. Apart f m an unsuccessful attempt to oxidize ethylene oxide, no fitter attempts were made by the authors to examine further the scope of this novel transformation. In a series of subsequent publications and a patent, Wolf and his coworkers went on to exploit the reaction in the preparation of aldosterone and relr steroids (equation 1). 

Apart from acid-base titrations various addition-, substitution- and redox-reactions have been found to be of analytical interest. Iodine numbers of fats and essential oils may be determined i and bromine may be used to titrate organic compounds which can form bromoderivatives i. For the titration of phenol with bromine the addition of sodium acetate has been recommended. Redox reagents are in acetic acid chromium(VI) oxide, sodium permanganate, bromine, titanium(III) chloride and chromium(II) saltsi32,i33 xhe titrations are usually carried out in perchloric acid solutions and in an inert atmosphere but traces of water are tolerable. 

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