Alcohols, primary with ruthenium tetroxide

The conversion of primary alcohols and aldehydes into carboxylic acids is generally possible with all strong oxidants. Silver(II) oxide in THF/water is particularly useful as a neutral oxidant (E.J. Corey, 1968 A). The direct conversion of primary alcohols into carboxylic esters is achieved with MnOj in the presence of hydrogen cyanide and alcohols (E.J. Corey, 1968 A,D). The remarkably smooth oxidation of ethers to esters by ruthenium tetroxide has been employed quite often (D.G. Lee, 1973). Dibutyl ether affords butyl butanoate, and tetra-hydrofuran yields butyrolactone almost quantitatively. More complex educts also give acceptable yields (M.E. Wolff, 1963). 

The ruthenium tetroxide dioxide catalytic system is effective for the oxidation of alkanols, although it will also react with any alkene groups or amine substituents that are present. The catalyst can be used in aqueous acetonitrile containing tetra-butylammonium hydroxide with platinum electrodes in an undivided cell Primary alcohols are oxidised to the aldehyde and secondary alcohols to the ketone [30]. Anodic oxidation of ruthenium dioxide generates the tetroxide, which is the effective oxidising agent. 

In another procedure, oxidation is carried out in the presence of chloride ions and ruthenium dioxide [31]. Chlorine is generated at the anode and this oxidises ruthenium to the tetroxide level. The reaction medium is aqueous sodium chloride with an inert solvent for the alkanol. Ruthenium tetroxide dissolves in the organic layer and effects oxidation of the alkanol. An undivided cell is used so that the chlorine generated at the anode reacts with hydroxide generated at the cathode to form hypochlorite. Thus this electrochemical process is equivalent to the oxidation of alkanols by ruthenium dioxide and a stoichiometric amount of sodium hypochlorite. Secondary alcohols are oxidised to ketones in excellent yields. 1,4- and 1,5-Diols with at least one primary alcohol function, are oxidised to lactones while... 

Ruthenium tetroxide readily converts secondary alcohols to the corresponding ketone, and primary alcohols to aldehydes and acids.288,294 It is particularly recommended for converting alcohols which are difficult to oxidize with other reagents, for example, the hydroxylactone (105a) in equation (112).325... 

Sodium hypochlorite is used for the epoxidation of double bonds [659, 691] for the oxidation of primary alcohols to aldehydes [692], of secondary alcohols to ketones [693], and of primary amines to carbonyl compounds [692] for the conversion of benzylic halides into acids or ketones [690] for the oxidation of aromatic rings to quinones [694] and of sulfides to sulfones [695] and, especially, for the degradation of methyl ketones to carboxylic acids with one less carbon atom [655, 696, 697, 695, 699] and of a-amino acids to aldehydes with one less carbon [700]. Sodium hypochlorite is also used for the reoxidation of low-valence ruthenium compounds to ruthenium tetroxide in oxidations by ruthenium trichloride [701]. 

Sodium ruthenate, Na2Ru04, is prepared in situ from ruthenium tetroxide (in solution in carbon tetrachloride) and 1 M sodium hydroxide by shaking for 2 h at room temperature. The reagent remains in the aqueous layer, which acquires bright-orange color [937]. It oxidizes primary alcohols to carboxylic acids and secondary alcohols to ketones and is comparable with but stronger than potassium ferrate [937]. 

Besides ruthenium tetroxide, other ruthenium salts, such as ruthenium trichloride hydrate, may be used for oxidation of carbon-carbon double bonds. Addition of acetonitrile as a cosolvent to the carbon tetrachloride-water biphase system markedly improves the effectiveness and reliability of ruthenium-catalyzed oxidations. For example, RuCl3 H20 in conjunction with NaI04 in acetonitrile-CCl4-H20 oxidizes (Ej-S-decene to pentanoic acid in 88% yield. Ruthenium salts may also be employed for oxidations of primary alcohols to carboxylic acids, secondary alcohols to ketones, and 1,2-diols to carboxylic acids under mild conditions at room temperature, as exemplified below. However, in the absence of such readily oxidized functional groups, even aromatic rings are oxidized. 

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