Hydroperoxides and Peroxides of Acetylene

Acetylene Peroxides. See Acetylene Hydroperoxides and Peroxides Acetylene Reactions are described in the following references l)Beil 1,232-37,(101-3), [211-16] l892-9O7I 2)J. A.Nieuwland R.R. Vogt, "The Chemistry of Acetylene, Reinhold,NY( 1945) 3) A. W. John son, "The Chemistry of Acetylenic Compounds, Arnold, London, 1(1946)... 

The [Con(bipy)2 ]2+ species has also been reported to activate hydrogen peroxide and ter -butyl hydroperoxide for the selective ketonization of methylenic carbons, the oxidation of alcohols and aldehydes, and the dioxygenation of aryl olefins and acetylenes (36). Later reports (37), however, while confirming that the cobalt complexes did indeed cata-... 

Tertiary alcohols are resistant to oxidation. rcr -Butyl alcohol is frequently used as a solvent in oxidations. However, some tertiary alcohols are converted into tertiary hydroperoxides on treatment with hydrogen peroxide in sulfuric acid [177, 179]. Dimethylphenylcarbinol added to a mixture of 87% hydrogen peroxide and sulfuric acid at a temperature below 0 °C gives a 94% yield of cumyl hydroperoxide after 3.5 h [777]. Similarly, acetylenic alcohols with the tertiary hydroxyl group adjacent to the triple bonds are converted into the corresponding hydroperoxides in high yields [179] (equation 272). 

Recently, purified terminal aliphatic acetylenes were copolymerized with liquid SO2 in the presence of f-BuOOH at low temperature [54a]. The use of benzoyl peroxide, hydrogen peroxide, and p-chloropeibenzoic acid initiators was ineffective. Aged (impure) aliphatic alkynes could be copolymerized without the need to add hydroperoxides. All the resulting aIkyne/S02 copolymers were alternating with a 100% trans configuration regardless of the alkyne, temperature, or solvent used. Infinred spectroscopy and NMR were used to characterize the polymers. 

In this work, we develop a consistent set of oxygenated peroxy-hydrocarbon and acetylene-alcohol groups derived from the thermodynamic properties data of a set of hydroperoxides, peroxides, ethers and alcohols determined in previous chapters. 

Palladium(ii) complexes of trimethylsilyl enol ethers derived from ketones can be carbonylated (50 atm. CO) in the presence of an alcohol to give /S-keto-esters only three examples are quoted in this preliminary report. a, -Unsatur-ated esters can be converted into -keto-esters in ca. 70% yields using Na2PdCl4 in aqueous acetic acid containing t-butyl hydroperoxide or hydrogen peroxide. This method may be inappropriate if the starting ester contains other olefinic (and presumably acetylenic) bonds as these will probably also be attacked. 

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