Ketones, Esters and Related Compounds

Acyclic [87, 88], cyclic, cage [89-91] and poly [91, 92]-perfluoroketones have been successfully synthesised by direct perfluorination (Figs. 29 and 30). 

Phloroglucinol, which is regarded as the tri-enol form of cyclohexane-1,3,5-trione, gives the hexahydrate of the corresponding perfluoro-trione upon fluorination in formic acid (Fig. 31) [93] (see 3.1.1.2 for a discussion of the fluorination of carbonyl compounds). 

Highly branched ketones may undergo rearrangement upon fluorination, as for instance pivalone, which gives perfluoroprovalone as the major product (Fig. 32) [94]. 

Perfluorinations of many related oxygen containing substrates, such as acid halides (Fig. 33) [11], esters (Fig. 34) [14, 95, 96] and polyesters (Fig. 35) [14, 97-99] have been carried out. 

The preparation of many long-chain perfluorocarboxylic acids and diacids is now carried out on the industrial scale using direct fluorination techniques (Fig. 36) [15,16,100]. 

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Carbonyi reductions. In an alcohol solvent sodium reduces ketones, esters, and related compounds. 3-Anisyl-methylenecamphor gives 3-en-(p-methoxybenzyl)-isoborneol, which is a potential chiral auxiliary. 1,3-Amino alcohols are obtained from )3-enamino ketones, but there is lack of stereoselectivity in the reduction. 

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