AbstractThe chemistry of polyfluorinated ketones has recently received a great deal of attention.A. Ya. Yakoubovich, Usp. Chim.25, 3 (1956).H. P. BraendlinandE. T. McBeein: Advances in Fluorine Chemistry. Butterworths, London 1963, Vol. 3, p. 1.The review byBraendlinandMcBee[2] does not deal only with perfluorinated ketones; moreover, though published in 1963, it is already outdated. The papers discussed in [1,2]will not be reviewed in the present article.. The carbonyl and imino groups of the fluorinated ketones and their imines react in many different ways. In particular, the electron‐attracting perfluoroalkyl groups intensify the electrophilic properties and weaken the nucleophilic properties of the carbonyl group. The perfluoroalkyl group also hinders the heterolytic removal of the hydroxyl group from adducts by reducing the stability of the carbonium ion . The increased electrophilicity of the carbonyl group and the increased stability of the addition products leads not only to a change in reactivity in the characteristic ketone reactions, but also to numerous new reactions which are not observed with non‐fluorinated ketones. Thus it is possible to synthesize a wide variety of fluoroorganic compounds from perfluorinated ketones.We have been concerned mainly with hexafluoroacetone, since in addition to being the most readily available and simplest perfluorinated ketone, this is also a typical representative of this class of compoun