Table of contents

The review surveys data obtained in recent years for chemical reactions of organofluorine compounds. Data for new reactions of these compounds are considered in combination with new concepts concerning the mechanisms of processes known previously separated ionic and radical reactions. The bibliography includes 280 references.

Methods for the synthesis and the chemical properties of perfluoromethacrylic acid derivatives are examined. The most characteristic reactions of these compounds are those with nucleophiles, including very weak nucleophiles; cycloaddition reactions are very common, and some perfluoromethacrylic acid derivatives polymerise and copolymerise with various unsaturated compounds. The bibliography includes 83 references.

Methods for the generation and reactions of the perfluoro-t-butyl anion — a convenient model for the investigation of the chemistry of perfluoroalkyl carbanions, are examined. Syntheses based on this anion lead to the formation of a wide variety of compounds containing the (CF₃)₃C group. The bibliography includes 76 references.

The current state of the problem of the electrochemical fluorination of organic compounds is surveyed, and the mechanism of the substitution of hydrogen by fluorine during anodic oxidation in anhydrous hydrogen fluoride and in aprotic organic solvents is discussed. Formation of a carbon–fluorine bond during oxidation at platinum in the latter solvents is shown to be due to reaction of an organic radical-cation with a fluoride anion present in the electrolyte. Arguments are given in support of a mechanism of electrochemical fluorination in hydrogen fluoride not involving oxidation of the fluoride anion. A list of 160 references is included.

Methods of obtaining imines of fluorinated ketens are surveyed, together with their dimerisation and nucleophilic addition. Cycloaddition at the carbon–nitrogen bond and 1,4-dipolar cycloaddition involving the aromatic ring are most characteristic of fluorine-containing N-arylketenimines. A two-stage mechanism is suggested, involving intermediate formation of small rings. The Review concludes with 92 references.

The principal methods for synthesising 1,2-dithiolans are surveyed, together with their advantages and disadvantages. Information is given on the geometry of the 1,2-dithiolan ring. The polarography, photolysis, and spectra of 1,2-dithiolans are discussed, and results are given for their polymerisation, reduction, oxidation, and chlorolysis, as well as the removal of a sulphur atom. Data are presented on the biological importance and application of 1,2-dithiolans. The major part of the review is devoted to the chemistry of unsaturated five-membered cyclic disulphides — the 3-thiones, 3-ones, 3-imines, and 3-ylidenes of 1,2-dithiolens — with methods of preparation and both chemical and physical properties. A detailed examination is made of their reactions with electrophilic and nucleophilic reagents, as well as condensations. Fields of practical application of 1,2-dithiolens are surveyed. The review concludes with 233 references.

Comparison of non-empirical calculations on analogous nitrogen and phosphorus compounds shows that the presence of vacant d orbitals in the valence shells of the elements in the Third Period cannot be the real cause of the differences between the properties of nitrogen and phosphorus compounds and that the effects are ultimately determined by the differences between the effective sizes of the valence s and p orbitals of these elements. The bibliography includes 47 references