Reactive Intermediates, Softcover reprint of the original 1st ed. 1982 Volume 2

The field of reactive intermediates has been blossoming at a rapid rate in recent years and its impact on chemistry, both "pure" and "applied," as well as on biology, astronomy, and other areas of science, is enormous. Several books have been published which cover the area; one, edited by McManus, * surveys the subject in general at the senior undergraduate or beginning graduate level. In addition, a number of monographs have appeared which deal with individual topics such as carbenes, nitrenes, free radicals, carbanions, carbenium ions, and so on, in great depth. Our objective is somewhat different. We hope that these Advances in . . . type of volumes will appear at irregular intervals of a year to 18 months each. We intend to publish up-to-date reviews in relatively new areas of the chemistry of reactive intermediates. These will be written by world authorities in the field, each one of whom will give the reader a current in-depth review of all aspects of the chemistry of each of these species. It is our plan that the subjects to be reviewed will cover not only organic chemistry but also inorganic, physical, bio-, industrial, and atmospheric chemistry. The volumes themselves, we hope, will end up being reasonably interdisciplinary, though this need not and probably will not be the case for the individual reviews.

1. Current Aspects of the Solution Chemistry of Arylnitrenes.- I. Introduction.- II. Intermodular Reactions.- III. Intramolecular Reactions.- IV. Decomposition in the Presence of Protonic and Lewis Acids.- V. Current and Future Application.- References.- 2. Nitrile Ylides and Nitrenes From 2H-Azirines.- I. Generation of Nitrile Ylides.- II. Features of the Photocycloaddition Reaction of 2H-Azirines.- III. Photochemical Dimerizations of 2H-Azirines.- IV. Intramolecular 1,5-Electrocyclization Reactions of Vinyl Substituted 2H-Azirines.- V. Properties of Nitrile Ylides.- VI. Intramolecular Photocycloaddition Reactions of 2H -Azirines.- VII. Further Reactions of 2H-Azirines.- VIII. Thermal Reactions of2H-Azirines.- References.- 3. Radical Cyclizations by Intramolecular Additions.- I. Introduction.- II. General Presentation: The Early Results.- III. Attempts to Rationalize the Selectivities Observed in the Cyclization of 5-Hexenyl Radicals.- IV. Alkyl Substituted 5-Hexenyl Radicals.- V. Alkenyl Radicals Other than 5-Hexenyl.- VI. Carbon-Centered Alkenyl Radicals Containing Heteroatoms.- VII. Alkenyl Radicals Bearing Stabilizing Groups on the Carbon Radical Center.- VIII. Heteroatom-Centered Radicals.- IX. Intramolecular Addition to Other Carbon-Carbon Bonds.- X. Intramolecular Addition to Polar Multiple Bonds Such as Carbonyl or Cyano.- XI. Synthesis of Bi- and Poly cyclic Compounds. Stereochemical Features of Free Radical Intramolecular Additions.- XII. Free Radical Intramolecular Addition as a Mechanistic Tool and a Kinetic Standard.- XIII. Conclusion.- References.- 4. Reactions of Silicon Atoms and Silylenes.- I. Introduction.- II. Methods of Generation of Silicon Atoms.- III. Reaction Modes of Silicon Atoms.- IV. Modes of Formation of Silylenes.- V. Spectroscopic and Thermodynamic Properties of Silylenes.- VI. Chemical Properties of Silylenes.- References.- 5. Five-Membered Hetarynes.- I. Introduction.- II. Chemistry of Arynes.- III. Five-Membered Hetarynes.- IV. Summary.- References and Notes.- 6. A Survey of Favorskii Rearrangement Mechanisms. Influence of the Nature and Strain of the Skeleton.- I. Introduction.- II. Symmetrical Mechanisms.- III. Unsymmetrical Mechanism.- IV. The Favorskii Rearrangement in Bridged Polycyclic and Cage Compounds.- V. General Conclusion.- References.