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From their discovery in the last decade of the nineteenth century on, the nitrile oxides comprised a rather small group of little-known and little-investigated unstable organic derivatives of hydroxylamine. Around 1950, the astonishingly wide variety of their reactions started to become gradually unveiled. This reactivity has made them increasingly important as valuable tools for many syntheses. Simultaneously, the newly dis covered transformations raised interesting theoretical questions and their pursuit has generally enriched our understanding of reaction mechanisms of organic chemistry. At the same time, when nitrile oxides finally had won on their own a position of justified interest in the eyes of the organic chemist, came the discovery that fulminic acid, was in fact the parent member of this series. Thus, suddenly the nitrile oxides had acquired the most illustrious ancestry. Fulminic acid was discovered in 1800, at the dawn of modern chemistry, and since then the riddle of its true structure as well as the proteus-like variability of the molecule in its multitude of re actions has at one time or another attracted some of the most brilliant minds of organic chemistry, among them Berthollet, Gay-Lussac, Liebig, Wohler, Berzelius, Gerhardt, KekuTe, Griess, Armstrong, Holleman, Scholl, Nef, H. Wieland.
List of contents
I: Introduction.- A. Definition, Nomenclature.- B. History.- C. General Properties.- II: Physical Properties.- A. General.- B. Electronic Spectra.- III: Preparation.- A. General.- B. Formonitrile Oxide (Fulminic Acid) and Derivatives.- C. Other Nitrile Oxides.- D. Preparation in situ.- E. Functional Groups in Nitrile Oxides.- IV: Chemical Reactions Involving Only the Nitrile Oxide.- A. Isomerization to Isocyanates.- B. Deoxygenation to Nitriles.- C. Polymerization.- V: Addition Reactions Leading to Cyclic Structures: 1,3-Dipolar Cycloadditions.- A. General.- B. Reactions with C=C Derivatives.- C. Reactions with C?C Derivatives.- D. Reactions with C=O and C=S Compounds.- E. Reactions with C = N Compounds.- F. Reactions with Nitriles.- G. Reactions with Other Unsaturated Systems.- VI: Addition Reactions Leading to Open-Chain Structures; 1,3-Additions.- A. General.- B. Addition of Hydrogen.- C. Addition of Water (Hydrolysis).- D. Addition of Alcohols and Phenols.- E. Addition of Sulfides and Thiols.- F. Addition of Inorganic and Organic Acids and their Derivatives.- G. Addition of Ammonia and its Derivatives.- H. Addition of Azide, Cyanide and Thiocyanate Ions ..- I. Addition of Metallo-Organic Compounds.- K. Addition of Free Radicals.- L. Other Addition Reactions.- VII: Miscellaneous Reactions.- VIII: Physiological Properties and Applications of Nitrile Oxides.- IX: Tabular Survey.
