Cyanocarbon chemistry

E. Ciganek, W. J. Linn, and O. W. Webster, in Z. Rapport, ed.. The Chemistry of the Cyano Groups Interscience PubHshers, London, 1970, pp. 423—638. An extensive review of cyanocarbon chemistry. 

Cyanocarbon chemistry therefore covers a wide field of materials the properties of which depend largely on the presence of one ( nitriles ) or more ( polycyano compounds ) nitrile groups. The possible role of HCN and polycyano compounds in prebiotic synthesis is one of the most fascinating chapters in the processes that preceded the appearance of life on earth. ... 

Cyaiioalkylation s. Cyano-ethylation, -methylation Cyanocarbon chemistry... 

R. H. Boyd, J. Phys. Chem. 1963, 67,737-744. Cyanocarbon chemistry. XXIII. The ionization behavior of cyanocarbon acids. 

Cyanocarbon chemistry s. Tetracyanoalkenes a-Cyanocarboxylic acid tert-butyl esters 17, 237 Cyanocarboxylic acid esters... 

The most important members of the cyanocarbon class are the alkenes tetracyanoethylene, hexacyanobutadiene, and tetracyanoquino dime than the alkanes tetracyanomethane and hexacyanoethane dicyano acetylene hexacyanobenzene tetracyanoquinone cyanocarbon acids oxacyanocarbons thiacyanocarbons and azacyanocarbons. Tetracyanoethylene is described first because its chemical versatility makes it a rich source of other polycyano compounds. Moreover, an understanding of its chemistry is helpful in understanding the chemistry of other cyanocarbons. 

Dick turned up some interesting chemistry of caprolactam and its O-alkyl imino ethers. He and collaborators went on to explore the chemistry of allene, for example, its reactions with acetylene, carbon monoxide, and tetrafluo-roethylene. He did extensive work on the chemistry of cyclooctatetraene and of ferrocene. In the cyanocarbon area he collaborated on studies of the anion radical of tetracyanoethylene, that is, tetracyanoethylene bearing an extra electron. He was author or coauthor of 45 papers and 16 U.S. Patents that came out of the Central Research Department. 

The dicyanopolyacetylenes 14-18, which are also of importance in connection with interstellar chemistry and novel forms of carbon, have been obtained very recently by vaporizing graphite in the presence of cyanogen under Kratschmer-Huffman conditions [21]. The polyyne fraction obtained consisted of 55% 14, 35% 15 and 10% of the higher homologs 16-18 as analyzed by HPLC. Cyanocarbon 14 has been obtained in analytically pure form as expected, it is only stable in dilute solution under occlusion of light and moisture at low temperatures [21]. 

The halocyanoacetylenes 23-25 have been prepared by standard methodology [Eq. (7) see below] from cyanoacetylene (1) [30-32]. Although they have been investigated in detail from the structural and spectroscopic viewpoint, their chemistry remains largely unexplored. These compounds are not particularly unstable, and can thus be handled by more or less routine laboratory techniques. Of particular interest should be their behavior in high-temperature pyrolysis as well as their photochemical behavior. Metal-catalyzed oligomerization could turn out to be another interesting field of application of these functionalized cyanocarbons. 

In their review on cyanocarbon and polycyano compounds Ciganek et al. [11 a] wrote in 1970 Although their [i.e., the cyanoacetylenes] physical properties have received considerable attention, reports on the chemistry of these compounds are not as abundant as might be expected in view of their high reactivity . For nearly a quarter of a century this situation has not changed very much in fact, it was one of the reasons why we began our own work in this area. 

This statement, made in 1983 did not lose its actuality the field of synthetic applications of cyanocarbons is still expanding. A steadily increasing number of patents on cyano compounds as biologically active materials, dyes, organic metals, etc. indicates the importance of nitrile chemistry for industrial applications. 

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