Cyanogen derivatives

Molybdenum and Nitrogen, Phosphorus, and Arsenic—Heteropoly-compounds— Carbides— Molybdenum Canjonyl—Complex Cyanogen Derivatives—Compounds with Sdioon and Boron. 

Tungsten and Nitrogen, Phosphorus, Arsenic, Antimony, and Bismuth—Complex Salts containing Vanadium—Carbides—Complex Cyanogen Derivatives— Compounds with Silicon, Titanium, 2areonium, and Boron. 

The war gases belonging to the class of cyanogen derivatives are characterised by the presence of the CN— radicle in their molecules. It has been found that this radicle may have one of the following two formulae ... 

This is proven by the fact that allyl cyanide on hydrolysis yields crotonic acid in which the double bond is at carbon-2 (p. 173). Of the other cyanogen derivatives of propene the following are known though the position of the double bond is not established in all cases. 

These di-cyanogen and other poly-cyanogen derivatives are of importance only in this connection as nitriles of the poly-carboxy acids sjnA those that are necessary to be considered will be referred to later as we come to them in the study of these acids. The simplest di-cyanogen compound is the gas cyanogen NC—CN, which has been referred to as an example of a radical which exists as such in the free state. 

Capillary and packed (GC) columns are of value in the analysis of complex mixtures of lipids. The best capillary column length will depend on the complexity of the material injected, however, 30-m columns are often employed. In packed columns, many types of stationary phases are available for lipid separation, and these include silicone and alkylated or cyanogenated derivatives, polyesters, polyglycol, and carboranes. It is also common to derivatize the fatty-acid side chains to the corresponding methyl esters by reaction in BF3/ methanol prior to chromatographic analysis to achieve more distinct and uniform separations. 

Cyanogen derivatives arc numerous and capable of great complexity. Platinous cyanide Pt(CN)3, is obtained as a yellow precipitate when mercuric cyanide is added to a solution of alkali chlorplatinite. Double cyanides of the general formula M 2Pt(CN)4 are formed by such reactions as 6 KCN + PtCL = K2Pt(CN) + 4 KC1 + (CN),. These platino-cyanides do not respond to the ordinary tests for platinum. These compounds yield beautifully colored hydrates, and the barium and calcium hydrates have optical isomeric modifications.2 Certain of these hydrates become remarkably fluorescent under excitation from ultraviolet light or radium. 

Structure determinations by X-ray and electron diffraction methods have demonstrated the presence of unbranched chains of up to six divalent sulfur atoms in inorganic polysulfides, four divalent ones in salts of polythionic acids, and three in disulfonyl, dialkyl, and cyanogen derivatives. The synthetic and Raman-spectroscopic work of Feh6r has established the presence of unbranched structures with up to five sulfur atoms in organic polysulfides, and eight in the cyanogen polysulfide, polysulfur dichloride, and hydrogen polysulfide series. The results are supported by extensive physicochemical evidence of less conclusive nature. 

A prominent absentee from the roll-call of cyanogen derivatives is the isotopic species DCN Band and Freed do not find this surprising since they predict a huge deuterium isotope effect in the predissociation of DCN on the basis of their quantum mechanical treatment of photodissociation. The bound-continuum overlap integrals in the predissociation... 

Major Structural Types of Cyanogens Cyanogens Derived from Phenylalanine Cyanogens Derived from Tyrosine Cyanogens Derived from Valine and Isoleucine Cyanogens Glycosides Derived from Leucine Cyanolipids... 

Fig. 16.9. Cyanogens derived by oxidative cleavage of tyrosine and 3,4-dihydroxy-phenylacetonitrile.

At present, ferns are known only to produce phenylalanine-derived cyanogens such as prunasin (19) and vicianin (25). Gymnosperms produce only taxiphyllin (16) (derived from tyrosine). The Magnoliales and their close relatives primarily produce cyanogens derived from tyrosine, as do some monocotyledonous plants. There are several exceptions to this generality, however (Nahrstedt, 1987a). 

Methinophosphide readily adds hydrogen chloride to give methylphosphonous dichloride (reversal of (6.558), and with cyanogen azide gives the cyanogen derivative, cyanophosphaethyne (6.560) which can also be made by reaction (6.561)). These molecules have been observed spectroscopically. 

Clarence J. West, Cyanogen Derivatives, Chloride, Bromide, Iodide, Sulfide, Chemical Warfare Monographs, vol. 25, April 1919. 

---