Alcohols reaction with cyanogen chloride

Aqueous solutions of cyanogen chloride do not react with silver nitrate, but aqueous-alcoholic solutions form silver chloride. Unlike cyanogen bromide, the Prussian blue reaction does not take place with cyanogen chloride. ... 

This reaction is accelerated by the alkali hydroxides. Cyanogen chloride reacts quantitatively with an alcoholic solution of ammonia to form cyanamide ... 

CHLORCYAN (506-77-4) CNCl C-N-CL Noncombustible gas. Violent polymerization can be caused by chlorine or moisture. Violent reaction with alcohols, alkenes, and alkynes (violent exothermic reaction) acids, acid salts, amines, strong alkalis, olefins, strong oxidizers. Contact with acid forms toxic hydrogen cyanide gas. Mixtures with benzene or cyanogen halides yield hydrogen chloride. In cmde form, this chemical trimerizes violently if catalyzed by traces of hydrogen chloride or ammonium chloride, forming cyanuric chloride. Alkaline conditions will convert this chemical to... 

Liq. cyanogen chloride added at 0° to a soln. of phenol in acetone, then triethylamine added dropwise with vigorous stirring and ice-cooling below 10, stirring continued 10 min. phenyl cyanate. Y 94. F. e., also from certain alcohols, s. E. Grigat and R. Putter, B. 97, 3012 (1964) reactions s. the following papers of this series. 

Stanislao Cannizzaro (Palermo, Sicily, 1826-Rome, 10 May 1910) studied in Palermo and Naples. In 1847 he took part in the Rebellion. In 1850 he became Piria s assistant in Paris and in 1851 published his first research, on cyanogen chloride and cyanamide, done jointly with Cloez in Chevreul s laboratory. In 1852 he was appointed in Alessandria and in 1853 published an important researdi on the action of caustic potash on benzaldehyde, obtaining potassium benzoate and benzyl alcohol ( Cannizzaro s reaction ) 2C,H5CHO+KOH=C.HsCOOK+C,H8CH,OH. In 1855 he became professor in G noa, where at fimt there was no laboratory, and there he wrote his famous pamphlet. In i860 he joined Garibaldi at Palermo. In 1861 he became professor in Palermo and in 1870 in Rome, where he was created senator. ... 

Allyl alcohols readily react with trichloroacetonitrile to give the corresponding trichloroacetimidates 145. Activation of the double bond with electrophilic reagents results in ring closure to yield oxazolines 146. The most commonly employed electrophiles include iodine, iodine monochloride, phenylselenyl chloride, and mercuric trifluoroacetate. Other nitriles including cyanogen bromide and N,N-dimethylcyanamide can also be used. Since oxazolines readily hydrolyze to amides, the net effect of this reaction sequence is to produce p-amino alcohols 147 from an allyl alcohol. This strategy has been employed in numerous total syntheses of natural products. Examples are listed in Table 8.18 (Fig. 8.7 Scheme 8.43). ° ... 

The reaction products of cyanogen with alcohols, dialkyl oximidates (44) and alkylcyanoformimidates (45), also available through the reaction of sodium cyanide with chlorine in aqueous alcohol, both react with the sulfur chlorides forming the appropriately substituted thiadiazole. Wen reported the synthesis of diethoxy-1,2,5-thia-diazole (46) from 44 and sulfur dichloride. Several analogs of 45 were converted to 3-chloro-4-alkoxy-l,2,5-thiadiazoles (46a) by treatment with sulfur monochloride. 

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