With cyanogen chloride

When the benzenesulfinates were substituted with electron-withdrawing groups, e.g., p-nitro- and p-cyanobenzenesulfinate, the yields were slightly improved when the reaction time with cyanogen chloride was lengthened to 1 hour. 

Whereas sulfonyl halides have been known for a long time and, especially the chlorides, have become of great synthetic value, sulfonyl cyanides were unknown until 1968. They were first prepared by van Leusen and co-workers from the reaction of sulfonylmethylenephos-phoranes with nitrosyl chloride. The same group also investigated part of their chemistry. Since then, two more, completely different, methods of synthesis were published from sulfinates with cyanogen chloride,and by the oxidation of thiocyanates. ... 

The pyrrolidine enamine of 2-tetralone (177) was converted to l-cyano-2-tetralone, which exists almost entirely in the enolic form (178), by reaction with cyanogen chloride (J23). Reaction of 177 with cyanogen bromide gave N-naphthylpyrrolidine (179), presumably via the unstable bromoenamine (180). The latter observation is in accord with the mode of reaction of the heterocyclic enamine (126) with cyanogen bromide, which resulted in the... 

Dibenz[b,/]azepinc-5-carbonitrile (14), an alternative intermediate for the synthesis of Car-bamazepine, is obtained (47%, as the hydrobromide) by stirring 5//-dibenz[b,/]azepine (5) with cyanogen bromide in chloroform solution at room temperature,203 or with cyanogen chloride in dimethylacetamide.204... 

The preparation of chlorosulfonyl isocyanate is described in Org. Syn., Coll. Vol. 5, 226 (1973). This compound is highly corrosive, reacts explosively with water, and may be contaminated with cyanogen chloride. 

Also reported as a mixture with Cyanogen chloride (C07-A003) Arsenic trichloride (C04-C006). 

Lonza (2) A process for making malononitrile. Acrylonitrile is reacted continuously with cyanogen chloride, in the vapor phase, in a quartz tube at 900°C. Developed by Lonza, Basle. German Patents 1,921,662 1,946,429. 

Sulfur trioxide, reaction with cyanogen chloride, 46, 24... 

Although 334 is very air sensitive, products of substitution by electrophiles are stable. Compounds 334 react with acylating agents to yield 335, and with cyanogen chloride, 359 is produced. The observed direction of electrophilic substitution in 334 is consistent with charge distribution and... 

For the quantitative synthesis of thiocyanates by reaction with cyanogen chloride or cyanogen bromide it is essential to start with thiolates instead of thiols. The product salts are then removed by washing of the products with water. Thus, the various heterocyclic thiocyanates 224a-d are easily obtained in pure form by either gas-solid (CICN) or solid-solid (BrCN) reaction [92] (Scheme 29). 

Preparation of Alkynenitriles by Reaction of Alkynyllithium with Cyanogen Chloride EijO (hexane)... 

The cyanation with cyanogen chloride is not a general reaction. 2-Thienyllithium, for example, reacts with CICsN to give mainly 2-chlorothiophene [2]. 

Of the various published methods of preparing phenylurea, such as treatment of aniline salts with potassium cyanate in water solution,1 heating aniline with urea,2 with cyanic acid,3 or with cyanogen chloride,4 and the interaction of phenyl isocyanate or phenylcarbamine chloride with ammonia,5 the only ones to be considered as practical methods for preparation are the first two. The first suffers from the disadvantage that potassium cyanate is not easily prepared in the laboratory and rapidly undergoes spontaneous decomposition in storage while by the action of urea on aniline alone, carbanilide is formed in rather larger proportion than phenylurea. 

Cyanothiophene is most conveniently derived from the aldehyde oxime by dehydration (equation 23), but has also been obtained by reaction of the 2-thienyl Grignard reagent or 2-thienyllithium with cyanogen chloride. Activated halogens are readily displaced by cyanide ion (equation 24 Section 3.14.2.7). 

An analogous product (252 X = Cl) is formed in the reaction of sulfur trioxide with cyanogen chloride (68AG(E)172). Aryl cyanates also condense with sulfur trioxide to give 1,2,3,5-oxathiadiazines analogous to those formed from dialkylcyanamides (67CB3736). 

Caution Cklorosulfonyl isocyanate is highly corrosive and may be contaminated with cyanogen chloride. This preparation should be carried out in a good hood, and rubber gloves should be worn. 

If the reaction, say, with cyanogen chloride, is carried out in ether solution, ammonium chloride precipitates and is filtered off, and the cyanamide is procured as a syrup by allowing the ether solution to evaporate spontaneously and later as crystals by allowing the syrup to stand over sulfuric acid in a desiccator. Cyanamide may also be prepared by removing the component atoms of hydrogen sulfide from thiourea by means of mercuric oxide. Thionyl chloride effects the corresponding removal of water from urea. 

G. Pellizzari and co-workers found that with cyanogen chloride or bromide, hydrazine in aq. soln. furnishes diaminoguanidine, NH C(NH.NH2)2. E. J. Cuy and W. C. Bray found that in alkaline soln., hydrazine is quantitatively oxidized to nitrogen by potassium ferrocyanide, R. von Rothenburg found that chloroform is not acted on in boiling soln., while iodoform is slightly attacked. 

Amino-4,5-dicyanoimidazole [40953-34-2] can be made by reaction of dia-minomaleonitrile with cyanogen chloride. By coupling with aniline couplers and alkylating the resultant azo dye precursor bright reds such as 27 are obtained. 

The reaction of silylamines 9 with cyanogen chloride in diethyl ether affords mono silyl carbodiimides 10. On standing only the t-butyl and the phenyl derivatives are stable, the other derivatives rearrange to give the cyanamide isomers 11. ... 

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