Diazonium cyanide

A further example of bonding isomerism that depends on the solvent may be taken from purely organic compounds. The following equilibrium exists between anisolesyndiazo cyanide and the corresponding diazonium cyanide (63) ... 

The diazonium cyanide in the solid state is able to exist only as the solvate with two molecules of HCN (63), which is analogous to the case of the solvate formed by SbCU with CH3CN. 

Hantzsch then found evidence for the existence of diazonium cyanide in solution, in addition to the two stereoisomeric diazo-cyanides. Bamberger regarded the isomeric metallic salts of diazobenzene as (i) and (2), whilst Hantzsch regarded them as (3) and (4), maintaining that a real ammonium hydroxide cannot form a compound like (i), and there are no diazonium metal salts ... 

Copper 1) chloride, bromide and cyanide were used by Sandmeyer to introduce a chlorine, a bromine atom and a cyanide group respectively into a benzene ring by addition to the phenyl diazonium salt. 

Then, while the diazonium solution is standing in ice-water, dissolve 55 g. of powdered copper sulphate (CuS04,5Ha0) in 200 ml. of water contained in a 1500 ml. flat-bottomed flask, for which a steam-distillation fitting is available for subsequent use. Place a thermometer in the copper sulphate solution and warm the latter to 60-65 . Now cautiously add a solution of 60 g. of powdered potassium cyanide in too ml. of water to the copper... 

Now add the diazonium solution to the potassium cupro-cyanide in small quantities at a time so that the temperature of the mixture remains between 60° and 70° shake the mixture vigorously after each addition of the diazo solution. Then fit a reflux air- or water-condenser to the flask, and heat the latter on a boiling water-bath for 15 minutes to complete the reaction. Finally steam-distil the solution until no more oily benzonitrile passes over (usually until about 600 ml. of distillate have been collected). 

The Sandmeyer reaction may also be applied to the preparation of nitriles. The solution of the diazonium salt is added to a solution of cuprous cyanide in excess of sodium or potassium cyanide solution (sometimes improved yields are obtained by substituting nickel cyanide for cuprous cyanide), for example CH3 CH, CH3... 

R—N=N Aryl diazonium 10ns are formed by treatment of primary aromatic amines with nitrous acid They are ex tremely useful in the preparation of aryl halides phenols and aryl cyanides... 

Preparation of aryl nitriles Cop-per(l) cyanide converts aryl diazonium salts to aryl nitriles. 

An analogous regioselective effect of silver ions on an addition reaction of arene-diazonium ions was found by Ignasiak et al. (1975) with cyanide salts. Potassium cyanide yields diazocyanides (Ar— N2 — C = N see Sec. 6.6), i.e., C-coupling products, but with silver cyanide - albeit in low yield (7-9%) - diazoisocyanides (Ar—N2 — N = C) are formed (a better synthesis of diazoisocyanides is described in Sec. 6.4). 

The arenediazocyanides have been known since 1879. They played an important role in the Hantzsch-Bamberger debate on the (Z)/( ,)-isomerism of diazo compounds (see Sec. 7.1). When an aqueous solution of a diazonium salt is added to a solution of sodium or potassium cyanide, both in relatively high concentration, at a temperature below 0°C, a yellow to red (Z)-arenediazocyanide starts to crystallize. Hantzsch and Schulze (1895 a) found that these compounds rearrange into the (ii)-isomers, which have a bathochromically shifted visible absorption (see Sec. 7.1). Under strongly alkaline conditions a 1 2 adduct is formed, to which Stephenson and Waters (1939) assigned the structure 6.36. It was never corroborated, however, by modern instrumental analysis. 

When aqueous solutions of aromatic and heteroaromatic diazonium salts are treated with cuprous chloride, -bromide, or -cyanide, the corresponding aromatic chlorides, bromides, or cyanides are formed, respectively. In many cases the anions mentioned must be present in excess. This reaction, the Sandmeyer reaction, was discovered by Sandmeyer in 1884. A variant carried out with copper powder and HBr or HC1 was for many years called the Gattermann reaction (Gattermann, 1890). As it is often confused with the Gattermann-Koch reaction (ArH + CO + HC1 ArCHO), and as it is mechanistically not significantly different from Sandmeyer s procedure, the name Gattermann reaction should be avoided. 

A second group of aromatic substitution reactions involves aryl diazonium ions. As for electrophilic aromatic substitution, many of the reactions of aromatic diazonium ions date to the nineteenth century. There have continued to be methodological developments for substitution reactions of diazonium intermediates. These reactions provide routes to aryl halides, cyanides, and azides, phenols, and in some cases to alkenyl derivatives. 

While the cuprous cyanide solution is warmed gently (to 60°-70°) on the water bath, a solution of p-tolyldiazonium chloride is prepared as follows Heat 20 g. of p-toluidine with a mixture of 50 g. of concentrated hydrochloric acid and 150 c.c. of water until dissolution is complete. Immerse the solution in ice-water and stir vigorously with a glass rod so that the toluidine hydrochloride separates as far as possible in a microcrystalline form. Then cool the mixture in ice and diazotise with a solution of 16 g. of sodium nitrite in 80 c.c. of water, added until the nitrous acid test with potassium iodide-starch paper persists. The diazonium chloride solution so obtained is poured during the course of about ten minutes into the warm cuprous cyanide solution, which is meanwhile shaken frequently. After the diazo-solution has been added the reaction mixture is heated under an air condenser on the water bath fox a further quarter of an hour, and then the toluic nitrile is separated by distillation with steam (fume chamber, HCN ). The nitrile (which passes over as a yellowish oil) is extracted from the distillate with ether, the p-cresol produced as a by-product is removed by shaking the ethereal extract twice with 2 A-sodium hydroxide solution, the ether is evaporated,... 

Aryldiazonium salts, usually obtained from arylamines, undergo replacement of the diazonium group with a variety of nucleophiles to provide advantageous methods for producing aryl halides, cyanides, phenols and arenes by reductive removal of the diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines give rise to the formation of azo dyes. 

The amine is then used to introduce a nitrile by diazotization followed by treatment of the diazonium salt with cuprous cyanide (180) the methyl ether is then cleaved by means of aluminum chloride. Treatment of the phenolic ketone 181 with benzoyl chloride and sodium benzoate serves to build up the chromone ring (182). The nitrile is next hydrolyzed to the acid with sulfuric acid. Esterification of the carboxyl as—its acid chloride—with N-(2-hydroxyethyl)piperi-... 

Amines are easily identified because they re readily soluble in dilute acid. Sodium fusion converts the cimine to the cyanide ion, which is detectable by a Vciriety of methods. The ready formation and decomposition of diazonium salts (discussed in the earlier section Reactions with nitrous acid ) leads to the identification of primary amines. The Hinsberg test (see the nearby sidebcir) is useful in identifying amines. 

ALKYL NITRATES Icwis acids CYANIDES hypochlorites DEVARDA S ALLOY DIAZONIUM TETRAHALOBORATES ISOXAZOLES NITROBENZALDEHYDES NITROBENZYL COMPOUNDS... 

Potassium nitrite is an antidote to cyanide poisoning. It also is a vasodilator. An important application is in the dye industry to prepare diazonium salts and azo dyes. Another use is in curing certain meat products where the salt imparts an appetizing pink color to cured meats and retards microbial growth on the meat. The commerical product is usually a nitrite-nitrate mixture, containing 85% KNO2 and 15% KNO3... 

Nitration of hydroxypropiophenone (7-1) followed by conversion of the phenol to its methyl ether by means of methyl iodide provides the intermediate (7-2) the nitro group is then reduced to the corresponding amine (7-3) by catalytic reduction. The newly introduced amine is then replaced by a nitrile group by successive conversion to the diazonium salt by means of nitrous acid followed by treatment with cuprous cyanide (7-4). Reaction with aluminum chloride removes the methyl ether to afford the ortho acylphenol (7-5). This is converted to the chromone (7-6) as above by reaction with benzoyl chloride and sodium benzoate. The nitrile is next hydrolyzed to the carboxylic acid (7-7) by means of sulfuric acid. The acid is then converted to its acid chloride by means of thionyl chloride and that treated with 2-(A -piperidyl)ethanol (7-8). There is thus obtained flavoxate (7-9) [8], a muscle relaxant whose name reflects its flavone nucleus. 

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