2. Replacement of -NH2 by halogens and by the -CN and -CNO groups:—The diazonium salt is warmed with an acid solution of the corresponding cuprous salt (T. Sandmeyer, Ber., 1884, 17, p. 2650), or with copper powder (L. Gattermann, Ber., 1890, 23, p. 1218; 1892, 25, p. 1074). In the case of iodine, the substitution is effected by adding a warm solution of potassium iodide to the diazonium solution, no copper or cuprous salt being necessary; whilst for the production of nitriles a solution of potassium cuprous cyanide is used. This reaction (the so-called “Sandmeyer” reaction) has been investigated by A. Hantzsch and J. W. Blagden (Ber., 1900, 33, p. 2544), who consider that three simultaneous reactions occur, namely, the formation of labile double salts which decompose in such a fashion that the radical attached to the copper atom wanders to the aromatic nucleus; a catalytic action, in which nitrogen is eliminated and the acid radical attaches itself to the aromatic nucleus; and finally, the formation of azo compounds.

3. Replacement of -NH2 by -NO2:—A well-cooled concentrated solution of potassium mercuric nitrate is added to a cooled solution of benzene diazonium nitrate, when the crystalline salt 2C6H5N2·NO3, Hg(NO2)2 is precipitated. On warming this with copper powder, it gives a quantitative yield of nitrobenzene (A. Hantzsch, Ber., 1900, 33, p. 2551).

4. Replacement of -NH2 by hydrogen:—This exchange is brought about, in some cases, by boiling the diazonium salt with alcohol; but I. Remsen and his pupils (Amer. Chem. Journ., 1888, 9, pp. 389 et seq.) have shown that the main product of this reaction is usually a phenolic ether. This reaction has also been investigated by A. Hantzsch and E. Jochem (Ber., 1901, 34, p. 3337), who arrived at the conclusion that the normal decomposition of diazonium salts by alcohols results in the formation of phenolic ethers, but that an increase in the molecular weight of the alcohol, or the accumulation of negative groups in the aromatic nucleus, diminishes the yield of the ether and increases the amount of the hydrocarbon formed. The replacement is more readily brought about by the use of sodium stannite (P. Friedlander, Ber., 1889, 22, p. 587), or by the use of a concentrated solution of hypophosphorous acid (J. Mai, Ber., 1902, 35, p. 162). A. Hantzsch (Ber., 1896, 29, p. 947; 1898, 31, p. 1253) has shown that the chlor- and brom- diazoniumthiocyanates, when dissolved in alcohol containing a trace of hydrochloric acid, become converted into the isomeric thiocyanbenzene diazonium chlorides and bromides. This change only occurs when the halogen atom is in the ortho- or para- position to the -N2- group.

Metallic Diazo Derivatives.—Benzene diazonium chloride is decomposed by silver oxide in aqueous solution, with the formation of benzene diazonium hydroxide, C6H5·N(OH)∶N. This hydroxide, although possessing powerful basic properties, is unstable in the presence of alkalis and neutralizes them, being converted first into the isomeric benzene-diazotic acid, the potassium salt of which is obtained when the diazonium chloride is added to an excess of cold concentrated potash (A. Hantzsch and W. B. Davidson, Ber., 1898, 31, p. 1612). Potassium benzene diazotate, C6H5N2·OK, crystallizes in colourless silky needles. The free acid is not known; by the addition of the potassium salt to 50% acetic acid at -20° C., the acid anhydride, benzene diazo oxide, (C6H5N2)2O, is obtained as a very unstable, yellow, insoluble compound, exploding spontaneously at 0° C. Strong acids convert it into a diazonium salt, and potash converts it into the diazotate. On the constitution, of these anhydrides see E. Bamberger, Ber., 1896, 29, p. 446, and A. Hantzsch, Ber., 1896, 29, p. 1067; 1898, 31, p. 636. By the addition of the diazonium salts to a hot concentrated solution of a caustic alkali, C. Schraube and C. Schmidt (Ber., 1894, 27, p. 520) obtained an isomer of potassium benzene diazotate. These iso-diazotates are formed much more readily when the aromatic nucleus in the diazonium salt contains negative radicals. Potassium benzene iso-diazotate resembles the normal salt, but is more stable, and is more highly ionized. Carbon dioxide converts it into phenyl nitrosamine, C6H5NH·NO (A. Hantzsch). The potassium salt of the iso-diazo hydroxide yields on methylation a nitrogen ether, R·N(CH3)·NO, whilst the silver salt yields an oxygen ether, R·N:N·OCH3. These results point to the conclusion that the iso-diazo hydroxide is a tautomeric substance. The same oxygen ether is formed by the methylation of the silver salt of the normal diazo hydroxide; this points to the conclusion that the isomeric hydroxides, corresponding with the silver derivatives, have the same structural formulae, namely, R·N:N·OH. These oxygen ethers contain the grouping -N:N-, since they couple very readily with the phenols in alkaline solution to form azo compounds (q.v.) (E. Bamberger, Ber., 1895, 28, p. 225); they are also explosive.

By oxidizing potassium benzene iso-diazotate with alkaline potassium ferricyanide, E. Bamberger (Ber., 1894, 27, p. 914) obtained the diazoic acids, R·NH·NO2, substances which he had previously prepared by similarly oxidizing the diazonium salts, by dehydrating the nitrates of primary amines with acetic anhydride, and by the action of nitric anhydride on the primary amines. Concentrated acids convert them into the isomeric nitro-amines, the -NO2 group going into the nucleus in the ortho- or para- position to the amine nitrogen; this appears to indicate that the compounds are nitramines. They behave, however, as tautomeric substances, since their alkali salts on methylation give nitrogen ethers, whilst their silver salts yield oxygen ethers:

Phenyl nitramine, C6H5NH·NO2, is a colourless crystalline solid, which melts at 46° C. Sodium amalgam in alkaline solution reduces it to phenylhydrazine.

Constitution of the Diazo Compounds.—P. Griess (Ann., 1866, 137, p. 39) considered that the diazo compounds were formed by the addition of complex groupings of the type C6H4N2- to the inorganic acids; whilst A. Kekulé (Zeit. f. Chemie, 1866, 2, p. 308), on account of their ready condensation to form azo compounds and their easy reduction to hydrazines, assumed that they were substances of the type R·N:N·Cl. The constitution of the diazonium group -N2·X, may be inferred from the following facts:—The group C6H5N2- behaves in many respects similarly to an alkali metal, and even more so to the ammonium group, since it is capable of forming colourless neutral salts with mineral acids, which in dilute aqueous solution are strongly ionized, but do not show any trace of hydrolytic dissociation (A. Hantzsch, Ber., 1895, 28, p. 1734). Again, the diazonium chlorides combine with platinic chloride to form difficultly soluble double platinum salts, such as (C6H5N2Cl)2·PtCl4; similar gold salts, C6H5N2Cl·AuCl3, are known. Determinations of the electrical conductivity of the diazonium chloride and nitrate also show that the diazonium radical is strictly comparable with other quaternary ammonium ions. For these reasons, one must assume the existence of pentavalent nitrogen in the diazonium salts, in order to account for their basic properties.

The constitution of the isomeric diazo hydroxides has given rise to much discussion. E. Bamberger (Ber., 1895, 28, pp. 444 et seq.) and C. W. Blomstrand (Journ. prakt. Chem., 1896, 53, pp. 169 et seq.) hold that the compounds are structurally different, the normal diazo-hydroxide being a diazonium derivative of the type R·N(∶N)·OH. The recent work of A. Hantzsch and his pupils seems to invalidate this view (Ber., 1894, 27, pp. 1702 et seq.; see also A. Hantzsch, Die Diazoverbindungen). According to Hantzsch the isomeric diazo hydroxides are structurally identical, and the differences in behaviour are due to stereo-chemical relations, the isomerism being comparable with that of the oximes (q.v.). On such a hypothesis, the relatively unstable normal diazo hydroxides would be the syn-compounds, since here the nitrogen atoms would be more easily eliminated, whilst the stable iso-diazo derivatives would be the anti-compounds, thus:

Normal hydroxide
(Syn-compound)		Iso hydroxide
(Anti-compound)