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Diazo Compounds

DIAZO COMPOUNDS, in organic chemistry, compounds of the type R·N·2·X (where R = a hydrocarbon radical, and X = an acid radical or a hydroxyl group). These compounds may be divided into two classes, namely, the true diazo compounds, characterized by the grouping −N = N−, and the diazonium compounds, characterized by the grouping N ∶ N <.

The diazonium compounds were first discovered by P. Griess (Ann., 1858, 106, pp. 123 et seq.), and may be prepared by the action of nitrous fumes on a well-cooled solution of a salt of a primary amine,

C6H5NH2·HNO3 + HNO2 = C6H5N2·NO3 + 2H2O,

or, as is more usually the case (since the diazonium salts themselves are generally used only in aqueous solution) by the addition of a well-cooled solution of potassium or sodium nitrite to a well-cooled dilute acid solution of the primary amine. In order to isolate the anhydrous diazonium salts, the method of E. Knoevenagel (Ber., 1890, 23, p. 2094) may be employed. In this process the amine salt is dissolved in absolute alcohol and diazotized by the addition of amyl nitrite; a crystalline precipitate of the diazonium salt is formed on standing, or on the addition of a small quantity of ether. The diazonium salts are also formed by the action of zinc-dust and acids on the nitrates of primary amines (R. Mohlau, Ber., 1883, 16, p. 3080), and by the action of hydroxylamine on nitrosobenzenes. They are colourless crystalline solids which turn brown on exposure. They dissolve easily in water, but only to a slight extent in alcohol and ether. They are very unstable, exploding violently when heated or rubbed. Benzene diazonium nitrate, C6H5N(NO3)∶N, crystallizes in long silky needles. The sulphate and chloride are similar, but they are not quite so unstable as the nitrate. The bromide may be prepared by the addition of bromine to an ethereal solution of diazo-amino-benzene (tribromaniline remaining in solution). By the addition of potassium bromide and bromine water to diazonium salts they are converted into a perbromide, e.g. C6H5N2Br3, which crystallizes in yellow plates.

The diazonium salts are characterized by their great reactivity and consequently are important reagents in synthetical processes, since by their agency the amino group in a primary amine may be exchanged for other elements or radicals. The chief reactions are as follows: -

1. Replacement of -NH2 by -OH: - The amine is diazotized and the aqueous solution of the diazonium salt is heated, nitrogen being eliminated and a phenol formed.

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)

In support of this theory, Hantzsch has succeeded in isolating a series of syn- and anti-diazo-cyanides and -sulphonates (Ber., 1895, 28, p. 666; 1900, 33, p. 2161; 1901, 34, p. 4166). By diazotizing para-chloraniline and adding a cold solution of potassium cyanide, a salt (melting at 29° C.) is obtained, which readily loses nitrogen, and forms para-chlorbenzonitrile on the addition of copper powder. By dissolving this diazocyanide in alcohol and reprecipitating it by water, it is converted into the isomeric diazocyanide (melting at 105-106° C.), which does not yield para-chlorbenzonitrile when treated with copper powder. Similar results have been obtained by using diazotized para-anisidine, a syn- and an anti- compound being formed, as well as a third isomeric cyanide, obtained by evaporating para-methoxy-benzenediazonium hydroxide in the presence of an excess of hydrocyanic acid at ordinary temperatures. This salt is a colourless crystalline substance of composition CH3O·C6H4·N2·CN·HCN·2H2O, and has the properties of a metallic salt; it is very soluble in water and its solution is an electrolyte, whereas the solutions of the syn- and anti- compounds are not electrolytes. The isolation of these compounds is a powerful argument in favour of the Hantzsch hypothesis which requires the existence of these three different types, whilst the Bamberger-Blomstrand view only accounts for the formation of two isomeric cyanides, namely, one of the normal diazonium type and one of the iso-diazocyanide type.

Benzene diazonium hydroxide, although a strong base, reacts with the alkaline hydroxides to form salts with the evolution of heat, and generally behaves as a weak acid. On mixing dilute solutions of the diazonium hydroxide and the alkali together, it is found that the molecular conductivity of the mixture is much less than the sum of the two electrical conductivities of the solutions separately, from which it follows that a portion of the ions present have changed to the non-ionized condition. This behaviour is explained by considering the non-ionized part of the diazonium hydroxide to exist in solution in a hydrated form, the equation of equilibrium being:

On adding the alkaline hydroxide to the solution, this hydrate is supposed to lose water, yielding the syn-diazo hydroxide, which then gives rise to a certain amount of the sodium salt (A. Hantzsch, Ber., 1898, 31, p. 1612),

This assumption also shows the relationship of the diazonium hydroxides to other quaternary ammonium compounds, for most of the quaternary ammonium hydroxides (except such as have the nitrogen atom attached to four saturated hydrocarbon radicals) are unstable, and readily pass over into compounds in which the hydroxyl group is no longer attached to the amine nitrogen; thus the syn-diazo hydroxides are to be regarded as pseudo-diazonium derivatives. (A. Hantzsch, Ber., 1899, 32, p. 3109; 1900, 33, p. 278.) It is generally accepted that the iso-diazo hydroxides possess the oxime structure R·N:N·OH.

Hantzsch explains the characteristic reactions of the diazonium compounds by the assumption that an addition compound is first formed, which breaks down with the elimination of the hydride of the acid radical, and the formation of an unstable syn-diazo compound, which, in its turn, decomposes with evolution of nitrogen (Ber., 1897, 30, p. 2548; 1898, 31, p. 2053).

J. Cain (Jour. Chem. Soc., 1907, 91, p. 1049) suggested a quinonoid formula for diazonium salts, which has been combated by Hantzsch (Ber., 1908, 41, pp. 3532 et seq.). G. T. Morgan and F. M. G. Micklethwaite (Jour. Chem. Soc., 1908, 93, p. 617; 1909, 95, p. 1319) have pointed out that the salts may possess a dynamic formula, Cain's representing the middle stage, thus:

Diazoamines. - The diazoamines, R·N2·NHR, may be prepared by the action of the primary and secondary amines on the diazonium salts, or by the action of nitrous acid on the free primary amine. In the latter reaction it is assumed that the isodiazohydroxide first formed is immediately attacked by a second molecule of the amine. They are yellow crystalline solids, which do not unite with acids. Nitrous acid converts them, in acid solution, into diazonium salts.

C6H5N2·NHC6H5 + 2HCl + HNO2 = 2C6H5N2Cl + 2H2O.

They are readily converted into the isomeric aminoazo compounds, either by standing in alcoholic solution, or by warming with a mixture of the parent base and its hydrochloride; the diazo group preferably going into the para-position to the amino group. When the para-position is occupied, the diazo group takes the ortho-position. H. Goldschmidt and R. U. Reinders (Ber., 1896, 29, p. 1369, 1899) have shown that the transformation is a monomolecular reaction, the velocity of transformation in moderately dilute solution being independent of the concentration, but proportional to the amount of the catalyst present (amine hydrochloride) and to the temperature. It has also been shown that when different salts of the amine are used, their catalytic influence varies in amount and is almost proportional to their degree of ionization in aqueous solution. Diazoaminobenzene, C6H5N2·NHC6H5, crystallizes in golden yellow laminae, which melt at 96° C. and explode at a slightly higher temperature. It is readily soluble in alcohol, ether and benzene. Concentrated hydrochloric acid converts it into chlorbenzene, aniline and nitrogen. Zinc dust and alcoholic acetic acid reduce it to aniline and phenylhydrazine.

Diazoimino compounds, R·N3, may be regarded as derivatives of azoimide (q.v.); they are formed by the action of ammonia on the diazoperbromides, or by the action of hydroxylamine on the diazonium sulphates (J. Mai, Ber., 1892, 25, p. 372; T. Curtius, Ber., 1893, 26, p. 1271). Diazobenzeneimide, C6H5N3, is a yellowish oil of stupefying odour. It boils at 59° C. (12 mm.), and explodes when heated. Concentrated hydrochloric acid decomposes it with formation of chloranilines and elimination of nitrogen, whilst on boiling with sulphuric acid it is converted into aminophenols.

Aliphatic Diazo Compounds. - The esters of the aliphatic amino acids may be diazotized in a manner similar to the primary aromatic amines, a fact discovered by T. Curtius (Ber., 1833, 16, p. 2230). The first aliphatic diazo compound to be isolated was diazoacetic ester, CH·N2·CO2C2H5, which is prepared by the action of potassium nitrite on the ethyl ester of glycocoll hydrochloride, HCl·NH2·CH2·CO2C2H5 + KNO2 = CHN2·CO2C2H5 + KCl + 2H2O. It is a yellowish oil which melts at -24° C.; it boils at 143-144° C., but cannot be distilled safely as it decomposes violently, giving nitrogen and ethyl fumarate. It explodes in contact with concentrated sulphuric acid. On reduction it yields ammonia and glycocoll (aminoacetic acid). When heated with water it forms ethyl hydroxy-acetate; with alcohol it yields ethyl ethoxyacetate. Halogen acids convert it into monohalogen fatty acids, and the halogens themselves convert it into dihalogen fatty acids. It unites with aldehydes to form esters of ketonic acids, and with aniline yields anilido-acetic acid. It forms an addition product with acrylic ester, which on heating loses nitrogen and leaves trimethylene dicarboxylic ester. Concentrated ammonia converts it into diazoacetamide, CHN2·CONH2, which crystallizes in golden yellow plates which melt at 114° C. For other reactions see Hydrazine. The constitution of the diazo fatty esters is inferred from the fact that the two nitrogen atoms, when split off, are replaced by two monovalent elements or groups, thus leading to the formula for diazoacetic ester.

Diazosuccinic ester, N2·C(CO2C2H5)2, is similarly prepared by the action of nitrous acid on the hydrochloride of aspartic ester. It is decomposed by boiling water and yields fumaric ester.

Diazomethane, CH2N2, was first obtained in 1894 by H. v. Pechmann (Ber., 1894, 27, p. 1888; 1895, 28, p. 855). It is prepared by the action of aqueous or alcoholic solutions of the caustic alkalis on the nitroso-acidyl derivatives of methylamine (such, for example, as nitrosomethyl urethane, NO·N(CH3)·CO2C2H5, which is formed on passing nitrous fumes into an ethereal solution of methyl urethane). E. Bamberger (Ber., 1895, 28, p. 1682) regards it as the anhydride of iso-diazomethane, CH3·N:N·OH, and has prepared it by a method similar to that used for the preparation of iso-diazobenzene. By the action of bleaching powder on methylamine hydrochloride, there is obtained a volatile liquid (methyldichloramine, CH3·N·Cl2), boiling at 58-60° C., which explodes violently when heated with water, yielding hydrocyanic acid (CH3NCl2 = HCN + 2HCl). Well-dried hydroxylamine hydrochloride is dissolved in methyl alcohol and mixed with sodium methylate; a solution of methyldichloramine in absolute ether is then added and an ethereal solution of diazomethane distils over. Diazomethane is a yellow inodorous gas, very poisonous and corrosive. It may be condensed to a liquid, which boils at about 0° C. It is a powerful methylating agent, reacting with water to form methyl alcohol, and converting acetic acid into methylacetate, hydrochloric acid into methyl chloride, hydrocyanic acid into acetonitrile, and phenol into anisol, nitrogen being eliminated in each case. It is reduced by sodium amalgam (in alcoholic solution) to methylhydrazine, CH3·NH·NH2. It unites directly with acetylene to form pyrazole (H. v. Pechmann, Ber., 1898, 31, p. 2950) and with fumaric methyl ester it forms pyrazolin dicarboxylic ester.

(F. G. P.*)

See G. T. Morgan, B.A. Rep., 1902; J. Cain, Diazo Compounds, 1908.

Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)

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