Fig. 7.—Indigo Plant(Indigofera tinctoria).
Imagine the industrial revolution which would be caused by the discovery of a process for obtaining indigo synthetically from a coal-tar hydrocarbon, at a price which would compare favourably with that of the natural product. This has not actually been done as yet, but chemists have attempted to compete with Nature in this direction, and the present state of the competition is that the natural product can be cultivated and made more cheaply. Nevertheless the dye can be synthesised from a coal-tar hydrocarbon, and this is one of the greatest achievements of modern chemistry in connection with the tar-products. For more than half a century indigo had been undergoing investigation by chemists, and at length the work culminated in the discovery of a method for producing it artificially. This discovery was the outcome ofthe labour of Adolf v. Baeyer, who commenced his researches upon the derivatives of indigo in 1866, and who in 1880 secured the first patents for the manufacture of the colouring-matter. It is to the laborious and brilliant investigations of this chemist that we owe nearly all that is at present known about the chemistry of indigo and allied compounds.
Fig. 8.—Woad(Isatis tinctoria).
Two methods have been used for the production of artificial indigo—benzal chloride being the starting-point in one of these, and nitrobenzoic aldehyde in the other. The generating hydrocarbon is therefore toluene. By heating benzal chloride with dry sodium acetate there is formed an acid known as cinnamic acid, a fragrant compound which derives its name from cinnamon, because the acid was prepared by the oxidation of oil of cinnamon by Dumas and Peligot in 1834. The acid and its ethers occur also in many balsams, so that we have here another instance of the synthesis of a natural vegetable product from a coal-tar hydrocarbon. The subsequent steps are—(1) the nitration of the acid to produce nitrocinnamic acid; (2) the addition of bromine to form a dibromide of the nitro-acid; (3) the action of alkali on the dibromide to produce what is known as “propiolic acid.” The latter, under the influence of mild alkaline reducing agents, is transformed into indigo-blue. The process depending on the use of nitrobenzoic aldehyde is much simpler; but the particular nitro-derivative of the aldehyde which is required is at present difficult to make, and therefore expensive. If the production of this compound could be cheapened, the competition between artificial and naturalindigo would assume a much more serious aspect.[5]
The light oil of the tar-distiller has now been sufficiently dealt with so far as regards colouring-matters; let us pass on to the next fraction of the tar, the carbolic oil. The important constituents of this portion are carbolic acid and naphthalene. The carbolic oil is in the first place separated into two distinct portions by washing with an alkaline solution. Carbolic acid or phenol belongs to a class of compounds derived from hydrocarbons of the benzene and related series by the substitution of the residue of water for hydrogen. This water-residue is known to chemists as “hydroxyl”—it is water less one atom of hydrogen. Carbolic acid or phenol is hydroxybenzene; and all analogous compounds are spoken of as “phenols.” It will be understood in future that a phenol is a hydroxy-derivative of a benzenoid hydrocarbon. Now these phenols are all more or less acid in character by virtue of the hydroxyl-group which they contain. For this reason they dissolve in aqueous alkaline solutions, and are precipitated therefrom by acids.This will enable us to understand the purification of the carbolic oil.
The two layers into which this oil separates after washing with alkali are (1) the aqueous alkaline solution of the carbolic acid and other phenols, and (2) the undissolved naphthalene contaminated with oily hydrocarbons and other impurities. Each of these portions has its industrial history. The alkaline solution, on being drawn off and made acid, yields its mixture of phenols in the form of a dark oil from which carbolic acid is separated by a laborious series of fractional distillations. The undissolved hydrocarbon is similarly purified by fractional distillation, and furnishes the solid crystalline naphthalene. The tar from one ton of Lancashire coal yields about 1½ lbs. of carbolic acid, equal to about 1 per cent. by weight of the tar, and about 6¼lbs. of naphthalene, so that this last hydrocarbon is one of the chief constituents of the tar, of which it forms from 8 to 10 per cent. by weight.
The crude carbolic acid as separated from the alkaline solution is a mixture of several phenolic compounds, and all of these but the carbolic acid itself are gradually removed during the process of purification. Among the compounds associated with the carbolic acid are certain phenols of higher boiling-point, which bear the same relationship to carbolic acid that toluene bears to benzene. Thatis to say, that while phenol itself is hydroxybenzene, these other compounds, which are called “cresols,” are hydroxytoluenes. The cresols form an oily liquid largely used for disinfecting purposes under the designation of “liquid carbolic acid,” or “cresylic acid.” Carbolic acid is a white crystalline solid possessing strongly antiseptic properties, and is therefore of immense value in all cases where putrefaction or decay has to be arrested. It was discovered in coal-tar by Runge in 1834, and was obtained pure by Laurent in 1840.
The gradual establishment of the germ-theory of disease, chiefly due to the labours of Pasteur, has led to a most important application of carbolic acid. Once again we find the coal-tar industry brought into contact with another department of science. Arguing from the view that putrefactive change is brought about by the presence of the germs of micro-organisms ever present in the atmosphere, Sir Joseph Lister proposed that during surgical operations the incised part should be kept under a spray of the germicidal carbolic acid to prevent subsequent mortification. No operation upon portions of the body exposed to the air is at present conducted without this precaution, and many a human life must have been saved by Lister’s treatment. To this result the chemist and technologist have contributed, not only by thediscovery of the carbolic acid in the tar, but also by the development of the necessary processes for its purification. It should be added that the phenol used must be of the greatest possible purity, and the requirements of the surgeon have been met by chemical and technological skill.
From surgery back to colouring-matters, and from these to pharmaceutical preparations and perfumes, are we led in following up the cycles of chemical transformation which these tar-products have undergone in the hands of the technologist, guided by the researches of the chemist. It was observed by Runge in 1834 that crude carbolic acid, on treatment with lime, gave a red, acid colouring-matter which he separated and named “rosolic acid.” The observation was followed up, and many other chemists obtained red colouring-matters by the oxidation of crude phenol. In 1859, the colour-giving property of carbolic acid acquired industrial importance from a discovery made by Kolbe and Schmitt in Germany, and by Persoz in France. These chemists found that a good yield of the colouring-matter was obtained by heating phenol with oxalic and sulphuric acids. Under the names of “corallin” and “aurin” the dye-stuff was introduced into commerce, and it is still used for certain purposes, especially for the preparation of coloured lakes for paper-staining.
The scientific development of the history of this phenol dye is full of interest, but we can only give it a passing glance. Its interest lies chiefly in the circumstance that it is related to magenta, as was first pointed out by Caro and Wanklyn in 1866. In fact they obtained rosolic acid from magenta by the action of nitrous acid on the latter. We now know that a diazo-salt is first formed under these circumstances, and that the decomposition of this unstable compound in the presence of water gives rise to the rosolic acid. Later researches have shown that by heating rosolic acid with ammonia it is converted into rosaniline. It is also known that the commercial corallin, like the commercial magenta, is a mixture of closely related colouring-matters. The close analogy between magenta and rosolic acid was further shown by Caro in 1866. In the same way that Hofmann found that magenta could not be produced by the oxidation ofpureaniline, Caro found that a mixture of phenol and cresol was necessary for the production of rosolic acid when inorganic oxidizers were used. It is indeed this series of investigations upon the phenol dyes—investigations which have been taken part in not only by the chemists named, but also by Graebe, Dale and Schorlemmer, and the Fischers—which led up to the discovery of the constitution of the colouring-matters of therosaniline group, and, through this, to the far-reaching industrial developments of the discovery as traced in the last chapter. It is evident, from what has been said, that rosolic acid and its related colouring-matters are members of the triphenylmethane group. They are in fact the hydroxylic or acid analogues of the amido-containing or basic dyes of the rosaniline series.
In the fragrant blossom of the meadowsweet (Spiræa ulmaria) there is contained an acid which is found also as an ether in the oil of wintergreen (Gautheria procumbens). This is salicylic acid, a white crystalline compound which has been known to chemists since 1839. In 1860 Kolbe prepared the sodium salt of this acid by passing carbon dioxide gas into phenol in which metallic sodium had been dissolved. It was found subsequently that the same transformation was brought about by heating the dry sodium salt of carbolic acid in an atmosphere of carbon dioxide. This process of Kolbe’s is now worked on a manufacturing scale for the preparation of artificial salicylic acid. The acid and its salts and ethers find numerous applications as antiseptics, for the preservation of food, and in pharmacy.
Salicylic acid is employed also for the manufacture of certain azo-dyes in a way that it will be very instructive to consider, because the processused may be taken as typical of the general method of preparing such compounds. Solutions of diazo-salts act not only upon amido- and diamido-compounds, as we have seen in the case of aniline yellow and chrysoïdine, but also upon phenols, forming acid azo-colours. This important fact was made known in 1870 by the German chemists Kekulé and Hidegh, but more than six years elapsed before this discovery was taken advantage of by the technologist. Large numbers of these acid azo-dyes are now made from various diazotised amido-compounds combined with different phenols and phenolic acids. The mode of procedure is to diazotise the amido-compound by sodium nitrite and hydrochloric acid in the manner already described, and then add the diazo-salt solution to the phenolic compound dissolved in alkali. The colouring-matter is at once formed. Salicylic acid possesses the characters both of an acid and a phenol. It combines readily with diazo-salts under the circumstances described, and gives rise to azo-dyes, some of which are of technical value.
The manufacture of azo-dyes from salicylic acid brings us into contact with certain amidic compounds which figure so largely in the tinctorial industry that they may be conveniently dealt with here. These bases are not azo-compoundsthemselves, but they are prepared from azo-compounds, viz. from the azobenzene and azotoluene which were spoken about in the last chapter. When these are reduced by acid reducing-agents, they become converted into diamido-bases which are known as benzidine and tolidine respectively. These bases can be diazotised, and as they contain two amido-groups, they form double diazo-salts,i.e.tetrazo-salts, which are capable of combining with amido-compounds, or phenols, in the usual way. Thus diazotised benzidine and tolidine combine with salicylic acid to form valuable yellow azo-dyes known as “chrysamines.” The dyes of this class obviously contain two azo-groups.
Some other uses of carbolic acid must next be considered. Of the colouring-matters derived from coal-tar, none is more widely known than the oldest artificial yellow dye, picric acid. This is a phenol derivative, and was first obtained as long ago as 1771 by Woulfe, by acting upon indigo with nitric acid. Laurent in 1842 was the first to obtain this dye from carbolic acid, from which compound it is still manufactured by acting upon the sulpho-acid with nitric acid. Chemically considered, it is trinitrophenol. It has a very wide application as a dye, and has been used as an explosive agent. A similar colouring-matter was made from cresol in 1869, and introduced underthe name of “Victoria yellow,” which is dinitro-cresol. Other dyes derived directly or indirectly from phenol will take us back once again to toluene.
A new diazotisable diamido-compound was obtained from this last hydrocarbon, and introduced in 1886 by Leonhardt & Co. One of the three isomeric nitrotoluenes furnishes a sulpho-acid which, on treatment with alkali, gives a compound derived from a hydrocarbon known as stilbene, and this, on reduction, is converted into the diamido-compound referred to. The latter, which is a disulpho-acid as well as a diamido-compound, can be diazotised and combined with phenols, &c. The stilbene azo-dyes thus prepared from phenol and salicylic acid, like the chrysamines, are yellow colouring-matters, containing two azo-groups. It is a valuable characteristic of these secondary azo-dyes that they all possess a special affinity for vegetable fibre, and their introduction has exerted a great influence upon the art of cotton-dyeing. We shall have to return to these cotton-dyes again shortly.
Before leaving this branch of the subject, the following scheme is presented to show the relationships and inter-relationships of the products thus far dealt with in the present chapter—
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The existence of naphthalene in coal-tar was made known in 1820 by Garden, who gave it this name because the oils obtained from the tar by distillation went under the general designation of naphtha. The greater portion of the hydrocarbon is contained in the carbolic oil, and is separated and purified in the manner described. A further quantity of impure naphthalene separates out from the next fraction—the creosote oil, and this is similarly washed and purified by distillation. The large quantity of naphthalene existing in tar has already been referred to, but although it is such an important constituent, it was only late in the history of the colour industry that it found any extensive application. In early times it was regarded as a nuisance, and was burnt as fuel, or for the production of a dense soot, which was condensed to form lampblack. It will be remembered that the first of the coal-tar colours made required only the light oils. There are at present only a few direct uses for naphthalene, but one of its applications is sufficiently important to be mentioned.
The hydrocarbon is a white crystalline solid melting at 80° C., and boiling at 217° C. Although it has a high boiling-point, it passes readily into vapour at lower temperatures, and the vapour on condensation forms beautiful silvery crystalline scales. This product is “sublimed naphthalene.”The vapour of naphthalene burns with a highly luminous flame, and if mixed with coal-gas, it considerably increases the luminosity of the flame. Advantage is taken-of this in the so-called “albo-carbon light,” which is the flame of burning coal-gas saturated with naphthalene vapour. The burner is constructed so that the gas passes through a reservoir filled with melted naphthalene kept hot by the flame itself (Fig. 9).
Fig. 9.—Albo-carbon Burner.
To appreciate properly the value of thosediscoveries which have enabled manufacturers to utilize this hydrocarbon, it is only necessary to recall to mind the actual quantity produced in this country. Supposing that ten million tons of coal are used annually for gas-making, and that the 500,000 tons of tar resulting therefrom contain only eight per cent. of naphthalene, there would be available about 40,000 tons of this hydrocarbon annually. Great as have been the recent advancements in the utilization of naphthalene derivatives, there is still a larger quantity of this hydrocarbon produced than is necessary to supply the wants of the colour-manufacturer. From this last statement it will be inferred that naphthalene is now a source of colouring-matters. Let us consider how this has been brought about.
The phenols of naphthalene are called naphthols—they bear the same relationship to naphthalene that carbolic acid bears to benzene. Owing to the structure of the naphthalene molecule there are two isomeric naphthols, whereas there is only one phenol. The naphthols—known as alpha- and beta-naphthol, respectively—are now made on a large scale from naphthalene, by heating the latter with sulphuric acid; at a low temperature the alpha sulpho-acid is produced, and at a higher temperature the beta sulpho-acid, and these acids on fusion with caustic soda furnish the correspondingnaphthols. Similarly there are two amidonaphthalenes, known as alpha- and beta-naphthylamine respectively. As aniline is to benzene, so are the naphthylamines to naphthalene. The alpha-compound is made in precisely the same way as aniline, viz. by acting upon naphthalene with nitric acid so as to form nitronaphthalene, and then reducing the latter with iron dust and acid. Beta-napthylamine cannot be made in this way; it is prepared from beta-naphthol by heating the latter in presence of ammonia, when the hydroxyl becomes replaced by the amido-group in accordance with a process patented in 1880 by the Baden Aniline Company. The principle thus utilized is the outcome of the scientific work of two Austrian chemists, Merz and Weith. Setting out from the naphthols and naphthylamines we shall be led into industrial developments of the greatest importance.
The first naphthalene colour was a yellow dye, discovered by Martius in 1864, and manufactured under the name of “Manchester yellow.” It is, chemically speaking, dinitro-alpha-naphthol; but it was not at first made from naphthol, as the latter was not at the time a technical product. It was made from alpha-naphthylamine by the action of nitrous and nitric acids. When a good method for making the naphthol was discovered in 1869, the dye was made from this. The process is just thesame as that employed in making picric acid; the naphthol is converted into a sulpho-acid, and this when acted upon by nitric acid, gives the colouring-matter. Manchester yellow is now largely used for colouring soap, but as a dye-stuff it has been improved upon in a manner that will be readily understood. The original colouring-matter being somewhat fugitive, it was found that its sulpho-acid was much faster. This sulpho-acid cannot be made by the direct action of sulphuric acid upon the colouring-matter—as in the case of acid yellow or acid magenta—but by acting upon the naphthol with very strong sulphuric acid, three sulphuric acid residues or sulpho-groups enter the molecule, and then on nitration only two of these are replaced by nitro-groups, and there results a sulpho-acid of dinitro-alpha-naphthol. This was discovered in 1879 by Caro, and introduced as “acid naphthol yellow.” It is now one of the standard yellow dyes.
The history of another important group of colouring-matters dependent on naphthalene begins with A. v. Baeyer in 1871 and with Caro in 1874. Two products formerly known only as laboratory preparations were called into requisition by this discovery. One of these compounds, phthalic acid, is obtained from naphthalene, and the other, resorcin or resorcinol, is prepared from benzene. Phthalic acid, which was discovered in 1836 by Laurent, isa product of the oxidation of many benzenoid compounds. Chemically considered it is a di-derivative of benzene,i.e.two of the hydrogen atoms of benzene are replaced by certain groups of carbon, oxygen, and hydrogen atoms. We have seen how the replacement of hydrogen by an ammonia-residue, amidogen, gives rise to bases such as amidobenzene (aniline), or diamidobenzene. Similarly, the replacement of hydrogen by a water-residue, hydroxyl, gives rise to a phenol. The group of carbon, oxygen, and hydrogen atoms which confers the property of acidity upon an organic compound is a half-molecule of oxalic acid—it is known as the carboxyl group. Thus benzoic acid is the carboxyl-derivative of benzene, and the phthalic acid with which we are now concerned is a dicarboxyl-derivative of benzene. It is related to benzoic acid in the same way that diamidobenzene is related to aniline. Three isomeric phthalic acids are known, but only one of these is of use in the present branch of manufacture. The acid in question, although a derivative of benzene, is most economically prepared by the oxidation of certain derivatives of naphthalene which, when completely broken down by energetic oxidizing agents, furnish the acid. Thus the dinitronaphthol described as Manchester yellow, if heated for some time with dilute nitric acid, furnishes phthalic acid.The latter is made on a large scale by the oxidation of a compound which naphthalene forms with chlorine, and known as naphthalene tetrachloride, because it contains four atoms of chlorine.
The other compound, resorcinol, was known to chemistry ten years before it was utilized as a source of colouring-matters. It was originally prepared by fusing certain resins, such as galbanum, asafœtida, &c., with caustic alkali. Soon after its discovery, viz. in 1866, it was shown by Körner to be a derivative of benzene, and from this hint the technical process for the preparation of the compound on a large scale has been developed. Resorcinol is a phenolic derivative of benzene containing two hydroxyl groups; it is therefore related to phenol in the same way that diamidobenzene is related to aniline or phthalic acid to benzoic acid. The relationships can be expressed in a tabular form thus—
Resorcinol is now made by heating benzene with very strong sulphuric acid so as to convert it into a disulpho-acid, and the sodium salt of the latter is then fused with alkali. As a technical operation it is one of great delicacy and skill, and the manufacture is confined to a few Continental factories.
When phthalic acid is heated it loses water, and is transformed into a white, magnificently crystalline substance known as phthalic anhydride,i.e.the acid deprived of water. In 1871, A. v. Baeyer, the eminent chemist who subsequently synthesised indigo, published the first of a series of investigations describing the compounds produced by heating phthalic anhydride with phenols. To these compounds he gave the name of “phthaleïns.” Baeyer’s work, like that of so many other chemists who have contributed to the advancement of the coal-tar colour industry, was of a purely scientific character at first, but it soon led to technological developments. The phthaleïns are all acid compounds possessing more or less tinctorial power. One of the first discovered was produced by heating phthalic anhydride with an acid known as gallic acid, which occurs in vegetable galls, and in the form of tannin in many vegetable extracts which are used by the tanner. The acid is a phenolic derivative of benzoic acid, viz. trihydroxybenzoic acid, and on heating it readily passes into trihydroxybenzene, which is the “pyrogallic acid” or pyrogallol familiar as a photographic developer. The phthaleïn formed from gallic acid and phthalic anhydride really results from the union of the latter with pyrogallol. It is now manufactured under the name of “galleïn,” and is largely usedfor imparting a bluish grey shade to cotton fabrics. By heating galleïn with strong sulphuric acid, it is transformed into another colouring-matter which gives remarkably fast olive-green shades when dyed on cotton fibre with a suitable mordant. This derivative of galleïn is used to a considerable extent under the name of “cœruleïn.” These two colouring-matters were the first practical outcome of v. Baeyer’s researches. There is another possible development in this direction which chemistry may yet accomplish, and another natural colouring-matter may be threatened, even as the indigo culture was threatened by the later work of the same chemist. There is reason for believing that the colouring-matter of logwood, known to chemists as hæmateïn, is related to or derived in some way from the phthaleïns, and the synthesis of this compound may ultimately be effected.
The dye introduced by Caro in 1874 is the brominated phthaleïn of resorcinol. The phthaleïn itself is a yellow dye, and the solutions of its salts show a splendid and most intense greenish yellow fluorescence, for which reason it is called “fluoresceïn.” When brominated, the latter furnishes a beautiful red colouring-matter known as “eosin” (Gr.ἕως, dawn), and the introduction of this gave an industrial impetus to the phthaleïns which led to the discovery of many other related colouring-mattersnow largely used under various trade designations. About a dozen distinct compounds producing different shades of pink, crimson and red, and all derived from fluoresceïn, are at present in the market, and a few other phthaleïns formed by heating phthalic anhydride with other phenolic compounds instead of resorcinol or pyrogallol (e.g.diethylamidophenol), are also of industrial importance. By converting nitrobenzene into a sulpho-acid, reducing to an amido-sulpho-acid, and then fusing with alkali, an amido-phenol is produced, the ethers of which, when heated with phthalic anhydride, give rise to red phthaleïns of most intense colouring power introduced by the Baden Aniline Company as “rhodamines.”
It remains to point out that the scientific spirit which prompted the investigation of the phthaleïns in the first instance has followed these compounds throughout their technological career. The researches started by v. Baeyer were taken up by various chemists, whose work together with that of the original discoverer has led to the elucidation of the constitution of these colouring-matters. The phthaleïns are members of the triphenylmethane group, and are therefore related to magenta, corallin, malachite green, methyl violet, and the phosgene dyes.
It has been said that the phenolic and amidicderivatives of naphthalene,i.e.the naphthols and naphthylamines, are of the greatest importance to the colour industry. One of the first uses of alpha-naphthylamine has already been mentioned, viz. for the production of the Manchester yellow, which was afterwards made more advantageously from alpha-naphthol. A red colouring-matter possessing a beautiful fluorescence was afterwards (1869) made from this naphthylamine and introduced as “Magdala red.” The latter was discovered by Schiendl of Vienna in 1867. It was prepared in precisely the same way as induline was prepared from aniline yellow. The latter, which is amido-azobenzene, and which is prepared, broadly speaking, by the action of nitrous acid on aniline, has its analogue in amido-azonaphthalene, which is similarly prepared by the action of nitrous acid on naphthylamine. Just as aniline yellow when heated with aniline and an aniline salt gives induline, so amido-azonaphthalene when heated with naphthylamine and a salt of this base gives Magdala red. The latter is, therefore, a naphthalene analogue of induline, as was shown by Hofmann in 1869, and the knowledge of the constitution of the azines which has been gained of late years, enables us to relegate the colouring-matter to this group. This knowledge has also enabled the manufacture to be conducted on more rational principles, viz. by the methodemployed for the production of the saffranines, as previously sketched.
The introduction of azo-dyes, formed by the action of a diazotised amido-compound on a phenol or another amido-compound, marks the period from which the naphthols and naphthylamines rose to the first rank of importance as raw materials for the colour manufacturer. The introduction of chrysoïdine in 1876 was immediately followed by the manufacture of acid azo-dyes obtained by combining diazotised amido-sulpho-acids with phenols of various kinds, or with bases, such as dimethylaniline and diphenylamine. From what has been said in the foregoing portion of this volume, it is evident that all such azo-compounds result from the combination of two things, viz. (1) a diazotised amido-compound, and (2) a phenolic or amidic compound. Either (1) or (2) or both may be a sulpho-acid, and the resulting dye will then also be a sulpho-acid.
The first of these colouring-matters derived from the naphthols, was introduced in 1876-77 by Roussin and Poirrier, and by O. N. Witt. They were prepared by converting aniline into a sulpho-acid (sulphanilic acid), diazotising this and combining the diazo-compound with alpha- or beta-naphthol. The compounds formed are brilliant orange dyes, the latter being still largely consumedas “naphthol orange.” Other dye-stuffs of a similar nature were introduced by Caro about the same time, and were prepared from the diazotised sulpho-acid of alpha-naphthylamine combined with the naphthols. By this means alpha-naphthol gives what is known as “acid brown,” or “fast brown,” and beta-naphthol a fine crimson, known as “fast red,” or “roccellin.” Diazotised compounds combine also with this same sulpho-acid of alpha-naphthylamine (known as naphthionic acid), the first colouring-matter formed in this way having been introduced by Roussin and Poirrier in 1878. It was prepared by diazotising a nitro-derivative of aniline, and acting with the diazo-salt on napthionic acid, and this dye is still used to some extent under the name of “archil substitute.” In 1878, the firm of Meister, Lucius & Brüning of Höchst-on-the-Main gave a further impetus to the utilization of naphthalene by discovering two isomeric disulpho-acids of beta-naphthol formed by heating that phenol with sulphuric acid. By combining various diazotised bases with these sulpho-acids, a splendid series of acid azo-dyes ranging in shade from bright orange to claret-red, and to scarlets rivalling cochineal in brilliancy were given to the tinctorial industry.
The colouring-matters introduced in 1878 by the Höchst factory under the names of “Ponceaux”of various brands, and “Bordeaux,” although to some extent superseded by later discoveries, still occupy an important position. Their discovery not only increased the consumption of beta-naphthol, but also that of the bases which were used for diazotising. These bases are alpha-naphthylamine and those of the aniline series. The intimate relationship which exists between chemical science and technology—a relationship which appears so constantly in the foregoing portions of this work—is well brought out by the discovery under consideration. A little more chemistry will enable this statement to be appreciated.
Going back for a moment to the hydrocarbons obtained from light oil, it will be remembered that benzene and toluene have thus far been considered as the only ones of importance to the colour-maker. Until the discovery embodied in the patent specification of 1878, the portions of the light oil boiling above toluene were of no value in the colour industry. Benzene and toluene are related to each other in a way which chemists describe by saying that they are “homologous.” This means that they are members of a regularly graduated series, the successive terms of which differ by the same number of atoms of carbon and hydrogen. Thus toluene contains one atom of carbon and two atoms of hydrogen more than benzene. Abovetoluene are higher homologues, viz. xylene, cumene, &c., which occur in the light oil, the former being related to toluene in the same way that toluene is related to benzene, while cumene again contains one atom of carbon and two atoms of hydrogen more than xylene. This relationship between the members of homologous series is expressed in other terms by saying that the weight of the molecule increases by a constant quantity as we ascend the series.
The homology existing among the hydrocarbons extends to all their derivatives. Thus phenol is the lower homologue of the cresols. Also we have the homologous series—
The bases of the third column when diazotised and combined with the disulpho-acids of beta-naphthol give a graduated series of dyes beginning with orange and ending with bluish scarlet. Thus it was observed that the toluidine colour was redder than the aniline colour, and it was a natural inference that the xylidine colour would be still redder. At the time of this discovery no azo-colour of a true scarlet shade had been manufactured successfully. A demand for the higher homologuesof benzene was thus created, and the higher boiling-point fractions of the light oil, which had been formerly used as solvent naphtha, became of value as sources of colouring-matters. The isolation of coal-tar xylene (which is a mixture of three isomeric hydrocarbons) is easily effected by fractional distillation with a rectifying column, and by nitration and reduction, in the same way as in the manufacture of aniline, xylidine is placed at the disposal of the colour-maker.
Xylidine scarlet, although at the time of its introduction the only true azo-scarlet likely to come into competition with cochineal, was still somewhat on the orange side. The cumidine dye would obviously be nearer the desired shade. To meet this want, cumidine had to be made on a large scale, but here practical difficulties interposed themselves. The quantity of cumene in the light oil is but small, and it is associated with other hydrocarbons which are impurities from the present point of view, and from which it is separated only with difficulty. A new source of the base had therefore to be sought, and here again we find chemical science ministering to the wants of the technologist.
It was explained in the last chapter that aniline and similar bases can be methylated by heating their dry salts with methyl alcohol under pressure.In this way dimethylaniline is made, and dimethyltoluidine or dimethylxylidine can similarly be prepared. Now it was shown by Hofmann in 1871, that if this operation is conducted at a very high temperature, and under very great pressure, the methyl-alcohol residue,i.e.the methyl-group, does not replace the amidic hydrogen or the hydrogen of the ammonia residue, but the methylation takes place in another way, resulting in the formation of a higher homologue of the base started with. For example, by heating aniline salt and pure wood-spirit to a temperature considerably above that necessary for producing dimethylaniline, toluidine is formed. In a similar way, by heating xylidine hydrochloride and methyl alcohol for some time in a closed vessel at about 300° C. cumidine is produced. Hofmann’s discovery was thus utilized in 1882, and by its means the base was manufactured, and cumidine scarlet, very similar in shade to cochineal, became an article of commerce.
While the development of this branch of the colour industry was taking place by means of the new naphthol disulpho-acids, the cultivation of the fertile field of the azo-dyes was being carried on in other directions. It came to be realized that the fundamental discovery of Griess was capable of being extended to all kinds of amido-compounds.The azo-dyes hitherto introduced had all been derived from amido-compounds containing only one amido-group, and they accordingly contained only one azo-group; they wereprimaryazo-compounds. It was soon found that aniline yellow, which already contains one azo-group as well as an amido-group, could be again diazotised and combined with phenols so as to produce compounds containing two azo-groups,i.e.secondaryazo-compounds. The sulpho-acid of aniline yellow—Grässler’s “acid yellow”—was the first source of azo-dyes of this class. By diazotising this amidoazo-sulpho-acid, and combining it with beta-naphthol, a fine scarlet dye was discovered by Nietzki in 1879, and introduced under the name of “Biebrich scarlet.” Two years later a new sulpho-acid of beta-naphthol was discovered by Bayer & Co. of Elberfeld, and this gave rise, when combined with diazotised acid yellow and analogous compounds, to another series of brilliant dyes introduced as “Crocein scarlets.”
From these beginnings the development of the azo-dyes has been steadily carried on to the present time—year by year new diazotisable amido-compounds or new sulpho-acids of the naphthols and naphthylamines are being discovered, and this branch of the colour industry has already assumed colossal dimensions. An important departurewas made in 1884 by Böttiger, who introduced the first secondary azo-colours derived from benzidine. As already explained in connection with salicylic acid, this base and its homologue tolidine form tetrazo-salts, which combine with phenols and amines or their sulpho-acids. One of the first colouring-matters of this group was obtained by combining diazotised benzidine with the sulpho-acid of alpha-naphthylamine (naphthionic acid), and was introduced under the name of “Congo red.” Then came the discovery (Pfaff, 1885), that the tetrazo-salts of benzidine and tolidine combine with phenols, amines, &c., in two stages, one of the diazo-groups first combining with one-half of the whole quantity of phenol to form an intermediate compound, which then combines with the other half of the phenol to form the secondary azo-dye. In the hands of the “Actiengesellschaft für Anilinfabrikation” of Berlin this discovery has been utilized for the production of a number of such azo-colours containing two distinct phenols, or amines, or sulpho-acids. Tolidine has been found to give better colouring-matters in most cases than benzidine, and it is scarcely necessary to point out that an increased demand for the nitrotoluene from which this base is made is the necessary consequence of this discovery.
It is impossible to attempt to specify by nameany of these recent benzidine and tolidine dyes. Their introduction has been the means of finding new uses for the naphthylamines and naphthols and their sulpho-acids, and has thus contributed largely to the utilization of naphthalene. An impetus has been given to the investigation of these sulpho-acids, and chemical science has profited largely thereby. The process by which beta-naphthylamine is prepared from beta-naphthol, already referred to, viz. by heating with ammonia under pressure, has been extended to the sulpho-acids of beta-naphthol, and by this means new beta-naphthylamine sulpho-acids have been prepared, and figure largely in the production of these secondary azo-colours. The latter, as previously stated, possess the most valuable property of dyeing cotton fibre directly, and by their means the art of cotton dyeing has been greatly simplified. The shades given by these colours vary from yellow through orange to bright scarlet, violet, or purple.
In addition to benzidine and tolidine, other diazotisable amido-compounds have of late years been pressed into the service of the colour-manufacturer. The derivative of stilbene, already mentioned as being prepared from a sulpho-acid of one of the nitrotoluenes, forms tetrazo-salts, which can be combined with similar or dissimilar phenols, amines, or sulpho-acids, as in the case of benzidine andtolidine. Various shades of red and purple are thus obtained from the diazotised compound, when the latter is combined with the naphthylamines, naphthols, or their sulpho-acids. These, again, are all cotton dyes. The nitro-derivatives of the ethers of phenol and cresol, when reduced in the same way that nitrobenzene and nitrotoluene are reduced to azobenzene and azotoluene, also furnish azo-compounds which, on further reduction, give bases analogous to benzidine and tolidine. Secondary azo-colours derived from these bases and the usual naphthalene derivatives are also manufactured. It is among the secondary azo-dyes that we meet with the first direct dyeing blacks, the importance of which will be realized when it is remembered that the ordinary aniline-black is not adapted for wool dyeing. The azo-blacks are obtained by combining diazotised sulpho-acids of amidoazo-compounds of the benzene or naphthalene series with naphthol sulpho-acids or other naphthalene derivatives.
One other series of azo-compounds must be briefly referred to. It has long been known that aniline and toluidine when heated with sulphur evolve sulphuretted hydrogen and give rise to thio-bases, that is, aniline or toluidine in which the hydrogen is partly replaced by sulphur. One of the toluidines treated in this way is transformed intoa thiotoluidine which, when diazotised and combined with one of the disulpho-acids of beta-naphthol, forms a red azo-dye, introduced by Dahl & Co. in 1885 as “thiorubin.” By modifying the conditions of reaction between the sulphur and the base, it was found in 1887 by Arthur Green, that a complicated thio-derivative of toluidine could be produced which possessed very remarkable properties. The sulpho-acid of the thio-base is a yellow dye, which was named by its discoverer “primuline.” Not only is primuline a dye, but it contains an amido-group which can be diazotised. If therefore the fabric dyed with primuline is passed through a nitrite bath, a diazo-salt is formed in the fibre, and on immersing the latter in a second bath containing naphthol or other phenol or an amine, an azo-dye is precipitated in the fibre. By this means there are produced valuable “ingrain colours” of various shades of red, orange, purple, &c.
So much for the azo-dyes, one of the most prolific fields of industrial enterprise connected with coal-tar technology. From the introduction of aniline yellow in 1863 to the present time, about 150 distinct compounds of this group have been given to the tinctorial industry. Of these over thirty are cotton dyes containing two azo-groups. Sombre shades, rivalling logwood black, bright yellows, orange-reds, browns, violets, and brilliant scarletsequalling cochineal, have been evolved from the refuse of the gas-works. The artificial colouring-matters have in this last case once again threatened a natural product, and with greater success than the indigo synthesis, for the introduction of the azo-scarlets has caused a marked decline in the cochineal culture.
In addition to the azo-colours, there are certain other products which claim naphthalene as a raw material. In 1879 it was found that one of the sulpho-acids of beta-naphthol when treated with nitrous acid readily gave a nitroso-sulpho-acid. A salt of this last acid, containing sodium and iron as metallic bases, was introduced in 1884, under the name of “naphthol green.” It is used both as a dye for wool and as a pigment. It may be mentioned here that other nitroso-derivatives of phenols, such as those of resorcinol and the naphthols, under the name of “gambines,” are largely used for dyeing purposes, owing to the facility with which they combine with metallic mordants to form coloured salts in the fibre. In this same year, 1879, it was found that by heating nitrosodimethylaniline with beta-naphthol in an appropriate solvent, a violet colouring-matter was formed. This is now manufactured under the name of “new blue,” or other designations, and is largely used for producing an indigo-blue shade on cotton prepared with a suitablemordant. The discovery of this colouring-matter gave an impetus to further discoveries in the same direction. It was found that nitrosodimethylaniline reacted in a similar way with other phenolic or with amidic compounds. In 1881 Köchlin introduced an analogous dye-stuff prepared by the action of the same nitroso-compound on gallic acid. Gallocyanin, as it is called, imparts a violet blue shade to mordanted cotton. Other colouring-matters of the same group are in use; some of them, like “new blue,” being derivatives of naphthalene. These compounds all belong to a series of which the parent substance is constructed on a type similar to azine; it contains a nitrogen and oxygen atom linking together the hydrocarbon residues, and is therefore known as “oxazine.” The researches of Nietzki in 1888 first established the true constitution of the oxazines.
Closely related to this group is a colouring-matter introduced by Köchlin and Witt in 1881 under the name of “indophenol.” It is prepared in the same way as the azines of the “neutral red” group; viz. by the action of nitrosodimethylaniline on alpha-naphthol, or by oxidizing amidodimethylaniline in the presence of alpha-naphthol. Indophenol belongs to that group of blue compounds formed as intermediate products in the manufacture of azines, as mentioned in connection with “neutralred.” But while these intermediate blues resulting from the oxidation of a diamine in the presence of another amine are unstable, and pass readily into red azines, indophenol is stable, and can be used for dyeing and printing in the same way as indigo. The shades which it produces are very similar to this last dye, but for certain practical reasons it has not been able to compete with the natural dye-stuff.
The story of naphthalene is summarized in the schemes on pp. 164, 165.