1861. Methyl violet discovered; manufactured in 1866; leading to a new use of copper salts as oxidizing agents, and to the manufacture of dimethylaniline.
1862. Hofmann violets discovered; leading to manufacture of methyl iodide from iodine, phosphorus, and wood spirit.
1862. Phosphine (chrysaniline) discovered in crude magenta.
1863. Aniline black introduced; leading to a new use for potassium chlorate and copper salts, and to the manufacture of aniline salt.
1863. Aniline yellow introduced, the first azo-colour.
1864. Induline discovered; leading to new use for aniline yellow.
1866. Manchester brown introduced, the second azo-colour; leading to the manufacture of sodium nitrite, and of dinitrobenzene.
1866. Iodine green introduced; leading to further use for methyl iodide.
1866. Diphenylamine blue introduced; leading to manufacture of diphenylamine.
1868. Blue shade of methyl violet introduced; leading to manufacture of benzyl chloride.
1868. Saffranine introduced.
1869. Nitrobenzene process for magenta discovered.
1876. Chrysodine introduced, the third azo-colour.
1876. Methylene blue introduced; leading to manufacture of nitrosodimethylaniline.
1877. Acid magenta discovered.
1878. Methyl green introduced; leading to utilization of waste from beet-sugar manufacture.
1878. Malachite green discovered; leading to manufacture of benzoic aldehyde.
1878. Acid yellow discovered; leading to new use for aniline yellow.
1879. Neutral red and allied azines introduced; leading to a new use for nitrosodimethylaniline.
1883. Phosgene colours of rosaniline group introduced; leading to manufacture of phosgene.
CHAPTER III.
Among the most venerable of natural dye-stuffs is indigo, the substance from which Unverdorben first obtained aniline in 1826. The colouring matter is found in a number of leguminous (see Fig. 7), cruciferous, and other plants, some of which are largely cultivated in India, China, the Malay Archipelago, South America, and the West Indies; while others, such as woad (see Fig. 8), are grown in more temperate European climates. The tinctorial value of these plants was known in India and Egypt long before the Christian era. Egyptian mummy-cloths have been found dyed with indigo.
The dye was known to the Greeks and Romans; its use is described by the younger Pliny in his Natural History. Indigo was introduced into Europe about the sixteenth century, but its use was strongly opposed by the woad cultivators, with whose industry the dye came into competition. In France the opposition was strong enough to secure the passing of an act in the time of Henry IV. inflicting the penalty of death upon any person found using the dye. The importance of indigo as an article of commerce is sufficiently known at the present time; more than 8000 tons are produced annually, corresponding in money value to about four million pounds. It is of importance to us as rulers of India to remember that the cultivation and manufacture of indigo is one of the staple industries of that country, from which the European markets derive the greater part of their supply.
[Illustration: 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 of the 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.
[Illustration: 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 natural indigo 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 1-1/2 lbs. of carbolic acid, equal to about 1 per cent. by weight of the tar, and about 6-1/4lbs. 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. That is 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 the discovery 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 of _pure_ aniline, 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 the rosaniline 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 (_Spiraea 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 process used 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 chrysodine, but also upon phenols, forming acid azo-colours. This important fact was made known in 1870 by the German chemists Kekule 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-compounds themselves, 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 under the 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--
Tar --------------------------------------------------------- Light Oil Carbolic Oil / /-> Benzal Chloride / / / / Benzaldehyde / / Cinnamic acid Benzene Toluene Nitrobenzaldehyde Nitrocinnamic acid (+ acetone) / / ----------- Nitrobenzene Nitrotoluene Propiolic acid / / Phenols Naphthalene / / / ->Cresols Azobenzene Azotoluene Indigo<--/ Phenol Stilbene- Victoria derivative <------------------- yellow (Diazotised) Benzidine Tolidine Salicylic Picric Corallin / acid acid & Aurin (Diazotised) / --------------------------------
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).