Part 3 (1/2)

Nitrotoluene and toluidine each exist in three distinct modifications, so that it is more correct to speak of the nitrotoluenes and the toluidines; but the explanation of these differences belongs to pure chemical theory, and cannot now be attempted in detail. It must suffice to say that many compounds having the same chemical composition differ in their properties, and are said to be ”isomeric,” the isomerism being regarded as the result of the different order of arrangement of the atoms within the molecule.

Consider a homely ill.u.s.tration. A child's box of bricks contains a certain number of wooden blocks, by means of which different structures can be built up. Supposing all the bricks to be employed for every structure erected, the latter must in every case contain all the blocks, and yet the result is different, because in each structure the blocks are arranged in a different way. The bricks represent atoms, and the whole structure represents a molecule; the structures all have the same ultimate composition, and are therefore isomeric. This will serve as a rough a.n.a.logy, only it must not be understood that the different atoms of the elements composing a molecule are of different sizes and shapes; on this point we are as yet profoundly ignorant.

Now as long ago as 1856, at the time when Perkin began making mauve by oxidizing aniline with b.i.+.c.hromate of potash, it was observed by Natanson, that when aniline was heated with a certain oxidizing agent a red colouring-matter was produced. The same fact was observed in 1858 by Hofmann, who used the tetrachloride of carbon as an oxidizing agent. These chemists obtained the red colouring-matter as a by-product; it was formed only in small quant.i.ty, and was regarded as an impurity. In the same year, 1858, two French manufacturers patented the production of a red dye formed by the action of chromic acid and other oxidizing agents on aniline, the colouring matter thus made being used for dying artificial flowers. Then, a year later, the French chemist Verguin found that the best oxidizing agent was the tetrachloride of tin, and this with many other oxidizing substances was patented by Renard Freres and Franc, and under their patent the manufacture of the aniline red was commenced on a small scale in France. Finally, in 1860, an oxidizing agent was made use of almost simultaneously by two English chemists, Medlock and Nicholson, which gave a far better yield of the red than any of the other materials previously in use, and put the manufacture of the colouring-matter on quite a new basis. The oxidizing material patented by Medlock and Nicholson is a.r.s.enic acid, and their process is carried on at the present time on an enormous scale in all the chief colour factories in Europe, the colouring-matter produced by this means being generally known as fuchsine or magenta.

In four years the accidental observation of Natanson and Hofmann, made, be it remembered, in the course of abstract scientific investigation, had thus developed into an important branch of manufacture. A demand for aniline on an increased scale sprung up, and the light oils of coal-tar became of still greater importance. The operations of the tar-distiller had to undergo a corresponding increase in magnitude and refinement; the production of nitrobenzene and necessarily of nitric acid had to be increased, and a new branch of manufacture, that of a.r.s.enic acid from a.r.s.enious acid and nitric acid, was called into existence. Perkin's mauve prepared the way for the manufacture of aniline, and the discovery of a good process for the production of magenta increased this branch of manufacture to a remarkable extent. Still later in the history of the magenta manufacture, attempts were made, with more or less success, to use nitrobenzene itself as an oxidizing agent, and a process was perfected in 1869 by Coupier, which is now in use in many factories.

The introduction of magenta into commerce marks an epoch in the history of the coal-tar colour industry--pure chemistry and chemical technology both profited by the discovery. The brilliant red of this colouring-matter is objected to by modern aestheticism, but the dye is still made in large quant.i.ties, its value having been greatly increased by a discovery made about the same time by John Holliday and the Baden Aniline and Soda Company, and patented by the latter in 1877. Magenta is the salt of a base now known as rosaniline, and it belongs therefore to the cla.s.s of basic colouring-matters. The dyes of this kind are as a group less fast, and have a more limited application than those colouring-matters which possess an acid character, so that the discovery above referred to--that magenta could be converted into an acid without destroying its colouring power by acting upon it with very strong sulphuric acid--opened up a new field for the employment of the dye, and greatly extended its usefulness. In this form the colouring-matter is met with under the name of ”acid magenta.”

It must be understood that the production of magenta from aniline by the oxidizing action of a.r.s.enic acid or nitrobenzene is the result of chemical change; the colouring-matter is no more present in the aniline than the latter is contained in the benzene. And just in the same way that the colourless aniline oil by chemical transformation gives rise to the intensely colorific magenta, so the latter by further chemical change can be made to give rise to whole series of different colouring-matters, each consisting of definite chemical compounds as distinct in individuality as magenta itself. Thus in 1860, about the time when the a.r.s.enic acid process was inaugurated, two French chemists, Messrs. Girard and De Laire, observed that by heating rosaniline for some time with aniline and an aniline salt, blue and violet colouring-matters were produced. This observation formed the starting-point of a new manufacture proceeding from magenta as a raw material. The production of the new colouring-matters was perfected by various investigators, and a magnificent blue was the final result. But here also the dye was of a basic character, and being insoluble in water had only a limited application, as a spirit bath had to be used for dissolving the substance. In 1862, however, an English technologist, the late E. C. Nicholson, found that by the action of strong sulphuric acid the aniline blue could be rendered soluble in water or alkali, and the value of the colouring-matter was enormously increased by this discovery. The basic and slightly soluble spirit blue was by this means converted into acid blues, which are now made in large quant.i.ties, and sold under the names of Nicholson's blue, alkali blue, soluble blue, and other trade designations. There is at the present time hardly any other blue which for fastness, facility of dyeing, and beauty can compete with this colouring-matter introduced by Nicholson as the outcome of the work of Girard and De Laire.

Other transformations of rosaniline have yet to be chronicled. In 1862 Hofmann found that by acting upon this base--the base of magenta--with the iodide of methyl, violet colouring-matters were produced, and these were for some years extensively employed under the name of Hofmann's violets.

And still more remarkable, by the prolonged action of an excess of methyl iodide upon rosaniline, Keisser found that a green colouring-matter was formed. The latter was patented in 1866, and the dye was for some time in use under the name of ”iodine green.” The statement that technology profited by the introduction of magenta has therefore been justified.

It remains to add, that the tar obtained from one ton of Lancas.h.i.+re coal furnishes an amount of aniline capable of giving a little over half a pound of magenta. The colouring power of the latter will be inferred from the fact, that this quant.i.ty would dye 375 square yards of white flannel of a full red colour, and if converted into Hofmann violet by methylation, would give enough colour to dye double this surface of flannel of a deep violet shade. It should be stated also, that during the formation of magenta by the a.r.s.enic acid process, there are formed small quant.i.ties of other colouring-matters which are utilized by the manufacturer. Among these by-products is a basic orange dye, which was isolated by Nicholson, and investigated by Hofmann in 1862. Under the name of ”phosphine” this colouring-matter is still used, especially for the dyeing of leather. Even the spent a.r.s.enic acid of the magenta-still has its use. The a.r.s.enious acid resulting from the reduction of this a.r.s.enic acid is generally obtained in the form of a lime salt after the removal of the magenta by the purifying processes to which the crude product is submitted. From the a.r.s.enical waste a.r.s.enious acid can be recovered, and converted back into a.r.s.enic acid by the action of nitric acid. Quite recently the a.r.s.enical residue has been used with considerable success in America as an insecticide for the destruction of pests injurious to agricultural crops.

Concurrently with these technical developments of coal-tar products, the scientific chemist was carrying on his investigations. The compounds which science had given to commerce were made on a scale that enabled the investigator to obtain his materials in quant.i.ties that appeared fabulous in the early days when aniline was regarded as a laboratory curiosity, and magenta had been seen by only a few chemists.

The fundamental problem which the modern chemist seeks to solve is in the first place the composition of a compound, _i.e._ the number of the atoms of the different elements which form the molecule, and in the next place the way in which these atoms are combined in the molecule. Reverting to our former a.n.a.logy, the first thing to be found is how many different blocks enter into the composition of the structure, and the next thing is to ascertain how the blocks are arranged. When this is done, we are said to know the ”const.i.tution” or ”structure” of the molecule, and in many cases when this is known we can build up or synthesise the compound by combining its different groups of atoms by suitable methods. The coal-tar industry abounds with such triumphs of chemical synthesis; a few of these achievements will be brought to light in the course of the remaining portions of this work.

The chemical investigation of magenta was commenced by Hofmann, whose name is inseparably connected with the scientific development of the coal-tar colour industry. In 1862 he showed that magenta was the salt of a base which he isolated, a.n.a.lysed, and named rosaniline. He established the composition of this base and of the violet and blue colouring-matters obtained from it by the processes already described. In 1864 he made the interesting discovery that magenta is not formed by the oxidation of _pure_ aniline, but that a mixture of aniline and toluidine is essential for the production of this colouring-matter. In fact, the aniline oil used by the manufacturer had from the beginning consisted of a mixture of aniline and toluidine, and at the present time ”aniline for red” is made by nitrating a mixture of benzene and toluene and reducing the nitro-compounds.

From this work of Hofmann's suggestions naturally arose concerning the ”const.i.tution” of rosaniline, and new and fruitful lines of work were opened up. Large numbers of chemists of the greatest eminence pursued the inquiry, but the details of their work, although of absorbing interest to the chemist, cannot be discussed in the present volume. The final touch to a long series of investigations was given by two German chemists, Emil and Otto Fischer, who in 1878 proved the const.i.tution of rosaniline by obtaining from it a hydrocarbon, the parent hydrocarbon from which the colouring-matter is derived. The purely scientific discovery of the Fischers threw a flood of light on the chemistry of magenta, and enabled a large number of colouring-matters related to the latter to be cla.s.sed under one group, having the parent hydrocarbon as a central type. This hydrocarbon, it may be remarked, is known as triphenylmethane, as it is a derivative of methane, or marsh gas. The blues and violets obtained from rosaniline belong to this group, and so also do certain other colouring-matters which had been manufactured before the Fischers'

discovery. In order to carry on the story of the utilisation of aniline, it is necessary to know something about these other colouring-matters which are obtained from it.

It has been explained that by the methylation of rosaniline Hofmann obtained violet colouring-matters. Now as rosaniline is obtained by the oxidation of a mixture of aniline and toluidine, it seems but natural that if these bases were methylated first and then oxidized a violet dye would be produced. The French chemist Lauth first obtained a violet colouring-matter by this method in 1861. In 1866 this violet dye was manufactured in France by Poirrier, and it is still made in large quant.i.ties, being known under the name of ”methyl violet.” This colouring-matter, and a bluer derivative of it discovered in 1868, gradually displaced the Hofmann violets, chiefly owing to their greater cheapness of production. We are thus introduced to methylated aniline as a source of colouring-matters, and as the compound in question has many different uses in the coal-tar industry, a few words must be devoted to its technology.

Aniline, toluidine, and similar bases can be methylated by the action of methyl iodide, but the cost of iodine is too great to enable this process to be used by the manufacturer. Methyl chloride, however, answers equally well, and this compound, which is a liquid of very low boiling point (-23 C.), is prepared on a large scale from the waste material of another industry, viz. the beet-sugar manufacture. It is interesting to see how distinct industries by chemical skill are made to act and react upon one another. Thus the cultivation of the beet, as already explained, is largely dependent on the supply of ammonia from gas-liquor. During the refining of the beet-sugar, a large quant.i.ty of uncrystallisable treacle is separated, and this is fermented for the manufacture of alcohol. When the latter is distilled off there remains a spent liquor containing among other things pota.s.sium salts and nitrogenous compounds. This waste liquor, called ”vina.s.se,” is evaporated down and ignited in order to recover the potash, and during the ignition, ammonia, tar, gas, and other volatile products are given off. Among the volatile products is a base called trimethylamine, which is a derivative of ammonia; the salt formed by combining trimethylamine with hydrochloric acid when heated gives off methyl chloride as a gas which can be condensed by pressure.

Here we have a very pretty cycle of chemical transmigration. The nitrogen of the coal plants, stored up in the earth for ages, is restored in the form of ammonia to the crops of growing beet; the nitrogen is made to enter into the composition of the latter plant by the chemico-physiological process going on, and the nitrogenous compounds removed from the plant and heated to the point of decomposition in presence of the potash (which also entered into the composition of the plant), give back their nitrogen partly in the form of a base from which methyl chloride can be obtained.

The latter is then made to methylate a product, aniline, derived indirectly from coal-tar. The utilisation of the ”vina.s.se” for this purpose was made known by Camille Vincent of Paris in 1878.

The methylation of aniline can obviously be carried out by the foregoing process only when beet-sugar residues are available. There is another method which is more generally used, and which is interesting as bringing in a distinct branch of industry. The same result can, in fact, be arrived at by heating dry aniline hydrochloride, _i.e._ the hydrochloric acid salt of aniline, with methyl alcohol or wood-spirit in strong metallic boilers under great pressure. This is the process carried on in most factories, and it involves the use of pure methyl alcohol, a branch of manufacture which has been called into existence to meet the requirements of the coal-tar colour maker.[4] This alcohol or wood-spirit is obtained by the destructive distillation of wood, and is purified by a series of operations which do not at present concern us. It must be mentioned that the product of the methylation of aniline, which it is the object of the manufacturer to obtain, is an oily liquid called dimethylaniline, which, by virtue of the chemical transformation, is quite different in its properties to the aniline from which it is derived. By a similar operation, using ethyl alcohol, or spirit of wine, diethylaniline can be obtained, and by heating dry aniline hydrochloride with aniline under similar conditions a crystalline base called diphenylamine is also prepared.

Now these products--dimethylaniline, diethylaniline, and diphenylamine--are derived from aniline, and they are all sources of colouring-matters. Methyl-violet is obtained by the oxidation of dimethylaniline by means of a gentle oxidizer; a mixture of bases is not necessary as in the case of the magenta formation. Then in 1866 diphenylamine was shown by Girard and De Laire to be capable of yielding a fine blue by heating it with oxalic acid, and this blue, on account of the purity of its shade, is still an article of commerce. It can be made soluble by the action of sulphuric acid in just the same way as the other aniline blue. Furthermore, by acting with excess of methyl chloride on methyl violet, a brilliant green colouring-matter was manufactured in 1878, which was obviously a.n.a.logous to the iodine green already mentioned, and which for some years held its own as the only good coal-tar green.

These are the dyes--methyl violet and green, and diphenylamine blue--which were in commerce before the discovery of the Fischers, and which this discovery enabled chemists to cla.s.s with magenta, aniline blue, and Hofmann violet in the triphenylmethane group.

Later developments bring us into contact with other dyes of the same cla.s.s, and with the industrial evolution of the purely scientific idea concerning the const.i.tution of the colouring-matters of this group.

Benzene and toluene again form the points of departure. By the action of chlorine upon the vapour of boiling toluene there are obtained, according to the extent of the action of the chlorine, three liquids of use to the colour manufacturer. The first of these is benzyl chloride, the second benzal chloride, and the third benzotrichloride or phenyl chloroform.

Benzyl chloride, it may be remarked in pa.s.sing, plays the same part in organic chemistry as methyl chloride, and enables certain compounds to be benzylated, just in the same way that they can be methylated. The bluer shade of methyl violet, introduced in 1868, and still manufactured, is a benzylated derivative. By the action of benzotrichloride on dimethylaniline in the presence of dry zinc chloride, Oscar Doebner obtained in 1878 a brilliant green colouring-matter which was manufactured under the name of ”malachite green.” It will be remembered that this was about the time when the Fischers were engaged with their investigations.

These last chemists, by virtue of their scientific results, were enabled to show that Doebner's green was a member of the triphenylmethane group, and they prepared the same compound by another method which has enabled the manufacturer to dispense with the use of the somewhat expensive and disagreeable benzotrichloride. The Fischers' method consists in heating dimethylaniline with bitter-almond oil and oxidizing the product thus formed, when the green colouring-matter is at once produced. This method brings the technologist into compet.i.tion with Nature, and we shall see the result.

Benzoic aldehyde or bitter-almond oil is one of the oldest known products of the vegetable kingdom, and has from time to time been made the subject of investigation by chemists since the beginning of the century. It arises from the fermentation of a nitrogenous compound found in the almond, and known as amygdalin, the nature of the fermentative change undergone by this substance having been brought to light by Wohler and Liebig. The discovery of a green dye, requiring for its preparation a vegetable product which was very costly, compelled the manufacturer to seek another source of the oil. Pure chemistry again steps in, and solves the problem.

In 1863 it was known to Cahours that benzal chloride, on being heated with water or alkali, gave benzoic aldehyde, and in 1867 Lauth and Grimaux showed that the same compound could be formed by oxidizing benzyl chloride in the presence of water. It was but a step from the laboratory into the factory in this case, and at the present time the aldehyde is made on a large scale by chlorinating boiling toluene beyond the stage of benzyl chloride, and heating the mixture of benzal chloride and benzotrichloride with lime and water under pressure. By this means the first compound is transformed into benzoic aldehyde, and the second into benzoic acid. This last substance is also required by the colour-maker, as it is used in the manufacture of blue by the action of aniline on rosaniline; without some such organic acid the transformation of rosaniline into the blue is very imperfect.

Benzoic acid, like the aldehyde, is a natural product which has long been known. It was obtained from gum benzon at the beginning of the seventeenth century, and its preparation from this source was described by Scheele in 1755. The same chemist afterwards found it in urine, and from these two sources, the one vegetable and the other animal, the acid was formerly prepared. Its relations.h.i.+p to benzene has already been alluded to in connection with the history of that hydrocarbon. It will be remembered that by heating this acid with lime Mitscherlich obtained benzene in 1834. In one operation, therefore, setting out from toluene, we make these two natural products, the aldehyde and acid, which are easily separable by technical processes. The wants of the technologist have been met, and he has been enabled to compete successfully with Nature, for he can manufacture these products much more cheaply than when he had to depend upon bitter almonds or gum benzon. The synthetical bitter-almond oil is chemically identical with that from the plant. Besides its use for the manufacture of colouring-matters, it is employed for flavouring purposes and in perfumery, this being the first instance of a coal-tar perfume which we have had occasion to mention. The odour in this case, it must be remembered, is that of the actual compound which imparts the characteristic taste and smell to the almond; it is not the result of subst.i.tuting a substance which has a particular odour for another having a similar odour, as is the case with nitrobenzene, which, as already mentioned, is used in large quant.i.ties under the name of ”essence of mirbane,” for imparting an almond-like smell to soap.

The introduction of malachite green marks another epoch in the history of the technology of the triphenylmethane colours. The action between benzoic aldehyde and other bases a.n.a.logous to dimethylaniline was found to be quite general, and the principle was extended to diethylaniline and similarly const.i.tuted bases. Various green dyes--some of them acids formed by the action of sulphuric acid on the colour base--are now manufactured, and many other colouring-matters of the same group are synthesised by the benzoic aldehyde process.

One other development of this branch of manufacture has yet to be recorded. The new departure was made in 1883 by Caro and Kern, who patented a process for the synthesis of colouring-matters of this group.

In this synthesis a gas called phosgene is used, the said gas having been discovered by John Davy in 1811, who gave it its name because it is formed by the direct union of chlorine and carbon monoxide under the influence of sunlight. Caro and Kern's process is the first technical application of Davy's compound. By the action of phosgene on dimethylaniline and a.n.a.logous bases in the presence of certain compounds which promote the chemical interaction, a number of basic colouring-matters of brilliant shades of violet (”crystal violet”) and blue (”Victoria blue,” ”night blue”) are produced, these being all members of the triphenylmethane group. One of these dyes is a fine basic yellow known as ”auramine,” which is a derivative of diphenylmethane.

TAR.