The Art of Perfumery, George William Septimus Piesse [christmas read aloud .TXT] 📗

alcohol. The spirit is to be removed by distillation, and the remaining watery solution, from which the resin has been separated by filtration, treated with dilute sulphuric acid, to precipitate the benzoic acid. This method gives the greatest quantity of acid, but is attended with a sacrifice of time and alcohol, which renders it in an economical point of view inferior to the above process of Scheele. It is so far valuable, that the total acid contents of the resin can be determined by it.

Dr. Gregory considers the following process for obtaining benzoic acid the most productive. Dissolve benzoin in strong alcohol, by the aid of heat, and add to the solution, whilst hot, hydrochloric acid, in sufficient quantity to precipitate the resin. When the mixture is distilled, the benzoic acid passes over in the form of benzoic ether. Distillation must be continued as long as any ether passes over. Water added towards the end of the operation will facilitate the expulsion of the ether from the retort. When the ether ceases to pass over, the hot water in the retort is filtered, which deposits benzoic acid on cooling. The benzoic ether and all the distilled liquids are now treated with caustic potash until the ether is decomposed, and the solution is heated to boiling, and super-saturated with hydrochloric acid, which afterwards, on cooling, deposits, in crystals, benzoic acid.

Benzoic acid, as it exists in the resin, is the natural production of the plant from which the resin is derived. It may also be produced artificially. Abel found that when cumole (C18H12) was treated with nitric acid, so dilute that no red vapors were evolved for several days, this hydro-carbon was converted into benzoic acid. Guckelberger has, by the oxidation of casein with peroxide of manganese and sulphuric acid, obtained as one of the products benzoic acid. Albumen, fibrin, and gelatin yielded similar results when treated as above. Wöhler has detected benzoic acid in Canadian castor, along with salicin. It is also formed by the oxidation of the volatile oil of bitter almonds. Benzoate of potash results when chloride of benzoyle is treated with caustic potash. Benzoic acid in the animal economy is converted into hippuric acid, which may by the action of acids, be reconverted into benzoic acid.

Benzoic acid should be completely volatile, without leaving any ash or being carbonized when heated. When dissolved in warm water, to which a little nitric acid has been added, nitrate of silver and chloride of barium should produce no precipitates. Oxalate of potash should give no turbidity to an ammoniacal solution of this acid. When heated with an excess of caustic potash it should evolve no smell of ammonia, otherwise, it has been adulterated with sal ammoniac. In spirit, benzoic acid is easily soluble, and requires 200 parts of cold and 20 parts of boiling water to dissolve one part of it.

ON THE COLORING-MATTERS OF FLOWERS. BY FREMY AND CLOEZ.

Chemists possess only a very incomplete knowledge of the coloring matters of flowers. Their investigation involves difficulties which cannot be mistaken. The matters which color flowers are uncrystallized; they frequently change by the action of the reagents employed for their preparation; and, also, very brilliantly-colored flowers owe their color to very small quantities of coloring matter.

On the nature of the coloring matters of flowers several opinions have been expressed. Some observers have assumed that flowers owe their color to only two coloring matters, one of which is termed anthocyan, and the other anthoxanthine. Others will find a relation between the green coloring of leaves, the chlorophylle, and the coloring matters of flowers. They support their opinion generally on the results of the elementary analysis of those different bodies; but all chemists know that chlorophylle has not yet been prepared in a pure condition. Probably, it retains various quantities of fatty and albuminous bodies. Further, the coloring matters of flowers are scarcely known, so that it is impossible to establish relations supported by the necessarily uncertain composition of impure bodies.

Some time since the blue color of flowers was ascribed to the presence of indigo; but Chevreul has shown, in a certain way, that the blue substance of flowers is always reddened by acids; and that with indigo it is quite different, which, as is known, retains its blue color even when the strongest acids are allowed to act on it.

It is thus seen that the coloring matters of flowers have heretofore only in a superficial manner been examined, and that it is important to again undertake their complete examination, as these bodies are interesting to the chemist, because they are employed as reagents in the laboratory for the recognition of alkalies; and by an improved knowledge of them the florist might find the way by which he could give to cultivated flowers various colors.

We have believed that before undertaking their elementary analysis, methods must be carefully sought for which can be followed for the obtainment of the coloring matters of flowers, and that it should be proved whether these substances are to be considered as independent bodies, or whether they proceed from one and the same matter, which is changed in various ways by the juices of the plant.

We now publish the results of our first investigations.

Blue Coloring Matter of Flowers (Cyanine).—The blue coloring matter of flowers we propose to call cyanine. To obtain this substance we treat the petals of Centauria cyanus, Viola odorata, or Iris pseudacorus, with boiling alcohol, by which the flowers are decolorized; and the liquid acquires immediately a fine blue color.

If the coloring matter is allowed to remain some time in contact with alcohol, it is perceived that the blue of the liquid gradually disappears, and soon a yellow brown coloration takes its place. The coloring matter has in this case suffered an actual reduction by the prolonged action of the alcohol, but it will again assume its original color when the alcohol is allowed to evaporate in the air. Nevertheless, the alcohol must not be allowed to remain in contact too long with the coloring matter, because the alcoholic extract will not then again assume its blue coloration by the action of oxygen.

The residue remaining from the evaporation of the alcohol is treated with water, which separates a fatty and resinous substance. The watery solution which contains the coloring matter is then precipitated by neutral acetate of lead. The precipitate, which possesses a beautiful green color, can be washed with plenty of water, and then decomposed with sulphuretted hydrogen; the coloring matter passes into the watery solution, which is carefully evaporated in a water-bath; the residue is again dissolved in absolute alcohol; and lastly, the alcoholic solution is mixed with ether, which precipitates the cyanine in the form of blue flocks.

Cyanine is uncrystallizable, soluble in water and alcohol, insoluble in ether; acids, and acid salts color it immediately red; by alkalies it is, as known, colored green. Cyanine appears to behave as an acid, at least it forms with lime, baryta, strontia, oxide of lead, &c., green compounds insoluble in water.

Bodies absorbing oxygen, as sulphurous acid, phosphorous acid, and alcohols, decolorize it; under the influence of oxygen its color is restored.

We must here mention that Moroz has prepared a beautiful blue substance from Centauria cyanus by treatment with absolute alcohol.

Rose-red Coloring Matter.—We have employed alcohol to extract the substance which colors rose-red certain dahlias, roses, pœonias, &c. For the procuration of this coloring matter the method pursued is exactly as that for the preparation of cyanine.

By an attentive comparison of the properties of this coloring matter with those of cyanine, we have found that the rose-red coloring matter is the same as the blue, or at least results from a modification of the same independent principle. It appears in the rose-red modification, when the juice of the plant, with which it exists in contact, possesses an acid reaction. We have always observed this acid reaction in the juices of plants with red or rose-red coloration, while the blue juices of plants have always exhibited an alkaline reaction.

We have exposed most of the rose-red or red-colored flowers which are cultivated in the Paris Museum to the influence of alkalies, and have seen that they first become blue and then green by their action.

It is often perceived that certain rose-red flowers, as those of the Mallow, and in particular those of the Hibiscus Syriacus, acquire by fading a blue and then a green coloration, which change, as we have found, depends on the decomposition of an organic nitrogenous substance, which is found very frequently in the petals. This body generates as it decomposes ammonia, which communicates to the flowers the blue or green color. By action of weak acids, the petals can be restored to their rose-red color.

The alteration of color of certain rose-red flowers can also be observed when the petals are very rapidly dried, for example, in vacuo, by which it cannot be easily assumed that a nitrogenous body has undergone decomposition to the evolution of ammonia. But, before all things, it must be mentioned that in this case the modification of color passes into violet, and never arrives at green; and, further, that it is always accompanied with the evolution of carbonic acid, which we have detected by a direct experiment. Petals which were before rose-red, and have become violet by slight drying, evolve carbonic acid, and on that account it may be assumed that the rose-red color is produced in the petals by this carbonic acid, and that by its expulsion the petals assume the blue color, by which the flowers with neutral juices are characterized.

We believe that we are able to speak with certainty that flowers with a rose-red, violet, or blue color, owe their coloration to one and the same substance, but which is modified in various ways by the influence of the juices of plants.

Scarlet-red flowers also contain cyanine reddened by an acid, but in such cases this substance is mixed with a yellow coloring matter which we will now describe.

Yellow Coloring Matter.—The simplest experiments show that no analogy exists between the substance which colors flowers yellow and that of which we have already spoken. The agents which generate so easily with cyanine, the rose-red, violet, or green coloration, cannot in any case impart these colors to the yellow substance obtained from flowers.

By the examination of the various yellow-colored flowers, we have ascertained that they owe their coloration to two substances, which differ from one another in their properties, and appear not to be derived from the same independent principle. One is completely insoluble in water, which we have termed xanthine, a name which Runge has given to a yellow matter from madder. As this name has not been accepted in science, we have employed it to denote one of the coloring matters of yellow flowers. The other substance is very soluble in water, and is by us termed xantheine.

Xanthine, or the Yellow Coloring Matter insoluble in water.—We have prepared this coloring matter from many yellow flowers, but chiefly from Helianthus annuus.

To obtain it we treat the flowers with boiling absolute alcohol, which dissolves the coloring matter in the heat, and by cooling almost completely allows it again to precipitate. The yellow deposit which is obtained in this way, is not pure xanthine, as it contains a rather considerable quantity of oil. To separate this oil we have recourse to a moderate saponification; thus, we heat the yellow precipitate with a small quantity of alkali to saponify the fatty body mixed with the xanthine, which even contains the xanthine dissolved. As the coloring matter is soluble in the soap solution, we do not treat the mass with water, but decompose it with an acid which isolates the xanthine and the fatty acids resulting from the saponification. This precipitate we treat with cold alcohol, which leaves behind the fatty acids, and dissolves the xanthine. This substance is a fine yellow color, insoluble in water, but soluble in alcohol