MM. Vabet and Vienne, in a recent number of Comptes Rendus, state that by passing a current of acetylene through 200 grammes of benzene containing 50 grammes of aluminum chloride for 30 hours the oily liquid remaining after removal of the unaltered aluminum chloride by washing was found to yield, on fractional distillation, three distinct products. The first, which came over between 143° and 145°, and which amounted to 80 per cent. of the whole, consisted of pure cinnamene or styrolene (C6H5.CH.CH2), which is one of the principal constituents of liquid storax, and was synthetized by M. Berthelot by passing acetylene and benzene vapor through a tube heated to redness. The second fraction, coming over at 265°-270°, consisted of diphenyl ethane ((C6H5)2 CH.CH3); and the third fraction, boiling at 280°-286°, was found to consist entirely of dibenzyl (C6H5.CH2.CH2.C6H5), a solid substance isomeric with diphenyl ethane. These syntheses afford another instance of the singular action of aluminum chloride in attacking the benzene nucleus.
NOTES ON SACCHARIN.
By EDWARD D. GRAVILL, F.C.S., F.R.M.S.
Now that a supply of this reputed substitute for sugar has been placed upon the London market, it will doubtless have attracted the attention of many pharmacists, and as information having reference to its characters and properties is as yet somewhat scarce, the following notes may be of interest.
The sample to which these notes refer represents, I believe, a portion of the first supply that has been offered to us as a commercial article, and may therefore be taken to represent the same as it at present occurs in commerce. I think it desirable to call attention to this fact, because of the wide difference I have seen in other samples obtained, I think, by special request some weeks ago, and which do not favorably correspond with the sample under consideration, being much more highly colored, and in comparison having a very strong odor. Saccharin now occurs as a very pale yellow, nearly white, amorphous powder, free from grittiness, but giving a distinct sensation of roughness when rubbed between the fingers. It is not entirely free from odor, but this is very slight, and not at all objectionable, reminding one of a very slight flavor of essential oils of almonds. Its taste is intensely sweet and persistent, which in the raw state is followed by a slight harshness upon the tongue and palate. The sweetness is very distinct when diluted to 1 in 10,000. Under the microscope it presents no definite form of crystallization.
A temperature of 100° C, even if continued for some time, has no perceptible effect upon saccharin; it loses no weight, and undergoes no physical change. It fuses at a temperature of from 118° to 120° C., and at 150° C. forms a clear light yellow liquid, which boils a few degrees higher. At the latter temperature dense white fumes appear, and a condensation of tufts of acicular crystals (some well defined) is found upon the cool surface of the apparatus. These crystals, except for a slight sweetness of taste, correspond in characters and tests to benzoic acid. The sweet flavor, I think, may be due to the presence of a very small quantity of undecomposed saccharin, carried mechanically with the fumes. The escaping vapors, which are very irritable, and give a more decided odor of hydride of benzole than the powder itself, also communicate a very distinct sensation of sweetness to the back part of the palate. Heated over the flame, with free access of air, saccharin carbonizes and burns with a dull yellow smoky flame, leaving a residue amounting to 0.65 per cent. of sodium salts. It does not reduce an alkaline copper solution, but, like glycerine, liberates boracic acid from borax, the latter salt dissolving saccharin readily in aqueous solution, due no doubt to a displacement of the boracic acid.
The strong acids, either hot or cold, show no characteristic color reaction; the compound enters solution at the boiling point of the acid, and in the case of hydrochloric shows a white granular separation on cooling. Sulphuric acid develops an uncharacteristic light brown color.
The compound, like most of the organic acids, shows a characteristic reaction with ferro and ferrid cyanide of potassium. In the former case no change is perceptible until boiled when a greenish white turbidity appears, with the liberation of small quantities of hydrocyanic acid. In the latter case a trace also of this acid is set free, with the formation of a very distinct green solution, the latter reaction being very perceptible with a few drops of a 1 in 1,000 solution of saccharin in water. Heated with lime, very distinct odors of benzoic aldehyde are developed.
Saccharin possesses very decided acid properties, and combines readily with alkalies or alkaline carbonates, forming anhydro-ortho sulphamine-benzoates of the same, in the latter case at the expense of the carbonic anhydride, causing strong effervescence. These combinations are very soluble in water, the alkaline carbonate thus forming a ready medium for the solution of this acid, which alone is so sparingly soluble. Another advantage of some importance is that, while the harshness of flavor perceptible in a simple solution of the acid is destroyed, the great sweetness appears to be distinctly intensified and refined.