Mlt BALY OK THE; ACTION OF 11.-On the action of Baryta on Salicylic Elher. BY G. BALY,ESQ. One of the most interesting facts with which we have become acquainted by the investigations of M. Cahours,* is the remarkable decomposition which the oil of Gaultherin procumbens (salicylate of oxide of methyl) undergoes when subjected to the action of alkaline earths at a high temperaturc. On performing this experiment M. Cahoiirs obtained a fluid possessing all the properties of anisol a substance which he had previously discovered in acting with baryta upon anisic acid. Gaultheria oil and anisic acid are isomeric the composition of both these substances is expressed by the formula Cl H 06 but nobody can mistake the difference in their molecular arrange- ment and it was ccrtainly a startling result to see two such dissimilar compounds exhibiting the same behaviour when under the influence of powerful agents.The identity in the yroducts of decomposition of these isomeric bodies is by no nieans an isolated fact; several cases of a similar nature have since been observed. Anthranilic acid and nitrotoliiol are likewise isomeric and no two bodies coulcl present a more striking dissitnilarity in constitution ; nevcrtheless both these compounds * Ann. de Chimie et Phys. 3i.rne SEr. t. x. 1). 327. BARYT.4 Oh-SALICYLIC ETHER. when subjected to the action of heat undergo as pointed out by Drs. Hofmann and Muspratt,* exactly the same decomposition they are split into aniline and carbonic acid.In his mcmoir on gaultheria oil 31. Cahours mentions that salicylate of oxide of ethyl when acted on by baryta undergoes a similar decomposition to the methyl compound ; an oily liquid inso- luble in alkalies is produced carbonate of baryta remaining in the retort. It appeared extremely probable that the compound thus obtained was an analogue of phenol and anisol containing two more equivalents of carbon and hydrogen than the latter substance. &I.Cahours not having prosecuted this investigation Dr. Hofmann invited me to prepare the coinpound in order to establish its compo- sition by an analysis and study its properties. The salicylic acid used for the following experiments was pre-pared from gaultheria oil which readily yields this acid in a state of perfect purity.Salicylic acid is etherified with great facility. By distilling a mixture of salicylic acid alcohol and sulphuric acid I obtained the ether with all the properties M. Cahours mentions. The boiling point of the pure liquid was constant at 229O.5 C = (414O F.) a few degrees higher than the temperature specified by M. Cahours who found it to be 225O (4370 F.). The specific gravity of the ether is 1.097. On mixing pure salicylic ether with anhydrous baryta a very considerable evolution of heat takes place sufficient to effect complete decomposition iinless the experiment be made with sinall quantities at a time. In order to avoid loss it is necessary to add the ether drop by drop to the baryta until an increase of temperature is no longer observed on further addition.In this manner a dry solid compound of the ether with baryta is obtained corresponding evidently to the gaul- therate of baryta obtained by acting in the same manner on the methyl compound. On distilling this compound in a small glass retort a brownish yellow liquid passes over possessing a strong odour of phenol. The distillate thus obtained is a mixture of two liquids of which the one is soluble in potash and presents all the propertics of phcnol whilst the other is a liquid of an agreeable odour for which I propose the name of snlithol in order to indicate that it is formed from salicylic ether. Salithol is easily purified; for this purpose the crude product of the distillation is treated with a dilute solution of potash which yemoves at oace tlic odoirr of phenol that substance being dissolved leaving a yellow layer of oil on the top of the liquid.The oil is * Memoil c,f the Chemical Societ of I,on(Io;l Y. ii. p. 243. MR. BALY OW THE ACTIOS OF washed with water separated by means of a pipette dried over fused chloride of calcium and finally rectified. Salithol when pure is a colourless liquid of a very agreeable aro- matic odour. Its boiling point is l75O C. (3470 F.) An analysis, by combustion with oxide of copper gave the following results I. 0.1915 grm. of substance gave 0,5515 , carbonic acid and 1.1450 , water. 11. 0.1938 , of substance gave 0.5575 , carbonic acid and 0.1490 , water Per-centage composition I. 11.0 Carbon . 78-64! 78-45 Hydrogen . . 8-41 8.54 These numbers closely correspond with the formula c,,HlO 029 as may be seen from the following table Theory. Mean of experiments. -16 eq. of carbon . . . 96 = 78.68 78-49 10 , of hydrogen . . 10 = 8-19 8.47 2 , of oxygen . . 16 = 13.13 13.03 7 -1 , of Salithol . . 122 100.00 99.99 The formation of salithol is perfectly analogous to the production of phenol from salicylic acid and of anisol from anisic acid or salicy-late of oxide of ethyl. This will be evident from the following formulse C14 H C -f-2 BaO = 2 BaO CO 4-C, H R, *- Salicylic acid. Phenol. C16 H 0 + 2 BaO = 2 BaO CO + O, H 0, -’ - Anisic acid. Anisol. C, H, 0 + 2 BaO =2 2 BaO CO + C,,II, 0 Salicylic ether.Salithol. The simultaneous production of phenol arises from part of the salicylic ether being converted into salicylate of baryta when acted on by caustic baryta. BARYTA ON SALICYLIC ETHER. It is very probable that the progress of science will make us acquainted with an acid isomeric with salicylate of ethyl and belonging to the series of acids with six equivalents of oxygen of which salicylic and anisic acids are as yet the only members. An acid of this composition when distilled with baryta would evidently likewise be converted into salithol. I should have liked to control the formula of salithol by the study of some of its products of decomposition the difficulty however of obtaining it in sufficient quantity has prevented me from entering more minutely into the investigation.Chlorine acts very powerfully on salithol ; heat is evolved during the reaction and hydrochloric acid disengaged a viscid mass being produced which after standing for several weeks shewed a tendency to crystallize. Bromine forms in the same manner a heavy oily compound With salithol which solidifies after a few days to a hard crystalline mass soluble in boiling alcohol from which it crystallizes on cooling. The appearance of the crystals thus deposited as well as the results of several combustions indicated that the action of bromine gave rise to the formation of various compounds. It is very likely that a series of substitution-products like the following may be formed in this manner. The small quantity of material at my disposal did not admit of their separation by repeated crystalliza- tion.DINITRO-SALITHOL. Fuming nitric acid dissolves salithol producing a liquid of a beau-tiful violet colour which colour disappears completely on the appli- cation of heat. By ebullition the whole of the salithol is converted into a crystalline mass which is insoluble in water but dissolves in boiling alcohol from which it is deposited on cooling in needle-shaped crystals. These crystals likewise consist of various com-pounds; if however the ebullition with nitric acid has been continued for some time a product is obtained which after being washed with water and crystallized two or three times from alcohol seems to be nearly pure dinitro-salitbol.MR. JOHN MITCHELj ANALYSIS OF TKI By burning two products obtained at different times with oxide of copper in the above manner the following results ivere obtained I. 0.200grm. substance gave 0.316 , carbonic acid and 0.074 , water. 11. 0.282 , substance gave 0.452 , carbonic acid and 0*1015, water. Per-centage composition 1. 11. Carbon . 43.09 43.71 HydrogenThe formula . . 4-11 3.99 requires Carbon . 45.28 Hydrogen . . 3-77 The deficiency in the carbon probably arises from an admixture of trinitro-salithol. Unfortunately the last portion of rny substance being consumed I was prevented from repeating the analysis with a purer product.