ORGANIC ANALYSIS 287 ORGANIC ANALYSIS. Use of 4-4-Diphenylsemicarbazide in the Detection of Carbonyl Derivatives. B. Toschi and A. Angiolani. (Gazz. Chim. Ital., 1915, 45, 205- 213.)-Stable crystals of 4-4-diphenylsemicarbazide, (CGH&N .CO.NH.NH,, are readily obtained by mixing an alcoholic solution of commercial diphenyl-urea chloride with hydrazine hydrate in equimolecular proportions. I t reacts with carbonyl derivatives readily, and forms diphenylsemicarbazones, which are much less soluble than the corresponding semicarbazones.The diphenylsemicarbazones of aliphatic compounds are obtained by adding their aqueous or dilute alcoholic solution to an aqueous solution of the free base or its hydrochloride. The aromatic diphenyl- semicarbazones are readily hydrolysed by boiling with dilute acids.They dissolve in concentrated sulphuric acid, with characteristic coloration. Among the diphenyl- semicarbazones prepared were those of the following compounds : Acetone (m.-pt. 119" C.) ; acetaldehyde (153" C.) ; dextrose (164"-166" C.) ; cinnamic aldehyde (164"-166" 0.) ; salicylic' aldehyde (209" C.) ; vanillin (180"-181" C.) ; citronella1 (109"-110" C.); and camphor (154"-155" C.).C. A. M. Estimation of Cane Sugar by Double Polarisation, employing a New Method of Clarification. N. Deerr. (Intern. Sugar J., 1915,17,179-182; through J. SOC. Chem. Ind., 1915, 34, 503.)-To eliminate the error caused by the direct reading being takeh in an alkaline solution (due to basic lead acetate) and the inver- sion reading in a strongly acid medium (due to hydrochloric acid), the author takes the two readings in solutions having the same composition so far as non-sugars are concerned.Clarification of both solutions is effected by adding successively baryta and a mixture of aluminium sulphate and sulphuric acid, the small amount of sulphuric acid remaining in solution after the separation of the aluminium hydroxide and barium sulphate being insufficient to induce appreciable hydrolysis while taking the direct reading, but being sufficient to invert all the sucrose present a t a high temperature. The solutions required are-(a) A 0.52 N solution of baryta; (b) a solution of 165 grms.of crystallised aluminium sulphate and 135 C.C. of sulphuric acid per litre ; the titre of (b) is adjusted so that 25 C.C.of (a) are equivalent to 15 C.C. of (b). For the direct reading, 50 C.C. of the material under examination (containing 3.25 grms. in the case of cane molasses) are mixed with 25 C.C. of (a) and next with 15 C.C. of (b), the volume being completed to 100 c.c., and about 0.1 grm. of sodium hydrosulphite added. After filtering, the solution is polarised, the reading being increased by 0.7 per cent.to compensate for the volume of precipitate formed, or the volume may be completed to 100.7 c.c., instead of 100 C.C. For the inversion reading, 50 C.C. of the same solution of the material used for the direct reading are treated in a 100 C.C. flask with 15 C.C. of (b), and inversion effected at 95" to 97" C. during twenty minutes. After cooling, 25 C.C.of (a) are added, the volume made up to 100 c.c., the liquid filtered, and the saccharimeter reading ascertained, while from the direct and inversion readings is calculated the percentage of sucrose from the usual formula, a special constant, however, being used. Advantages of the proposed process, in addition to both readings being made under identical conditions, are that the influence288 ABSTRACTS OF CHEMICAL PAPERS of the lead salts is eliminated, and that the filtrate may be used for the determina- tion of the reducing sugars.On the other hand, in comparison with the ordinary procedure, its disadvantages are that the decolorisation is less intense (though reasonably efficient), and that the time required is somewhat greater. Constitution of the Glycerophosphoric Acid of Lecithin.0. Bailly. (Comptes rend., 1915, 160, 395-398.)-The alkaline hydrolysis of egg lecithin yielded 23-25 per cent. of calcium glycerophosphate with the composition of the calcium salt of a mono ester of glycerophosphoric acid, P0,Ca.C3H,(OH),. The solubility of this salt (2.88 per cent. at 1 2 . 5 O C.) was intermediate between that of the calcium salt prepared from crystalline sodium glycerophosphate (1-78 per cent.) and that of the calcium salt prepared from the uncrystallisable residue left in the preparation of the crystalline salt.The former was identified as calcium 8-glycerophosphate, while the latter consisted largely of calcium a-glycerophosphate. The crystalline sodium salt prepared from the lecithin calcium glycerophosphate yielded, when oxidised, only traces of phosphoric dioxyamtone (characteristic of the B-compound), while the mother liquor yielded this oxidation derivative in abundance (characteristic of the a-compound). Egg lecithin, therefore, consists of a mixture of at least two isomeric compounds with the following constitutional formulae, in which R represents a fatty acid radicle : OH C2H4<N (CH& 0 I I CH.0 HO-P=O I I CH2.O HO-P=O i I CH. - OB CH2- OZZ Lecithin a./\ CH2.0R CELOB Lecithin @. c. A. M. Method of Distinguishing between the Mono Esters of Glycero- phosphoric Acid. L. Grimbert and 0. Bailly. (J. Pharm. Chim., 1915, 11, 153-157.)-0n oxidising a-monoglycerophosphoric acid (0.25 grm.) by heating it with 10 C.C. of 0.25 per cent.bromine water, it yields a substance of the general formula, R.CO.CH,OH. This can be distinguished by the reactions of Denigds (Comptes rend., 1909, 148, 172, 282) from the product of the oxidation of the P-acid. Thus it gives a blood-red coloration with phloroglucinol and sulphuric acid, which the other does not ; while the @-derivative reduces Nessler’s and Fehling’s solutions in the cold, By these tests it was proved that the crystalline sodium glycerophosphate prepared by Poulenc’s process (Fr.Pat. 373112,1906) consists of the salt of p-mono- glycerophosphoric acid, the secondary alcoholic grouping of which is not trans- formed by oxidation into a ketonio grouping. C. A. M.ORGANIC ANALYSIS 289 Use of Hydrochloric Acid in the Estimation of Certain Forms of Organic Nitrogen.W. A. Drushel and M. M. Brandegee. (Amer. J. Sci., 1915, 39, 398-404; through J. SOC. Chem. Ind., 1915, 34, 514.)-The following method is proposed for the estimation of nitrogen in aliphatic nitriles, cyanogen-substituted esters, amides, and imides : 0.1 to 0-3 grm. of the substance is heated with 3 C.C. of hydrochloric acid of sp. gr. about 1.2 for two hours at about 200' C.in a sealed tube. A considerable pressure of carbon dioxide is developed in some ca8es. The product is rinsed out into a basin, evaporated to dryness, further heated for fifteen minutes on a water-bath, and afterwards for five minutes in an oven at about 110' C. By this means all free hydrochloric acid is eliminated without any appreciable loss of ammonium chloride, and the latter is then determined by titration with silver nitrate solution in presence of potassium chromate.The presence of acetic acid or its homologues does not affect the action of the chromate indicator; but if stronger acids, such as succinic acid, are present, it is advisable to add a very small quantity of sodium acetate-preferably before the addition of the indicator.Tested on acetonitrile, propionitrile, propionamide, succinimide, and the ethyl esters of a-cyano-acetic, -propionic and -butyric acids and n-dipropylcyanoacetic acid, the method gave exact results, except with cyanoacetic acid, which was probably not pure. Accurate results were also obtained with glycine, but only after heating for three to four hours at about 200' C.Qualitative Separation and Identification of Some Oxymethylanthra- quinones. E. M. Bailey. (Amer. J. of Pharm., 1915, 87, 145-154.)-0xy- methylanthraquinones are more or less characteristic constituents of the common cathartic drugs--e.g., senna, rhubarb, aloes, buckthorn, etc.-the principal re- presentatives being dioxymethyl and trioxymethyl derivatives, in the form of chrysophanic acid and ernodin respectively.The pink alkaline solution of chryso- phanic acid is decolourised by zinc dust and the colour returns by reoxidation on exposure to air or by treatment' with a few drops of hydrogen peroxide. This distinguishes it from phenolphthalein. To obtain the mixed colour principles from the drugs, 25 C.C. of the fluid extract are evaporated, taken up with 25 C.C.of water, and treated with excess of normal lead acetate. The lead precipitate is collected on a filter and digested for one hour with 10 per cent. sulphnric acid in the boiling water-bath. The liquid is filtered hot and the fiItrate extracted with hot benzene. I n the case of powdered drugs, 3 grms. of the sample are boiled with alcoholic potassium hydroxide for an hour, the alcohol is evaporated, the residue diluted with 50 C.C.of water, acidified, and extracted with hot benzene. The benzene solution is shaken out first with 25 C.C. portions of 5 per cent. ammonium carbonate solution until the washings are colourless. This removes unidentified anthraquinone derivatives. I t is next shaken similarly with 5 per cent. sodium carbonate until the washings come away pink.This removes the emodin fraction. Lastly, it is shaken with 5 per cent. sodium hydroxide, which takes out the chrysophauic acid. The three alkaline extracts are separately acidified and shakon out with ether, and the ethereal residues examined as to crystalline form and melting-point. The most important test is the colour reaction. The residue from ether is moistened with 4 to 5 drops of concen-290 ABSTRACTS OF CHEMICAL PAPERS trated sulphuric acid, then with 1 to 2 drops of strong nitric acid, and finally diluted with 1 C.C.of water. The emodin residue extracted by sodium carbonate from buck- thorn, rhubarb, and senna, shows with sulphuric acid alone a pink coloration, turn- ing yellow with nitric acid, and giving a pink solution when diluted. The similar fraction extracted from aloes shows with sulphuric acid red, then becomes brownish, turning yellow, with nitric acid, and giving a yellow solution on dilution.Chrysophanic acid (sodium hydroxide fraction) from all sources shows orange-red with sulphuric acid, yellow with nitric acid, and a yellow solution and precipitate on dilution. The unidentified oxymethylauthraquinones extracted from the benzene solution by ammonium carbonate show with sulphuric acid purple or violet, with nitric acid yellow, and a yellow solution on dilution.J. F. B. Tests for distinguishing Parchment Paper from Pergamyn Paper. G. Annoni and G. Rodano. (L’InrE. Chim., 1915, 2, 129; through J. SOC. Chem. Ind., 1915, 34, 487.)-True parchment paper, prepared by the action of sulphuric acid on rag paper, is resistant to boiling water and to a boiling 2 per cent.aolution of potassium carbonate, whereas the imitation pergamyn papers, prepared by mecbanical treatment of wood-pulp, are much less resistant to water and are immediately disintegrated by a boiling 2 per cent. solution of potassium carbonate. On treatment with a drop of ziuc chloride-iodine solution, a violet .stain is produced on both kinds of paper, though more slowly on the pergamyn; but on subsequent treatment with water the violet changes to an intense blue-due to hydrocellulose- in the case of parohment paper, whilst only a faint violet coloration is left on pergamyn paper.Pergamyq papers invariably contain resin, whilst this is absent from parchment papers ; hence the production of a reddish-violet coloration on applying Morawski’s reaction-treatment with acetic anhydride and sulphuric acid in succession-is a proof that the sample is a pergainyn paper.Colour Reaction for Salicylic Acid. P. A. W. Self. (PharTn. J., 1915, 94, 521.)-The usual colour tests for salicylic acid, although extremely delicate, are none of them perfectly characteristic; the author has found, however, that by combining Robert’s test with Mandelin’s, a series of colour-changes is obtained which is quite distinctive for salicylic acid and salicylates. The reagent is made by mixing equal volumes of 40 per cent.formaldehyde solution an2 concentrated sulphuric acid and cooling the mixture; a portion of the substance to be tested is moistened in a porcelain dish with this mixture; a littlo ammonium vanadate is added and stirred up.If salicylic acid is present, a Prussian blue colour appears immediately, rapidly changing to greenish-blue, and finally to green. If no sub- stance capable of yielding a colour reaction is present, the colour given by the reagents alone is yellowish-red or orange, changing after two or three minutes to greenish-yellow, and finally to green.The quantities of reagents should bo adjusted according to the amount of substanca to be tested; for a small trace, not more than sufficient liquid to moisten it should be taken, and only a fraution of a mgrm. of the vanadate. With about 1 mgrm. of salicylic acid, 2 drops of the formaldehyde and sulphuric aoid mixture and 2 or 3 mgrms. of ammonium vanadate are suitable.INORGANIC ANALYSIS 291 A very distinct colour is afforded by 0.02 mgrm. of salicyIic acid. A large number of substances, mostly of phenolic constitution, have been tested; many of these give colorations first on moistening with the acid reagent and again on the addition of the vanadate. The only substance giving the same blue coloration as salicylic acid is salicylic aldehyde, but this is differentiated by the formation of a yellow coloration when moistened with the formaldehyde-sulphuric acid mixture before the vsnadate is added. In testing solutions, the liquid is acidified, shaken out with a volatile solvent, and the extract evaporated with the addition of a trace of alkali. Methyl salicylate reacts as a salt of salicylic acid. J. F. €3.