sodium hydroxide solution, forming an oily liquid, which can be separated into sparteine and sparteine ethiodide, by means of ether. Sparteine ethiodide, CH2N2, EtI, is formed by the action of ethyl iodide on sparteine. It crystallises in thick prisms, and dissolves freely in water and alcohol. Sparteine methiodide crystallises in rhombic plates; a b c = 0·8989: 1:1-6009. The methyl hydroxide is a deliquescent substance, with a strongly alkaline reaction. The carbonate crystallises in needles. When sparteine is oxidised with potassium permanganate, the chief product is oxalic acid; acetamide is also formed, together with a small quantity of a pyridine-derivative. W. C. W. : Pseudomorphine. By O. HESSE (Annalen, 235, 229–232).— When potassium hydroxide (2 mols.) and potassium ferricyanide (1 mol.) are added to a solution of pure morphine hydrochloride dissolved in 40 parts of water, pseudomorphine is deposited; 100 parts by weight of morphine yield 884 parts of pseudomorphine. This result shows that the reaction takes place according to the equation 2C17H19NO3 + 2KOH + 2K,FeCy6 = 2C17H18NO3 + 2H2O +2K ̧FeCy (the yield is theoretically 996 per cent.); not according to the following reaction: 2CHNO, + 2KOH + 2K,FeCy, C17H7NO 3+ C1HNO2+ 2H2O + 2K,FeCys (the yield is only 49.65 per cent. of the morphine employed). This shows that the formula for pseudcmorphine is CHINO3 C17HNO3, as proposed by Polstorff (Abstr., 1889, 405), instead of C1HNO3, as formerly proposed by the author (Abstr., 1884, 616). W. C. W. 18 = Papaverine. By G. GOLDSCHMIEDT (Monatsh. Chem., 7, 485-505). -In this paper derivatives of papaveraldine, and the most convenient method for its preparation, are described. The nitrate, C20H19NO5,HNO,, crystallises in citron-yellow needles; the picrate, in needles grouped together in voluminous aggregates; the oxime, C20H0N2O5, in flat, white needles melting at 245°; the methiodide, in golden prisms melting at 135° with decomposition; and the ethobromide, in large prisms melting at 270°. Papaveraldine, if heated only for a short time with potash, yields veratric acid together with small quantities of a dimethoxyquinoline, the constitution of which is at present uncertain. With tin and dilute hydrochloric acid, papaverine yields a tetrahydro-derivative, CH25NO4, which crystallises in small, white prisms melting at 200°, soluble in benzene and acetone, sparingly soluble in ether and petroleum. Its hydrochloride crystallises in transparent prisms of the monoclinic system, melting with violent decomposition at 290°; when injected internally, it causes albuminuria with inflammation of the kidneys. The acid sulphate forms acicular, and the acid oxalate prismatic crystals; the dichromate, glistening prisms; and the picrate, lemon-yellow needles. The platinochloride crystallises in minute yellow needles, and the stannochloride in concentrically grouped needles. In an additional note, the author defends the formula C2H2NO, for papaverine, as against CHaNO, that proposed by Hesse, Beckett, and Wright, and others; exception is also taken to a statement of Hesse relative to the existence of an alkaloïd, pseudopapaverine. V. H. V. Papaverine Salts. By R. JAHODA (Monatsh. Chem., 7, 506-516). -As a further proof of the formula C2HNO, proposed for papaverine, a number of its salts have been prepared and analysed; the results attained afford a strong confirmation of the above view. : The neutral succinate forms large tabular crystals melting at 171°, soluble in hot water; the benzoate, triclinic crystals (a b c = 0·459:1:0·680; n = 95·27°), melting at 145°, soluble in alcohol, insoluble in water; the salicylate, monoclinic crystals (a: b:c 1161:1:1:685; 7 = 102·39), melting at 130°; the diodide of the hydroiodide, C20H21NO, HI,I2, purple crystals of the monoclinic system. = The hydrochloride gives with halogen salts of the metals double crystalline salts, of which the following are described :-The cadmiochloride, (C20H2NO,,HCI),CdCl2, small crystals, of the tetragonal system; a:ac 1: 1:0·646, melting at 176°; the cadmio-bromide and iodide, white precipitates, melting at 150° and 180° respectively; and the zincoiodide, crystallising in small leaflets. V. H. V. Constitution of Cinchonine. By Z. H. SKRAUP (Monatsh. Chem., 7, 517-518).—The author criticises the view of Bischoff and Rach that cinchonic acid is B-y-dicarboxyl-&-valerolactone (Abstr., 1886, 1012); a study of the syrupy oxidation product of cinchonine and quinine has indicated the presence of an amorphous acid, CH1зNO1, a base of the formula C,HNO2, difficult to obtain in the free state, although its salts form well-developed crystals, as also of a base of the formula C,H,NO, probably identical with kynurine, and an amorphous substance of the supposed composition C13H13NO2, and of doubtful origin. V. H. V. Specific Rotatory Power of Piperidine Bases. By A. LADENBURG (Ber., 19, 2584).-The results obtained in a previous paper (this vol., p. 160) are in accordance with Le Bel-Van't Hoff's hypothesis, since a-propylpiperidine contains an asymmetric carbon-atom in its constitutional formula. As this is true of all a-alkyl-derivatives of piperidine, the author has examined a-pipecoline and a-ethylpiperidine, and by converting them into their dextrotartrates has succeeded in obtaining optically active modifications of each. Dextrorotatory a-pipecoline has a specific rotatory power of 21° 8'. W. P. W. Action of Bromine on Dimethylpiperidine; New Synthesis of Piperidine-derivatives. By G. MERLLNG (Ber., 19, 2628-2632). -The author previously obtained (Abstr., 1884, 1385) by the action of bromine on dimethylpiperidine, two compounds-bromodimethylpiperidineammonium bromide and a hydrobromide. The latter is now shown to be dibromodimethylpiperidine hydrobromide. When the free base is warmed with alcohol, the alkaline solution becomes neutral, and characteristic crystals of monobromodimethylpiperidine ammonium bromide separate. These reactions can be explained by the constitutional formula assigned by Ladenburg to dimethylpiperidine: CH, CH·CH, CH, CH2 NMe. The constitution of dibromodimethylpiperidine and the ammonium bromide would then be .CHBrCH, CH2Br·CHBr·CH2CH2 CH2-NMe, and CH2<CH2-CH2>NMe2Br. The formation of the hydrobromide of dibromodimethylpiperidine is probably due to 2 mols. of the free base reacting with one another; this view was strengthened by the discovery of a base free from bromine in the last mother-liquor from dibromodimethylpiperidine hydrobromide. N. H. M. Hæmin Crystals. By K. BIKFALVI (Chem. Centr., 1886, 499).Blood free from chlorine yields no hæmin (chlorohæmatin) crystals when heated with glacial acetic acid. The author finds, however, that if NaCl, NaBr, KBr, NH,Br, NaI, or KI be first added to the blood, crystals resembling chlorohæmatin are formed. L. T. T. Diastase. By C. J. LINTNER (J. pr. Chem. [2], 34, 378—394). — The author has examined the different methods proposed for the preparation of pure diastase, and determined the diastatic activity of the substances obtained. He adopts Kjeldahl's law of proportionality (Abstr., 1880, 562), and uses the modification of Kjeldahl's method for determining diastatic activity, described in a former paper (Abstr., 1886, 386). In place of his former method for preparing soluble starch, he now recommends the following:-A quantity of pure potatostarch is mixed with a sufficient quantity of 7.5 per cent. hydrochloric acid to cover it; it is then allowed to remain for seven days at the ordinary temperature or for three days at 40°, when the starch has lost the power of gelatinising. The structure of the starch, however, remains unaltered. It is then well washed with cold water until every trace of acid is removed, and dried in the air. So obtained it is soluble in hot water to a bright and limpid solution. A 2 per cent. solution will remain clear for some days, but 10 per cent. solutions set to a jelly-like mass on cooling. The acid used must not exceed 7.5 per cent. as 10 per cent. acid causes the gelatinisation of the starch; with sulphuric acid, however, it requires at least 15 per cent. acid digested at 40° to effect the conversion into soluble starch. Lintner uses a 2 per cent. solution of this soluble starch instead of that prepared by the method previously given. The diastatic activity of the precipitated diastases is expressed as 100, when 3 c.c. of a solution of 0.1 gram diastase in 250 c.c. water added to 10 c.c. of a 2 per cent. starch solution produces in one hour, at the ordinary temperature, sufficient sugar to reduce 5 c.c. of Fehling's solution. Diastase is best prepared from green malt or from air-dried malt. Lintner examined the preparation obtained from these malts by extraction with water and glycerol and subsequent precipitation with alcohol, both before and after heating at 70°, and obtained, in all cases, a substance with a comparatively slight diastatic activity. As the result of his experiments, he recommends the following method of preparation:-1 part of green malt or sifted air-dried malt is extracted with 2 to 4 parts of 20 per cent. alcohol for 24 hours. The filtered extract is mixed with 2 volumes absolute alcohol; the precipitate quickly settles, and is washed on a filter with absolute alcohol; it is then transferred to a mortar, well mixed with absolute alcohol, thrown on a filter, and thoroughly washed with absolute alcohol and ether. Finally, it is dried in a vacuum over sulphuric acid. So obtained it is a light, yellowish-white powder with great diastatic activity. It is purified by repeated solution in water and precipitation with alcohol, and finally by dialysis. Loew's method of purification by means of precipitation with lead acetate is not to be recommended, since diastase loses three-fourths of its activity in the process. By purification, both the percentage of nitrogen and the diastatic activity are increased, whilst the amount of ash, which consists entirely of normal calcium phosphate, is diminished. A preparation obtained from green malt contained 8.3 per cent. nitrogen and diastatic activity = 96. After two precipitations the nitrogen = 9.06 per cent., and the activity = 100. This submitted to dialysis had the percentage of nitrogen raised to 9.9, and the percentage of ash diminished from 10-6 to 479. These and other analyses show that the diastatic activity increases with the amount of nitrogen. A purified diastase gave the following numbers on analysis, calculated on the ash-free substance. For the purpose of comparison the analyses of other soluble ferments are given: N. S. 7:35 10:42 Emulsin 7.17 14.95 Diastase gives all the reactions for the albuminoïds, but not the characteristic biuret reaction for peptones; it gives, however, a characteristic blue coloration with tincture of guaiacum and hydrogen peroxide, which is soluble in ether, benzene, chloroform, and carbon bisulphide, but not in alcohol. This reaction is given by no other soluble ferment or proteïn substance. G. H. M. Note.-Lintner appears to have overlooked the fact that O'Sullivan (this Journal, Trans., 1884, 2) described an almost identical method of preparing pure diastase. G. H. M. Action of Diastase and Invertin. By H. MULLER (Ann. Agronom., 12, 481-482).-The author has studied the action of these ferments under conditions such as prevail in the plant-cell, with a view to elucidate their physiological importance. Both ferments are active at 0°, but the activity increases until the neighbourhood of 50° is reached the temperatures being 0°, 10°, 20°, 30°, 40°; the energy of diastase is expressed by the numbers 7, 20, 38, 60, 98, and that of invertin by the numbers 9, 19, 36, 63, 93. : Underordinary conditions, cell-sap contains much carbonic anhydride, and is exposed to a pressure of several atmospheres. Both of these circumstances accelerate the activity of the ferments. Even at the ordinary pressure, saturation of the liquid with carbonic anhydride may have the effect of tripling the energy of diastase, and in presence of carbonic anhydride diastase has the power of acting on starch which has not been boiled to a paste. Between the limits of 2 and 20 per cent., concentration of a sugar solution has little effect on the action of invertin, which is a little more feeble in strong solutions than in weak ones, but the accumulation of invert sugar is strongly opposed to the continuance of the reaction. J. M. H. M. Physiological Chemistry. Natural and Artificial Digestion. By T. PFEIFFER (Zeit. physiol. Chem., 11, 1-24).-The author has previously criticised the work of Stutzer on this subject (see Abstr., 1886, 1053). Additional experiments on pigs are now brought forward, and from them the following results are drawn: 1. A comparison of the method of natural digestion of the nitrogenous constituents of the food combined with the investigation of the products of metabolism, with the method of artificial digestion of the food-stuff by pepsin and trypsin as devised by Stutzer, shows that there is an almost absolute agreement between the two. 2. By the help of Stutzer's method, the digestibility of the nitrogenous constituents of the food can be estimated with sufficient accuracy. This always gives results which agree more closely than those obtained with the method hitherto used, in which the products of nitrogenous metabolism in the fæces are not investigated. W. D. H. Glycogen in the Liver of New-born Dogs. By B. Demant (Zeit. physiol. Chem., 11, 142-144).—In the intra-uterine condition, the liver is stated to be very poor in glycogen. Hoppe-Seyler states the opposite to be the case. The present research investigates the matter in the case of the dog; the glycogen was estimated by Brücke's method, and the result found was that in the days following birth glycogen was present in exceedingly large quantities; this is illustrated by the following table : Lactic Acid in Animals. By A. HIRSCHLER (Zeit. physiol. Chem., 11, 41-42).-Lactic acid has been described as occurring in the grey matter of the brain, and in the parenchymatous juices of the spleen, thymus, lymphatic glands, &c. Which variety of lactic acid this is, |
