摘要:

MINERALOGICAL CHEMISTRY, Mineralogical Chemistry. 63 Contributions to Chemistry and Mineralogy. By FRANK W. CLARKE (Bull. US. Geol. Xuvuey, 1900, No. 167, 166 pp.).-This gives a collection of recently published researches which have been carried out in the laboratory of the United States Geological Survey by F. W. Clarke, W. F. Hillebrand, H. N. Stokes, G, Steiger, and N. H. Dart on. L. J. 5. Simultaneous Production of Two Nitrogen Compounds in the Crater of Vesuvius. By RAFF. VITT. MATTEUCCI (Compt. rend., 1900, 131, 963--965).-The simultaneous ejection, during the recent eruption of Vesuvius, of fragments of rock coated, on the one hand, with ammonium chloride and, on the other, with iron nitride points to the existence of a genetic relation between these two substances. This view is in accordance with Silvestri’s experiments.ARMAND GAUTIER states that he has already referred to iron nitride as one of the sources of ammonium salts in volcanic lavas (this vol,, Separation of Titaniferous Iron-Ores in Basic Igneous Rocks. By JOHAN H. L. VOGT (Chenz. Centr., 1900, ii, 818-819 ; from Zeit. prakt. Geol., 1900, 233-242).-Previous papers by the author have treated in detail the concentration (magmatic dif- ferentiation) of ores of iron, nickel, &c., in igneous magmas. A de- scription is now given of two types of separation, namely, of titan- iferous iron-ore and of magnesium silicate, from the same magma a t Lofoten in northern Norway. Analysis of spinel (pleonaste) from a basic separation at Solnor, Norway, gave : ii, 14). N.L. Al,O,. Fe,O3 FeO. MnO. MgO. Total. 61.8 4.6 18.1 1.05 14-75 100.3. L. J. S.64 ABSTRACTS OF CHEMICAL PAPERS, Chromite from North Carolina. By JOSEPH HYDE PRATT (Timans. Amey. Inst. 34ining Engineers, 1900, 29,17--39).-This covers the same ground as a previous paper (Abstr., 1899, ii, 494). The following additional analysis by C. Baskerville is given of chromite from Burnsville, Yancey Co. : Cr203. A1,03. FeO. MgO. SO,. CaO. 58.00 15.52 14.45 8-26 3.20 0.70. L. J. 8. Blodite from Hallstatt. Ey RUDOLF KOECHLIN (Ann. rzatuyhist. Hofmus. Wien, 1900, 15, 103-1 LO).-A crystallographic description is given of a new find of blodite (" simonyite ") from Hallstatt. Some of the crystals have a dull, weathered surface, but those in freshly- opened cavities are bright.As '' simonyite '' from Hallstatt was sup. posed to differ from bliidite in not efflorescing in the air, the following analysis by Ernst Brezina has been made of the dull crystsls : SO,. MgO. Na,O. H,O. Total. 47.45 12-16 19.79 20.99 100.39 This gives the blsdite formula, MgS0,,Na2S0,,4H20. A t 108', there is a loss of 8.51 per cent., and a t 200' all the water is expelled. Asso- ciated with the bliidite are polyhalite, anhydrite, salt, gypsum, and glauberite. A crystallographic description is given of the glauberite. By HENRT DUFET (Bull. Soc. f r a y . Min., 1900, 23, 147--250).--This occurs as turquoise-blue, clay-like masses in the Emma Luisa Mine at Huanaco, Taltal, Chili. Sp. gr., 2.803. Under the microscope, it is seen to be minutely crystalline. Analysis I gives the formula Cu0,2A120,,As20,,8H,0.A t 180°, there is a loss of only 1-45 percent. L. J. S. Ceruleite, EL New Mineral. As205. A120,. CUO. H,O. Si02. Total. 11. 1.8 3 8 9 trace 19.1 40.6 100.3 I. 34.56 31.26 11.80 22.32 - 99.94 Associated with the ceruleite is a white clay resembling halloysite, which on analysis gave the results under 11. Both minerals contain minute scales of gold, 1 per cent. of which has been deducted from analysis 11. L. J. S. Cordierite from Celebes and Germany. By HUGO BUCKING (Ber. Senckenb. Ges. FrccnkJht. a. M., 1900, 20 pp.).-Among the ejected blocks of andssite from the volcano Seputan in north Oelebes are a few shining black fragments which resemble obsidian in appearance. Thin sections under the microscope, however, shorn that this material consists almost wholly of minute fresh crystals of cor- dierite, with very little glass, iron-ore (about 4 per cent.) and either augite or sillimanite.The following bulk analysis by W. Bruhns of the material shows that, although the results are in approximate agreement with the formula of cordierite, most of the magnesium of normal cordierite is replaced by calcium and iron. -MINERALOGICAL CHEMISTRY. 65 Loss on SiOr A1,03. Fe,O,. FeO. CaO. MgO. ignition. Total. Sp. gr. 49.15 31-84 2.88 11.49 4.30 0.55 0.06 100.27 2.65 A description is also given of the cordierite which occurs in the altered (" vitrified ") sandstones in contact with basalt in central Germany. L. J. 8. Crystallographic Constants and Chemical Composition of Tourmaline. By ERNST ANTON WULFING (Programm x.82 Jahres- feier d. k. Wiirtternb. Zandwirt. Akad. Hohenheim, 1900, 99 pp. Com- pare Abstr., 1889,765 ; 1900, ii, 602)-Previously published constants are discussed, aud numerous new crystallographic, optical and density determinations are given of material which was, whenever possible, the same as that analysed by previous authors. For crystals from various localities the angle rr varies from 46'48' to 47O15', the cor- responding values of the c axis being 0.4469 and 0.4521 respectively. The refractive indices and double refraction also vary considerably : €=la6159 t o 1.6572; 0=1*6354 to 1.6918 (for line E). Sp. gr. 3.007 to 3.240. The double refraction and the sp. gr. both increase with the amount of iron. Four groups of tourmaline may be dis- tinguished, namely, those rich in lithium, ferrous iron, ferric iron or magnesium ; the iron tourmalines are black, but those of the second group have palo reddish-violet and blue as axial pleochroism colours, whilst those of the third group have brownish and dark green.The variations in the chemical composition of tourmaline are well illus- trated by a coloured plate giving graphically the results of 33 of the best analyses. L. J. 8. New Mineral Occurrences [Inesite] By OLIVER CUMMINGS FARRINGTON (Field Colurnbian Museum, Chicago, Geol. Series, 1900, 1, 221-231).-The rare mineral inesite has been found at San Cayetano mine, near Villa Corona, State of Durango, Mexico, where it occurs as radiating tufts of flesh-red crystals. Measurements and figures are given of the crystals, and an analysis gave the results under I.At l l O o there is a loss of 3.88 and at 240' of 1.94 per cent., the rest of the water being given off at a red heat; the formula is therefore written as H,(Mn,Ca,Fe)6Si601, + 3H20. SiO,. MnO. FeO. CaO. MgO. HzO. Total. Sp. gr. I. 44-89 36.53 2.48 8.24 trace 8.20 100.34 2.965 11. 1.18 28.27 22.46 2.878 A compact white dolomite from near Lakeport, Lake Co., California, gave the results under 11; it is used by the Indians as money. Crys- tallographic descriptions are also given of caledonite, gaylussite, epsomite and calcite from new localities in the United States. L. J. S. Granite Rocks of Butte, Montana [Analyses of Biotite and Hornblende]. By WALTER HARVEY WEED (J. Geol., 1899,7, 737-750).-1n a petrographical paper on the granite and associated rocks in the neighbourhood of Butte, the following mineral analyses,66 ABSTRACTS OF CHEMICAL PAPERS.by H. N. Stokes, are given : I, black biotite ; 11," very dark-green hornblende, with a large angle of optical extinction; both minerals were isolated from the Butte granite, of which the average composition i s given under I11 : SiO, TiO,. P,05. F. C1. A1,0,. Fe,O,. FeO. MnO. BaO, I. 35'79 3'51 0.10 0-76 0-20 13.70 5'22 13-72 0.19 0'13 11. 45.73 1'43 0.35 0.28 - 6.77 4-94 10.39 0.54 nil [III. 64.03 0.60 0.18 - 15-58 1.96 2.83 0.11 0.07 H,O H,O Total, below above less 0 for SrO. CaO. MgO. K,O. Na,O. Li,O. 110". 110". F. $C1. I. nil 0'05 12'13 9-09 0.15 trace 1'21 3-84 99.22 XI. nil 11'25 12'32 1'22 0.77 trace 0.49 2.29 98'65 111.0'04 4-20 2-15 4-11 2.76 - 0'20 0.73 99.87 By FRANK W. CLARKE (Bull. US. Geol. Swuey, 1900, No. 168, 308 pp.).-This is a new and enlarged edition of the second portion of Bulletin No. 148 (1897). It gives a collec- tion of 1404 detailed analyses of rocks (including igneous and crystal- line rocks, sandstones, carbonate-rocks, slates and shales, clays, soils, &c.) and meteorites, and of minerals isolated from them, which have been made during the years 1880-1899 in the laboratory of the United States Geological Survey. Meteorite from Laqon, France. By STANISLAS MEUNIEB, (Compt. rend., 1900, 131, 969--972).-This stone was seen to fall on June 20, 1897, a t Langon, Dept. Bouches-du-Rh8no. Besides the usual black crust, there are internal black surfaces which are seen on fractures as fine " cosmic lines." Prom a partial mechanical and .chemical analysis, the mineralogical composition is deduced as : nickel- iron 8-80 ; pyrrhotite, 6.35 ; chromite, 0.54 ; enstatite, and plagio- &se, 52.21 ; olivine, [32*10] = 100.00. Sp. gr. 3.482. The nickel- iron contains 8.21 per cent. of nickel. Thin sections under the L. J. S. Analyses of Rocks. L. J. S. microscope show an intimate mixture of crystalline fragments. L. J. S. Water from the Kiedrich Spring near Eltville, Rhine. By HEINRICH FRESENIUS (Jcchrb. Nussau. Ter. Naturk., 1900, 53,l-21).- Water from this saline spring in the Kiedrichthal issues at a tempera- ture of 24-3O, and has sp. gr. 1.006630 at 17.5'. It has a salty taste and is clear and colourless, but becomes cloudy on standing, The analytical results are compared with an analysis of the same water made by C. Bischoff in 1888, and with analyses of waters from several other salt springs. * In anal. I1 are inserted corrections made by the author ; compare Bselt. U. 8. ffeol. Survey, 1900, No. 168, 116. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9018005063

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 67 Peptic Digestion. By HANS MALFATTI (Zeit. physiol. Chem., 1900, 31, 43-48).-The prolonged action of pepsin-hydrochloric acid on Witte’s peptone leads to the formation of tryptophan. Leucine, tyrosine, and hexon bases were found in small quantities in some cases. These products are generally regarded as characteristic of tryptic digestion, and the question is discussed whether they are pro- duced by the activity of pepsin itself, or of another ferment which contaminates the pepsin, The former explanation is regarded as more probable, although it is weakened by the discovery that all pre- parations of pepsin, some of which may be intensely active, do not .cause the appearance of the products named. Attempts to separate a second ferment failed.The Rennet and Anti-Rennet-like Action of Blood. By E. FULD and KARL SPIRO (Zeit. physiol. Chem., 1900,31,132-155)- The rennet-like action of blood is not due to serum-albumin, but to that portion of the globulin which is precipitable by dialysis (euglo- bulin); the anti-rennet action is associated with the portion of the serum-globulin which is not precipitable by dialysis (pseudo-globulin) ; this action is probably associated with its affinity for calcium. W. D. H. W. D. H. Cryoscopy of the Human Sweat. By P. ARDIN-DELTEIL (Compt. rend., 1’300, 131, 844--845).-From determinations of the freezing point of 14 samples of healthy human sweat, the following conclusions are drawn : (l), the mean freezing point is - 0,237’ ; (2), this varies with different individuals between - O.OSOand - 0.46’; (3), the variations depend, for the greater part, on the amount of sodium chloride in the sweat, The lowest values observed were obtained during the summer.By ADALBERT GREGOR (Zeit. physiol. Chem., 1900,31, 98-1 18).-Experimeuts were made on the reducing power of creat- inine; the numbers obtained closely approximate to those of G. S. Johnson. Salkowaki’s method is regarded as the most accurate for quantitative purposes. Beer drinking was found to increase the reduc- ing properties of urine, but this is not due to variations in creatinine. Muscular exercise produces a marked increase in the urinary creatinine, and creatinine is regarded as a specific product of muscular metabolism. H. R. LE S. Creatinine. W.D. H. By R. MAGNUS (Chm. Centr., ii, 1900, 1031 ; from Arch. exp. Path. Pharm., 44, 396--433).-1sotonic solutions of sodium chloride and sodium sulphate produce equal dilution of the blood, but the latter is a more powerful diuretic, because of its direct action on the kidneys. Three kinds of diuresis are described : ( l ) , water diuresis dependent on increase of water in the blood ; (2), salt diuresis, as in that produced by Glauber’s Diuretic Action of Isotonic Salt Solutions.68 ABSTRACTS OF CHEMICAL PAPERS. salts; and (3), combined salt and water diuresis in which both factors are concerned. W. D. H. Pathology of Diabetic Coma. By KARL GRUBE (Chem. Centr., ii, 1900, 1030-1031 ; from Arch, exp, Path. Pharm., 44, 349-362)- Sternberg states (Zeit. klin. Med., 38, 65) that /3-aminobutyric acid is the toxic material in diabetic coma, this passing into the urine as P-hydroxybutyric acid.Injection of the amino-acid in cats produces coma ; the urine gives Fehling’s, Gerhardt’s, and Lieben’s reactions, and contains acetone. W. D. H. Metabolism in Gout. By CHALMERS WATSON (J. Puthol. a d Bacteriol., 1900, 7, 103--117).-A large number of observations are recorded, both as regards the blood, uric acid, and the influence of nucleic acid. The results suggest that in gout the formation of uric acid from the metabolism of the absorbed nucleins and its excretion are altered in no important way from the normal state. The primary changes in gout must probably be looked for in general intracellular metabolism. W. D. H. The Activity of Saliva in various Diseased Conditions.By W. G. AITCHIBON ROBERTSON (J. Puthol. and Bacteriol., 1900, 7, 118--128).-Attention is directed to the importance of examinirig the amount and activity of the saliva in disease. Numerous observations are recorded here both in children and adults. The practical import- ance of the question is seen in dieting ; starchy foods should naturally be withheld, or if given should be previously diastased, in cases where the secretion is scanty or in abeyance, as in fever, and the acute infec- tious diseases ; in dilatation of the stomach, the saliva contains almost no ptyalin ; morphine and atropine inhibit the secretion. W. D. H. An Albumose in Urine. By J. A, MILROY (L Pathol. und Bacteriol., 1900, 7, 95--102).-An account is given of the properties of an albumose occurring in the urine of a patient who probably suffered from bone disease. The characters of the albumose do not agree fully with those of any substance previously described, although they approach nearest to those of deutero-albumose. W.D. H. Interesting Abnormal Urines. By RUDOLF KOBERT (Chem.. Centr., 1900, ii, 919-920; from 8. Xmesp. BZ. AZZgenz. Mecklenburg. Aerzte- Ver., 1900, No. 21 2).--Cases of cystinuria, indicanuria and diacet- uria are described. These are somewhat rare conditions, but nothing new appears to have been made out. Poisonous Effects of Saline Solutions. By ANNE MOORE (Amey. J. Physiol., 1900, 4, 386-396).-The facts described by Loeb regarding the poisonous effects of pure sodium chloride solutions on marine organisms are also true for fresh-water animals (young trout and tadpoles). The chlorides of calcium, potassium, magnesium, and lithium are also poisonous. The poisonous effects of sodium chloride may be antagoniaed by calcium. W. D. He W. D. H.VEGETABLE PHYSrOLOGIY AND AGRICULTURE. 69 A Volatile Venom from the Skin of Iulus Terrestris. By C. PHISALIX (Compt. rend., 1900, 131, 955--957).-The cutaneous secretion of the myriapod IuZ& teweetvis has a yellow colour, and when injected intraperitoneally in guinea pigs proves fatal. The autopsy shows extensive peritonitis, The active material i n this venom is not proteid but some vo1:ttile substance. Quinone as the Active Principle of the Venom of Iulus Terrestris. By AUGUSTE BEHAL and C. PHISALIX (Compt. rend., 1900, 131, 1004--1007).-The aqueous solution of the venom of Iulus terrestris has a yellow colour and contains a quinonoid substance which, in all probability, is benzoquinone. W.D H. G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA9018005067

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

VEGETABLE PHYSrOLOGIY AND AGRICULTURE. 69 Chemistry of Vegetable Physiology and Agriculture. A Possible Cause of Clumping in Bacilli. By SIR THOMAS LAUDER BRUNTON ( J . Pathol. and Bacteriol., 1900,7,53-54).-Wooden matches covered with hard soap to imitate bacteria remain separate in neutral or alkaline water, but if the water is acidified they clump together. The same is true for the formation of rouleaux in cork models of red blood corpuscles. It is suggested that the formation of clumps and rouleaux respectively is due to some slight alteration of their surfaces produced by the liberation of some fatty substance by means of carbon dioxide. By ER. WEIS (Zeit. physiol. Chem., 1900, 31, 79-97).-1n the green and dry malt, there is present both a proteolytic (peptase) ferment and one which curdles milk.Most attention is directed to the latter; this acts best in an acid (especially lactic acid) medium, and plays an important part, not only in the germinatlng process in the plant, but also in the making of beer. Presence of Seminase in Non-germinating Seeds contain- ing Horny Albumen. By &MILE BOURQUELOT and HENRI HERISSEY (Compt. rend., 1900, 131, 903-905).-The non-germinating seeds of Nedicago sativa and Indigofera tinctoria contain a small quantity of seminase which can be extracted from the finely ground seeds by treatment with water. Like the seminase produced during germina- tion (Abstr., 1900, ii, 233), it converts the horny albumen of the seeds into assimilable sugars. Exosmosis of Diastase by young Seedlings. By JULES LAURENT (Compt.Tend., 1900, 131, 848--85l).-The germinating seeds of maize, wheat, peas, and buckwheat are able t o furnish a part of the diastase necessary for the digestion of their reserve food material, and are thus able t o assimilate insoluble organic substances such as starch. This phenomenon ceases at the end of the germinating period. Ex- periments carried out by a m?ethod previously described (Compt. rend., VOL. LXXX. ii. 6 W. D. H. A Proteolytic and Rennet-like Ferment in Malt. W. D. H. C. H. B.70 ABSTRACTS OF CHEVICAT, PAPERS. 1897, 125, 887) clearly show that the roots are incapable of exuding any appreciable quantity of amylase. Assimilation in two Cultivated Plants. By ALEXIUS VON SIGMOND (Chem. Centr., 1900, ii, 1087 ; from J. Landw., 48,251-264).-Maize plants develop slowly during the first period of growth, but more quickly from this time to the flowering period. Growth is then checked for a time, but afterwards quickens. During the deposition of starch, the growth is again checked, after mhich, during the ripen- ing of the grain, assimilation becomes very vigorous. On the whole, assimilation and development go together, and no special manure seems to be necessary. I n the case of tobacco, development was slow in the early stages of growth, and increased and diminished alternately during the subse- quent periods. There seems to be a slight temporary want of phos- phoric acid in the first period, and also of nitrogen; the importance of nitrogen increases before the beginning of the first period of greater activity. These results accord with what has been observed in practice.By C. HABTWICE a4d M. CAMPER (Arch. Pharm., 1900, 238, 568--587).-The interest of the paper is chiefly pharmaceutical, and that in the botanical direction. The bark of lhenbeckia febrtyuga (sym Evodia febrifuga), sold under the name of angostura bark, was examined chemically ; from it, 0.11 per cent. of a solid “ethereal oil ” melting at 37-42’ was obtained by dis- tillation with steam ; and by percolation with 1 per cent. aqueous tartaric acid, 3.9 per cent. of alkaIoids was obtained. From this mixture, five alkaloids were separated by taking advantage of the differences in the ease with which they are liberated by ammonia and by sodium hydroxide, and by the differences in their solubility in ether, chloroform, and absolute alcohol.By ALEXANDER ZEGA (Chern. Zed., 1900, 24, 871).-The green fruit of Hibiscus esculentus, which is sold in Servia as a vegetable under the name of ‘ Bamnje,’ has the following mean percentage composition : water, 80.74 ; nitrogenous material, 4.15 ; fat, 0.42 ; carbohydrates, 12.12 ; wood fibre, 1.15 ; ash, 1.41, the percentages of nitrogenous material and Carbohydrates on the dry material being 21.55 and 63.24 respectively. The ash contains SiO,, 0.06 ; SO,, 0.034 ; phosphoric acid, 0.043 ; CaO, 0.100 ; MgO, 0.016 ; K,O, 0.042; Na,O, 0.058 per cent. of the original substance. H. R. LE S. N. H. J. M. Angostura Barks. C. F. B. Hibiscus Esculeatus. T. H. P. L g Radix Naregamie.” By RUDOLPH HAUKE (Chem. C’entr., 1900 ii, 1129--1130 ; from Zeit.Oesterr. Apoth.-Verein., 38, 829-833).-An ethereal extract of “ Radix Naregamice” contained 0.3 per cent, of Hooper’s alkaloid naregamine, 2.0 of wax, 2.5 of resin, and 0.9 of fatty oil and colouring matter. The wax melted a t 58’, had a sp. gr. 0.9 1, acid number 5.9 (chloroform solution), 6.1 (alcoholic solution), ether number 21 *1, and saponification number 2 7.0. When the alcoholic solution was poured into water, a resin was precipitated, whilst ie tbe solutioq tbere still remained a substance which readilyVEGETABLE PHYSIOLOGY AND AGRICULTURE. 71 reduced Fehling’s solution (sugar). The aqueous extract had a faint acid reaction and gave a blue coloration with iodine; a crystalline compound, which is probably asparagine (Hooper), was also isolated and the extract contained proteids, gum, and pectin substances but not tannin.The drug left 5.73-7-1 per cent. of ash, that of the wood being 1.79 and that of the bark 5.97 ; 5.9 per cent. of dry residue was obtained from the alcoholic and 12.3 from the aqueous extract. E. w. w. Simarubaceae I. Samadera Indic. By J. L. B. VAN DER MARCK (Chem. Centr., 1900, ii, 1124-1125 ; from Ned. Tijd. Plharna., 12, 296-306).-The seeds of Samaderu Indic. contain 63 per cent. of fat, which consists of 87.7 per cent. of triolein, 8.41 of tri- palmitin, and 3.89 of tristearin. The alcoholic extract contains an alkaloid which appears to be identical with gliadine and a resin; glucosides and a bitter principle are present in the seeds. The bitter principle is also contained in the bast and is accompanied by tannic acid ; it is somewhat soluble in alcohol and acetone, melts at 2 5 5 O , and is apparently identical with Rost van Tonningen’s samaderin.It contains carboxyl groups but neither a methoxy- nor an ethoxy-group, and when administered to cold blooded animals cau3es paralysis of the voluntary nerves and death. A second bitter principle is found in the roots; it melts a t 209O, is soluble in alcohol and sodium hydroxide solution, and is apparently identical with quassin. [Feeding Experiments with Cows.] By EBERHARD RAMM (Bied. Centr., 1900, 29, 737; from Milch-Zeit., 1899, 52, 817. Compare Abstr., 1900, ii, 749).-A summary of the results of experiments al- ready described. Besides the actual results, corrected results are given, excluding the effects of period of lactation, on the assumption that the same food produces the same effect.The conclusion isdrawn that when rich foods are employed, it is undesirable - t o go beyond a certain limit as regards the amounts of proteid and fat in the rations. Certain foods exert a specific action which does not depend on the amounts of nutritive substances they contain. By MAX GONNERMANN (Chsm. Centr., 1900, ii, 1034 ; from Milch-Zeit., 29, 599).-0i1 seeds mixed with molasses may undergo considerable loss when long kept, and mixtures of brewer’s grains with molasses, if not quite dry, may decompose rapidly, owing t o the presence of yeasts and bacteria. Under these conditions, all the sugar and nitrogenous substances may be lost, and injurious compounds may be produced.The employment of peat-meal molasses is strongly recommended ; it may be mixed with oil-seeds as required. N. H. J. M. By FAUSTO GABRIELLI (Bied. Centv., 1900, 29, 780 ; from Stax. sper. agrar. hat., 1899, 32, 204).-The residues of oranges, &c., in Calabria are utilised as cattle food, especially after being allowed to decompose until they acquire a uniform buttery consistence. The following are the results of analyses of (1) lemon, (2) Bergamot orange, residues, and (3) the mixed E. W. W. N. H. J. M. Value of Molasses-Foods. Nutritive Value of Orange Residues in Calabria. 6-272 ABSTRACTS OF CHEMICAL PAPERS. residues, fermented; water in fresh substance (1) 89.10, (2) 88.63, (3) 92-91 per cent. Percentage composition of the dry matter : Non- Total Proteid nitrogenous Crude N.N. Fat. extract. fibre. Ash. K20. P,O,. 1. 0.60 0.36 0.97 80.39 12.03 4.34 0.53 0.36 2. 0.65 0.44 1.09 82.21 9.20 4.75 - 0.29 3. 1-38 0.78 5.51 61.33 21.80 6.52 1.36 0.38 Milk and meat from animals fed with the residues have a charac- teristic, but not unpleasant, taste. N. H. J. M. Relation between the Weight and the Percentage of Nitro- gen in Wheat Grain. By WILHELM JOHANNSEN and FR. WEIS (Bied. Centr., 1900, 29, 758-760 ; from Tidsskr. Landw. PZanteauZ., 1899, 5, 91-99).-The fesults of analyses of large, average, and small grains of different varieties of wheat show that, as in the case of barley (Abstr., 1900. ii, 363), a relation exists between the weight and the percentage of nitrogen, which is highest in the large grains.There are, however, many exceptions, and the rule cannot be adopted for improving varieties of wheat and barley. The large, mealy grains, which were always heavier than the average of the whole, invariably contained less nitrogen than the whole sample. Manurial Experiments with Hops. By MAX BARTH (Bied. Centr., 1900, 29, 728-731 ; from BZ. Gersten-, Hopfen-, u. Rartofel- hau., 1899, 323).-The results of field experiments showed that hops require mineral manures as well as nitrogen even on fertile soils. N. H. J. M. N. H. J. M. Green Manure Experiments with Potatoes. By CLAUSEN (Bied. Centr., 1900, 29, 733-735 ; from IZZust. Landw. Zeit., 1900, 129).-The average yield of potatoes, with various manures, after lupins as green manure, was 135, taking the yield of the potatoes with- out green manure as 100.The results of experiments with different varieties of potatoes showed that those varieties with the longer vegetative periods seem to benefit less than those with short vegetative periods. Both kainite and superphosphate, with green manure, further increased the yield of potatoes. Effect of Water and Manure on the Composition of Potato Ash. By A. TON DASZEWSKI (Chern. Centr., 1900, ii, 1086-1087; from ~naug.-D~ss. Gottingen, 1900).-An extension of the work com- menced by Wilms (Abstr., 1900, 164). With excessive moisture, the assimilation of potassium and phosphoric acid is absolutely greater and relatively less than with less moisture, whilst relatively greater amounts of calcium and chlorine are taken up.The application ef a substance as manure causes an increased amount of the substance to be taken up by the plant, especially by the leaves. Calcium and chlorine have the predominating action in decreasing the starch in presence of much moisture. I n preparing the ashes, Tucker's apparatus was employed, and it was found that the method rendered incineration more easy and checked N. H. J. M.ANALYTICAL CEEMISTRY. ‘73 volatilisation (Abstr., 1900, ii, 52 ; Shuttleworth and Tollens, ibid., 111 ; and Shuttleworth, ibid., 372). Alkali Soils of the Yellowstone Valley. By MILTON WHITNEY and THOMAS H, MEANS ( K S . Dept. A ~ Y . Div. of Soils, Bull., 1898, 14, pp. 39).-The ultimate source of the alkali is the sandstone. Before irrigation was introduced, the salts were well distributed throughout the soil, which then contained rather large, but not injurious, amounts of alkali. To get rid of the excess of alkali where it has become localised, a system of drainage will have t o be adopted, whilst great care must be exercised in irrigation. I n this manner, the original fertility of the soil may be restored in a few years. Movement of Water and Solutions of Salts in Soil. By S. KRAWKOW (Chem. Centr., 1900, ii, 1084-1085; from J. Landw., 48, 209--222).-The movement of water is much slower in loamy sand than in diluvial sand. The rate and height of capillary move- ment is ininverse ratio to the amount of moisture. The amount of drainage and the rate are directly proportional to the amount of rain. I n the case of solutions of salts, the rate of upward capiIIary move- ment depends on the degree of concentration and not on the nature of the salt. Application of gypsum and calcium carbonate increased the rate of drainage as well as that of the upward capillary movement. N. H. J. M. N. H. J. M. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9018005069

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

ANALYTICAL CEEMISTRY. ‘73 Analytical Chemistry. Estimation of Nitrites Alone or in the Presence of Nitrates. By HENRI PELLET (Cham. Centr., 1900, ii, 1089; from Ann. Chim. anal. appZ., 1900, 5, 361--365).-The author republishes a process given by him in 1879, and based on the fact that in the presence of ferrous salts and hydrochloric acid both nitrates and nitrites yield nitric oxide, but that when acetic acid is substituted for hydrochloric Estimation of Nitrites and their Separation from Nitrates. By LUCIEN L. DE KONINCK (Chenz Centv., 1900, ii, 1089-1090; from Ann. Chim. anal. appl., 1900, 5, 365--368).-The method proposed by Pellet (preceding abstract) is approved of. A large excess of hydro- chloric acid is essential for the reaction when dealing with nitrates. Nitrites are completely decomposed by boiling with ferrous ammonium sulphate alone. In the presence of ammonium chloride, free nitrogen is evolved, but this makes no difference, as the volume of gas evolved By 0.DUCRU (Compt. Tend., 1900, 131, 886--888).-The arsenic is precipitated as ammoniacal cobalt arsenate (this vol., ii, 23), the reagents required being a solution of 75 grams of acid only the nitrites are decomposed. L. DE I(. is the same. L. DE K. Estimation of Arsenic.74 ABSTRACTS OF CHEMICAL PAPERS. cobalt chloride in 1000 C.C. of water and a solution of ammonium acetate prepared by neutralising a 40 per cent. solution of glacial acetic acid with a 20 per cent. solution of ammonia. The arsenic solution is concentrated, acidified if necossary'with hydrochloric acid to decompose any alkali carbonates, and then just neutralised with ammonia. Ten C.C.of the cobalt solution for every 103 mgrms. of arsenic present are mixed with one-quarter its volume of the ammonium acetate solution, and to the mixture is added about 3 per cent. of a 20 per cent. solution of ammonia. This reagent and the arsenic solution are mixed and heated in a closed flask on a water-bath until the precipitate becomes crystalline ; it is then collected and washed with cold water. The precipitate may be dried at looo and weighed, when it has the composition Co3(As0,)~,NH,,7H,0, or it may be heated at dull redness until the weight is constant, which does not yield very good results ; or it may be dissolved in dilute acid, the arsenic separated and the cobalt precipitated by electrolysis in presence of ammonium sulpbate.The method yields accurate results even with very small quantities of arsenic. By J. WETZEL (Bey., 1900, 33, 3393--9394).-To insure the complete absorption of carbon dioxide in combixstions, where the gas is given off very rapidly, the author proposes the addition of a small moveable inverted funnel in each of the three bulbs, which contain the potash of the usual Geissler apparatus. By ANDREW A. BLAIR (J. Amev. Chem. SOL, 1900, 22, 719-723).-Twenty-five grams of pure potassium hydrogen sulphate are placed in a platinum boat 150 mm. long and 25 mm. wide and fused over a bunsen burner to destroy any carbonaceous matter. When cold, 1 gram of the finely powdered sample is sprinkled over it, and the boat is inserted into a larger one, which is then fitted witha cover soarranged that any particles spirted up from the melting mass run into the larger boat; by this means, the combustion tube is kept clean.The latter consists of a platinum tube 400 mm. long and 30 mm. in diameter closed with a ground joint at the rear. The forward end for a distance of 75 mm. is contracted to 12 mm. and filled with platin- ised asbestos. It is then further contracted to 6 mm. in diameter and 'it piece of glass tube filled with glass beads is fused to it after being bent downwards a t an angle of 904 The plugs are made of pumice wrapped with platinum foil and are pushed in after the boat. It will be noticed that the use of india-rubber stoppers is entirely avoided, which is very essential, as these may be a source of con- siderable error.The further details of the process are briefly as follows. The com- bustion is made in a slow current of purified oxygen, the bulk of the liberated sulphuric acid condenses in the tube containing the beads, and the gases are then passed through two glass flasks kept hot and containing a solution of chromic acid in sulphuric acid t o retain any suphur dioxide. After pissing over pumice stone saturated with chromic acid and over dry calcium chloride, the carbon dioxide is C. H. B. An Improvement on the Geissler Potash Apparatus. R. H. P. Estimation of Carbon in Ferrochrome.ANALYTICAL CHEMISTRY. 75 finally absorbed in the usual manner and weighed. The guard tube of the absorption apparatus is connected with a gasometer which acts as an aspirator and relieves the pressure in the apparatus, which other- wise might become excessive owing to the condensation of sulphuric Some Principles and Methods of Rock Analysis.By WILLIAM F. HILLEBRAND (Bull. U.S. Geol. Survey, 1900, No. 176, 114 pp.).- This, which is a new and enlarged edition of the first portion of Bulletin No. 148 (1897), gives detailed descriptions of the methods employed in the laboratory of the United States Geological Survey for the amalysis of silicctte rocks and minerals. Several diagrams of apparatus are given, and also a complete index. Separation of Tungsten Trioxide from Molybdenum Tri- oxide. By XAX J. RUEQENBERQ and EDGAR F. SMITH (J Amzr. Chem. Xoc., 1900, 22, 772-773).-The two oxides may be quantita- tively separated by heating them with about 50 times their weight of sulphuric acid of sp.gr. 1.378, which completely dissolves the molyb- denum trioxide but lertves the tungsten trioxide undissolved. The presence of even a large excess of ferric oxide does not interfere with acid in the bent tube. L. DE K. L. J. S. the estimation of the tungsten. L. DE K. W Estimation of Air in Water. By HENRI PELLET (C'hem. Centr. 1900, ii, 1088-1089; from Ann. Chim. anal. appl., 1900, 5, 369-370).--A (see Fig.) is a glass flask, E an india-rubber cork with a elass tube T, C a condenser the cork, R, of"which rests-on E. D is a graduated tube closed by the stopcock, G, and supported by H. I, J, and Ir' serve for regulating the refrigerating water. A is filled with the sample to be tested, the cooling water is admitted into C, the burette, D, is filled with water by applying suction and connected with T, On warming A , a portion of the water is expelled, the same volume which flows from J, is measured and deducted from the volume of the balloon, A .The air from the water collects in D, and its volume is measured with due regard to tempera- ture and pressure. The gas may be removed by opening G, and further examined. L. DE K, Preliminary Operations at the Spring for the Detection of Metals Present in Minute Quantities in Natural Waters. By F. GARRIGOU (Compt. rend., 1900, 131, 897-899).-1n order to avoid the evaporation of large quantities of water, the author collects the water at its source in large vessels of glass or wood, adds excess of barium hydroxide in very fine powder, and agitates briskly.After the precipitate has completely76 ABSTRACTS OF CHEMICAL PAPERS. settled, the clear liquid is drawn off and the precipitate collected in flasks. The liquid is mixed with a slight excess of sulphuric acid, and the precipitate, which carries down with it traces of metals not pre- cipitated by the hydroxide, is also collected. The two precipitates contain all the metals originally present in the water, with the exception of alkali metals. Quantitative Reactions to distinguish between Petroleum or Cannel Coal Pitches and Pitches from Distillation of Fats. By I). HOLDE and J. MARCUSSON (Ber., 1900, 33, 3171--3175).-Soft pitches from fat distillation, stearin pitch, wool pitch, &c., are readily distinguished from the soft and hard pitches from petroleum by means of the large amounts of fatty acids and esters contained in them.Hard wool and stearin pitches are somewhat difficult to differentiate from petroleum pitches, as they contain only small amounts of acids. The distillates from such pitches yield 14-17 per cent. of snow-white paraffin hydrocarbons; the sp, gr. of the distillate is always con- siderably below 1, as are the sp. grs. of the distillates from petroleum or cannel coal pitches. Coal t a r pitch, on the other hand, yields distil- lates of sp. grs. always above l. The best method of distinguishing hard fatty and ‘‘ mineral oil ” pitches is by the aid of a specially prepared alcoholic-ether extract. The ex- tract from hard fatty pitch gives an ‘‘ acid number ” * varying from about 9-23 and an ‘‘ ester number ” from 9-1 6 ; the corresponding numbers for a petroleum pitch vary between 0.6 and 3.0 and 3.4 and 5.9.In the titrations the authors have used a 2 per cent, solution of alkali-blue-6b as indicator. When the hard iatty pitches are distilled with superheated steam (300°), or even simply distilled, the first distillates always contain appreciable amounts of acid. The authors find that all fatty pitches contain small amounts of copper soaps, obtained from the copper vessels in which the distillation has been carried out. Petroleum pitches, on the other hand, are free from copper. New Colour Reaction for Distinguishing between certain Isomeric Ally1 and Propenyl Phenols. By ALFRED C.CHAPXAN (Analyst, 1900, 25, 313-314).-The reaction is brought about by dissolving 1 C.C. of the phenol in 5 C.C. of acetic anhydride and then adding a fragment of fused zinc chloride or one drop of sulphuric acid. Eugenol gives, with sulphuric acid, a brown coloration which quickly turns purple and finally wine-red ; with zinc chloride, a transi- tory pale yellow. isoEugencl gives, with sulphuric acid, a rose-pink coloration quickly changing to a light brown; with zinc chloride, a bright rase-pink. Safrole gives, with sulphuric acid, a bright emerald green coloration, becoming brownish-green and finally brownish ; with zinc chloride, a pale blue, fading after a time and finally turning light * The acid number indicates the number of milligrams of potassium hydroxide required to neutralise the acid contained in P gram of the substance ; the ester number gives the number of milligrams of potassium hydroxide required to hydro- lyse the esters contained in 1 gram of the substance.C. H. Is. J. J. S.ANALYTICAL CHEMISTRY, 77 brown. isosafrole gives, with sulphuric acid, a faint, transient pink coloration, turning reddish after a time; with zinc chloride, a pink becoming brownish-pink, and finally brown. Estragol gives, with sulphuric acid, a purple coloration turning to indigo blue and then to bluish-purple ; with zinc chloride, a blue-violet, becoming deep mauve and finally brownish. Anethole gives, with sulphuric acid, no colora- tion at first, but after a short time a yellowish tinge; with zinc chloride, a pale yellow, appearing slowly and deepening on standing, finally becoming brick-red. Every possible care was taken to ensure the purity of the phenols The Margarine Clause of the Food and Drugs Act.[By THOMAS E. THORPE, WALTER W. FISHER, ALFRED H. ALLEN, EDWARD report as to the manner of estimating the proportion of butter fat in margarine, which has been agreed to by the Principal Chemist of the used in the experiments. L. DE I(. J. BEVAN, and OTTO HEHNER] (Andy&, 1900, 25, 309-313).--8 Government Laboratory and a Committee appointed by the Society of Public Analysts. Five grams of the melted and filtered sample are introduced into a 300 C.C. flask (see Fig.), 2 C.C. of aqueous sodium hydroxide (1 : 1) free from carbon dioxide are added, and also 10 C.C.of 92 per cent. alcohol, and the mixture is heated under a reflux condenser, connected with the flask by a T-piece, for 16 minutes in a bath containing boiling water. The alcohol is distilled off by heating the flask on the water- bath for about half an hour, or until the soap is dry. One hundred C.C. of hot water which has been kept boiling for at least 10 minutes are The method recommended is as follows :78 ABSTRACTS OF CHEMICAL PAPERS. added, and the flask heated until the soap is dissolved. Forty C.C. of N-sulphuric acid an'd three or four fragments of pumice or broken pipe- stems are added, and the flask is a t once connected with the condenser, as indicated in the figure. The flask, which is supported on a circular piece of asbestos 12 cm. in diameter having a hole in the centre 5 cm.in diameter, is first heated with a very small flame, to fuse the insoluble fatty acids without causing the liquid to boil. The heat is then increased, and when fusion is complete 110 C.C. are distilled off into a graduated flask, the distillation lasting about 30 minutes (say from 28 to 32 minutes). The distillate is shaken, 100 C.C. are filtered off, trans- ferred to a beaker, 0.5 C.C. of phenolphthalein solution (1 gram in 100 C.C. of alcohol) added, and the filtrate titrated with N,,10 sodium or barium hydroxide. As the chemicals used may yield a slightly acid distillate, a blank experiment should be made, and the result allowed for ; this should, however, not exceed 0.3 C.C. of N/10 alkali. The final result multiplied by 1.1 is the Reichert-Wollny number. The following table gives, I, the' Reichert-Wollny number as deter- mined by this method, and, 11, the corresponding amount of butter fat that is assumed to be present in the margarine.I. 4.0 4.3 4'6 4.9 5.2 5.5 5'9 6-2 6.5 6'8 7.1 11. 10 11 12 13 14 15 16 17 18 19 20 No presumption against the margarine in regard to its content of butter fat should be raised unless the Reichert-Wollny number thus By W. G. A. INDEYANS (Chem., Centr., 1900, ii, 1134 ; from Ned. Tydschr. Pharm., 12, 306-310).-The presence of Ceylon oil in butters or margarines renders analysis more difficult on account of the considerable amount of volatilz fatty acids which i t yields. The adulteration may, how- ever, be detected by combining the Reichert-Meissl number with the refractometer number as shown in the following table : ascertained exceeds 4.L. DE K. Cleylon Oil in Margarine and Butter, Reichert-Meissl Refractometer number. number. Pure butter ........................... 27.13 46.25 Same adulterated with 20 per cent. of foreign fat ...................... 21.15 45.5 Margarine Ro. 1 ...................... 5-87 43.5 Margarine No. 2 ...................... 5.16 44.5 Ceylon oil .............................. 7.60 36.0 Margarine without Ceylon oil.. .... 1.32 54.0 Estimation of Fat in Faeces. L. DE I(. By OEFELE (Chem. Centr., 1900, ii, 1137 ; from Pharm. Centr. €Tulle, 41, 649--651).-The estimation of the fat in the portion of the ethereal extract which is insoluble in water by assuming its saponification number to be 200 is quite untrustworthy ; to obtain results which agree with the gravimetric estimation of the fatty acids, the saponification number must be supposed to vary from 92 to 350.It is recommended to estimate the fat by its ether-number, byANALYTICAL CHEMISTRY. 79 weighing, and by titration so as to get both the normal fat and the fatty acids. L. DE K. Analytical Chemistry of the Alkaloids. V. Employment of Tannic Acid for Purifying Alkaloid Residues in Chemico- toxicological Analysis. By KARL KIPPENBERGER (Zed. anal. Chem., 1900, 39, 627-633).-SalkowskiYs objections (Abstr., 1898, ii, 547) to the author’s “glycerotannic acid” method (Abstr., 1895, ii, 465) are admitted, as far as regards the behaviour of Witte’s peptone with this reagent, but if the extraction be made at 40’ as recommended, none of the proteids present in cadaveric matter will pass into solution, and to the objection that the alkaloid tannates may be partially precipitated by diluting the glycerol solution with much water, it is replied that this occurs only in the absence of acid.The author originally proposed the addition of tartaric acid ; hydro- chloric acid is even better. He, however, admits that the extraction of the glycerol solution by chloroform is an inconvenient operation. On the other hand, Salkowski’s propcsal to treat the alkaloid tannates with hide powder does not succeed in the case of alkaloids, such as brucine, which form very insoluble tannates. A more convenient solvent than glycerol for the alkaloid tannates is found in acetone, in which the freshly precipitated tannates of brucine, strychnine, atropine, morphine, aconitine, veratrine, papaverine, narceine, thebaine, codeine, emetine, nicotine, coniine, sparteine, quinine, narcotine, and cocaine dissolve readily.The majority of the proteid tannates, including Witte’s peptone, are insoluble in acetone, although there exist commercial peptones, of which traces dissolve. The presence of hydrochloric acid is to be avoided when extracting with acetone. Having obtained the acetone solution, a small quantity of glycerol and some dilute hydrochloric acid should be added before evaporating the acetone, and an aqueous solution is then obtained which is well suited for the extraction with chloroform. The acetone method is of course useless where volatile alkaloids have to be searched for.M. J. S. Estimation of Proteids in Fodder. By HENRIK SCHJERNING (Zeit. anal. Chem., 1900, 39, 633-639).-The author has now applied his method of precipitation by uranium acetate (Abstr., 1898, ii, 658; 1900, ii, 779) to the estimation of the total proteids in various feeding stuffs, in comparison with Stutzer’s method, which has generally been employed for the purpose. In consequence of the absenco from most fodders of the peptones which Stutzer’s reagent fails to precipitate, the two methods give in most cases closely concordant results, In the case of sunflower-seed cake and cotton-seed cake Stutzer’s reagent gave slightly the higher numbers, a result which is probably due t o the precipitation of amino-compounds. Special experiments showed that the uranium process was not interfered with by the presence of such non- proteid nitrogenous substances as piperazine, arginine, as- paragine, &c.The estimation is carried out as follows : 0.5-1 gram of the substance is digested at the ordinary temperature with 100 C.C. of water for 20 hours; the mixture is then heated to 50°, and 20 to 40 C.C. of saturated solution of uranium acetate (which should be free80 ABSTRACTS OF CHEMICAL PAPERS. from basic salt) are added. The mixture is kept at 50° for half an hour, direct light being excluded, and the precipitate collected on an extracted filter and washed with a cold 1-2 per cent. solution of uranium acetate. It is then evaporated nearly to dryness with addition of a little magnesia (Abstr., 1900, ii, ‘780) and the nitrogen is estimated by Ejeldahl’s process, adding 0.1 C.C.ot N/10 acid for every 100 C.C. of filtrate. By A. D, HALL (Analyst, 1900, 25, 281-286).-Recommendations of the Committee of the Agri- cultural Education Association, having for their object the securing of a certain uniformity in soil analyses. 1. Takiag sarnpZe.-This should be taken at a depth of 9 inches, but in the case of shallow soils a t such a depth as marks a natural line of demarcation. 2. Drying.-The sample should be air-dried. The dry- ing may be accelerated by warming for some time at 40°. 3. 8z;ftinq. -A sieve with round holes 3 mm. in diameter should be used to separate the fine earth from the stones and gravel. Aggregates of clay and silt may be broken up with a wooden pestle, but stones or lumps of chalk should not be crushed. For the determination of the available constituents, the fine earth is used without grinding, but in other casesit is sifted through a woven sieve of 40 meshes to the inch, or a sieve with round holes of 1 mm.in diameter. 4. Estima- tion of moistzcre.-The sample should be dried in the steam-oven to constant weight. 5. Determination of loss on ignition.-The result should be corrected for moisture and for any carbon dioxide expelled from the carbonates. 6. Betel-mincdion of nitrogen.-Kjeldahl’s pro- cess should be used. 7. Determination of ccclciurn carbonate.-This is calculated from the carbon dioxide evolved when the fine earth is treated with an acid, no discrimination being made bet ween calcium and magnesium carbonate. 8. Determination of totaZ mineral con- stituents.-The fine earth is first boiled with strong acid in an open flask and then digested in a loosely-stoppered flask on the wnter- bath for 40-48 hours. In this solution, the phosphoric acid, potash, and, if necessary, other mineral constituents are determined. 9. De- termination of available phosphoric acid and potash.--D yer’s citric acid process (Trans., 1894, 65, 115) is recommended. 10. Expression qf results.-Unless otherwise stated, results should be expressed as percentages calculated on the fine earth in an air-dry state. Experiments have been made with the object of supporting these recommendations. It has been found that hydrochloric acid acts more satisfactorily than nitric acid. As a rule, the ignited soil yielded more potash and less phosphoric acid than the raw sample. M. J. S. Uniformity in Soil Analyses. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9018005073

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

81 General and Physical Chemistry. Lamps for Spectra. 111. By ERNST BECKMANN (Zeit. physihut. Chem., 1900, 35, 652-660).-The paper contains a description and an illustration of an elaborate lamp constructed on the lines previously indicated (Abstr., 1900, ii, 701 ; this vol., ii, 53), and suitable for all sorts of spectroscopic investigations. I n another lamp, aapable of giving monochromatic light for polarimeter and refractometer work, the flame is circular, and the spray is produced either electrolytically or with the porous porcelain tube previously described. To secure an intense sodium flame, hydrogen should be substituted for coal gas, and the salts used should be those which readily give up oxygen, namely, chlorate, perchlorate, nitrate, or peroxide, Arc Spectra of some Metals as Influenced by an Atmosphere of Hydrogen.By HENRY CREW (Phil. Nag., [v], 50, 497-505),- It was found that arc spectra of metals are modified when the arc is formed in an atmosphere of hydrogen, some of the lines being enhanced, some weakened, and others not affected, The modifications of zinc and magnesium spectra and for a portion of the iron spectra are in- dicated by tables. From these, it is observed that all the lines in the arc spectrum which are affected by the hydrogen atmosphere belong also to the spark spectrum, whilst,on the contrary, those, lines which belong to Kayser and Runge’s series are not affected. Differences of Potential between Metals and Non-aqueous Solutiorm of their Salts. 11. By LOUIS KARLENBERG (J. Physical Chem., 1900, 4, 709-714.Compare Abstr., 1899, ii, 624).--The E.M.F.’s of a number of non-aqueous concentration cells were deter- mined; the ratio of the ion concentrations in the solutions were calculated from the molecular conductivities and the E.M.F.’s calcu- lated by the well-known Nernst formula : 7r = RT/ne.logcl/c,. The cells employed were (1) Ag.N/10AgN03.N/100AgN0,.Ag ; (2) A g.N/1 OAgNO3.N/5OOAgNO3.Ag ; (3) Ag.N/ 10AgNO,.N/1000AgNO,. Ag, in pyridine solutions ; (4) Ag.N/8AgN03.N/128AgN0,.Ag in aceto nitrile ; (5) Cd.N/48*9Cd12.N/2 14*7CdI,.Cd in acetonitrile. The deter- minations gave the following values in volts for the E.M.F. (1) 0.035, (2) 0.061, (3) 0.076, (4) 0,046, ( 5 ) 0.032, whilst those calculated were (1) 0.053, (2) 0.085, (3) 0.099, (4) 0.050, (5) 0.017 volt.Owing to these discrepancies, the author considers that Nernst’s expression cannot be applied to non-aqueous solutions, and considers i t desirable that the formula should be subjected to rigid tests in aqueous solutions (compare, however, Jahn, abstr., 1900, ii, 707). The Chlorine-Hydrogen Gas Cell. By IWAN AKUNOFF (Zeit. Elektrochem,, 1900, 7, 354-356).-The author finds the E.M.F. of the hydrogen-chlorine gas cell (the electrolyte being 3-normal hydrochloric acid saturated with potassium chloride) to b s 1.37125-0*000855t volts J. C. P. L. M. J. L. M. J. VOL. LXXX. ii. 7$9 ABSTRACTS OF CHEMICAL PAPERS. From this result, the heat developed by the reaction which gives rise to the E.M,F, is calculated by means of Helmholtz’s formula to be 37,107 cal.The heat of formation of hydrochloric acid in the above- mentioned solution from gaseous hydrogen and chlorine at constant pressure is 3’7,680 cal. Muller (Zeit. Elektrochem., 1900, 6, 578) has supposed the reaction to be H, + HClO = H,O + HC1; this would, however, develop 38,850 cal. It is therefore probable that the E . M . F . of the cell is due to the direct union of hydrogen and chlorine. By P. 8. WEDELL-~~EDELLSBORG (hk physikal. Chew., X900, 35, 604-607).-A .criticism, from a purely physical standpoint, of Mie’s paper (Abstr., 1900, ii, 703), and a sum- mary of the differences between the author’s views and those of Poynting and Thomson. Electrical Conductivity of Aqueous Solutions of Alkali Chlorides and Nitrates. By FRIEDRICH KOHLRAUSCH and MARa ARET E.MALTBY ( W i m Abkandl. phys.-tech. Reichsanstalt, 1900,3, 155-227). -An account of this work has already appeared (see Abstr., 1900, ii, 61), but the present paper contains very much fuller details of the experimental data. J. C. P. Electromotive Force and Optical Constants of Chromium. By F. JULES MICHELI (Chem. Centr., 1900, ii, 809 ; from Arch. 8ci. phya. %at, Gendue, [iv], 10, 122--131).-When the metals are arranged in the order of their electromotive efficiency, chromium in the inactive condition stands near platinum, in the active condition immediately after zinc (compare Hittorf, Abstr., 1898, ii, 363; 1900, ii, 127). Optical investigation must throw light, as in the case of iron, on the question whether the existence of the active and inactive states is due to two different modifications of chromium, or to a superficial layer of oxide in the latter case.The author finds, by an optical method, that there is no such layer of oxide formed. According to Hittorf and to Ostwald (Abstr., 1900, ii, 730; this vol., ii, 24), chromium which has been rendered active becomes inactive if left exposed t o the air ; the author, on the other hand, finds that chromium which has been rendered inactive gradually assumes the active condition, According to Hittorf, the activity of chromium can be increased by immersion in fused zinc chloride; optical investigation reveals, in this case, the presence of a, coating of oxide ; subsequent immersion in nitric acid renders the chromium inactive, without in any way affecting the layer of oxide.J. C. P. Concentration at the Electrodes in a Solution, with special reference to the Liberation of Hydrogen in the Electrolysis of a Mixture of Copper Sulphate and Sulphuric Acid, By HENRY J. S. SAND (Compt. rend., 1900, 131, 992-995; Phil. Mag,, 1901, [vi], 1, 45--79).-An expression is deduced for the concentration at an electrode of infinite area, in terms of the time, current, and diBusion coefficient. Pn mixtures, however, a formula cannot be deduced, but limiting values may be calculated between which the actual concentration should lie. These were applied to T. E. POynting’S Theorem. J. C. P.GENERAL AXD PHYSICAL CHEMISTRY, 83 caIculate the time in which the concentration of copper at an electrode in a mixture of copper sulphate and sulphuric acid would become zero, and the liberation of hydrogen would hence commence.The observed time was found in all cases to lie between the calculated limits. The calculations assume the absence of convection currents. the liberation of hydrogen being completely prevented by vigorous stirring L. M. J. Electro-capillary Properties of Mixtures, and Electro- oapillary Viscosity. By A. GOUY (Compt. rend., 1900, 131, 835-837).-I.f the curves for electro-capillarity against potential difference be taken in the case of (1) an aqueous solution of a pure compound A , and (2) the same solution to which a small quantity of a second compound, B, is added, it is found that in general these coincide for strong negative polarisations. If, however, the compound B is an active ' compound, for example, an iodide or bromide, a varia- tion of the maximum occurs, and near the maximum the curve resem- bles that of the solution of B, even though its concentration be very small compared with that of A .Thisvariation of the inaximum may attain the value of 0.2 volt, so that the maximum value does not always correspond with zero difference of potential. I n these mixtures also, the mercury only slowly reaches its stable position and this effect, which the author terms electro-capillary viscosity, is explained by the supposition of the accumulation at the mercurial surface of the ' active ' anions, the slow establishment of equibrium being due to the slight concentration of these in comparison with the other ions. L. M. J. Measurement of the Velocity of Gaseous Evolutions.Appli-, oation to the Voltameter. By ANDRI~ JOB (Bull. Xoc. Chim., 1901, [ iii 1, 25, 7-9).-1f a gas is allowed to escape through a long capillary tube from the vessel in which it is being evolved, the excess of the pressure of the gas in the vessel over that of the external air is a measure of the rate of evolution of the gas a t any instant. Use may be made of this principle in the continuous study of processes of fermentation, of the dissolution of metals in acids, and of other reactions in which gases are evolved j the method has been recently employed by Ostwald (this vol,, ii, 24) and Bredig and Hahn (Zeit. Elektrochem., 1900, '7, 254) for such purposes. A voltameter, when provided with a water manometer and a capillary exit tube, becomes virtually an amperemeter, the excess of pressure being proportiona 1 t o the rate of evolution of gas, and hence also to the intensity of the current, at any instant, N.L. Magnetism and Atomic Weight. By LEO ERRERA (Bull, Roy. Acad. Belg., 1900, 152--161).-The author reviews critically the work of Konigsberger (Ann. Phys. Chem., 189S, [ii], 66, 698) and Meyer (Abstr., 1899, ii, 587; 1900, ii, 7). It is simpler to connect the magnetism of the elements directly with their atomic weight, rather than with their atomic volume, and a table is drawn UF showing the connection referred to, J. C. P. 7-284 ABSTRACTS OF CHEMICAL PAPERS. Thermal and Electrical Conductivity, Thermal Capacity, and Thermo-electric Efficiency of some Metals. By WILHELM JAEGER and H.DIESSELHORST ( Wiss. Abh. phys.-tech. Reichsanstalt, 1900, 3, 269--424).-The chief result of this exhaustive investigation is the confirmation of the law of Wiedemann and Franz for copper, silver, g$d, nickel, zinc, cadmium, lead, and tin. For these metals, the ratio A/K, where X is the thermal and K the electrical con- ductivity, is, as required by the law, constant, although considerable deviations are found in some cases. The law of Lorenz is also ap- plicable, according to which the above ratio is proportional to tho absolute temperature. The exceptionally high value of the ratio in the case of iron is attributed to impurity (compare Gruneisen, Ann. Phys., 1900, [iv], 3,43). This is borne out by the investigation of alloys, for when a metal B is added to a metal A , the ratio A/K for the alloy is greater than for the pure metal A.Platinum and palladium are peculiar in giving an exceptionally large value both for the ratio X/K and its temperature coefficient, Aluminium shows a low value of the ratio A/K, but a large temperature coefficient, whilst the opposite holds for bismuth. J. C. P. Thermal and Electrical Conductivity of Copper-Phosphorus and Copper-Arsenic. By A. RIETZSCH (Ann. Phys., 1900, [iv], 3, 403--427).--Ry the introduction of small quantities of phosphorus and arsenic, the thermal conductivity (A) of copper is diminished more than is its electrical conductivity ( K ) . Thus if for pure copper both X and R a r e put = 100, then for an alloy containing 0.87 per cent. of phos- phorus A = 16, K = 20.6, and for one with 5.25 per cent.of phosphorus, X=4, K=5*6. Similar series of numbers are obtained for copper- arsenic. The influence of non-metals on the conductivities (thermal and electrical) of metals is opposite to that of other metals (compare preceding abstract). J. C. P. Molecular Specific Heats of Dissociable Gaseous Compounds. By A. PONSOT (Compt. Tend., 1900, 131, 990--992).-A mathematical paper, in which the author deduces that at extreme limits of rarefac- tion the molecular specific heat of a gaseous compound is less than that of the mixture of its dissociation products, whether at constant pressure or constant volume ; in the latter case, the diEerence may be regarded as approximately zero. Air Thermometer at High Temperatures. By LUDWIG HOLBORN and ARTHUR DAY (Ann.Phys., 1900, [ iv], 2,505--545).-The authors have studied the conditions which must be observed if a gas thermometer is t o be used with confidence a t high temperatures. The reservoir should be of platinum-iridium, and nitrogen should be used as the expanding gas. With this standard gas thermometer, they have compared a platinum-platinum rhodium thermo-couple, the E.M.F. of which, for the temperature interval of the experiments, 300-1150°, is given by an equation of the second degree. This thermo-couple was further used to determine the melting points of several metals by one of two methods. Either a short wire of the metal under observation was introduced into the junction of the thermo- L. M. J.GENERAL AND PHYSICAL CHEMISTRY. 85 couple, and the E.M.F.nited at the time of its fusion, or a larger quantity was put in a crucible, and the thermo-element, protected by a porcelain tube, immersed in the fused metal. The following melting points were determined : Gold (wire method) ............ Silver (wire method) . . . .. . . . . Silver (crucible, air admitted) Silver (crucible, air excluded) Copper (oxidising atmosphere) Copper (reducing atmosphere) 1064*0° Antimony (crucible) . . . 630.5' 953.6 Aluminium (crucible) .. 657.3 954.9 Zinc (crucible) ... . . . . . . 419.0 961.5 Lead (crucible) . , , . . . . . . 326.9 1065.0 Cadmium (crucible) . , . 321.7 1084*0 The authors consider that up to 1150O the correct temperature can be determined to within 1' with the use of a thermo-couple. The melting points of the metals, as above determined, are compared with the values obtained by Heycock and Neville (Trans., 1895, 67, 160, 1024), and Callendar (Phil.Mag., 1899, [v], 48, 519). By LUDWIG HOLBORN and ARTHUR DAY (Ann, Pl~ps., 1901, [iv], 4, 99--103).-The melting point of gold as de- termined by the crucible method (see preceding abstract) is 1063.5'. The valueobtained by the wire method for the same sample is 1063.9'. The authors think that in standardising thermo-couples the wire method may advantageously be used for determining the melting point of gold. J. C. P. Change of Temperature attending the Solidification of Melted Organic Substances. By BRONISLAW PAWLEWSKI (Re?., 1900, 33, 3727--3731).-The substance (5 grams) was placed In a test- tube so as t o surround the bulb of a thermometer; this tube was placed in a wider one.The temperature was then raised, by means of a gas burner, to 20-40' above the melting point of the substance, the apparatus allowed to cool, and the temperature read every 20 seconds and plotted against the time. Three types of curves were ob- tained; in the first, the temperature falls rapidly, then remains con- stant for a time, and finally falls again ; in the second, i t falls rapidly, then more slowly for a time, and 6nally more rapidly again; in the third, it falls rapidly, the substance becoming overcooled (in one case by as much as 40°), then rises rapidly as the substance solidifies, keeps constant for a time, and finally falls once more. The interval of con- stant temperature, or that where the fall is slow, is in all cases below the melting point observed in a capillary tube.To the first type belong p-dichlorobenzene, p-dibromobenzene, p-chloronitrobenzene, p-nitrophenol, p-toluidine, o-dichloroxylene, m-nitroaniline, triphenylmethnne, diphenyl, naphthalene, acenaph thene, stearic acid, phenglacetic acid, catechol, benzamide, methyl oxalate, azobenzene, formanisidine, acetanilide, diphenylamine, ,&naphthol, P-naphthylamine, &c. To the second, camphoroxime, benzylaniline, guaiacol, anisic acid. To the third, benzil, benzoin, benzylideneacetone, chloroacetic acid, m-nitrochlorobenzene, chloral hydrate, p-chloroaniline, ptoluonitrile, a-naphthylamine, vanillin, coumarin, phenol, phthalide, f ormanilide, resorciaol, acetyldiphen y lamine, &c, J.C. P. Melting Point of Gold. C. F. B.86 ABSTRACTS OF CHEMICAL PAPERS, Cryoscopic Researches. By PAUL CHRUSTCHOFF (Compt. rend., 1900, 131, 883-886).--In view of many discrepancies in cryoscopic observations, a new method was employed in which the temperatures were taken by a Callender and Griffiths' thermometer, the position along the wire of the Wheatstone bridge being read by a micrometer eyepiece ; a displacement of 0.2 mm. along the wire indicated a differ- ence of temperature of 0.001". The usual precautions regarding stir- ring, &c., were observed, and the observed depressions are given in scale readings, not in degrees, the rates of these depressions to con- centration being recorded. It is found that this ratio remains con- stant on dilution for sodium chloride, decreases for potassium bromide, and increases for sucrose and for potassium sulphate.By PAUL JULIU~BURGER (Ann. Phys., 1900, [iv], 3, 618-659).-The law is expressed in the equation l o g 2 = A - B/T- Clog. T, and the author finds that the various ways of deducing it are all equally valid. Theoretically, the law holds strictly only when the tension is small, but practically i t is applicable over a wide range, for some substances even up to the critical temperature. The formula may also be used in cases where P is the dissociation pressure OF a system. Vapour Tension of Water at Temperatures between -12' and 2 5 O , especially at 0'. By Max THIESEN and XARL SCHEEL (TViw. Abh. phys.-tech. Reichsunstalt, 1900, 3, 71--94).-The mean value of the vapour tonsion of water a t 0", as determined in a number of very careful measurements, is 4.575 mm.Experiments on Fractional Distillation. By SYDNEY YOUNU (J. Soc. Cliern. Ifid., 1900, 19, 1072--1075).-The rate at which a mixture is distilled largely influences the extent of the separation effected; for efficiency, the number of drops per minute should not exceed 60, and good oontact should be ensured between the ascending vnpour and the condensed liquid (compare Trans., 1899, 75, 679). The value of plotting curves between the weight of each fraction and its temparature range as a means of recognising the boiling point of the ingredients of a mixture, is discussed with reference to a former paper (Thomas aud Young, PPOC., 1895, 172) ; the isolation of hexamethylene from American petroleum is also dealt with (compare Fortey, Trans., 1898, '73, 932).A method is described for ascertaining approximately, without completely separating them, the proportion of the constituents of a liquid mixture, for instance, one containing 31.7 per cent. of methyl acetate, 3802 of ethyl acetate, and 30.1 of propyl acetate ; the boiling points of the esters are 57.1", 77*15', and 101*55", and the two middle points 67.1' and 89.35'. It is found that after a few fractionations the percentage of the mixture boiling below 67.1' remains constant (305 per cent.), and represents the proportion of methyl acetate ; the propor- tion boiling below 89.35' is also constant, namely 69.3 per cent., and 69*3 - 30.5 or 38.8 represents the proportion of ethyl acetate present, whence by difference the amount of propyl acetate is 30.7 per cent, This method is shown to hold for other homologyes (for instance, L.M. J. Dupr6-Rankine Vapour Tension Law. J. C. P. J. C. P.GENERAL AND PHYSICAL CHEMISTRY. 87 beneene and toluene, mixed in the proportions 1 : 9 and 9 : l), but additional experiments will be necessary to ascertain whether it is available for substances which are not homologous. It is essential that the rate of distillation should remain nearly constant. W. A. D. Distillation in a Vacuum with Hempel’s Dephlegmator. By WILHELM HIRBCHEL (Chem. Centr., 1900, ii, 1193-1194 ; from Oester?’. Chem. Zeit., 3, 517).-When Hempel’s dephlegmator is used for the distillation of liquids in a vacuum, the usual tendency of the liquid to accumulate in the glass beads instead of running back into the flask becomes so marked that satisfactory distillation is often impossible.This disadvantage may be avoided by inserting a platinum spiral in the wider tube and of the same diameter in such a way that the glass beads are raised and do not rest directly on the constricted portion ; the lower tube also requires to be at least 15 mm. in diameter and is fused on to the neck of the distilling flask. E. w. w. Determination of Vapour Density under Reduced Pressure, By CARL SCHALL (J. pr. Chem., 1900, [ii], 82, 536-542. Compare Bleier and Kohn, Abstr,, 1899, ii, 643).-This paper contains the discussion of a formula for the calculation of K, a constant of the apparatus employed by the author for the determination of vapour density under diminished pressure (Abstr., 1889, 331).By BENEDIKT WORINGER (Zeit. physikal. Chem., 1900, 35, 723-724).- A reply to Winkelmann’s criticism (this vol., ii, 57) of the author’s previous work (Abstr., 1900, ii, 709). Exact Relation between Osmotic Pressure and Vapour Pressure. By ARTHUR A. NOYES (Zeit. physikcd. Chem., 1900, 35, 707-721. Compare Abstr., 1897, ii, 395; 1899, ii, 357).-The exact thermodynamical relation between the osmotia pressure P, and the vapour pressure p , of a solution, is given by the equatiou p O ~ . d p = (P, +po - pl)V,[ 1 +‘$(PI f p , - p J ] where p,, V,, k,, are respectively the vapour pressure, the specific volume, and the coefficient of compressibility of the liquid solvent. The only supposition made in the deduction of this equation is that k, is constant between the pressures p , and p , - P,.Seeing that the latter pressure is generally negative, the value of k, has to be got by extrapolation, a process which is justified especially by the work of Worthington (PhiZ. Trans., 1893,183, 355). From the above equation, i t follows that to calculate the osmotic pressure from the vapour pressure integral, the latter should be divided by the ordinary specific volume of the solvent, and not, as is usually done, by the volume change of the solution. In the course of the paper, the author replies to the criticism of Dieterici (Abstr., 1899, ii, 547). By ALEXANDER A. JAKOV~IN (J. Buss. Phys. Chem. Xoc., 1900, 32, 721--727),-From E. G. Vapour Pressure of a Series of Benzene Compounds. J.C. P. /PI J. C. P. Osmotic Pressure of Complex Solutions.88 ABSTRACTS OF CHEMICAL PAPERS. theoretical considerations, the author arrives a t the following expres- sion, which relates to the osmotic pressure of a solution of a sub- stance in a mixture of two solvents : (Po/P)"= ( ~ ~ / p ) ~ , where p represents the partial pressure of one of the solvents for the solution, determined in a Pfeffer's cell, p o its partial pressure for the complex solvent, and m the molecular weight of the solvent in the gaseous state ; P, Po, and M represent the corresponding magnitudes for the second solvent. The above expression simplifies to : PO/pOk = P/pk, where A stands for the ratio of the molecular weights of the two liquids, M : m.T. H. P. Theory of the Capillary Layer between the Homogeneous Phases of Liquid and Vapour. By G. BAKKER (Zeit. physil%ccl. Chem., 1900, 35, 598--603).-A mathematical paper, unsuitable for abstraction. J. C. P. Dissociation of Antimony Pentachloride. By MARCEL NOTHOMB (Bull. Roy. Acad. Belg., 1900,551-558).-The normal vapour density of antimony pentachloride is 10.35, but in the interval 180-360°, the value obtained by Victor Meyer's method, gradually falls from 7.58 to 5 34. The application of Planck's law to this case leads to the equation c:/c, =a.e e.6/p, where c1 and cq are the con- centrations of the undissociated molecules and the products of dissocia- tion respectively, 8 is the absolute temperature, p is the pressure in mm. of mercury, a and b are constants.The values calculated for the dissociation by this equation agree closely with those actually obtained. By WILDER D. BANCROFT (J. Physical Chem., 1900, 4, 705--708).-Abnormal reaction velocities have been explained by the assumption that the reaction proceeds in two or more stages, on one only of which depends the experimentally found velocity. Inasmuch as this has not hitherto been found in the case of a reversible reaction, it is sometimes assumed that irreversi- bility is a necessary condition for the production of these abnormal velocities. Suppose, however, a reversible reaction is represented by the equation 2A + B = A,B ; the equilibrium equation is then x = A(A - ~ ) ~ ( 6 - z). If, however, the reaction proceeds in two stages A + B = A B ; A B + A - A,B, then the final equilibrium is given by x = k(m- x - ~ ! , ) ~ .( b - x - y), and since the intermediate product is finally of concentration practically zero, this reduces t o the first expression, so that the equilibrium result would lead to an equation of the third order, although the reaction velocity might be of the second order, and abnormal velocities may occur in reversible reactions. The author hence protests against the practice of deducing equilibrium relations from reaction velocities instead of solely from the stochiometric rela- tions. L. M. J, Velocity of Intramolecular Migration of BromoamideB under the Influence of an Alkali. By W. VAN DAM and J. H. ABERSON (Rec. Traw. Pays. Bat?., 1900, 10, 318-331).-The trans- formation of browoamides under the influence of potassium hydroxide b - J.C. P. Reaction Velocity and Equilibrium.GENERAL AND PIIYSIC'AL CHEMISTRY. 89 has been previously found to be a reaction of the first order (van Dam, Abstr., 1900, i, 1'71). This indicates that the transformation is really an intramolecular change and not a reaction between two molecules. The effect of concentration of alkali was investigated, and i t was found that for concentrations above N/2 the curve for velocity con- stant against concentration was a straight line. For lower concentra- tions, however, the velocity constant increases during the progress of the reaction, and i t was found that a different reaction also proceeds by which benzoylphenylcarbamide is produced. The action of primary and secondary amines was also investigated; these were found to occasion condensation without the formation of aniline, but values for a reaction velocity constant were not obtained.The effect of tem- perature between 16O and 33O was found to be in accord with Arrhenius' formula, logill/,%,= A.(5!\ - T2)/Tl.T2, the value for A being 14.48. The velocity constants for ,374 potassium, sodium, and lithium hydroxides are in the ratio 175 : 166 158, the conductivities of the same solutions being in the ratio 175 : 154 : 140; on the same scale, the values for barium and strontium hydroxides are 169 and 169, but lack of data prevent the comparison with conductivity. L. M. J. Inversion of Cane Sugar. By EDMUND 0. VON LIPPMANN (Bey. , 1901, 33, 3560--3564).-A criticism of the theories of Arrhenius (Abstr., 1889, 1103 ; 1899, ii, 359), Rothmund (ibid., 1896, ii, 593), Sigmund (ibid., 1899, ii, 146), and Euler (ibid., 1900, ii, 269). A.L. Theory of Solutions. By GUSTAV JAUMANN (Ann. Phys., 1900, [iv], 3, 578-617),-? object of the paper is to make the theory of solutions independent of Arrhenius' ionic hypothesis, and to connect i t with the Faraday-Maxwell theory. The author attacks the basis of the molecular theory, and regards Avogadro's hypothesis as unnatural the new basis suggested in the paper involves the introduction o simpler chemical formult~ than are used a t present. Solvent Action of Vapours. By AZARIAH T. LINCOLN (J. Physical Chew., 1900, 4, 715-731).-The author discusses the question of a solvent action of vapour, and considers i t probable that such solvent action exists.The vapour pressure curves for benzoic and salicylic acids were determined between 80' and 190°, and i t was found that the acids were present in the vapours passing from saturated solutions boiling a t various pressures. No conclusive results concerning a solvent action of the vapour were obtained, however, inasmuch as the quantities of acid present in the vapour were no greater than those corresponding with the vapour pressure of the solid at the temperature of ebullition. To obtain decisive results, experiments at a considerably higher temperature and pressure are necessary, L. M. J. Dilute Solutions, By N. TARUGI and GTUSEPPE BOJIBARDINI (Gazzetta, 1900, 30, ii, 405-420).-The degree of dissociation of a number of aqueous salt solutions of various strengths has been deter- mined, (1) from the depression of the freezing point, (2) from the J.C. P.90 ABSTRACTS OF CHEMICAL PAPERS. lowering of the vapour pressure, and (3) from the electrical conductivity of the solutions. The salts examined were cobalt ohloride, ferrous sulphate, and the sulphates of cobalt, nickel, manganese, aluminium, copper, cadmium, sodium, and zinc, The results obtained by the first two methods agree fairly well among themselves, but in some cases differ considerably from those yielded by the third method. The experiments show that nickel, cobalt, and manganese salts can exist completely undissociated in solutions coloured respectively green, red, and pink. T. H. P. Size of the Particles present in Colloidal Solutions or pseudo-Solutions.By C. A. LORRY DE BRUYN (Rec, Trav. C h k , 1900, 19, 251--258).-According to the laws of optics, the smallest particles capable of polarising the light reflected from them are 50-100 times smaller than the wave-length of light. Assuming a mean wave-length of 0.5 p, the diameter of such particles is therefore 5-10 pp. The value deduced in this way from purely physical con- siderations is in agreement with that calculated from chemical data. Thus, Brown and Millar’s researches on starch hydrolysis (Trans., lS99, ’75, 331) have led them to assign to soluble starch a molecular weight of about 32,500, and an almost identical result has been arrived a t by Rodewald and Kattein (Abstr., 1900, i, 477) from a study of starch iodide.Since van der Waals estimates the diameter of ordinary gaseous molecules as 0.1-0.3 pp, and Jager assigns the value 0.66 pp to the chlorine molecule, it follows, assuming that the specific volumes of the molecules are approximately equal, that the starch molecule has a diameter of about 5 pp, as before. The author comments on the work of previous investigators, and emphasises his opinion that there is no real distinction between true solutions and pseudo- or colloidal solutions. There is no criterion of the homogeneity or heterogeneity of a liquid, and it is possible t o pass continuously from undoubted solutions to liquids containing Method of obtaining Crystals in a Solution without Forma- tion of Superficial Crust. By AUGUSTTN WR~BLEWSKI (Bull. Acad. Xci. Cracow, 1900, 319-325 ; Zed. plqsikal.ClLesn., 1901,36, 84-86). -The tube with the solution is closed at the bottom by a membrane of vegetable parchment, and fits tightly in the neck of a surrounding larger bottle, containing pieces of calcium chloride. As the solution is shut off from the air by a Uptube containing water, evaporation takes place only through the parchment, and crystals are formed in the solu- tion when i t has become sufficiently concentrated. The method has been successfully applied in the crystallisation of ammonium sulphate and other inorganic compounds, also in the preparation of diastase (compare the author’s previous work, Abstr., 1898, i, 500, 713); in this way, crystals of albumipous substances can be obtained in a purer state than by Hoffmeister’s method.Ciystallisation of difficultly Crystallisable Substances. By A. RUMPLER (Bw., 1900, 33, 3474--3475).-Substances which are soluble in water but insoluble in alcobol can be obtained crystalhe obvious particles in suspension, N. L, J. C. P.GENERAL AND PHYSICAL CHEBIIS!TRY, 91 by adding alcohol to the aqueous solution until a turbidity appears, filtering, and evaporating slowly in a vacuum over quicklime. By this method, the author has obtained crystals of peptone (prepared from gelatin or from albumin) and of arabic acid from gum arabic. W. A. D. Lecture Experiments Illustrating the Electrolytic Dissocia- tion Theory and the Laws of the Velocity and Equilibrium of Chemical Change. By ARTHUR A. NOYES and A. A. BLANCEIARD (J. Amer. Chem SOC., 1900, 22, 726-752 ; Zeit.physikal. Chem., 1901, 36, 1-27).-Full descriptions are given of seventeen experiments, for the details of which reference must be made to the original. That colour is an additive property in salt solutions is shown by adding water to alcoholic solutions of copper and cobalt salts. The different rates of double decompositions in inorganic and organic *systems are illustrated by the action of silver nitrate on potassium bromide, isopropyl bromide, ethyl bromide, and bromobenzene, all in alcoholic solution. Experiments are described showing the nature of the ions in salt solutions, and their rates of migration during the passage of a current, Simple apparatus serves to show the increase of mole- cular conductivity with dilution, as well as the different moliicular conductivities of equivalent solutions of hydrochloric, sulphuric, mono- chloroacetic, and acetic acids. The reaction between potassium iodide and bromate (Abstr., 1896, ii, 470) is used to illustrate the influence of the concentrations of the reacting substances, and the catcllytic efficiency of different acids ; that the dissociation and consequently the catalytic efficiency of a weak acid is diminished by the addition of a neutral salt may be shown by the same reaction. The influenoe exerted by strong acids on the dis- sociation of weak acids is illustrated by several experiments with indi- oators. When to a saturated solution of a salt A a salt B with a common ion is added, the salt A is partly thrown out of solution ; this principle is illustrated by adding either sodium acetate or silver nitrate to a saturated solution of silver acetate. By P. N. RAIKOW (Chem. Zeit., 1900, 24, 1089--1090).-These funnels are essentially constructed as follows. The top of the stem enters the bulb and repre- sents the outer casing of a stopcock. This has an opening of about 3-4 mm. diameter which is placed so low that the liquid may run rsmpletely out of the bulb. To this outer casing is fitted a tube, the upper part of which forms the stopper of the funnel, whilst the lower part forms the tap of the stopcock. The tap has an opening corre- spanding with the one in the outer casing so that communication may be established at will. There is also a communication between an opening in the neck of the funnel and a channel in the tube which admits the outer air when the funnel is being used. The liquid is introduced through a special opening fitted with a stopper. Illustrations are given of two kinds of separating funnels which do not greatly differ from each other. The advantage of these funnels is the prevention of loss of liquid by evaporation or leakage through the J. C. P. New Dropping and Separating Funnels. stopcock. L. DE K,

ISSN:0368-1769    

DOI:10.1039/CA9018005081

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

92 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Volume of Hydrogen Evolved by the Action of Acids on Granite. A Correction. By ARMAND GAUTIER (Compt. rend., 1900, 131, 1276. Compare Abstr., 1901, ii, 14).-The author corrects his previous statement that 915 C.C. of hydrogen are evolved from 1 kilogram of granite on treatment with acids. The actual volume evolved is much less than this. The higher value was obtained with granite which contained some metallic iron which had been introduced during the pulverisation of the mineral. Molecular Constitution of Water. Ey WILLIAM SUTHERLAND (Pld. Mag., [v], 50, 460--489).-Assuming the correctness of Mendel- 6ef's expansion formula cl, = d,(l - at), the density curve is a straight line ; the density curve for water, however, has a maximum at 4", but at high temperatures appears t o be asymptotic t o the straight line for which a =0.001.It is hence considered that this line represents the expansion of one of the ingredients of water, which i t is found by ex- trapolation has a t 0' a density = 1,083. Ice probably consists of the other pure constituent, and from analogy with the increase of volume of other solids on fusion, the author calculates that this, when liquid, should have a density of about 0.88. Water a t 0' is a mixture of these two, and, assuming no shrinkage occurs, the proportion of the lighterconstituentis 0.375. Thesetwoconstituentsare regarded as (H20)2 ' dihydrol,' and (H20)3 ' trihydrol,' and, by the aid of empirical formuh, the quantities of ' dihydrol ' in water a t temperatures from Oo to ZOOo are deduced.It is shown that these values reproduce fairly satisfactorily the variation of the index of refraction of water with temperature, the values for (p2 - 1)/(p2 + 2\12, being 0.20968 for ' trihydrol ' and 0.20434 for ' dihydrol.' The compressibility of water and the dissociation of ' tri- hydrol ' into ' dihydrol ' by pressure are considered. From the values deduced for the dissociation, it appears that, a t about 2300 atmospheres pressure, the ' trihydrol ' would be completely dissociated at 0' ; this is in accord with the observed fact that a t pressures below 3000 at- mospheres the anomalies in the expansion curve of water disappear. The surface tension in thin films is, however, sufficient to convert almost the whole of the ' dihydrol ' into ' trihydrol ' for temperatures below about 60°, and the exceptional properties of solutions in regard to surface tension are probably due to t h i s difference in constitution between the film and the body of water.The latent heat of fusion of ice is largely the heat of dissociation of 'trihydrol' and the high specific heat of water is also due t o this factor. Steam consists solely of H,O, ' hydrol,' and the latent heat of evaporation hence includes the heat of dissociation of ' dihydrol.' The author calculates the thermal values of these dissociation changes, the values obtained being represented by the equations 2H,O = (H20)2 + 189 x 2 x 18 cals.; and 3(H20), = 2(H20), + 177 x 6 x 18 cals. The decrease of viscosity of water with pressure is ascribable to the lower viscosity of ' dihydrol,' whilst the anomalous viscosity of many solutions is due to the effect of the solute in increasing the dissociation of ' trihydrol.' These various molecular states H.R. LE S.INORGAKIC CHEMISTRY. 93 of water are considered from the point of view of the quadrivalency of oxygen and the actual molecular constitutions are discussed. A sum- mary of the various physical constants for ' dihydrol ' and ' trihydrol ' Apparatus for the Evolution of Dry Hydrogen Chloride. By A. GWIGGNER (Zeit. angew. Chem., 1900, 1308--1309).-The apparatus consists of a 10 em. wide cylindrical generating vessel, the bottom of which is drawn out to a tube 15 mm. wide and 12 em. long ; this cylinder fits by a ground joint into a waste acid vessel, t o the bottom of which is sealed a 25 mm.wide beaker, into which the tube passes to a depth of 10 cm. The waste acid vessel has a sid3 opening to carry off the excess of hydrogen chloride which is trapped into a wash bottle containing water. The top of the cylinder, which is 7 cm. wide, is fitted with a ground, tubulated bulb through which passes a pear- shaped separating funnel, and also a side tube fitted with a stopcock as an outlet for the gas; the stem of the funnel is drawn out to a tube 2 mm. wide and slightly bent sideways. The funnel, which holds about 200 c.c., is filled with strong sulphuric acid. The conical part of the generating cylinder is filled with pieces of glass tubing, on which are placed large lumps of ammonium chloride.By allowing the acid to drop on the lumps and turning the funnel round occasionally, hydrogen chloride is evolved and escapes through the side tube a t the top, whilst the solution of the ammonium sulphate runs into the beaker and in tbe waste acid vessel. is given at the end of the paper. L. M. J, L. DE K. Autoxidation : Supplementary Note. By FRITZ HABER (Zeit. physihl. Chem., 1900, 36, 608-609. Compare Abstr., 1900, ii, 720). -An acknowledgment that the catalytic influence of benzoic acid on the action of hydrogen peroxide had already been noticed by Engler and Weissberg (Abstr., 1900, i, 399). SchSnbein's example of oxidation, Pb + 0, + H,SO, = PbSO, + H20,, is resolved by the author into P b + 0, + 2H' = Pb' ' + H,O,, by an application of the ionic theory to his fundamental conception, the latter being interpreted by the equation : M + 0, + H,O = MO + H,02.By WIL- HELM MANCHOT (Annulen, 1900, 314, 177-199. Compare Manchot and Herzog, Abstr., 1'300, ii, 546).-With the object of throwing light on the rendering active of oxygen, the author has studied the oxida- tion of certain phenols in air. The hydroxy-derivatives of the higher hydrocarbons, which are easily converted iuto stable products, can be studied with ease, and it is found that hydrogen peroxide is always present at the close of the operation. I n the case of the hydroxy- benzenes, a more complicated series of actions takes place. Alkaline quinol, for instance, is converted into quinone and quinhydrone, all three substances absorbing oxygen and producing hydrogen peroxide, which can then act on the materials mentioned.The investigation has been extended to hydrazobenzene, hydrazotriazole, and hydrazo- methyltriazole, which, when agitated with barium hydroxide in air, give rise t o barium peroxide. J. C. P. The Rendering Active (" Activirung ' I ) of Oxygen.94 ABSTRACTS OF CITEMICAL PAPERS. For experimental details and the author's theoretical considerations, reference must be made to the original paper. M. 0. F. Action of Hydrogen Peroxide on Thioaulphates. By ARNOLD NABL (Bey., 1901, 33, 3554--3555).-The author withdraws his pre- vious statement as t o this action (compare this vol., ii, 16). The alkaline reaction developed on adding hydrogen peroxide to a solution of sodium thiosulphate, is due t o liberation of sodium hydroxide in ac- cordance with the equation 2Na2S,0, + H,02 = Na2S,0, + 2NaOH, and the green fluorescence in the liquid is probably due t o a compound of the litmus with barium tetrathionate.By Q. PELLINI and ALFREDO MENIN (Gaxxetta, 1900, 30, ii, 465-475).-The refractive powers of the following compounds have been measured for the line Ha : (1) tellurium tetrachloride (in benzene) ; (2) tellurium tetra- bromide (in ether) ; (3) potassium tellurite (in water); (4) telluric acid (in water) ; and (5) telluriumdiphenyl. Calculation of the atomic re- fraction of tellurium from these results gives the following mean numbers. According to the Gladstone formula : (1) 32.53, (2) 33.82, (3) 26.10, (4) 24.65, (5) 32.07 ; for the Lorenz-Lorentz formula: (1) 15.28, (2) 16.66, (3) 17.25, (4) 14.08, (5) 15.52.Thus, for t$e Glad- stone formula, the atomic refraction of tellurium is less in the oxygen- ated compounds than in the organic and haloid derivatives, a relation which holds also for sulphur and selenium. The difference between the specific refractions of telluric and sulphuric acids (15.57) is almost identical with the difference between those of telluriumdiphenyl and sulphurdiphenyl (15.01). The dispersion of telluriumdiphenyl is high, as is shown by the following numbers : (pxp) - pHa/d =I 0.02226 and (p& - l)/(pLu - 1) = 1.0778. Hydrogen Telluride. By EDMUND ERNYEI (Zeit. anorg. Chem., 1900, 25, 313--317).-Hydrogen telluride mixed with 5-6 per cent. of hydrogen is obtained when telliiriuni as the negative pole is subjected to a current of 220 volts in an electrolyte of 50 per cent.sulphuric acid. It is essential that the electrolyte should be cooled to - 15' or - 20'' that organic substances and a i r should be excluded, and that the mixed gases should be dried at once with c:iIcium chloride and phosphoric oxide. The hydrogen telluride separates in lemon-yellow needles melting at -54' when the mixture of gases is cooled with solid carbon dioxide. It is a colourless, poisonous gas, decomposes immediately in contact withair, or even in a sealed tube, and in two days when kept in a mixture of ice and salt. It burns with a bright blue flame, is somewhat soluble in water, and with potassium and sodium hydroxides yields colourless tellurides which become red and decompose on exposure to the air.It reduces ferric t o ferrous chloride and mercuric to mercurous chloride, and decolorises iodine and bromine solutions. The vapour density, determined by Dumas' method, was found to be 65.1 (H = 1) or 4.49 (air = 1) agreeing with the formula TeI-I,. Combustion of Nitrogen. By ROBERTO SALVADORI (Gaxxetta, 1900, 30, ii, 389--404).-1n order t o obtain the non-absorbable A. L. Refractive Power of Tellurium in its Compounds. T. H. P. E. C. R.IHORGANIC CIIENISTRT;. 95 portion of gas emanating from the earth, the author burns the gas in oxygen in a special apparatus which admits of the products of com- bustion being absorbed and the residue collected. The combustion takes place in the bulb of an inverted retort, into which the gas is led by a tube which is surrounded by a wider tube for the admission of the oxygen; the products of combustion pass along the neck of the retort into an adapter and thence into the absorbing bulbs, &c.By this means, the whole of the combustible portion of the gas is readily removed, but it is found that when a large excess of oxygen is used, a part of the nitrogen also undergoes combustion. With the same apparatus, a series of experiments has been carried out on the com- bustion of hydrogen in various mixtures of nitrogen and oxygen, with special reference to the amount of nitrogen consumed and the quantities of ammonia and of nitrous and nitric acids produced. One of the experiments, chosen at random from the table given, had the following results : between 60 and 70 litres of hydrogen were burnt in 80 litres of a mixture containing 67.64 per cent. of oxygen and 32.36 per cent, of nitrogen, the total nitrogen transformed being 254.58 C.C.or 0,3182 gram. As the proportion of nitrogen to oxygen in the mixture is gradually increased, the quantity of nitrogen undergoing combustion rises to a maximum and then falls. Previous heating of the gases does not seem to have an appreciable effect on the proportion of nitrogen attacked, which is, however, increa3ed by in- creasing the capacity of the combustion chamber. *Using for the latter a flask of about 18 litres capacity, kept cool by means of water flowing over it and passing also a current of steam into the flask, 40 litres of hydrogen when burnt in 50 litres of a mixture containing 60 per cent.of oxygen and 40 per cent. of nitrogen, gave a yield of 456.12 C.C. of nitrogen entered into combination ; this represents the greatest amount of transformation obtained in the author's experi- ments. Berthelot's experiments (Abstr,, 1899, ii, 648 ; 1900, ii, 475, 476, 538) are referred to. 'l', H. P. Action of Alkali Hydroxides and Alkaline Earths on Arsenic Pentasulphide. By LE ROY TV. MCCAY (Zeit. anorr.9. Chern., 1900, 25, 459-467).-The author has repeated his work on the preparation of thioxyarsenic acids (Abstr., 1899, ii, 745) in con- sequence of a statement by Weinland and Lehmann (Chem. Zeit., 1889, 23, 865) that monothioxyarsenates are not formed. The results confirm those previously obtained, namely, that when arsenic penta- aulphide is dissolved in warm solutions of an alkali hydroxide, ammonia or calcium, strontium or barium hydroxides, monothioxy- arsenates and dithioxyarsenates are formed, of which the monothioxy- arsenate predominates.E. c. R. Density of Carbon Dioxide in the Solid and Liquid State. By U. BEHN (Ann. Phys., 1900, [iv], 3,733-'743).--By means of sus- pension in ether, the density of solid carbon dioxide at - 79" and under the pressure of 1 atmosphere is found t o be 1.53. The density of the liquid under the pressure of its saturated vapour between + 25" and -57" has been determined by a float method, allowance being madeOG AESTRACTS OF CHEMICAL PAPERS, for the contraction of the float a t the high pressures. The following are the values obtained : Temperature.Density. Temperature. Density. 24.3' 0.7202 - 14.7' 1.0051 22.4 0,7395 - 26.9 1.0626 19.7 0,7740 - 37.4 1.1054 16.4 0.8061 - 48.6 1.1503 9.s 0.8661 - 57.5 1 *l809 0-1 0.9265 The results obtained agree well with those of Amagat (Abstr., 1592, 934), so far as the range of temperature is the same. Electrolytic Preparation of Alkali Metals from fused Alkali Chlorides. By ARTHUR FISCHER (Zeit. EZektrochem., 1900, 7, 349-354).--The author's experiments were made with a mixture of potassium and sodium chlorides in molecular proportion, from which sodium containing about 1 per cent. of potassium is obtained by electrolysis. The anode was of carbon, the cathode of iron, and the cathodic current density 5 to 10 amperes per sq. cm., the salt being fused by the current itself.The chief source of loss of sodium was found in the circulation set up in the liquid by the evolution of chlorine at the anode. The flow of liquid thus produced carries globules of metal away from the cathode towards the anode, where it recombines with chlorine. After many unsuccessful attempts, this source of loss was almost entirely eliminated by interposing a partition, dipping a little below the surface of the bath, between the electrodes. The partition consisted of a water-cooled iron tube of rectangular section covered externally by plates of marble. J. C. P. T. E. Solubility of Alkali Chlorides and Chlorates. By F. WINTELER (Zeit. EZektrochem., 1900, 7, 360--362).-Tables are given of the solubility of (1) potassium chloride in solutions of potassium hydroxide, (2) sodium chloride in solutions of sodium hydroxide, (3) sodium chlorate in solutions of sodium chloride, and (4) potassium chlorate in solutions of potassium chloride, all at 20°.The specific gravities of the solutions are also included. Properties of Sodium Peroxide. By GEORGE F. JAUBERT (Compt. rend., 1901, 132, 35--36).-Sodium peroxide prepared by the action of oxygen on the metal is yellow and not white, and the colour deepens on heating. I t becomes very dark when heated to a high temperature in contact with silver, but the metal is attacked, Commercial samples of the peroxide which are white owe the absence of colour to the presence of a considerable proportion of the hydroxide and carbonate. Contrary to the usual statements, pure sodium peroxide does not deliquesce even after prolonged exposure to the air; it changes from yellow to white owing to its conversion into carbonate. If, however, the peroxide is Bxposed to air freed from carbon dioxide, the results are different and will be described subsequently.C. H. B T. E.INORGANIC CHEMISTRY. 97 Combination of Silver and Oxygen. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1300, 131, 1159-1 167).-Pure silver foil, when heated at 500-550' in sealed tubes containing dry oxygen, is disintegrated and partly converted into a yellowish-white powder giving the reactions of arg&ntous oxide, Ag,O, which seems to consist of a mixture of this compound with the finely divided metal. Comparable experiments made with dry air gave similar results, When moist oxygen or air is employed, the disintegration of the metal is more pronounced and the absorption of gas is greater.There is an appreciable action at 200', but no alteration of the metal is observed at 100'. No disintegration occurs when the metal is heated at 550' with nitrogen, steam, or carbon dioxide. Carbon Monoxide and Silver. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1900, 131, 1167-1169. Compare preceding abstract). -Pure silver foil, when heated for 4 hours at 500' in a sealed tube containing dry carbon monoxide, is found to have withdrawn a con- siderable amount of carbon from this oxide, whilst an analysis of the gaseous residue indicates a diminution in the volume of gas and a production of 3.6 per cent. of carbon dioxide. This reaction begins even at 300°, but at this temperature its progress is very slow.Carbon monoxide, when heated at temperatures not exceeding 550°, yields carbon dioxide without depositing carbon ; it is therefore probable that the deposition of carbon in the foregoing experiment results from the decomposition of a silver carbonyl compound analogous to the corre- sponding iron derivative. Hydrogen and Silver. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1900, 131, 1 169-1 170. Compare preceding abstracts).-Silver, when heated for 5 hours a t 500-550' in sealed tubes containing hydro- gen, shows signs of disintegration, which are, however, less pronounced than when produced by heating the metal in oxygen or carbon monoxide. The metal is permeable by gases at a red heat, for on heating a silver crucible containing sodium hydrogen carbonate over a gas flame at a temperature below the fusing point of sodium carbonate, it is found that, after 20 to 30 operations, the crucible has become charged with sodium and is very brittle.The presence of the alkali metal in the substance of the crucible is due to the reduction of the carbonate by the gases, particularly hydrogen and carbon monoxide, arising from the gas flame. By JOHANN SCHURGER (Zeit. anoi-g. Chem., 1900,25,425-429). -Calcium amalgam, CaHg5, obtained by heating a mixture of calcium with mercury in an atmosphere of carbon dioxide at 200 -230', crystallises in rhomhic prisms or needles. It is a reducing agent, is unaltered a t the ordinary temperature by dry hydrogen, nitro- gen, or nitrous oxide, and oxidises slowly in dry air but very quickly in moist air.When heated with dry ammonia a t the boiling point of mercury, it is converted into a mixture of calcium hydride and nitride, which decomposes violently in contact with water, with evolu- tion of hydrogen and ammonia. When heated with nitrous oxide, it is converted into calcium oxide without the formation of nitride or G. T. M. G . T. M. G. T. M. Calcium Amalgam. VOL LXXX. ii. 898 ABSTRACTS OF CHEMICAL PAPEIRS. nitrosyl calcium. phosphide and a yellow sublimate of mercury phosphide. When heated with phosphine, it; yields calcium E. C. R. Calcium Carbide and Silicon Carbide as Reducing Agents for Metallic Oxides, Salts, and Ores. By B. NEUMANN (Chem. Zeit., 1900, 24, 1013-1014). -Chlorides are most easily reduced by calcium carbide ; they must be quite dry, and are mixed with oxide, 80 that the reaction is M,O + 2MCl+ CaC, = 6M -+ CaCl, -+ 2CO [M 3 a metal]. Sodium chloride, or,*better, a mixture of sodium and potass- ium chlorides, may be added as a flux.Copper, lead, and nickel can be obtained in a button; some metals remain in small mattered globules, and others volatilise to a large extent. Sulphates, mixed with oxides, can be reduced according to the equation M,SO, + SM,O + CaC, = 6M + CaSO,+ 2CO ; in the absence of oxide, a sulphide is formed. Carbonates are reduced according to the equation M,CO, + 2M20 + CaC, = 6M + CaCO, + 2CO. Oxides and roasted ores can be reduced in many cases, not in others; the reaction is 3M20 + CaC, = CaO + 6M + 2CO. The reduction was effected in a clay crucible, which was heated in a gas furnace.The method is too expensive to find general applica- tion on the manufacturing scale; in the case of the rarer metals, where its cost is of less importance, the aluminium method is prefer- able, as it is neater, and requires no external heat, Carborundum (silicon carbide) also reduces metallic oxides ; sodium carbonate must be added as a flux. C. F. B. Reduction by means of Calcium Carbide. By FR. VON KUGELGEN (Chem. Zeit., 1900, 24, 1060-1061. Compare Neumann, preceding abstract).-When calcium carbide is heated with a chloride in the absence of an oxide, the reaction is 2MC1+ CaC, = 2M + CaCl, + 2C, and the reduced metal does not fuse to a single button. A mixture of chloride and oxide, or an oxide alone, is not reduced according to the equations given by Neumann; the reactions are really 4M,O + 2MCl+ CaC2 = l O M + CaCI, = 2C0, ; 5M,O + CaCz=.CaO + l O R l + 2CO,, the gas evolved being almost entirely carbon dioxide.C. F. B. Electrolysis of Calcium Chloride with Reference to the Formation of Chlorate. By SAMUEL A. TUCKER and HERBERT R. MOODY (J. Xoc. Chem. had., 1900, 19, 977--981).-The electrolysis of aqueous calcium chloride gives rise to a mixture of calcium chlorate and hypochlorite in proportions depending on the conditions ; details are given of a large number of experiments made to determine the conditions most favourable to the formation of chlorate, with a view to utilibing practically the waste calcium chloride of the ammonia soda process.The best concentration appears to be approxi- mately 20 per cent., with horizontal platinum electrodes separated by 10 cm. ; platinum is the only metal capable of withstanding the action. The electrodes should be of the same size, with a current density of 8 amperes per sq. decimetre; the best temperature is SOo. TheINORGAXJIC CHEMISTRY. 89 addition of sodium dichromate or hydroxide is advantageous under certain specified conditions. After the electrolysis has proceeded for about 14 hours, there is an appreciable drop in the efficiency, but this is not so great as to seriously interfere with the working value of the process, the efficiency after the 49th hour being about 76 per cent. Radioactive Substances. By FRITZ GIESEL (Bey., 1900, 33, 3569-3671.Compare this vol., ii, 19).-The mother liquor from the recrystallisation of 2 kilos. of radium-barium chloride, after removing the greater portion of the lead and practically the whole of the radium, yields a precipitate with ammonia which is strongly radio- active, the activity of the insoluble oxalates oE the rare earths subsequently obtained from the filtrate being quite small in comparison, The active precipitate, when dissolved in hydrochloric acid and subjected to the action of hydrogen sulphide, furnishes a sulphide which is yellow at first and then turns brown, the total product weighing 3 mg. and being as strongly radio-active as highly concentrated radium preparations. The rays emitted by the sulphide resemble those of polonium, readily undergoing absorption, and behaving similarly in the magnetic field.After one month, the preparation showed no diminution in radio-activity ; it does not contain bismuth, but yields an insoluble sulphate, probably the lead salt, which is, however, far less active than the product subsequently obtained by precipitation with ammonia; the residue left on evaporating the final filtrate is also decidedly active. The radio- activity of these active fractions does not equal that of the original sulphide. RGntgen rays and those emitted by radium are similar in their physiological action. About 0.2 gram of radium-barium chloride contained in a celluloid capsule, and applied for 2 hours to the inner side of the arm,. produced a slight irritation which after 3 weeks developed into acute inflammation followed by desquamation and recovery of the affected part.The leaves of plants, when submitted to the rays, lose their chlorophyll and fade ; paper when similarly treated becomes brown and friable. Plumbic Sulphate. By KARL ELBS and F. FISCHER (Zeit. Elektrociiem., 1900, 7, 343--347).-Plumbic sulphate is formed by electrolysis of sulphuric acid of sp. gr. 1.7 to 1.8 at temperatures not exceeding 30° with a current density at the anode of 0*02 to 0.06 amperes per sq. cm. The anode is of lead and should be immersed in a considerable volume of acid and separated from the cathode by a porous pot. The salt is partially deposited during the electrolysis in the form of a mud containing 60 to 85 per cent. of plumbic sulphate; a purer salt is afterwards deposited in indistinct crystals from the anode liquid.Plumbic sulphate has a faint greenish-yellow shade, 100 C.C. of concentrated sulphuric acid dissolve about 0.345 gram of it at 30'; it reacts with or is insoluble in all ordinary solvents. Water decomposes it at once into sulphuric acid and lead peroxide. Sul- phuric acid of sp. gr. less than 1*65 produces the same change more 8-2 W. A. D. G. T. M.100 ABSTRACTS OF CREMICAL PAPERS. or less quickly at the ordinary temperature. Concentrated hydro- chloric and acetic acids dissolve it, forming lead tetrachloride and tetracetate. As an oxidising agent, it resembles but is more energetic than lead peroxide. With cold concentrated sodium hydroxide solution, a plumbate is formed. Plumbic sulphate forms double salts with the sulphates of the alkali metals, ammonia, and the amines such as K2Pb(S04), and (NH4)2Pb(S04),.These are more stable than the single salt. They may be prepared by adding the finely powdered alkali sulphates to the solution of plumbic sulphate in concentrated sulphuric acid or by electrolysis (with lead anode) of sulphuric acid to which these salts have been added. The ammonium and potassium salts are yellow, indistinctly crystalline powders, almost insoluble in sulphuric acid of sp. gr. 1.7 ; toward reagents, they behave like plumbic sulphate. The formation of plumbic sulphate explains the rapid disintegration of the positive plates of accumulators when charged with too high currents. T. E. By VICTOR THOMAS (Compt. rend., 1900,131,1208-1211. Compare this vol., ii, go).-The orange powder, obtained by adding to thallous chloride suspended in water sufficient bromine to convert it into a compound of the type Tl,X,, dissolves in boiling water and its solution on cooling to 2 4 O deposits a bromo- chloride, T14C13Br3, crystallising in orange, hexagonal plates.A deposit of orange needles grouped in fern-like aggregates is produced on concentrating the solution but it is invariably contaminated with crystals of the preceding compound. The mother liquors on evaporation yield first a second crop of hexagonal plates and then a second crop of acicular crystals. These products all contain less bromine than the compound obtained in the first crystallisation. By ADELBERT ROSSING (Zeit. unorg. Chrn., 1900, 25, 407-41 4).-Copper hexasulphide, Cu2S6, is formed in very small quantity when copper salts are precipitated with yellow sodium sulphide solutions.It is easily prepared by fusing a mixture of anhydrous copper sulphate, sodium carbonate, and sulphur, dissolving the fused mass in cold water in an atmosphere of hydrogen, and precipitating the clear solution with hydrochloric acid ; the orange-red precipitate is dried over sulphuric acid and extracted with carbon disulphide. All operations must be conducted a t a low temperature and with the least possible exposure to the air. Copper bexasulphide dissolves in solutions of alkali or barium polysulphides, is decomposed into copper sulphide by colourless alkali sulphides, and is converted into the dark blue suZphide, Cu4S5, when shaken with concentrated ammonia.The trisuZphide, Cu2S3, obtained by treating the hexasulphide in a reflux apparatus with boiling ether or carbon disulphide, is a dark brown, amorphous powder, more stable than the hexasulphide, and is converted into cupric sulphide when boiled with alcoh 01. E. C. R. Copper Selenides. By HENRI FONZES-DIACON (Compt. rend., 1900, 131, 1206--1208).-Cupric selenide, CuSe, formerly prepared Thallium Bromochlorides. G . T. M. Polysulphides of Copper.IKORGANIC CHEMISTRY. 101 by Berzelius, is obtained in bluish-black, prismatic needles by heating cupric chloride at 200° in a stream of hydrogen selenide ; at higher temperatures, the product fuses and begins to decompose. Cuprous selenide, Cu2Se, is produced as an olive-green precipitate by the action of hydrogen selenide on a hydrochloric acid solution of cuprous chloride. This substance is obtained in lustrous octahedra and tetrahedra either by passing hydrogen selenide over the heated chlorides of copper or by reducing cupric selenide at a red heat in a current of hydrogen.Copper selenite, when reduced by hydrogen a t high temperatures, yields only metallic copper, but crystals of cuprous selenide are produced when the salt is heated with carbon. The selenides are decomposed by hydrogen chloride either in solution or at high temperatures, in the former case, hydrogen selenide being evolved; they are readily attacked by chlorine, oxidised to cupric selenite by nitric acid and dissolved by sulphuric acid with the evolution of sulphur dioxide.Ammonia attacks the cuprous selenide rather more readily than the cupric compound, whilst both substances are partially soluble in ammonium hydrosulphide. * G. T. M. Reduction of Mercurous Compounds by Animal Tissues. By MARCO SOAVE (Chem. Centr., 1900, ii, 114'7-1148; from Giorn. Fccrrn. Chim., 1900, 50, 433-439).-The author has been unable to confirm Piccardi's observation that when powdered calomel, calomel ointment, or calomel suspended in water is heated at 37", mercury vapour is evolved. Mercurous chloride and other mercurous compounds are decomposed, however, by the action of the gastric juice, intestinal fluids, the liver, kidneys, or blood, muscular tissue or proteids, with formation of mercury vapour. E. W. W. Solubility of Mercury Haloid Salts, and especially of Mercuric Iodide, in Organic Solvents.By OTTOKAR SOLC (Zeit. anorg. Chem., 1900, 25, 399--404).-The solubilities of mercuric chloride, bromide, and cyanide and of mercurous chloride at 18-20° in chloroform, tetrachloromethane, bromoform, ethyl bromide, and ethylene dibromide are given, as are those of mercuric iodide in chloroform, tetrachloromethane, ethylene dichloride, isobutyl chloride, ethyl bromide, methyl, ethyl, isopropyl or isobutyl alcohol, methyl or ethyl formate, methyl or ethyl acetate, ether, acetone, acetal, chloral, epichlorhydrin, hexane, and benzene. OE these solvents for the iodide, methyl alcohol (6.512 in 100) is the best and hexane (0.072 in 100) the worst. The solutions of the iodide are yellow except in the case of ethyl bromide ; the crystals which separate from them are either yellow or red, and all become red on standing (Kastle and Clark, Abstr., 1900, ii, 141).The red colour of the solutions in ethyl bromide and bromoform is due to the liberation of iodine, which does not take place in the dark. Lead iodide is slightly Alleged Volatility of Mercurous Chloride at 37". decwposed in a similar manner when dissolved in ethyl bromide, - E. C. R. Double Compounds of Mercuric and Potassium Iodides. By WLADIMIR PAWLOFF (J. Bass. Pliys. Chem. Xoc., 1900, 32, 732-'741).-A solution of mercuric iodide in aqueous potassium iodide102 AnSTRACTS OF CHEMICAL PAPERS, containing the salts in molecular proportion deposits hygroscopic, acicular crystals of the composition HgI,,KI,H,O, which are soluble in alcohol without change, but are decomposed by water.The crystals melt at about 105q and at 116.5' are completely decomposed with formation of a deep red liquid which boils a t 191-193'. If the two salts are present in the aqueous solution in the ratio HgI, : ZKI, the crystals obtained have the composition HgI2,2KI,2H,O; at high temperatures, these decompose into potassium iodide and the double salt, HgT,,KI. Cerium. By G. P. DROSSBACH (Bev., 1900, 33, 3506-3508).- Commercial cerium carbonate was partially purified and then con- verted into the double nitrate, Ce2(N0,)6,3NH4N0,,10H20 ; this salt was fractionally crystallised some 200 times, but all fractions appear to be identical in every respect with the preparations obtained by older methods. The dioxide which is formed on ignition always has a pale yellow colour.The double nitrate and also the compound Ce2(N03)6,xNH4N03 + aq are only slightly hygroscopic ; they crystallise well, and any didymium salts are left in the mother liquors. Salts of lanthanum and the ytterite earths are somewhat more difficult to remove, but, after three crystallisations can be proved to be absent. All metals of the cerium and yttrium groups dissolve readily in alkali carbonate solutions. Spectra of Samarium and Gadolinium. By EUGBNE DEMARQAY (Compt. rend., 1900, 131, 995-998).-The spectra of samarium and gadolinium previously described by the author (Abstr., 1900,597, 656) differ considerably from those described by Exner (Sitx. Acad. Vim Fien, 1900, 19), and although the actual measurements of the latter are probably more accurate, yet many of the lines are wrongly identified.This is due to the fact that the specimens were impure, and Exner attributed to samarium all lines which were strong in the samarium spectrum and weak in the gadolinium, and vice uersd. This negative evidence leads to errors ; to obtain more certain results, the author has repeatedly purified his specimens, and observed the variation of the lines with each increase of purity, only those being attributed to samarium which remain of constant intensity ; the wave-lengths of these with their relative intensities are given. Position of Indium in the Classiflcation of the Elements. By CAMILLE CHABRIE and ETIENNE RENGADE (Compt. rend., 1900, 131, 1300-1 303. Compare Abstr., 1873, 846).-Ccesium indium suZphate, Cs,S04,1n2(S0,),, 24H,O, was prepared by mixing hot concentrated solutions of the sulphates of the two metals, and on cooling separated in crystals belonging to the cubic system. One hundred parts of water at 16.5' dissolve 3.04 gmms of the salt.I t s aqueous solutions are acid t o litmus and deposit a precipitate on heating. Rubidium indium sulphate, Rb,S0,,In2(S0,),, 24H20, was prepared in a similar manner and crystallises in transparent octahedra. The existence of these two double sulphates of indium and also of its corresponding ammonium compound, and the fact that its hydroxide is soluble in T. H. P. J. J. S. L. M. J.INORGANIC CHEMISTRY. 103 alkalis, point to indium being more allied in properties to aluminium than to iron.Indiumacetylacetore, In,(CHAc,),, prepared by the action of acetyl- acetone on indium oxide, crystallises in flat, hexagonal prisms, melts at 1 8 3 O , and sublimes and decomposes a t 260-280'; it is insoluble in boiling water or cold alcohol, but dissolves readily in boiling alcohol. Hexahydrate of the Double Iodide of Manganese and Mercury. By D. DOBROSERDOFF (J. Russ, Phys. Chem. Xoc., 1900, 32, 742--744).-A saturated solution of mercuric iodide in saturated aqueous manganous iodide deposits yellowish, prismatic crystals of the composition MnIS,2Hg12,6H20, which when heated melt in their water of crystallisation and at higher temperatures decompose com- pletely, leaving a residue of trimanganic tetroxide. Soluble Alkali Salts of Ferric Oxide a n d of Ferric Acid.By FRITZ HABER [and in part WALDEMAR PICK] (Zeit. Elektrochem., 1900, 7, 215-221).-Poggendorf has stated that an anode of cast iron, in a concentrated solution of potassium hydroxide is oxidised to sodium ferrate; with other kinds of iron, this is not the case. The authors find that, immediately after closing the electric circuit, all varieties of iron are oxidised to ferrate and that the action is con- tinuous provided that the solution of alkali hydroxide -is concentrated and the current density low (about 0.001 ampere per sq. cm.). Under similar conditions, the yield of ferrate is greatest with cast iron and smallest with wrought iron ; it is also greater with sodium than with potassium hydroxide, probably on account of the greater solubility of sodium ferrate.The quantity of ferrate reduced at the cathode (a platinum wire) in a cell without a diaphragm is comparatively trifling. The yield of ferrate depends on the temperature; under the same conditions, traces only of ferrate were formed at Oo, whilst at 70" the current efficiency was almost 100 per cent. When the ferrate solution is boiled for a sufficiently long time, ,it becomes colourless or pale yellow, provided that care has been taken to use materials which are free from manganese. The yellowish solution contains a soluble ferrite and when kept deposits colourless crystals of a compound which very quickly decomposes when it is removed from the strongly alkaline liquid. The same solution of ferric oxide is obtained by boiling ferric hydroxide with a concentrated solution of sodium hydroxide.Addition of an alkaline sulphide gives a red coloration, due to the formation of the double alkali iron sulphide to which the '' red liquors " of the Leblanc alkali manufacture owe their colour. When pure iron is boiled gently for a few minutes with concen- trated sodium hydroxide solution, the liquid is found to contain ferrous oxide: When exposed to air, this solution readily oxidises, to the ferric oxide solution. Both the solutions of ferrous and ferric oxide are readily oxidised to ferrate by electrolytic oxygen. Crystalline Form of Luteocobaltic Chlorosulphate and Cbloroselenate. By TIMOTHEE KLOBB (Compt. rend., 1900, 131, 1305-1308).-Luteocobaltic chlorosulphate, Co(NH,),SO4C1,3H,O, H. R. LE S. T. H. P. T.E.104 ABSTRACTS OF CHEMICAL PAPERS. crystallises in prisms belonging to the rhombic system; they are isomorphous with the crystals of luteocobaltic selenate, Co(NH,),Se0,C1,3H20. Full crystallographic measurements of the crystals of both salts are given in the paper, H. R. LE S. Solubility of Some Salts in Water. By RUDOLF DIETZ, ROBERT FUNK, J. VON WROCHEM, and FRANZ MYLIUS (Wiss. Abhandl. phys.-tech. Reichsanstalt, 1900,3, 425-477, and in part Bev., 1901, 33, 3686--3696).-The greater part of this work has aIready been published (see Mylius and Funk, Abstr., 1897, ii, 316, 442 ; Dietz, Abstr., 1899, ii, 222 ; Funk, Abstr., 1899, ii, 209), The paper, however, describes also an investigation of sodium and calcium chromates. Normal sodium chromate, Na2Cr04, exists as decahydrate, tetra- hydrate, and anhydrous salt, each form having its own characteristic solubility ; whilst the solubility of the decahydrate increases rapidly with rising temperature, that of the anhydrous salt increases only very slightly, a behaviour analogous to that of the isomorphous sodium sulphate.The dichromate, Na2Cr207,2H20 is stable up to 8 3 O , a t which temperature i t changes into the anhydrous salt. The existence of sodium trichromate, Na,Cr,OIo (compare Stanley, Abstr., 1887, 1 lo), is confirmed, but the authors show that it crystallises with 1H20; the saturated solution at 0' contains 80 per cent. of the salt. Sodium tetrachromate, Na2Cr,0,,,4H20, has been prepared ; it is stable in aqueous solution up to 40°, about which temperature it decomposes into chromium trioxide and trichromate.When a saturated sodium hydroxide solution is added to a concen- trated solution of normal sodium chromate, rhombohedral, yellow crystals separate of the composition Na,CrO,, 1 3H20-tetrasodium chromate; these crystals are very deliquescent, take up carbon di- oxide from the air, and melt about 50'; they cannot be obtained below Oo. The solubility has been determined, and the conditions of existence studied, of five different modifications of calcium chromate ; these are (1) monoclinic dihydrate, CaCr0,,2H20, (2) rhombic dihydrate, (3) monohydrate, CaCr0,,H20, (4) hemihydrate, CaCrO,,&H,O, (5) anhy- drous salt. A crystallographic investigation of the first two modifica- tions is added. The monohydrate is charncterised by the fact that its solubility falls rapidly with rising temperature, the saturated solution containing 11.5 per cent.of the salt at O', and 3.1 per cent. a t 100'. The above five modifications all exist in solution within a certain range of temperature ; thus, a t 1 So, five distinct saturated solutions of calcium chromate may be obtained. J. C. P. Uranium Nitrate. By WILLIAM OECASNER DE CONINCK (Compt. rend., 1900, 131, 1219--1220).-Uranium nitrate is insoluble in petroleum, the aromatic hydrocarbons, carbon disulphide, or glycerol ; it dissolves in methyl, ethyl, propyl, isobutyl, or amyl alcohol and also in acetone, ether, ethyl acetate, or formic or acetic acid, but is only sparingly soluble in turpentine. One part of the salt dried at 85' dissolves in 2 parts of distilledINORGANIC CHEMISTRY.105 water at 13-14O ; the heat of dissolution of UO*N0,,3H20 at 17-18' is 3,s Gal. The nitrate dissolves in lime-water, but the solution subsequently yields a yellow, flocculent deposit ; i t is insoluble in solutions of ammonia or the alkali hydroxides, but is readily soluble in mineral acids, whether dilute or concentrated. G. T. M. Uranium Nitrate. By WILLIAM OECHSNER DE CONINCK (Compt. rend., 1900,131, 1303--1305).-Aqueous solutions of uranium nitrate are slowly decomposed by diffused sunlight; if the solutions are acidified with hydrochloric acid or acetic acid, they become extremely stable. Solutions of uranium nitrate in commercial methyl alcohol or ethyl alcohol are readily decomposed by diffused sunlight, a black uranium oxide being deposited.One part of uranium nitrate, dried at goo, dissolves in 55 parts of methyl alcohol a t 11-12-6'; 30 parts of ethyl alcohol (85') at 12-9-13'; 65 parts of pure acetone at 11.9-12*2°, and in 5.6 parts of acetic acid of sp. gr. 1.035, a t 14-14.5O. Tables are given of the sp. gr. of solutions of uranium nitrate in commercial methyl alcohol and in acetic acid. Production of Alloys of Tungsten and of Molybdenum in t h e Electric Furnace. By CHARLES L. SARGENT (J. Arne?*. Chem. Xoc., 1900, 22, 783-791).-Tht? author has prepared small specimens of alloys of both tungsten and molybdenum with other metals, by heating a suitable mixture of the oxides of the desired metals with sugar carbon in the electric furnace in a carbon crucible, sometimes with a magnesia lining.By operating on 5 to 10 grams of mixture of oxides and carbon with a current of 70 t o 90 volts, and 100 t o 150 amperes, the operation was finished within 1 to 5 minutes. Whilst tungsten and bismuth did not yield an alloy, definite results were obtained with molybdenum and bismuth. Copper alloyed with tungsten, but it refused to do so with molybdenum. Both tungsten and molybdenum failed to alloy with tin, and whilst the former failed to combine with manganese, the latter readily united with it. Both metals seemed to alloy with the greatest ease with cobalt, chromium, and nickel; these alloys may, perhaps, prove to be technically import- ant, if readily obtainable in large quantities. By ED. DEFACQZ (Compt. rend., l901,132,32--35).-When tungsten diphosphide is heated with copper in the electric furnace, it is decomposed; but if it is heated with a large excess of copper phosphide in a graphite crucible in a wind fur- nace and the product treated with dilute nitric acid, a new phosphide, WP, is obtained in grey, lustrous, prismatic crystals of sp.gr. 8.5. This tungsten monophosphide burns in air or oxygen at a red heat, and is likewise attacked by chlorine, but i t is not decomposed by hydro- fluoric or hydrochloric acid, or by hydrogen chloride. It is slowly oxidised by hot nitric-acid, and is rapidly dissolved by a mixture of nitric and hydrofluoric acids, or by aqua regia. Sodium and potassium hydroxide solutions have no action on the phosphide, but the fused hydroxides and fused mixtures of alkali carbonates and nitrates readily H.R. LE S. L. DE K. A New Tungsten Phosphide.106 ABSTRACTS OF CHEMICAL PAPERS. oxidised it, whilst fused potassium hydrogen sulphate attacks it slowly. C. H. B. Physico-chemical Researches on Tin, 111. By ERNST COHEN (Zed. physihl. Chem., 1900, 35, 588-597. Compare Abstr., 1900, ii, 83,212,408).-The change of white tin into grey tin can be observed in filings of the metal, proving the incorrectness of the old view of Lewald, according to which the change took place only in block tin, and mas probably due to a strained condition of the crystals. Me- chanical vibration is found, so far, t o be without influence on the transformation of white into grey tin. The presence of cobalt nitrate affects, not only the velocity of the transformation grey tin white tin, but also the temperature of the maximum velocity.The velocity of the transformation is, further, very dependent on the history of the tin investigated, and consistent results can be obtained only with specimens which have been subject to the same conditions. Composition of Thorium Hydride and Nitride. J. C. P, By CAMILLE MATIGNON and MARCEL DELBPINE (Compt. rend., 1901,132, 36-38).- The hydride obtained by the action of hydrogen on thorium at a dull red heat has the composition ThH,, and is readily dissociated at high temperatures. The nitride obtained by heating thorium to redness in a current of nitrogen has the composition Th,N,, and is slowly decomposed by cold water, but more rapidly on heatiDg. The hydride and the nitride burn in oxygen without incandescence, Hydrated Bismuth Oxide. C.H. €3. By PAUL THIBAULT (2 Phawn., 1900, [vi], 12, 559-561).-Bismuth oxide, prepared by the addition of an alkali to a solution of bismuth nitrate or chloride, always contains some basic nitrate or chloride. It may, however, be obtained free from these compounds by taking advantage of the fact that bismuth oxide is soluble in a solution of potassium hydroxide which contains glycerol. Bismuth nitrate is intimately mixed with glycerol, water is added until the salt is entirely dissolved, and then potassium hydroxide until the precipitated oxide is redissolved. If dilute sulphuric acid is then added, a precipitate of bismuth oxide is produced, which is entirely free from any combined acid, and after drying in air, or in a vacuum over sulphuric acid, or at 100-105°, has the composition Ei2O3,H,O.H. R. LE S. Soluble Bismuth Phosphate. By CLEMENTE MONTEMARTINI and U. EGIDI (Gaxxetta, 1900, 30, ii, 421--446).-The preparation sold under the name of ' Bismuthum phosphoricum solubile ' contains bismuth, sodium, and phosphoric acid, and is soluble in water. It is obtained by fusing together in certain proportions bismuth oxide, sodium hydr- oxide, and phosphoric acid. Its composition does not correspond with any formula representing the phosphorus present as either ortho-, meta-, or pyro-phosphoric acid, but agrees well with BiRNa50P390125, 3H,O, After precipitating and removing the bismuth from the solution as sulphide, the phosphorus is found to be present mostly as metaphos-INORGANIC CHEMISTRY.107 phoric acid, together with small quantities of the pyro-acid. I n concentrated solution, the compound undergoes rapid hydrolytic dis- sociation, whilst with dilute solutions the change takes place slowly in the cold, but quickly on boiling; in all cases, a white precipitate is obtained, consisting of a mixture of bismuth oxide and phosphate containing the whole of the bismuth, the liquid a t the same time acquiring an acid reaction and answering to the tests for meta- and pyro-phosphoric acids. On electrolysing an aqueous solution of the suhstance, bismuth is deposited on the anode, and a mixture of bismuth oxide and phosphate is precipitated. The depression of the freezing point of an aqueous solution shows that the compound is resolved into a number of ions, and, notwithstanding the precipitation of bismuth phosphate and oxide, the depression continuously increases ; the electrical resistance, in a similar manner, shows a gradual decrease.From aqueous solutions alkalis precipitate mixtures of bismuth oxide and phosphate, whilst hydrochloric acid precipitates bismuth metaphos- phate. On suspending the compound in ethyl or methyl alcohol and passing a current of hydrogen sulphide through the liquid, no precipita- tion of bismuth sulphide occurs, but this immediately takes place on adding water. T. H. P. Reduction of Nitroso-compounds of Ruthenium and Os- mium. By LJ~OPOLD BRIZARD (Ann. Chirn. Phys., 1900, [vii], 21, 311--388).-The paper contains a very detailed account of a study of ruthenium double salts, some of the results having been already pub- lished (Abstr., 1899, ii, 559, 664).Dihydroruthenium nitrosohydroxide, NO*RU,H,(OH)~,~III,O, pro- duced either by the reduction of the nitrosohydroxide, NO*Ru(OH),, with an alkaline solution of formaldehyde or by the action of am- monia on potassium ruthenate, forms a gelatinous, dark-brown pre- cipitate which on treatment with hydrochloric acid and potassium chloride yields the crystalline double chloride, NO*R,H2C1,,3KC1,2HC1; this salt is also obtained by the addition of potassium chloride to a solution of ruthenium nitrosochloride, NO-RuCl,, or the double nitrite, Ru2(N0,),,4KNO,, reduced by boiling with stannous chloride. Although stable a t 360°, the double salt decomposes at higher tem- peratures with evolution of nitrogen, chlorine, hydrogen chloride, and water; it is reduced by hydrogen at a dull red heat, the volatile products being ammonium chloride, hydrogen chloride, and water, whilst the residue consists of ruthenium and .potassium chloride.The crystals of the double salt are very sparingly soluble in cold water, and when dissolved in this solvent the substance exists in a parti- ally dissociated condition, the amount of dissociation increasing as the temperature rises. Chlorine passed into the freshly-prepared solution of the double chloride yields a precipitate of ruthenium tetroxide. The oxychlovide, NO*Ru2H,C1,*OH,2H20, is precipitated by the addition of potassium hydroxide to the aqueous solution, whilst excess of this reagent produces the hydroxide NO~Ru2H,(OH),,2H20. The double ammonium chlovide, NO*Ru,H,Cl,, 2HC1,3NH4C1, is pro- duced on adding excess of ammonium chloride to the aqueous solution108 ABSTRACTS OF CHEMICAL PAPERS. of the corresponding potassium salt ; the silver salt has a similar com- position, NO*Ru2.H,C13,2HC1,3AgC1. Dihydrorutheneum natrosochloride, NO*Ru,H,Cl,, 2HC1, is an amor- phous reddish-brown precipitate obtained on evaporating to dryness the hydrochloric acid solution of the corresponding oxychloride or hydroxide. Ammoniodihydrorutlienium nitrosochloride, NO*Ru,H,(NH3),Cl3, 2HC1, prepared by the action of ammonia on the preceding double chlorides, separates in orange-yellow crystals. The double sult, NO*RU,H,C'~~,~HC~,~KB~, produced by adding potassium bromide to a hydrochloric acid solution of dihydroruthenium nitrosochloride, separates in brown, anisotropic crystals sparingly soluble in water ; it yields the oxychloride, NO*Ru,H,Cl,*OH, on treat- ment with potassium hydroxide. The double bomide, NO*Ru2H,Br,,2HBr, 3KBr, and the ammonio- derivative, NO*RU,H,(NH~)~B~,,~ HBr, are obtained by methods similar to those employed for the chlorine derivatives ; it mas, however, found impossible to isolate the corresponding double iodides. The dou6Ze silver nitrite, Ru,H2(N0,),,3 AgN0,,2H20, is a brownish- yellow precipitate produced by adding silver nitrate to a cold solution of the corresponding potassium salt (compare Abstr., 1899, ii, 664), on double decomposition with ammonium chloride, it yields the cor- responding double ammonium salt, Ru,H2(N0,),,3NH,NO2,2H,O. Potassium anzinochloro-osmte, NH2*OsC1,,3KCl, is a crystalline salt prepared by reducing potassium osmiamate with stannous chloride; its hydrochloride has the composition indicated by the formula NH2*OsC1,,2KC1,HC1. The solutions obtained by reducing the osmiamate with formaldehyde or ferrous chloride do not yield crys- tallisable double salts, G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA9018005092

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

108 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Enrichment of Mineral Veins by Later Metallic Sulphides. By WALTER HARVEY WEED (Bull. Geol. Xoc. Amer., 1900,11,179-206). --Silver, copper, lead, &c., may be leached out as carbonates and sul- phates from the upper gossan zone of mineral veins, and carried down by surface waters t o be reduced again by sulphides of iron in the un- altered portions of the vein. Rich secondary deposits of sulphides may thus be formed in veins which are in other parts poor. These cbanges are discussed in detail, and suggestions are made as to the nature of the chemical reactions which may take place. Mohawkite, Stibio-domeykite, Domeykite, Algodonite and some Artificial Copper Arsenides. By GEORGE A. KOENIG (Amer. J. Sci., 1900, [iv], 10, 439--488).-General notes are given of the occurrence of copper arsenides in the Lake Superior copper mining L.J. S.MINERALOGICAL CHEMTSTHY. 109 region, and two new ones are described under the names mohawkite and stibio-domeykite. Mohawkite from the Mohawk mine, Keweenaw Go., Michigan, is massive and very brittle; the colour is grey with a tinge of yellow, tarnishing easily to dull purple. Analysis I gives the formula (Cu,Ni,Co),As ; the mineral is therefore a nickeliferous dorneykite (Cu,As). Domeykite from the Sheldon-Columbia mine gave 11. Crystallised domeykite was produced by heating together copper and arsenic; the arsenide, CU~AS, is also formed a t the same time. Stibio-domeykite (anal. III), from the Mohawk mine, differs only from ordinary domeykite in containing a small percentage of antimony, amounting in one specimen to 1.29.Analysis IV (also CaCO,, 2.41 ; MgCO,, 0.60) is of an intimate mixture of mohawkite and whitneyite; as shown by other analyses, this mixture varies in composition. Algo- donite, of a steel-grey colour, from the Pewabic mine gave V. As. Sb. Cu. Ni. Co. Fe. Total. Sp. gr. I. 28.85 - 61-67 7.03 2.20 trace 99 75 8.07 11. 26.14 - 74.00 0.06 100*20 7.9486 111. 26.45 0.78 72.48 0.24 99-95 7.902 IV. 15.07 - 79.36 0.61 0.82 0.36 99.23 - L V / V. 16.08 - 83.72 0.08 99.88 8.383 L. J. S. Tellurides from Colorado. By CHARLES PALACHE (Arneq.. J. Sci., 1900, [iv], 10, 419--427).-Sylvanite has already been inferred to be present in the telluride ores of Cripple Creek (Abstr., 1896, ii, 61 2, 613), and recently crystals have been found in several of the mines, A detailed crystallographic description is given of this new material.The habit is tabular parallel t o (OlO), or prismatic parallel to the zone [lll, 0101, and some crystals are twinned on (101). Sp. gr. 8,161. Analysis of crystals gives results agreeing with the sylvanite formula, A uAgTe,. Au. Ag. Te. Fe. Insol. Total, 26.09 12.49 60.82 1-19 1-02 101.61 The goldschmidtite of Hobbs (Abstr., 1899, ii, 493) is shown to be crystallographically identical with sylvanite, the habit and twinning being the same as for the crystals now described. In an accompanying note, W. H. Hobbs admits this identity, and remarks on the untrust- worthiness of his analysis, which had to be made on a very small sample.Hessite crystals from Colorado are described ; these, although cubic, are rhombohedra1 in habit. Opals from Tuscany. By GIOVANNI D'ACHIARDI (Jahrb. Min., 1900, ii, 348-350 ; from Atti Xoc. Toscana Sci. Nit. Proc. Verb., 1899, 11, 114--136).-Determinations of the chemical and optical characters are given for seven varieties of opal from various localities in Tuscany. Analysis I is of grey, almost colourless, transparent opal occurring as nodules in serpentine a t San Piero, Elba ; thin sections are optically isotropic. 11, Opaque, milk-white opal occurring with, and graduatinq into, the last; the porcellaneous appearance is due t o enclosed air, L. J. S.110 ABSTRACTS OF CHEMICAL PAPERS. it is almost isotropic. 111, Black opal, as pitch-like blocks at the contact of serpentine and granite from the same locality; it is in part feebly birefringent, and encloses bastite, iron oxides, zircon, and garnet.IV, Grey opal from Jan0 ; this is a silicified serpentine, and is veined with chalcedony; it is almost isotropic. V, Red and grey opal occurring with serpentine a t Impruneta. VI, Fiorite, from Santa Fiore, Monte Amiata, is of different origin from the above, and has been formed in water through which silicon fluoride has bubbled; it consists of alternate layers of isotropic opal and bire- fringent chalcedony. VII, Diatomaceous earth from Caste1 di Piano, Monte Amiata. I. 11. 111. IV. v . VI. VII. SiO, ............... 89.55 86-54 82.11 87.62 83.13 - - Al,O, ............I o,49 1.73 { i::: 3.43 - - Fe,O, ............CaO .............. 0.63 0.55 1.57 0.36 0.81 - - 80-90" ... 1-02 5.68 5.50 4.90 4.18 0.22 5-98 H2O { 130-320" 6.48 3.15 2.49 1-24 3.18 2.96 1.97 red heat ... 0.53 0.57 1.09 0.60 1-87 2-29 3.57 MgO ............... 0.57 0.74 trace 0.47 1.73 - - Total H,O ...... 8.03 9.40 9.14 6.74 9.23 5.47 11.52 Sp. gr .......... 1.99-2.03 1.94-1-97 2,065 - - - - - - - - - - 99.27 98.96 99.93 98.35 98.33 - - - - - - . _ _ - - Curves are given showing the amounts of water given off at different temperatures for each of these opals. The total water present and the temperature a t which it is lost, depends on the origin and the nature of the material; for those of primary origin (I and VI) little water is lost below 100". No definite formula can be given for opal. L. J. S. Chromite from Kraubat, Upper Styria.By FRANZ RYBA (2eit.prakt. Geol., 1900,337-341).--Here, as at other localities (Abstr., 1899, ii, 494), chromite occurs as a concentrated primary constituent in olivine-rock, which is usually altered to serpentine. Analysis of the chromite by R. Vambera gave : SiO,. MgO. COO[?]. FeO. A1,03. Cr,O,. Total. 4.3 9-7 6.4 9.1 13.7 56.2 99-4 L. J. S. Dolomite from Ceylon. By EMIL CHR. SCHIFFER (Inaug.-Diss. Munchen, 1900, 32-45).-A coarsely crystalline dolomite occurring as a band in gneiss at Wattegama contains numerous mineral en- closures, of which the following analyses (in each case the mean of two or more) are given. Selected clear rhombohedra of dolomite gave the results under I ; cleavage angle, 73'43'; sp. gr., 2.896. The rough material is shown by analysis I1 to be also normal dolomite : cop CaO.MgO. Gangue. Total. I. 47.72 30.45 21.87 - 100.04 11. 46-88 31.12 20.85 0.8'7 99.72MINERALOGICAL CHEMISTRY, 111 Rounded prismatic crystals of sky-blue apatite gave the results undor I11 : Total 111. 40.19 54.43 1.16 1.20 1-06 3.16 Nil. 99.63 Phlogopite as light brown, pyramidal crystals and scales with 2E = 14O23', gave IT. Hydrophlogopite occurs as globular and vermiform masses of a lighter colour than the phlogopite, with which i t is often intergrown, and of which it is an alteration product ; analysis V shows it to differ from phlogopite in containing less alkalis and more water, and to differ from the vermiculites in containing more alkalis. Pale green serpentine, occurring as irregular and small globular masses, gave results (VI), indicating that it has been derived from forsterite.Snow-white serpentine gave VII, which agrees, like the last, with the formula, H,R,"Si,O,,,. P,O,. CaO. FeO. MgO. C1. F. H20. less 0 for C1,F). SiO,. A1,0,. CaO. MgO. Na,O. H,O. Total. IV. 39.71 15.48 - 28.53 8.99 5-59 98.30 V. 40.13 14.24 - 23.78 7-69 13.49 99.33 VI. 39.29 1.78 1.82 39.04 - 18.15 100.08 VII. 39.66 3.18 1.75 38.60 - 16.53 99.71 Pyrites occurs as crystals and grains, but is usually represented by Analysis gave : Fe 44.99, S 53.79, gangue Spinel and pyrrhotite are also present as enclosures in the dolomite. Minerals of Ceylon. By FR. GRGNLING (Zeit. Kryst. Min., 1900, 33, 209-239).-An account of a mineralogical expedition to Ceylon. Several analyses of minerals by E.C. Schiffer are given (compare preceding abstract). L. J. S. Influence of the Presence of Iron on the Change in State of Boracite. By FRIEDRICH RINNE (Jahrb. Min., 1900, 11, 108-1 16). -Crystals of boracite which contain iron (up to 7.9 per cent. FeO) have a more or less pronounced greenish tint. With increase in temperature the colour gradually becomes deep bluish-green, but t h i s change takes place before, and is not connected with, the change from the rhombic to the cubic modification of boracite. In boracite containing iron, the temperature at which the change in state takes place is sensibly higher (285') than in colourless boracite (265'), and the change takes place less sharply. At 285', the birefringence of iron-boracite becomes much weaker, the division into fields, as seen in polarised light, becomes different ; even at 400°, the material is not wholly isotropic.These optical anomalies, which are described in detail, are considered t o be due to the isomorphous mixing of iron- and magnesium-boracite. limonite pseudomorphs. 1 *22 = 100.00. L. J. S. L. J. S. Robellazite, a new Mineral, By E. CUMEKGE (BUZZ. Soc. fpanp. Min., 1900, 23, 17--lS).-This was found in Colorado by M. Robellaz as small, black, concretionary masses associated with carnotite (Abstr., 1899, ii, 434 ; 1900, ii, 599). From qualitative tests, it appears to be112 ABSTRACTS OF CHEMICAL PAPERS. a niobate, tantalate, and tungstate of vanadium, with aluminium, iron, and manganese. L. J. S. By ANDERS HENNIG (Jahrb. Min., 1900, ii, Ref.354-357 ; from Geol. Por. Forh., 1899, 21,391-415)- Apophyllite from Mount Sulitelma, in northern Scandinavia, forms, with stilbite, a crust on pyritiferous quartz. The weathered crystals on the exterior are white and opaque, but the inner ones are colourless and transparent. Measurements are given of the numerous vicinal faces, which are more abundant on the cloudy, weathered crystals; these appear to be connected with a loss of water, since they may be artificially developed by simply heating the crystals. The optical ex- amination shows the presence of a central portion of (‘ chromocyclite ” surrounded by leucocyclite, and the change in the optical characters observed on heating the isolated ‘‘ chromocyclite ” suggests that the latter has been derived from the former by the loss of about 2 per cent.of water, The following analysis of crystals, by L. Ramberg, gives the formula Ca(CaP,,K,)Si,0,,2H20. Numerous determinations are given of the loss of water, a t different temperatures, of apophyllite from various localities : SiO,. AI,03(Pe203). CaO. K20. Na,O. H20. F. Total. 52-61 2.23 23.82 4.96 0.05 15.67 1.24 100.58 By STANISLAUS J. THUGUTT (Bull. Intei-ncct. Acad. Sci. Cracow, 1899, 168-169; and Jahd. Min., 1900, ii, 65-79).-Analysis I is of partially altered nephelite isolated by means of a heavy liquid from the nephelinite of Lobau, Saxony; I1 is of an alteration product, referred to zeagonite, of the nephelite. Other analyses of mixtures of these are given. The figures under 111, which are nssumed to represent the true composition of zeagonite, are calculated from I1 by deducting the residue insoluble in hydrochloric acid, 13.97 per cent.of nephelite (calculated from Na20, 1.93) and 4.43 per cent. of limonite (assuming the excess of the molecular ratio 1 : 1 of sesquioxides over other bases to be due to Fe203) : SiO,. A1,0,. F?,O,. CaO. MgO. K,O. Na,O. Tnsol. H,O. Total. I. 42‘69 33‘51 2.50 0’10 4.49 14.24 1.10 1-59 100.22 11. 38.97 26.03 7.47 0.25 4’60 1-93 3-01 16.80 99.06 111. 42-34 22.77 - 9‘10 0’31 5.10 - - 20.38 100-00 8 CaA1,Si3010, 3K,A12Si3010,55 H,O, to be in conformity with the author’s constitutional formula for nephelite, namely, 8Na,hl,Si30,0,4Na,A1204,3KzA12Si~Olo (Abstr., 1895, ii, 358). As represented by these formulae, the alteration from nephelite to zeagonite could be effected by water containing calcium salts.Zeagonite [ = gismondite] usually occurs as crystals lining the cavities of rocks, but in the case here described it penetrates the whole rock as a pseudomorph after nephelite, the usual alteration products of which are natrolite, mica or cancrinite. Apophyllite from Sulitelma. L. J. S. Zeagonite as a new Alteration Product of Nephelite. u From I11 the formula of zeagonite is given as L. J. S.MINERALOGICAL CHEMISTRY. ’113 “Blue Asbestos” [Crocidolite]. By H. F. OLDS (Trans. Inst. Mining and Netallurgy, 1899; and Eng. and Mining J., New York, 1899, 67, 528).-The crocidolite or ‘‘ blue asbestos ” of Griqualand West occurs as veins in dark brown shale. It is mined to a consider- able extent for commercial purposes. The composition is : 4 SiO?.FeO. MgO. Na,O. H,O. Total. 51.1 35.8 2.3 6.9 3.9 100.0 L. J. S. Minerals [Garnet] from the Fichtelgebirge. By ERNST DULL (Jahrb. Min., 1900, ii, Ref. 357-359 ; from Beil. 2. Juhresb. k. Luitpold-KreiweaZschuZe irt Miinchen, 1899, 8, 47 pp.).-A description is given of the minerals from fragments of an albite-bearing phyllite- gneiss found near Schonbrunn in the Fichtelgebirge. These include secondary minerals present throughout the rock, and also minerals occurring in veins. A green garnet, in rhombic-dodecahedra1 crystals, is the most prominent; the following analysis proves this to be topazolite, and not grossularite as formerly supposed : SiO,. TiO,. Fe,O,. A1,0,. FeO. CaO. MnO. MgO. Total. 36.65 0.40 18-48 9-07 0.82 34.04 trace trace 99.46 L.J. 8. Chemical and Mineralogical Constituents of Keuper Marl. By ERNST ANTON WOLFING (Jahred. Ver. vaterl. Naturk. Wurttemberg, 1900, 56, 1-46).-An attempt is made to determine the mineralogical composition of red and green marls from the Keuper beds near Tubingen. Bulk analyses of the same samples have aIready been published (Ber., 1899, 32, 2214). Under the microscope, minute grains of quartz, orthoclase, mica, rhombohedra1 carbonates, &c., may be recognised ; and from analyses of the portions soluble in acids of various strengths and temperatures is inferred the presence of a chlorite having the composition 2MgO,A1,0,,2Si0,~2H,O, a clay of the composition A1,0,,4Si0,,2H20, and some kaolin. The relative amounts of each of these constituents vary very considerably in the different samples.The name geolyte is proposed to replace the term ‘‘ Bodenzeolith ” used by agricultural chemists for those constituents of soils which are easily soluble and of undefinable mineralogical com- position, but which have little i n common with zeolites. L. J. S. Carbonaceous Gneiss in t h e Black Forest. By HARRY ROSENBUSCH (Mitteil. Grossh. Badischen Geol. Landesanst., 1899, 4, 9-48).-The gneisses of the Black Forest have been derived from both sedimentary and igneous rocks. Those derived from sedi- mentary rocks often contain carbon in the form of small scales of graphite or as graphitoid. The latter, as a dull, very fine dust, im- pregnates the whole rock, but only surrounds, and is not included in, the mineral grains; it is probably of organic origin.The rock with graphitoid gives off ammonia when heated; it contains free carbon, 1-31, nitrogen, 0.081 per cent, The residue obtained on dissolving VOL. XXXL. ii. 9114 ABSTRACTS OF CHEMICAL PAPERS. the rock in hydrofluoric and sulphuric acids gave, on analysis by Mohr : 77.4 1.2 3.5 16.1 98.2 C. N. H,O. Residue. Total. L. J. 5. Average Composition of British Igneous Rocks. By ALFRED HARKER (Geol. gag., 1899, N.S. Dec. iv, 6, 220-222).-The mean of 397 published analyses of British igneous rocks is given under I; corrections have been made for TiO, and MnO, but not for Fe,O, and FeO. With this is compared F. W. Clarke's mean (11) of 680 analyses of American rocks : The mean sp. gr. of 736 rocks is 2.763.SiO,. TiO,. A120,. Fe20,. FeO. MnO. MgO. I. 58.46 0.69 15-13 5.34 2.40 0.40 3.84 11. 59.77 0.53 15.38 2.65 3.35 0.09 4-40 CaO. N%O. K,O. H,O. p20,. Total. I. 4-98 3-25 2.74 2-23 0.25 99.71 11. 4.81 3-61 2-83 1.51 0 21 99-14 Taking rocks from special districts, other mean values are obtained. The mean silica percentage of 96 rocks from the English Lake district is 58.75, and the mean sp. gr. of 113 is 2.737. Of 82 Malvern rocks the mean silica percentage is 54.81, and the mean sp. gr. of 38 is 2.841. By E. WIENER (Chem. Centr., 1900, ii, 1185; from Wien.-kZin. Woch, 1900, 13, 646-648). -Mud deposited in the salt mines a t Ischl, in Salzburg, possesses therapeutic properties and consists of gypsum and clay with sodium chloride, &c. Analyses are given of the portions soluble in water and dilute acid. L. J. S. Salt Lakes of Roumania. By PAUL BUJOR ( A m . Xci. Univ. Jccssy, 1900, 1, 149--186).-A list of the salt lakes of Roumania is given, and two of them are described in detail, with chemical analyses of the water and mud. Hot 8prings of Gastein. By ERNST LUDWIG and THEODOR PANZER (Tsch. Min. Mitth., 1900, 19, 470-488; and Wien. klin. Woch., 1900, 13, 617-623).-Near Gastein in Salzburg there are 18 hot springs which issue from an intrusive mass of granite-gneiss. The temperature varies from 24.4' to 49.4' in the different springs. An analysis is given of water from the Elizabeth spring of which the temperature is 49.1'; sp. gr. 1.00036'7. The results obtained agree closely with those of earlier analyses made a t various times since 1828. L. J. S. Mud from the Salt Mines of Ischl. L. J. S. L. J. S. Composition of a Sulphated Calcareous Water at Lautaret (Hautes-Alpes). By JOSEPH A. MULLER (Bull. Xoc Chim., 1900, [iii], 23, 910-912).-The temperature of this water is sensibly constant at about 25.3O. It yields a solid residue of 5.216 grams per kilogram, consisting chiefly of sodium chloride, calcium carbonate, and calcium, magnesium and sodium sulphates. N. L.

ISSN:0368-1769    

DOI:10.1039/CA9018005108

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

Organic Chemistry. Composition of Shale Naphtha, By BASIL STEUART (J. Xoc. Chent. Ind., 1900, 19, 9S6-989).-The olefines were removed by successive treatment with concentrated sulphuric acid and aqueous Bodium hydroxide, and the aromatic hydrocarbons by shaking with a mixture of sulphuric and nitric acids; the nature and amount of the olefines were not determined, but they appear to be present in larger quantity than in natural petroleum. After the foregoing treatment, the naphtha boiling between Z O O and 105O was repeatedly fractionated. n-Hexnne was by far the principal hydrocarbon present, traces only of isohexane being found, along with, possibly, methylpentamethylene ; the n-hexane was purified by heating for three days with fuming nitric acid, when the latter was found to contain propionic and succinic acids with a trace of oxalic acid.n-Heptane and isoheptane were present to a considerable extent but could not be separated from one another by fractional distillation ; the high values for the sp. gr. OF the heptane fractions between 89O and 100' appear to indicate the presence of, possibly, both hexamethylene and methylhexamethylene and the absence of dimethylpentamethylene. The difficulty ex- perienced in separating the n-heptane and isoheptane may be due t o the presence of the isomeric y-ethylpentane (triethylmethane) boiling at 96", but this hydrocarbon has not yet been identified in American or Russian petroleum. wPentane was present in small proportion compared with the hexanes and heptanes, and isopentane in small proportion to n-pentane.The sp. gr. and vapour density of a small fraction boiling between 48" and 5 7 O appear to indicate the presence in small quantities of pentamethylene ; a small fraction boiling between 38" and 42" similarly appeared t o contain methyltetramethylene. The greatest proportion of benzene was found in the original fractions boiling between 70" and 75" and 65" and 704 and was separated as rn-dinitrobenzene ; the fraction 75-80" contained only traces of benzene, owing to the bulk of the latter having distilled at a lower temperature along with the hexane (compare Young and Jackson, Trans., 1898, 73, 922). Benzene appears to constitute 2.6 per cent. of the original fractions boiling between 55" and 75" ; it is probable, however, that an additional quantity may have been removed by the preliminary treatment t o eliminate olefines.Toluene forms about the same proportion of the fraction from 95--105O, its distilling below its boiling point being due to the presence of heptane (compare Zoc. cit.). W. A. D. By KARL ELBS and FRITZ FOERSTER (Zeit. Elektrochem., 1900, 7, 341)- A reply to Dony-HBnault (Abstr., 1900, i, 577) with reference to the electrolytic formation of iodoform. Electrolytic Synthesis of Organic Substances. T. E. VOL. LXXX. i. i110 ABSTRACTS OF CHEMICAL PAPERS Derivatives of Tetradecylacetylene. By FRIEDRTCH KRAFFT and G. HEIZMANN (Ber., 1900,33,3586-3590. Compare Abstr., 1832, 11 63).-T'etradecylacetyle.ne tetrabvornide, C,4H29* CBr,* CHBr,, a colour- less liquid which cannot be distilled under 15 mm.pressure, is prepared by mixing together tetradecylacetylene and bromine a t a low tempera- ture and then gradually heating the mixture to 60'. The copper com- pound, Cl4HZg* Ci C*Cu*OH, is a greenish-grey substance produced by shaking together the hydrocarbon and ammoniacal cuprous chloride solution ; the mercurichloride, C14H,,* CiC*HgCl, is a white compound, whilst the mercuronitrate, C,4H2gS* CiC*Hg,*NO,, is white, turning grey on exposure t o light, The sodzum derivative, C,,H,,*CiCNa, is a yellowish-white substance regenerating the hydrocarbon on treatment with water or methyl alcohol. Nitrotetradecylcccetylene, C16H29* NO,, produced by slowly adding fuming nitric acid t o tetradecylacetylene cooled t o - 1 6 O , yields amino- tetradecylacetylene, C1,H,,*CiC*NH2, on reduction with zinc dust and acetic acid; this base is a white, crystalline mass melting at 41-42O, and boiling a t 195' under 15 mm.pressure ; its platinichloride forms a yellow, flocculent precipitate. T'etradecyZacetylenesuZphonic acid, C14H29* CIC*SO,H, is obtained in the form of its barium salt, (CI,H2,S0,),Ba, by mixing the hydrocarbon with concentrated sulphuric acid, neutralising the solution with dilute sodium hydroxide solution, precipitating the sulphonate by means of sodium chloride, redissolving this product in hot water, and reprecipitat- ing with barium chloride. Tetradecylacet ylenecarboxylic acid (tetradec ylpopiolic acid), C14H2,* CiC*CO,H, prepared by passing carbon dioxide over sodium tetradecylacetylide heated at 1 20°, crystallises from dilute methyl alcohol in white leaflets melting at 44-45' ; when distilled under 15 urn. prebsure, i t decomposes into carbon dioxide and tetradecylacetyl- ene.SilL er nitrate in aqueous ammoniucal solution forms the silver salt, C14 H CiC*C02Ag. P'etradecy Zlol-o~io~umide, C14H29* CiC*CO *NH,, produced by adding a mixture containing equivalen t proportions ot phosphorus pentachloride and the acid t o cold concentrated amruonia, crystallises from absolute alcohol in leaflets melting a t 76-77" ; the benzoyl derivative melts at Tetradecylbenxo ylacetylene, C,,H,,C I C COPh, a very unstable ketone, it obtained by condensing crude tetradecylpropiolic chloride with benzene in the prebence of aluminium chloride; i t distils at-145' in a high vacuum, and solidifies to a yellowish-white, waxy mass.11 4 -1 15'. G. T. M. Presence of Methyl Alcohol in the Fermented Juice of several Fruits. By JULES WOLFF (Compt. rend., 1900, ' 131, 1323-1324. Compare Abatr., 1899, ii, 387).-The fermented juice of black currants, plums, mirabelles, cherries, apples, or grapes contains methyl alcohol, but the unfermented juice does not, except black currant juice, which contains it in small quantities. Rum and whisky do not contain methyl alcohol, but traces of it are present in brandy. H. R. LE S.ORGANIC CHEMISTRY 111 Absence of Methyl Alcohol in Rum. By HENRI QUANTIN (J. Pharm., 1900, [vi], 12, 505-50'7. Compare Abstr., 1899, ii, 387, and preceding abstract).-Formaldehyde, methyl formate, and methyl alcohol were found to be absent from the distillates obtained by the fractional distillation of 85 hectolitres of rum.Hydrolysia of Ethyl Nitrate by Water. By EUGEN VON BIRON (J. Buss. Phys. Chem. Xoc., 1900, 32, 656-667) -The solubility of ethyl nitrate in 100 parts of water between 55' and 85' is given by the following formula, in which t represents the temperature : 2.2839 The hydrolysis of ethyl nitrate was studied in an aqueous solution kept saturated at 709 The reaction is unimolecular, so that if x be the quantity of nitric acid formed after a time, 0 (hours), and K the velocity constant of the reaction, dx/d6 = K, whence K= (x - xo)/O. The results show that the value of K increases from about 0.134 when 8 = 5 to 0.150 when 6 = 114, indicating that the nitric acid formed exerts an accelerating influence on the hydrolysis. Taking k, as the constant of the hydrolysis of ethyl nitrate by water and k, as that of the accelerating action of the nitric acid, C representing the constant con- centration, the velocity of the reaction is represented by : dx/dO- (k, + k,)C.The values of k1 and k, calculated on the basis of the above measurements are : k, = 0.004246, which means that in a solution of constant concentration water hydrolyses in 1 hour 0.004246 of the total quantity of ethyl nitrate present ; k, = 0.0135 (for normal acid), the total action of the acid and water being given by the constant (El + k,) -- 0*0177. Other experiments with non-saturated solutions of ethyl nitrate, with and without the addition of nitric acid, confirm these numbers.These results are quite different from those obtained in the hydrolysis of esters of organic acids; thus Ostwald (Abstr., 1884, SSl), in determining the velocity of hydrolysis of methyl acetate by normal nitric, hydrochloric, and other acids, did not take into account the action of the water present. From numbers given by Ostwald, i t is seen that at 25Owater hydrolyses in 30 days some 20-25 per cent. of the methyl acetate in solution, whilst with the same initial concentration of the ester, normal acetic acid hydrolyses 67 per cent. in the same time.. The ratio between these two velocities is of the same order as in the hydrolysis of ethyl nitrate by nitric acid, although the actual velocities are widely different in the two cases. Action of Ethyl Iodide on Silver Nitrate.By EUUEN VON BIRON (J. Buss. Phys. Chem. Soc., 1900, 30, 667-673).-When ethyl iodide is gradually added t o powdered silver nitrate, the mixture being kept cool, nearly the theoretical yield of ethyl nitrate is obtained. I n presence of water, however, part of the ethyl nitrate formed is con- verted into alcohol and nitric acid (see preceding abstract), whilst if the reaction is carried out in absolute alcoholic solution, ether and nitric acid are formed along with the ethyl nitrate, as has been already shown by Nef (Abstr., 1900, i, 4). The results of Bertrand (Bull. SOC. Chirn., 1880, 33, 556), who, on boiling ethyl iodide in absolute alcohol with silver nitrate, obtained ethyl nitrate and nitrite and acetalde- hyde, are explained by the fact t h a t he distilled off the excess of alcohol H.R. LE S. - 0.03642 t + 0.0003512 t2. T. H. P. i 2112 ABSTRACTS O F CHEMICAL PAPERS. and ethyl nitrate from the resultant products, the nitric acid thus being concentrated and acting on the remaining alcohol according to the equation : 2EtOH + HNO, = MeCHO + EtNO, + 2H,O. Nef (Zoc. cit.) explains the action of silver nitrate on ethyl iodide in alcoholic solu- tion as due t o the preliminary formation of methylene derivatives, caused by the splitting off of hydrogen and iodine atoms from the same carbon atom of the ethyl iodide, this and the subsequent reactions being expressed by the following equations : (1) Me*CH,II=Me*CH + HI,(2)HI + AgNO, = AgI + KNO,, (3)MeoCH + HNO, = Me*CH,*NO,, (4) Me*CH + Me*CH,*OH = Et,O.According to this view, the whole re- action should be unimolecular, since reaction (2), being ionic, has an im- mense velocity, and removes all the hydrogen iodide formed by reac- tion (I), which would hence proceed to an end. It has, however, been shown by Chiminello (Abstr., 1896, ii, 354) that the action of ethyl iodide on silver nitrate is bimolecular at O', although at higher temperatures, where the reaction proceeded much more rapidly, the velocity constant calculated for a bimolecular reaction was found t o increase appreciably; this increase is shown by the author to be due t o the rapid development of heat by the reaction, and the consequent heating of the solutions, since by using solutions with less concentra- tion, in which the velocity of reaction is correspondingly diminished, he finds the reaction t o be strictly bimolecular. From these considera- tions and also from the facts (I), that in the reaction in which tert- butyl iodide takes part (also considered by Nef) no dissociation with formation of a methylene derivative is possible, and (2), that with propyl iodide and silver nitrate in alcoholic solution, ethyl propyl ether is obtained, whilst with isopropyl iodide, ekhyl isopropyl ether is formed, whereas Nef's scheme would lead to the formation of ethyl isopropyl ether in both cases, the author concludes that Nef's views are erroneous and that the action of ethyl iodide on silver nitrate is one of double decomposition.The formation of ether in this reaction is assrimed to be due to the action of alcohol on the ethyl nitrate in statu rzascendi.T. H. P. a-Chlorovaleric Acids, By L ~ O N SERVAIS (BUZZ, Acad. Roy. BeZg., 1900, 695-724).-a-H.ydroxyvaleronitrile, formed by the interaction of butaldehyde with hydrogen cyanide, readily reacts with phos- phorus pentachloride to form a-chZorovaleronitriZ~,CH,Me*CH,*CHCl*CN, R slightly yellow liquid boiling a t 161'. a-ChZorovaZeric mid, obtained on hydrolysis with conceatrated hydrochloric acid, melts a t - 15', boils at 132-135' under 32 mu. and at 222' under 763 mm. pressure, has a sp. gr. 1.141 at 13*2', nD 1.44807 at ll', and is insoluble in water. The chboride, CH,Me*CH,* CHCl*COCl, is a pungent, fuming liquid ; it boils a t 155-157' under 763 mm. pressure, and has a sp. gr. 1.246. Ethyl a-chlorovalerate is a colourless oil with -an agreeable mint-like odour; i t boils at 185' under 752 mm.pressure, has a sp. gr. 1.040 at 11.8', and nD 1.43071 a t 11'. a-ChZoroisovaZeronitriZe, CHMe,. CHCl.CN, obtained from a-hydroxy- i8ovaleronitrile and phosphorus pentachloride, boils at 154-155' under 750 mm. pressure ; the corresponding bromo-derivative distils and decomposes at 175-180" under a pressure of 754 mm. a-Chlooro-ORGANIC CHEMISTRY. 113 isovnleric ucid is a crystalline mass which melts at 16' aria boils at 125-126' under 32 mm., and at 210-212' with slight decomposition under 756 mm. pressure; it has a sp. gr. 1.135 a t 13.2' and nD 1.44496 at 11'. The chloride, CHMe,-CHCl*COCl, is a pungent liquid of sp. gr. 1.135 at 13*2', and boils at 14S-149O under 759 mm.pressure. Ethyl a-chloroisovalerate has a penetrating, mint-like odour, boils at 177-1 79' under 756 mm. pressure, has a sp. gr. 1.021 at 13.2' and nD 1.42951 at 11'. a-Chloro-a-methylbzctyronitriZe, CMeEtCI-CN, prepared by the action of phosphorus pentachloride on the cyanohydrin derived from methyl ethyl ketone, is a colourless, mobile liquid which boils unchanged at 55-60' under 32 \mm. and at 120-135' with decomposition under 762 mm. pressure; it has a sp. gr. 0.8969 at 15'. a-Chloro-a- methylbutyric acid boils a t 123-124' under 36 mm. pressure, has a sp. gr. 1.101 a t 10' and nD 1.45077 a t 11'; i t distils at 200-205' under 754 mm. pressure, with loss of hydrogen chloride, and crystals of a methylcrotonic acid (1) separate from the distillate.The chloride, CMeEtCl*COCl, is a fuming liquid, boiling a t 143-144' under 749 mm. pressure, and having a sp. gr. 1-187 a t 14'. Ethyl a-chZoro-a-methyZ- butyrate boils at 175' under 747 mm. pressure, has a sp. gr. 1.069 a t 14', and nD 1.43683 at 11'. The relationship between the boiling points of these compounds is discussed at some length. W. A. D. Preparation of the Higher Acid Anhydrides (C,H2, - tO),O. By FRIEDRICH KRAFFT and W. ROSINY (Bey., 1900, 33, 3576-3579). -The anhydrides of the higher fatty acids are readily obtained by the action of the acid chlorides on the alkali salts when these com- pounds are thoroughly dried and purified. n-Heptoic anhyd&de, (C,H,,O),O, is a colourless, oily liquid boiling at 164.5' under 15 mm. pressure; it solidifies on cooling, and melts at 17'; it has a characteristic odour resembling that of ozone, and ab- sorbs moisture from the atmosphere, becoming converted into n-heptoic acid.n-Octoic anhydde, (C8H,,0),0, boils at 186" under 15 mm. pres- sure, and melts at - lo. n-Nonoic unhyd?*ide, (C,HI7O),O, forms a white, crystalline mass melting a t 16' and boiling at 207' under 15 mm. pressure. n-lauric anhydvide (n-dodecoic anhydride), (C,,H,,O),O, obtained in hard, white crystals melting at 41°, boils at 166' when distilled by the aid of von Babo's mercury-air pump. Myristic anhydride (tetradecoic anhydride), ( C,,H,70),0, forms white crystals, melts at 51', and boils at 198' in a high vacuum. Palrnitic anhydride (hexaclecoic anhydride) is a white solid, the melting point of which lies close t o that of palmitic acid.f'henylheptccdecenoic acid, C,H,* C,,H,,* CO,H, prepared by heating it mixture of benzaldehyde, palmitic anhydride, and dry sodium palmitate up t o 170', crystallises in slender needles and melts a t 87-88' ; the replacement of palmitic anhydride by acetic anhydride lessens the yield and purity of the product. The silver salt, C23H2502Ag, obtained by adding silver nitrate to the ammoniacal solution of the acd,114 ABSTRACTS OF CHEMICAL PAPERS. forms a voluminous precipitate which becomes crystalline on repeated washing, G. T. M. Action of Reducing Agents on the Two Isomeric Ethyl Nitrodimethylacrylates. By LOUIS BOUVEAULT and A. W AHL (Compt. rend., 1900, 131, 1211-1213. Compare this VOI., i , 4)- The a isomeride, CMe,:C(NO,)*CO,Et, yields ethyl dimethylacrylate when treated with stannous chloride or tin and hydrochloric acid, and gives rise to products very soluble in water by the action of sodium sulphite or bisulphite.Sodium nitrodimethylacrylate is pro- duced from the ester by the action of sodiumand moist ether, and the acid set free by the action of hydrochloric acid loses carbon dioxide and gives rise to a nitroisobutylene, probably identical with the pro- duct of direct nitration (Haitinger, Abstr., 1879, 700). Ethyl aminodimethylacrykate, CMe,:C(NH,)*CO,Et, produced by the action of aluminium amalgam on a moist ethereal solution of the a-nitro-ester, is a colourless liquid with an unpleasant odour; it boils at 93-95O, and has a sp. gr. 1.018 at Oo/4O. The compound is basic, and dissolves in dilute acids ; it is slightly soluble in water and is miscible with the ordinary organic solvents.Its carbamide and phenykcarbamide crystallise [n neevdles melting respectively at 175-1 76' and 130'. isoPropenylphenylhydantoin, CO<-NHph*CO, NH*CMe obtained by boil- ing the phenylcarbamide with dilute alcohol, melts at 225-226'. Phenylcarbaminodirnethy~ac~~ylic acid, produced by the action of sodium hydroxide solution on the phenylcarbamide, melts at 195-196'; the reaction also gives rise to a certain amount of the preceding compound. G. T. M. Condensation of Ketones with Ethyl Cyanoacetate. By GUSTAV KOMPPA (Be?*., 1900, 33, 3530-3534).-An ice-cold mixture of pure, dry acetone (1 mol.), and ethyl cyanoacetate (2 mols.), when treated with a few drops of diethylamine, undergoes condensation which is complete after the mixture has been left a t the ordinary temperature for a month, and then gradually heated on the water-bath for several hours ; when distilled under 10 mm.pressure, it yields a fraction boiling a t 100-120°, consisting mainly of ethyl dimethyl- methylenecyanoacetate, and a fraction 120-1 75" containing mainly ethyl dimethylmethylenedicyanoacetate. Ethyl dirnethylmethylenecyanoacetate [ethyl a-cyano-P-rnethylcrotonate], CMe,:C(CN)*CO,Et, is a colourless, mobile oil distilling at 108' under 10 mm. pressure, and solidifying t o a crystalline mass melting at 28', and readily soluble in all organic solvents. It is readily oxidised, but does not combine with bromine, Ethyl dimethylmethylenedicyanoacetate, [ethyl aa'-dicyano-PP-dimethyt?- glutarate], CMe,[CH(CN)*CO,Et],, is a thick oil distilling at 186-188' under 10 mm.pressure; it crystallises from ether and lighh petroleum in four-sided plates melting at 53-54'. With sodium ethoxide, i t yields a yellow, crystalline sodium derivative ; when hydrolysed with 50 per cent. sulphuric acid, it yields /3P-dimethyl glutaric acid. J. J. S.ORGANIC CHEMISTRY. 115 Transformation of LK-Undecenoic Acid into 6c-Undecenoio By FRIEDRICH KRAFFT and R. SELDIS Acid and Brassylic Acid. (Ber., 1900, 33, 35 7 1-3575).-i-Bromo-0~-undecenoic acid, CMeBr:CH*[CH,]7*C02H, prepared by saturating a carbon disulphide solution of undecolic acid (m. p. 59.5') at 50' with hydrogen bromide, is an oil solidifying at low temperatures and boiling with slight decomposition a t 202' under 16 mm.pressure. Bc- Undecenoic acid, CHMe:CH*[CH,]7eC0,H, ob- tained by reducing the preceding compound in alcoholic solution with sodium containing a trace of mercury, aluminium, or iron, boils at 165' under 10 mm. pressure, and melts below 19'. The new acid is distinguished from its isomeride, mundecenoic acid, by its lower melting point and by its behaviour towards an acetic acid solution of chromium trioxide, the former compound yielding azelaic acid, whilst the latter gives rise to sebscic acid. The Bt-acid forms a dibrornide, CllH,,Br,O,, an amide, C , , ~ , , O ~ H , , melting at 86-87', an insoluble silver salt, and a barium salt closely resembling that of the wisomeride. Komppa (Abstr., 1900, i, 201) successively prepared from methyl bromo-undecoate by the malonic ester synthesis a methyl diethyl unde- canetricarboxylate boiling at 223-224' under 10 mm. pressure, an oily undecanetricarboxylic acid, and a normal undecamethylenedicar boxylic acid melting a t 82'; as this dicarboxylic acid appeared to be isomeric and not identical with brassylic acid, he concluded that the latter must contain a branched chain.The authors find, on repeating this work, that the tricarboxylic ester boils at 233-234' under 10 mm. pressure, and that the acid is a solid which, on heating, yields brassylic acid melt- ingat 113-114', and corresponding in every respect with the product obtained from erucic acid. G. T. M. Derivatives of the Higher Unsaturated Carboxy-acids.By FRIEDRICH KRAFFT and F. TRITSCHLER (Ber., 1900,33,3580-3585). -iK-Undecenoic chloride, Cl,Hl,~COCl, obtained in quantitative yield by the action of phosphorus pentachloride on wundecenoic acid, is an oil boiling at 128.5' under 14 mm. pressure; the anhydride, (C,,H,,O),O, produced by heating together a mixture of the preceding compound and dry sodium undecenoate, melts at 13-13*5', and boils a t 170-179' in a high vacuum ; its tetrabromide, (C,,H1,Br2*CO),0, melts at 36.5'. wundecenarnide, C,,H,,O*NH,, prepared by treating the chloride with ice-cold aqueous ammonia, crystallises in white scales and melts at 87". LK- Undecenonitde, C, ,H,*CN, produced when the amide is warmed with phosphorus pentachloride, boils at 129-130' under 14 mm. and at 257" under the ordinary pressure.Amino-i~-undecylene, C,l~H,l*NH2, a colourless liquid solidifying in a freezing mixture and boiling a t 123' under 16 mm. pressure and at 238-240' under the ordinary pressure, is formed by reducing wun- decenonitrile with sodium and absolute alcohol ; its benxoyl derivative crystallises from benzene in leaflets, and melts a t 41-42' ; its phenyl- thiocarbamide forms colourless leaflets melting at 48'. Biundecenylthiocarbamide, produced from the base and carbon di- sulphide, crystallises in white leaflets and melts at 50.5'. Undecelz- amidoxime, C,,H1,*C(NH,):NOH, formed_by the addition of hydroxyl-116 ABSTRACTS OF CHEMICAL PAPERS. amine to the nitrile, crystallises from benzene in lustrous, white leaflets melting at 69'. Elaidic chloride, Cl7H,,*COC1, is a colourless, slightly fuming liquid boiling with partial decomposition at 216' under 13 mm.pressure ; it solidifies in a freezing mixture ; its amide melts at 89-90' ; elaido- lz~trik melts at - lo, and boils at 213-214' under 16 mm. pressure. Haidamine, C18H35*NH2, forms a white, crystalline mass melting at 25' and boiling at 194-195' under 13 mm. and a t 338-340' under the ordinary pressure; it rapidly absorbs carbon dioxide from the air. The hydrochloride crystallises in lustrous, white scales, and decomposes at 185'; the platinichloride and the benxoyl derivative form yellow scales and lustrous leaflets respectively, the latter melting at 63-64'. Dielaidylt~iocarbamide, iCS( NH C18H35)2, and p~enylelaidykhiocarbamide, C,,H,,NH*CS*NHPh, crystallise in white leaflets melting respec- tively at 73' and 65'.Oleic chloride is a colourless liquid boiling a t 213' under 13.5 mm. pressure ; the amide melts at 75', and yields elaidonitrile on treatment with phosphorus pentachloride. Brcwic chloride, C,,H,,*COCi, yields the amide melting at 94'. Brass- onitrile, C2,H,1*CN, melts at 21-22' to a colourless, inodorous liquid boiling a t 257' under 17 mm. pressure. Brassamine, C,,HgNH2, melts a t 45--46O, and boils at 250° under 11 mm. pres- sure ; Its benxoyl derivative crystallises in lustrous leaflets and melts at 74 -75O ; the hydrochloride and platinichloride are described, \the former melting and decomposing at 130O. Erucamide, melting at 78-79', when treated with phosphorus pentachloride, yields brass- onitrile.GI. T. M. By A. SCH~NE and BERNHARD TOLLENS (Zeit. Ver. deut. Zucl%e?*ind., 1900, 980-981).-Lactic acid is invariably found in beet-molasses, and owes its origin to the boiling of the sucrose solution with lime in the process of defecation. Action of Amy1 Formate on Ethyl Sodiocyanoace'tate. By E. GR~OOIRE DE BOLLEMONT (Bull. Xoc. Chim., 1901, [iii], 25, 15-18). -The principal product of the action of amyl formate on ethyl sodio- cyanoacetate at 100' is not ethyl formylcyanoacetate, which might be expected to be formed, but a compound, CN *C( :CH*ONa)*CO,*C,HII, in the production of which an interchange of the amyl and ethyl groups has taken place, whilst the formyl group must be ,considered, from analogy with homologous compounds (see following abstracts), to have assumed the enolic form.The barium salt, (C,H1,O3N),Ba, in which form the compound was isolated, crystallises in nacreous leaflets, and the silver salt i n tufts of slender needles. The former is identical with the barium salt obtained from the product of the action*of amyl By E. GREGOIRE DE BOLLEMONT (Bull. Soc. Chim , 1901, [iii], 25,18-28).- The following compounds were prepared by heating together molecular proportions of ethyl (or methyl) orthoformate with various alkyi cyanoacetates in the presence of acetic anhydride. Ethyl ethoxymethylenecyanocccetccte [a-cyano-P-sthoxyacrylccte] Lactic Acid in Beet-molasaes, T. H. P. formate on amyl sodiocyanoacetate. N. L. Ethoxy- and Methoxy-methylenecyanoacetic Esters.ORGANIC CHEMISTRY. 117 OEt*CH:C(CN)*CO,Et, from ethyl cyanoacetate and ethyl ortho- formate, crystallises from boiling alcohol in large, colourless needles melting a t 52-53O and boiling at 190-191' under 30 mm.pressure. The methyl ester crystallises from alcohol in large, transparent tablets melting a t 28' and boiling at about 200° under 32 mm. pressure; it has a sp. gr. 1.1255 at 2 3 O / 4 O . Determinations of the molecular refraction and dispersion of this compound, both in the pure state and when dissolved in toluene, gave values considerably higher than those calculated from Briihl's data, a result which is probably to be explained by the presence of the ethylenic linking. The propyl ester forms large, colourless crystals melting a t 31° and boiling a t 189' under 15 mm. pressure. The amyl ester could only be obtained as an oily liquid boiling a t about 211O under 35 mm.pressure. Methyl rnethoxymethylenecyanoacetate Ca-c?/ano-P-metho~yacrykcts], OMe*CH:C(CN)*CO,Me, obtained by the action of methyl orthoformate on methyl cyanoacetate and also by the action of methyl iodide on the silver derivative, OAg*CH:C(CN)*CO,Me, derived from methyl cyano- ethoxyacrylate, crystallises in slender needles melting a t 88' and boiling at 185O under 25 mm. pressure. The ethyl ester crystallises in small prisms melting at 99O and boiling at 190' under 17 mm. pressure. All these esters are only slightly soluble in water, but more or less soluble in organic solvents. Their aqueous solutions, when treated with barium hydroxide, yield the corresponding barium salts, whilst with ammonia or aniline, amides or anilides are obtained.N. L. Hydroxymethylenecyanoacetic Esters. By E. GR~GOIRE DE BOLLEMONT (Bull. Xoc. Chim., 1901, [iii], 25, 28-38).-These com- pounds are readily obtained by treating the corresponding ethoxy- and methoxy-cyanoacrglates (see preceding abstract) with barium hydr- oxide and decomposing the barium salts thus obtained with sulphuric acid. The alkyl hydroxycyanoacrylates are strong acids, capable of displacing acetic acid from its salts, and readily estimated alkali- metrically. They are slightly soluble in water, but more soluble in alcohol or ether. The lower members of the series crystallise well; all undergo more or less decomposition when distilled under diminished pressure. Their aqueous solutions give an intense orangebrown coloration with ferric chloride, Methyl hydroxymethylemcyanoacetute [a-cyuno-P hydroxyacrykate], OH°CH:C(CN)*CO,Me, has a pungent odoar and melts a t 136-137'.Determinations of the electric conductivity of t,he sodium salt a t 25' gave a result p-d1024-32= 12-01, approaching the value (11.3) usually found for the salts of monobasic acids. The affinity coefficient ( K 1.505) of the ester itself shows that i t must be considered as a strong organic acid, occupying a position between chloroacetic and dichloroacetic acids. The barium, copper, and silver salts have been prepared and analysed ; they are well crystallised compounds. The ethyl eater crystallises in colourless plates melting at 6 9 O and has a less pronounced acid char- acter than the preceding compound.The burium and copper salts have been prepared and analysed, The amyl eater could only be obtained118 ABSTRACTS OF CHEMICAL PAPERS. in an impure state. The barium and silver salts of this ester have Transformation of 0-Acyl Derivatives of Ethyl Acetoacetate into the Isomeric C-Acyl Derivatives. By LUDWIU CLAISEN and E. HAASE (Ber., 1900, 33, 3778-3784).-Acetophenone acetal, CH,*CPh( OEt),, can be converted into isoacetophenone ethyl ether, CH,:CPh*OEt, and this is transformed into phenyl prop91 ketone, CH,Et*CPhO, when it is boiled under a pressure of two atmospheres (Abstr., 1897, i, 188). It has not been found possible in any way to effect a similar transformation with ethyl P-ethoxycrotonate (ethyl O-ethyl- acetoacetate), CO,Et*CH:CMe*OEt.On the other hand, ethyl 0-acetylacetoacetate, CO,Et*CH:CMe*OAc, is converted into ethyl diacetoacetate, CO,Et*CHAc*CMeO or CO,Et*CHAc,, when it is dis- solved in ethyl acetate (a little ethyl acetoacetate being added) and heated with potassium carbonate on the water-bath, A similar transformatiw can be effected with methyl 0-acetykacetoacetate, which was prepared in like manner to the ethyl ester (Abstr. 1900, i, 373), boils at 95' under 17 mm. pressure, and has sp. gr. 1.1006 a t 18'; the copper derivativo of methyl diacetoacetate melts at 226-227', and does not decompose from 200' onwards, as stated previously (Abstr., 1894, i, 32).9 Without the addition of a little ethyl acetoacetate, the reaction takes place very slowly. The authors assume that even then a little of this substance is first formed, and then brings about the reaction described, first forming the potassio-derivative by means of the potassium carbonate present. '' The transformation of the 0-acetate by potassium carbonate into the potassium salt of the C-acetyl derivative is effected by means of a small quantity of ethyl potassioacetoacetate.The 0-acetate reacts with this, forming ethyl potassiodiacetoacetate and ethylacetoacetate ; and the regenerated ethyl acetoacetate reacts again as before." This view is borne out by the fact that ethyl sodioacetate and 0-acetylacetate give a good yield of diacetoacetate when heated together on the water-bath. The transformation in question is analogous to that of sodium phenyl carbonate into sodium salicylate ; such a migration of an acyl group from an 0 to a C atom is rare, however.Probably the formation of C-acyl derivatives of ethyl acetoacetate when the sodium derivative of this substance is treated with acid chlorides is to be explained, as a rule, in the same way, an 0-acyl derivative being formed at first, and then undergoing transformation. C. F. B. Decomposition of Normal Ammonium Oxalate. By HENRI GILLOT (BUZZ. Acad. Roy. BeZg., 1900, 744-'767).-On boiling an aquews solution of ammonium oxalate, the whole of the ammonia is progressively evolved, somewhat rapidly at first and more slowly later ; in the case of a solution of 0-151 gram of the salt in 750 C.C. of water, elimination is complete after boiling for 15 hours, the source of heat being an oil-bath at 130-140'.The ovalic acid simultaneously undergoes partial decomposition into carbon dioxide and formic acid. At 70°, the decomposition of ammonium oxalate by water takes place already been described (preceding abstracts), N. L.ORGANIC CHEMISTRY. 119 very slowly, whilst at 50° it ceases altogether. Cold, dry air does not alter the composition of the hydrated salt, (NH,),C,O,,H,O ; dry air at 65O, however, gradually expels the water of crystallisation, but not the ammonia; exposure of either the hydrated or anhydrous salt to moist air for 3; months at 19-22O yields a salt containing approxi- mately 2.7H20 without ammonia being lost. This stability towards air is noteworthy, since most other ammonium salts, under similar conditions, lose a large part of their ammonia.Aqueous solutions of ammonium oxalate evolve ammonia when ex- posed to light, the action being proportional to the intensityof illumi- nation; thus, in bright sunlight after 46 days, 2.30 per cent. of the salt was decomposed ; in diffused light, 0.85 per cent. ; and in dark- ness, only 0.42 per cent. Cineolic Acid. Resolution of r-Cineolic Acid into its Optically Active Components, By H A N ~ RUPE and MAX RONUS (Ber., 1901, 33, 3541-3546. Compare Abstr., 1900, i, 371)- Strychnine d-cineolate, C,,H,,O,N,, crystallises from hot water in large, compact prisms which melt at 195-197'. The mother liquors from this salt, on further evaporation, yield successively the salts of the inactive and laevo-acids. d- and Z-Cineolic acids separate from water in large, transparent crystals which melt at 79O and contain 1H,O.The anhydrous acids, obtained by exposure of the hydrated crystals in dry air, melt a t 138--1339O, and have [aIn + 18.56 and - 19.10 respectively at 20' in aqueous solution. They are readily soluble in water, alcohol, or cold chloroform (unlike the racemic acid, which is sparingly soluble in chloroform); when crptallised from dry ethyl acetate or ether, they separate in the form of aggregated leaflets. The difference in solubility of the racemic and active acids in water is remarkable; the former dissolves in 133.3 parts of water at So, the latter in 11.2. The crystals of the Lacid belong to the rhombic system, [a : b : c = 0.9815 : 1 : 1.47711. It has been observed on more than one occasion that the active acids undergo auto-racemisation when crystnllised, but no explanation of this is forthcoming.It was frequently observed, too, that on re- crystallising the d-acid from water, an acid in the form of large plates or prisms, containing 1H20 and melting at 123-126', was formed, but after dehydration had the same melting point as the original acid. d-Cineolic anhydride, Cl,Hl4O4, boils at 165-1 67" under 15 mm. pressure, dissolves sparingly in light petroleum, and crystallises from cold benzene in large, transparent, six-sided tablets melting a t 1 0 8 O . I n benzene solution, it gave [a]= + 45.37 at 20'. Attempted Synthesis of app-Trimethylglutaric Acid. By G. BLANC (BUZZ. Xoc. Chirn., 1901, [iii], 25, 68--73).-When Pp-di- methyllsvulic acid is treated with hydrocyanic acid, and the cyanohydrin thus produced is hydrolysed, the lactonic acid, PPy-trimetlLy~entane-ay- olidoic acid, CMe,<CH, b0 , is obtained, which crystallises from water in small, colourless prisms melting at 163-164'.This acid has the same melting point as the isomeric lactonic acid, W. A. D. A. L CMe(C0 H)*O120 ABSTRACTS OF CHEMICAL PAPERS. CH(CO,H)*? CMe2<CHMe-C0 ' which Balbiano (Abstr., 1900, i, 202) ob- tained by the oxidation of cnmphoric acid with potassium perman- ganate, but the two acids are essentially different, since a mixture of them melts between 110' and 120'. Moreover, the calcium and barium salts of the acid now described crystallise with 4 and 5H20 respec- tively, whereas the corresponding salts of Balbiano's acid crystallise with 2 and 4H20.Attempts to obtain aPP-trimethylglutaric acid by reducing the new lactonic acid with hydriodic acid were unsuccessful, however the experimental conditions were varied, although Balbiano's acid is stated to be readily reduced. This difference in the behaviour of the two acids is probably due to the fact that in the one the lactonic oxygen is connected with a tertiary carbon, and in the other to a secondary carbon atom. N. L. New Formal (Methylene) Compounds of Hydroxy-acids. By WILLIAM ALBERDA VAN EKENSTEIN (PYOC. K. Acud. Amst., 1900, 3, 400-403. Compare Weber and Tollens, Abstr., 1898, i, 61)-Form- aldehyde reacts with certain hydroxy-acids in aqueous solution, and methylene derivatives are produced which differ from those already known, inasmuch as the carboxyl group takes part in the condensation.These compounds are obtained by the repeated evaporation of the solutions of the hydroxy-acids with excess of formaldehyde ; the yield is small, and the product is separated from the unaltered material by extraction with ether, chloroform, or benzene. -co co*p The compound, gH ,o>CH*CH<o-CH~ , obtained from d-tartaric acid, crystallises in w6ite needles, melts at f17', and has [a], 112' ; the substance has a neutral reaction and is hydrolysed by acids or alkalis. Mesotartaric acid yields a similar compound which melts a t 106' and is inactive ; racemic acid, however, does not interact with formaldehyde. QH,*O The compound, o-co >C(CR,*CO,H),, from citric acid, melting a t 2004 may be titrated in the cold as a dibasic acid.The oily com- pound obtained from malic acid contains one methylene group and is laxorotator y. Formaldehyde has no action on salicylic and oxalic acids in aqueous solution, but it certainly reacts with the sugars, for their optical rota- tion is greatly affected, that of dextrose being doubled ; the rotatory powers of galactose, laevulose, arabinose, and mannose are considerably decreased, whilst d-rhamnose becomes lzevorotatgry. The methylene compounds of these carbohydrates are very unstable and have not been isolated. Benzaldehyde seems to interact with the sugars and hydroxy-acids in a similar manner, but the products are oily and unstable. G . T. M. Dilactones. By RUDOLPH FITTIG (Awnalen, 1900, 314, 1-96. Compare Abstr., 1898, i, 1 l).-[With ERNST RoTH]-T~~ ketodi-ORGANIC CHEMISTRY.121 lactone of P-acetylglutaric acid, CO<o--Q"e--o>CO, prepared by CH,*CH*CH, heating dried sodium tricarballylate with* acetic anhydride (1 8 11101s.) a t 120-130° during 36 hours, melts a t 99O, and is identical with the substance described by Emery (Abstr., 1897, i, 325) ; i t is completely hydrolysed when boiled with water during 24 hours. According to Emery's statement, P-acetylglutaric acid melts a t 47-50', but the author has obtained it in aggregates of long leaflets melting a t 58' ; it is best prepared by converting the dilactone into %he calcium salt, decomposing the aqueous solution with two-thirds the calculated quantity of hydrochloric acid, and allowing the ethereal extract to evaporate spontaneously. The calcium salt contains 3H20, and the silver salt is anhydrous.The aniline derivative of the ketodilactone crystallises in leaflets and neeclles, and melts a t 149O; according to Emery. the substance melts a t 153-1554'. .I- 0-YHMe Valerolactoneacetic acid, CO< repared by CH,~CH~CH,~CO,H' P z z , reducing the ketodilactone with sodiim amalgam, crystallises from chloroform in aggregates of small needles and melts at 84'; according t o Emery, the substance melts at 78-79'. The 6arium salt is amorphous, and the calcium salt contains 2H,O. Hydroxyethylglutccric acid, OH*CHMe*CH(CH,* C02H),, arising from valerolactoneacetic acid on hydrolysis, has not been isolated, the lactone being regenerated very easily ; the barium, cahium, and silver salts are anhydrous.r With WILHELM STERNBERG1 .-The ketodihctone of benzvlidene-& acetylglutaric acid, CO< 0 FMe-O>CO, obtained by heating C(: CHPh)*CH*CH, dried sodium tricarballylate with acetic inhydride (lg mols.) and benzaldehyde (1 mol.), crystallises in lustrous leaflets, and melts a t 162' ; the dibvomide, C1,H,,O,Br,, crystallises from hot benzene in small needles, and melts and decomposes at 16 3'. Benaylidene-P- acetylglutavic acid, C ~ ~ H I ~ O , , obtained by hydrolysing the dilactone, is converted into that substance so readily that it has not been isolated ; the calcium salt contains 1&H20, the barium salt lH,O, and the silvev salt is anhydrous. When the ketodilactone of benzylidene-P-acetylglutaric acid is reduced with sodium amalgam, two isomeric substances, C14H,404, are produced.The a-ke%etodiZactone crystallises from beuzene and melts at 134' ; hydrolysis converts it into a benzyl-P-glutaric acid, of which the calcium and barium salts contain 2H20, whilst the silver salt is anhydrous. The P-ketodilactolze crystallises from alcohol in stellate aggregates of leaflets, and melts a t 169'; the calcium salt of the benzyl-P-glutaric acid, which it yields on hydrolysis, contains 2$H20, the barium salt 4H20, and the silver salt is anhydrous. [With ERNST ROTH].-T~~ ketodilactone of benzylidene-P-acetyl- glutaric acid is also produced when dried sodium P-acetylglutarate is heated with benzaldehyde and acetic anhydride. [With TOM GuTHRIE].-T~~ ketodilactone of P-butyrylglutaric acid, 0-QPr-0 >CO, produced on heating dried sodium tricarb- '*<CH,.CH. CH,122 ABSTRACTS OF CHEMICAL PAPERS, allylate with butyric anhydride at 125O during 12 hours, crystallises in needles on adding ether or petroleum to the solution in chloroform, and melts at 55". P-Butyryylglutaric acid, COPra*CH(CH2* CO,H),, crystallises in prisms or leaflets, and is readily soluble in water or alcohol ; it melts a t 88', and belongs to the monoclinic system [p = 58'30'1. The barium salt contains 2H,O, the calcium salt 2+H,O, and the silver 0-QHPP CH,. CH* CH,. CO,H,', salt is anhydrous. Heptolactoneacetic acid, CO< formed when the ketodilactone is reduced with sodium amalgam, crystallises in rosettes of white needles and melts a t 53' ; the crystals belong to the monoclinic system [a : b= 1.5443 : 1 ; /3 = 78'56'1.The calcium salt contains 2H,O, the barium and silver salts being anhydrous. Heptolactoneacetic acid is hydrolysed with difficulty, but the protracted action of concentrated barium hydroxide solution yields the dibasic acid, CBHIGO5, which could not be isolated; the calcium, barium, and silver salts are anhydrous. The ketodilactorne of P-isobutyrylglutaric acid, prepared from dried sodium tri&rballyla<e and isobutyric anhydride, melts at 89-90'. /3-isoButyryZgZutaric acid, COPra*CE(CH *CO,H),, melts at 99', and crystallises in the monoclinic system fa : b : c= 1.5927 : 1 : 2.5159 ; p=8l06']. The barium salt contains 2H20, and the calcium salt 3H,O, the silver salt being anhydrous. [With HARRY SALOMON].-T~~ ketodikactone of /3-benzoylglutaric acid, >CO, obtained from dried sodium tricarballylate and benzoic anhydride, melts at 137', and separates, on adding ether to the chloroform solution, in rhombic crystals [a : b : c = 0.6478 : 1 : 0.86591.P-Benxoplylutaric acid, COPh*CK( CH,*CO,H),, crystallising from a mixture of ether and petroleum in bundles of needles, melts at 122'; the barium salt contains 4H,O, the calcium and silver salts being anhydrous. Phenqylbutyvoylacetoneacetic mid, 0-YPh-0 H,*CH*CH, - - - 0-YHPh CO<cH,~cH~cH,~co,H, prepared by reducing the dilactone with sodium amalgam, &ystdlises from water in transparent prisms and melts at 114'; the barium salt contains 3B,O, and the calcium salt 2 H,O, the silver salt be1 n g anhydrous. Phen y 1 bu tyrolactoneace tic acid is hydrolysed only slowly, and the dibasic hydroxy-acid, C,,H1,O,, could not be isolated ; the calcium and b a k m salts contain lH,O, and the silver salt is anhydrous.When dried phenylbutyrolactoneacetic acid is distilled, P-methylphenylisocrotonic acid and P-methylnaphthol are produced. [With OSKAR GOTTSCHE].-T~~ ketodiluctorne of P-phthaloylglutaric >GO(?), prepared from dried sodium tricarballylate and phthalic anhydride, crystallises from chloroform in colourless needles, and melts a t 208'. P-Phthaloylglutaric acid, C0,H*C,H,-CO*CH(CH,*C0,H)2, produced by the action of boiling O-?(C6 K,*CO,H)*O acid, CO<CH,.CH-- CH*ORGANIC CHEMISTRY. 123 water on the dilactone, crystallises from ether in small needles, buf; has no definite melting point, undergoing a change at 135-140°, and finally becoming liquid at the melting point of the dilactone; the calcium salt contains 5H20, the barium salt 9H,O, and the silver salt is anhvdrous.J O-YH*C,H,*CO,H Carboxyphen y l but yrolact oneucetic acid, CO< CH;CH*CH,*CO,H (t>, obtained by reducing the ketodiladone with sodiuk amalga.cn, ciystal- lises from boiling water in lustrous plates containing 1H,O, which is removed a t 100'; acetone also deposits i t in monoclinic plates, and when anhydrous it melts a t 165'. The calcium salt contains 2H20, and the 6ariurn salt 6H20, the silver salt being anhydrous. Hydro- lysis with alkalis proceeds slowly, and the dibasic hydroxy-acid, C,,H,,07, has not been isolated; the barium and calcium salts contain lOH,O, whilst the silver salt is anhydrous.[With HARRY SALOMON] .-The ketodilactone of P-acetyl trimet hyl- glutaric acid, CO<CH2.CMe. axe2 >CO, obtained from dried sodium camphoronate and acetic anhydride, crystallises from chloroform in long needles, and melts a t 147.5-148'. P-Acetyltrimethylglutaric acid, C02H*CH,*CMe(COMe)*CMe2*C0,H, crystallises from boiling water in prisms, softens at 125', and melts at 140'; the barium salt contains 3hH,O, the culcium salt 2H20, and the silver salt is anhydrous. The acid resists the action of sodium amalgam. Syntheses with Ethyl Sodioacetoacetate and the Formation of Rings of Four Carbon Atoms by means of Sodium Ethoxide. By ARTHUR MICHAEL (Ber., 1900, 33, 3731-3769).- The ester of a substituted malonic acid was mixed with a solution of sodium in absolute alcohol, and the ester of an unqnturated acid was added; the whole was sometimes warmed to complete the reaction.The alcohol was distilled off, the residue dissolved in ether, and sub- stances of an acid nature removed by shaking with dilute aqueous potassium hydroxide; of these acid substances, a part could be set free by saturating the alkaline liquid with carbon dioxide. The neutral product of the reaction was thus obtained pure ; other observers (Auwers, Abstr., 1891, i, 5 4 6 ; 1892, i, 4 1 ; Ruhemann and Cunnington, Trans., 1898, 73, 1006) have omitted the extraction of the acid products, and obtained only mixtures of different substances. Ethyl e thylmalonate and fumarate give ethyl pentane-apyy-tetra- carboxylate, CO,Et*CH,*CH(CO,Et)*CEt(CO,Et),, which boils at 197' (corr.) under 13.5 mm.pressure ; the ethyltricarballylic acid obtained from it by hydrolysis melts a t 155-157'. Of the acid products, one is soluble in aqueous alkali carbonate, and appears t o be the triethyl hydrogen ester, for at 180' it loses carbon dioxide and forms a liquid that boils at 168-169' under 11 mm. pressure and has the com- position of ethyl pentane-apy-tricarboxylate. Sodium dissolves in an ethereal solution of the tetrethyl salt, and when the product is freed from ether and heated with methyl iodide a t loo", ethyl a-methylpentane- apyy-tetracarboxylate is obtained ; this boils a t 201-202' (corr.) under 12 mm. pressure, is acted on further by sodium in ethereal solution. O-?Me-0 M. 0. F.124 ABSTRACTS OF CHEMICAL PAPERS.and when hydrolysed with boiling, dilute hydrochloric acid, yields a product melting at 138-146' after several recrgstallisations, presumably a mixture of stereoisomeric met hylethylt ricar ball y lic acids. Ethyl methylmalonate and fumarate give ethyl butane-apyy-tetra- carboxylate. This boils a t 206 5-207' (corr.) under 20 mm. pressure ; when hydrolysed, it yields only P-methyltricarballylic acid melting a t 143-146', and not a mixture of stereoisomerides. Sodium acts on it, and the product reacts at 100' with methyl iodide to form ethyl a-methyl- butane-a/3yytetracarboxyZute ; this boils at 198-199' under 13 mm. prewure, reacts further with sodium, and can be hydrolysed, although with difficulty, to a-methylbutane-apy-tricarboxylic acid, which melts at 190-1 93' ; probably a little of the stereoisomeric acid is formed at the same time.Ethyl malonate and citraconate give ethyl P-meth?/Z~o~ane-aPyy-tetrcc- cavboxylute. This boils a t 199-199-5' (corr.) under 11 mm. pressure, and can be hydrolysed, although with difficulty, to P-methyltricarballylic acid melting at 168-113'. From its sodium derivative and methyl iodide, ethyl P-methylbutane-apyy-tetracarboxylate can be obtained ; this boils a t 202-205O (corr.) under 13 mm. pressure, is attacked slowly by sodium, and can be hydrolysed, although with difficulty, to a mixture of stereoisomeric /3-methylbutane-apy-tricarboxylic acids, from which a product melting a t 196-198' was obtained by repeated recrystallisa- tion. By using ethyl instead of methyl iodide, ethyl P-methylpentane- a&y-tetracarboxylate is obtained ; this boils at 199-200' (corr.) under 10 mm.pressure, can be hydrolysed slowly, and reacts further with sodium. When the sodium derivative of ethyl p-methyIpropane.a/3yy- tetracarboxylate is treated with water, the solution freed from neutral substances by extraction with ether, and saturated with carbon dioxide, ethyl methylketotetramethylenetricarboxylate is formed ; the sodium derivative of: ethyl P-methylpentane-apyy-tetracarboxylate yields an analogous ketotetramethylene derivative (see below). Ethyl methylmalonate and crotonate give p-methylbutane-ayy-tricar6- oxylate; this boils at 1605-161' (corr.) under 10 mm. pressure, and reacts readily with sodium; the product of this reaction, when heated with methyl iodide, yields ethyl dimethylbwtane-ayy-tricar6oxyhte, boiling at 161-162' (corr,) under 9 mm.pressure. Ethyl malonate and crotonate give ethyl P-methylpropane-ayy-tri- carboxylate, boiling at 165-166' (corr.) under 11 mm. pressure, to- gether with a little ethyl /36-dimethylpentane-ayyetetracarboxylate, boiling and decomposing slightly a t 204-207' (corr.) under 9 mm. pres- sure ; the second product must have resulted from the condensation of the first with ethyl crotonate. The sodium derivative of ethyl P-methyl- propane-ayy-tricarboxylate reacts with methyl iodide ; the resulting methyl derivative boils a t 166-167' (corr.) under 10 mm. pressure, and reacts only slowly with sodium; it is not identical with the ethyl P-methylbutane-ayy-tricarboxylate described above. Ethyl propane-aP/3- tricarboxy late (from ethyl e t henyltricarboxylate, sodium ethoxide, and methyl iodide) appears to form a little of a sodium derivative, but only with great difficulty.Ethyl ethylmalonate and citraconate yield hardly any of the normalORGANIC CHEMISTRY. 125 condensation product. The chief product is soluble in alkali hydr- oxides, but is liberated by saturation with carbon dioxide; it boils at 204-205' (corr.) under 13 mm. pressure, and yields an oxime, phenyl- hydraxone and semicurbaxone, all oily in consistency. It was identified as ethyl methylethylketotetramethylenetriccwboxylate, CO<gE$$)$!:)>CM e*CO,Et ; it is hydrolysed readily by boiling dilute hydrochloric acid to a mixture of isomeric methyZethylketotetrunzethyZenecurboxyZic acids, CO<CH2-->CMe*C0,H.CHEt Of these, the one which is less soluble in water melts at 72-74'; its silver salt and semicctrbazone (melting at 193-194') were analysed ; the more soluble one melts a t 37-39", its sernicarbaxone at 191-192'; when distilled (at 180-182' under 15 mm. pressure) or heated in aqueous solution, it undergoes a partial transformation into the less soluble isomeride. Ethyl methylmalonate and citraconate yield ethyl dimethylketotetra- methyllenetricarboxylate, boiling at 207-208' (corr.) under 20 mm. pressure. When hydrolysed, this yields a mixture of isomeric dimethylketotetramethylenecarboxylic acids, which boils at 187' (corr.) under 25 mm. pressure, and melts at 56-59' ; the semicarbaxone melts at 195-196'.Ethyl malonate and citraconate yield, in addition to the product described above, ethyl methylketotetramethylenetricarboxylate, boiling at 213-214' (corr.) under 17 mm. pressure. When hydrolysed, this yields a single methyZketotetramethylenecarboxylic acid, melting at 62-64' ; the semicarbaxone melts a t 192-193'. When ethyl cinnamate in ethereal solution is digested with sodium until the latter has dissolved, the product poured into water, and the aqueous solution extracted with ether, an oil boiling at 205-210° under 15-17 mm. pressure is obtained, probably a product of poly- merisation. From ethyl crotonate, a product was obtained boiling at 126' (corr.) under 9 mm., a t 258-259' under 773 mm. pressure. It has a composition and vapour density corresponding to a bimolecular polymeride of the ester, C,,H,,O,.When hydrolysed, it yields a dibasic acid, C,H,,O,, which melts at 128-129', and is oxidised almost instantly by permanganate; its silver and barium salts, the latter with 1H,O, were prepared and analysed. I n an introduction to the paper, the mechanism of the reactions described is considered from the point of view occupied by the author (Abstr., 1900, i, 321). C. F. B. Action of Formaldehyde Solution on Calcium Carbide. By LUDWIQ VANINO (Chem. Centr., 1900, ii, 1150 ; from Pharm. Centr.-H., 1900, 41, 666).-Formaldehyde may be used to moderate the action of water on calcium carbide. With a solution of formalin in 8 vols. of water, the rate of evolution of acetylene is much slower than with water, whilst in 40 per cent.solution the aldehyde almost completely inhibits the action. E. W. W. VOL. LXXX. i. k126 ABSTRACTS OF CHEMICAL PAPERS. Specific Difference between Ketones and Aldehydes. By WILLIAM OECHSNER DE CONINCK and SERVANT (Bull. Acad. Roy. Belg., 1900, 313-316).-Whereas ketones, either alone or in presence of water or dilute alkali, are not changed at the ordinary temperature by the long-continued passage through them of a current of air, alde- hydes under the same conditions are sensibly oxidised to acids ; the experiments were made with acetone, benzophenone, and acetaldehyde. W. A. D. Methyl Ethyl Ketone. By L ~ O N VAN REYMENANT (Bull. Xoc. Roy. Rely., 1900, 724-744).-The product of the action of chlorine (1 mol.), or of sulphuryl chloride on methyl ethyl ketone, consists, two-thirds of the secondary chloro-derivative, COMe*CHMeCl (Vladesco, Abstr., 1892, 424, SlO), and nearly one-third of chloro- methyl ethyl ketone, CH,Cl*CO*CH,Me.The former boils a t 116' under 758 mm. pressure, has a sp. gr. 1.032 at O', and, on oxidation, yields a-chloropropionic acid ; the latter boils at 125' under 756 mm. pres- sure, has a sp. gr. 1-08 a t 13', n, 1.42701 at lo', a mol. refraction 25-35 (calc. 25*55), and yields cnloroacetic acid on oxidation. With bromine, similar uhiwatiwes, COMe*CHMeBr and CH,Br*CO*CH,Me, are obtained, the former boiling at 133-134', and the latter a t 145-1 46' ; both are nearly colourless, tear-exciting liquids, which become coloured in the light. P-Acetylethyl acetate, CH,*CO,*CHMeAc, obtained by boiling the foregoing secondary chloro-derivative with alcoholic potassium acetate, boils a t 164' under the ordinary presgure, has a sp.gr. 1.027 at 13", nD 1.4143 at 13.5", and a mol. refraction 31.62 (calc. 31.61) ; propionylmethylacetate, CH,*CO,*CH,COEt, corre- sponding with the primary chloro-derivative, boils at 176', and has a sp.gr.1-029 at 13*4', n, 1.4151, and amol. refraction 31.37 (calc. 31.37). Methylacetylcarbinol, CHMeAcOOH, obtained by hydrolysing either the corresponding chloro-derivative or acetate, melts at 15', boils a t 148", and has a sp. gr. 1.012 at 16.5', n, 1.4272, and a mol. refraction 22.20 (calc. 23.32). Propionylcarbinol, OH*CH,* CO*CH,Me, boils at 160'. Although cyanoacetone, CH,Bc.CN, cannot be obtained by the interaction of chloroacetone with potassium cyanide, the latter readily converts the foregoing halogen derivatives of methyl ethyl ketone into their cyanides a t the ordinary temperature.a-AcetyZpropionitriZe, CHMeBc.CN, boils at 145-146' (Vladesoo, loc. cit., gives 156"), has a sp. gr. 1.494 at 13', and a mol. refraction 25.03 (calc. 25.33) ; with sodium ethoxide, it forms a sodium derivative, CNaMeAC.CN, which, with methyl iodide, yields dimethylacetylacetonitde, CMe,Bc.CN, a yellow liquid which boils a t 163-164', and has a sp. gr. 1.008 at 13'. The sodium derivative reacts with chlorine, forming a-chloro-a-acetyl- propionitrile, CClMeAc. CN, a yellowish liquid boiling a t 95' under 45 mm. pressure ; the analogous bromo-derivative, CBrMeAc.CN, boils at 122' under 30 mm, pressure. Both these compounds react energetically with potassium cyanide to form methylacetylmalononitrile, CMeAc(CN),, which boils at 195'.a-Acetylpopionic acid, CHMeAc*C:O,H, obtained by hydrolysing itsORGANIC CHEMISTRY. 127 nitrile, boils at 224O under 34 mm. pressure. a-Chloro-a-acetylpropionic acid, CClMeAc*CO,H, boils at 141O under 45 mm. pressure, and a-bromo-a-acetylpropionic ucid, CBrMeAc*CO,H, at 150' under the same pressure. Propionplacetonitrile, COEt*CH,* CN, obtained from the correspond- ing chloro-derivative, boils at 164O, has a sp. gr. 0.976 at 9' and a mol. refraction 25.00 (calc. 27.03). W. A. D. Derivatives of Methyl Nonyl Ketone. By HENRI CARETTE (Compt. rend., 1900, 131, 1225--1227).-Methyl nonyl ketone and benzaldehyde do not interact even at 130' unless they are mixed to- gother in the presence of potassium hydroxide.The compound, C,,H,,O, produced when a cold 0.25 per cent, solution of the alkali in dilute alcohol is added to a mixture of the ketone and aldehyde in mol. proportions, readily dissolves in the ordinary organic solvents, melts at 41-42', and boils at 245O under 35 mm. pressure. The polymeride, (C,8H260)2, obtained either by boiling the preceding compound with a 1 per cent. solution of potassium hydroxide in 95 per cent. alcohol, or by heating its generators in the same medium, crystallises in needles, melts at 116O, and boils with partial decomposition at 310-340' under 35 mm. pressure. G. T. M. Birotation of Dextrose. By YUKICHI OSAKA (Zeit. physikul. Chem., 1900, 35, 661-706).-The change of rotation of dextrose takes place in accordance with the equation li: = l/t.log,(uo - ao)/(a - ao), where uO and a.are the initial and final rotations, and a is the rotation at the time t. This has been proved by Levy (Abstr., 1895, i, 586) and Trey (Abstr., 1S96, ii, 139 ; 1897, ii, 299), and the author now finds, using numbers obtained by Tollens and others, that the same law holds in the case of lzevulose, rhamnose, I-arabinose, fucose, I-xylose, d-galactose, maltose, and milk sugar. I n the case of dextrose, the change of rotation is accelerated in the presence both of hydroxyl and hydrogen ions, the catalytic effect of the former, however, being much greater than that of the latter. The velocity of the retrogression of the rotation is approximately proportional to the concentration of the hydroxyl ions, and to the square root of the concentration of the hydro- gen ions.Neutral salts appear to increase the catalytic efficiency of the hydroxyl ions, but to be practically without effect on t h a t of the hydrogen ions. The author agrees with Cohen (Abstr., 1900, ii, 716) in regarding dextrose as a very weak acid. J . C. P. Influence of the Nature and Intensity of Light on the In- version of Sucrose by Mineral Acids. By HENRI GILLOT (Bull. Acud. Rog. Belg., 1900, 863-874).-The author has examined com- paratively the rate of inversion of sucrose in aqueous solution containing sulphuric or hydrochloric acid, when exposed to light of different wave- lengths; in each case, the fall of rotatory power and the increase of cupric-reducing power were compared with similar values obtained with a solution left in darkness. Light of all wave-lengths promotes in- version, but rays in the blue, violet, and ultra-violet are much more active than those in the yellow or red.W. A. D. k 2128 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Sucrose Solutions towards Strontia Ltt 125-128". By A. SCHONE and BERNHARD TOLLENS (Zeit. Ver. deut. Zucker-lnd., 1900, 978--979).-When aqueous solutions of sucrose and strontium hydroxide are heated together in a n autoclave a t 125-128', no trace of raffinose is formed, The raffinose present in molasses hence comes from the beet. T. H. P. Diagnosis of Primary and Secondary Amines. By OSCAR HINSBERU (Ber., 1900, 33, 3526-3529.Compare Abstr., 1891,49).- Solonina (J. Russ. Phys. Chem. Soc., 1897, 29, 404 ; Abstr., 1900, i, 147) and Bamberger (Abstr., 1899, i, 701) have shown that benzene- or toluene-sulphonic chloride cannot always be used with success in the diagnosis of primary and secondary amines. The author now recom- mends P-anthraquinonesulphonic chloride in the presence of excess of alkali (MacHoul, Abstr., 1881, 51). The amide thus obtained, if dis- coloured, is recrystallised and then 0.05 gram dissolved in hot alcohol, and t o the colourless, or only pale yellow, solution, 0.5 C.C. of 25 per cent. potassium hydroxide is added. If a secondary amine were originally present, the colour remains unaltered, and on addition of more alkali, the sulphonamide is precipitated in a crystalline form; with a primary amine, however, the solution assumes a deep yellow or yellowish-red colour owing t o the formation of a salt. The method has been tried with a number of bases and has given very satisfactory results.P-AnthraqzcinonesuZphone-n-~eptylc, C14H702* SO, *NH* C7H15, forms yellow needles melting at 160' and insoluble in water. /3-AmthraquinonesuZphonemethyZaniZide, C14H702*S02*NMePh, forms pale yellow needles melting at 182'. J. J. S. Alternation of' Volatility in the Series of Normal Primary Diamines. By LOUIS HENRY (Bull. Acad. Roy. BeZg., 1900, 795-803). -In the series of normal primary monoamines, NH,. CH,* [CH21n* CH3, there is a regular progressive increase in the boiling point of about 27', the difference between tho boiling points of the even pair, C, and C, (57'), being practically the same as that of the odd pair, C, and C, (54').In the case of the diamines, NH2*[CH,],*NH,, how- ever, there is an alternation in boiling point similar to that traced in the case of the acid chlorides (Abstr., 1899, i, 735), the snccessive differences in boiling point of the C,, C,, C,, and C, diamines being 19', 25', and 19'. The difference between the even pair, C, and C, (44'), is, however, the same as that between the odd pair, C, and C, (44"). Similar relationships connect the boiling points of the two classes of amines and those of the parent hydrocarbons; for these, the original should be consulted. W. A. D. Action of a-Chlorohydrin on some Tertiary Amines. By ALEXANDER BIENENTHAL (Ber., 1900,33, 3500--3506).-The additive compound, NEt,Cl* CH,* UH(OH)*CH,* OH, formed on heating a-chloro- hydrin with triethylarnine for 8 hours a t looo, is a non-crystal- lisahle syrup which, when treated with moist silver hydroxide in aqueous solution, yields a strongly caustic base; the picrate of theORGANIC CHEMISTRY. 129 latter forms long prisms melting at 114', and the platinichloride mono- clinic plates melting at 215.5'.The additive compound, NPr,Cl* CH,. CH(OH)*CH* OH, of triprop- ylamine, obtained similarly, is also a syrup ; the picpate of the base, OH*NPr3* C3H702, crystallises from alcohol in small, yellow prisms, and melts a t 79-80", the aurichloride melting a t 94-95', The compound, C,NH,,MeCI* C,H702, formed by the interaction of 1-methylpiperidine and a-chlorohydrin at loo', crystallises from alcohol in long prisms, sinters at 229' and melts a t 233-234'; the platinichloride of the derived base crystallises from alcohol in thick, yellow prisms, and decomposes at 206-207", the crystalline mercuri- chloride melting at 169-170'.The compound, C,N H,Cl* C3H702, derived from quinoline, crystal- lises from alcohol in small, white leaflets, melts at 170', and, with moist silver oxide, yields a base the platinichlovide of which forms small, yellow plates melting at 282-283'; the aurichloride is amor- phous and melts at 100-101', the mercurichloride forms transparent, white needles melting a t 114-115', and the picrate melts at 120'. The strychnine derivative, C2,H2,02N,C1* C3H702,, formed on heat - ing the components for 1 hour at 190', crystallises from alcohol in white prisms, and does not melt at 290'; it is not acted on by alkalis, but with moist silver oxide yields a base the platinichloride of which crystallises from alcohol in small, yellow needles melting at 230' ; the aurichloride melts at 214', and the mercurichloride at 199O, whilst the picpate decomposes a t 280'.No well-chamcterised derivative could be obtained by the inter- action of 2-picoline with a chlorohydrin. W. A. D. Conversion of Amino-fatty Acids into the Corresponding Chloro-acids. By EMIL JOCHEM (Zeit. physiol. Chem., 1900, 31, 119-131. Compare Curtius, Abstr., 1884, 42 ; Tilden, Trans., 1895, 67, 489).-Chlorinated acids are readily obtained when 1 mol. pro- portion of sodium nitrite in concentrated solution is added drop by drop to the amino-acid dissolved or suspended in 10 times its weight of concentrated hydrochloric acid.The method has given good results with amino-derivatives of the acetic and oxalic acid series, also with aromatic-amino acids which contain the amino-group in a side chain, but not when' the amino-group is directly attached t o the benzene nucleus, or yet with fatty or aromatic amines. This reaction accounts for the formation of chloro-acids when albumin is treated with hydrochloric acid and sodium nitrite. a-Chloroglutaric acid, C5H,0,Cl, crystallises from a mixture of ether and light petroleum in well developed pyramids, sinters at 9 7 O , and is completely melted a t 100' ; it dissolves readily in most solvents, with the exception of benzene, chloroform, or light petroleum ; aqueous solutionsof the acid or of its salts readily decompose, yielding a-hydroxy- glutaric acid.The copper and barium salts are both readily soluble in water, but are precipitated on the addition of alcohol; the diethyE ester is an oil distilling a t 140-145' under 15 mm. pressure, and has a sp. gr. 1.14 at 23'. a-Chloraisohexoic acid, C,H,,O,Cl, has been obtained from leucine in130 ABSTRACTS OF CHEMICAL PAPERS, the form of an oil insoluble in water, and readily undergoes decom- position, evolving hydrogen chloride even at 40' ; its ethyl ester distils at 190' under atmospheric, or a t 91-95' under 15 mm., pressure, and has a sp. gr. 1-01 at 23'; when hydrolysed, it yields an a-hydroxyiso- hexoic acid melting at 67-70', the zinc salt of which contains 2H20 (compare Waage, Anlzalen, 1861, 118, 87; Gmelin, Abstr., 1894, i, 501).J. J, 8. Action of Pyruvic Acid on its Ammonium Salt, By A. W. K. DE JONG (Rec. Trav. Chim., 1900, 19, 259-310),-The pyruvic acid employed was prepared by a modification of the methods devised by Visser (here described for the first time) and Simon, namely, by heating together potassium hydrogen tartrate, potassium hydrogen sulphate, and sulphuric acid. The estimationof the acid is effected by means of its phenylhydrazone, and the corrections necessary for the solubility of the compound are given. When solid ammonium carbonate is gradually added to a concen- trated solution of pyruvic acid, a considerable elevation of temperature occurs, carbon dioxide is evolved, and ammonium a-acetylaminopropionate slowly crystallises out.Estimation of the amount of carbon dioxide evolved shows that for each rnol. of the latter a mol. of ammonia enters into reaction. The free acid is obtained by adding to pyruvic acid half the quantity of ammonium carbonate required for neutralisation, or by treating the ammonium salt with an equivalent quantity of pyruvic acid. a-Acetylaminopropionic acid, NHAc* CHMe*C02H, crystal1 ises in large, rhombic plates or needles [a : b : c = 0.7729 : 1 : 1 *0983], melts at; 132-133', and is soluble in water or alcohol but almost insoluble in ether. When heated with hydrochloric acid orpodium hydroxide solution, it is hydrolysed to acetic acid and a-alanine. Conversely, a-acetylamino- propionic acid is readily obtained by heating a-alanine with a slight excess of acetic anhydride a t about 70'.The following metallic salts of a-acetylaminopropionic acid have been prepared ; the sodium and potass- ium salts could only be obtained as hygroscopic syrups, the others are crystalline : ammonium with H20, barium with lQH,O, calcium with liH,O, magnesium with 7H20, zinc with H20, lead with 3H20, copper, and silver with H,O. Ethyl a-acetylaminopropionate crystallises in hygroscopic needles melting a t 39-40', and by the action of chlorine is converted into the corresponding chloroethyl ester, C,H,O,N*CHClMe, which, on hydrolysis, yields hydrogen chloride, acetaldehyde, and a-acetylaminopropionic acid. The amide, C,H,O,N*NH,, crystallises in small, rhombic prisms melting at 157-158'.The hydro- chloride, C,H,O?N,HCl, crystallises in hygroscopic needles and is un- stable. The nztrate crystallises in very soluble needles melting and decomposing at 64-65'. When neutralised with calcium carbonate, the well-crystallised double salt, (CSH,03N)2Ca,(N03)2Ca,6H20, is formed. Ammonium pyruvate, when pure, forms white needles. As an explanation of the formation of a-acetylaminopropionic acid, it is suggested that ammonium pyruvate is tautomeric with the as yet a-Acetylnminopropionic acid also forms salts with acids.ORGANIC CHEMISTRY. 131 unknown a-aminohydroxypropionic acid. On tbis hypothesis, the re- actions concerned in the formation of a-acetylaminopropionic acid are brought into harmony with the views generally held as to the action of ammonia on aldehydes and ketones.From the mother liquors obtained in the preparation of a-rtcetyl- aminopropionic acid, two new acids of the composition C,H,,O,N have been isolated by means of their barium salts. The one crystallises in needles decomposing at 220°, whilst the other crystallises, with 1H20, in small prisms which decompose at 2089 The barium and silver salts of these acids have been prepared and analysed. N. L. Action of Ammonia and Aniline on Hydroxymethylene- cyanoacetic Esters and their Alkyl Derivatives. By E. GR~QOIRE DE BOLLEMONT (Bull. SOC. Chim., 1901, [iii], 25, 39--46).-The alkyl hydroxy-, methoxy-, and ethoxy-cyanoacrylates (this vol., i, 116), when treated with ammonia, yield one and the same series of amino-deriva- tives, NH,* CH:C(CN)*CO,R.These are stable, crystalline compounds which are very slightly soluble in water, but soluble in alcohol, ether, or excess of ammonia; their solutions are neutral, and give no colora- tion with ferric chloride. Meth yl nminome thylenecyanoacetate CP-amino-a-cy~noacrylatel, NH,*CH:C(CN) *C02Me, crystallises in long, colourless needles melting a t 128'. The ethyl ester crystallises in slender needles melting at 130' and boiling at 2 16' under 19 mm. pressure, The propyl ester crystallises in small prisms melting at 46', and the amyl ester in large, white scales melting at 1019 The following anilino-derivatives are precisely analogous to these amino-derivatives. Ethyl anilinomethylenecyccnoacetate [P-anilino-a-cyanoacrylate], NH Ph* C H: C( CN) CO,Et, crystallises from alcohol in long needles or thin, monoclinic plates, according to the temperature and concentration.The methyl ester crystallises in slender, white needles melting at 175", the pvopyl ester in large tablets melting at 89-90°, and the amyl ester in white scales melting at 90'. N. I;. Constitution of Nitroferricyanides. By ARTURO MIOLATI (Zeit. anorg. Chem., 1900, 25, 318).-A question of priority (compare Hof- mann, Abstr., 1900, i, 591). E. 0. R. Ph ysico-chemical Researches on the Behaviour of Uric Acid and its Salts in Solution. By WILHELM HIS, jun., and THEODOR PAUL (Zeit. plhysiol. Chem., 1900, 31, 1-42, and 64-78. Compare Abstr., 1900, i, 591).-The authors review previous work on the solubility of uric acid, and they find that 1 part of the acid is soluble in 39,480 parts of water a t 18'.When the finely divided acid is shaken with water at 1S0, a saturated solution is obtained in an hour ; i B is not permissible to cool a solution saturated a t a high temperature, on account of decomposition of the uric acid. The molecular conductivity of a, saturated uric acid solution is 33.24 at IS', wheq allowance has132 ABSTRACTS OF CHEMlCAL PAPERS. been made for the conductivity of the solvent water, Indirectly, by work on sodium and potassium urate solutions, i t is found that the molecular conductivity of uric acid for infinite dilution is 339 a t 18'. Hence, in a saturated uric acid solution, 9.5 per cent. of the acid is electrolytically dissociated. Further, the sanity constant has the value 0*00000151. The authors confirm the observation made by other workers, that uric acid is decomposed on prolonged contact with water, this leading to an increased solubility.A saturated solution of uric acid in contact with platinised electrodes is more rapidly de- composed, and its conductivity diminishes. As regards the solubility of uric acid in solutions of mineral acids, theory requires a repression of the dissociation and consequent dimin- ution of the solubility. This conclusion is borne out both qualitatively and quantitatively by experiment : 1 part of uric acid dissolves in 42,430 parts of ,V-hydrochloric acid and in 44,140 parts of N-sulphuric acid. Even in more concentrated acid solutions, the solubility is less than in pure water, whence it follows that uric acid cannot act as a base.The tendency of ufic acid to decompose when in contact with water practically disappears in the presence of mineral acids. The estima- tion of uric acid in urates by precipitation with excess of hydrochloric, or, better, sulphuric acid is an exact process ; a correction of 2 mg. for each 100 C.C. of liquid at 18' should be applied, Bisazoxyacetic Acid, Bisaaoxymethane, and Hydraziacetic Acid. By ARTHUR HANTZSCH and MARTIN LEHMANN (Bey., 1900,33, 3668-3685).-The substance described by Curtius (Abstr., 1889,369) as triazoxyacetic acid is in reality bisazoxyacetic acid, J. C. P. ~ \ - and is best prepared by exposing poGdired bisdiazoacetic acid to the gas evolved from nitric acid and arsenious oxide, although it is also formed by the action of bromine vapour and chlorine on the acid.It is a purple-red powder, which forms a carmine-red solution in water, and decomposes at 148' evolving purple vapours of bisazoxymethane. It is quantitatively reduced in aqueous solution a t 0' by hydrogen sulphide to bisdiazoacetic acid. The aqueous solution of the acid rapidly decomposes and becomes colourless, hydraziacetic acid being formed. The solution in 1 mol. of sodium hydroxide also rapidly de- composes, whilst the solution of the normal sodium salt is quite stable. This salt, C2H202N4(C02Na)2, crystallises in flat, hygroscopic, red plates. The barium salt is a heavy, orange-yellow, microcrystalline powder, and the silver salt is a dark green powder which explodes very violently at 210'. The silver salt reacts with alkyl iodides, but the resulting esters could only be obtained in the form of impure, viscid oils.N*CH *N Bisaxoxymathccne, O<h.cH:.&>O, is formed in very small amount (1-2 per cent. of that calculkted) when bisazoxyacetic acid is gently heated, carbon dioxide being a t the same time formed and a residue of impure bisdiazomethane left. It is obtained pure by sublimation, in delicate, purple-red needles often 1 centimetre in length, and whenORGANIC CHEMISTRY. 133 quickly heated melts at 75”. It dissolves in water and many organic solvents, and decomposes when preserved. I n benzene solution, the molecular weight determined by the cryowopic method agrees with that required for the formula just given, On reduction with hydrogen sulphide in aqueous solution, it is converted into biudiazomethane, CH, <si:>CH,.NH Hydraziacetic acid, hH>CH*CO,H, is formed from bisazoxyacetic acid according to the equation C,H,O,N, = C,H,0,N2 + 2C0, + N,, when the aqueous solution of the latter IS allowed to decompose at 25-30’. It is a very sparingly soluble, crystalline powder, and de- composes a t 190”. It has a conductivity p 73 (at 25’ and v 32), and is, therefore, as strong an acid as monochloroacetic acid, and forms stable soluble salts. The methyl ester, prepared from the silver salt, crystal- lkes in small needles melting at 102O, and has the calculated molecular weight in benzene solution. It is readily soluble in water, and when treated in this solution with mercuric oxide yields methyl diazoacetate.Hydraziacetic acid decomposes when its solution is boiled, or when it is treated with acids, into hydrazine and glyoxylic acid, and the latter then undergoes a secondary reaction, yielding oxalic and glycollic acids, Both bisdiazoacetic acid and bisazoxyacetic acid are converted by alkaline reduction into hydraziacetic acid. A. H. New Reactions of Organometallic Derivatives. By EDMOND E. BLAISE (Compt. rend., 1901, 132, 38--41).-The author has in- vestigated the reactions between nitriles, alkyl haloids, alkyl salts of the a-bromo-acids of the acetic series, and alkylcarbimides in presence of magnesium bromide or iodide, or zinc bromide. I n the case of nitriles, the reaction is R*CSN + MgBrR = RR’C:N*MgBr and the imino-deriva- tives thus obtained yield ketones, R-COeR’, on treatment with dilute acids.The condensation of nitriles of the benzene series with alkyl iodides in presence of magnesium yields new ketones and also the corresponding semicarbazones, the o-nitriles reacting less readily than the p-nitriles. Nitriles of the acetic series likewise yield ketones when treated with the organo-metallic derivatives, With the alkyl salts of a-bromo-acids of the acetic series the reaction is R:CN + Zn + CR’HBr*CO,Et = ZnBr*N:CR*CHR’*C02Et, and the products yield alkyl salts of the /?-ketonic acids, R*CO*CHR’*CO,Et. This method is of very general application, since the rndicles may be varied in both the nitrile and the bromo-acid. With ethyl bromo- acetate, however, the condensation goes further, but this difficulty is got over by condensing ethyl cyanoacetate with alkyl iodides in pre- sence of rnagnesium,CN*CH,*CO,Et + EtMgI = CO,Et*CH,*CEt:N*MgI and, subsequently, CO,Et*CH,*COEt.No other general method admits of the preparation of the alkyl salts of the acylacetic acids. With dinitriles, the reaction is CN*CN + EtMgI = CN*CEt:N*MgI and CN*CEt:N*MgI + EtMgI = MgI*CN + CEt,:N*MgI, a ketone being obtained from this product in the usual way. With carbimides, the reaction is NPh:C:O + RMgI = NPh:CR*O*MgI and subsequently NPh;CR*OH and NRPh*CO-R, Other similar resctions are under134 ABSTRACTS OF CHEMICAL PAPERS. investigation. dense with organo-metallic derivatives under the usual conditions. Caprylene, hexylene, and phenylacetylene do not con- C. H. B. Electrolytic Oxidation of Toluene.By AARON MERZBACHEB and EDGAR F. SMITH (J. Amer. Chern. Soc., 1900, 22, 723-725).- The electrolytic oxidation of toluene has already been attempted (see James, Abstr., 1899, i, 909). Tho authors have varied the conditions and succeeded in obtaining a small quantity of benzaldehyde and ethyl benzoate at the anode. The anode liquid was an alcoholic solu- tion of toluene, and the cathode liquid was a sulphuric acid solution. Similar results have been obtained with ethylbenzene in place of toluene. J. C. P. Phenyl-p-nitro-o-tolylsulphone and some of its Derivatives. By R. 8. NORRIS (Amer. Chem. J., 1900, 24, 469-491).- p-Nitro-o-toluenesulphonic chloride crystallises in large, yellow rhombe, and melts at 44'. When this compound is heated with benzene in presence of aluminium chloride, phenyl-p-nitro-o-tolykulphone, NO2*G6H,Me*SO2Ph, is obtained which crystallises from hot alcohol in thin plates, melts at 158', and is easily soluble in benzene, acetone, or hot light petroleum.The sulphone dissolves in concentrated sulphuric and nitric acids and is reprecipitated on dilution with water ; when treated with fuming sulphuric acid, it is converted into a sulphonic acid, C,,Hl1O7NS,, the barium salt of which was prepared and analysed. Sodium and potassium hydroxides react with the sulphone with formation of a purple precipitate. PhenyEp-amino-o-tolylsulphone, NH,*C,H,Me*So,Ph, obtained by reducing phenyl-p-nitro-o-tolylsulphone with ammonium sulphide, crystallises from alcohol in thin plates, melts at 156', and dissolves readily in alcohol, acetone, or benzene.Phenyl-p-nitro-o-tolylsulphone is not attacked by chromic acid, but when treated with aqueous potassium permanganate, it is converted into pnitro-o-phenyZsuZphonebenxoic acid, NO,*C,H,( SO,Ph)*CO,H, which crystallises in white needles, melts a t 196O, and is easily soluble in acetone ; its barium and calcium salts are described. This acid is isomeric with the p-nitro-o-benzoylbenzenesulphonic acid obtained by Hollis (Abstr., 1900, i, 293). Phosphorus pentachloride readily reacts with the acid with production of pnitro-o-p~elzolsulphonebenxoic chloride, which separates from chloroform in colourless, rhombic crystals, melts at logo, and dissolves easily in chloroform, ether, benzene, or light petroleum; it is not affected by water at the ordinary temperature, but is readily decomposed by hot water or dilute alkali hydroxides.By the action of dilute ammonia, the chloride is converted into p-mitro-o-phenylsulphonebenxamide, which crystallises from chloroform in prisms, melts at 191-192', and is readily soluble in acetone or hot alcohol. On the addition of aluminium chloride to a warm solution of p-nitro-o-phenylsulphone- benzoic chloride in benzene, a brown, tarry mass was obtained which was not further investigated. With a view to obtaining pnitro-o-cyanodiphenylsulphone which, on hydrolysis, would yield p-nitro-o-phenylsulphonebenzoic acid, aORGANIC CHEMISTRY. 135 solution of p-nitro-o-cyanobenzenesulphonic chloride in benzene was heated with aluminium chloride, but only a tarry product was obtained from which p-nitro-o-cyanodiphenylsulphone could not be isolated.E. G. Systematisation and Nomenclature of Dicyclic Compounds. By ADOLF YON BAEYER (Ber., 1900, 33, 3771-3775).-The paper constitutes an attempt to systematise the nomenclature of compounds derived from those dicyclic hydrocarbons which contain two or more atoms of carbon common t o both rings. Nitroanthracene. By JACOB MEISENHEIMER (Ber., 1901, 33, 3547 -3549).-Liebermann and Lindemann’s nitrosoanthrone,” M. 0. F. C,H4GzN>C,H, (Abstr., 1881, 99) is in reality 10-nitro- . r CH C(NO,) anthracene, C,H,< I >CsH4, as it is not identical with anthra- quinonemonoxime. On r<duction with stannous chloride, it is converted into 10-anthramine, C,H,< I >C,H4, which for complete identi- fication was converted into its acetyl derivative, CIGH1,ON.This separates from alcohol in greenish needles melting at 273-274’, and in alcoholic solution shows a beautiful blue fluorescence. Compounds of Metallic Salts with Aromatic Amines. By DANIEL TOMBECK (Ann. Chinz. Phys., 1900, [vii], 21, 383-419).- This paper contains a detailed account of the preparation and proper- ties of the compounds from metallic salts and organic amines ; the majority of these substances have already been described (compare Abstr., 1897, i, 463, 560 ; 1898, i, 566). Aniline and its homologues form compounds with silver oxy-salts, two mols. of the base com- bining with one of the metallic sulphate or nitrate. These substances dissolve in cold water without alteration, but decompose when their solutions are warmed, producing silver mirrors on the walls of the containing vessels.Ethylaniline unites with silver nitrate to form a compound of this type, but does not combine with other oxy-salts. The three anhydrous calcium halogen salts combine with two molecular proportions of aniline, forming deliquescent compounds separating in tabular crystals. Electrolytic Reduction of Nitro-compounds. By ALBERT ROHDE (Zeit. Elektrochem., 1900, 7, 328-332, and 338-341).-The experiments were made by the method of Elbs (Abstr., 1899, i, 270 ; this vol., i, 74). m-Nitrodimethylaniline gives tetramethyl-m-diaminoazobenzene ; yield 93 per cent. Further reduction yields the hydrazo-compound. Dimethyl-m-nitro-o-tohidine, (Me : NMe, : NO, = 1 : 2 : 4), was prepared by nitration of dimethyl-o-toluidine dissolved in a large excess of con- centrated sulphuric acid, in the cold, the yield being 91 per cent, of the calculated quantity.The compound is a yellowish oil which, when reduced electrolytically, yields tetramethyl-m-diamino-p-azotoluene ; yield 86 per cent. By recrystallisation from alcohol, it i s obtained CH C(NH,) A. L. G. T. M.136 ABSTRACTS OF CHEMICAL PAPERS. in leaflets melting a t 99'. Further reduction leads to the hydrazo- compound, which forms colourless crystals melting a t 127'. When exposed to the air, this is oxidised to the azo-compound, which, how- ever, appears to be a different modification, since it crystallises in more needle-shaped crystalq, and melts at 119'.The hydrazo- compound did not yield a benzidine derivative. m-Nitromethylaniline gives, on reduction, dimethyl-m-diaminoazo- benzene, in yield of about 85 per cent. Further reduction gives a solution of the hydrazo-compound, which was not isolated in the solid form. pNitrodimethylaniline gives dimethylamine, and p-aminophenol, when reduced in a hot solution in the usual way ; in the cold, p-amino- dimethylaniline is formed. A n azo- or hydrazocompound was not formed in either case. These results are readily explained on the assump- tion that a phenylhydroxylamine derivative, OH*NH*C6HgNMe,, is first formed, which undergoes intermolecular change, yielding a diiminoquinone, NH:C6H,: NMe,*OH. I n the hot liquid, this com- pound decomposes into dimethylamine and NH:C,H,: 0, from which p-aminophenol is derived, whereas in the cold solution it is reduced without decomposition to p-aminodimethylaniline. Benzoyl-p-nitrodiphenylamine yields p-azoxybenzoyldiphenylamine when the solution is not allowed to become too strongly alkaline; the substance forrnP, yellow leaflets and melts at 1.78'.Further reduction gives the corresponding azo-compound, melting at 172'. p-Nitrodiphenylamine gives paminodiphenylamine in yield of 70 per cent. , 0- and pNitroanilines yield 70 per cent. and 86 per cent, respectively of the theoretical quantity of 0- and p-phenylenediamine. 1-Nitro-2-ethoxynaphthalene yields 1-amino-2-ethoxynaphthalene. If, however, the reduction is carried out in a solution of ammonium acetate instead of sodium acetate, a comparatively small quantity of an azoxy-compound is obtained as intermediate product.By ROBERT BEHREND, FERDINAND C. MEYER, and YNCVE BUCHHOLZ (Alznalelz, 1900, 314, 200-230. Compare Behrend and Dietrich, Abstr., 1900, i, 120).-Although it has been supposed that the formula NMe<:g:gz>CMe expresses the constitution of a-dimethyluracil as well as of the P-modification (Zoc cit.), it is now found that the structure of the former substance is represented by the expression NH<g&$>CMe. I n the course of this investigation, the existence of two ethyl 6-aminocrotonates was revealed (Behrend, Abstr., 1899, i, 331, and Knoevenagel, ibid., 478). The labile ester melts at 20°, and separates from light petroleum in large, prismatic crystals belonging to the monoclinic system [a : b : c = 0.97 : 1 : 2; P= 53.5'1.The stable form, melting at 33O, crystallises in the same system [a : b : c = 1 *0111 : 1 : 1 *2 108 ; p = 88' 27' 14"]. Bthyl imi~oacetylmalonoanilate, NH:CMe*CH(CO,Et)*CO*NHPh, obtained in asswiatioq with ethyl phepyluraminocrotopate when T. E. Ethyl /3- Aminocrotonate.ORUANIC CHEMISTRY, 137 phenylcarbimide acts on ethyl p-aminocrotonate, crystallises from alcohol in needles, and melts at 125-126'; the crystals helong to the monoclinic system [a : b : c = 1.627 : 1 : 1.045 ; /3 = 78'0'1. Alcoholic potassium hydroxide resolves the substance into aniline, ammonia, carbon dioxide, acetic acid, and acetylacetanilide ; concentrated hydro- chloric acid gives rise to aniline, ammonia, and carbon dioxide, whilst concentrated sulphuric acid converts i t into ethyl acetylmalonoanilate. Ethyl phenyluraminocrotonate, NHPh*CO*NH*CMe:CH*CO,Et, crystsllises from light petroleum in broad needles, and melts at 98-99' ; concentrat,ed hydrochloric acid resolves it into carbon dioxide, aniline, and ammonia.PhenylmethyluraciZ, NPh<CO.NH>CMe, coo CN prepared by heating ethyl phenyluraminocrotonate with alkali hydroxides, melts at 244-245', and crystallises from hot water in microscopic, six-sided leaflets belonging to the monoclinic system [a : b : c = 1.41 : 1 : I] Dibromo- hydroxyphenylmethyluracil, NPh<CO . N,$>CMe*OH, obtained by the action of bromine on finely divided phenylmethyluracil suspended in water, is an amorphous substance containing 1 &H,O, and decomposes a t 190'.Bromophenylmethyluracil, NPh<CO CO*UB .NG>CMe, produced when dibromohydroxyphenylmethyluracil is heated with alcohol in a reflux apparatus, crystallises in nacreous leaflets, and melts at 241-242', when it becomes brown. Ethyliminoacetylmalonothionanilate, NH: CMe*CH( C0,Et) *CS*NHPh, prepared from ethyl /3-aminociotonate and phenylthiocarbimide, melts at 135-136O, and crystallises from dilute alcohol in yellow prisms belonging to the monoclinic system [a : b : c = 1.463 : 1 : 1.040; /3 - 76'34'1. T'hionphenylmeth ylurucil, N P h < ~ ~ : ~ ~ > C M e , melts a t 25 3 -255', and crystallises from hot dilute alcohol in colourless, six-sided leaflets belonging to the monoclinic system [a : b : c = 1.45 : 1 : '2 1. When heated with concentrated hydrochloric acid at 170' during 5 hours, it yields hydrogen sulphide and phenylmethyluracil.By WILLEM A. VAN DORP and P. M. VAN HAARST (Rec. Trav. Chim., 1900, 19, 31 1--317).-When malephenylamic acid, CO,H*CH:CH*CO*NHPh, is heated at 100' with phosphorus oxychloride, a compound, C16H1,0,N,Cl,P, is produced, which crystal- lises in yellow needles, decomposes when heated a t 145O, and is decorn- posed by water with the formation of hydrochloric and phosphoric acids and of nearly the theoretical quantity of maleanilide, C,H,( CO-NHPh),. Maleanilide crystallises in prisms melting at 175-180°, and is insoluble in water, but more or less soluble in organic solvents. The hydrochloride, Cl,H,O,N,,HC1, crystallises in yellow needles which decompose when heated to about 160'; it is also decomposed by cold water, and when boiled with methyl alcohol is converted into maleauil, CH,CO>NPh, with elimination of aniline CO*CBr M. 0.F. Maleanilide. p ' C O138 ABSTRACTS OF CHEMICAL PAPERS. hydrochloride. meric fumaranilide, which crystallises in needles melting a t 31 2'. compound, C16H1504N2C12P, chlorosuccinanil, When fused, maleanilide is converted into the iso- From the mother liquors obtained in the preparation of the yellow >NPh, was yHCl*CO CH,-CO isolated ; it crystallises in colourless needles melt Lng at 11 8- 11 9'. N. L. Action of Nitrosoacylamines on Primary Bases. By H. APITZSCH (Ber., 1900,33, 3521--35%. Compare Abstr., 1899, i, 268)- When nitrosobenzoylbenzylamine (Abstr., 1899, i, 134) (1 mol.) and anil- ine (2 mols,) are heated together,firstverygentlyand finally on the water- bath, until the evolution of nitrogen ceases, the products are benzanilide, benzylaniline, a little benzoie acid, and oily neutral substances.With p-toluidine, the products are p-benzotoluidide melting at I 56-15S0, and benxyl-p-toluidine, which was isolated in the form of benxyltolyl- benzenesulphonamide, CH,Ph*N(CGH,Me) *S02Ph ; this crystallises in long, colourless needles melting a t 123-1 2 4 O . Nitrosobenzoyl benzylamine and phenylhydrazine yield s-benzoyl- phenylhydrazine (Fischer, Abstr., 1878, 308), and probably benzyl- phenylhydrazine, but this could not be isolated. By JOHANNES PINNOW [and in part RICHARD MAYER] (J. p. Chem., 1900, [ ii], 62, 505-522. Com- pare Abstr., 1897, i, 338)-When P-dinitromethyl-ptoluidine is re- duced with ammonium sulphide, it is converted into 5-nitromethyltolyl- ene-2 : 4-diumine, [Me :NH2 : NHMe :NO2 = 1 : 2 : 4 : 53, which crystallises in long, lustrous brown leaflets, melts at 168O, and dissolves easily in acetone, ethyl acetate, glacial acetic acid, hot alcohol, chloroform, or hot benzene.The acetyl derivative crystallises in yellowish- brown prisms or needles, melts at 205*5-207°, and is soluble in most organic solvents, but only sparingly so in cold benzene, ether, or hot water. By the action of amyl nitrite on a solution of nitromethyltolylene-2 : 4-diamine in pyridine, dinitrodiaminodimethyl- diazoaminotoluene is obtained in small, yellow prisms of the compo- sition 3C,,H,,0,N7,2C,H,N ; this substance melts and decomposes at 2675O, is fairly soluble in hot pyridine or nitrobenzene, and, when heated, loses its pyridine of crystallisation ; if reduced with zinc dust in neutral solution, it is converted into methyl-2 : 4 : 5-tri- aminotoluene.When P-dinitromethyl-ptoluidine is reduced with zinc and hydro- chloric acid, a mixture of y-diamino-p-toluidine and diaminomethyl- cresol is produced; these substances may be separated by means of their acetyl derivatives. Triacetylmethyl-2 : 4 : 5-triarninotoZwne crystallises in rhombic prisms, melts and decomposes at 257-258', and is fairly soluble in hot water or hot alcohol. Diacetylmethyl- diarninocresol crystallises in slender needles containing lH,O, which it loses slowly at 115-125'; it melts at 151-152', and dissolves easily in hot alcohol. Diacetylmethyltolylene-2 : 4-diamim3, obtained by the action of acetic J.J. S. Two Dinitromethyl-ptoluidines.ORGANIC CHEMISTRY. 139 aniydride on methyl-p-tolylenedinmine, crystalli ses in prisms, melts at 183-184', and dissolves readily in the usual organic solvents when hot, but less readily in the cold; when heated with hydro- chloric acid, trimethylbenziminazole is produced, AcetyZ-P-dinitromethyltoluidine, prepared by the addition of sul- phuric acid to a hot solution of 2 : 3-dinitromethyl-ptoluidine i n acetic anhydride, crystallises from alcohol or pyridine in bright yellow needles, melts at 151°, and dissolves readily in acetone, chloroform, glacial acetic acid, benzene, hot alcohol, or ethyl acetate. Nitromet?~yZtoZyZenedia;mine, obtained by the reduction of 2 : 3-di- nitromethyl-p-toluidine with alcoholic ammonium sulphide, crystal- lises in lustrous, nearly black prisms, melts at 127-12So, and is very easily soluble in chloroform, methyl alcohol, or hot benzene.Methyl-2 : 3 : 4-triaminotoluene hydrochloride, obtained by reducing 2 : 3-dinitromethyl-ptoluidine with zinc and hydrochloric acid, crye- tallises in double truncated pyramids, and melts and decomposes at 161-171'; by the action of acetic anhydride, it is converted into diacetylrnethyl-2 : 3 : $-tviaminotoluene, which crystallises in needles or prisms, melts at 198-198*5', and is soluble in alcohol, chloro- form, glacial acetic acid, acetone, ethyl acetate, benzene, or water. When diacetylmethyl-2 : 3 : 4-triaminotoluene is heated with glacial acetic acid, 4-acetylamino-1 : 2 : 5-trimethyZbe.lzximidaxoZe is produced, which crystallises in needles, melts at 21 7-218', and dissolves easily in alcohol or glacial acetic acid.By the action of nitrous acid on diacetylmethyltriaminotoluene, diacetyZmethyZaximinotoluene [4-acetylmet h y Zarnino- I -acet yZ- 7-methyl benxotriatxo Ze] , YH : C (N Me Ac) 8-N CH== CMe*C*NAc %, is obtained in slender, white needles; it melts at 169O, and is fairly soluble in alcohol and sparingly so in benzene, ether, or water. BenxoyLydinitrornethyltolzcidise crystallises from alcohol in prisms and melts at 110.5'. Acetyl-y-dinitromethyltoluidine crystallises in slender, yellow needles, melts at 90*5O, and is soluble in most organic solvents; when re- duced with zinc and hydrochloric acid, a substance is produced which crystallises in rhombic prisms, melts and decomposes at 2225O, and appears to consist of a mixture of C10H1302N3,~H20 and C,,,H,,O,N,CI,xH,O. E.G. p- and o-Toluidinoacetic Acid and a-p- and a-o-Toluidinopro- pionic Acid. By FRIEDRICH STEPPES (J. p r . Chem., 1900, [ii], 62, 481-504).-The principal product of the action of monochloroacetic acid on p-toluidine is not p-toluidinoacetic acid (p-tolylglycine), as stated by Meyer (Abstr., 1896, i, 401) and by Schwebel (Abstr., 1878, 302), but a substance which melts at 174', and is the p-toluidine salt of an acid; this acid, however, could not be isolated, on account of its instability. A small quantity of ptoluidinoacetic acid is produced ; it melts at 120-121", and is identical with the acid obtained by Meyer (Zoc.cit.) by the hydrolysis of its ethyl ester, and also with that pre- pared by Sieber (Abstr., 1899, i, 128) from the corresponding nitrile,140 ABSTRACTS OF CHEMICAL PAPERS. When monochloroacetic acid reacts with o-toluidine, a nearly quanti- tative yield of o-toluidinoacetic acid is obtained, as previously shown by Staats (Abstr., 1880,387). 'If o-toluidine is treated with hydrocyanic acid, and the mixture added to a solution of formaldehyde (40 per cent.), o-toluidinoacetonitrile is obtained as a thick, uncrystallisable oil ; it is converted by concentrated sul huric acid into o-toluidinoacetamide, water or alcohol, fairly so in warm benzene, and sparingly in ether, and on hydrolysis yields o-toluidinoacetic acid.By the action of a-bromopropionic acid on ptoluidine, a-ptoluidino- propionic acid is produced almost quantitatively ; it crystallises in pearly leaflets, melts at 158O, and is identical with the acid obtained by Tiemann and Stephan (Abstr., 1883, 199) from the corresponding nitrile. a-o-Toluidinopropionic acid may be prepared by the action of a-bromo- propionic acid on o-toluidine ; i t crystallises in colourless needles, melts at 1 1 8 O , and dissolves readily in glacial acetic acid, alcohol, ether, or hot water. When an ethereal solution of o-toluidine and hydrocyanic acid is added to acetaldehyde, small, colourless needles, melting at 8O-Sl0, and plates or prisms, melting at 9 6 O , are produced in approxi- mately equal quantities ; the former are soluble in 20 per cent.hydro- chloric acid, whilst the latter are insoluble, Both these substances yield a-o-toluidinopropionamide when dissolved in strong sulphuric acid ; if the acid solution of the plates is poured into water, acetalde- hyde is produced, but this does not occur in the case of the needles. The needles consist of a-o-toluidinoacetonitrile, whilst the plates have the composition : C, 74.73; H, 6.90; N, 19.33 per cent. The amide corresponds in its characters with that described by Tiemann and Steyhan (Zoc. cit.), and on hydrolysis yields a-o-toluidinopropionic acid. E. G. which crystallises in needles, me f ts at 140°, is easily soluble in hot Mechanism of the Conversion of Arylhydroxylamines into Aminophenols. By EUGEN BAMBERGER (Ber., 1900,33,3600-3622).-By the action of sulphuric acid, or of alum-solution, or occasionally by the action of water alone, on arylhydroxglamines, a paminophenol is usually produced, but when the para-position is occupied by a halogen, o-aminophenols are produced, and these occasionally appear even when the para-position is occupied by hydrogen ; p-aminophenolsulphonic acids are occasionally formed, and ethyl- or methyl-alcoholic sulphuric acid gives rise to derivatives of p or o-phenetidine or anisidine ; other occasional pi oducts arep-aminodiphenylamine bases, p-hydroxydiphenyl- amines, quinols (the hydroxy-groups sometimes causing a methyl group to wander from the para- to the meta-position), resorcinol ethers, and polymeric benzylenimines. These facts are explained by the assumption that water is first split off, C,H,*NH*OH - C,H,*N<, and that the product, if methyl- ated in the para-position, may then pass into a benzylenimine, Me*C,H,'N< - CH2:C,H,: NH, but usually recombines with water -- H to an ' iminoquinol ' [imino-+ quinol], ,FJH:C,H4<OH ; this usually passes directly into a paminophenol, NH2*C6H,*OH, but may beORGANIC CHEMISTRY 141 etherified to NH:C,H4<fR, or hydrolysed to O:C,H4<:H, or con- verted into a sulphate, NH:c6H4<o.so,H, and thus give rise, by H further isomeric change, to anisidines, aphenetidines, quinols, and sulphonic acids. I n the case of the para-methylated hydroxylamines, a number of the intermediate products can be isolated, although this has not been found possible in other cases, owing to the rapidity with which the changes occur.The ' iminoquinols ' [imino-$-quinols] cannot be isolated, although they can be shown to be present, as they rapidly hydrolyse to the ' quinol ' [+-quinol], O:C,H4<0H3, CH the constitution of which is proved by reduction to the phenol HO*C,If,Me, and isomeric change to the bivalent phenol, HO*C,H,Me*OH ; in presence of alcoholic sulphuric acid, the reversion to the true benzene structure takes place in two directions, by the wandering of the methyl group, 0:C6H4<0H3 - OH*CGH,Me*OEt [ = 1 : 3 : 41, or by the wander- ingof t h e h y d r o x y l g r ~ u p , O : c , ~ ~ < ~ ~ - OEt*C,H,Me*OEt[ = 1 :4:3]. By the action of p-nitrophenylhydrazine or of semicarbazide, the ' quinols ' [$-quinols] are converted into hydrazones or semicarbazones, which cannot be isolated, as they immediately lose water and give dicyclic derivatives : O H NO,* C,H4*NH*N:C6H4<~~ - NO,*C,H,*N< N I I C6H4'Me ' and NH,*CO*NH*N:C6H4<f;' - NH,*CO*N<# The ' quinols ' [$-quinols] are analogous to the alkali-insoluble oxida- tion products of the phenols and phenol-bromides (Auwers, Abstr., 1900, i, 161).Mesitylhydroxylamine and Nitrosomesitylene. By EUGEN BAMBERGER and ADOLF RISING (Bey., 1901, 33, 3623-3636).- Mesitylhydroxylamine, C6H,Me3*NH*OH, melts at 11 6', and when quite pure can be kept in closed vessels for 3 weeks without decom- position, but usually changes into a mixture of nitrosomesitylene and mesidine, together with nitromesitylene and azomesitylene, which are probably formed from the preceding compounds; a similar decom- position is brought about by air-free solutions of sodium hydroxide, whilst water and dilute sulphuric acid give, in addition, a small amount of trimethyl-$-quinol, O:C6H2Me,*OH (see the following abstracts).PhenyZmesityZhydroxycar6tcmide, NHPh*CO *N(OH) *C,H,Me,, pre- pared by the action of phenylcarbimide on mesitylhydroxylamine, crystallises from benzene in white, felted needles, and melts and decomposes at 116'. isoBenxcddoxime rnesit y8 ether, C,H,* CH<b 'GHgMe8, prepared by the action of mesityl hydroxylamine on benzaldehyde, crystallises from light petroleum in transparent needles, melts at 101*5-102°, and is 6H4Me T. M. L. VOL. LXXX. i. I142 ABSTRACTS OF CHEMICAL PAPERS.hydrolysed by dilute mineral acids. pNitroisobenxaldoxime mesityl ether, NO,* C,H,* CH<r' C6H2Me3, forms yellow needles, and melts at 156-5-157'. m-NitvoisobenxaZdoxime mesityl ether forms yellowish- white needles and melts a t 140*5-141". isoAnisaZdoxime mesilyl ether OMe* C,H,* CH< N*C6H2Me3, I forms white, silky needles and melts a t Nitrosomesitylene, C,H2Me3*N0, crystnllises in glistening, iridescent, orthorhombic tablets or needles and melts at 122' to a green liquid ; at the freezing point of benzene, the solutions consist chiefly of double molecules, and are almost colourless, whilst at the boiling point the solutions are green, and the molecular weight is normal; the sub- stance is decomposed by boiling water into nitromesitylene and mesidine, together with a small quantity of trimethyl-$-quinol ; unlike nitrosobenzene, it does not reduce Fehling's solution, and does not condense with the hydroxylamine to form an azoxy-derivative.0 0 1 5 2- 1 5 2.5". T. M. L. Mesityl-$-quinol. By EUGEN BAMBERGER and ADOLF RISING (Ber., 1901, 33, 3 63 6 -3643).--MesityZ-+-p.winoZ, O:C,H,Me,* OH (compare preceding page), prepared by passing a current of air through mesityl- hydroxylamine suspended in water, crystallises from light petroleum in flat, mhite,.glistening needles, and melts at 45.5-46'. The benxoyl derivative, 0.C6H2Me,*OBz, forms glistening prisms and melts at 128.5'. By heating with sodium hydroxide in a current of hydrogen on a water-bath, the $-quinol is converted into cumoquinol, C6HMe,(OH), [Me, : (OH), = 1 : 2 : 4 : 3 : 61 ; it is also readily reduced by zinc and ammonium chloride, sulphurous acid, or ferrous sulphate and sodium hydroxide to mesitol, C,H,Ne,*OH.2 : 4- Dimethylphenylhydroxylarnine and 2 : 4 - Dimethyl-+- quinol. By EUGEN BAMBERGER and F. BRADP (Ber., 1901, 33, 3642-365S).-as-Axoxy-m-q/Zene, N,0(C6H,Me2),, [Me, : N,O = 1 :3 : 41, prepared by atmospheric oxidation of the hydroxylamine, forms glisten- ing, yellow needles and melts at 76-76.5". Dilute sulphuric acid a t 1 OOo converts the hydroxylamine into cc8.m-xylidine, nitroso-m-xylene, and azoxy-nt-xylene, together with 2 : 4-dimethyl-$-quinol, and amino- nz-xylenol, [Me, : OH : NH2 = 1 : 4 : 2 : 51, which are probably produced by hydrolysis and reduction respectively from dimethylimino-$-quinol, NH:C,H,Me<OG, and 2 : 4-dimethylquinol, formed by isomeric change from the +-quinol, which is the chief product of the action. Similar products are obtained at atmospheric temperatures, or by the action of alum solution, but the proportion of dimethyl-$-quinol is larger.2 : 4-DimethyZ-+-quinol hydyate, O:C,H,Me,* OH + H,O, crystallises in glistening, colourless, rhombic prisms, melts at 53-54' (corr.), and loses its water on exposlire to the air. The $-quinoZ forms glistening, colourless prisms, melts at 73-73-5" (corr.), dissolves moderately in MORGANIC CHEMISTRY. 143 boiling water and readily in most organic solvents, and volatilises at 100'. Sodium hydroxide a t 100' converts it into the isomeric 2 : 4-dimethylquinol, no trace of. 4 : 6-dimethylresorcinol being pro- duced ; acids act similarly, but give a much smaller yield of the quinol ; the +-quinol is also decomposed by light ; it is very readily reduced to as.m-xylenol.Benxoyl-2 : 4-dimethyl-$-qzcinol, O:C,H3Me2*OBz, crystal- lises from light petroleum in clear, glistening prisms and melts at 72.5- 73.5'. Anhydvo - 2 : 4-dimethyL$-puinol-p rtitro~l~enyll~~dra~orte, C-CMe /CH= = CH\ CH-CMe, prepared by the action of p-nitrophenyl- ~N-N(c~H,*NO,)// hydrazine on tho quinol, crystallises from alcohol in glistening, dark orange-red needles, melts a t 126*5--127O, and is insoluble in alkali hydroxides. Anhyd~o-2 : 4-dimethyl-$ qzcinol senaicccrbaxone, cH\ ~ N ( C O N H J / /CH = C-CMe = CH --CMe, separates in orange-red, silky flakes, and melts and decomposes at 134-1 35'.2 : bDimethylimino-~-qzcinoZ, NH:C,H,Me,* OH, has not been isolated in a pure state, but its presence is proved by continued decomposition into ammonia and the $-quinol. Substance formed in the Iodination of Phenols. By WILHELM VAUBEL (Chem. Zeit., 1900, 24, 1059-1060 ; 1077--1078).-When a solution of phenol in saturated aqueous sodium hydrogen carbonate is treated at 25' with an excess of a solution of iodine in aqueous potassium iodide, an insoluble red substance is formed. This contains 64-7-64.8 per cent. of iodine, corresponding with l g I per mol. of phenol; when treated with alcoholic potash, it is converted into a white substance with 64.5 per cent. of iodine, and when reduced with zinc dust in alkaline alcoholic solution it forins a compound, C,,H,,O,, which is a yellowish-brown powder soluble in alkalis, melts at 74-76", and yields a bromo-derivative, CI8Hl7O3Br, when it is dissolved in acetic acid, and treated with aqueous potassium bromide, hydrochloric acid, and bromate.Other phenols behave in a more or less similar manner when iodinated in sodium hydrogen carbonate solution, several molecules frequently condensing. The phenols are enumerated below, with the number of iodine atoms present in the product per mol. of the phenol. Salicylic acid, 15 (with elimination of the carboxyl group); m-cresol, 2-3; o-cresol dibromide, 1 ; o-nitrophenol, 1 -6 ; p-nitrophenol, 3 ; tyrosine, 0.5. Similar results by other observers are quoted in addition. T. M. L. C. F. B. Aryl Hydrogen Sulphates. By ALBERT VERLEY (BULL XOC.Chim., 1901, [iii], 25, 46-49).--8 general method for the preparation of potzlssium aryl sulphates consists in adding the phenol to a cooled mixture of pyridine and chlorosulphonic acid in carbon disul- phide solution, removing the carbon disulphide by distillation, and decomposing the double sulphate of pyridine and the phenol thus produced by distillation with potassium hydroxide solution. Potassium eugelnyl sulphate is thus obtained in the form of white, nacreous scales 1 2144 ABSTRACTS OF CHEMICAL PAPERS, melting at 2039 When heated in acid solution it is decomposed, with the formation of eugenol and potassium hydrogen sulphate, whilst when boiled with excess of potash it is converted into potassium isoeugenyl sulphate which melts at 223'.This salt is readily con- verted into potassium vanillin sulphate by the action of oxidising agents, ozone being the most suitable. Potassium vanillin sulphate forms small, yellow crystals which decompose at 200°, and yields vanillin when heated with dilute sulphuric acid. The method described has also been applied to the preparation of sodium phenyl sulphate, potassium phenyl sdphate, potassium thymyl sulphate melting at SO", potassium /3-naphthyl sulphate melting at 210°, potassium benzyl sulphate, which crystallises in brilliant, white needles melting a t 233O, and potassium geranyl sulphate which does Derivatives of Phenyl Ether. By A. N. COOK and HOMER W. HILLYER (Amer. Chem. J., 1900, 24, 525-529).-o-NitrophenyZ p-tolyl ether, NO,*C,H,*O*C,H,Me, obtained by the action of o-bromo- nitrobenzene on the potassium derivative of p-cresol, crystallises in large, sulphur-yellow, monoclinic prisms, melts at 49O, boils a t 220° under 25 mm.pressure, but suffers partial decomposition when dis- tilled under the ordinary pressure ; it is not volatile with steam ; it dissolves easily in ether, acetic acid, chloroform, benzene, or hot alcohol. not crystallise. N. L. 2-Nitro-4'-cai.box~phenyZ sther, [4-o-nitrophenoxybenxoic acid], NO,*C,H,*O*C,H,*CO,H, prepared by oxidising o-nitrophenyl p-tolyl ether with a solution of chromium trioxide in glacial acetic acid, melts a t 182-183O, crystallises from hot water in yellow needles, and is very soluble in glacial acetic acid or warm alcohol; its cadmium, silver, and bmhm salts are de- scribed.The hydrochloride of o-aminophenyl-p-tolyZ ether, NH2*C,H,*O*C,H,Me,HCl, obtained by reducing the nitro-compound with tin and hydrochloric acid, crystallises in needles, and melts a t 220'; the base may be pre- cipitated from a solution of the hydrochloride, but rapidly decomposes; the platinichloride melts and decomposes a t 150'. By A. ASTRUC and H. MURCO (J. Yharm., 1900, (vi], 12, 553-556).-Guaiacol cacodylate (Barbary and Rebec, BUZZ. Xoc. Pharm., 1900,11, 1 2 1 ) crystallises in small prisms which are soluble in alcohol, glycerol, or water; it is a very unstable salt, and on solution in water is immediately decomposed into cacodylic acid and guaiacol, which separates out in oily drops. Cirtnamylcacodylic acid, C,H7 *CO,H,AsMe,O*OH, prepared by the direct combination of mol. proportions of cacodylic acid and cinnamic acid, crystallises in prisms melting at '79-8l0, and is only slightly soluble in ether, glycerol, or oils, but dissolves readily in alcohol.Cinnamic acid is precipitated on the addition of water to its alcoholic solutions. When treated with water i t is decomposed into cacodylic acid, which dissolves in the water, and cinnamic acid, which remains undissolved. H. R. LE S, E. G. Derivatives of Cacodylic Acid.ORGANIC CHEMISTRY. 145 Polymeric Phenylisocrotonic Acid. By RUDOLPH FITTIG (Be?*. , 1900, 33, 3519-3521).-W hen phenylisocrotonic acid is boiled for 6 hours with dilute hydrochloric acid (1 vol. commercial acid to 3 vols. of water), 65 per cent. of it is converted into phenylbutyrolactone; the reaction is never complete and the lactone when similarly boiled is partially converted into phenylisocrotonic acid.When stronger acid is employed, the polymeric phenylisocrotonic acid previously described (Abstr., 1888, 595) is also formed. It has the molecular formula, C2,H2,04, and is a monobasic lactonic acid and not dibasic; when oxidised, it yields benzoic acid and thus the group C,H, must be intact. An intermediate product on oxidation is the ketonic acid, C2,H2,,05, melting at 132' ; when this is reduced, it is converted back into the lactonic acid ; according t o the author, this must contain the J. J. S. p-Methyl-o-benzylbenzoic Acid. By HEINRICH LIMPRICHT (Annalen, 1900, 314, 237-251. Compare Abstr., 1898, i, 322).- pMethyl-o-benzylbenzoic acid, C,H,Me*CH,*C,H,*CO,H, crystahes from alcohol in large, six-sided plates, and melts at 133' ; the sodium salt crystallises in long needles coutaining 2H,O, and melts a t 270°, the silver salt is anhydrous, and the methyl ester crystallises from alcohol in thin, lustrous leaflets, and melts at 126'.The chlovide is a yellow oil which does not combine with hydrocarbons under the in- fluence of aluminium chloride, and when heated changes very readily into methylanthranol. of concentrated sulphuric acid on p-methyl-o-benzylbenzoic acid, is also produced when the acid chloride is heated a t 95' in a vacuum; it crystallises from alcohol in plates, melts at loo', and sublimes in needles and leaflets when strongly heated. Chromic acid oxidises the substance to p methylanthrttquinone.Solutions of methylanthranol in alkalis and alkali carbonates decompose rapidly, and besides methyl- anthraquinone, it has been found possible to isolate two compounds melting at 150" and 207' respectively ; the latter has the composition 4>CH*C,H,Me*N02, produced when methyl- benzylbenzoic acid is dissolved in concentrated nitric acid, separates from alcohol in colourless crystals and melts at 137'. Tvinitro- ntethylbenxylbenxoic acid, C15H110SN3, forms small, white crystals, and melts at 213'; the barium salt crystallises from water in colourless prisms. T'rinityotoluoylbenxoic acid, C15H,0,N,, cry s talli ses from acetic acid in small prisms and melts a t 215'; the barium salt contains 3H,O. ArninomethyEbenxyZbenzoic acid, NH2*C,H3Me*CR2*C6H4*C0,H, pre- pared by reducing nitrotolylphthalide and nitrotoluoylbenzoic acid with zinc dust and ammonia, crystallises from dilute alcohol in slender, white needles and melts at 155'; the bccrium and silver salts are C H co.0 C3oH2202.NitrotolyZphthaZide, I146 ABSTRACTS OF CHEMICAL PAPERS. anhydrous, and the hydyochloride and nitrate melt a t 215' and 214' respectively. M. 0. F. By N. TARUGI (Gaxxetta, 1900, 30, 487-492).--The action of chlorine on potassium salicylate yields a mixture of mono- and di-chlorosalicylic acids. I n presence of in- creasing quantities of potassium hydroxide, the proportidn of dichloro- acid formed increases, until the mixture consists of 3 mols. of potass- ium hydroxide t o 1 , mol. of salicylic acid, when the disubstituted acid alone is formed together with a small quantity of chlorophenol. If the proportion of potassium hydroxide be further increased, the dichloro- acid diminishes in quantity and finally vanishes, the amount of 2 : 4-di- chlorophenol formed showing a corresponding increase.The dichloro- salicylic acid formed in the above reaction has the constitution [CO,H : OH : C1, = 1 : 2 : 3 : 51 ; when heated with lime, it yields 2 : 4-dichlorophenol, whilst with nitric acid the dichloronitrophenol [OH : C1, : NO,= 1 : 2 : 4 : 61 is obtained. Similarly, the action of excess of chlorine on a solution of 1 mol. of p-hydroxybenzoic acid i n 3 mols. of potassium hydroxide solution yields the dichlorohydroxy- benzoic acid of the constitution [CO,H : C1: OH : C1= 1 : 3 : 4 : 51 ; this acid with nitric acid gives 2 : 6-dichloro-4-nitropheno1, whilst when heated with lime i t yields 2 : 6-dichlorophenol, which is also obtained in increasing quantities as the proportion of potassium hydroxide in the above reaction is increased beyond 3 mols.The action of chlorine on o-nitrophenol (1 mol.) dissolved in potassium hydroxide (3 mols.) solution yields 2 : 4-dichloro-6-nitropheno1, whilst when p-nitrophenol is employed, 2 : 6-dichloro-4-nitrophenol is obtained. Thus when an excess of chlorine acts in alkaline solution on a disubstituted benzene derivative having an acid function, two atoms of chlorine enter the benzene nucleus and, in the case of 0- or p-com- pounds, always take up given stable positions. By ALBIN HALLER and ALFRED GUYOT (Bull. Soc.Chinz., 1901, [iii], 25, 49-56).-The unsuccessful attempts to prepare two methyl esters corresponding with the two hypothetical tautomeric forms of benzoylbenzoic acid have already been described (Abstr., 1900, i, 170). It is now also shown that the acid behaves normally when heated with phenylcarbimide at SO", diphenylcarbamide and benzoylbenzoic anhydride being formed. At the ordinary temperature, however, an unstable additive product seems to be produced. Dichlorohydroxybenzoic Acids. T. H. P. Tautomerism of o-Benzoylbenzoic Acid. N. L. Tolylphthalide. By HEINRICH LIMPRICHT (Anncdem, 1900, 314, 4>CH*C,H4Me, crystallises in long, C H co.0 251-258).-Tolylphthalide, I flat, colourless needles melting at 129O, and distils under 15 mm. pressure without decomposing ; it dissolves in alkalis and alkali car- bonates, but the acid, of which salts are thereby produced, cannot be isolated.Ammonia and zinc dust convert it into methylbenzylbenzoic acid, and potassium permanganate oxidises it t o toluoylbenzoic and benzophenonedicarboxylic acids. Concentrated nitric acid converts the substance into nitrotolyl-ORGANIC CEEMISTRP. 147 phthalide (this vol., i, 145) which melts at 137'. AminotolyZphthalide, ~6H4>CH*C,H3Me*NH2, obtained by reducing the nitro-derivative co.0 with stannous chloride, crystallises in colourless, four-sided, rhombic plates melting at 144' ; the nitrate and hydrochloride crystallise in slender, long needles, and the latter decomposes at 205'. Triniti-o- tolylphthalide, CI5H9O8N3, crystallises from acetone in white, micro- scopic leaflets, and melts a t 215'.Isomeric Ammonia Derivatives of Ethyl Benzylidenebis- acetoacetate. (Benzylideneacetoacetic-p-aminocrotonate or Phenylaminohepteneonedicarboxylate.) By PAUL RABE (Bey., 1900, 33, 3803-3806).--Ethyl P-benzylidenebisacetoacetate is readily converted by ammonia into ethyl 8-phenyl-P-anzino-P-hptene-C-one-y : E- dicarboxylate, NH,*CMe:C(CO,Xt)*CHPh*CHAc*CO,Et, which exists in two distinct forms. The a-form consists of woolly needles, which melt at 58' and then pass into the /3-form. The p-form separates from alcoholic solution in coarse, well-developed crystals melting at 98". When water is added to an alcoholic solution of either form, a hydrate is produced which contains lH,O, melts at about 72", and over sul- phuric acid loses water and yields the a-form.The two forms are alike in their behaviour towards alcoholic ferric chloride, and the exact nature of their isomerism has not yet been ascertained. M. 0. F. A. H. Addition of Diethyl Succinate to up-Unsaturated Ketones and Esters. By HANS STOBBE (Annalen, 1900, 314, 111-146. Compare Abstr., 1899, i, 900; 1900, i, 179).-[With KARL R~SSWURM].- y-Phenacyl-y-phenylp?~rotartaric acid, COPh*CH,* CHPh*CH(CO,H)*CH,* CO,H, produced in the form of its sodium derivative when an ethereal solution of benzylideneacetophenone and diethyl succinste is added to sodium ethoxide suspended in ice-cold ether, crystallises from water or ether in rhombic plates, and melts at 175-177'; it is sparingly soluble in cold water, and requires 500 parts of hot benzene for dissolution.The sodium salt forms long needles containing 4&H20, the barium salt contains 3H20, and the calcium and silver salts are amorphous. The dirnethyl ester crystallises from a mixture of ether and light petroleum in large plates melting at 77-79', and the diethyl ester molts at 60-62'; the anhydride crystallises from a mixture of benzene and light petroleum in stellate aggregates of needles, and melts a t 119-121*5'. The oxime is sparingly soluble in water, from which it separates in minute crystals, melting a t lSQ-184', when it becomes deep red; the semicarbaxone melts and evolves gas at 194-198", and forms a crystalline sodium derivative, which becomes yellow at ZOO', and decomposes completelv at 245-250'.A " O-CHPh--?H, "*<CHtC€€n* COnH\ CHPh' PG-Diphenylvalerolactoneacetic acid, \ A prepared by reducing y-phenacyl-y-phenylpyrotartaric acid $it& sodium amalgam, crystallises from 50 per cent. alcohol in lustrous needles, which soften at 170', and melt between 185" and 187'. The barium salt cf the148 ABSTRACTS OF CHEMICAL PAPERS. hydroxydicarboxylic acid, C1,H,,O,, obtained by heating the lactone acid with barium hydroxide, crystallises in leaflets. When phenacylphenylpyrotartaric acid is oxidised with nitric acid, i t is decomposed completely, yielding only benzoic acid and its pro- ducts of nitration. Potassium permanganate, however, gives rise to P-benzoylpropionic and benzoylformic acids. The compound, C,,H,,O,, a bye-product in the preparation of y-phenacyl-y-phenylpyrotartaric acid, crystallises from 90 per cent.alcohol in slender needles, and melts a t 224-227'. [With RICHARD FIsCHER] .-kfethyl 2-benxoy~-~-~heny~cyclo~entunone- yHoC*2Me, prepared by adding an I ethereal solution of dimethyl-y-phenacyl-y-phenylpyrotartrate to sodium methoxide suspended in ether, and acidifying the product, crystallises from absolute alcohol in slender needles and melts at 115-116'; the semicurbaxone melts and decomposes at 23 1-232'. M. 0. F. Dibenzoylmaleio and Dibenzoylfumaric Esters. By CARL PAAL and HEINRICH SCHULZE (Bey., 1900, 33, 3784--3795).-Ethyl dibenzoylethylenedicarboxylate exists in cis- and trans-forms, the configurations of which have been determined by their reaction with hydrazine hydrate. This substance reacts with the cis-form almost quantitatively to produce a pyridazine derivative, whilst with the trans-form it only reacts slowly and incompletely to produce the same compound, Eihyl dibenzoylmaleate (ethyl &s-dibenzoylethylenedicarboxylate), which was formerly described by Paal and Hartel (Abstr., C0,E t *g Bz CO,Et*C*Bz' l&7, i, 598) as ethyl dibenzoylfumarate, when treated with hydrazine hydrate, readily yields ethyl 3 : 6-dipheny~yrid~xilze-4 ; 5-dicurboxylate, :CPh*~:co2Et which crystallises in long, flat, colourless needles N: CPh* C*CO,E t' melting at i!27-128' Diphenylpyridaxinedicarboxylic acid crystal- lises in long needles containing 2 mols. of alcohol, and melts and decom- poses at 202'.The potassium salt crystallises in silky needles, and the silver salt in sparingly soluble, microscopic needles. When the acid is heated above its melting point, it yields carbon dioxide and N-N 3 : 6 -diphen y Zpyrida ziae, C PhCC,.H>C Ph, which cry s t allise s in large, nacreous plates melting at 221-222'. chlwide, aurichloride, and pZatinichloride are all decomposed by water. The crystalline hydro- Ethyl dibenxoyrumarate (ethyl truns-dibenzoylethylenedicarboxglate), . - - - Bz*!?Co2Et, is formed when the cis-compound is heated with a C0,Et C*Bz sm& amount of aniline in a closed vessel at loo', and crystallises in well developed, colourless, asymmetric prisms melting at 87-88'. Both ethyl dibenzoylmaleate and ethyl dibenzoylfumarate are reduced by phenylmethylhydrazine t o ethyl dibenzoylsuccinate. When the fumaric ester is treated with alcoholic potash at the ordinary temper- ature, pure potassium dibenzoylfumarate is formed, which crystallisesORGANIC CHEMISTRY, 149 in Bat needles containing alcohol.The silver salt, which is a faintly yellow, microcrystalline powder, is converted by ethyl iodide almost quantitatively into the original ethyl dibenzoylfumarate. When a solu- tion of the potassium salt is acidified, the acid obtained is not dibenzoyl- fumaric acid, but dibenzoylmalic acid, C02H*CBz(OH)*CHBz*C02H (Paal and Hartel). On the other hand, this acid does not yield corre- sponding salts, but when treated with the requisite amount of aqueous potash yields potassium dibenzoylfumarate. That the acid is not dibenzoylfumaric acid containing 1H,O is proved by the fact that by heating the water cannot be removed without decomposition occurring (compare this vol., i, 154).Ethyl dibenzoylmaleate is converted by hydrolysis into a mixture of potassium dibenzoylmaleate with a small amount of potassium dibenzoylfumarate. This mixture of potassium salts is decomposed by acids in a similar manner to potassium di benzoylf umarate, dibenzoyl- malic acid being produced, A. H. Lichens and their Characteristic Constituents. V. By OSWALD HESSE (J. pr. Chem., 1900, [ii], 62, 430-480. Compare Abstr., 1898, i, 531, 679; 1899, i, 381 ; this vol., i, S5).-Usnea plicuta from Java cinchona bark contains d-usnic acid, usnaric acid, usnarin and plicatic acid. Usnaric acid contains no alkyloxy-groups ; when heated with alcoholic potassium hydroxide or aqueous barium hydroxide, it loses carbon dioxide, and a brown, amorphous substance is produced.If a solution of usnaric acid in acetic anhydride is heated for 24 hours and allowed to cool, a substccnce, which melts at 209O and is slightly soluble in alcohol, separates in white needles ; on diluting the mother-liquor with water, another substance is obtained, which melts at 128', and dissolves readily in alcohol; both these compounds exhibit an acid reaction, and do not give any coloration with ferric chloride. Plicatic ucid, C,oH,,O,*OMe, is dibasic ; it crystallises in lustrous, white leaflets, melts at 133O, dissolves easily in alcohol, acetone, or ether, and gives no coloration with ferric chloride; its barium salt was prepared. Usnea barbata var. dasypoga and jlorida yield d-usnic acid, usnaric acid and alectoric acid (see later).Alectoria jubata var. implexa (Bryopogon jubatum var. irnplexum) contains not only salazinic acid as stated by Zopf (Abstr., 1898, i, go), but also alectoric acid. Akctoric acid is dibasic; it dissolves sparingly in alcohol, ether, or hot glacial acetic acid, and crystallises from the last-mentioned solvent in needles; it melts and decomposes at l86O, gives a reddish-brown coloration with ferric chloride, contains no alkyloxy-groups, and is converted by acetic anhydride into a colourless resin ; its barium and potassium salts are described. When this acid is heated with solution of barium hydroxide, the solution becomes dark red, and yields an acid, which crystallises in white needles, is more soluble in ether or alcohol than alectoric acid, and melts and decomposes at about 2 2 0 O .Evernia divaricuta does not contain usnic acid as asserted by Zopf (Abstr., 1898, i, go), but only divaricatic acid. Ramaha cuspidata yields czcspidatic acid, Cl,H,,Ol,, which150 ABSTRACTS OF CHEMICAL PAPERS. cfystallises in white needles, melts a t 2189 dissolves easily in ether, acetone, or alcohol, and gives a violet-blue coloration with ferric chloride. Thamnolic acid, Cl,H,,O1,*OMe, obtained from Fhamnolia verrnicu- Zccris (Abstr., 1899, i, 381), melts and decomposes a t 213'; when this acid is heated with barium hydroxide solution, it loses carbon dioxide and yields thananolinic acid, C16H2007, which crystallises in long, colourless needles, melts at 163O, dissolves readily in alcohol, ether, glacial acetic acid, or hot water, and gives a purple coloration with ferric chloride, Stereocaulon coralloides contains atranorin, a small quantity of usnetic acid, and an acid, which Zopf (Abstr., 1896, i, 103) seems to have mistaken for psoromic acid (parellic acid) ; this new acid crystallises in small, white needles, is soluble in hot glacial acetic acid, hot alcohol, hot acetone, or benzene, and gives a violet-blue coloration with ferric chloride; when heated, it does not melt, but darkens a t 250' and is quite black at 260'.The 'stereocaulic acid' obtained by Zopf from 8. aZpinum is identical with usnetic acid. X. salaxinurn contains not only salazinic acid, as stated by Zopf (Abstr., 1897, i, 362), but also a considerable quantity of atranorin.Salazinic acid contains no alkyloxy-groups ; it crystallises from hot alcohol in spherical, crystalline aggregates, and blackens at 2 60-262' without melting. It dissolves in dilute potassium hydroxide to form a yellow solution which rapidly darkens, and yields red crystals of the potassium salt of an acid, which is a decomposition product of salazinic acid j the same acid is produced when salazinic acid is dissolved in con- centrated sulphuric acid. Cladonia Hoerkeana yields coccellic acid, as previously shown by the author (Abstr., 1899, 382), and also a small proportion of thamnolic acid. When coccellic acid is heated with hydriodic acid, it is converted into a mixture of rhizonic and coccellinic acids, the former of which Buffers decomposition with formation of methyl iodide, carbon dioxide, and betorcinol, whilst the latter remains unchanged.C'occellinic acid, C,,H,,O,, crystallises in white needles, melts at 176-177', dissolves easily in ether or alcohol, and gives an intense violet-blue coloration with ferric chloride ; if heated above its melting point, it decomposes and yields a crystalline sublimate, which is probably mesorcinol. C. fimbriata (E-chordalis) yields protocetraric acid. C. unciizuta does not contain usnic acid, as stated by Knop (Amnncqlen, 1844, 48, 124), but uncinatic acid, G23H2809, is obtained as a white, crystalline powder which melts and decomposes at 212', is sparingly soluble in ether, chloroform, glacial acetic acid, or cold alcohol, but freely in hot alcohol, and gives a purple coloration with ferric chloride ; its potassium, ammonium, and barium salts were prepared.C. squumosa (a-ventricosa) yields spamutic acid, which crystallises in short prisms, melts and decomposes at 215O, has a slightly bitter taste, dissolves sparingly in ether, alcohol, benzene, chloroform, or acetone, and more easily in glacial acetic acid, and gives a purple coloration with ferric chloride ; it contains one methoxyl group. ParmeZia tiliacea (Imbricccricb tiliacea).-Re-examination of thisORGANIC CHEMISTRY. 151 lichen has confirmed the opinion previously expressed by the author (Abstr., 1899, i, 382) that Zopf's ' parmelialic acid is identical with lecanoric acid. P. sorediatcc contains lecanoric acid but no atranorin.P. perZatcc.-The lichen previously examined by the author consisted of a mixture of P. pedata, P. perfoyata, and 2'. olivetorum. P. perlnta yields atranorin and a trace of lecanoric acid. P. perforatcc furnished atranorin and a small proportion of lecanoric acid, whereas Zopf (Abstr., 1898, i, 90) found salaeinic acid and very little atranorin. P. olivetorum proved on re-examination t o contain stranorin and lecanoric acid,.as previously stated (hbatr., 1898, i, 679), but not erythric acid, as Zopf asserts. P. tinctorum ( = P. comlloides) yields atranorin and 23.58 per cent. of lecanoric acid, P. saxatilis var. sulcata furnished protocetraric acid only, whereas Zopf (Abstr., 1897, i, 436) found atranorin and ' stereocaulic acid.' P. saxatilis var. panniformis contains atranorin, protocetraric acid, and usnetic acid (Abstr., 1877, ii, 896).Usnetic acid has the com- position C,,H,GO,, and not C,HloO, as previously stated; it melts at 192'. When usnetic acid is heated with barium hydroxide, i t yields carbon dioxide and usnetol, C2,H2,07, which crystallises in white needles, melts at 166', and is very soluble in ether or alcohol; a small quantity of another substance is also produced, which crystallises in white needles, and is soluble in ether, but differs from usnetol in being insoluble in solution of potassium hydrogen carbonate. 2'. acetabulum contains atranorin and salazinic acid, as previously shown by Zopf (Abstr., 1898, i, 489). Umbilicaria pustulata yields gyrophoric acid, which melts at 200-202', dissolves easily in alcohol or acetone, is optically inactive, and contains no alkyloxy-groups.The formula C1,H,,O7 was pre- viously assigned$ to this acid, but the author now finds that i t is isomeric with lecanoric acid, C1,H1*OT. When gyrophoric acid is heated with glacial acetic acid, i t is converted into orsellic acid; if boiled with alcohol, i t yields orsellic acid and ethyl orsellate; under other conditions, the acid decomposes into orcinol and carbon dioxide. The author considers that gyrophoric and lecanoric acids are probably the cis- and trans-forms of the acid, C 02H C6H2Me( OH)*O* GO C6H,Me (OH),. Placodium saxicolum var. cornpacturn furnishes atranorin, and a P. gypsaceurn yields parellic acid, but no usnic acid, as stated by P. circinatum contains parellic acid.Icmadophila ce~uginosa furnished only an uncrystallisable brown oil, whereas Bachmann obtained icmadophilic acid. Blastenia ayenaria var. teicholytum (Callopisma teicholytum).-Re- examination of this lichen has confirmed the author's view (Abstr., 1899, i, 382) that it contains atranorin and gyrophoric acid. Hcematomma ventosum contains d-usnic acid, divaricatic acid, and an acid which does not possess the properties of the ventosaric acid de- crystalline acid, which is soluble in alcohol or ether. Zopf (Abstr., 1898, i, 90).152 ABSTRACTS OF CHEMICAL PAPERS. scribed by Zopf (Abstr., 1897, i, 364), but rather resembles alectoric acid. Lecccnora subfusca yields atranorin, as found by Zopf (Abstr., 1897, i, 436). - Asiicilia calcarea furnishes aspicilin, which crystallises in white prisms, melts a t 178*5', dissolves readily in hot alcohol, glacial acetic acid, chloroform, or benzene, but less easily in ether; when heated strongly, it sublimes and distiIs without decomposition.This lichen also contains oxalic acid and erythric acid (Abstr., 1898, i, 532), which the author now considers to be either erythrolecanoric or ery t hrog yrophoric acid. Ui.ceoZaria scruposa var. arenaiia yields a small proportion of leca- noric acid. Lecidea griselka furnishes gyrophoric acid. Gmphis scripta yields salazinic acid. An appendix to the paper contains a detailed cyiticism of Zopf's recent work (this vol., i, 87). E. G. Usnic Acid. Rotation of other Lichen Acids. By HEINRICH SALKOWSKI (Annalen, 1900,314, 9 7 -1 1 1. Compare Widman, Abstr., 1900, i, 235).-The author has exanlined specimens of usnic acid derived from more than twenty different lichens, and finds that although considerable variations in the melting point occur, the limits of specific rotatory power are comparatively narrow.Analyses of the insoluble yellow barium, strontium, and calcium salts of usnic acid are given. Rhizocarpic acid is optically active, but atranoric, chrysophanic, pinastric, soloric, usnolic, and vulpic acids, and calicyn, are inactive. M. 0. F. Action of @Naphthol on Aldehydes. By M. ROGOFF (Ber., 1901, 33, 3535--3538).-In continuation of Claisen's work (Abstr., 1887, 494) the author has prepared the following compounds by heat- ing P-naphthol with aldehydes and acetic acid in closed tubes at 190-200".C28H2003, from vanillin, separates from glacial acetic acid in microscopic needles melting a t 2 1 1'. C28H1803, from piperonaldehyde, crystallises in six-sided tablets melting at 237'. C,,H2,0, from cuminaldehyde, forms microscopic tablets and melts at 238'. C28H2002, from anisaldehyde, forms six-sided plates melting at 208'. CZ7Hl,O,, from salicylaldehyde, crystallises in long prisms and me1 ts at 20s'. These compounds are all of the type CHR<clOHe>O, and are insoluble in alkalis ; when warmed with sulphuric acid, they assume varying tints of red, and at the same time exhibit a greenish fluorescence. A. L. C H 10 6 Intramolecular Rearrangement of isoAIdoxime Ethers. By FRIEDRICH WEGENER (Alznalen, 1900, 314, 231-236. Compare Neubauer, Abstr., 1898, i, 134).-Contrary to a previous conclusion,ORGANIC CHEMISTRY.153 the transformation of benzyl-m-nitroisobenzaldoxime into m-nitro- benzylisobenzaldoxime is reversible. The same remark applies to the relation between o-chlorobenzylisobenzaldoxime and benzyl-o-chloroiso- benzaldoxime. M. 0. F. Benzophenone-o-sulphonic Acid and some of its Homologues. By CARL KRANNICR (Ber., 1900, 33, 3485-3494).-L)etds are given for preparing ammonium o-sulphobenzoate From its imide ('' saccharin") ; it forms orthorhombic crystals [a : b : c = 0.6686 : 1 : 1.21031. o-Sulpho benzoic acid crystallises with 3H,O and melts at 69O, the anhydrous acid melting at 134'. The following compounds were prepared by heating o-sulphobenzoir anhydride in presence of acetyl chloride with benzene and its homo logues.Benxophenonesulphonic [benxoylbenxeneszclpl~onic] acid, COPh*C,H,- SO& is very soluble in water, and cannot be obtained crystalline. The ammonium salt, with lH,O, forms monoclinic crystals [a : b : c = 1.9224 : 1 : 1.5921 ; /3= 108'20'1 and melts a t 202' ; the potassium salt (Remsen and Saunders, Abstr., 1895, i, 474), with 1H,O, melts at 211'; the sodium salt, with 4H20, melts a t 60°, the anhydrous salt melting at 236' ; the barium salt, with 1H,O, melts a t 197-198'. p-MethylbenxoyZbenzene-o-sulphonic acid, CGH,Me*CO*C,H4*S0,H, prepared from toluene, is very deliquescent ; the ammonium salt, with lH20, melts at 104'; the potassium salt, with 1H20, melts a t 248O; the sodium salt, with 4H,O, melts initially a t 53', and, when an- hydrous, at 247'; the barium salt, with lH,O, melts at 215'.The structure of the acid follows from its yielding p-toluic acid when fused with alkali. The substance obtained by the interaction of m-xylene and o-sulpho- benzoic anhydride in presence of aluminium chloride is, by analogy with similar reactions (Abstr., 1882, 848, and 1896, i, 462), probably 2 : 4-dirnethylbenxoylbenxene-o-suZphonic acid, C,H,Me,* CO*C,H,*SO,H ; it crystallises in slender, white needles with 2H,O, melts a t 8O0, and yields an ammonium salt, with +H,O, melting at 235-236". The potassium salt (anhydrous) melts and darkens at 300" ; the sodium salt could not be obtained crystalline ; the barium salt, with 2H,O, melts at 207'. The +-cumem derivative is probably a 2 : 4 : 5-trimethylbenxoylbenx- ene-o-suZplAonic acid, C,H,Me,*CO*C,H,-SO,H (compare Abstr., 1887, 940) ; it crystallises from chloroform in slender, white needles, sinters a t 167O, melts at 169', and yields an easily soluble, crystalline am- monium salt melting at 255-256O; the potassium salt melts and de- composes at 286'; the sodium salt, with l$H,O, sinters at 272' and melts at 274"; the barium salt melts at 267'.s-Z'rimethylbenzoylbenxene-o-sulphonic acid, obtained by using mesit- ylene, crystallises from water, in which i t is sparingly soluble, in colourless, lustrous plates, with 4H,O, which melt at 98', lose their contained water at 100-110', and then melt at 184'; the ammonium salt melts at 272', the potassium salt begins to sinter at 315', -the sodium salt, with lH20, melts at 171°, whilst the 6arium salt, with 4H,O, sinters at 248' and melts at 252'.W. A. D.I54 ABSTRACTS OF CHEMICAL PAPERS, Action of Nitrogen Tetroxide on the Benzilmonoximes. By GIACOMO PONZIO (J. pr. Chem., 1900, [ii], 62, 543--544).-When an ethereal solution of a- or y-benzilmonoxime is treated with nitrogen tetroxide, benzil, . p-nitrobenzil, and small quantities of benzoic and p-nitrobenzoic acids are produced, but neither phenyldinitromethane nor its benzoyl derivative is formed, The Stereoisomeric Symmetrical Dibenzoylethylenes. By CARL PAAL and HEINRICH SCHULZE (Ber., 1900, 33, 3795-3800, (Compare this vol., i, 148).-When dibenzoylmalic acid is heated above its melting-point, it loses water and carbon dioxide, and is converted into a mixture of the two stereoisomeric dibenzoylethylenes.Bz'!?*H is the chief product of this decomposi- H* C*Bz' trans Dibenxoylethylene, tion, and crystallises in long, deep yellow needles melting a t 11 1". By reduction, it is converted into diphenacyl and combines with bromine to form dibenxogbthylene bromide, COPh.CHBr*CHBr*COPh, which crystallises in small, white prisms melting a t 1 7 8 O . When warmed with hydrazine hydrate, it yields about 25 per cent. of the calculated amount of 3 : 6-diphenylpyridazine. It also combines with aniline to form anilinodibenxoylethane (anilinodiphenacyl), NHPh*CHBz*CH2Bz, which crystallises in thin, sulphur-yellow prisms melting at 138' and is decomposed by boiling with acetic acid into the original trans-dibenzoylethylene and aniline. Bz*!?H which is only formed in small Bz*C*H' cis-Di6enxoyZethyZene, amount by the decomposition of dibenzoylmalic acid, crystallises in colourless, silky needles melting at 134O, and is more readily soluble in most reagents than the tmms-modification.By hydrazine hydr- ate in the cold, it is converted quantitatively into 3 :6-diphenyl- pyridazine and hence must have the cis-configuration. It unites with aniline to form the same anilinodiphenacyl as the trans-form, and also forms a dibromide. A. H. Thermochemistry of Quinones : Constitution of Quin- hydrones. By AMAND VALEUR (Ann. Chim. Phys,, 1900, [vii], 21, 470-574).-The thermochemical data -relating to the unsubstituted quinones and their dihydro-derivatives have already been published (Abstr., 1898, ii, 420, 500).The following constants have been determined for the chlorine derivatives of quinone (see table, p. 155). The heats of oxidation of the monochloro-, dichloro-, trichloro-, and tetrachloro-quinols to the corresponding quinones are 29.4, 35.6, 46.7, and 45.3 Cal. respectively. The substitution of two chlorine atoms by two hydroxyl groups in the formation of chloroanilic acid from chloroanil is accompanied by a generation of 92 Cal. ; this value approximates to the heat change which attends the production of a dibasic acid from its dichloride, the heat of hydrolysis of malonic chloride being 103.7 Cal. Sodium chloroanilate is described as a red compound crystallising with 4H20 ; the author has obtained another hydrate containing 3H,O which forms opaque, black crystals ; the latter separates from concea- E.G.ORGANIC CHEMISTRY. 155 Heat of combustion. Heat of Constant volume. Chloroquinone ..................... 2 : 6-Dichloroquinol .............. Trichloroquinone .................. Trichloroquinol .................... Tetrachloroquinone ............... Tetrachloroquinol ................. Chloroanilic acid .................. Chloroquinol ........................ 2 : 6-DichloroquinoneI. ............ 618.5 Cal. 647.6 580.9 615.9 548% 595.0 520 -1 566.1 487'3 -I formation Constant pressure. 618.2 Cal. 647'6 580.4 615.7 547.8 594.5 519.0 564.3 486'2 56 '0 Cal. 95 '6 64'2 97-9 67.2 89.5 66.4 90.1 158.4 Heat of substitution of chlorine for hydrogen. 32.6 Cal. 30.6 62 -8 54 '6 87.8 68'2 109.0 90 *8 trated solutions at 35' , whilst the former is produced at 18'.The paper contains a detailed account of the estimation of halogens in organic compounds by the calorimetric bomb, and a, description of a method for the quantitative estimation of quinones (compare Abstr., 1900, ii, 57 and 172). The action of hydroxylnmine on the quinones under varying conditions has been studied; it is found to reduce the p-quinones with considerable generation of heat, and in this way, tetra- chloroquinol is readily obtained from chloroanil. The thermochemical data deduced from the study of the quinone- monoximes have already been published (Abstr., 1898, ii, 500). A quinhydrone is produced by the direct combination of a quinone of higher molecular weight with the dihydro-derivative of a quinone of lower molecular weight, and the same product is obtained by mixing the less complex quinone with the quinol of higher molecular weight.I n the second mode of formation, the first action is probably the oxidation of the quinol by the quinone of lower molecular weight, owing to the'fact that the heat of reduction of the simpler quinone is greater than that of the quinone of higher molecular weight. This hypothesis is justified by the fact that quinone and dihydr- oxyphenanthrene interact, forming quinol and phenanthraquinone. The author discusses the formuh suggested by Graebe and by Jackson and Oenslager for quinhydrones and suggests the following /CH,-CO\ constitution, CHLOnC~H,*OLCH, as being most in accordance with \CO--CH,/ the properties of these comiounds. G. T.M. Terpenes and Ethereal Oils. By OTTO WALLACH (Annaleu, 1900, 314, 147--167).-[With JULIUS SALKIND].-~~~'?J~ P-methylcyclo- CH,. CHMe 7H2 hexandacetic m i d , I produced by the CH,-OH,-C( OH) *CH2* C0,Et' action of zinc on a mixture of methylhexanone and ethyl bromo- acetate, is a liquid having the odour of ethyl benzoate ; it boils at 127-129Oand 254-256' under pressures of 21 mm. and 760 mm.156 ABSTRACTS OF CHEMICAL PAPERS. respectively, has a sp. gr. 1.0035, and m, 1.4581 at 18'. The methyl ester boils a t 120-125' and 240' under pressures of 23 mm. and 760 mm. respectively. Ethyl /3-naethyZcyclohexeneacetnte, C,Hll*CH,*CO,Et, obtained on heating ethyl methylhexanolacetate with finely powdered potassium hydrogen sulphate at 160' during 2-3 hours, boils at 111-112' and 229-231' under pressures of 23 mm.and 760 mm. respectively, has a sp. gr. 0.9555, and nD 1.46207 at 20'. The methyl ester boils at 103-105' and 214-217' under pressures of 2.3 mm. and 760 mm. respectively; i t has a sp. gr. 0.97 and n,, 1.4635 at 25'. P-Methylcyclo- hexeneacetic acid, C7Hl,*CH,-C0,H, boils at 146-1 49' and 245-255' under pressures of 23 mm. and 760 mm. respectively; it has a sp. gr. 1,015 and a, 1.4807 at 27'. The acmide crystallises from dilute methyl alcohol in colourless leaflets and melts a t 149-150'. 2>C(OH)*CH2-C0,Et, [With VAN ~EECK-VOLLEN~~~EN].-~ethy~~ubero~acetate, yH,*CH,* CH CH,*CH,*CH, prepared from snberone and methyl bromoacetate under the influence of zinc, boils at 141-145' and 249-257' under pressures of 12 mm.and 760 mm. respectively ; it has a sp. gr. 1,037 and nD 1.47017 at 20'. Methyl suberenencetate, C,H,,*CO,Me, obtained from the foregoing substance and potassium hydrogen sulphate, boils a t 125-126' under 13 mm. pressure; the ethyl ester boils at 135-136' under 23 mm. pressure. Subes*eneacetic acid, C9Hl4O2, is a viscous liquid which boils at 158-159' under 1'7 mm. pressure, has a sp. gr. 1.035 and nD 1.4920 at 20'. The Iqdrocarbon, C8H14, produced when subereneacetic acid is distilled under atmospheric pressure, boils a t 138-140', has a sp. gr. 0.S24, and n D 1.4611 a t 20' ; its constitution is probably repre- sented by the expression (?H2*CH2*CH2>C:CH2, the formula of a CH,*CH,* CH2 methylenecycloheptane. [With NICOLAI SPERANSKI] .--Ethyl rnethylcy clopentanolncetnte, YH Me CH, CH,-CH2 >C(OH)*CH,-CO,Et, produced by the influence of zinc on /3-methylcyclopentanone and ethyl brornoacetate, boils a t 1 15-120' under 12 mm.pressure ; the methyl ester boils at 110-115' under 12 mm. pressure. The unsaturated ester, C,H,&Ie*CO,Et, prepared by the action of potassium hydrogen sulphate, boils a t 88-91' under 15 mm. pressure. 2-Methyl-5-isopropyZphenyZucetic acid, C,H,MePrp*CH,*CO,H, melts at 69-70', and boils a t 180-183' under 15 mm. pressure; cold fuming nitric acid converts it into the dimitro-derivative, C12H1406N2, which crystallises from dilute methyl alcohol in white leaflets and melts a t 196-197'. The ethyl ester, obtained from carvone and ethyl bromoacetate, boils at 155' under 15 mm. pressure. Di~~ds~occcrveoZacetic acid, OH*C,,Hl,*CH2*C02H, boils at 196-208' under 14 mm.pressure, and when distilled under atmospheric pressure yields an unsaturated hydrocarbon, which should be homo- limonene ; the ethyl ester, prepared from dihydrocarvone and ethyl bromoacetate, boils at 150-1 70' and 282-288" under pressures ofORGANIC CHEMISTRY. 157 14 mm. and 760 mm. respectively, has a sp. gr. 0.997, and n, 1.47664 at 20'. [With L ~ ~ ~ s a c ~ ] . - T h u ~ o k a c e t ~ c acid, OH*CloHl,*CH,*C02H, crystallises from a mixture of benzene and petroleum in leaflets, and melts at 90-91O; the ethyl ester, prepared from thujone and ethyl bromoacetate, boils at 154-164' under 14 mm. pressure. Isothujole- acetic acid melts at 168-1709 Condensation of Methylhexanone with nthyl a-Bromopro- pionate and Ethyl a-Bromsisobutyrate. By JULIUS VON BRAUN M.0. F. (Annalen, 1900, 314, 168 -177. Compare foregoing abstract).-Ethyl ~ i e t hylc y clohexanolpropionate, pre- yH,*CHMe*$!H, CH,-CH,-C(OH\* CHMe* CO-Et' pared by the action of zinc on me<hyIcy~ohe&m~ne and ethyf a-bromo- propionate, boils a t 128-133' under 8 mm. pressure ; hydrolysis does not yield the acid, but gives rise to a mixture of methylcyclohexanone, methylcyclohexanol, and propionic acid. Ethyl methylcyclohexanolisobutyrate, yH,*CHMe*VH, CH,-CH,--C(OH)* CMe,* C0,Et' obtained from methylcyclohexanone and ethyl a-bromoisobutyrate, boils at 134-139' under 10 mm. pressure ; sodium ethoxide resolves it into methylcyclohexanone and butyric acid. When the hydroxy-ester is heated with potassium hydrogen sulphate at 150-160', the unsatur- ated ester, C,,H,,O,, is produced, boiling at 116' under 8 mm.pres- sure; the acid from this compound, when heated under the ordinary pressure, yields the hydrocmbon, CI0Hl8, which must be a menthene of the meta-series. M. 0. F. Compounds of the cycloCitra1 Series. By FERDINAND TIE- MA" [and R. SCHMIDT] (Bey., ~900,33,3703-371O).-The conversion of the open chain ketone, $-ionone, into the cyclocitral derivative, ionone, by the agency of acids (Tiemann and Kruger, Abstr., 1894, i, 82) is now recognised as a change undergone by all compounds of the citral series. Further investigation of ionone has shown that this substance is a mixture of two isomerides, a- and p-ionones, which do not correspond with isomeric +-ionones.In the following papers, t o which the present communication is an introduction, the isomerism of the two modifications is proved to be dependent on the position of the unsaturated linking; it is also found that the production of two isomeric cyclocitrals characterises the action of acids on other members of the citral group. The constitution of U L cyclocitrals belonging to the a- and p-series is represented by the formulae CH,<gEg!:>CHR and C H , < ~ ~ ~ ~ ~ > C R respec- tively. M. 0. F. Inversion of Compounds belonging t o the Citral Series. By FERDINAND TIEMANN [with R. SCHMIDT] (Ber., 1900,33,3710-3713). -The inversion of geraniolene is effected in three days by continued agitation with 65 per cent. sulphuric acid. The cyclogeraniolene boils between 130' and 140'' the major portion distilling at 138' (uncorr.), and when oxidised with potassium permanganate yields isogeronic VOL.LXXX. i. rn158 ABSTRACTS OF CHEMICAL PAPERS, acid, derived from the a-cyclogeraniolene, CH2<CH=CMe CH2*CMe2>C€I,, and geronic acid from P-cyclogeraniolene, CH2<CH,-CMe CH,*CMe,>CH* L aeranic acid is converted likewise into a-cyclogeranic acid, CH~<:~Z?~$;>CH CO,H, which melts a t 1 0 6 O , and /3-cyclogeranic acid, CH2<CH9--CMe CH,*0M432>(-3CO2H, which has not been yet obtained in crystals. Constitution of a-cycloGeranic Acid. By FERDINAND TIEMANN and HERMANN TIGGES (Ber., 1900, 33, 371 3-371 9).-The isogeranic acid of Tiemann and Semmler (hbstr., 1894, i, 85), which melts at 106', will be called a-cyclogeranic acid, in order to distinguish it from the aliphatic isogeranic acid (Tiemann, Abstr., 1900, i, 275) and from the 6-cyclogoranic acid which corresponds with /3-ionone.Experiments on the oxidation of this compound have shown that it has the constitu- tion CH2<zg2'-!%:>CH* C0,H. M. 0. F. Di~ydroxydi~~~drocyclogeranic acid, QH2- CXe2-yH*C02H pro- CH,-CH(OH)*CMe*OH ' duced on oxidising a-cyclogeranic acid wich potassium permanganate (Tiemann and Semmler, Zoc. cit.), melts a t 198-200' ; the ethyl ester crystallises from petroleum, and melts at 92'. Hydroxyketodihydro- cyclogeranic acid, ?H20CMe2'?H'co2H, which is also formed, crystal- lises from water or from ethyl acetate and petroleum in prisms melting at 145'; the semicarbazone melts a t 216'.isoGeronic (4-dimethylheptan-6-onoic) acid (compare Tiemann and Schmidt, Abstr., 1898, i, 377), produced when the dihydroxy- and ketohydroxy-acids are oxidised with chromic acid, yields the semicarb- azone melting at 198'. The hydrogen ethyl salt of a-acetyl-/3P-dimethyladipic acid, C02Et* CHAo. CMe,. CH,* CH,* CO,H, prepared by oxidising ethyl dihydroxydihydrocyclogeranate with chromic acid, is an oil ; the semi- carhazone crystallises from absolute alcohol and melts at 157'. When this ester is heated with aqueous potassium hydroxide in a reflux apparatus, it undergoes the ketone hydrolysis, yielding isogeronic acid, COMe*CH,*CIMe,*CH,*CH,*CO,H. M. 0. F. By FERDINAND TIEMANN [with R. SCHMIDT] (Ber., 1900, 33, 3719-3725).-Although compounds of the citral series, CMe,:CH* CH2* CH,*CMe:CHR, give rise to the cyclocitrals by union of the carbon atoms in positions 1 and 6, citral itself is converted into cymene.If, however, the sensitive aldehyde group is protected, as in citralidenecyanoacetic acid (Tiemann, Abstr., 1900, i, 331), the normal cyclic product can be obtained. CH2-CO-CMe* OH cycZoCitra1. - - P-cycloCitraZ, CH2<E21\E$G CHO, obtained by invertingORGANIC CHEMISTRY. 159 & and b citralidenecyanoacetic acids, and hydrolysing the cyclo-acids produced, is nearly colourless, has the odour of carvone, and boils at 88-91"and 96-100'under pressuresof 10 mm. and 15 mm. respectively; it has sp. gr. 0.959 and 0.957 at 15' and 20' respectively, and nD 1.49'715 at 15'. The semicarbmone crystallises from methyl alcohol in large, transparent prisms containing the solvent, and melting at 165-166O; boiling ethyl acetate deposits it in thin leaflets melting at 166-1 67".The additive compound of semicarbazide and cyclocitral, having the composition C,,H,,O,N,, instead of CllH190N3, crystallises from a mixture of ethyl acetate and benzene in slender needles, and decomposes at 250'. /3-cycZoCitra1 yields p-ionone when condensed with acetone, P-cycloGeranic acid, CH2<CK,- OH,* CMez>C*CO,H, CMe formed when the aldehyde is exposed to air, crystaliises from petroleum in large, trans- parent prisms or plates, and melts at 93-94' ; it decolorises bromine very slowly, yielding hydrogen bromide. Oxidation with alkaline per- manganate gives rise to the hydroxy-acid, C,,H,,Oq, which melts and decomposes at 186O, and the &to-acid, C,H,,O,, which melts at 189O, and yields a semicarbazone melting at 240"; the main product of oxidation is aa-dimethylglutaric acid.M. 0. F. Constitution of a-Ionone. By FERDINAND TIEMANN [and R. SCHMIDT] (Bey., 1900, 33, 3726-3727).-The constitutional formula, C H , < ~ ~ & ! ~ ~ > C H : C H * COMe, for a-ionone is established by con- verting the ketone into isogeronic acid under the influence of ice-cold potassium permanganate followed by chromic acid. M, 0. F. Constituents of West Indian Sandalwood Oil. 11. By HUGO VON SODEN and WILHELM ROJAHN (Chem. Centr., 1900, ii, 1274-12175; from Plmrm. Zeit., 45,878. Compare Abstr., 1900, i, 401).-Attempts to separate amyrol into two components by fractionally distilling in a vacuum have shown that it probably consists of two secondary or tertiary sesquiterpene alcohols.Of these the alcohol, C,,H,,* OH, of higher boiling point, present in the larger proportion, is a very viscous liquid, boils at 299', has a sp. gr. of about 0-987 at 15", and a rotation of about + 36'. The second alcohol has not been isolated in a pure state, but appears to have the composition C15H,,*OH, and to be optically inactive. Prom West Indian sandalwood oil, 0.1 per cent. of anzyrolin, C,,H,,O,, has also been isolated; it crystallises from methyl alcohol in stout crystals, is colourless, odourless, and tasteless, melts at 11 7O, and dis- solves in hot alcohol or in alcoholic potash, giving in the former case a solution with a blue and in the latter a solution with a yellowish- green fluorescence, By the action of bromine in glacial acetic acid, a soluble and an insoluble product, are formed.The latt,er is probably a dibyomide, Cl4H,,Fr2O3; i t is a white powder and melts a t 167-1599 Amyrolin appears to be an aromatic compound of the character of a lactooe. E. W. W, 172 2160 ABSTRACTS OF CHEMICAL PAPERS, Oil of Sweet Orange. By KARL STEPRAN (J. pr. Chem., 1900, [ ii], 62, 523-535).-The author has investigated the constituents of a large sample of the essential oil of sweet orange-peel which possessed the following characters : sp. gr. 0.851 at 15' ; [a], + 96'3' at 20' ; n, 1.47245 at 20'; the residue left on evaporation amounted to 2.29 per cent. After the removal of the terpenes by fractional distillation under 14 mm.pressure, the residual oil was shaken with sodium hydrogen sulphite solution ; by this means, n-decaldehyde was separated, which boils at 93-94' under 12 mm. and at 207-209' under 755 mm. pressure, has a sp. gr. 0.828 a t 15' and n, 1.42977 at 15'. When rt-decaldehyde is treated with P-naphthylamine and pyriivic acid, a substituted naphthacinchonic acid, C2,H,70,N, is obtained, which crystallises in white needles and melts a t 237". n-Decoic acid is produced when n-decaldehyde is oxidised with silver oxide; it has a sp. gr. 0.895 at 30'and 0.889 at 37', and rt, 1.43078 at 30'. The author was unable to confirm the statements of Semmler (Abstr., 1891, 539) and Parry (Chemist and Druggist, 1900, 462, 722) that the oil contains citral, or that of Flatau and Labbe (Abstr., 1899, i, 422) that a small proportion of citronella1 is present.The oil remaining from the bisulphite treatment, when hydrolysed with alcoholic potassium hydroxide, yielded n-octoic acid. The alcohols were dried and treated with phthalic anhydride; an ester was pro- duced which on hydrolysis furnished rt-nonyl alcohol of sp. gr. 0.840 at 15' and n, 1.43582 at 15'. The portion which was not converted into an ester was carefully fractionated under 22 mm. pressure; d-linalool (coriandrol) was found in the earlier fractions, whilst the later fractions consisted of d-terpineol which gave [a], + 95'9'. d-Terpineol yields a nitrosochloride which is converted by piperidine into the terpenylnitrolpiperidine melting at 159' ; it also combines with phenylcarbimide with formation of terpenylphenylurethane. The alcohol obtained by Wright (Annalen, 1884,227, 289) and supposed to be myristicol is d-terpineol.The residue is a waxy mass which melts at 67-68'and gives a saponification number 65 ; it yields on hydrolysis a solid, saturated acid, C27H5402, melting at 77-78', and an oil which solidifies on cooling, and melts at 138'; the latter substance gives Liebermann's cholesterol reaction, and appears to be related t o phytosterol. When the residue is left far several days with warm sulphuric acid (32 per cent.), a substance separates in yellow crystals which melts at 192-193', and contains 6.9 per cent. of sulphur. The quantitative composition of the oil is as follows : terpenes, 96 per cent.; compounds containing oxygen, 1 per cent. ; residue, 3 per cent. The compounds containing oxygen conaist of n-decaldehyde, 5.7 per cent. ; ester (CloH1702C8H15), 8.5 per cent. ; nonyl alcohol, 7.0 per cent. ; d-terpineol, 39.4 per cent. ; and dhlinalool, 39.4 per cent, Ononin. By FRANZ VON HEMMELMAYR (Ber., 1901,33, 3538-3540. Compare Hlasiwetz, J. pr. Chem., 1855, 65, 419).-Onospin has the formula C,,H,,O,,, and its melting point is 172', not 162' as given by Hlasiwetz. E. G.ORGANIC C AEMISTRY. 161 On subjecting onospin to acid hydrolysis in the mode recommended by Hlasiwetz, an impure product is obtained melting indefinitely at 140-1 50'. After several crystallisations from dilute alcohol and subsequent extraction with water, a compound is obtained in white, glistening needles melting at 122', but in quantity too small for analysis.The portion undissolved by water, after repeated extraction, yields a mixture of two substances, one in the form of long, flat needles melting a t 155-157", the other in white leaflets melting at 158-160'. The former, on analysis, gave numbers almost identical with those found by Hlasiwetz for his ononetin, so that the crude material is probably a mixture of isomerides (CllH1003)1P. I n accord- ance with the above formula for onospin, its hydrolysis may be repre- sented by the equation C,,H,,O,, = C2,H,,06 + C,H,,O,. A. L. By EMIL VOTO~EK and V. F R I ~ (Zeit. Zuckerind. Biihm,, 1900, 25, 1-7).--Besides rham- nose, xanthorhamnin yields galactose on hydrolysis, the ratio between the quantities of the two sugars obtained being 2 mols.of anhydrous rhamnose to 'I mol. of galactose. Quercitrin yields no sugar but rham- nose on hydrolysis. Conversion of Hyoscyamine into Atropine by means of Sodium Alkyloxides in Alcoholic Solution. By ARRIGO MAZZUCCHELLI (Gccxzetta, 1900, 30, ii, 476--487).-The conversion of hyoscyamine into atropine by means of (1) a methyl alcohol solution of sodium methoxide, (2) sodium ethoxide in ethyl alcohol, ( 3 ) an alcoholic solution of sodium hydroxide, and (4) sodium propoxide in propyl alcohol, has been studied. The mean values of K for the various cases are (1) 0.001295, (2) 0.00788, ( 3 ) 0*00764, and (4) 0.0114. Solution (a), prepared by dissolving sodium in absolute alcohol, and solution (3), obtained by dissolving carefully dehydrated sodium hydroxide in absolute alcohol, show identical behaviour. The energy of the sodium alkyloxides, as given by the velocity with which they con- vert hyoscyamine into atropine, does not appear to depend on the extent to which they are electrolytically dissociated, as the transform- ation proceeds most quickly in the solvent having the smallest ionising power.T. H. P. By A. I. ROSSOLIMO (Z Russ. Phys. Chem. Xoc., 1900, 32, 727-?32).-Ca$eine ethiodide, C,Hio02N,,EtI, prepared by heating caffeine with excess of ethyl iodide in a sealed tube a t 160-170° for 20 hours, separates from ab- solute alcohol in short, pale yellow, acicular crystals which melt with evolution of gas at 1&2-183', have a-bitter taste, and are readily soluble in water, which, however, quickly decomposes them.Cafeine ethochloride, formed on heating an alcoholic solution of the iodide with an excess of freshly precipitated silver chloride, crys- tallises from alcohol in colourless, transparent, superposed plates or from a mixture of alcohol and benzene in thin, silky, white rods melting a t 182-1839 Its platinichloride is precipitated as an orange powder composed of microscopic acicular crystals which readily decom- pose on heating. The auvichloride separates from alcohol in micro. rseopic, lemon-yellow, acioular cryatals melting at 188O. Sugars of Xanthorhamnin and Quercitrin. T. H. P. Action of Ethyl Iodide on Caffeine. T, H, P,162 ABSTRACTS OF CHEMICAL PAPER,$, 0.8666 m. p. 178-181" { mitpi:;090, ] decomposes m.p. 129-130" Action of Bromine on Ginchonidine. Two Isomeric a-and P-Dibromocinchonidines. By J. GALIMARD (Bull. Xoc. Chirn., 1901, [ iii], 25, 84-88).-When cinchonidine sulphate is heated with fuming hydrobromic acid and the liquid subsequently neutralised with ammonia, or sodium carbonate, cinchonidine hydrobromide, C19H2,0N,,HBr, is precipitated as a nearly white powder which is very soluble in hot alcohol, but insoluble in water or ether. When cinchonidine sulphate is warmed with bromine in dilute hydro- bromic acid solution and the liquid left t o cool, a-dibrmocinchnidine hydromide, C19H,oBr,0N,, 2HBr, crystallises out in colourless needles, which melt and decompose a t 205--206°. When treated with am- monia or sodium carbonate, it yields a-dibromocinchonidine, which decomposes without melting a t 180O.One of the atoms of bromine in a-dibromocinchonidine has probably replaoed the hydrogen of a hydroxyl group, since it is readily removed by boiling with water or alkalis, or by the action of silver nitrate. a-Dibromocinchonidine is unstable, and on keeping, or when treated with nitric acid, it is converted into the isomeric P-dibromocinchonidine. a-Dibromocinchonidine hydrobromide also, when subjected t o pro- longed boiling with alcohol, yields more highly brominated compounds, including amixed hydrobromide of dibromocinchonidine and tribromocin- chonidine, C19H,oON2Br,,C,QH,QON,Br,,HBr, which, on treatment with lime, is converted into B-dibromocinchonidine. This base forms colourless crystals decomposing at 200' without melting, and is lsvorotatory ; bromine is not removed from it by treatment with aqueous alkalis or By ARTHUR HANTZSCH (Bey., 1900, by silver nitrate, N.L. The Formula of Gotarnine. 33, 3685-3686).-A reply to Decker (Abstr., 1900, i, 683). A. H. 719 mm. 0 '8651 181-182" { melts and } decomposes at 208-210" 129-130" 2-Ethylpiperidine and its Properties. By ANDREAS LIPP (Bey., 1900, 33,3513-3519. Compare Ladenburg, Abstr., 1898, i, 339).- The compound obtained by the reduction of picolylalkine (compare Abstr. 1897, i, 230) is shown to be 2-ethylpiperidine. A number of Boiling point . , , . . , Sp. gr. at 0" ....., Hydrochloride.. . . Platinichloride ... Aurichloride . . . . . . Mercuric chloride. 2-Eth ylpiperidine. Ladenburg. I LiPP. I 1 -Methyl-2-etliylpiperidine.Lad enburg. 150-151 '5" 0 '8515 obtained crystalline 122-123' Lipy. 153 '5-1 54 '5" at 730 mm. 0.8541 crys t a1 I ine 11 8-1 19" 202-205" 153-1 54"ORGANIC CEEMISTRY. 163 derivatives have been prepared and investigated, but the properties of these differ only slightly from those given by Ladenburg. By HANS FRESE (Ber., 1900, 33, 3483-3484).-The author corrects the values for the physical con- stants of d- and I-2-ethylpiperidine formerly given by Ladenburg (Annulen, 1888, 247, 71). The pure d-tartrate melts a t 105*5', and yields a base which distils at 142-143.5' and has a'sp. gr. 0.8680 at 4' ; [a]= + 1'7.5". The I-tartrate was not obtained pure ; the derived base boils at 138-142" and has [a], - 14.55'. The Occurrence of Intermediate Products in the Synthesis of Pyrroles from 1 : 4-Diketones. By LUDWIG KNORR and PAUL RABE (Ber., 1900,33, 3801-3803).-When ethyl P-diacetylsuccinate is treated with dry ammonia gas at 0" in the presence of ether, it dis- solves and the solution then deposits ethyl p-amino-/?-hexene-E-one-y8- dicarboxylate, NR,*CMe:C(CO,Et)*CHAc*CO,Et, in compact, well- developed crystals. This substance gradually loses the elements of water when it is preserved, and passes into ethyl 2 : 5-dimethylpyrrole- 3 : 4-dicarboxylate, a change which also occurs when it is dissolved in acetic acid, hot alcohol, or dilute mineral acids.The aminohexenone compound evolves ammonia when treated with concentrated aqueous soda and reacts with hydrazine hydrate to form bis-3-methylpyrazol- one. Ethyl diacetylsuccinate therefore forms an intermediate aminoketone when treated with ammonia, and in this respect resembles the ay-ketones and some of the a€-ketones, such as ethyl benzylideneacetoacetate.A. H. Compounds of Bismuth Salts with Organic Bases. By CLEMENTE MONTEMARTINI (Gaxxetta, 1900, 30, ii, 493-494).--8 preliminary note, published on account of the appearance of a paper by Hauser and Vanino (Abstr., 1900, i, 641). On adding pyridine to an ethereal solution of bismuth chloride, a white precipitate is obtained, consisting of a double salt of 1 mol. of bismuth chloride with 1.5 mols. of pyridine. Constitution of Platinum Bases, By SOFUS M. JORGENSEN (Zeit. anorg. Chem., 1900, 25, 353-377. Abstr., 1900, i, 542).- Several methods are described for the preparation of platopyridinetri- ammine chloride, PtPy(NH,),C1,,H20.The salt crystallises in lustrous, white, rhombic tablets ; when heated at 1 20-130", it loses ammonia and pyridine and yields a bright yellow powder containing the com- pounds Pt(NH,),C12, PtPyNH,Cl, and PtPy,CI, ; heated with hydro- chloric acid on the water-bath, it yields the compound PtPyNH,Cl, and platosammine chloride ; with potassium platinochloride, it yields the salt PtPyNH,Cl,,PtCI,,H,O,. which is very characteristic, crystallises in flat, crimson needles, and is decomposed by heating at 115". Anderson's salt, PtPy2C1,, Balbiano's salt, and chloroplatinsemidi- pyridine chloride, when reduced with sodium thiosulphate, all yield the platopyridineammine chloride a, whereas the chloroplatinpyridine chloride, PtPy2C1,, corresponding with Gerhardt's chloride, is not reduced by sodium thiosulphate, and when treated with hydrogen sulphide yields the platopyridineammine chloride p.J. J. S. d- and I-2-Ethylpiperidine, W. A. D. T. H. P.164 ABSTRACTS OF CHEMICAL PAPERS. Ethylenediamine platinochloride, PtC2H,(NH2C1),,. when heated with water on the water-bath, is converted into platosemidiethylenediamine chloride. These reactions are in harmony with the view that Peyrone's chloride is the symmetrical compound, Cl*NH,*Pt*NH,* C1, and Reiset's chloride the unsymmetrical compound, Cl*NH,*NH,*Pt* C1. Compounds of Metallic Salts with Bases of the Pyridine Series. By DANIEL TONBECK (Ann. Chim. Phis., 1900, [vii], 21, 433-469. Compare this vol., i, 135).-The halogen salts of zinc and cadmium combine with two molecular proportions of the correspond- ing salts of the aromatic amines t o form compounds of the type ZnC12,2NH3PhC1 ; pyridine also forms an analogous derivative, ZnC1,,2C5NH,CI.Two mols. of a pyridine base unite with 1 mol. of a halogen salt of zinc or cadmium to form a salt of the type CdC1,,2C,H7N, and the combination has been effected in the case of picoline, lutidine, and collidine. These bases also form similar com- pounds with silver bromide, iodide, and cyanide, but the chloride interacts only with picoline. The connection between the dissociation pressures of these double compounds and the temperature has been studied ; the results obtained are tabulated, and the paper also contains the corresponding dissociation pressure curves.G. T. M. E. C. R. Action of Bromine on 3-Picoline. By E. DEHNEL (Ber., 1900, 33, 3498-3500).-A monobromo-derivative, C,NH,* CH,Br, is the principal product when 3-picoline is heated with bromine (2 mols.) and concentrated hydrochloric acid for 10 hours a t 150' ; the base was not isolated owing to its instability, but was converted into the picrate, which crystallises fro= benzene in rosettes of yellow needles, melts at 114', and on boiling with water for 2 hours yields the p*crate of 3-picolylalkine (3-hydroxymethylpy&dine), C,NH,* CH,* OH, in the form of long, yellow needles. The base, formed on decomposing this salt, could not be obtained pure, but the aurichloride forms small, yellow crystals melting at 136-1 37', and the platinichloride, brownish-red plates melting at 193-195".More complex derivatives of 3-picoline were also formed in the bromination; on distilling in a vacuum, a liquid boiling at 40--50', and a solid distilling at 90-loo', were isolated, both apparently having the composition C,,H,,,N2Br,. Hantzsch's Synthesis of Ethyl Dihydrocollidinedicarb- oxylate. By PAUL RABE and ADOLF BILLMANN (Bey., 1900, 33, 5806-3811. Compare this vol., i, 147).--Both the mono- and diethyl esters of ethylidenebisacetoacetic acid are converted by alcoholic ammonia a t Oo into ethyl P-amilzo-8-methyl-P-heptelze-~-oocne- y ; e-dicarb- oxylate, NH,* CMe: C(CO,Et)-CRMe-CHAc42O2Et, which forms large, well-developtd, non-fluorescent triclinic crystals melting at 140'. It is not affected by alkalis, and by phenylhydraxine is converted into the phenylhydraxone of ethyl ethylidenebisacetoatcetcctc, HHPh-N; Cl\le*CH( CO,Et)*CHMe*CH4c*CO,Et, W.A. D.ORGANIC CHEMISTRY. 165 which crystallises in needles melting a t about 203'. Ethyl dihydro- collidinedicarboxylate could not be obtained by the action of ammonia on ethyl ethylidenebisacetoacetate, and the statement of Knoevenagel and Klages (Annulen, 1894, 281, 105) must therefore be inaccurate. This fact also shows that in Hantzsch's synthesis of ethyl dihydro- collidinedicarboxylate from ethyl ace toacetate and aldehyde ammonia, ethyl ethylidenebisacetoacetate cannot be formed as an intermediate product. Ethyl methylenebisacetoacetate, on the other hand, as stated by Knoevenagel, readily forms ethyl dihydrolutidinedicarboxylate.A. H. o-Nitrophenyl-2-picolylalkine and its Derivatives ; Phenyl- 2-picolylalkine. By E. ROTH (Ber., 1900, 33, 3476-3479).-- o-Nit~ophenyZ-2-picolylalkine (P-o-nitrophanyl-~-hydroxy-2-ethyZpyridine), NO,* C,H,* CH(OH)*CH,- C5NH,, obtained by heating 2-picoline with o-nitrobenzaldehyde and water for 7-8 hours 6t 137-1 40°, separates from dilute alcohol in snow-white crystals, melts at 137--138O, is not volatile with steam, and yields an aurichloride which forms prisms and melts at 155' ; the platinichloride melts at 212', the green ferrocyanide at 148' with decomposition, and the picrate a t 161'. The acetate, NO,* C,H,* CH(OAc)*CH,* C,NH4, crystallises from alcohol and melts at 8 2'. 0- Aminophen yl-2-pic0 I y Zalkine (P-o-aminophen yl -P-?h ydroxy-2- ethylpyridine), obtained by reducing the nitro-compound with zinc or iron and hydrochloric acid, separates from alcohol as a snow-white mass which melts at 97-98', and becomes red in the air ; the picrate, platinichloride, and ferrocyanide were prepared. P?~enyZ-2-picolylalkine (P-phenyl-P-hydroxy-2-et?~ylp~ridine), OH* CHPh*CH,* C5NH4, obtained by heating 2-picoline with benzaldehyde and water for 10 hours at 135', crystallises from dilute alcohol in white leaflets and melts at 96-97'; the platinichloyide, with 3H,O, melts at l04", the atwichloride at 131-132', and the mercwrichlo~*ids at 1624 W.A. D. 2-Phenyl-6-stilbazole and 2-Phenyl-6-o-hydroxystilbaeole. By E. DEHNEL (Be?., 1900, 33, 3494-3497).-2-Phenyl-6-stilbccxole (2-phenyl-6-styryZpyridine), C,H,* C,NH,* CH:CHPh, obtained by heat- ing 2-methyl-6-phenylpyridine (Scholtz, Abstr., 1895, i, 562) with benzaldehyde for 5-6 hours at 250-260°, crystallises from dilute alcohol in beautiful, white needles and melts at 79' ; the ?hydrochloride, with 4H,O, crystallises from dilute hydrochloric acid in long needles melting at loo", and in yellow plates from alcohol or acetone.The aurichloride forms thick, red crystals and melts a t 179*, and the platini- ahloyide melts at 220' ; the xinaochloride forms yellow crystals. With bromine, the base yields the compound CI9H,NBr4,HBr, which forms rose-coloured, six-sided plates, melts at 172", and, when boiled with alcohol, yields 2-phenyl-6-stilbacmole dihornide, C,NH,Ph*CHBr * CHPhBr, in the form of lustrous, white leaflets melting at 190' ; on reduction, the base gives rise to 2-phsnyl-6-stilbazoline, C,NH,Ph*CH,* CH,Ph, which forms a non-crystallisable, white syrup? and yields a hydro- chloride crystallising from water in stellar aggregates of white needles,166 ABSTRACTS OF CHEMICAL PAPERS.which darken at 160° and deoompose at 200' j the platinichloride melts at 155-156'. 2-Phenyl-6 : o-hydroxystilbaxole (2qhenyZ-6 ; o-hydroxystyryZpyridine), C,NH,Ph* CH:CH* CGH4* OH, obtained by heating salicylaldehyde with 2-phenyl-6-methylpyridine for 8-1 0 hours at 200°, crystallises from benzene in spherular aggregates of white needles and melts at 138' ; the hydrochloride forms dark yellow needles and melts at 126-127O ; the aurichloride brownish-red needles melting at 189' ; the amorphous platinichloride melts at 190'.Sulphur Derivatives of Aromatic Amines. By ALBERT EDINGER (Bey., 1900, 33, 3769-3770).-This is a preliminary paper, occasioned by Gutbier's communication (this vol., i, 96). From acr- idine and flowers of sulphur mesothioacridone is obtained; this has, W. A. D. presumably, the constitution CGH4<&>CGH,, cs and is analogous to Graebe's mesoacridone (Abstr., 1893, i, 650), from which it can be obtained by the action of phosphorus and sulphur a t 260'. It crystal- lises in red needles and melts at; 275' ; phosphorus pentachloride con- verts it into Graebe's mesochloroacridine, phosphorus and bromine into mesobromoacridine, which melts at 11 go, and forms mesoiodoacr- idine, melting at 169', when it is treated with alcoholic sodium iodide.It dissolves in alkalis, and from the solution benxvl and benxowl deri- vatives, C,,H,N*S*CH,Ph and C,,H8N*SBz, can b i prepared. " C. F. B. 3 : 3'-Dichlorobenzidine. By PAUL COHN (Ber., 1901, 33, 355 1-3554).-3 : 3'-Dichlorobenzidine was made by reducing o-nitro- chlorobenzene with zinc dust and sodium hydroxide and heating the resulting hydrazo-compound with strong hydrochloric acid ; it is identical with the base prepared by'chlorinating diacetylbenzidine (Ger- man Patents, 94410 and 97101). The hydrochloyide, CI2H,,-,N2Cl,,2HCI, dissolves readily in alcohol, but is sparingly soluble in water ; the latter statement is also true of the suZphate, nitrate, and oxalaie. The platini- chloride is unstable. The dibenxoyl derivative, C,2HGC12(NHBz)2, crystallises from xylene in bundles of white needles and melts at 2659 3 : 3'-Dichlorobenzidine yields a tetraxo-dye on uniting the diazotised substance with naphthionic acid; this has a bluish-red tint and its colour, unlike that of the simple congo red, is not altered by dilute acetic acid ; it is best used in faint!y acid baths.By ALEXANDER EIBNER and FR. A. SENF (Ber., 1901, 33, 3549-3551).-The capacity of the cyanohydrins of alkylideneamines to take part in condensations with aldehydes in presence of potassium cyanide or alcoholic potash appears to be general (compare von Miller and Plochl, Abstr., 1896, i, 609) and extends to the cyanohydrins of hydrazones. With propylidenehydrazone cyanohydrin and benzaldehyde, the substance NHPh*NH*CHEt*CO*N:CHPh is formed; this separates from light petroleum in rhombic tablets and melts at 123'.I n this instance, the best results are obtained when the two substances are allowed to remain together for 24 hours in alcoholic solution without any condensing agent. A. L. An Additive Reaction of Nitriles. A. L.ORGANIC CHEMISTRY. 167 Action of Methylacetylacetone and Ethylacetylacetone on Diaaochlorides. By G. FAVREL (Comnpt. rend., 1901, 133, 41-42). -The action of methylacetylacetone on diazobenzene chloride yields a hydrazone, NHPh*N:CMe%OMe, which melts at 134' and seems to be identical with the compound obtained by von Pechmann by the action of phenylhydrazine on dikcetyl and by Japp and Klingemann by the action of diazobenzene chloride on methylacetoacetic acid.Ethylacetylacetone yields the corresponding ethyl derivative, which melts a t 117' and was likewise prepared by Japp and Klingemann. Diazo-o-tolyl and diazo-p-tolyl chlorides behave in a similar manner, whilst the bisdiazochlorides from benzidine and its homologues yield t h dihydrazones of diacetyl or propionylacetyl, as the case may be. Diacety~ip~e.lzyZdi~ydra~one melts at 2 83-2 84O, and the corresponding propionylacetyl compound at 265-268'. Stereoisomerism of the two Crotonic Acids. 4-Methyl- pyrazole-5-carboxylic Acid. By HANS VON PECHMANN and EMIL BURKARD (Ber., 1901, 33, 3590-3594).-As in the interaction of methyl diazoacetate with methyl maleate and fumarate (Buchner, Abstr., 1893, i, 431), identical products are obtained by the action of diazomethane on the methyl esters of crotonic and isocrotonic acids.C. H. B. CH* CHMe Methyl 4-methyZ'pyraxoline-5-carboxylate, N<NH.bH.CO,Me, is acolour- less syrup which decomposes on distillation. bromine to methyl 4methylpyraxole-5-carboxylate, N< It <s oxidised by CH*fjMe NH°C-CO,Me' which melts a t 170-1 71", crystallises from dilute alcohol, dissGlves in most solvents, and in dilute alkalis and mineral acids, but not in acetic acid; the ethyl ester melts at 156-158'; the acid, C,H,O,N,, crystallises from water in small, glistening prisms, and melts a t 218-220'. By distilling with soda-lime, the acid is converted into CH* CMe 4-methylpyrazole, NqNH,grr: , which boils at 204-205' under 730 mm. pressure, and differs in odour and in solubility from 3-methyl- pyrazole ; the double salt, with siEver nityate, crystallises from hot water,in glistening needles, and melts at 142', that of the isomeride melting at 121' ; by the actioq of nitric acid, a yellow oil is produced, and not a crystalline nitro-compound; the picrate, like that of the isomeride, melts at 142'.Pyrazole Derivatives from Diazomethane and Oleflnemono- carboxylic Acids. By HANS VON PECHMANN and EMIL BURKARD (Ber., 1901, 33, 3594-3596).-By the action of diazomethane on T. M. L. , - NHaYH, CH* CH*CO,Me' methyl acrylate, methyl pyrazoline-3-carboxylate, N< is produced, and on oxidation and hydrolysis is converted h t o Buchnsr and Papendieck's 3-pyrazolecarboxylic acid (Abstr., 1893, i, 431). In a similar way, methyl cinnamate is converted into methyl 5-phe.nyl- NH*vHPh which melts at 128O, CH* CH*CO,Me' yyrazolin~e-4-carboxylate, N<168 ABSTRACTS OF CHEMICAL PAPERS, crystallises in colourless prisms from alcohol, acetone, or benzene, and is insoluble in wafcr.Methyl 5~~enyZ~~rclzoZe~4-ca.rboxyZate, NGCE. fcllec0 Me, prepared by the action of bromine on the preced- NH-CPh 0 ing compound, >rystallises from alcohol in small prisms and melts at 188-190' ; the acid is identical with the 5-phenylpyrazole-4-carboxylic acid described by Knorr (Abstr., 1895, i, 396), and decomposes at its melting point into carbon dioxide and 5-phenylpyrazole. Combination of Diazomethane with Citraconic and Mes- aconic Acids. By HANS VON PECHMANN and EMIL BURKARD (Ber., 1901, 33, 3597--3598).-Esters of citraconic and mesaconic acids combine with diazomethane to form an ester of the same 5-methyl- T.M. L. CH*CH*CO H pyrazoline-4 : 5-dicarboxylic acid, NqNH. hMeecinH ; by the action of bromine on this ester and subsequent hydrolysi$, a mol. of carbon dioxide is eliminated, and 5-methylpyrazole-4-carboxylic acid, NqNHeCMe , is produced. T. M. L. Pyrimidine from Barbituric Acid. By SIEGMUND GABRIEL (Ber., 1900,33,3666-3668. Compare A bstr., 1899, 638).-Pyrimidine can be prepared more readily than from methyluracil by treating barbituric acid (malonylureide) with phosphorus oxychloride and re- ducing the resulting trichloropyrimidine. 2 : 4 : 6-~~ichZoropyrimidine, CH<ccl.N>CCI, is a heavy, colourless oil the vapour of which attacks the eyes ; i t boils at 213' under 755 mm.pressure, and after solidification melts at 21'. When heated with zinc dust and water, it is converted into pyrimidine. The yield amounts to about 16 per cent. of that calculated from the barbituric acid. Conversion of Anil Compounds of isovaleraldehyde into A. W. von Hofmann's corresponding Alkyl-substituted Ethyl- ene Bases. By ALEXANDER EIBNER and GEORG PURUCKER (Bey., 1900, 33, 3658-3664. Compare Abstr., 1892, 1189).-The base previously obtained by the reduction of isovaleraldehydeaniline with sodigm and ethyl alcohol has the constitution of a diisobutylethyleneaniline, C4Hg* CH(NHPh)*CH(NHPh)*C14H,. It is not affected by boiling with concentrated hydrochloric acid, but condenses with ethylene bromide to form d i i s o ~ 2 c t y Z d i ~ ~ ~ ~ ~ y Z ~ ~ ~ ~ r ~ ~ ~ ~ ~ , N P h < C H 2 '=?>NPh, which crystallises in silky needles melting at 121°, and yields a p-mitroso-derivative crystallising in yello wish-green needles.The base also reacts with benzaldehyde to form a glyoxaline derivative, NPh*~H*C4HQ which separates in tabular crystals melting a t CHPh<NPh*CH*C,H,' 109'. isoValeraldehyde-~-toluidine is also converted by reduction with sodium and ethyl alcohol into an ethylene base, which is a thick, colourless oil boiling at about 270'. The hydrochlorids CH. S*CO,H CC1.N A. H. CH(C,H,)*CH(C,H9) C,Hd c,a 0) ,Po C6H4M9) 2 3ORGANIC CHEMISTRY, 169 crystallises in white plates, and the diacetyl derivative in vitreous monoclinic tablets melting at 1 3S0, whilst the monobenzoyl deriva- tive forms thin plates melting at 156'.The dinitrosoarmine, C24H3+02N,, crystallises in pale yellow needles or cubes, melts at 92O, and is not affected by treatment with alcoholic hydrogen chloride, With benn- aldehyde, the base forms a gZyoxccZine derivative, C,H,*yH*N( C,H,Mej >CHPh, C,H,*CH*N( C,H,Me) which crystallises in large tablets melting at 154'. aniline, an intermediate product of the formula NHPh*CH( C4H,)*NPh*CH,*C,H, is probably formed, and the mononitrile previously obtained by the action of dilute hydrocyanic acid on isovaleraldehydeaniline appears to be a derivative of this substance of the formula NHPh*CH(C4H,)*NPh*CH(C,H,) *CN. On reduction with sodium and ethyl alcohol, it yields the ethylene- niline, whilst on distillation it yields the original base and the impler nitrile.A. H. By GIACOMO PONZIO and P. ROSSI (Gaxxetta, 1900, 38, ii, 454--458).-This compound has been prepared by removing a molecule of acetic acid from the acetyl deriva- tive of pa-acetylbeDzoylhydrazoxime by means of sodium carbonate. In the reduction of isovalera.ldehydeani1ine to diisobutylethylene- 1 : 3-Diphenyl4methylosotriaaole. 1- The acetyl derivative of cccetylbenxoyllhydraxoxime, NOAc* CMe*CPh*N,HPh, crystallises from alcohol in faintly yellow prisms melting at 134.5'. yMe:N>NPh, separates from CPh :N 1 : 3-Diphen y Z - 4 -rneth y Zosotriaxo Ze, alcohol in almost colourless prisms melting a t 37*5-38', and is soluble in the cold in the ordinary organic solvents, but insoluble in water. The dinitro-derivative, C,,H,,N3(N0,)2, crystallises from acetic acid in prisms melting a t 230-251'.The tetranitro-compound separates from acetone in yellow prisms melting at 172'. C,N,MePh* C,H,Br, crystallises from alcohol in slender, white needles melting a t 97'. 1 -p-BromophenyZ-3 -phnyL4-meth ylosotriaxo Ze, Ace t y Z benxo y l- p- bromophen y Zh y draxoxime, NOH:CMe*CPh:N,H*C,H,Br, separates from alcohol in yellowish needles melting at 206-207O. l-p-lodo~~nyl-3-phen~Z-4-rnet~yZosotriccxole crystallises from alcohol in sparkling lamina melting at 106O, and on treating with nitric acid yields the dinitrodiphenylmethylosotriazole melting at 230-231'. T. H. P. Oxidation of Hydrazoximes. V. By GIACOHO PONZIO (Gasxettcr;, 1900, 30, ii, 459-465).-2-Methyl-3 : n-diphe@-1 : 2-oxypyrro-1 : 4- C Me-g Ph N*NPh*N diaxole [4 : 5-oxy-1 : 3-diphenyZ-4-methyZosotriuzoZe],O< I , ob- tained by oxidising p : a-acetylbenzoylhydrazoxime in chloroform solu- tion by meam of mercuric oxide, crystallises from light petroleum in shining, faintly yellow needles melting at 83', and is soluble in all ordinary organic solvents.It does not yield a hydrochloride when170 ABSTBACTS OF CHEMICAL PAPERS. hydrogen chloride is passed through its ethereal solution, but on re- duction either in alcoholic solution with zinc and hydrochloric acid, or with hydriodic acid in sealed tubes, it gives 1 : 3-diphenyl-4-methyloso- triazole. Its dilzitro-compound separates from acetic acid in micro- scopic, yellowish prisms melting at 260', and is soluble in acetone, benzene, or chloroform. Tpiphenyl-l : 2-oxypyrro-1 : 4-diaxole [4 ; 5-oxy-1 ; 3 : 4-triphnyloso- tpiazoze], O<&.NPh.N ph, prepared by oxidising benzylhydrazoxime CPh-- in chloroform solution with mercuric oxide, crystallises from acetone in aggregates of yellowish needles melting at 169O, and is soluble in benzene and slightly so in light petroleum or alcohol.By the action of zinc and hydrochloric acid in alcoholic solution, or of hydriodic acid in a sealed tube at 140') it is converted into triphenylosotriazole, the hexalzitro-compound of which, C2,,H9N,(N02),, separates from acetic acid in shining, yellow prisms melting at 205-206O, and is almost in- soluble in all other organic solvents. By MARTIN KRUGER (Ber., 1900, 33, 3665. Compare Abstr., 1898, i, 699 j 1899, ii, 233).-The 6-methylxanthine previously isolated,from human urine readily yields theophylline (4 : 6- dimethylxanthine) on methylation, the latter being isolated by pre- cipitating its sodium salt with sodium hydroxide in the cold.6-Methyl- xanthine is best crystallised from acetic acid, and separates in very thin, six-sided, rhombic plates, A. H. By S. SAMELSON (Ber., 1900, 33, 3479--3483).-The following azo-compounds were prepared by combining dimethyl-m-toluidine with diazotised bases. Dimethyl-m-toluidineaxobenzene, NMe,*C,H,Me*N&'h, obtained by using aniline, crystallises from alcohol in lustrous, bright-red needles, melts at 66O, and yields a dark-brown, amorphous platinichloride, which sinters at 200°, but does not melt at 280'. The sui'phonic acid, NMe2*C,H,~~e*NzgC,H,*S0,H, obtained with sulphanilic acid, is a reddish-brown, hygroscopic powder which is sparingly soluble in water, softens at 210', carbonises at 225O, and yields a barium salt in the form of lustrous, brown crystals; on reduction, the acid gives sulphanilic acid and p-aminodimethyl-m- toluidine.Dimeth yl-m-tohidine-azo-p-t olwne, NMe,*C,H,Me *N,'C,H,Me, pre- pared with p-toluidine, crystallises from alcohol in lustrous, bright red needles, and melts at 121'; the hydrochloride crystallises from alcohol and melts at 172O ; the platinichloride is a dark-red, amorphous powder, whilst the sulphccte separates in greenish needles from methyl alcohol and melts at 201'. DimethyZ-m-toluidirzeaxo-m-tolzcene, NMe,*C,H,Me*N,*C,H,Me, from rra-tohidine, separates from alcohol in scarlet crystals, melts at 73-74', and yields a brown, amorphous platinichloride which carbonises at 1974 Dimethyl-m-toluidineaxo-p-phenetole, obtained by using p-phenet- idine, forms small, brown crystals and melts at 136-13'7'; the platinichloride, a bluish-grey, amorphous powder, carbonises at 197'.T. H. P. 6-Methylxanthine. Aeo-compounds Derived from m-Toluidine.ORGANIC CHEMISTRY. 171 Dirnethyl-m-tol~~irceazo-p-an~~ole, separates from alcohol in reddish- brown crystals, melts at 135-136', and yields a blue, crystalline hydrochloride melting at 164O which dissolves in alcohol to a red solution ; the sulphnte crystallises from methyl alcohol in dark blue needles and melts at 1 9 8 O , and the platinichloride is amorphous and decomposes at 2 0 2 O . isoDiazotisation of Arylamines.By EUCIEN BAMBERGER and ERNST RUST (Ber., 1900, 33, 3611-3512, Compare Abstr., 1894, i, 511)- Aromatic bases, when diazotised in alkaline solution, that is, with amyl nitrite and sodium ethoxide, yield isodiazotates and no trace of the normal compounds. That the iso-compound is not a secondary product obtained by the action of sodium ethoxide on diazoamino- benzene has been proved by the fact that these compounds do not react on one another. Aniline, 0- and p-toluidine, p-chloroaniline p-bromoaniline all react in a similar manner, but mesidine appears t a be incapable of yielding an isodiazotate. Methylamine and benzyl- m i n e do not react, nor can phenylnitroamine be obtained by the action of amyl nitrate and sodium ethoxide on aniline.By EUGEN BAMBERGER (Ber., 1900, 33, 3508-3510. Compare Abstr., 1900, i, 193, and Spitzer, this vol., i, 98).-According to the author, molecular quantities of nitrosobenzene and 1s-diphenylhydrazine react in hot alcoholic solution to give a quantitative yield of azobenzenezand Prphenylhydroxylamine. Nitrosobenzene and phenylhydrazine yield dlazohydroxylaminobenzene and phenylhydroxylamine. p-Tolylhydr- azine- and nitrosobenzene give p-toluenediccxohydroxylaminobenxene, C,H,Me*N:N*NPh*OH, me1ting:at 130-1 31" and phenylhydroxyl- amine, p-nitrosotoluene, and phenylhydrazine yield benxenediaxohydr- oxylamino-p-toluene, NPh:N*N(OH)*C6H4Me, melting at 123.5-124" and p-tolylhydroxylamine. J. J. S. Arylt hiolsulp honat es and Arylsulphinit es of Diazo-corn- pounds. By JULIUS TROEGER and ERICH EWERS (J.p. Chem., 1900, [ ii], 62, 369-430).-When benzidine or tolidine is diazotised, and the cold, neutral solution treated with a solution of the potassium salt of a thiolsulphonic acid, the corresponding thiolsulphonate of the diazo-compound is immediately precipitated. The products thus obtained sometimes undergo a remarkable transformation ; for example, the benzene- and p-toluene-thiolsulphonates of bisdiazodiphenyl and bisdiaxoditolyl separate in well-defined crystals which, when kept, lose their crystalline structure and become amorphous. The products obtained when diazo-compounds are treated with the salts of sulphinic acids are, however, always amorphous. The substances, both from thiolsulphonates and from sulphinites, are all of a golden- or orange- yellow colour.The thiolsulphonates cannot be purified by recrystalli- sation, since decomposition readily occurs with evolution of nitrogen ; some of the products obtained with sulphinites dissolve in cold ethyl acetate or chloroform, and can be reprecipitated by means of light petroleum. When heated with aniline or nitrobenzene, solution of either series of compounds is effected with simultaneous evolution of the nitrogen, and this reaction has been employed for the estimation W. A. D. J. J. S. Action of Nitrosobenzene on Aromatic Hydrazines.172 ABSTRACTS OF CHEMICAL PAPgRS. of the nitrogen. All the salts of diazo-compounds described in this paper yield a carmine red coloration with alcoholic potassium hydroxide. By the action of thiolsulphonates on bisdiazodiphenyl chloride, the following salts were obtained.Bisdiaxodiphenyl dibenxenethioZsuZphonate, C1,H,(N,* S*SO,Ph),, decomposes at 129-130', the di-p-toluenethiol- sulphonate at 147', the di-o-toluenethiolsuZphonate at 1409 and the di-a- and -P-nuphthaZenethioZsuZphonates at 125' and 131-1 33' respectively. The following compounds were prepared by the addition of thiol- sulphonates to solution of bisdiazoditolyl chloride. Bisdiaxoditolyl dibenxenethiolsulphonate decomposes at about 132' ; of the di-o- and -p-toluenethioZsu@honates, the latter decomposes at 135-1 36' ; di-a- and -P-naphthulenethiolstdphonates decompose at 108' and 1 12' respectively. By the action of sulphinites on the diazo-compounds as well in acid as in neutral solution, the following sulphones were obtained: di- phnylsul'phone bisdiaxodiphen y!, C,,H, (N2* S02Ph),, and the corresponding d&o- and -p-tolyl-, di-a- and -P-naphthyF, and the d~6romophenyl-suZphones.Diphen~Zsu~~onebidiaxoditoZyZ decomposes at 1 1 9', the corresponding di-o- and -p-tolyZsuZphones decompose at 11 9' and 128', and the di-a- and -P-naphthylsuZphones at 1 30' and 128' respectively ; the dibromophenyl- suZphone decomposes at 128'. The arylthiolsulphonates of diazo-compounds, derived from primary amines, are comparatively stable and indifferent towards acids and alkalis. When kept, they sometimes decompose spontaneously with evolution of nitrogen ; a similar decomposition occurs on heating. They react with alkaline phenol solutions with formation of oxyazo- compounds and the alkali salts of the thiolsulphonic acids.The thiolsulphonates of these diazo-compounds are nearly insoluble in water, but more or less soluble in alcohol, ether, chloroform, or carbon di- sulphide ; as the substances dissolve, decomposition occurs, and hence the original products cannot be recovered from their solutions. The compounds are obtained both amorphous and crystalline ; many solu- tions yield at first oily precipitates which gradually harden, whilst a further quantity afterwards separates in leaflets or needles ; some products are at first crystalline and soluble in water, but after a time become amorphous and insoluble. The colour of these substances is yellow, orange, red, or brown. The following compounds were prepared by the action of thiol- sulphonates on diazobcnzene chloride.Diaxobenxene benxelzethiolsulphon- ate, Ph*N,*S*SO,Ph, decomposes at 75'; if its solution in carbon disulphide is treated with alcohol and evaporated by means of a current of air, a yellow, crystalline residue is obtained, which consists of a mixture of diazobenzenephenylsulphone and diazobenzene benzenethiol- sulp honat e. Diazo benzene p-to Zuenethio ZsuZphonate decomposes at 8 8-8 go, the a-naphthaclenethiolsulphonate melts and decomposes at 95-96', and the p-naphthalenethiolsdphonate decomposes at 79-80'. The following salts result from the action of thiolsulphonates on p-diazotoluene chloride. p-Diaxotoluene benze~thiolsul~horte, C,H,Me-N,* S*SO,Ph, melts and decomposes at SO', the p-toluenethiol- sulphonate decomposes at 9 3', the a-~~hthalenethiolulphonate decomposes at 1 15', and the p-nc~phthalenethiolsulphonate melts and decomposes at 92'.o-Diaxotoluene 6enxenethiolsuZphonate melts a t 52' and decomposes atORGANIC CHEMISTRY. 173 about 55' ; the p-tolzcenethiolsulphonate melts and decomposes at 79' ; the a-naphthalenethiolsulphonate decomposes at 86*5O, and the P-naph- thdcnethiolsuZphonate melts and decompoFes a t 92.5'. The compounds obtained by the action of potassium benzene- and p-toluene-thiolsulphonates on m-diazo-xylene chloride are extremely unstable. m-Diaxo-qlene a- and p-~zaphthalenethiolsuZp~oncctes melt and decompose at 98-99' and 87-88' respectively ; both these compounds readily react with alkaline resorcinol with formation of m-xyleneazo- resorcinol. Diazo-$-curnene benxenethiolsuZphonate, C,H,Me,*N,* S-SO,Ph, melts and decomposes a t 73', the p-toluenethiolsulphonate melts and decomposes at 87', the a-naphthalenethiolsulphonate softens at 52-53') and melts and decomposes at 90-9 lo, and the ,L3-nc~phthalenethiolsulphonctte decom- poses a t 8 5 O ; the last-mentioned compound reacts with alkaline resorcinol in the cold with formation of $-cumeneazoresorcinol, and when warmed with alkaline phenol solution yields $-cumeneazophenol.a-Diazonaphthalene benxenethiolsulpho*lzate, C,oH7*N,*S*S0,Ph, melts and decomposes at 90-9 lo, the p-toluenethiolsulphonate decomposes at 97O, and the a-naphthalenethiolsulphonate decomposes a t 108' ; the P-naphthslernethiolsul~~Lonate melts and decomposes at 101-1 02') and reacts with alkaline solution of resorcinol with formation of a-naph- t haleneazoresorcinol. P-Dkcxonaphthalene benxenethiolsubhonate decomposes a t 87" ; the p-toluenethiokufphonate melts and decomposes a t 104' ; and the a-naph- thalenethiolsulphonate decomposes at 115-1 16O; the /3-naphthalenethioI- sulphonate softens a t 55', decomposes a t 95-96', and reacts with alkaline solution of phenol with formation of /3-naphthaleneazophenol.o-Chlorodiazobenxene benxenethiolsulphmate melts and decomposes at S7-$8' ; the p-toluenethiolsulphonate decomposes at 89-90' ; the a- and /3-.naphthaZenethiolsuZphonat~8 are extremely unstable, and could not be obtained in a pure, dry state. The corresponding m- and p-chloro-compounds were prepared. p-Bromodiaxobenxene benzf!nethiolszclphonate decomposes a t 99 -100' ; the p-toluenethiolsulphonate melts and decomposesat 11 1'; thea-naphthal- enethiolsulphonate melts a t 105-106', and the P-naphthalenethiol- sulphonccte melts and decomposes at 108-109° m-Bromodiaxobenxene benxenethiolsuZphonate melts at 60°, and decom- poses a t 80' ; the p-toluene- and a- and P-naphthalene-thiol8uZphonates could not be obtained in a pure, dry state. p-Nitrodic~xobenxene benxenethiolsulphonate melts and decomposes at 1 13' ; the p-toluenethiolsulphonate melts and decomposes at 11 6', and when warmed with alkaline solution of resorcinol yields p-nitrobenzene- azoresorcinol ; the a-napht~~ulenethioIsulphonate decomposes at 5 8 O , and the P-naphtha2enethiolsulphonate me1 ts and decomposes at 137O.m-Nitrodiaxobenxene benxenethiolsuZphonate melts and decomposes a t 109-1 10'; the p-toluenethiolsu&honate decomposes a t 92-93; both the a- and ~-napl~thaZenethio~uZphonates soften at 50' and decompose at 56-57".The thiolsulphonates of o-nitrodiazobenzene are very unstable ; only the a-naphthalsnethiolsulphonate could be obtained in a pure state. p-Dkoanbole benxenethioku~honate, OMe* C,H,*N, S SOzPh, me1 t s VOL. LXXX. i. !a174 ABSTRACTS OF CHEMICAL PAPERS. at 70-7'1" and decomposes at 73" ; the p-toluenethiolsulphonate melts and decomposes at 102 -103' ; the a-naphthalenethiolsulphonate melts and decomposes at 100-101', and the p-napl~thalenethiobul'l~onate decomposes at 91.5" ; the three last-mentioned substances react mith alkaline solution of resorcinol, with f vrlvation of p-anisoleazoresorcinol. 0-Diaxoanisole benxenethiolsulphonccte melts and decomposes at 73' ; the p-toEuenethiolsuZphonute melts and decomposes a t 82' ; the a-naplithal- enethiolsulphonate melts and decomposes at 95-96', and the P-naphthcd- enethiolsuZphonate decomposes at 92'.p-Diazophrtetole 6enxenethiolsulphonccte, OEt*C,H,*N,*S*SO,Ph, melts and decomposes at 81-82' ; the p-toluenethiolsuZphonate melts and decomposes a t 11 6" ; the a- and P-.naphtRale~thiolsu~honates melt and decompose at 121" and 122' respectively, and react mith alkaline resorcinol solution with formation of p phenetoleazoresorcinol. Diaxoaxo6enzerte ben~nethiolsulpl~onate, Ph* N,* C,EL,*N, S* SO,Ph, melts and decomposes at 120'; the p-toZzcenethiolsul;uhonate melts and decomposes a t 11 a", and the a- and P-nc~pht~alenethioZau~~onates melt and decompose at 117.5" and 116.5' respectively, The stability of the thiolsulphonates of the diazo-compounds is largely dependent on the nature and position of the substituting radicles in the benzene nucleus.Nega4ive atoms or groups, such as U1, Br, NO,, increase the stability if they enter the para-position to the diazo-group, whilst, on the other hand, if they occupy the meta-position, the products are less stable. The thiolsulphonates of m-nitrodiazobenzene are less easily decomposed than those of m-chloro- and m-bromo-diazobenzene, for whilst the salts of m-nitro- diaxobenzene could all be obtained in a pure, dry state, in the case of the m-chloro- and m-bromo-diazobenzene only the benzenethiolsul- phonate could be prepared.Among the ortho-compounds, the thiolsulphonates of o-nitrodiazo- benzene are less stable than those of o-chlorodiazobenzene ; the a-naphthalenethiolsulphonate of o nitrodiazobenzene was with difficulty obtained in a pure state, and the product decomposed within 12 hours ; the benzene- and p-toluene-thiolsulphonstes of o-chlorodiazo- benzene can be kept for months without change, whilst its naph- thalenethiolsulphonates rapidly decompose. The naphthalenethiolsulphonates of diazo-compounds substituted in the ortho- or meta-position by negative radicles are the most un- stable, whilst the benzenethiolsulphonate is the most stable. The entrance of a methyl group into the benzene nucleus of the diazo-compound increases the stability of the thiolsulphonate ; the naphthalenethiolsulphonates of such compounds are more stable than the p-toluene- and benzene-thiolsulphonstes ; the thiolsulphonates of qdiazotoluene are all somewhat more stable than the corresponding diazobenzene compounds, The benzene- and p-toluene-thiolsulphonates of 0-diazotoluene can only be obtained with difficulty, and rapidly decompose, whilst the a- and P-naphthalenethiolsulphonates are readily prepared in a pure state.The thiolsulphonates of diazo-+-cumene can all be obtained pure, but the benzene- and ptoluene-thiolsulphonates are the least stable. Since the thiolsulphonates of the diazo-compounds can, in manyORGANIC CHEMISTRY. 175 cases, be kept for months without change, they rather resemble the diazo-sulphones than the unstable diazo-chlorides, -nitrates, and -sulp hat es.The behaviour of many of these compounds points t o the existence of two modifications ; for example, the P-naphthalenethiolsulphonate of p-diazotoluene, the p-toluenethiolsulphonate of a-diazonaphthalene, the benzenethiolsulphonate of P-diazonaphthalene, and the p naphthalene- thiolsulphonate of p-chlorodiazobenzene are for a short time after their formation soluble in water and crystalline, and on drying pass into insoluble, amorphous modifications. Many substances are at first crystalline, and become resinous when dry; for example, the a- and P-naphthalenethiolsulphonates of P-diazonaphthalene and m-chloro- diazobenzene ; with some of the benzenethiolsulphonates of diazo-com- pounds containing a halogen in the meta- or ortho-position, this change takes place so rapidly that the formation of the crystalline modification can only be observed with difficulty.The existence of these two modifications can be explained by means of the stereoiso- meric formula suggested by Hantzsch (Abstr., 1894, i, 465). E. G. Proteids of the Thymus Gland. By CORNELIS A. PEKELHAR- INB and HUISKAMP (Proc. K. Acad. Amsterdam, 1900, 3, 383-386).- Hammarsten has shown that fibrin cannot be regarded as a calcium compound of fibrinogen. This, however, does not alter the views held by the present authors regarding the nature of the fibrin-ferment ; but recent work on the thymus proteids confirms it. Two nucleo-proteids can be separated from aqueous extracts of thymus.One of these (Lilienf eld’s nucleo-histon) is quite insoluble, the other is incompletely soluble in water containing from 0.1 to 0.5 per cent. of calcium chlor- ide; by increasing the amount of calcium salt, or by adding other neutral salts, both dissolve readily. The precipitates produced from thymus extract by the addition of the necessary amount of calcium chloride are t o be considered as calcium salts, in which the nucleo-proteid plays the part of an acid. By treatment of these compounds with potassium oxalate, the potassium compound of nucleo-proteid is formed. The potassium nucleo-proteid, like the sodium and ammonium compound, is soluble in water. The magnesium and barium compounds are insoluble in water, but dissolve in ammoniated water. All these compounds of nucleo-histon are precipitated by the addition of so much salt that the fluid contains 0.9 of sodium chloride, 1.13 of potassium chlor- ide, 0.1 of calcium chloride, and 0.2 of magnesium sulphate per cent.respectively. Elementary analyses of the calcium compounds of the two nucleo-proteids gave the following percentages : Calcium nucleo-histon : Ca, 45.3 ; H, 6.5 ; N, 17.1 ; P, 3.75 ; 8, 0.51 ; Ca, 1.34. Calcium nucleo-proteid : C, 4908 ; H, 7.3 ; N, 15.9; P, 0.95 ; S, 1.19; Ca, 1.34. Both these calcium proteids can act as fibrin-ferment, but this action is influenced by the amount of calcium salt in solution as well, being most effective in fibrin formation when t h e solution contains from 0.1 t o 0.5per cent. of calcium chloride. Beyond this, no coagu- lation occurs, Horne has previously shown t h a t the chlorides of cal- cium, barium, and strontium, when present to an extent exceeding 0.5176 ABSTRACTS OF CHEMICAL PAPERS.per cent., hinder blood coagulation. The same is true for the fibrin- ferment prepared from blood. If fresh blood is mixed with calcium chloride, so that 1 per cent. of that salt is present, it remains fluid but clots on dilution, and clots best when the percentage amount of calcium salt in solution is 0.25 per cent., that is, in the strength in which the calcium nucleo-proteids are least soluble. The Influence of Various Substances on the Crystallisation of Hamoglobin. By STANISLAUS VON STEIN ( Vi~chow’~ Archiv, 1900, 162, 477--4S7).--The experiments were performed on the blood of the guinea-pig, and the author’s Canada balsam method of preparing crystals was used.Various reagents, such as distilled water, sodium chloride, potassium chloride, &c., were added to the blood, and in all cases beyond a certain limit (the numbers are given in detail) the addition finally prevents crystallisation. An interesting point noticed is that, with a certain percentage addition of sodium and potassium salts, the crystals obtained are principally six-sided plates instead of tetrahedra. W. D. H. W. D. H. Antipeptone and Amphopeptone. By MAX SIEGFRIED (Bey., 1900, 33, 3564-3568. Compare this vol., i, 57).-The greater part of the paper is a reply t o Kutscher’s criticisms (this vol., i, 10s). Fibrin or Witte’s peptone, digested with pepsin in the presence of hydrochloric or sulphuric acid, yields two monobasic acids, C,,H,,O,N,, and C,,H3,OloN, ; these subst,ances give the biuret reaction and are strongly acidic, yielding salts on boiling with zinc oxide or barium carbonate.G. T. M. Chemical Composition of the Brain Tissue. By EMIL WORNER and HANS THIERFELDER (Zeit. physiol. Chem., 1900, 30, 542-551).- The following substances have been obtained from brain tissue by ex- traction with a mixture of benzene and alcohol or chloroform and alcohol at 45-50’. 1. Cerebron (C=69 16, H=11.54 and N = 1.76 per cent,) separates first ; i t forms perfectly white characteristic amorphous, nodular masses, does not contain phosphorus, and is insoluble in water, but dissolves in most organic solvents ; when heated in a capillary tube, i t becomes moist a t about 130’and melts a t 209-212’.When warmed with 85 per cent. alcohol at 50°, the rounded masses become trans- formed into well-defined hexagonal plates ; this transformation is ac- companied by an addition of water. It forms an amorphous bromo- derivative, and when warmed with hydrochloric acid reduces Fehling’s solution owing to the formation of galactose. 2. A compound containing 56-1-5605 per cent. of carbon and melt- ing and decomposing at about 270’. It is characterised by the pro- perty it possesses of melting when warmed with alcohol containing benzene. 3. A substance crystallising in rosettes of small needles and having all the appearance of ‘‘ protagon”; it is probable that this is a mixture. J. J. S. Myrosin. By THOMAS BOKORNY (Chem.Zed., 1900, 24,817 and 83% Compare Abstr., 1900, ii, 746).-Some CrucyercE! contain both m j rosinORGANIC CHEMISTRY. 177 and potassium myronate (or a glucoside yielding allylthiocarbimide, others contain myrosin alone with no corresponding glucoside, whilst in some cases neither is present. No instance has ar yet been observed of the occurrence of potassium myronate without myrosin ; the state- ment of Spatzier (PT. Journ., 1893, 25) that this is the case with Capella bursa pastoris (Shepherd's purse) is erroneous, Bussy (Journ. Pharm., 26, 39) prepared myrosin by extracting mustard seed with cold water, evaporating a t 40" to a syrup, and repeatedly precipitating with alcohol ; the author finds, however, that the activity of myrosin is destroyed by 50 per cent.aqueous alcohol, whilst on drying expresred radish-juice, even at 2 5 O , no active ferment can be obtained. The action of myrosin is destroyed by a 5 .per cent, formaldehyde solution, but not by a 1 per cent. solution, whilst a solution of the strength 1 : 10,000 is fatal to protoplasm. The fermenting power of myrosin is destrayed by 1 per cent. sulphuric acid, 0.1 per cent. silver nitrate solution, or 0.1 per cent. mercuric chloride solution, whilst hydroxylamine is without action. I n presence of water, the ferment loses its power at 70-75", protoplasm under the same conditions being killed a t 50-60". T. H. P. Sensitiveness of Enzymes ; their relation to- Pro toplasm. R~THOMASBOKORNY (Chem. Zeit., 1900, 24, 1113-1114; 1136-1138). -A parallel is drawn between enzymes and the protoplasm of lower organisms with respect to the action on both of poisons, temperature, or strong illumination. Some facts are tabulated that illustrate the parallelism, C.F. B. Action of Enzymes on Chromatophores and Dissolved Dyes. By C. J. KONING (Chem. Centr., 1900, ii, 1279-1280; from Pharm. Weekbl., 1900, No. 21, 23, 24).-The death of organisms resulting from the destruction of the protoplasm, but in which an enzyme still remains active, is named necrobiose. The change of colour of the dying leaves of Isatis tinctoria is due to the action of the enzyme isatase on isatan, which is an unstable indoxyl compound. I n order to preserve the natural colour of plants, such as, for instance, Campanula rotundifolia, the plant must be heated a t a higher temperature to insure necrose or the destruction of both protoplasm and enzyme.The enzymes may also act as catalytic agents and in cases of necrobiose the glucosides are often decomposed by the action of the enzymes. The action of the colouring matters which accompany chlorophyll is also described more particularly in reference to carotin and anthocyanin. E. W. W. Vegetable Oxidases. By €3. SLOWTZOFF (Zed. physiol. Chem., 1900, 31, 227--234).-Laccase loses its activity at high temperatures ; its action is proportional to the square root of its quantity. The amount of the product obtained is a function of the quantity of ferment, not of the quantity of tho oxidisable substance. The action goes on best in the presence of a slightly alkaline reaction.I n composition and reactions, laccase is a proteid; it is, however, not destroyed by acids or by peptic or pancreatic digestion. W. D. H.178 ABSTRACTS OF CHEMICAL PAPERS. Lipase, the Fat-splitting Enzyme, and the Reversibility of its Action. By J. H. KASTLE and A. 8. LOEVENHART (Amer. Chem. J., 1900, 24, 491-525).-The authors have employed ethyl butyrate to determine the activity of solutions of lipase, since it is much more rapidly hydrolysed than fats by this enzyme. The most convenient source of lipase is the pancreas of the pig? but it can also be obtained from other tissues, the lipolytic activity of which stand in the following ratio : pancreas, 1.0 ; liver, 2.93 ; kidney, 0.50 ; sub- maxillary gland, 0.36. Since the liver of the pig showed such remark- able activity, it was compared with the livers of the ox, sheep, chicken, and duck; in a series of parallel experiments, the liver of the pig hydrolysed 8.66 per cent. of the ethyl butyrate employed, that of the sheep 4.77, that of the duck 2.70, that of the ox 2.20, and that of the chicken 1.95 per cent. The extract of the stomach of the pig was found to possess lipolytic activity in neutral solution, but was rendered permanently inactive by free hydro- chloric acid in the quantity normally present in the gastric juice. Lipase also occurs in the small intestine of the pig, the mucous lining of which possesses a lipolytic activity equal t o three-fourths of that of the fresh pancreas. Lipase is much more stable than is usually supposed ; it hydrolyses ethyl butyrate most rapidly at 40°, and a t 65-70° the enzyme is de- stroyed. It is almost completely removed from its solutions by repeated filtration through paper. The behaviour of lipase towards ethyl formate, ethyl acetate, ethyl propionate, and ethyl butyrate was studied; it was found that the higher the molecular weight of the ester, the more readily is it hydrolysed by lipase, whilst the converse is true for the hydrolysis of esters by acids. The effect of several of the commoner antiseptics on lipase was examined; it is shown that such substances as silver nitrate, mercuric chloride, salicylic acid, and osmic acid are much more detrimental than the more feeble antiseptic substances, such as tolu- ene, chloroform, and thymol ; sodium fluoride, hydrofluoric acid, and acids generally are particularly harmful. The rate of hydrolysis, in the case of the extract of the pig’s liver, is directly proportional to the concentration of the enzyme, but independent of the concentration of the ester; the reaction is not complete in ordinary circumstances, but if the extract of lipase is very concentrated and the ester present in only small quantity, the hydrolysis approaches completion, The velocity of the reaction is not constant, but diminishes as the hydrolysis proceeds. The authors have found that the synthesis of ethyl butyrate from butyric acid and alcohol can be effected by means of lipase, thus proving that the hydrolysis of an ester by this enzyme is a re- versible reaction. The paper concludes with a discussion of the relation of this fact to the absorption of fat in the animal organism and the translocation of fatty reserve materials in plants. By T. MASZEWSKI (Zeit. p?hysiol. Chern., 1900, 31, 58--64).-1n the first series of experiments, equal quantities of saliva, and equal volumes of starch paste, were taken, but the amount E. G. Ptyalin Activity.ORGANIC CHEMISTRY. 119 of starch in the paste was variable, The amount of sugar formed in- creased with the increase in the amount of starch. I n the second series, the volume of starch pastewas the variable quantity. The amount of sugar formed increased with the volume of the starch solution. I n the third series, the volume of the saliva was the variable quan- tity. Here the amount of sugar formed hardly varied a t all ; there was often a slight decrease in the amount of sugar formed, never an increase. I n the light of such experiments, the faultiness of methods used for the estimation of enzymes is revealed. W. D. H. Tannase. By AUQ.FERNBACH (Compt.rend., 1900,131,1214-1215). -Aspergillus niger, a mould which plays an important part in the industrial processes of gallic fermentation, yields, when macerated with cold water, a solution which promotes the hydrolysis of tannin. This extract, when concentrated in a vacuum and treated as in Lintner's preparation of amylase, yields a grey powder containing the tannin ferment tannase. Tannin dissolved in 10 parts of water is completely hydrolysed by a solution of this enzyme; the course of the fermenta- tion is readily followed by means of the polarimeter, the rotation of the solution becoming nil when the action is completed. The same transformation is effected by the action of a tannase solution, passed through a Chamberland filter, on a- sterilised solution of tannin. G. T. M. Tannase ; a Diastase decomposing Gallotannic Acid. By HENRI POTTEVIN (Compt. rend., 1900, 131, 1215-1217. Compare preceding abstract).-Spores of Aspevgillus rziger are cultivated at 30' in Raulin's liquid, containing tannin instead of sucrose, until the mycelium begins to fructify ; the mould is then washed and macerated in the dark with chloroform and water, the extract being passed through a Chamberland filter. Sterilised solutions of tannin are com- pletely hydrolysed by the filtrate, but no action takes place if the tannase is destroyed by heating the solution to boiling. Variable quantities of dextrose are produced, together with gallic acid, during fermentation. Aspergillus niger, cultivated in the ordinary Raulin's liquid, does not yield tannase unless the sugar of the solution is re- placed by gallic acid or tannin. Phenyl and methyl salicylates are hydrolysed by tannase, and since they have a constitution similar to that proposed by Schiff for digallic acid, these results go to confirm the suggested formula. Tannase also hydrolyses tannates such as gelatin tannate; the ferment is in all probability widely distributed in nature and has been found in sumach leaves; this accounts for the fact that gallic acid always accompanies tannin. G. T. M. Zymase from Sterilised Yeast. By EDUARD BUCHNER (Ber., 1900, 33,. 3307-3310. Compare Abstr., 1897, ii, 380).-Washed and pressed bottom yeast was dried for 3 or 4 hours a t temperatures from 35' to looo under 30 mm. pressure, and was then sterilised by heating in hydrogen180 ABSTHACTS OF CHEMICAI, PAPFRS. for several hours at temperatures varying from 98’ to 110’. The material thus obtained, which was incapable of development in beer wort, was mixed with glycerol and water, and ground with sand and kieselguhr. The juice expressed from this mass possessed active fer- mentative powers, 20 C.C. of i t when mixed with 8 grams of cane sugar yielding, on the average, about 0-5 gram of carbon dioxide. Similar results were obtained with yeast dried in the air and then heated a t 97’ in a current of carbon dioxide, The ’author regards this result as decisive against the view that the fermentative powers of expressed yeast juice are due to the presence of fragments of living protoplasm in the juice, since, in his experimenfs, no living protoplasm could be present. It was observed that thoroughly dried yeast was extremely difficult to sterilise, and sometimes withstood heating at 100’ for 8 hours. A. H. Simple Experiment to illustrate the Aotion, of Zymase. Ry ROBERT ALBERT (Bev., 1900, 33, 3775-3778).-Fresh brewery yeast is freed from water by pressing, and rubbed through a sieve into a mixture of absolute alcohol and ether (3 : 1). After 4-5 minutes, the liquid is poured off, the residue drained, washed with ether, and spread out in a thin layer on fiIter-paper to dry. A yellowish-white powder is obtained, which contains no live yeast cells, but ferments sugar solution vigorously. The zymase is contained within the dead cells, and cannot be ex- tracted with water directly. To obtain a fairly strong solution of it, the powder is rubbed with very fine quartz sand in a large mortar, water then added, and the mixture rubbed for 10 minutes more. It is then filtered with the aid of a pump through hardened filter-paper, some of the dilute zymase solution precipitated with alcohol and ether, the powder so obbained dissolved in a little water, a little kieselguhr added, and filtered. The clear filtrate so obtained ferments cane sugar almost instantaneously, even a t the ordinary temperature. C. F. B. Invertase from Yeast. By ERNST SALKOWSKI (Zeit. physiol. Chew%., 1900, 31, 305-328. Compare Kolle, Abst,r., 1900, i, 572).-In- vertaso obtained by Barth’s method (Ber., 1878, 11, 474) always con- tains an appreciable amount of yeast-gum (Abstr., 1894, i, 222, 316 ; 1895, i, 166), which can be isolated in the form of its copper sodium derivative. Four different specimens examined contained from 17.1 7 to 65.3 per cent. of this gum. The gum, on hydrolysis, yieldsd-man- nose (Hessenland), and this is probably the origin of the mannose ob- tained by Osborne and by Kolle from so-called invertase. Contact with alcohol appears to rapidly destroy the hydrolytic power of diastase. The isolation of “sucrase,” the actual enzyme of cane sugar inversion from yeast in a pure form by any of the ordinary methods, appears to the author to be hopeless, on account of the large number of other enzymes present, namely, maltase, zymase, and the three enzymes previously described by him (Zeit. physiol. Chrn., 1889, 13, 506). J. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9018000109

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 115 The influence of Sterilised Air on Animals. By J. 3. KIJANITZIN ( Virchow’8 Archiv, 1900, 162, 5 15--533).-The experiments were made on rabbits, and the apparatus used for supplying them with steri- lised air is described and figured. Under these circumstances, the metabolic functions are reduced, and the animals waste. This is con- sidered to support the author’s previous contention, that the micro- organisms of the atmosphere play a useful part in metabolism. Their special function is considered to be to provide the blood with oxidising ferments, as in their absence the oxidation changes in the organism are diminished, and this leads to an accumulation of intermediate waste products of metabolism (leucomaines). By J.J. R. MACLEOD (Proc. Physiol. Xoc., 1900, vii-viii).-The creatinine excreted .in the urine may be divided into an endogenous portion arising during metabolism, and an exogenous portion from the creatine and creatinine of the food. I n order t o investigate the first of these, a diet must be taken free from creatine and creatinine. The experiments indicate that urea does not arise from creatinine. In cases of muscular atrophy, no diminution was noted. In cases of splenic enlargement, the creatinine excreted was only hali the normal amount. It is probable that the spleen exercises some control over creatinine metabolism. The number of leucocytes in the blood does not influence the amount excreted. Further experiments are in pro- gress. w. D. H. By ADOLF JOLLES (PJEiiger’s Archiv, 1900, 82, 553--55S).--On the administration of hippuric acid, all the nitrogen appears as urea.It is regarded as probable that in the oxidation processes of proteids in the body, of which the final pro- duct is urea, glycine and other amino-acids are in part formed, which are ultimately oxidised to form urea. By OTTO VON PUETH (Zed. physiol. Chem., 1900, 31, 353-380).--8 historical review of this subject is followed by a description of the method adopted of collecting large quantities of urine from the octopus. A sediment found in some cases contains uric acid. The fluid contains ammonia, but no urea ; a number of other products of nitrogenous katabolism were also sought for, but in the main with negative results. The most striking fact is the presence of proteid ; albuminuria appears to be in these animals a physiological process. W.D. H. Estimation of Rennet-ferment in Gastric Juice. By L ~ O N MEUNIER (J. Pharm., 1900, [vi], 12, 457-465).-The amount of rennet-ferment in gastric juice is estimated by the time required for a known volume of the gastric juice to produce coagulation in a milk which is kept a t 40-41°, and to which a small quantity of calcium chloride has been added. The strength of the gastric juice in rennet- W.D. H. Metabolism of Creatinine. Metabolism of Hippuric Acid. W. D. H. Metabolism in Cephalopods. 9-2116 ABSTRACTS OF CHEMICAL PAPERS. ferment is defined as the amount of milk coagulated by unit volume of the gastric juice in 10 minutes and under the conditions of experiment described in the paper.A standard milk was used for all the experiments and was prepared as follows. Several samples of fresh milk were mixed together, boiled, and filtered from the precipitated albumin. The filtrate was then boiled and when boiling was poured into small flasks which were then corked, and heated at 115O for 10 minutes. The following conclusions were arrived at : (1) Rennet- ferment keeps very well in the gastric juice. (2) The secretion of rennet-ferment in adults reaches its maximum one hour after the partaking of a meal consisting of bread and tea, and remains at a maximum until the end of the digestive period. (3) I n normal cases, the ‘‘ strength in rennet-ferment ” varies between 500 and 2000. (4) In pathological cases, a diminution in the amount of rennet-ferment gives valuable information as to the condition of the glandular structure of the membrane of the stomach.Alkalinity of the Blood. By WALDVOGEL (Chem. Ceratr., 1900, ii, 1156; from Deutsch. med. Zeit., 28, 6S5-686).-A number of estimations of the alkalinity of the blood were performed by a modification of the Salkowski-Schlgsing method. The alkalinity is lessened in typhoid fever, but there is no parallelism between rise of temperature and fall of alkalinity, Glycolytic Decomposition of Sugars. By P. PORTJER (Compt rend., 1900, 131, 1217--121S).-When blood is collected and preserved under aseptic conditions, the amount of dextrose which it contains rapidly diminishes, the rate of disappearance of this sugar varying with the temperature.It is found that small quantities (0.2 per cent.) of galactose, Izevulose, and maltose are similarly decomposed when added to the blood of the dog or rabbit, whilst sucrose, lactose, and xylose remain unaltered. H. R. LE S. W. D. H. G. T. M. Effect of Intravenous Injection of Milk on the Coagul- ability of the Blood. By L. CAMUS (Compt. rend., 1900, 131, 1309--1312).-1f cow’s milk is freed from cream by the centrifuge and injected intravenously into dogs, the blood of the latter animals is rendered incoagulable. The substance to which this is due has not been determined, but it is not a lysin, as boiling does not affect the action. Dog’s milk injected into dogs has the same effect. Dogs differ somewhat in their reaction to the injection, and this probably accounts for Delezenne’s statement that dogs are refractory in thls particular to dogs’ milk.Delezenne’s suggestion that this refractive- ness is most marked in dogs during the lactation period has not yet been experimentally tested. By R. QUINTON (Compt. rend., 1900, 131, 905-908, 952--955).-The experiments recorded do little more than confirm what Fredericq found in 1882 (Bull. Acad. Roy. Belg , 4,. 209), namely, that in many marine forms the salts in the haemolymph are the same as those in the sea. The outer membrane OP these animals simply plays the part of a membrane as in physical osmosis. W. D. H. Osmosis in Marine Invertebrates. W. D. H.PHYSIOLOGICAL CHEMISTRY. 117 Muscular Serum. By CHARLES RICHET (Compt. Tend., 1900,131, 1314--1316).-The term muscular serum is applied to the richfy albuminous fluid which can be expressed from flesh that has under- gone rigor.It has the following percentage composition (from beef) : Dry residue ............................................ 6.71 Ash ......................................................... 0.89 Total nitrogen .......................................... 1.05 Nitrogen from proteicis .............................. 0.8 Nitrogen from substances soluble in hot alcohol.. 0.25 Of the mineral matters, potassium phosphate is the most abundant. The serum contains small quantities of sugar, hemoglobin, and myohae- matin (9). Injected under the skin or into a vein, 5 C.C. per kilo. of body weight produces a fall of blood pressure, stupor, and death in from 24-48 hours; 3 C.C.produce the same effects more slowly. The blood is coagulable. Abdominal congestion is the most marked ap- pearance post mortem. Boiling destroys the toxic properties. Given by t h e mouth, the serum is harmless, and is even stated to cure inociilated tuberculosis in dogs. By OTTO VON FURTH (Zeit. physiol. Chem., 1900, 31, 338--352).-1t is possible t o obtain from the muscles of invertebrate animals a muscle plasma which coagulates spontaneously. Most of the experiments recorded were performed with the muscles of cephalopods (octopus and sepia), but holothurian muscle gave also corresponding results. The proteids separated out differ in various points (coagulation temperature, precipitability by salts, &c.) from the myogen and myosin previously described by the author in mammalian muscle, The paper concludes with a discussion of the dependence of heat rigor on the heat coagulation temperature of the proteids in muscle.No reference, however, is made t o the work of Brodie, who was the first to demonstrate the connection. Thiocyanates in Nasal and Conjunctival Secretion. By 0. MUCK (Chem. Centr., 1900, ii, 1157-1158 ; from Munch. med. Woch., 4’7, 1168-1 169).-The presence of potassium thiocyanate can be showqin the nasal secretion as well as in the saliva. This, however, originates from the secretion of the conjunctiva. I n ozaena, the amount hore, and in the saliva, sinks. W, D. H. Solubility of Pigments in Fats and Soaps. By JOSEPH NERKINQ (PJEuger’s Avchiv, 1900, 82, 538-540).-The general con- clusion arrived at is t h a t the pigments recently used in experiments in fat absorption which are soluble in fats, are also soluble in neutral solutions of soaps. W.D. H. By ERNST P. PICE and KARL SPIHO (Zeit. physiol. Chem., 1900, 31, 235--281).-A review of past work shows how numerous and diverse are the various organic substances a n d extracts that, like ‘ peptone,’ produce a non-coagulable condition of the blood. Experiments with fibrin show that the products of ppptic digestion, or of digestion w h acid alone, have this power, but W. D. H. Proteids of Invertebrate Muscle. W. D. H. Anti-coagulating Agents.118 ABSTRACTS OF CHEMICAL PAPERS. that the products obtained by tryptic digestion, by digestion with alkali alone, or by autolysis, have no such power. From pure proteids, however (edestin, casein), no anti-coagulating agent is obtained by any method.The products formed from fibrin by acid or gastric digestion lose this action when they are purified. Thus pure proto- albumose and heteroalbumose are inert, but a mixture of the two does not lose its power when they are purified by the ammonium sulphate method, but it does so after treatment with alcohol. Treatment of the fibrin beforehand with alcohol does not hinder it from yielding the anti-coagulating agent on subsequent treatment with acid or gastric juice. This agent is, however, destroyed by alcohol in a weakly alkaline but not in an acid solution. Acid-albumin prepared from fibrin is inactive. Not only does ‘peptone’ lose its anti- coagulating power by such treatment, but its other actions (on blood- alkalinity, on lymph formation, on blood pressure, and in the produc- tion of narcosis) disappear also.The anti-coagulating substance, whatever it is, must be present in small quantity, and be very active, It is not characteristic of digestion products, but is contained in extracts of various tissues, particularly of the digestive organs, and these, especially if fresh, contain little or often no peptone. The name ‘peptozyme’ is suggested for this active substance, and the material in fibrin, liver, &c., from which it is derived, is termed ‘ peptozymogen.’ Many authors distinguish the action of so-called peptone from such a substance as leech extract by saying that the latter contains a n anti-thrombin, whilst the action of peptone is to first produce an anti-thrombin within the body by acting on some organ like the liver.This theory is discussed, and it is shown that the peptozyme has a direct anti-thrombic action on blood in uitro. It is also shown that peptozyme-immunity is independent of its anti- coagulating activity. W. D. H. Immediate Action of Intravenous Injection of Blood-serum. By THOMAS GREGOR BRODIE (J. Physiol., 1900, 26, 48--71).--The in- travenous injection of blood-serum from any source into a cat causes arr est of respiration, inhibition of the heart, and vascular dilatation. The effect is due to excitation of the pulmonary nerves, and the effect on the heart is reflex, It is abolished by section of the vagi, or of i t s pulmonary branches. Some degree of immunity is produced by re- peated injections.The active Substance is of proteid nature, of the albumin class, and is coagulated at 86O. It is produced only when the blood clots, but the interaction of the blood corpuscles is also necessary for its formation. 1 Injection of Tetanus Toxin and Antitoxin into the Sub- arachnoid Space. By FRANCIS RANSOM (Zed. physiol. Chem., 1900, 31, 282-304).-Injection of ‘tetanus toxin or antitoxin into the sub- arachnoid space is quickly followed by the passage of these fiubstances almost entirely into the blood-stream. An increase in the normal power of the central nervous system t o neutralise the poison after sub- arachnoid injection of antitoxin does not occur in uitro. After in- jection of the toxin, the nerve substance is more poisonous, probably Serum obtained from plasma is inactive. W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 119 because it contains more poison in its blood. After sub-arachnoid in- jection of the poison, a small part is found in the cerebro-spinal fluid, part in the blood and lymph, and part in the central nervous system. After intravenous or subcutaneous injection, little or none finds its way into the cerebro-spinal fluid. If the blood has high anti- toxic value, the cerebro-spinal fluid is also anti-toxic, but in a smallcr degree. Much interest attaches to the fact that toxin and antitoxin pass from the blood to the lymph, but in the case of the cerebro-spinal fluid, tbe passage is in the contrary direction. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9018005115

出版商:RSC    

年代:1901

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 119 Chemistry of Vegetable Physiology and Agriculture. Biology of the Peptonising Bacteria of Milk. By OTTO KALISCHER (Arch. Bygiene, 1900, 37, 30--53).-The bacteria in milk, which are aerobic or facultative anaerobic, are not destroyed by heating at 90-95’, and form spores not easily destroyed by heat, are termed L L peptonising ” bacteria. I n milk, they slowly form am- monia and cause a diminution of the lactose, decompose dextrose, but not fat, and convert casein into peptone. The enzyme produced by them is very similar to trypsin, except that in the fermentation of casein by it, aromatic hydroxy-acids are formed in addition to peptone, leucine, and tyrosine; it will invert cane sugar, but not lactose. R. 33. P. Lactic Acid Fermentation and its Practical Use.By STANISLAUS EPSTEIN (Arch. Bygiene, 1900, 37, 329-359).-The ripen- ing of cheese is due to the organisms which induce the lactic acid for- mentation. Each kind of cbeese is produced by the agency of bpecial organisms, which act chemically by means of an enzyme, and cause the peculiar odour of the cheese. If pure cultures are to be employed in the preparation of cheese, it will therefore be necessary to choose these, not only with regard to the character of the bacteria inducing the acid fermentation in the butter, but also with regard to the peculiar kind of cheese required. Formation of Hydrogen Sulphide in Sewers, and the New Genus Aerobacter. By MARTINUS W. BEYERINCK (Arch. Ngerkand Sci. Exact. Nat., 1900, [ii], 4,1--18).-TThe author proposes to include in a new genus Aerobacter such bacteria as ferment sugar with the forma- tion of hydrogen, carbon dioxide, and laevorotatory lactic acid. These are the agents which cause the formation of hydrogen sulphide from sulphur, sulphites, thiosulphates, and proteids.The formation of this gas, which is also a characteristic of the genus, is easily de- monstrated by the introduction of a little white lead into the cul- ture media (gelatin or agar), The bacteria reduce nitrates to nitrites, b u t not to ammonia; the addition of a small quantity of a nitrate to a culture medium containing sugar prevents fermentation, but does R. H. P.120 ABSTRACTS OF CHEMICAL PAPERS. not stop the development of the organisms, thus, in the preparation of Dutch cheese (" rijzers "), a small percentage (0.05) of saltpetre is added to hinder the formation oE gas.The fermentation of in- dican, due entirely to organisms belonging to this genus (and in- duced by all the species composing it, with the exception of A. coli var. commune = Bacterium colis var. commune), results in the forma- tion of dextrose and indoxyl, which in the presence of air is con- vorted into indigo, the fermentation being due to the living organ- isms and not to an enzyme. The bacteria of this genus cannot transform sulphates into hydrogen 'sulphide, this reduction being brought about by Spirillum desu&rricans. The nauseous odours of putrefaction are not due t o sulphides. R. H. P. Influence of Temperature on the Energy of the Decompo- sition of Proteid in Germination. By DMITRI N.PRIANIscmrKoFF (Ann. Agron., 1900, 26, 627-6283 from Ber. deut. bot. Ges., 1900, 18, 285. Compare Abstr., 1900, ii, 233).-The temperature most favourable to the growth of the embryo is 2S0, whilst the energy of respiration continues t o increase as the temperature is raised. The energy of the decomposition of proteid, and the formation of asparagine increases up to 35-37' ; this decomposition does not depend on the growth of the embryo. N. H. J. M. Chemical Changes during the Evolution of Buds. By GUSTAVE AWDRB (Compt. rend., 1900, 131, 1222--1225).-Buds of Bsculzcs hippocastanurn were annlysed a t seven different periods from February 26, when they showed no development, to April 28. The total dry matter, nitrogen, amides, carbohydrates, cellulose, ash, potass- ium, calcium, phosphoric acid, and silica in 100 buds were determined at each date; also the percentage of water.As in the germination of seeds, there was n considerahle absorption of water. There was first a loss of dry matter, but by April 18 there was again a slight increase; subsequently there was a very rapid and great increase both in.dry matter and total ash. The calcium remained almost the same up t o April 18, whilst the potassium and phosphoric acid greatly increased ; afterwards there was a great increase in all the ash constituents determined. The increase in the amount of potassium coincides with the appearance of the first leaves. The amounts of phosphoric acid and total nitrogen were both tripled a t the time when the buds recovered their original weight (April 18).The arnide nitrogen increased from the beginning ; the soluble nitro- gen is presumably transformed into insoluble proteid nitrogen. Up to April 18, the soluble carbohydrates showed a remarkable decrease (9.12 to 2.85) ; by April 23 and 28, the amounts were 6.01 and 17.92 respectively. The above changes indicate that the evolution of buds may be com- pared with germination. N. H. J. M. Development of Etiolated Plants after Exposure to Light. By H . RICOME (Compt. rend., 1900, 131, 125 1-1 253).--The plants were kept in darkness for different periods and afterwards exposed t oVEGETABLE PHYSIOLOGY AND AGRICULTURE. 121 normal conditions, Similar plants were kept the whole time under normal conditions.I n the case of etiolated plants from small seeds, the growth of the stems was checked the moment the plants were exposed to light, the growth being then slower than that of normal plants; with plants from large seeds, the growth of the stems after exposure to light did not appreciably differ from t h a t of normal plants. The length of stem of the full grown plant is abnormally great when the etiolation ceased before the exhaustion of the reserve substances of the seed, but ab- normally short when the reserve substances have been almost all consumed at the time when the plants had access to light. The leaf development of etiolated plants also becomes abnormally large after exposure to light when there is plenty of reserve substance. The weight of the dry matter (stems and leaves) is less in plants which were etiolated and afterwards exposed to light than in normal plants.As soon as the plants are exposed t o light there is a great loss of water as well as gain in dry matter. Etiolated plants which afterwards have access to light weigh less, but contain more dry matter than plants kept in darkness during the whole period. The above results show the importance OF seed reserves which, to a great extent, enable the plant to 2evelop without chlorophyllic action. N. H. J. M. Hydrolysis and Utilisation of Raffinose by Penicillium Glaucum. By HENRI GILLOT (Bull. Acad. Roy. Belg., 1900, 99 -127).-In a solution containing a mineral acid, PeniciZZium glaucum secretes an enzyme capable of inverting raffinose ; neutralisa- tion does not prevent this secretion, but diminishes the rapidity of germination of the spores.The action of the enzyme is accompanied by an increased acidity of the solution, due to the production of oxalic and succinic acids. Using the enzyme either iri the form of an aqueous infusion of the fungus, or of the precipitate obtained from this infusion by adding alcohol, the intensity of the inversion gradually diminishes, if care be taken to exclude foreign organisms. I n a solution containing 2 per cent. of raffinose, but no other nutritive materials, inversion still occurs, but the germination of the spores is slow, and the morphology of the mould is modified. I n alkaline solution, germination is retarded, tho action of soda beirg less than that of either potash or ammonia ; subsequently, how- ever, when the mould has developed, the secretion of enzyme is but little affected, the solution gradually becoming acid.By MARTIN HAHN (Ber., 1901, 33 3555--3560).-1n the hope of throwing more light on the question of the cause of the heat developed by certain plants, the bulbs of Arum maculatum were divided so as to separate the upper or sterile from the lower or flower-producing parts, and these were then subjected to the process applied by Buchner to yeast-cells in isolating the cell-free juice. The greenish liquids thus obtained, which were free from organised forms, were neutral a t first, but finally developed a reddish tinge, and became acid in reaction. Both liquids decolorised a considerable W. A. D. Chemical Processes in the Juice of Arum Maculatum.122 ABSTRACTS OF CHEMICAL PAPERS.quantity of PI10 iodine solution, reduced Fehling's solution rapidly, and when heated deposited albumin, With alkalis, the liquids became bluish-green and with acids red. I n investigating the properties of the juices, 20 C.C. were brought into a flask fitted with a suiphuric acid valve, mixed with 0.5 C.C. of toluene, and the temperatures maintained at 25' ; after the completion of the digestion the whole was rendered neutral, boiled, diluted to 100 c.c., filtered, and aliquot portions of the clear liquid were employed for the estimation of the contained nitrogen and sugars j the sterility of the liquids was assured. It was found that the amount of dextrose in the liquids slowly increased a t low temperatures, indicating that a dinstatic ferment is present, a fact which was confirmed by observations of the sucrose inverting power of the residues obtained by evaporating the juice in a vacuum.The presence of a proteolytic ferment was inferred, as after several days digestion a t 2 5 O , the liquids no longer deposited albumin when boiled, and were free from dextrose. The manner in which the dextrose is degraded has not been ascer- tained; small quantities of carbon dioxide appear to be evolved, but no alcohol could be detected. Attempts have been made to prepare an active, pulverulent extract by evaporation of the liquids, but these have hitherto met with only partial success. A. L. Toxicity of Sodium, Potassium, and Ammonium Com- pounds as regards Higher Plants. By HENRI COUPIN (Ann.Agron., 1900, 26, 575-577; from Rev. gzn. bot., 12, 177. Compare Ann. Agron., 26, 350, and Demoussy, Abstr., 1900, ii, 16l).-Young wheat plants were subjected to the action of 21 sodium salts, 22 potass- ium salts, and 13 ammonium salts. The results are given in a table showing the minimum amounts of the various salts per cent. which kill the plants. Comparing the haloid salts, it is shown that the toxicity increases with the mol. weight of the halogen. As a rule, potassium salts are less toxic for plants than the corresponding sodium salts, Oxalates, especially potassium hydrogen oxalate, are very toxic ; the toxic equivalent of potassium hydrogen oxalate is 0.0033, that of potassium oxalate 0.25 per cent. With one or two exceptions, the toxicities of the analogous com- pounds of sodium, potassium, and ammonium are similar. The toxic equivalents of the three chlorides (in the order as given) are : 1.8, 1.9, and 1.6 ; nitrates, 1.7, 3.0, and 3.9 ; carbonates, 1.1, 1.7, and 0.3 ; .phosphates, 1-5, 6.0, and 0.4 ; sulphates, 0.8, 2.3, and 2.5.The toxicity of sodium hydrogen carbonate is 0.6. N. H. J. M. By HUGO BORN- TRAEQER (Chem. Centr., 1900, ii, 1202; from Oesterr. Chm. Zeit., 3, 516-51'7).-Humic acid in presence of water is capable of absorb- ing a considerable quantity of ammonia, which it retains with some obstinacy. The ammonia is removed, however, by the action of the acid of sprouting seeds, humic acid being regenerated. Under ceitain conditious, humic acid also attacks the plant fibres, forming Humic Acid and its Function in Nature.VEGETABLE PHPSIOLOQY AND AGRICULTURE.123 sugar and vegetable gum. By treating 100 grams of fibre with 20 of humic acid (Cassel brown) and 20 of water under pressure, 8 grams of sugar and 20 of gum were obtained, but the sugar was not formed even by prolonged boiling under the ordinary pressure. E. W. W. Cultivation of Barley. By A d PAGNOUL (Ann. Agron., 1900,26, 561-567).-Experiments were made in pots, to show the effect of nitrogenous manure and phosphate on the growth of barley in different soils, both with small and large amounts of water, to correspond with very dry and very wet seasons. It was found that the development of the plants was greatest under the influ- ence of much water, but that the percentage of dry matter was lower in these plants (9.6) than in those which had less water (12.6).Com- paring the different soils, the clay soil gave the worst results. Nitric nitrogen was more abundant in the wet than in the drier soils; the sandy soil contained the most nitrate, and the clay soil much the least. When the plants were cut at the end of July, the yields were found to vary in the same order as in the plants taken up in May, The yields of straw and grain, in the case of the plants which received much water, were about double those of the plants with little water. With nitrogenous manure, the yield of straw was above, the yield of grain below, the average ; with superphosphate, the yield of straw was below, and the yield of grain above the average, Superphosphate gave much heavier grain than nitrogenous manure.All the plants were attacked by rust, the effect of which was to greatly diminish the weight of the seed, whilst the percentage of nitrogen and phosphoric acid was very greatly increased. The seeds were sown on March 5. On May 7 a number of plants were removed from each pot. N. H. J. M. Influence of the [Mode of] Distribution of Manures on their Action. By J. M. POMOR~KI (Cheni. Centr., 1900, ii, 1249 ; from Zed. landw. Versuchs. Wesens Oesterr., 3, 649-683). [Cornpal e Berthault, Abstr., 1930, ii, 7531.-The results of field experiments with oats showed that the localisation of sodium nitrate in furrows increased the amount of nitrogen taken up, and that the utilisation of nitrate by oats depends on the distance of the manure from the plants. In pot experiments, it was found that nitrate had the same effect, whether mixed with the first, second, or third 10 centimetres of soil, but that better results were obtained when the manure was mixed with the whole of the soil. Further experiments were made, the results of which showed that the mode of distribution of manures affects assimilation and growth, and that oats and barley behave differently. The subject is thought to be of practical importance, as manures may be economised by being applied in the manner best adapted for the various crops. N. H. J. & I .

ISSN:0368-1769    

DOI:10.1039/CA9018005119

出版商:RSC    

年代:1901

数据来源: RSC