摘要:

86 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Libollite. By JACINTO PEDRO GOMES (Comm. Direc. Trabalhos Geol. Portugal, 1898,3, 244-250, 290--291).-Libollite is the name given to an asphalt resembling albertite which is found near Libollo, province of Angola, in Portuguese West Africa. Analysis gave : C . H. 0. N. Ash. Sp. gr. 74 74 7-83 8.80 1.71 6.92 1 *1 L. J. S. By ROSSITEB w. RAYMOND (Trans. Amer. Inst. Mining Eng., 1899, 28, 235-239). -The auriferous alluvial deposits in the Srtramacca district of Dutch Guiana contain cubes of limonite pseudomorphous after pyrites ; these are sometimes hollow and are partly filled with a reddish powder. Analyses by A. R. Ledoux of the outer light red crust gave I, and of the interior darker red material gave II. Limonite Pseudomorphs from Dutch Guiana.Fe,03 A120,. SiO,. H,O. Total . I. 42.90 17.70 30.44 5-90 96.9 4 IT. 87.94 0-90 2-34 7.50 98.68 A small amount of gold is present in 11, but not in I. Chromite from Newfoundland. By GEORGE W. MAYNARD (Tmns. Amer. Inst. Mining Eng., 1898, 27, 283 -288).-Deposits of chromite are found in serpentine a t Port-au-Port Bay, on the west coast of Newfoundland. Analysis by E. Waller of a selected sample of the ore gave : L. J. S. Cr,O,. FeO. MgO. AI20,. SiO,. Total. 49.23 17.21 18.66 7.50 6.51 99.1 1 Also traces of calcium, vanadium, copper and manganese. L. J. S. Occurrence of Nickel in Silesia,. By 0. H. ASCXERMANN (Zeit. Kryst. Min., 1899,32, 106 ; from Inaug. Diss. Breslau, 1897, 43 pp.). --Nickel occurs at Frankenstein, Silesia, as silicates in a red decom- position product of serpentine (Abstr., 1895, ii, 514).The unaltered serpentine contains, according to two determinations, 0.0866 and 0.148 per cent. of nickel. L. J. S. Leverrierite. By PIERRE TERMIER (Bull. Xoc. franq. Min., 1899, 22,27-31).-Previous analyses of this mineral are unsatisfactory, owing to the presence of admixed quartz and cla7. A new analysis made on more pure material from Rochebelle, Gard, gave the following results. Sp. gr. 2.598.MINERALOGICAL CHEMISTRY. 87 Loss on SiO,. A1,0,. Fe,Os. MgO. CaO. K,O, ignition. Total. 49.90 37.02 3.65 0.30 trace 1.13 8-65 100.65 The material analysed was dried at 110". The loss on ignition is mainly water with a very little carbonaceous matter. The colourless crystals become white a t 500". This analysis agrees approximately with the formula (H,K),O,(A1,Fe),0,,2SiO2. The mineral therefore differs from kavlinite ( 2H2~,A1,0,,2Si0,), and resembles muscovite, but has water largely replacing potash, Optical determinations are also given.Minerals of Japan. L. J. S. By KOTORA JIMB~ (J. Xci. CoZZ. Imp. Univ. Toky6, 1899, 11, 213-28l>.-A description, dealing mainly with occurrences, is given of 128 mineral species found in Japan. Some of the information has been previously published in Japanese journals. Analyses are given of the following. Topaz. Good crystals of topaz are found at Takayama, &c., in province Mino, and a t Tanokamiyama in province Omi. The crystals from omi are usually brownish and occur with flesh-red felspar; analyses by Takayama gave the results under I and 11.OZivine in brown crystals occurs with crystals of augite in a basalt at Nishinotake in Hizen; analysis 111 by Konda. SiO,. A1,0, MgO. PeO. CaO. F. Total. - 18.36 106.38 11. 31-95 56.59 - - - 18.01 106.55 111. 38.74 - 43.53 16.60 trace - 98.87 Axinite occurs in the copper mine a t Okuradani, Obira, province Bungo, associated with hedenbergite, garnet, copper pyrites, mispickel, pyrrhotite, fluor, &c. The crystals are dark brown to dark violet, and are somewhat prismatic in habit instead of the more usual sharp- edged or thin-tabular habit characteristic of the mineral. Analysis IV, by Kajiura. SiO,. A1,03. Fe20,. Mu,O,. B,O,. CaO. MgO. Na,O. K,O. H,O. Total. 1V. 41-87 19.25 11 79 5'62 1.59 17'75 trace 1.79 trace 0-87 100.53 The pegmatite at Tanokarniyana in Omi contains several varieties of mica.Analysis V, by Kodera, is of dark green plates of biotite ( 8 ) which is nearly optically uniaxial. Zinnwaldite (?), from the same place, is reddish-brown to nearly colourless; the plane of the optic axes is parallel to the plane of symmetry, and the axial angle is large. I. 31.30 56.72 - - Biotite '1 Analysis VI by Kodera. A dirty, dark brown mica from Kai gave VII, by Hida. SiOa. TiO2. Al2O3. Fe&. FeO. MnO. CaO. MgO. K20. NazO. H2O. F. Total. V. 85-87 0.35 22.69 20.90 - 5-65 - 0.32 6.70 2.52 1.00 3.19 99-19 VI. 46.13 2.77 17.03 4-64 - 6-27 - 0.43 10.09 4'12 2'31 6.89 100.68 7'11. 38.45 - 15.53 22'73 1.71 - 2-22 7-85 2'25 2'16 7-20 - 100.10 Hedenbergite occurs as large crystals in biotite-hornfels associated with axinite, &c.(ante) a t Okuradani. Analysis VIII : Si02. FeO. MnO. CaO. MgO. K20. Na,O. H,O. Total. V l I I . 47'13 24'46 0'73 23-23 2.40 0.13 0.98 1'48 100'5488 ABS’l’ftAC“i’f3 OF CHEMICAL PAPERS. Orthoclase and Microcline. Several types of potash felspars occur in druses in pegmatite at Tmokamiyama, Omi. Analysis IX of white, translucent crystals, usually twinned, and up to 20 cm. long. Analysis X, reddish-white to flesh-red crystals occurring with topaz; XI and XII, of glassy crystal8 mostly twinned (Analysis IX-XI1 by Kodera). SO,. Al,O,. Fe,O,. CaO. XgO. K20. Na,O. Total. IX. 64-78 17.86 1.46 0.14 0.11 18-87 2.25 99.47 X. 64.62 21.00 0.33 0 2 0 0.09 12-22 2.41 100.87 XI. 63.77 19.52 1.39 - 0.08 13-70 1.84 100.30 XII.64.98 22.17 0.33 - 0.86 10.59 0.60 99.52 SzAene. IIeuZmdite. Small yellow crystals in diorite a t Kamioka in Hida gave White, translucent crystals showing optical anomalies, analysis XIII, by Yoshida. from Ohara, gave analysis XIV, by Shinowara. SiO,. Ti02. AI,O,. Fe20,. CaO. MgO. H,O. Total. X1I.I. 30.81 40.21 0.61 0.51 26.42 1.21 - 99.77 XLV. 58.4 - 14.4 - 12.2 - 14.9 99-9 L. J. S. New Minerals from Franklin, New Jersey. By SAMUEL I;. PENFIELD and CHARLES H. WARREN (Amer. J. Sci., 1899, [iv], 8, 339-353).-The new minerals were found in the zinc mines at Franklin, in association with native copper and lead (Abstr., 1898, ii, SO,.), clinohedrite (Abstr., 1898, ii, 607), rceblingite (Abstr., 1897, ii, 563), axinite, willemite, datolite, garnet, phlogopite, &c.They are probably of metamorphic (pnenmatolitic) origin. This occurs as brownish-red, cellular masses of minute, lath-shaped crystals, which are monoclinic, and have nearly the same habit and angles as epidote. Single crystals are yellowish-brown with a vitreous lustre, and are pleochroic. Sp. gr. 4.030. Analysis by Warren gave : Hancockite. SiO,. Al,O,. Fe,O,. Mn,O,. PbO. MnO. MgO. CaO. 30.99 17.89 12-83 1-38 18-53 3.12 0.52 11.50 SiO. H,O. Total. 3.89 1-62 100.77 R2(R”* OH)R”‘2(Si0,), i but the mineral differs from epidote in containing lead and strontium isomorphous with calcium. Like epidote, the mineral is decomposed by hydrochloric acid only after ignition. Glaucoch~~oite. This occurs em bedded in nasonite as columnar, orthorhombic crystals of a bluish-green colour.Twins are sometimes present with individuals intercrossing at angles of about 60’. The parameters are a.pproximately a : b : c = 0.440 : 1 : 0.566 ; these ratios, as well as the optical characters, indicate that the mineral belongs to the olivine group. Analysis I, by Warren, gives the formula CaMnSiO,, showing that t.he mineral takes a place next t o monticellite (CaMgSiO,). This gives the epidote formula, H2R4R”69i6026, or Sp. gr. 3.407.MINERALOGICAJ, CHEMISTRP. 80 Nusonite. This is white and massive, with a greasy to adaman- tine lustre. Tbin sections under the microscope show the mineral to be crystalline and optically uniaxial ; the system is probably tetra- gonal. Sp. gr. 5.425. After deducting 2.16 per cent. of clino- hedrite (H,CaZnSi05), analysis I1 (by Warren) gives the formula Pb6Ca,C1,(Si,07), = P b,(PbC1)’2Ca4(Si20s)3.This is closely related t o the tetragonal ganomalite from Sweden, of which the formula is usually given as- Pb3Ca,Si3OIl = Pb,(Pb,O)”Ca,( Si207)3’ Lindstrom’s analysis (1883) of ganomalite shows the presence of small quantities of water and chlorine, and i t agrees with the formula which is now proposed for ganomalite. Nasonite therefore differs from ganomalite in containing chlorine in place of bydroxyl. The acid, H,SI,07, of which nasonite and ganomalite, as well as cordierite, barysilite (Pb,Si,07) and hardgstonite (dbstr., 1899, ii, 435) are salts, is intermediate between ortho- and meta-silicic acids, or it may be considered as 2Si(OH),- H,O. For this acid, which is usually called diorthosilicic, t$he name mesosilicic m i d is proposed. This is of a purplish-red or raspberry colour ; it has a crystalline structure, though the crystal system, probably monoclinic, could not be determined. Sp.gr. 3.S48. Analysis I11 (also Na20, 0.39; K,O, 0-24), by Warren, agrees with the formula H2R7Si3OI4, or, as the water is not expelled below a red heat, R,(R*OH)’2(Si0,),. This represents a basic orthosilicate, and the mineral is therefore a manganese humite with hydroxyl in place of fluorine. SiO,. PbO. MnO. 2110. MgO. CsO. FeO. C1. H,O. Total. b4( b*0H)2Ca4( si$?07)3, Leucophenicite. I. 31.48 1.74 38.00 - - 28-95 trace - - 100.17 111. 26.36 - 60.63 3-87 0.21 5.67 trace - 2.64 100.01 11. 18.47 65.68 0.83 0.82 - 11.20 0.10 2.81 0.26 99.54 L.J. S. Hydrated Aluminium Silicates and Clays. By KONSTANTIN D. GLINKA (Zeit. Kryst. Min., 1899, 32, 79-81 ; from Me‘rn. Inst. ugron. forest. 13 Nowo-Alexandria [Gouu. Lublin], 1899, 12, 41-84).- Various clays were found t o contain quartz, orthoclase, muscovite, rutile, zircon, tourmaline and garnet, together with kaolin, bauxite and diaspore, but no zeolites. Quartz and aluminium hydroxides may occur together, and in this case their presence will not be indicated by a bulk analysis of the clay. Their presence is, however, indicated when the material, after ignition, is treated with a 33 per cent. solution of potassium hydroxide ; under these circumstances, most of the silica, but very little of the alumina, goes into solution. Several other experi- ments of a similar nat.ure were made on clays and various silicates, the object being to determine the constituent minerals of clays.Stokesite, a New Mineral from Cornwall. By ARTHUR HUTCHINSON (Phil. Mag., 1899, [ v], 48, 480-481).--6 preliminary notice is given of a new mineral, of which only a single crystal, about 10 mm. long, has been found. It is colourless and transparent. System, orthorhombic (a : 6 : c = 0.3479 : 1 : OnSl17]. Sp. gr. 3,185, L. J. S.90 ABSTRACTS OF CHEMICAL PAPERS. H = 6. The lustre is vitreous. Analysis gives the formula CaO,SnO,, By HERBERT E. GREGORY (Amsr J. Sci, 1899, [iv], 8, 359-369).-A description is given of the andesites of the Aroostook volcanic area of northern Maine, An analysis by Hillebrand is quoted. Hot Sulphur Spring of Deutsch-Altenburg. By ERNEST LUDWIG and THEODOR PANZER (Chem.Centr., 1899, ii, 402 ; from Ken. klin. Wochensch., 12, 708-710).-The hot sulphur spring of Deutsch-Altenburg belongs to the same type as the hot salt-sulphur springs of Aachen and of the Hercules bath in Mehavia. It is a clear water, with a strong odour of hydrogen sulphide, and becomes turbid on keeping and deposits sulphur. It has a sp. gr. 1.00289 a t 18.70' and contains traces of cssium, rubidium, titanic oxide and formic acid. A full analysis is given, E. W. W. Origin of Graubunden Mineral Waters. By GUSTAV NUSSBERGER (Jahresber. Naturforsch. Ges. Grsubiindens, 1899, 42, 1-35. Compare Abstr., 1897, ii, 569)-A detailed account is given of the mineral waters of the Canton Qritubiinden (= Grisons), Smitaer- 3Si0,,2H20 (compare Nature, 1899, 61, 119).L. J. s. Andesites from Maine. L. J. S. land, and their origin discussed. Several analyses are quoted. L. J, S. Mineral Waters of Lutraki, Greece. By ANASTASIUS K. DAMBERGIS (Chem. Centr., 1899, ii, 568 ; from Oesterr. Chem,-Zeit., 2, 437)-The mineral waters of Lutraki, on the north coast of the Gulf of Corinth, consist of three groups, which differ in temperature and quantity, but have an almost identical composition The clear, odourless water has a sweet taste, with a somewhat saline after-taste, does not become turbid on exposure to air, and leaves no residue as it flows from the spring. The group containing the most dissolved matter contains 1,912 grams of dissolved substances per litre, has a temper- ature of 31°, and a sp. gr. 1*0018. An analysis is quoted. The springs belong to the class of alkaline calcareous hot springs. E. W. W. The Water of Monsummano. By PIETRO ALBERTONI and GIUSTO CORONEDI (Chem. Centr., 1899, ii, 591-592; from Ann. Farm. Chirn., 1899, 214-235).-The water of Monsummano has a tem- perature of 32' and a sp. gr. 1.000154, and 10,000 parts leave a residue of 13.012 dried at 180'. An analysis of the residue is quoted. I n the original paper, the action of this water is discussed on the basis of the ion theory and clinical experiments on its therapeutic and physiological effects are also described. The small amount OF calcium and magnesium salts present, and its power of dissolving uric acid, are remarkable. Uric acid dialyses much more readily into this water than into distilled water. E. W. W.

ISSN:0368-1769    

DOI:10.1039/CA9007805086

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 91 Influence of Bile, of Acid, and of Alkalis on the Proteolytic Action of Pancreatic Juice. By BENJAMIN K. EACHFORD (J. Physiol.; 1899, 25, 165-178. Compare Abstr., 1890, ii, 567).-Experiments were made with the pancreatic juice (not extracts, as Chittenden used) and bile of the rabbit. These confirm the conclusion arrived at pre- viously, although denied by Chittenden, that bile much favours the proteolytic action of the juice. Bile, however, retards the albuminous fermentat ions carried on by organised ferments. When pancreatic juice is added to fibrin half saturated with hydrochloric acid, it does as much work as on neutral fibrin, If the fibrin is nine-tenths satur- ated with the acid, proteolysis is retarded ; this retardation also occurs in the presence of bile.Free hydrochloric acid greatly inhibits, but does not destroy, the proteolytic action, whilst sodium carbonate is favourable, especially in dilute solutions of pancreatic juice. The general conclusion is drawn that the conditions in the entire small intestine are favourable to the proteolytic activity of pancreatic juice. The Influence of Removalof Water on Metabolism and Circulation. By WALTHER STRAUB (Zeit. Biol., 1899,38, 537-4566). -The effect of sodium chloride in producing a slight increase of proteid katabolism is attributed to its diuretic action, water being removed from the tissues. The present experiments on dogs were designed to test this theory by a removal of water from the food; this was found to increase proteid katabolism, but to have no influence on fat.The blood pressure is not altered, but the quantity of water lost by skin and lungs is slightly lessened. Influence of the Kind and Amount of Nutriment on Meta- bolism. By EDUARD PFL~~GER (PJiiger'g Archiv, 1899, "7,425-482). -The object of the paper is to show that proteid is the great source of energy ; it increases metabolism, and raises the resistance and power of the animal ; it does so by increasing the substance of the living cells, sometimes even doublir! t heir weight. Fat and carbohydrate have no such power. Fat wver arises from proteid in the animal body. Man cannot take all his nutriment in the form of proteid simply because of the limitation which exists in his digesting power. W. D. H. W. D.H. W. D. H. Metabolism of Nucleins. By T. H. MILROY and J. MALCOLM (J. Physiol., 1899, 25, 105-130. Compare Abstr., 1899, ii, 479).-1n a case of lymphatic leucocythaemia, the phosphoric oxide excreted was diminished both absolutely and relatively to the nitrogen excreted, whilst the excretion of uric acid and alloxuric bases was hardly affected. I n a case of medullary leucocythsmia where the number of leuco- cytes was falling, the excretion of phosphoric oxide underwent no diminution, whilst the alloxuric excretion varied greatly. An investi-92 ABSTRACTS OF CHEhIICAL PAPERS. gation of the characters of the granules in the colourless corpuscles of marrow and blood was carried out by micro-chemical means. Nucleic acid, and its principal decomposition products (thymic acid, adenine, guanine, cytosine) alter the staining affinities of oxyphil granules, making them finally basophil.The granules are nucleoproteid, and the action of the nucleic acid is to cause the cell to give up the albumin and leave a more acid. residue, nuclein. The su bseqiient discharge of the residue leads to an increase OF excreted phosphoric anhydride; this probably occurs in the body when nucleic acid is liberated. The granules readily undergo changes, and a study of them is important, for these affect the general metabolism. W. D. H. The Proteid-sparing Action of Alcohol. By RUDOLF ROSEMANN (Pjiiger’s ArcJLiv, 1899, 77, 405--424).-Miura, Schmidt, and Schoneseiffen found that alcohol has no protcid-sparing action. The present paper confirms this, and criticises Neumann’s recent work, which appeared to show the contrary.’VV. D. H. Koppe’s Theory of the Formation of Hydrochloric Acid in the Stomach. By JOHN A. WESENER (PfEigev’s Archiu, 1899, 77, 483-484).-Koppe’s theory of the formation of hydrochloric acid in the stomach is that ionisation of the sodium chloride in the stomach, and of the acid carbonates and phosphates in the blood, occurs, and t h a t an exchange of the hydrogen ions in the blood, and sodium ions of the stomach then takes place. The following experiments show this cannot be the case, but that the acid is the result of cell activity. If the stomach is well washed out, and a 0.7 per cent. solution of sodium chloride introduced, there is no formation of free acid, but if the stomach be irritated by the rotation of a revolving sound in its interior, whether the sodium chloride solution be there or not, free hydrochloric acid appears, reaching a percentage of 0.1 in a few minutes.W. D. H. Origin of Fat from Proteid. By EDUARD PFL~GER (Pjiiger’s Archiv, 1899, 77, 521-554).-Polemica~l. Pfliiger is well known to be an unbeliever in Voit’s doctrine that fat can originate from proteid in the body; his remarks here are mainly directed against Max Cremer, the latest exponent of Voit’s theory. W. D. H. Phosphorus in Muscle. By J. J. R. MACLEOD (Zeit. p?~ysioZ. Chem., 1899, 28, 535-558).-By muscular work, the organically united phosphorus in aqueous extracts of muscle is greatly diminished but the inorganic phosphates are increased. The lessening is due partly to a diminution of phosphorus in nucleon, but especially to that in organic phosphorus compounds other than nucleon. W.D. H. Sodium Chloride in Cartilage. By GUSTAV VON BUNUE (Zeit. plhysiol. Chem.., 1899, 28, 452-458).-Cartilage, one of the oldest tissues, phylogenetically, is the richest of the tissues in sodium. A number of analyses of cartilage frorrr mammals show that the sodium is most abundant in embryonic life, and least so in old animals. Corn-PH l!SI OL 0 G IC A L C H Ehi I S'fH Y . 03 paring the cartilage of adult selachians with that of adult and embry- onic mammals, the former is richest in sodium ; doubtless the sodium is principally present as chloride. By ERNST WEINLAND (Zeit. Biol. 1899,38, 607-617).-1n both young and adult dogs, the pancreas in virtue of a lactase converts lactose into dextrose and galactose, this power being increased by a milk diet. By prolonged boiling with citric acid, lactose is similarly acted on.There is no exidence of any intermediate substance between lactose and its hydrolytic products. W. D. H. W. D. H. The Lactase of the Pancreas. The Retention of Phytosterol in the Animal Body a f t e r Feeding with Cotton-seed Oil. By C. VIRCHOW (Chem. Centr., 1899, ii, 395 ; from Zeit. Unters. Ncciw. u. Genussmittl., 2, 559-575. Compare Abstr., 1899, ii, 689).-The results of experiments in which dogs and pigs were fed with cotton-seed oil showed that phytosterol did not pass into the fat, so that the presence of phytosterol in lard is important evidence of adulteration.It was found that glycerides of hydroxy-fatty acids passed into the fatty tissues. Albumin in the Cell of the Queen Bee. By P. Siiss (Clmz. Centr., 1899, ii, 560 ; from Phccrm. Centr.-H., 40, 458).-h\lIore than a gram of a yellowish-white, rather transparent mass with the appear- ance of salve was found on the floor of a queen bee cell and proved t o be albumin. A. KLETT (ibid., 602) points out t h a t it has been long known that the cell of the queen bee contains albumin, and, indeed, differs from those of the working bees only in containing a larger proportion of it. E. W. W. By HORACE M. VERKON (J, Physiol., 1899, 25, 131--138).-1n a number of marine animals belonging to various groups, the death temperature is generally a little higher than the paralysis temperature, and varies from 32.5' t o 43.5'.Even among transparent pelagic animals, the differences are nearly as great. The differences can only be partly explained by the differences in the amount of solids in the tissues, hence protoplasm must vary chemically as well as physically. From observations on the death temperature of echinoid embryos, i t is shown that it rises with the progress of development. By MARTIN KR~GER (Ber., 1899,32,3336-3337. Compare Abstr., 1898, i, 699 ; 1899, ii, 233, and this vol., ii, 30 and 31).-Caffeine (1 : 4 : 6-tri- methylxanthine) was given to a rabbit during 22 days in daily doses of 0.1 gram, the animal being fed on oatmeal and cabbage; the urine was found to contain paraxanthine (1 : 6-dimethylxanthine), heteroxanthine (1 -methylxanthine), and 6-methylxanthine.I n the systems of the rabbit and man, the methyl group in position 4 appears t o be most labile, whilst in the dog the alkyl radlcle in position 1 is most readily removed. N. H. J. M. Death Temperature of Marine Organisms. W. D. H. Degradation of Caffeine in the Organism of the Dog. G. T. M. VOL. LXXVIII. ii. 794 ABSTRACTS OF CHEMICAL PAPERS. Influence of Theine on the Excretion of Alkalis in the Urifle. By K. KATBUYAMA, T. KUWAHARA, and K. SENO (Zeit. physiol. Chem., 1899, 28, 587-594).-Experiments on rabbits show that the ad- ministration of theine increases the output of alkali in the urine; there is increase in sodium, but not in potassium. Estimation of the Reducing Substances in Urine by Pegke’s Method. By A. GREGOR (Chem.Centr., 1899, ii, 231 ; from Centv. Krank. Ham. und Sexunlorgane, 10, 240).--The method of Pegke (Proc., 1895, 11, 43) for the estimation of dextrose is equally applic- able t o urine. Normal urine shows a reducing power varying from 0.0825 to 0.347 per cent, It rises after a meal, more strongly after a n amylaceous than after a flesh diet. It i s constant during the night, having the same value (0.085 per cent.) as when fasting or employing a pure flesh diet. Excessive use of carbohydrates does not increase i t ; alcohol does so. It is lomered by hard, muscular work. M. J. S. Relations between the Diuretic Effects and Osmotic Pro- perties of Sugars. By E. H~DON and J. ARROUS (Compt. rend., 1899, 129, 778-781).-Sugars are toxic only in very large doses, and can be injected into the animal system without producing either im- mediate or subsequent accidents.The maximum diuretic effect is produced by a particular dose at a particular degree of concentration, which varies with different sugars. There is an approximately constant relation, the diuretic coeficient D, between the quantity of sugar solu- tion injected and the volume of urine eliminated, but this coefficient varies with the concentration of the solution ; with dextrose solution containing 25 per cent. it is 2*S, with 50 per cent. 4.8, and with 10 per cent. 1.0. The coefficient also varies with different sugars at the same degree of concentration ; with dextrose a t 25 per cent. it is 2.8 ; laiwulose and galactose, 2.4 ; sucrose, 2.0 ; lactose and maltose, 2.2; raflinose, 0.9; arabinose, 3-4; erythritol, 4.0.It follows that the diuretic coefficients of these sugars vary inversely as their molecular weights, but directly as their osmotic pressures. Some sugars of the same molecular weights and osmotic pressures have not, however, exactly the same diuretic coefficients, but these differences are probably due to the different chemical functions of the sugars or to the fact that different proportions of them are consumed by the organism. The toxic effect of t h e sugars generally follows the same order as their diuretic coefficients. The toxic dose is 30-35 grams per kiIo- gram of body weight in the case of sucrose; 20-25 grams with dextrose ; and 5 grams with arabinose and erythritol. [Physiological Action of] Cyanotetramethylpyridone. By LUIGI SABBATANI (Chem.Centr., 1899, ii, 528; from Atti Real. Accad. Torino, %).--A 1 per cent. solution of the 3-cyano-1 : 2 : 3 : 4-tefra- methylpyridone, prepared by Guareschi (Atti ReaZ. Accad. Torino, 34), has an extremely bitter taste, which is similar t o that of quinine and magnesium sulphate. With Bouchardat’s reagent, this compound forms a reddish-brown precipitate which easily decomposes and with Nessler’s reagent, even in very dilute solutions, i t gives a lemon-yellow, W. D. H. The urine requires to be diluted. C. H. B.P H Y S I 0 1, OG I C A 1, C H EM IS TRY, 95 amorphous precipitate, but its presence in urine could not be detected by means of these reactions. Physiologically i t proved to br w r y active, but comparativ ly hartnleqs, its operation being of ,short duration and chiefly affecting the spinal marrow, When dropped into the eye, it induces myosis and subcutaneous injections have a purgative action.Dilute solutions of the pyridone cause more or less violent contraction of the muscles. Physiological Action of Quinosol [o-Hydroxyquinoline- sulphonic Acid]. By CARL BBAHM (Zeit. physiol. Chem., 1899, 28, 439--451).-The urine of animals (dogs and rabbits) which had been dosed with quinos1)1 deposits crystals of o-hydyoxyquinoline- gEycu~ou'L'c acid, C,5H,,07N + 2H,O, and this does not show a definite melting point, but turns yellow a t 102-105° and decomposes a t 151'; it dissolves in 815 parts of water a t 1 5 O , but readily in hot water, the solution being strongly acid ; it does not reduce Fehling's solution.The cadmium, strontium, barium, and potassium salts were prepared ; an aqueous solution of the latter is 12evorotatory [a], 83.83-76.59O. When boiled with dilute acids, the acid is resolved in to o-hy droxyquinoline and glycuronic acid. Nothing certain is known of the origin of glycuronic acid in the body; the administration of a-methylglucoside did not lead to its appearance in the urine. Action of Lymphagogues on the Proteids of Blood and Lymph. By DMITRI J. TIMOF~EFFSKY (Zeit. B i d , 1899, 38, 618--651).--The percentage of globulin in relation to the total proteid is higher in normal blood than in lymph. Lymphagogues of Heidenhain's first kind increase this relationship, either only in the lymph (for example, with toxins and crayfish extract), or in both lymph and blood (as when peptone is used); this, however, lasts but a short time, the normal ratio being quickly re-established.The change in the proteids has no direct relation t o the increase of lymph secretion, or the rise in the total proteids of the lymph, W. D. H. Acute Alcoholism : Estimation of Alcohol in the Blood and the Tissues. By NESTOR GR~HANT (Compt. Tend., 1899,129,746-7'48). -A 10 per cent, solution of alcohol was introduced into the stomach of dogs, in quantity corresponding with 5 C.C. of absolute alcohol per kilogram of body weight, After half-an-hour, 10 C.C. of arterial blood were withdrawn, and the alcohol in it estimated by distillation and titration with potassium dichromate, this operation being repeated every half-hour.After an hour and a half, the quantity of alcohol in the blood becomes constant and is 0.57 C.C. per 100 C.C. of blood. After four-and-a-half bo five hours, the quantity of alcohol begins to be less and the animal slowly recovers. I n the case of a dog killed by bleeding from the carotid artery, the following quantities of alcohol were found in the various tissues : brain, 0.41 C.C. ; muscles, 0.33 C.C. ; liver, 0.325 C.C. ; kidneys, 0.39 C.C. per 100 grams of tissue in each case. C. H. B. Effect of Poisons on the Eye-Muscles. By GUILLERY (PJuger's A ~ c h i v , 1899, 77, 321 -404).-A considerable number of measure- E. W. W. W. D. H. P- I - 296 ABSTRACTS OF CHEMICAL PAPERY. ments of the movements of the ocular muscles were made under normal circumstances, and these were compared with others made under the influence of various poisons. Alcohol lessens the contrac- tive-energy : this is principally manifested by the internal recti. The paralysing action of morphine falls also chiefly on the same muscles ; the action on the external muscles begins later. The action of chloral hydrate on the eye-muscles is shown by quite small doses ; the pupil is enlarged, and the near point is made more distant. Much larger doses of paraldehyde are necessary to produce corresponding effects; the action of sulphonal and trional is small but unmistak- able. Cocaine has little or no action beyond that on the pupil. Chloroform is the most active of the inhalation poisons examined. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9007805091

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

96 ABSTRACTS OF CHEMICAL PAPERY. Chemistry of Vegetable Physiology and Agriculture. Do the Bacteria, of Alinit assimilate Atmospheric Nitrogen 3 By JULIUS STOKLASA (Chem. Centr., 1899, ii, 132 ; from Centr. Bakt. Parasit., II., 5, 350-354).-Whilst Lauck (Chern. Centr., 1899, i, 443 and 858, and Centr. Bukt. Parasit., II., 5, 20, 54, and 87) believes t h a t the alinit bacteria are Bacillus subtilis, the author considers them to be B. megatheiizcm. The two bacilli differ essentially; the former converts nitrates into nitrites, the latter into nitrites and ammonia. I n a mixture of xylose and galactose (3 : 1) with mineral matter and a little nitrogen (as peptone) the alinit bacteria develop quickly and fix free nitrogen. I n presence of much combined nitrogen there is no fixation.I n the same mixture, B. subtilis grows less and there is only a slight fixation of free nitrogen. Influence of Organic Substances on the Work of Nitri- fying Organisms. By SERGEI WINOGRADSKY and V. OMELIANSKY (Chem. Centr., 1899, ii, 132-133, 217, and 264; from Centr. Baht. Parasit., If., 5, 329-343, 377-387, and 429--440).-Sodium carbonate is essential for the growth of nitric and nitrous organisms. I n the case of nitrate organisms, the oxidation of the nitrite and the growth of the microbe are inseparable. Peptone in excessive amount cannot alter the specific function of the microbe, but destroys or completely checks it under certain conditions. Addition of 0.025 per cent. of dextrose is favourable; the limit of f:ivourable action is reached when 0.3 per cent.is present. Urea is without effect when the amount is only 0.05 per cent. ; 05-0.8 per cent, hinders nitrifica- tion ; asparagine (0.05 per cent.) is injurious, and glycerol behaves similarly. Infusion of hay (14 per cent.) is beneficial ; addition of urine (2 per cent.) resulted in the time required for oxidation being increased five times. Urea is without action N. H. J. M. Broth (8 per cent.) had no effect,V EG ET AB L E P HY S I 0 LO G Y AN D AG li LC U LT U RE . 97 and it is to ammonia that the depressing effect of urine is attributed (compare Warington, Trans., 1891, 521). Sodium acetate (2 per cent.) checked oxidation, whilst the butyrate had only a slight effect. Iron salts seem to assist the process. The nitrite bacterium is much more sensitive to nitrogenous sub- stances such as peptone and asparagine than the nitrate bacterium. The more complex, unstable, and, for most microbes, the more assimilable the substance, the more injurious is its effect on nitric organisms.The following arrangement of nitrogenous subatances, according to their nutritive value, also corresponds with their anti- nitrifying effect : peptone, dextrose, asparagine, urea, acetates, and but yra tes . By V. OMELIANSKI (Chern. Centr., 1899, ii, 347-348; from Centr. Bakt. Pay-asit., II., 5, 473-490). -Experiments with amides, proteids, urine, &c., showed that the nitrifying organisms are not able to attack organic nitrogen; the nitrogen must be first converted into ammonia. A cultivation containing an ammonia microbe (Bacillus ramosus), a nitrite bacterium, and a nitrate bacterium converted organic nitrogen successively into ammonia, and nitrous and nitric acids.If the nitsite bacterium is omitted, only ammonia is formed, whilst if the nitrate bacterium is omitted, the change stops after production of nitrites. N. H. J. M. Micro-organisms observed in the Formation of Nitrates. By ALBERT STUTZER and R. HARTLEB (Chem. Centr., 1899, ii, 448-449 ; from Mitt. Zandw. Inst. k. Univ. Breslau, Heft. 2).-A nitric organism, Nitromicrobiurn germinnns, which is not a bacterium, was obtained from soil. It only oxidises nitrites to nitrates. As nitrogenous food, i t can utilise ammonium compounds and nitrates as well as nitrites, but not complex compounds such as peptone and the con- stituents of broth.It utjlises free carbon dioxide, but not carbonates, and it cannot assimilate the carbon compounds, such as sugars, usually employed for bacteria. Action of Bacillus Coli and Bacillus D'Eberth on Nitrates. By L&ON GRIMBERT (Alzn. de I'Inst. Pasteur, 1899,13, 67-76).-Nitrogen is not evolved, and only a trace of nitrite is formed, when Bacillus coZi and R. d'Eberth are cultivated in a 1 per cent. peptone solution containing 1 per cent. of a nitrate. If, however, they are cultivated in peptonised broth containing a nitrate, then a part of this nitrate is decomposed, nitrogen and carbon dioxide are evolved, and a con- siderable amount of nitrite remains in solution. With B. pyocyaneus the whole of the gas evolved consists of nitrogen, no carbon dioxide being formed.Similar results are obtained with a peptone solution containing extract of meat and a nitrate. The evolution of nitrogen is no doubt due to a secondary reaction between the nitrous acid pro- duced by the reduction of the nitrate by the bacillus, and the amino- nitrogen contained in the broth or extract, for the amount of nitro- gen evolved is twice that corresponding with the amount of nitrate decomposed and half that corresponding with the aminic nitrogen N. H. J. M. Nitriflcation of Organic Nitrogen. N. H. J. M.98 ABSTRACTS OF CHEMICAL PAPERS. contained in the broth or extract. Peptone itself contains a small amount of aminic nitrogen, and it is therefore possible for B. coli and B. d’E6erth to evolve nitrogen from a 5 per cent. peptone solution, for the amount of peptone in the solution is sufficient to furnish the aminic nitrogen required.Nitrogen is evolved when B. d’Escherich and B. d’EbertA are cultivated in a peptone solution containing potassium nitrite. Denitriflcation. By KURT WOLFF (Chem. Centr., 1899, ii, 133-134 ; from Hygien. Rundsch., 9, 538--547).-Besides the eleven known deni t rif ying organ isms, Baaillus fluo~~*~scens Ziquefaciens possesses this property, although it will not reduce nitrates in pure well or river water, or in milk, As regard8 the question whether denitrifying organisms obtain oxygen wholly, or in part, from nitrates, it was found that the same amount of atmospheric oxygen was absorbed whether nitrates were present or not. On inoculating peptone containing calcium nitrate with B.Juores- cens, nitrogen was eliminated, nitrous anhydride being formed as an intermediate product. Calcium carbonate was formed ; the liberation of nitrogen cannot therefore be the result of the interaction of nitrate and amino-compounds in acid solution, as Marpmann suggested (Chem. Centr., 1899, i, 702, and Centr. Bakt. Parasit., 11, 5, 67). The fact that with abundant aijration nitrogen is not liberated may be due t o t h e removal of most of the carbon dioxide. Other examples of microbes which only denitrify in presence of plenty of carbon dioxide are given. Ordinary pressed yeast destroys nitrates completely both in broth containing sodium nitrate or with calcium nitrate. This is not a case of action of pure yeast, as numerous bacteria are present.Fermenta- tion can take place without liberation of free nitrogen from the nitrate present. Which forms of Carbohydrates do Denitriflcation Bacteria require for their Vital Processes? By JULIUS STOKLASA (Bied. Centr., 1899, 2’7, 707-708 ; from Zeit. Zandw. Versuchswesen Oesterr., 1898, i, 371).-The activity of denitrifination bacteria was found to be greatest in presence of xylose; arabinose is a less suitable food. Experiments were also made with pure dextrose, lzvulose, galactose, and sucrose. I n experiments with Bacillus defiitrijkans, i t was found that oats grew normally in presence of dextrose, whilst with xylose the yield was reduced to about one-fourth as compared with that of pots manured with nitrate and superphosphate. With arabinose, the results were similar to those obtained with glucose.Bacillus megcctherium and B. mycoides had no effect on the growth of oats in presence of xylose, nitrate, and phosphoric acid. It is probable t h a t both bacteria reduce the nitrate to ammonia and also accumulate atmospheric nitrogen in the soil. Fermentation Experiments with Trehalose. By ARMINIUS BAU (Chern. Centr., 1899, ii, 130-131 ; from Woch. Brauerei, 16, 305--306),-The constituent of certain yeasts which causes the break- H. R. LE S. N. H. J. M, N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 99 ing up of trehalose into dextrose must be of a nature differing from that of ordinary enzymes. It cannot be assumed that trehalose, which Bourquelot found in mould fungi, occurs in genuine yeasts. The hydration of trehalose is attributed t o the living protoplasm or its constituents. Trehalose is not suitable for distinguishing between different yeasts. Cellulose Enzymes.By FREDERICK C. NEWCOMBE (Chem. Centel*., 1899, ii, 129 ; from Annals of Bot., 13, No. 49).-The extract of Aspe.r*giZZus Ovyxce attacks reserve cellulose more vigorously than starch; the enzymes of Lupinus albus and of Phanix dactylifeel-a behave similarly, but the latter hydrolyses somewhat more starch than Lupinus albus, whilst the enzyme acts very strongly on cellulose and less on starch than the extracts of Lupinus and Phenix. The enzymes of barley malt, besides those already mentioned, attack cellulose when very much diluted. The effect of all these ferments is to render the cell-walls more and more transparent.The enzymes of Lupinus and Phmnix may be considered as cytase, and are not to be regarded as diastase. N. H. J. M. Raf3nose as a Carbohydrate for the Nutrition of Asper- gillus Niger. By HENRI GILLOT (Chem. Centr., 1899, ii, 129-130; from Bul. Acnd. roy. Belg., 1899, 221--226).-When sucrose is em- ployed for the nutrition of Aspevgillus niger, i t is inverted by a diastase before being assimilated, oxalic acid being formed as an intermediate product. I n a similar manner, raffinose is inverted ; the melibiose produced is further hydrolysed to dextrose arid laxulase. Like sucrose, raffinose is completely utilised, and to the same extent in a, given length of time. Oxalic acid is formed. Nitrogen Nutrition of Leguminous Plants. By JAN LUTOSLAWSKI (Bied. Centel-., 1897, 27, 688-689 ; from Bey.physiol. Lab. bndw. Inst. Univ. Halle, 1898).-Peas were grown in pots con- taining sandy loam (6-6 kilograms) from a field on which peas had been grown the year before. Mineral manure was given to each pot, and to some sodium nitrate (1.277 grams) as well. Plants were taken up at five periods, (1) after the end of the germinating process (8th to 10th leaf), (2) commencement of flowering, (3) full flower, (4) after flowering, (5) ripe. The balance of nitrogen, taking into account the amounts in produce and in soil, gave the following gain per cent. of the original nitrogen in soil and seed (9-269 grams), (1) without, and (2> with nitrate at the different periods : Invertin has no effect on trehalose. N. H. J. M.N. H. J. M. I. I J. 111. IV. V. 1. 1.0 1.65 3.1 4 5-1 7 3.40 2. 0.0 1.45 1.89 2.95 2.20 in absence of nitrate, fixation of nitrogen commenced soon after the germinating period, whilst with nitrate it was later. For green manuring and for feeding, peas should be ploughed in or cut when fruit begins to be formed ; or, in unfavourable weather, a t earlier periods. Similar experiments with vetches failed in absence of nitrate. N. H. J. M.100 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of the Cell. By JAN SOSNOWSKI (Chem. Centr., 1899, ii, 587 ; from Centr. physioZ., 13, 267--270).-The infusorie obtained from ordinary hay infusion are for the most part easily soluble in a 0.2 per cent. solution of an alkali hydroxide and in a 0.3 per cent. solution of sodium carbonate, only a few lustrous granules remaining undissolved.The solutions give the biuret reaction and the Pam- rnceciurn gives Millon’s reaction. They are only attacked by pepsin- hydrochloric acid with difficulty. The extracts obtained by grinding the infusorie with quartz and treating with water, contain albumin which cannot be coagulated when the solutions are neutral, but is partly precipitated by adding sodium chloride or acids. The proteids are completely precipitated from the aqueous extract by barium hydroxide, and the precipitate contains phosphorus even after repeated treatment with dilute hydrochloric acid, alcohol, and ether. When the fat, lecithin, &c., have been removed from the cells by means of alcohol, only a portion of the residue is soluble in a 0.3 per cent.solu- tion of sodium hydroxide, and the precipitate obtained by acidifying the alkaline solution with acetic acid contains phosphorus, gives the biuret reaction, and when boiled with phloroglucinol dissolved in hydrochloric acid exhibits the bands char&teris& of the pentoses. E. W. W. Absorption of Iodine by Plants. By PAUL BOURCET (Compt. rend., 1899, 129, 768-770).-Twenty-eight plants belonging to nine different natural orders were grown in carefully prepared soil contain- ing 0.83 mg. of iodine per kilog., and when the plants reached maturity they were cropped, and the proportion of iodine in them was deter- mined. It was found to vary from nil (potato, gherkin, black radish, pat sley, carrots, chicory, endive) t o 0.32 (green haricots), 0.38 (Beta cycla), and even 0.94 (garlic) mg.per kilogram. Certain families, such as Liliacece and Chenopodiacecxz, absorb more iodine than others, such as Xolanacece and Urnbellifem, but different species of the same order show considerable differences. C. H. B. Phyrsiological Importance of Furfuroids in Sugar Beet. By JULIUS STOKLASA (Chem. Centy., 1899, ii, 57-58 ; from Zeit. Zucker- Ind. Bohmen, 23, 387-397. Compare Abstr., 1899, ii, 792).-Inas- much as pentosans are important constituents of the cell membranes, i t may be concluded that they are formed from sucrose. As new organs containing pentosans develop in the second year of vegetation, the sucrose gradually disappears from the roots. I n water-culture experiments with peas and maize, it was found that only a slight excess of furfuroids was produced in presence of sucrose as compared with dextrose; when, however, root heads of beet were fed under condi- tions of sterilisation with sucrose and dextrose respectively, in absence of carbon dioxide, it was found that a far greater amount of furfuroids was produced with sucrose than with dextrose. Potassium chloride assists the production of furfuroids.Furfuroids are essential in the building up of cell membranes. The celluloses of the embryo are hydrolysed, and thus furnish the material for the production of the new hemicellulose group of theVEGETABLE PHYSIOLOGY AND AGRICULTURE. 101 seedlings. The hemicell uloses are transformed into lignocelluloses (which protect the roots from infection by parasitic fungi) and lignin substances.N. H. J. M. Occurrence of Indioan in the Chlorophyll Grains of the Indigo Plants. By HANS MOLISCR (Chem. Centr., 1899, ii, 482 ; from Ber. deutsch. hot. Ges., 17, 228--233).--Indican is usually found in the mesophyll and external skin of the leaves of the indigo plant, Inside the green cell itself, it occurs mainly in the chlorophyll grains. It is best detected by converting i t into indigo-blue by means of alcohol, ammonia, or chloroform vapour. The discovery of indican in the chlorophyll grains is the first proof of the presence of a glucoside con- taining nitrogen in the chlorophyll grains of the indigo plants. E. W. W. Histidine and Lysine in the Decomposition Products of the Proteid of Conifer Seeds. ERNST SCHULZE and ERNST WINTERSTEIN (Zeit.physiol. Chem., 1899, 28, 459--464).-The proteid material of the seeds of various conifers has been shown to yield arginine on de- composition. The present research shows that, on decomposing the proteid with hydrochloric acid, histidine and lysine are also obtained. From 300 grams of dry material, 3 grams of histidine chloride, 19 grams of arginine nitrate, and 3 grams of lysine picrate were ob- tained. W. D. H. Histidine and Lysine in Seedlings. By ERNST SCHULZE (Z~it. physiol. Chem., 1899, 28, 465 -470).-- From the present and previous work it is shown that from the seedlings of Lupinus luteus eight nitrogenous derivatives of proteid are obtainable, namely, asparagine, leucin e, aminovaleric acid, tyrosi ne, phenylalanine, arg inine, his t id ine, and lysine.W. D. H. Progressive Development of Essence of Bergamot. By EUG~NE CHARABOT (Compt. s*end., 1899, 129, 728--'731).-Analyses of two samples of essence of bergamot, one prepared from the green but fully developed fruit, and the other from the ripe f r u i t of the same trees, show that during the process of ripening, the free acids, calculated as acetic acid, decrease from 0.289 to 0.283, the total linnlool from 40.5 to 35.5, the free linalool from 13.9 to 5.9, andthe bergaptene from 5.9 to 5.5 per cent., whilst the linalyl acetate increases from 33.8 to 37.3 per cent. An increase is also observed in the terpenic constituents of the oil, but the relative proportions of limonene and dipentene remain unchanged. From these results, it is concluded that the primary development of the fruit is characterised by the active formation of linalool, and that during the subsequent ripening this reacts with the free acetic acid and is partly converted into linalyl acetate, partly dehydrated with the production of limonene and By Jos.HA NU^ (Chem. Centr., 1899, ii, 557-558; from Zed. Unters. Nahr.-Genussm., 2,617-622).-From the ripe fruit of Corylus aveZZana, L., 50-60 per cent. of a clear, golden-yellow oil may be extracted by means of ether. T t has a pleasant taste, itn odour like dipentene. N. 1,. Hazelnut Oil.102 ABSTRACTS OF CHEMICAL PAPERS. that of fresh butter, and the following constants: sp. gr., 0.9169 at 15’ ; saponification number, 193.7 ; iodine number, 90.2 ; Hehner’s number, 95.6 ; Reichert-Meissl number, 0.99, and acetyl number, 3.2.The insolubIe fatty acids have : saponification number, 200.6 ; iodine number, 90.6, and mean molecular weight of 279.0. The unsatarated fatty acids have : saponification number, 198.5 ; iodine number, 91.3 ; Maumene’s number, 36.2, and mean molecular weight of 282. The oil does not give characteristic reactions with the usual reagents, but yields a greenish, semi-solid elaidin, and consists of 85 per cent. of oleic acid, 10 of palmitic and stearic acids, 10-41 of glycerol, and 0.5 of phytosterol. Oleic acid is the only unsaturated acid present, and the oil does not contain arachic acid. By W. P. H. VAN DEN DRIESSEN MAREEUW (Chem. Centr., 1899, ii, 589 ; from Ned. Ted. Pharrn., 11, 227-234).-The bark, Cortex Lokri, is obtained from Hymenea Courbaril; it con- tains 2.7 per cent.of catechin, 23.6 of catechu-tannic acid, 0.6 of fat, and 7.6 of ash. By P. I;. SHERMAN and C. H. BRIaas (Pharrn. Archives, 1899, 2, lOl-l16).-The saw palmetto (Xabal serrulata) is a tree which is found along the S.E. coast of the United States ; the fruit is dark purple in colour, about the size of an olive, and consists of a juicy pulp and a very hard seed or nut. The fruit is pressed in a hydraulic press; when the juice is allowed to remain, an oil rises to the surface, in amount equal to about 1.5 per cent. of the fruit. This oil consists of acids, chiefly hexoic, octoic, decoic, lauric, palmitic, and oleic, and their ethyl esters, about 37 per cent. consisting of esters, the remainder of the free acids. The dry nuts form 17.5 per cent.of the fruit ; they were cracked, and the very hard kernels broken, ground to a meal, and extracted with boiling benzene ; in this way, an oil was obtained in amount equal to about 2 per cent. of the fruit. This oil contained about 97-7 per cent. of glycerides of octoic, decoic, lauric, palmitic, stearic, and oleic acids, the rest consisting of the free acids. The fruit contains in addition about 5.4 per cent. of sugar, estimated by its cupric reducing power, and calculated as invert sugar; also a small amount of pentoses. E. W. W. Cortex Lokri. E. W. W. Saw Palmetto. No alkaloid could be detected. C. F. B. By CHARLES CORNU (J. Phccrm., 1899, [vi], 10, 342-343).-The vine contains an oxidising enzyme which belongs to the class of “aQroxydases,” or enzymes, which only cause oxidation in the presence of air.The activity of the ferment is greater in the spring than in the autumn. H. R. LE S. Presence of an Oxidihg Enzyme in the Vine. Accumulation of Nitrogen by the Cultivation of Inter- mediate Crops on Loamy Soil. By MAX MAERCKER (Bied.-Centr,, 1899, 2’7, 655-656 ; from Candw. Jahrb., 1898,27, 157).-A mixture of beans (50), peas (loo), and vetches (50 kilos. per hectare) accumu- lated 154.4 kiloq. of nitrogen, whilst a3 mwh RS 4624 kilos. of organic matter was produced on a hectare. The least favourable resultsVEGETABLE PHYSIOLOGY AND AGRICULTURE. 103 showed an accumulation of nitrogen corresponding with 5-6 cwt. of sodium nitrate. A mixture of lupins and lathyrus proved to be unsuitable for the soil.I n the dry season of 1898, the effect of the intermediate crop on the succeeding crop of oats was very striking, partly owing to the water supplied by the deep roots OF the Legzcminosce. N. H. J. M. Experiments with Different Lupins. By A. SEMPOLOWSKI (Bied. Centr., 1899, 27, 716; from Puhling's Landw. Zeit., 1898, 47, 517).-The yield of corn (I) in kilos. per hectare, and (11) the per- centage of alkaloids, was determined in the following varieties of lupins :-(I) Lupinus nngustifolius, var. 3. rose0 ; (2) var. J . albo ; (3) L. h6rsutus ; (4) var. 3. cceruleo ; (5) L. angustifolius ; (6) L. hirszctus, var. $. albo ; (7) L. albus ; (8) L. Zuteus, var. semine nigvo ; (9) vai'. semifie a260 ; (10) L. luteus ; (1 1) L. perennis. 1 . 2 . 3 . 4 . 5 . 6 .7 . 8 . 9 . 1 0 . 1 1 . I. 3321 3310 3236 3154 3088 2924 2708 1736 1717 15.50 323 II. 0.430 0.345 0.378 0.378 0.641 0.378 0'250 0'290 0'788 0.833 - The narrow leaved varieties gave the greatest yields; yellow lupins gave the least, and contained most alkaIoids. L. angust. var. Jz., gave a high yield of corn, with a comparatively low percentage of alkaloids. N. H. J. M. [Experiments with] Cows at Lauchstadt, 1896-1897. By FRIEDRICH ALBERT (Bied. Centv., 1899, 27, 663-667 : from Lcmdw. Jahrb., 1898, 27, 188. Compare Abstr., 1899, ii, 689).--Experimenfs were made with 10 cows (two kindg) to ascertain theeffect of food-fats on the production of milk and of milk fat. There were five experi- mental periods of 7-14 days, with longer intermediate periods for gradually changing the foods.The amounts of fat in the concentrated foods were as follows :-Period preceding the experiment (0.504 kilo- gram); (1) palm cake, 0.937 kilogram of fat ; (2) lupins, 0,297; (3) cocoa nut cake, 0.747; (4) cocoa nut cake, (1.706) ; (5) lupins, 0.297 kilogram of fat. Increasing the amount of f a t in the food had no effect; on milk production so long as theamount of fat did not exceed 1 per thousand of the live weight of the cows; with 1.706 kilograms of fat to 1000 kilograms of live weight the production of milk was considerably diminished. Palm cake and cocoa nut cake increased the percentage of fat in the milk; with the largest amount of fat, the average increase was 0.75 per cent. ; with rations (1) and (3) the percentage increase of fat in milk was 0.36 and 0.28.The rations with low percentage of f a t had very little effect on the percentage of f a t in the milk, and the lupins affected the taste of the milk. Feeding with large amounts of f a t increased the live weight of the cows considerably ; in the case of one breed, the cows became unwieldy and had to be killed. The rations with low percentage of fat caused great loss of weight, N. H. J. 31.104 ABSTRACTS OF CHEMICAL PAPERS. Experiments on Feeding Cows with Brewery Residues. By EBERH. RAMM and E. M~LLER (Bied. Centr., 1899, 27, 668-670; from Milchxeit., 1899, 97).-The food contains brewery refuse and other materials, and consists of brown, worm-shaped lumps as hard as glass. It contains 42.48 per cent. of digestible proteids, 0.8 per cent.of fat, 26.96 per cent. of non-nitrogenous extract, and 1.3 per cent. of woody fibre. Feeding experiments mere made in which the COWS received hay (14), straw (4*5), roots (50), and dried brewers' grains (4 kilograms for 1000 kilograms of live weight). I n addition, they received either earth-nut cake (containing 6.5 per cent. of fat), or brewery residues (6 kilograms). After 14 days, the COWS which had brewery residues weighed rather more than the others (average 1.97 kilograms), and had yielded 94 grams more milk but 33 grams less fat and 45 grams less dry matter in the milk per head per day. The percentage of fat in the milk mas : with earth-nut cake 3.322, and with brewery residues 3.062. The butter, after feeding with (1) earth-nut cake and (2) brewery residues, contained : water, 27.7 and 16.0 ; fat, 70.91 and 82.10 ; casein, &c., 1.22 and 1.76 ; ash, 0.17 and 0.14 per cent.The examination of the fat showed the butter in both cases t o be normal. N. H. J. M. Amounts of Plant Food withdrawn from Peaty and Sandy Soil by cutting Heather and Turf, By HEINRICH IMMENDORFF (Bied. Centr., 1899, 27, 649-652; from Lrcndw. Jahrb., 1898, 27, iv, 503).-In order to ascertain the losses which moor-land undergoes where turf and heather are cut for litter, samples were taken from measured areas, both from peaty and sandy soil, the ordinary imple- ments being employed. Determinations of the different constituents were then made. The results calculated to kilograms per hectare are as follows : ( I ) sandy soil, and (2) peaty soil : Fresh Dry Fe203, substance, matter.N. K20. CaO. MgO. Al,Os. P205. SO,. 32,500 20,858 179.7 53.4 72.7 31.0 64.6 22.4 40.4 48,760 21,231 201.5 34.0 89-2 4.0.3 '78.6 19.1 53.1 The dry substance removed from the sandy soil consisted of vege- table matter (18,222) and humous sand (2636 kilograms). Assuming the cutting to take place about every 15 years, it is seen that the land must be impoverished in a comparatively short time, and it is concluded that the benefits resulting from the practice by no means compensate for the injury done to the land. N. H. J. M. Amount of Humus in Soils, and the Percentage of Nitrogen in the Humus, as affected by the Application of Air-slaked Lime and other Substances. By HOMER J. WHEELER, C. L. SARGENT, and B. L. HARTWELL (J. Amer.Chem. Soc., 1899, 21, 1032- 1037).-Zinc vessels, *with holes for drainage, were filled with soil, (254 lbs.), t o which different manures were added, Maize was grown the first year, oats the second, and rye the third year. At the end of the experiment, humus, and nitrogen in tbe humus, wQreVEGETABLE PHYSIOLOGY AND AGRICULTURE. 105 determined. Nitrogen, as ammonia or nitrate, was applied to some pots a t the rate of 2.65 grams per pot, lime a t the rate of 4 tons per acre (147.2 grams per pot), and gypsum in amounts corresponding with the lime. All the manured pots had potassium chloride and dissolved bone black. The percentage amounts of (1) humus nitrogen, and (2) humus in the dry soil, and (3) nitrogen in dry hnmuy, were as follows : No Bm,SO,, Am,S04, Am,S04, No N or NdO,, manure.Am,S04. CaO. CaO. CaSO,. CaO. CaO. NaN03. CaO. 1. 0.130 0.128 0.133 0.126 0.139 0.129 0.139 0.143 0.133 2. 3.86 3.93 3.77 3.63 3-65 3.75 3.51 3.93 3.42 3. 3-37' 3-26 3-53 3.47 3.81 3.44 3.68 3.64 3-89 The results in the third column were obtained with 36.8 grams of CaO instead of 147-2 grams. Potassium chloride and phosphoric acid alone (column 6) slightly decreased the humus and humus nitrogen. Lime and gypsum lowered the humus, but increased the nitrogen in the humus. Ammonium sulphate, without lime, reduced the nitrogen in the humus, whilst nitrate increased it. It would seem tha,t lime increased the amount of humus nitrogen, notwithstanding that the lime pots had yielded the heaviest crops. Although there was also a decrease in the amount of humus, there is probably no danger of injuring soil by the application of lime, as lime gives rise to greatly increased root production, when the land is laid down to grass for a few years.It is thought probable that nitrates become converted into soluble organic compounds, probably by the intervention of denitrifying organisms. l n presence of lime, as well as nitrate, the increase in humus nitrogen was less than with nitrate alone, owing, perhaps, to the destruction of denitrifying organisms by the lime. N. H. J. M. Losses of the Nitrogen of Stable Manure i n Covered and uncovered Stalls. By MAX MAERCKER and W. SCHNEIDEWIND (Bied. Centr., 1899, 27, 656--657 ; from Landw. JaA?*b., 1898, 2'7, 215) : Conservation of Manure. By W. SCHNEIDEWIND (ihid., 658 ; from Landw.Jahrb., 1898, 2'7, 234).-The loss of nitrogen in manure in stalls where animals are fattened was comparatively slight (13.2 per cent.) so long as they remain on it, but rose to 34.8 per cent. when the manure remained for 4 weeks withour; the animals. Manure should therefore be spread on the fields, or treated with a preservative, as soon as the animals leave the stalls. The loss of nitrogen i n uncovered and covered manure heaps was 37.4 and 36.9 per cent. respectively. The higher result, with covered heaps, is attributed to loss of moisture, greater concentration, and increased temperature. Heaps under cover should be kept moist and compact. Addition of slight excess of 0.5 per cent. sulphuric acid causes pro- duction of ammonia compounds from proteids. I n fattening experiments with sheep in stalls, the loss of manure nitrogen was again satisfactory, but the manure lost considerably after the sheep were removed.106 ABSTRACTS OF CHEMICAL PAPERS. AS regards preservatives, it was found that marl (30 per cent.) reduced the loss of nitrogen from 22.6 to 9.9 per cent.; with marl (30) and peat litter (2 per cent.), the loss was 6.1 per cent. Sodium hydrogen sulphate (6 per cent.) reduced the loss of nitrogen to 1.3 per cent. and at the same time rather improved the quality of the manure by increasing the nitrogen directly available. Bat Guano found at Cagliari, Sardinia. By GIULIO PARIS (Chern. Centr., 1899, ii, 65 ; from Stax. sper. ccgrar. ital., 32, 176-185. Compare Abstr., 1897, ii, 383).-The guano has the following percentage composition :-Moisture, 13.85 ; organic matter, 58.78; ammonia, 1.32; nitric acid, 0.75; uric acid, 0.63; Na,O, 3.10; K,O, 1.77; CaO, 1-72; MgO, 0.48; Fe,O, and A1,0,, 5.20; P,O, (organic, citrate soluble, and insoluble respectively), 0.50, 4.20, and 0.66 ; SO,, 2.28 ; SiO, (soluble and inaoluble in HC1, sp. gr. l e l l ) , 1.17 and 3.65 ; CO,, 1.80. Value of Lime Gompounds in Phosphatic Manures. By 0. BOTTCHEB (Biecl. Centr., 1899, 27, 662-663: from D. Landw. Presse, 1899, 91, 222). -In reply to Ullmann (ibid,, No. 13), it is stated that the value of basic slag as a lime manure is not less at the present time than formerly; the amount of free lime is usually only slightly less. Citric acid (2 per cent,.) dissolved, in half a n hour, 42-45 per cent. of lime ; and in 12 hours, 45-52 per cent. N. H. J. M. N. H. J. M. N. H. 5. M.

ISSN:0368-1769    

DOI:10.1039/CA9007805096

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

106 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Estimation of Oxygen in Water. By L. MUTSCHLER (Chem. Centr., 1899, ii, 225 ; from Zeit. Unters. Nahr.-Ge.nussm., 2, 4Sl).- The method consists in enclosing in a bottle of about a litre capacity three sealed glass tubes, one of which contains an alkali, the second a known volume of N/10 ferrous ammonium sulyhate, and the third an excess of 50 per cent. sulphuric acid. The acid tube is attached t o the caoutchouc stopper, the others lie at the bottom. After filling the bottle with the water, the two former are fractured by a glass ball and the ferrous hydroxide diffused through the water. After a sufficient time, the acid tube is also fractured and the unoxidised ferrous salt titrated with N/10 permanganate. By M. J.MOORE (.I Anter. C'hern. Soc., 1899, 21, 972-975).-1n the estimation of sulphur i n pig iron, much less sulphur is always obtained by the volumetric process than by the gravimetric method. The practice of pouring the molten metal into water and obtaining a (' shot sample " is not a good one ; it is preferable t o catch a small M. J. S. Estimation of Sulphur in Pig Iron. test in a sand mould. L. DE K.ANALYTICAL CHEMISTRY. 103 Estimation of Sulphur in Petroleum. By SIEGFRIED FRIEDLANDER (Chem. Centr., 1899, ii, 406-407 ; from Arhb. Kais. Ges.-A,, 15, 565--372).-The sample is burnt in an Ohlmuller lamp, which is weighed before and after the experiment, the products of combustion being drawn through two mash-bottles containing a 5 per cent. solution of potassium hydrogen carbonate.The solution is then oxidiaed by means of potassium permanganate and hydrochloric acid, and the sul- By SIEGFRIED FRIED- LANDER (Chem, Centr,, 1899, ii, 629-630; from Chercl. I d . , 22, 343-349).-Equally good results are obtained by the use of the ap- paratus and processes of Heusler, Engler, Kiessling, or Ohlmuller, but the lstter is by far the quickest, it being possible to effect an analysis in half an hour. Attention is called to the occasional presence of sulphur compounds in the air, and to the means for removing them, phuric acid estimated as usual. L. DE K. Estimation of Sulphur in Petroleum, L. DE Ka Estimation of Sulphur in Naphtha. By ALEXANDEB P. LIDOFF (Chem. Centr., 1899, ii, 493; from J. Buss. Chem. Xoc., 1899, 31, 567-570).-1 gram of the sample is dissolved in ether and care- fully mixed with 30 grams of a mixture of 17 parts of potassium nitrate and 1.3 parts of sodium carbonate.When the ether has com- pletely evaporated, the mixture is put by small degrees into a platinum dish heated to redness, The fused mass contains the sul- phur as sulphate, which is then estimated in the usual may. Estimation of Sulphur in Organic Substances. L. DE I(. By ROBERT HEKRIQUES (Chem. Zeit., 1899, 23, 869).-The process recommended for the estimation of total sulphur in rubber wares may be safely used for the analysis of other not readily volatile organic substances (com- Detection of Nitrogen in Organic Compounds containing Sulphur, By ERNST TAUBER (Ber., 1899,32,3150-3154).-Jacobsen’s method (Ber., 12, 2318) which consists in adding iron-powder to the substance before heating with potassium, is entirely untrustworthy, since the addition of the iron greatly facilitates the absorption of nitrogen from the air, and cyanides are formed even when the substance contains no nitrogen; the method is useless unless carried out in a stream of hydrogen.Magnesium has asimilar, but very slight, effect in facilitating the absorption of nitrogen ; tungsten, chromium, and nickel are still less effective, and copper produces no effect at all. The method recommended consists in using a large excess of potassium and then an excess of ferric chloride to oxidise the potassium sulphide which is formed. NoTE.-The inaccuracy of Jacobsen’s method was pointed out at the time by Remsen (Abstr., 1880, 473).-EDITORS. New Method for Estimating Nitric Acid.By J. F. POOL (Chem. Centr., 1899, ii, 227 ; from i’ederl. Tijdschr. Pharm., 11, 171).- The nitrate is evaporated to dryness with excess of sodium chloride pare this vol., ii, 123). L. DE K. T. M. L.I08 ABSTRACTS OF CHEMICAL PAPERS, in a flask. The air is expelled by carbon dioxide, and concentrated sulphuric acid is introduced ; water is added and the gases are driven over by boiling into a solution of potassium iodide. The liberated iodine is then titrated. M. J. S. Estimation of Phosphorus by Reed’s Method. By D. GERHARDT (Chent. Centr., 1899, ii, 227 ; from Nederl. Tijdschv. Pharm., 11,174),-Reed’s method(Abstr., 1899, ii, 451) dependson the fact that phosphorus dissolved in carbon disulphide combines with 5 atoms of bromine in presence of alcohol.The author finds that the presence of alcohol is not necessary ; in a simple carbon disulphide solution 5 atoms of bromine are absorbed, not 3, as stated by Reed. The method isuseless in presence of fats. M, J. S. Estimation of Phosphorus in Organic Compounds. By CH. MARIE (Compt. ~errzd., 1899,129,766-767).--The substance is oxidised by nitric acid and potassium permanganate, $he phosphoric acid pre- cipitated with ammonium molybdate, the precipitate washed until quite free from manganese, redissolved in ammonia, and precipitated with magnesia mixture. The ammonium magnesium phosphate should be washed until the filtrate gives no coloration when treated with excess of hydrochloric acid, a small quantity of ammonium thiocyantzte, and a fragment of zinc.15 to 20 C.C. of concentrated nitric acid are used for each gram of substance, heated on a watar-bath, and from 5 to 6 grams of finely powdered potassium yermanganateareadded in successive small portions until the liquid remains red for several minutes. Excess of perman- ganate is decomposed by adding a small quantity of sodium or potass- ium nitrite. Even cqmpounds difficult to oxidise by Citrius’ method are readily dealt with in this way. Separation of Barium, Strontium, and Calcium by Mixed Carbonate and Sulphate Solutions of varying Composition. By FRIEDRTCH W. KUSTER (Zeit. unorg. Chem., 1899,22, 161).-A short criticism of Morgan’s theoretical calculations (Abstr., 1899, ii, 627). The author points out that in the calculation of the solubility product, Morgan has entirely neglected the effect of the hydrolysis on the barium carbonate solution.Composition of Ammonium Magnesium Phosphate. By Huao NEURAUER (Zeit. unorg. CAem., 1899, 22,162), and by PHANK A. GOOCH and MARTHA AUSTIK (ibid., 1 63).--Neubauer claims priority in deter- mining the composition of the magnesium ammonium phosphate pre- cipitated in the usual method of estimation, and Gooch and Austin admit the justness of his claim (compare Neiibauer, Abstr., 1893, ii, 236, 489; 1896, ii, 73, 674). Analysis of ‘‘ Weissmetall.” By H. NISSENSON (Chens. Zeit., 1899, 23, 868-869).-This alloy consists chiefly of lead with tin and antimony. It is dissolved in dilute nitric acid containing tartaric acid, sulphuric acid added, and the nitric acid expelled by heat, taking care not to char the tartaric acid.It is then diluted with water and the undissolved lead sulphate collected, the filtrate rendered alkaline C. H. B. E. C. R. E. C. K.ANATJYTICAJ, CHEMISTRY. 109 with aqueous caustic soda, excess of sodium sulphide added, and the whole boiled and filtered from any copper sulphide. The liquid is then electrolysed at 80°, using a current of 3 volts and 1.5 amperes, when the antimony is deposited. To obtain the tin, sufficient ammonium sulphate is added to convert all the sodium sulphide into the ammonium Electrolysis of Metallic Phosphate Solutions. By HARRY M. FERNRERGER and EDGAR F. SMITH (J. Amer. Chem. Xoc., 1899, 21, 1001--1007).-The best conditions for tho separation of copper from iron, aluminium, chromium, cobalt, zinc, nickel, or manganese in phosphoric acid solution have been determined. I n every case, a solution containing a little over 0.1 gram of each metal was employed, the phosphate was precipitated by adding 30-60 C.C.of disodium hydrogen phosphate solution of sp. gr. 1 -0358, then dissolved by adding 5-10 C.C. of phosphoric acid solution of sp. gr. 1.347, and the solution electrolysed with a normal current density of from 0*035--0*072 ampPre and a voltage of 1.5-2.6. I n each case, the amount of liquid was 225 c.c., the time occupied 5 to 7 hours, and the temperature was kept at 60-'70°. Nickel may also be deposited from phosphoric acid solution by em- ploying a current of 0.5 ampere and 7-S volts.It has been found impossible to completely separate nickel from manganese, chromium, or zinc, mercury from cadmium or uranium, and copper from uranium. Mercury may, however, be separated from zinc. Analysis of Bronzes. By A. FOMIN (Chem. Cen.fr., 1899, ii, 495-496; from J. Russ. Chem. Soc., 31, 565--56'7).--About 0.3 gram of bronze filings, freed from iron particles by aid of a magnet, is treated with nitric acid. Ammonium nitrate is added and the whole evaporated to dryness. The residue is treated with water, neutralised with ammonia, and again acidified with nitric acid, and the insoluble matter, consisting of tin oxide slightly contaminated with antimony, iron, and traces of copper, is removed by filtration. The filtrate, measuring about 100 c.c., is mixed with 30 drops of nitric acid and submitted to electrolysis by means of a current of 0.14-0.34 ampere and 2 volts.After 3-4 hours, 5 C.C. of satur- ated solution of ammonium nitrate are added, and in 24 hours the operation is finished. The electrodes are washed twice with water and once with alcohol. The one with the copper deposit is dried quickly, and the other, coated with lead dioxide, is dried for 15 minutes at 1 8 0 O . Iron is then searched for in the usual way. Estimation of Manganic Acids in the presence of Man- ganese Salts or of both Manganese Compounds in the presence of each other, by means of an Alkaline Solution of Arsenious Acid. By C. REICRARD (Chem. Zeit., 1899, 23, 86'7-868).- Aqueous sodium hydroxide is added in sufficient quantity to precipitate the manganese salts as manganous or mangano-manganic hydroxide.Standardised alkaline solution of arsenious acid is then added and the operation is conducted as previously described (Abstr., 1899, ii, 813). compound and the liquid again electrolysed. L. DE K. J. J. S. L. DE I(. VOL. LXXVIII. ii. 8110 ABSTRACTS OF CHEMICAL PAPERS. The residue left on the filter is then ignited and weighed; the difference in the total manganese and that found by titration repre- sents the manganese salts. Two other processes are also suggested, but not supported by Estimation of Chromium in Iron and Steel. By E. DOELER (Chem. Zeit., 1899, 23, S6S).-The sample is dissolved in hydrochloric acid, and from this solution the chromium is precipitated by repeated treatment with excess of barium carbonate in a closed Bask.The precipitate is then fused in a porcelain crucible with potassium nitrate and potassium sodium carbonate, and the chromium estimated in the Estimation of Chromium in Steel. By R. W. MAHON (J Arne?*. Chem. Soc., 1899, 21, 1057--1060).-This is a slight modification of McKenna's process based on the oxidation of chromium to chromic acid by means of nitric acid and potassium chlorate, and titration with ferrous sulphate and potassium permanganate. Nitric acid and potassium chlorate are employed in greatly reduced quantities, and paper instead of asbestos is used as a filtering medium. By ALEXANDRE LEYS (J. Pharm., 1899, [vi], 10, 337-340).--The white ash obtained by the evaporation and subsequent ignition of 100-150 C.C. of the milk is moistened with distilled water and filtered.A portion of this filtrate is added to 5 C.C. of pure concentrated hydrochloric acid, previously coloured wit'h indigo-carmine, when, if a chromate is present, the solution will be immediately decolorised. A second portion of the filtrate is added to 5 C.C. of an acetic acid solution of pure aniline and commercial toluidine, when, if a chromate is present, a cherry-red coloration, due to magenta, will be produced on heating, These reactions only prove the presence of an oxidising substance, and in order to further identify the chromate, the rest of the filtrate is acidified with dilute sulphuric acid and a few drops of a solution of hydrogen peroxide added, when the production of a blue coloration fully proves the presence of a chromate. Iodometric Estimation of Gold.By FRANK A. GOOCH and FREDERICK H. MORLEY (Amer. J. Sci., 1899, 8, 26 1--266).--Contrary to Peterson's statement that gold chloride cannot be estimated by the iodine set free when i t is treated with potassium iodide, the authors have found this t o be a very accurate method for the estimation of very small quantities of gold, The gold, which should be in the metaIlic state arid not exceed 0.01 gram, is dissolved in chlorine water, and the excess of chlorine is then removed by adding ammonia, boiling and acidifying with hydrochloric acid ; this treatment should be repeated. After diluting to 200 c.c., 10 C.C. of the liquid are mixed with 0.02 gram of potassium iodide, and the liberated iodine then found by titrating with N/lOOO solution of sodium thiosulphate, using starch as indicator ; it is advisable experiments. L.DE K. aqueous extract in the usual manner. L. DE K. L. DE K. Detection of Alkali Chromates in Milk. H. R. LE S.BNALYTICAL CHEMISTRY. 111 to add a very slight excess and then to titrate back with N/lOOO Parting of Gold Platinum Alloy. By EDUARD PBIWOZNIK (Chem. Centr., 1899, ii, 539 ; from Oesterv. Zed. Berg.-Hiitt., 4’7, 356--358).-The following process i s used in the imperial Austrian assay office, The alloy is first treated with nitric acid of sp. gr. 1.199, which also dissolves a little of the platinum if silver is present. The mass is then treated with diluted aqua regiu (100 C.C. of strong hydro- chloric acid, 43 C.C. of strong nitric acid, and 143 C.C.of water), which dissolves the gold with moderate ease, but does not perceptibly attack the platinum. If there should be any silver left, the metal gets coated with silver chloride and the gold is prevented from dissolving ; in that case, the liquid is poured off and the silver chloride removed by means of ammonia. The gold solution is heated with hydro- chloric acid until the nitric acid is expelled, and the platinum then precipitated with excess of ammonium chloride. If the alloy is composed of gold, silver, and platinum, each in large proportion, i t must be fused with thrice its weight of zinc; after treating with sulphuric acid, the undissolved mass is treated as just Method and Apparatus for Incinerating Vegetable and Animal Substances.By A. E. SHUTTLEWORTH and BERNHARD TOLLENS (Chem. Centr., 1899, ii, 144 ; from Jahrb. Landw., 4’7, 173). -Addition of calcium acetate prevents the sintering which so often forms an obstacle t,o complete incineration. The authors have devised a special platinum apparatus (not described) by the use of which the time necessary for incineration is much shortened, and volatilisation of chlorides is prevented. Tucker (this vol., ii, 52) has described a modified form of this apparatus.-EDITORS. Application of the Kjeldahl Method of Destroying Organic Substances in the Detection of Metals. By OTTO GRAS and WILHELM GINTL, jun. (Chem. Centr, 1899, ii, 145 ; from Oesterr. Chem. Zeit., 2, 308)-Halenke’s process (Abstr., 1899, ii, 696) is especially suitable for the examination of coal-tar dyes.10 grams of the sub- stance is heated for 6-8 hours with 60-80 C.C. of sulphuric acid con- taining 10 per cent. of potassium sulphate, with final addition of some potassium nitrate. After diluting and warming, the solution is ready to be examined for metals. Estimation of Ferrocyanides in Spent Gas-purifying Material. By RUDOLF RIECHELMANN (Chem. Centr., 1899, ii, 144 ; from Zed. o f l e d Chem., 5,188).-The methods of Donath and Margosches (hbstr., 1899, ii, 527) and that of Knublauch (Abstr., 1890, 87) do not yield concordant results, since the former expresses as ferro- cyanogen the iron soluble in other forms in the alkaline solution. solution of iodine. 5. DE K. directed. L. DE K. M. J. S. M. J. S. M. J. S. Improvement in Trillat’s Process for the Detection of Methyl Alcohol in Alcohols.By JULES WOLFF (Chenz. Centr., 1899, ii, 229--230; from Ann. chim. anal. appZ., 4, 183).-Pure ethyl 8 2112 ABSTHACTS OF CHEMICAL PAPERS. alcohol when treated by Trillat's process (Abstr., 1899, ii, 130) yields a condensation product which gives an identical reaction with that from methyl alcohol, but the former is not produced at atmospheric temperatures or below 60'. The following modification is therefore proposed : 100 C.C. of the alcohol is distilled; the first 10 C.C. are mixed with a solution of 15 grams of potassium dichromate in 130 C.C. of water and 70 C.C. of sulphuric acid (1 : 5) ; after 20 minutes, the mixture is distilled, the first 25 C.C. are rejected, and 50 C.C. from the following 100 C.C.are mixed with 1 C.C. of dimethylaniline and left at the ordinary temperature for 24 hours. After adding a little phenolphthalein, the liquid is accurately neutralised with soda and 30 C.C. distilled from it. To the residue there are added 25 C.C. of water and 1 C.C. of acetic acid, and the colour produced by lead peroxide is observed. M. J. S. Estimation of Alcoholin the Blood and Tissues. By NESTOR GREHANT (Compt. rend., 1899, 129, 746--748).-See this vol., ii, 95. Bromination of Phenols.-By WILHELM VAUBEL (Zeit . angew. Chem., 1899, 1031-1032. Compare Abstr., 1893, i, 560 ; 1894, i, 19, 453; 1S95, i, 55; 1896, i, 147, ii, 507).-A reply to Ditz and Cedivoda (this vol., ii, 54).-The author claims that good results are obtained by his method when a large excess OF acid is present during the bromination and titration.Estimation of Carbolic Acid and other Phenols, By 11. RIEGLER (Chem. Centr., 1899, ii, 322 ; from Bull. soc. sci. Bucu~*esci, 8, 51-53).-50 C.C. of the aqueous solution, containing not more than 0.1 gram of the phenol, are mixed with 10 C.C. of a 5 per cent. solu- tion of sodium hydroxide and 20 C.C. of diazo-solution. The red solution is now gradually acidified with dilute sulphuric acid (1 : 5), which causes the precipitation of a yellow compound, NO,. C,H;N; C,H,- OH, which is washed, dried at, loo0, and weighed ; it is practically insoluble in water, 100 C.C. only dissolving 0.0002 gram. The diazo-solution is prepared b mixing 5 grams of p-nitraniline, 3 grams of sodium nitrite dissolved in 25 C.C. of water are then added, and the whole diluted to 200 C.C.The reagent must be kept in a dark New Method for the Gravimetric Estimation of Sugars. By PH. CHAPELLE (J. Pharm., 1S99, [vi], 10, 395--398).-The sugar solution and 25 C.C. of Fehling's solution are placed in the tube of a centrifugal machine, diluted to 37.5 c.c., and heated in a calcium chloride ba,th at 110" for 6 minutes, in the case of dextrose solutions, and 10 minutes for lactose solutions. The whole is then whirled in the centrifuge for 3-4 minutes, and the liquid poured off from the precipitate, which adheres firmly to the sides of the tube. Boiling water is then added, and the whole again whirled, The water is then poured off, the tube and precipitate rapidly dried at 150-180" for 5 minutes and weighed. The method is rapid, and is applicable to the estimation of sugar in milk, urine, or gastric juice, from which J.J. 8. 25 C.C. of water, and 6 C.C. of sulp i uric acid; 100 C.C. of water and place. L. DE K.ANALYTICAL CHEMISTRY. 113 the proteids have been previously removed. applicable to the estimation of sugar by means of Sachsse’s solution. H. R. LE S. The method is also Influence of Lead Acetate and Basic Acetate on the Estima- tion of Reducing Sugars in Wines and Lees, By HENRI PELLET (Chem. Centr., 1899, ii, 5 7 3 4 7 4 ; from Ann. china. a n d appl., 4, 256--257).--Normal lead acetate is recommended in place of the basic salt in clarifying wines for polarisation, as the latter precipitates some of the sugar and so causes low results. By HENRI PELLET (Chem. Centr., 1899, ii, 574; from Ann.chim. anal. uppl., 4, 256-257).-When preparing urine for polariscopic purposes, it is best to clarify with normal lead acetate or mercuric nitrate. When using basic lead acetate, there is a danger that loss of sugar may occur, especially if the urine is neutral or alkaline. L. DE K. Estimation of Invert Sugar in the Presence of Sucrose. By H. JESSEN-HANSEN (Chent. Centr., 1899, ii, 574 ; from Compt. rend. trav. Lub. Carlsberg, 1899, 103).-By operating as follows, the reduc- tion of the alkaline copper solution by sucrose is reduced to a mini- mum : 10.4 grams of potassium sodium tartrate are dissolved in 15 C.C. of Kjeldahl’s aqueous caustic soda, 15 C.C. of copper solution are added, and then the saccharine liquid; the whole is heated for 5 minutes on the boiling water-bath, a current of hydrogen being transmitted meanwhile, L.DE K. L. DE K. Estimation of Sugar in Urine. Estimation of Starch in Yeast. By GUSTAVE BRUYLANTS and H. DRUYTS (Chem. Centr., 1899, ii, 154-155 ; from Bull. ussoc. Bely. Chin&., 1899, 2O).-The yeast is diffused in water, and the starch iodised by addition of a solution of iodine in potassium iodide. Its specific gravity is thereby increased and its tendency to ferment di- minished. Any cell-residues are removed by passing the liquid through a silk sieve, and the mixture is allowed to deposit in a cylindrical glass vessel. As soon as the blue sediment becomes covered with a thin layer of yeast, the upper liquor is decanted and water added. The washing is continued until the microscope shows only traces of yeast.Hydrochloric acid is then added until the liquidcontains 2 per cent. of acid, the mixture is heated until the starch dissolves and a small quantity of potassium sulphite added, M. J. S. Estimation of Glycogen. By ARMAND GAUTIER (Compt. Tend., 1899, 129, 701-705. Detection of Acetic Acid in Urine. By V. ARNOLD (Chern. Centr., 1899, ii, 146-147; from Wien. Klin. Toch., 12, 541).-1 gram of p-aminoacetophenone is dissolved in 80-100 C.C. of water with addition of hydrochloric acid; a 1 per cent. solution of sodium nitrite is also required. 2 vols. of the former solution and 1 vol. of the latter are mixed, and 3 vols. of urine are added with 2-3 drops of strong ammonia. All urines give a more or less intense brownish-red coloration, which, on addition of 10-12 vols.of concentrated hydro- Compare this vol., i, 81).114 ABSTRACTS OF CBEMICAL PAPERS. chloric acid, passes into purple violet if acetic acid is present, but other- wise into yellow. Dark coloured urines are first decolorised by animal charcoal. For the detection of bilirubin, an excess of aniline-p-sulphonic acid is added to 1 per cent. hydrochloric acid ; then to 4 C.C. of this liquid, mixed with 0.5-1 C.C. of a 5 per cent. sodium nitrite solution and 50 C.C. of water, there is added 4-1 vol. of the urine. I n presence of bile colouring matters, the mixture becomes orange-red, and on addi- tion of a few drops of strong hydrochloric acid, violet. p-Diazo- benzenesulphonic acid, which, as well as p-aminoacetophenone, can be employed for the detection of ethyl acetate in ether, does not give so marked a reaction with free acetic acid.Estimation of the Insoluble Fatty Acids in Butter, and the Cause of Differences in the Results. By V. MAINSBRECQ (Chew. Centr., 1899, ii, 154 ; from Rev. intern. falsijic., 12,87).-The want of agreement in the results obtained by different analysts in the estimation of the Hehner value appears to be due to differences in the time of heating and the amount of washing. From the author’s experiments the loss amounts t o 0.7 per cent. for each one and a half hours boiling. Litmus paper is not sufficiently sensitive for ascertaining the point of complete washing. I n one experiment,0*6 per cent. was removed by wash- ing, and titration of the washings with NjlO alkali and phenolphthalein proved the continuous removal of soluble acids, after litmus ceased to show any acid reaction.It is therefore recommended that there should be a general agreement respecting the time of heating, and that the washing should be continued until 100 C.C. (with phenolphthalein) requires only 0.2 C.C. of N/10 alkali. By J. LABORDE and L. MOREAU (Ann. de Z’lnst. Pasteur, 1899,13,657-664). -When a solution containing succinic acid and glycerol is evaporatedon the water-bath, a part of the succinic acid is converted into its glyceryl ester. This accounts for the low results obtained in the estimxtion of succinic acid in wines or other fermented liquids which invariably con- tain glycerol. This difficulty may be overcome thus : the succinic acid separated from the liquid is first titrated with decinormal alkali, and then the esters are hydrolysed by a known volume of decinormal alkali, and when the hydrolysis is complete the excess of alkali is titrated with deci- normal acid.Only a small part of the succinic acid present in fermented liquids exists in the free state, the greater portion being present as a salt, from which the whole of the acid maybe liberated by the addition of tar- taric acid or potassium hydrogen sulphate. Tartaric acid is, however, slightly soluble in ether, and the amount dissolved by the ether must consequently be determined. This is done by converting the neutral tartrate into the acid tartrate by adding acetic acid and alcohol to the liquid which has been titrated, evaporating to dryness, and estimating the acid tartrate thus formed by titrating with decinormal alkali.If the fermented liquid, in which succinic acid is to be estimated, contains more than 1 per cent. of sugar, it is evaporated to a syrup, 10 to 20 C.C. of alcohol are added, and the succinic acid separated by repeated extraction with ether. M. J. S. M. J. S. Estimation of Succinic Acid in Fermented Liquids. H, R. LE S.ANALYTICAL CHEMISTRY. 115 Colour Reaction for Tartaric Acid and its Compounds. By JULES WOLFF (Chew. Centr., 1899, ii, 569; from Ann. chim. anal. uppZ., 4, 263).-Attention is called to a forgotten test for tartaric acid. A few centigrams of resorcinol are heated in a porcelain capsule with a little sulphuric acid until fumes are given off and the tartrate is added, when an intense dark red coloration is obtained.Detection of Urochloralic Acid in Urine after Administra- tion of Chloral Hydrate, especially in Gases of Poisoning. By DIOSCORIDE VITALI (Chem. Centr., 1899, ii, 147; from Boll. Chm. Farm., 1899, 38, 377).-The urine is concentrated to half its volume, and treated with a small excess OF lead acetate and ammonia to feeble alkaline reaction. The precipitate of lead urochloralate is washed, then warmed with dilute sulphuric acid, and the filtrate cohobated f o r half an hour with zinc powder and sulphuric acid. The trichloro- ethyl alcohol resulting from the hydrolysis of urochloralic acid is thereby reduced to ethyl alcohol, which, after removal of the zinc by sodium carbonate, can be distilled over lime and recognised by odour, inflammability, conversion into iodoform, and into acetaldehyde (which may further be confirmed by Rimini’s reaction), m d by Vitali’s reaction (treatment with carbon disulphide, potash, ammonium molybdate, and excess of dilute sulphuric acid, which produce the red colour of molybdenum xan thate).Modified Soxhlet Apparatus for the Extraction of Fats from Liquids. By ALONZO ENGLEBERT TAYLOR (Amer. J. Physiol., 1899, 3, 183--185).-The apparatus, which is figured and fully described, is stated to extract f a t from solutions much more effectively than the Soxhlet apparatus, or the modifications of t h a t instrument which have been hitherto devised. By W. G. INDEMANS (Chews. Centr., 1899, ii, 495 ; from Ned.Ilijds. Pimrm., 11, 219-226).-The chief points in butter analysis are, A , The nJmber of molecules in a definite quantity of fat. C, The solubility of the fatty acids in water. The density, the electric resistance, the saponification number, the refractomer number, and the critical temperature of solution depend on A ; the Hub1 and Asboth’s numbers depend on B ; the melting and solidifying points depend on A and B, and the Reichert-Meissl and the Hehner-Angel1 numbers depend on C. As regards the number of molecules and the small amount OF olein, butter-fat is surpassed by Ceylon oil, as it is also. in density, electric resistance, and refractomer indication. The chief point of difference of butter from its surrogates, however, consists in the high percentage of fatty acids soluble in water and of the volatile acids ; the latter vary with the season. L.DE K. By C. A. BROWNE,.~~~. (J. Amer. Chem. Soc., 1899, 21, 975--994).-The so-called rancidity of fats is a much more complex phenomenon than hitherto believed. As the rancidity of butter-fat increases, a decided increase in the acid, saponification, and Reichert numbers takes place ; also a slight Neither oxalic nor citric acid gives the reaction. L. DE K. M. J. S. W. D. H. Butter and Butter Substitutes. B, The amount of olein. Rancidity in Butter-fat.116 ABSTRACTS OF CHEMICAL PAPERS;, increase in the ether number and a very marked decrease in the iodine absorption. Finally, an increase is noticed in the acetyl number and a decrease in the percentage of soluble acids and glycerol.The physical constants of butter-fat, such as the specific gravity, refractive index, and heat of combustion, are aIso affected by rancidity. L. DE K. The Becchi Test. By ALPH. VAN ENGELEN (Chem. Centr., 1899, ii, 147-148 ; from Rev. irttern. falsiJic., 12, 90).-Several variations in the mode of applying this test are in use. The author shows that in applying it to the free fatty acids (Millieau’s method) the presence of small quantities of free mineral acid is prejudicial ; the fatty acids must therefore be thoroughly washed with hot water, and the form of the test in which the reagent is acidified with nitric acid should be abandoned. To ascertain whether cotton-seed oil could be detected in the butter of cows fed with cotton-seed cake, two reagents were em- ployed.The first consisted of 1 gram of silver nitrate dissolved in the smallest quantity of water and mixed with 200 C.C. of absolute alcohol ; the second, of a solution of 1 gram of silver nitrate, 250 C.C. of 98 per cent. alcohol, 40 C.C. of ether, and 0.2 C.C. of nitric acid. The fat was dissolved in an equal volume of amyl alcohol, mixed with 1 C.C. of the reagent, and heated in the water-bath for 15 minutes. With the first reagent, the butter gave a coffee-brown, with the second a lemon-yellow, coloration. These reactions, and others obtained with the fatty acids, are not regarded as decisive of the question. M. J , S. Becchi’s Test for Cotton-seed Oil. Ey PAUL SOLTSIEN (Chenz. Centr., 1899, ii, 539 ; from Zeit. ofentl. Chem., 5,306-308).-The Becchi silver reduction reaction is chiefly due to the presence of sulphur, this occurring in decided amount in samples of cotton oil which have been extracted from the seed by means of light petroleum ; oil obtained by pressure contains but a trace of sulphur, and it loses this on heating a t 200’.I n the original Becchi test, it mas recommended that some rape oil should be added to intensify the reaction; this must, however, By WILHELM KERP (Chem. Centr., 1899, ii, 228-229 ; from Zeit. Unters. Nahr.-Genussm., 2, 473).-Commercial f urf uraldehyde requires to be purified by two distillations under reduced pressure ; a dilute alcoholic solution keeps well in completely filled bottles in the dark. The production of a violet coloration with hydro- chloric acid alone depends both on the strength of the furfuraldehyde solution and on the amount of acid added.When the solution is sufficiently dilute and the quantity of acid small enough, the violet colour is not produced immediately, whilst the sesame oil reaction is both more rapid and more sensitive. The concentration of the acid is also of importance. Acid of sp. gr. 1.127 gives the Baudouin reaction, but produces no violet colour in the absence of sesame oil ; a stronger acid (1.16) may be used in doubtful cases, Heating must be avoided. The lower limit of the reaction is a t a dilution of 0.2 per cent. of previously be heated a t 150’ t o desulphurise it. L. DE I(. Baudouin’s Reaction.ANALYTICAL CHEMISTRY. 117 Mesame oil : i t follows that 2-2.5 grams of the oil can be detected in a kilogram of butter.The method cannot, however, be used as a quanti- tative colorimetric one. The behaviour of the red sulnstance with various solvents is described, and some notes on its absorption spectrum are given, Colour Tests for Sesam6 Oil: Three New Gharacteristio Tests. By J. BELLIER (Chem. Centr., 1899, ii, 453-454; from Ann. chim. anal. appZ., 4, 217--220).-The known tests are criticised. Behrens’ reagent, a mixture of equal parts of sulphuric and nitric acids, is said to give better results i f made of 100 C.C. of sulphuric acid, 10 C.C. of nitric acid, and 50 C.C. of water. As new tests are proposed : Ammonium vu,nadate.-lOO C.C. of sulphuric acid, 50 C.C. of water, and 2 grams of ammonium vanadate ; this, on shaking with sesame oil, gives a green colour, gradually becoming blackish. FormuZdehyde.-lOO C.C.of sulphuric acid, 50 C.C. OF water, and 10 C.C. of 40 per cent. formaldehyde. Equal volumes of this reagent and sesame oil gives, on shaking, a permanent bluish- black colour; an admixture of 1 per cent. of sesame oil in olive oil may thus be detected. 2 C.C. of the suspected oil is put into a test-tube, 2 C.C. of a saturated solution of resorcinol in benzene are added, and then 2 C.C. of nitric acid of sp. gr. 1.38 free from nitrogen oxides. I n the presence of sesame oil, an intenseviolet- By M. WIXTGEN Ciiern. Centr., 1899, ii, 454-455 ; from Hygien. Rdsch., 9, 753-757). -A controversy with Peerenboom on the subject of the estimation of formaldehyde in the air by Romijn’s process (Abstr., 1898, ii, 166).Detection of Aldehydes in Alcohols. Ey CONSTANTIN I. ISTRATI (Chem. Centr., 1899, ii, 148-149 ; from Rev. intern. falsiJic., 12, 91). -Barbe and Janvier’s method (Ann. chinz. and. appl., 1, 325), a s improved by the author, consists in mixing exactly 2 C.C. of the alcohol with 0.2 C.C. of a saturated. alcoholic solution of the special reagent, and pouring 1 C.C. of sulphuric acid down the side of the test- tube. The colours produced are observed immediately, then half a n hour later with gentle shaking, then after thorough mixing, and, finally, after addition of 10 C.C. of water. The colours produced by such reagents as pyrogallol, a- and P-naphthols, phenylhydrazine, quinol, guaiacol, &c., with various aldehydes are given. Estimation of Carvone in Volatile Oils.111. By F. W. ALDEN and S. NOLTE (Pharm. Archives, 1899, 2, 81-91).-In a 500 C.C. flask, fitted with a reflux condenser, 10 grams of the oil, 25 C.C. of alcohol, 5 grams of hydroxylamine hydrochloride, and 6.5 grams of sodium hydrogen carbonate are boiled together for a-4 hour on the water-bath, only a small surface of the flask being heated; 25 C.C. of water are then added, the alcohol and much of the limonene distilled off on the water-bath, and then steam is passed through, the distillate being collected in fractions of 5-10 C.C. in test-tubes until it is seen to contain crystalline carvoxime. The last fraction and the tube of tha M. J. S. Besorcinol. blue or greenish-blue coloration is obtained. L. DE K. Estimation of Formaldehyde in the Air.With care, this process gives satisfactory results. L. DE K. M. J. S.118 ABSTRACTS OF CHEMICAL PAPERS, condenser are rinsed back into the flask with hot water ; when cold, the solid cdrvoxime is filtered off and drained by aid of a filter pump, and finally dried in the air. Should any oxime separate from the previous fractions of the distillate during the next day or so, it is added to the main quantity. The whole is then heated for an hour in a tared glass dish on the water-bath over an opening 43 mm. in diameter, and weighed; 0.100 gram is added, to correct for loss by volatilisation during the heating, and the sum is multiplied by 0,909, to calculate the equivalent amount of carvone. The error of the method amounts to severdl units per cent.; the influence on it of varions modifications of the conditions of the experiment was in- ves tigated, C. F. B. Examination of Resins. X. Storax. By KARL DIETERICH Chem. Centcl.., 1899, ii, 541 ; from Pharm. Centi..-Hcdle, 40, 423-428, 439-443. Compare Abstr., 1898, ii, 58) -When testing storax, it is preferable to work on the crude sample instead of using the alcoholic extract. To determine the acidity number, 1 gram of the sample is dissolved in 100 C.C. of cold 96 per cent. alcohol, and titrated with N/2 alcoholic potash, using phenolphthalein as indicator. The saponification number is found by dissolving 1 gram of the sample in 20 C.C. of NIB alcoholic potash, and 50 C.C. of benzene, and, after 24 hours, titrating the excess of alkali with A72 sul?huric acid.The following figures may be held to indicate the average composition of genuine storax : Water, not over 30 per cent.; ash, not over 1 per cent. ; soluble in alcohol, not less than 60 per cent.; insoluble, not more than 3 per cent. Acidity nuEber, 55-75 ; ethw number, 35-75 ; saponifica- Testing Storax. By FERD. EVERS (Chem. Centr., 1899, ii, 594 ; from P?Larrn. Zeit., 44, 592-593).-The author objects to Dieterich’s proposal of applying tests to the crude resin (see preceding abstract). Examination of Resins. XI. Anime, Caranna, .Dammar, LaDdaQurn, Mastic, Sandarac, Tacamahaca, and Turpeth. By KARL DIETERICH (Chem. Centr., 1899, ii, 541; from Pharm. Centr.- Halle, 40, 453-457).-A table giving the acidity, ether, and saponi- fication numbers of the following resins: East and West Indian anime, caranna resin, several varieties of dammar, dammar adulterated wihh colophony, several varieties of mastic, labdanum, sandarac, tacamahaca resin, and turpeth resin.The acidity numbers of dammar and sandarac should be determined by dissolving 1 gram of the sample in 20 C.C. of A72 alcoholic potash, adding 50 C.C. of benzene, and, after 24 hours, titrating the excess of alkali with N/2 sulphuric Examination of Resins. XII. Ammoniacum, Bdellium, GaXioan >am, Oposonax and Sagapenurn. By KARL DIETERICH (Chew. Centr., 1899, ii, 542-543 ; from Pltccrin. Centr.-Hcclle, 40, 467--471).-A table showing the acidity, ether, and saponification tion number, 100-140. L. DE K. L. DE K. acid. L. DE K.ANALYTICAL CHEMISTRY, 119 numbers of gum ammoniacum, bdellium, gal banum, opoponax, and sagapenum.The acidity numbers of ammoniacum and galbanum are obtained by boiling 1 gram of the finely powdered sample with 50 grams of water and 100 grams of alcohol for 15 minutes in a reflux apparatus, 75 grams of the filtrste are then mixed with 10 C.C. of N/2 alcoholic potash, and after waiting for 5 minutes, the excess of alkali is titrated with N/2 sulphuric acid. The saponification number is found by using the author’s cold benzene process. The other resins are treated as follows : 1 gram of the sample is heated for 15 minutes with 30 C.C. of water, 50 C.C. of alcohol are added and the boiling continued for the same time; the liquid is then at once titrated with N/2 alcoholic potash. The saponification num- bers are found by boiling 1 gram of the sample first wit,h 30 C.C.of water and then adding 25 C.C. of N/2 alcoholic potash, the excess of which is afterwards titrated. L. D E K . Detection of “Saccharin” in Beer, By R. ROSSING (Chem. Centr., 1899, ii, 274; from Zeit. ofentl. Chem., 5, 2W-208).-The beer is acidified with phosphoric acid and shaken with an equal bulk of ether. The residue left on evaporating the ethereal extract is mixed with a little sand, dried in the water-oven, the powdered mass extracted with absolute ether, and an equal volume of benzene is added. The filtrate is then evaporated on a watch glass and the residue dried over sulphuric acid, saccharin ” is thus obtained The in white crystals of characteristic sweet taste. L. DE K. Colour Reaction for the Detection of Benzidine and Tolidine.By JULES WOLFF (Chem. Centr., 1899, ii, 569; from Ann. chim. anal. appZ,, 4, 263--264).-The substance is dissolved in a little glacial acetic acid, the liquid diluted with water, and lead dioxide suspended in water added; a splendid blue coloration is developed which is permanent in the cold. If other organic acids are used, the colour is not so intense. With a small amount of bromine, a blue coloration forms, but with excess a blue precipitate is obtained Mineral acids prevent the reaction with either lead dioxide or bromine. L. DE K. Simple Alkalimetric Method for the Estimation of Salt- forming Alkaloids with the Aid of Phenolphthalein as Indi- oator. By HARRY M. GORDIN (Phcc~m. Archives, 1899, 2, 313-318, and Ber., 1899, 32, 2871--2876).-The periodides (Abstr., 1899, i, 89) or mercuriodides (Prescott, Abstr., 1882, 664) of alkaloids, precipitated respectively by Wagner’s and by Mayer’s reagent, contain an indefinite amount of iodine or mercuric iodide, but apparently always a definite amount of hydrogen iodide, a s represented by the formula, mAlk., HI + nT, or mAlk., HI + n,Hg12.This fact may be utilised for the estimation of alkaloids by titration. About 0.2 gram of anhydrous morphine is dissolved in 30 C.C. of standard hydrochloric acid (about hT/20) in a 100 C.C. flask, Wagner’s reagent (containing about 1 per cent. of free iodine and 18 of potassium iodide) added120 ABSTRACTS OF CHEMICAL PAPERS. gradually, the whole being shaken well after each addition, until further addition produces no further precipitate, when the contents are diluted t o 100 C.C.and again shaken well. After the precipitate has settled thoroughly the liquid is filtered, 50 C.C. of the red filtrate decolorised by the gradual addition of 10 per cent. sodium thiosulphate solution, a few drops of phenolphthalein added, and the excess of acid titrated with NIB0 potassium hydroxide. It is found that 1 C.C. of the acid is removed by 0,0137 gram of morphine; the equivalent quantities are, of hydrastine, 0.0184 ; strychnine, 0.0160 ; caffeine cryst., 0.0102 ; cocaine, 0.0146, and atropine 0,0139 gram. These alkaloids were then estimated in the same way, the factors just quoted being used in the calculation; the amounts found differed by about 1 per cent.only from those taken. Of Mayer’s and Wagner’s reagents that one is used which effects the more com- plete precipitation ; if they are equal in this respect, Mayer’s reagent is to be preferred, as the precipitate i t produces settles more easily; when it is used, too, the subsequent addition of thiosulphate is unnecessary. Caffeine requires 50 C.C. of acid; colchicine cannot be estimated by this method, nor can berberine, which does not carry down any acid. Alkaloid resembling Aconitine found in a Corpse. By MECKE (Chem. Centr., 1899, ii, 256-257 ; from Zed. ofentl. Chem., 5, 204-206. Compare Abstr., 1899, 31 l).-A ptomaine with properties very similar to those of aconitine has been found in a corpse. This alkaloid is extracted from alkaline. solutions by ether, and gives the general reactions of the alkaloids, forming with phosphotungstic acid a white, with phosphomolybdic acid a yellow, and with a solution of iodine in potassium iodide a brownish precipitate.I t gives a faint turbidity with mercuric chloride, and with concentrated sulphuric acid it forms, after a time, a reddish-violet coloration, which changes to a darker shade on warming. It remains colourless with dilute sulphuric or phosphoric acid, but becomes violet on evaporating. The yellowish solution in nitric acid, when evaporated, leaves a yellow residue which turns orange when moistened with potassium hydroxide solution. Even very small quantities instantly reduce potassium ferricyanide, and with Frohde’s reagent the alkaloid gives a greenish coloration, changing t o yellowish-brown on warming.It is not precipitated by tannic acid, and after adding bromine water it is nDt attacked by concentrated sulphuric acid ; potassium dichromate has also no action on it. The violet coloration obtained by treating aconitine with phosphoric acid or concentrated or dilute sulphuric acid is only slowly formed, and differs from that of the corpse alkaloid both in shade and infen- sity. Delphinine, although stated by Otto to give a violet coloration with phosphoric acid, was found to produce only a brownish colora- tion, and its behaviour with sulphuric acid and bromine is not like that of the ptomaine. The present methods of testing for acouitine are only to be trusted when considerable quantities are present and decomposed animal matter absent.Hilger and Tamba’s reaction with phosphoric acid is C. F. B.ANALYTICAL CHEMISTRY, 121 not available in presence of ptomaines, and, moreover, is scarcely characteristic of aconitine, for the different commercial varieties give different reactions. Urine which is several days old, when evaporated with phosphoric acid, also gives the same violet coloration as aconitine. The reactions with concentrated sulphuric acid, potassium ferricyanide (Brouardel-Boutmy’s reaction), and FI ohde’s reagent are also un- trustworthy. According to Jurgeos, characteristic crystals of aconi- tine potassium iodide are obtained by dissolving the alkaloid in a drop of dilute acetic acid, evaporating with a grain of potassium iodide, and washing with water, but in many cases this test gave only amorphous precipitates or the tabular crystals of pseudoaconitine. E.W. W. Delicate Test for Caffeine. By ANDREARCHETTI (Chem. Centr., 1899, ii, 453; from Boll. Chim. Fkwrn., 38, 340--341).--A solution of potassium ferricyanide is mixed with half its volume of nitric acid and heated to boiling. On adding an aqueous solution of caffeine a deposit of prussian blue will be noticed. The reaction is aIso given by other xanthine bases and uric acid, but only very feebly. L. DE K. Estimation of Cornutine. By FI~ANZ MUSSET (Chem. Centr., 1899, ii, 323 ; from Phnrm. Centr.-Halle, 40, 396).-The ethereal solution obtained according to Keller’s directions contains, besides the cornutine, a resinous matter causing high result. By treating the weighed residue repeatedly with water containing 0.5 per cent.o€ hydrogen chloride, the cornutine dissolves and the insoluble resin By RUDOLF KOBERT (Chem. Centr., 1899, ii, 149-150 ; from Sondembdruck aus Apoth.-Zeit., 14, No. 37).-The reagent proposed by the author’s pupil Marquis is prepared by mixing 2-3 drops of formaldehyde solution with 3 C.C. of concentrated sulphuric acid. The pulverised alkaloid is added t o this in a porcelain basin. Morphine gives a t first a purpie- red, passing through violet to almost pure blue ; i f partially protected from the air by placing in a test-tube, the blue colour remains for a long time. Dionine gives ft deep blue, codeine a violet, heroine a reddish-violet turning to bluish-violet, peronine, a permanent reddish- violet, rnethylphenomorpholine an intense red.The absorption spectra of these coloured solutions show small differences. may be weighed and allowed for. L. DE K. Recognition of Morphine and its Derivatives. M. J. S. Estimation of Chloral Hydrate and Morphine in Organs. By RUSSWURM (Chem. Centr., 1899, ii, 794 ; from Pharm. Centr.-lZaZZe, 40, 543--544).-The united distillates from a n acid and an alkaline distillation, containing therefore both chloral hydrate and chloroform, is diluted with alcohol to a definite bulk, and the chlorine estimated by boiling a n aliqnot part with alcoholic potash in a reflux apparatus, neutralising with nitric acid, and titrating with silver nitrate. Morphine is estimated by first extracting the ammoniacal solution with hot arnylic alcohol, which is, in turn, shaken with dilute hydro- chloric acid.According t o the author, the alkaloid may now be122 ABSTRACTS OF CHEMICAL PAPERS, obtained by supersaturating the liquid with ammonia and agitating with chloroform; this is then concentrated to a few C.C. in a small weighed beaker, and the morphine completely precipitated by adding 50 C.C. of light petroleum of low boiling point. L. DE K. Estimation of Santonin in the Flower Buds of Artemisia Maritima. By KARL THAETER (Arch. Phccrrn., 1899,237,626-632). -The author defends his method (Abstr., 1898, ii, 59) against Katz’s criticisms (Arch. Phurrn., 1899, 23’7, 245). The extraction with ether must be continued for 12-18 hours. Before the magnesia is added, the solution should be evaporated to dryness, and the residue powdered ; after mixture, the whole is moistened evenly with water and dried as rapidly as possible ; there is then little fear that any of the santonin will be converted into magnesium salt.C. F. B. Estimation of Urinary Indican. By EYVIN WANG (Zeit. physiol. Chern., 1899, 28, 576-584. Compare Abstr., 1898, ii, 659 ; 1899, ii, 458)-The author defends his method against the criticisms of Bouma (hbstr., 1899, ii, 568). H e holds that the method of purifica- tion described is necessary and correct, for the reddish-brown pigment removable by alcohol does not originate from indigo. By HENRI IMBERT and A. ASTRUC (J. Pharm., 1899, [vi], 10, 392-395).- Cacodylic acid is neutral to methyl-orange, but behaves as a monobasic acid towards phenolphthalein, whereas pure sodium cacodylate is alka- line to methyl-orange and neutral to phenolphthalein.The commercial salt, however, is always acid to phenolphthalein, due t o the presence of free acid. 1.6 grams of sodium cacodylate are dissolved in 100 C.C. water and to 10 C.C. of this solution carefully neutralised, using phenol- phthalein as indicator, decinormal hydrochloric acid or sulphuric acid is then added until the liquid is neutral to methyl-orange. The number of C.C. of acid required multiplied by ten gives the percentage of pure sodium cacodylate. W. D. H. Volumetric Estimation of Sodium Cacodylate. H. R. LE S. Separation of Proteids from Flesh-bases by meansof Chlorine and Bromine. By HARVEY W. WILEY (Cliem. Centr., 1899, ii, 586 ;, from Chem. News, 80, 88--89).-The freshly powdered dry material, from which the fat has been removed by ether, is first extracted with cold and then with hot water and the extract filtered.The amount of proteids insoluble in water is calculated by multiplying the difference between the amount of nitrogen in the original material and that in the insoluble portion by 6.25. The filtrate, after acidify- ing with hydrochloric acid, is oxidised by repeatedly shaking with bromine. After remaining over night, the precipitated proteids are filtered and washed with water. Theamount of flesh bases is obtained by multiplying the difference between the total amount of nitrogen and the sum of the amount of nitrogen in the soluble and in the insoluble proteids by 3.12. Liebig’s extract was found by this method to contain 8.92 per cent.of proteids, previous determinations having given lower results. E. W. W.ANALYTICAL CHEMISTRY. 123 Source of Error in Testing for Albumin in Urine. By E. DEROIDE and OUI (Chent. Centr., 1899, ii, 570 ; from Ann. chim. anal. appZ., 4, 261--262).-Before being tested for albumin, the urine, if not quite clear, should be filtered ; if, however, the turbidity i s caused by micro-organisms, the ordinary filter fails and n so-called Kitasato filter must be employed. It has been proposed t o clarify the urine by means of calcined magnesia, but the authors find t h a t this also precipitates mosc of the De- tection of Blood. By CASIMIR STRZYZOWSKI (Chem. Centr., 1899, ii, 140, 225 ; from Oesterr. Chem. Zeit., 1899, 2, 305, 333-325).-Largely a repetition of earlier work.Ox-blood freed from salts, cholesterol, and fat was employed. None of Husson’s results can be confirmed, except those relating to the formation of bromine and iodine compounds of haematin. Axenberg’s mercury and manganese hzmatin compounds are non-existent. Buffalini’s method (Abstr., 1886, 184) must also be rejected, since the halogens (iodine, however, the least) destroy the colouring matter of blood. The results olscained by Bikfalvi (Abstr., 1887, 165) by adding acetic acid and a haloid salt of a n alkali metal to dialysed blood, appear to be perfectly correct. The so-called hRmidin crystals obtained by Dannenberg and others (Abstr., 1887, 408) are nothing but sulphur. Teichmann’s method simplified as follows will detect 0.000025 gram OF blood.To the dried substance on a microscope slide with cover, acetic acid mixed with 1/50 vol. of hydriodic acid is added and the object is heated for a, short time; well formed black crystals are obtained. Another very sensitive reagent is a mixture of 10 C.C. of glycerol of sp. gr. 1.26 with 2-3 drops of concentrated sulphuric acid. Blood, when heated with n very small quantity of this reagent on a n object glass and examined with a magnifying power of 400 diameters, shows small, dark needles of haematin sulphat e. By MECKE (Chem. Centv., 1899, ii, 321-322 ; from Zeit. ofentl. Chern., 5, 231-232).- Margarine melted at 45Ois shaken with half i t s volume of a 1 per cent. solution of salt. The aqueous liquid is freed from f a t by agitating with light petroleum and then cleared by alumina-cream.The filtrate is diluted with 5 times its bulk of water, when if yolk of egg is present in the sample, a n abundant, flocculent precipitate of vitellin will be obtained. Or the margarine may be dissolved i n light petrol- eum, the undissolved matter washed with ether, and then tieated By LUDWIG VON ~ L D O R (Chem. Cent?.., 1899, ii, 728-729 ; from Bed. Klin. Woch., 36, 764-767, 785-787).-Any albumin is first removed by precipitation with triozhloroacetic acid. 6-10 C.C. of the urine a r e acidified with 1-2 drops of hydrochloric acid and precipitated with slight excess of 5 per cent, solution of phosphotungstic acid. The precipitate i s repeatedly whirled in a centrifugal apparatus with absolu l e alcohol albumin.L. DE K. Microchemistry of C r y s t a l l i n e Haematin Compounds. M. J. S. Detection of Yolk of Egg in Margarine. with salt solution, L. DE K. Detection of Albumoses in Urine.124 ABSTRACTS OF CHEMICAL PAPERS. until all colouring matter is extracted and then suspended in water and mixed with aqueous sodium hydroxide. A blue coloration is noticed, which, however, fades on exposure t o the a i r ; t h e colourless liquid is then treated, as usual, with copper sulphate. By ROBERT HENRIQUES (Zeit. angew. Chem., 1899, 802-804. Compare Abstr., 1893, ii, 399, and 1895, ii, 96, 191).-Estimation of the total Sulp?mr and Metals. The process does not materially differ from the former one, being carrred out by oxidising with nitric acid, neutralising with excess of soda, and fusing the dry mass ; the aqueous solution of this will contain the sulphur as sodium sulphate, whilst the metallic compounds remain as oxides or carbonates in the insoluble residue. For t h e detection and estimation of vermilion, which is often present in small quantities, the sub- stance is digested with nitric acid, which gradually decomposes and dissolves the mercury sulphide ; after expelling the bulk of the acid and diluting with water, the liquid is precipitated with hydrogen sulphide and the mercury looked for in the metallic sulphides so ob- tained. Estimation of “Fuktis” in Vulcanised Wares.-It is now recommended that the mass which has been exhausted with alkali shall be removed from the filter before drying t o constant weight. Estimation of Unsaponijcdde Oils in Yulcanised Wares.-The mass, after being extracted with alkali, dried, aud weighed, is again extracted with ethe 1, the loss in weight representing the unsaponifiable matter, such as rosin-oil, paraffin, &c. Estimation of ‘‘ Faktis ” in Non-vulcanised Wares.-The old process was not always satisfactory, and the following method has been sub- stituted for it : 5 grams of the rasped sample is covered with 25 C.C. of beuzene and heated on a boiling water-bath for an hour, the Erlen- meyer flask being sttached to a reflux condenser; the whole is then left over night. The mass may now be successfully attacked by alcoholic soda. Estimation of Unscbponv&dle Oils in. Non-vulcunised Wares.-Boiling acetone is substituted for ether and after evaporating the solvent, the residual unsaponifiable matter is weighed. Bstirnation of Carbonic Anhydride.-Attention is called to the importance of estimating the carbonic anhydride present in combina- tion with calcium, lead, zinc, &c. When dealing with non-vulcanised wares, the sample should first be repeatedly extracted with boiling nitrobenzene to remove the bulk of the rubber so as to facilitate the L. DE K. Analysis of Rubber Wares. action of acids. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9007805106

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

125 General and Physical Chemistry. Indicee of Refraction of Metals. By EDMOND VAN AUBEL (Zeit. phyeikaZ. Chenz., 1899, 30, 565--566).-A comparison of the indices of refraction of metals obtained by calculation from the molecular refraction of salt solutions with those obtained directly by Drude (Ann. Phys. Chem., 1890, [ ii], 37, 537). The values shorn fair agree- ment in some cases, but in others are of a different order of magnitude, for example, silver, 2.37 and 0.203. Kundt’s law, which states that the product of the index of refraction and electrical conductivity is constant, does not hold for either the direct or calculated values. L. M. J. Colour Changes of Illuminated Substances. By HEINRICH BILTZ (Zeit. physikal. Chem., 1899, 30, 527--528).-Marckwald has given an account of these changes to which he has applied the term ‘phototropy’ (this vol., ii, 2).To the sensitive compounds there mentioned may be added the hydrazone of benzaldehyde and cuminil- osazone, anisilosazone, and piperilosazone. These compounds are yellow or greyish-yellow, but on exposure to light become red or orange in about an hour, returning again to the original colour in the dark. Benzilosazone, salicylosazone, and vanillylosazone are, however, not phototropic. L. M. J. Chemical Effects produced by Becquerel Rays. By P. CURIE and SBLODOWSEA CURIE (Compt. rend., 1899, 129, 823-825). -The radiations from highly radio-active barium salts convert atmo- spheric oxygen into ozone, and the latter is readily detected in the air of closed flasks containing the radio-active compounds.The com- pounds producing this result are all luminescent and highly radio- active, but their effect on oxygen seems to be connected with radio- activity rather than with luminescence. The radiations also affect glass, and the vessels containing the salts gradually become deep violet and almost black, especially where the glass is in contact with the salt, even if the glass does not contain lead. The intensity of the coloration and the time required f o r its production depend on the intensity of the radio-activity. Barium platinocyanide, under the influence of these radiations, be- comes dark coloured and less fluorescent, but regains its original colour when exposed to sunlight, and at the same time becomes phosphorescent. Villard has obtained similar results with Rontgen rays (compare also Giesel, Ann.Phys. Chern., 1899, [ ii], 69, 91). C. H. B. Chemical Action of the X-Rays. By P. VILLARD (Compt. rend., 1899, 129, 882-883. Compare preceding abstract).-The darken- ing of the wall of a Crookes’ tube, which has been working for some time, is due to the reduction of the lead present in the glass to the metallic state by the cathode says, If these are cut off by a thin VOL, LXXVIII, ii. a126 ABSTRACTS OF CHEMICAL PAPERS. sheet of aluminium, which is transparent to the X-rays, the glass is coloured violet. This is due to the oxidising action of the X-rays, and the coloration is no doubt due to the manganese present in the glass. H. R. LE S. Phosphorescence Phenomena produced by the Radiations from Radium.By HENRI BECQUEREL (Compt. rend., 1899, 129, 912-917).-The author finds that, in general, substances which phosphoresce when exposed to the action of ultra-violet rays, or of the X-rays, also become luminous under the influence of the radiation emitted by radio-active barium chloride ; the order of the relative intensities of the luminous effects is, however, not the same in the two cases. The phosphorescence excited by radium in certain minerals shows great persistence ; fluorite, for example, remains luminous 24 hours after the influence of the radium has ceased. When phosphorescent substances, which have been heated and thus rendered incapable of phosphorescence, are subjected to the action of an electric spark or t o the prolonged action of the violet and ultra- violet rays, they are found to possess the property of exhibiting phosphorescence on heating.Fluorite, in these circumstances, emits a greenish-bIue light, and the author finds that this mineral, after heating and exposing it to the radium radiation,.gives out when heated a greenish-blue light which spectroscopic analysis shows to be identical with that produced by the electric spark. Influence of the Magnetic Field on the Rays Emitted by Radio-active Substances. By HENRI BECQUEREL (Compt. rend., 1899, 129, 996--1001).--The radio-active substance used was barium chloride, and the influence of the magnetic field on the rays emitted by it was investigated by means of a fluorescent screen or a photographic plate. The author confirms the observations of Meyer and von Schweid- ler (PhysikaZische Zeitschrift, No.10, 1 13-1 14) that some of the rays follow the direction of the magnetic field and are undeflected, whereas those in a plane a t right angles to the magnetic field are deflected. The results obtained point to a close relationship between cathodic rays and the rays emitted by radio-active substances. Radiation of Radio-active Substances. By HENRI RECQUEREL (Compt. rend., 1899, 129, 1205-1207). Action of the Magnetic Field on Becquerel Rays : Deflected and Undeflected Rays. By P. CURIE (Compt. rend., 1900, 130, 73-76), Penetration of Undeflected Becquerel Rays. By SKLODOWSKA CURIE (Compt. rend., 1900, 130, 76-79).--The rays emitted by a very active specimen of Curie’s polonium are not deflected in the magnetic field ; the experi- ments were made about a month after the preparation of the sub- stances, and the results are contrary to those obtained by Giesel with freshly prepared polonium compounds (this vol., ii, 19).A portion of the rays emitted by radium are deflected by the electro- magnet ; these behave like Rontgen rays, their velocity is of the same order, and their penetrating power increases with the thickness of the absorbent layer ; the undeflected rays correspond with those from T. H. P. H. R. LE S.GENERAL AND PHYSICAL CHEMISTRY. 127 polonium, and their penetrating power varies in the opposite sense t o that of the deflected rays. Electromotive Behaviour of Chromium. By WILHELM KITTORF (Zeit. physikal. Chenz., 1899, 30, 4Sl-507).-The peculiarities in the electromotive behaviour of chromium are further investigated (com- pare Abstr., 1898, ii, 363), and the author advances many arguments in support of the view that the inactive state cannot be due to the formation of a film of oxide.Owing to the existence of the different classes of chromium compounds, the metal may exhibit any potential between the two extreme values; the highest value corresponds with the active state in which chromium gives rise to the lower compounds. This active state is assumed when the metal is placed in sulphuric, oxnlic, hydrofluosilicic, or the halogen acids, at temperatures which are lower the more concentrated the acid ; it is also active in fused halogen salts or in their boiling solutions. The metal becomes inactive when immersed in solutions containing free chlorine or bromine, or in strong oxidising agents.The limiting values, however, last but a short time after removal from the liquids, the metal speedily assuming an intermediate state ; the most stable active state is that produced by fused halogen salts. The activity is also lowered in all cases when the metal serves as an anode for a current produced either externally or internally, and, with sufficiently strong currents, chromic acid is pro- duced, either by decomposition of water by anion and subsequent union of the metal and oxygen, or by the intermediate formation of a compound of the anion and chromium. When the metal is used as a cathode, it rapidly assumes the active state. The author points out that Berzelius and Wohler had previously observed differences in chromium under different conditions.G. T. M. L. M. J. Influence of the Addition of a Salt with one similar Ion on Electromotive Force and Diffusion Velocity. By RICHARD ABEUG and EMIL BOSE (Zeit. physikal. Chew&., 1899, 30, 545-555)- A theoretical investigation of the above question. It is shown that if u and v are the cation and anion velocities, the addition of a salt with a similar cation or anion causes change of velocity of dif- fusion, tending to the values V. (u +v)/2v or V. (u+v)/2u respectively. I n acids, the cation has a velocity about six times that of the anion, whilst in bases the velocity of the OH anion is about three times that of the cation. The velocity of diffusion of an acid or of a base hence is greatly increased by the addition of one of its neutral salts, and ex- periments are recorded in verification of this.Similarly, owing to the slight velocity of MnOk and (21-0, ions, the diffusion of potassium permanganate or potassium chromate is decreased by the addition of potassium chloride. The increase of the catalytic action of an acid caused by the addition of i t s salts may be due t o the increased mobility of the hydrogen ion. Molecular Susceptibility of the Salts of the Rare Earths. By H. DU BOIS and OTTO LIEBKNECHT (Bey., 1899,32,3344-3348).- In determining the molecular susceptibility of a paramagnetic salt, L. M. J, 9-2128 ABSTRACTS OF CHEMICAL PAPERS, the substance is added to water until its paramagnetism just counter- balances the diamagnetism of the solvent; when this is the case, the meniscus of a portion of the solution contained in a capillary tube placed between the poles of an annular electromagnet remains stationary, whereas i t moves backwards or forwards if the solution is either para- or dia-magnetic.The molecular susceptibility of the salt is then calculated from the equation i,, = - ?n.M,/M,.x where m is the molecular weight of salt, Mw/M, the ratio between the weights of water and salt in the non-magnetic solution, and x the specific suscepti- bility of water a t 18'; the exact value of this constant is not known, and the number 0.75 x is employed as an approximation; the results, however, may be expressed in the form -imlx, and this expression is independent of the constant. The results obtained with the salts of eight of the rare earths are tabulated in the following manner : a,.-- Atom. wt. Mol. wt. Mw. - Salt, RCI,. (0=16). m. M, a: a,. 1. Yttrium chloride ......... 89.0 195.35 1.41 276 0*00021 Cerium ,, ......... 140.0 246-3.5 13.197 3250 OsO0243 '* { ,, bromide .... , ... 379.88 8.4398 3210 0.00240 3. Praseodymium chloride. 1i6.4 246.75 17.72 4370 0.00328 4, { Neod;mium ,, . 143.6 249.95 27.995 7000 0.00525 nitrate.. . . . . 329.72 20.138 6920 0.00519 5 . Samarium chloride ...... 155 256.35 6P52 15510 0.01164 6. Gadolinium ,, ...... 156 262.35 130.24 34170 0.02563 7. Erbium ,, ...... 166 272.35 179.59 48910 0,03668 8. Ytterbium ,, ...... 173 279.35 33.95 9480 0.00711 These figures show that the salts investigated are derived from a well-defined group of paramagnetic elements, corresponding with the group chromium, manganese, iron, cobalt, nickel, and copper.I n both cases, it is found that when the elements are arranged in the order of their atomic weights, the susceptibility is least for the salt of lowest atomic weight, also that it rises to a maximum, and then falls again, I n the chromium-copper group, the maximum is reached at the third member (iron) ; cobalt is more paramagnetic than nickel, although recent atomic weight determinations place the latter nearer to iron. I n the rare earth group, the maximum is reached only at the seventh stage (erbium), and then drops suddenly to ytterbium ; in this group the increase and decrease of paramagnetism is strictly in accordance with the ascending order of the atomic weights.G. T. M. Change of Thermal Conductivity during Melting. By EDMOND VAN AUBEL (Zeit. pAysikuZ. Chem., 1899, 30, 563--564).-The results of Lees (Phil. Trans., 1898, 101, 428) have shown that fusion is not necessarily accompanied by a sudden change of conductivity. In the case of water, however, the conductivity at 0' is 0.072 and in the solid state between - 21' and Oo about 0.30, so that, most prob- ably, a sudden change occurs during the melting of ice. L. hf. J,GENERAL AND PHYSICAL CHEMISTRY, 129 Influence of Pressure on the Critical Temperature sf Com- plete Mixture. By N. J. VAN DER LEE (Proc, K. Akad. JVetelzsch. Amsterdam, 1898, 1, 158--165).-For two liquids, only partly soluble in each other, there exists a temperature above which mixture in all proportions is possible.The influence of pressure on this phenomenon has been investigated for mixtures of water and phenol, the critical temperature of complete mixture being in this case about 67'. The mixture to be investigated was contained in a thick glass tube of small bore, and subjected to .pressures of 1-180 temperatures ; an electromagnetic stirring apparatus secured thorough mixing of the components in the tube, By means of a thermostat, in which ethyl alcohol boiled under varying pressures, the mixture could be kept at the desired temperature. The temperature of complete mixture mas in all cases found to rise slightly with increase of pressure; thus, in a case where 34 per cent. of phenol was present, the temperature of complete mixture was 67.6' under R pressure of 1 atmosphere, and 68.1' under a pressure of 130 atmospheres. The temperature of complete mixture was highest for the composition just referred to.Theoretical considerations point t o the curve p =f(x), connecting the composition and pressure of the saturated vapour of the mixture, having a maximum or minimum when there is 34 per cent. of phenol present. The vapour pressures of numerous mixtures of water and phenol have accordingly been determined for the temperature range 71-90', The composition of the mixture with maximum vapour pressure for any given temperature, cannot be exactly determined from the numbers obtained, but it is close to 34 per cent. of phenol. J. C. P. Rydrate of Sodium Dioxide and Preparation of Hydrogen Peroxide.By ROBERT DE FORCRAND (Compt. rend., 1899, 129, 1246--1249).-The heat of dissolution of the hydrate Na,0,,8H20 is - 14.868 Gal. ; its heat of formation from sodium dioxide and water is 34.081 Cal., and from the dioxide and ice, 22.641 Cals. These values in- dicate that the hydrate is possessed of considerable stability, and on this account it may be employed in the preparation of hydrogen peroxide ; it furnishes a strong solution of this compound when dissolved in cold hydrochloric acid. The reaction Na,O diss. + H202 diss. = Na202 diss. is accompanied by an evolution of 4.713 Cals. For the solid substances, the stable condition is Na202, for 27.755 Cals. are evolved during the combination of oxygen with solid Na20; in solution, the stable condition is Na,O + 0, for the addition of oxygen to dissolved Na20 is attended by a n absorption of heat equal to - 16.987 Cals.G. T. M. Compound Metallic Radicles : Mercury Derivatives. By MARCELLIN P. E. BERTHELOT (Compt. rend., 1899, 129, 918-920),- The following heats of combustion and formation have been deter- mined ;130 ABSTRACTS OF CHEMICAL PAPERS. Combustion. A t const. vol. At const. press, Formation. 431 -8 cal. - 36.2 cal. Mercurydimethyl (liq.) . . . . . . 430.8 cal. Mercurydiethyl (liq.) .. . . . . . . 733.6 ,, '735.0 ), - 12.8 ,, Mercurydiphenyl (cryst.) . . .1563*S ,) 1565.3 ,, -88.5 ,) T. H. P. Compounds of Lithium Chloride with Ethylamine. By J. BONNEFOI (Comnpt. rend., 1899, 129, 1257--1259).-The compound, LiCl,NH,Et, produced when ethylamine is passed over lithium chloride heated above 70°, is a white, porous substance the heat of dis- solution of which in water is 7.503 Cal.; its heat of form:ition determined experimentally is 13.834 Cal., the value calculated by Clapeyron's formula being 13.717 Gal.The substance closely resembles the corre- sponding methylamine and ammonia compounds the heats of formation of which are respectively 13.S20 and 11.S42 Osls. (Abstr., 1897, ii, 371; 1899, ii, 96). The compound LiC1,2NH2Et is formed a t temperatures between 5s' and 70"; the heat of dissolution is 9-43 Gal. and the heat of formation is 24.817 Gal. The heat evolved by the fixation of the second molecule of the amirie calculated from the dissociation pressures of the substance by Clnpeyron's formula is 11-09 Cal.The compound LiC1,3NH2Et is obtained below 5S0, and even when the liquid amine was employed no further combination took place; the heat of dissolution is 11.77 Gal. and the heat of formation 35.387 Cal. The heat evolved during the fixation of the third molecule of the amine is 10.57 Cal. determined calorimetrically, and 10.503 Cal. calculated by Clapeyron's formula from the dissociation pressures. G. T. M. Lactic Acid. By MARCELLIN P. E. BERTHELOT and MARCEL DEL&PIRE (Co7npt. vend., 1899~129,920-926).-Thermochemical data for silver and zinc lactates and for Iactide are given in the following table : Heat of Heat of combustion formation solution. 1 mol. at 1 mol. at from 1 gram. const. vol. const. press. elements. C,H,03Ag ...... 1609.7 cal.316.6 Gal. 316.5 Cal. 138.9 Cal. -2.05 Csl. (C,H,O,!,Zn ..> 2592'1 ,, 640-15 ,, 640.15 ,, 355.45 ,, +8'00 ,, C,H,O, ......... 4542.8 ,, 327'1 ,, 327*1 ,, 93% ,, +2*10 ,, The heats of neutralisation of lactic acidare: with $Ag20, 4.1 Cal. ; with SZnO (hydrated), +9.95 Gal.; and with +ZnO (anhyd.) + 9.3 Cal. These numbers give, for the heat of formation of lactic acid from its elements, mean values of 163.2 Ual. for the pure liquid acid and 164.3 Cal. for the dissolved acid. Heats of Fractional Neutralisation of Carbonylhydroferro- cyanic Acid compared with those of Hydroferrocyanic Acid. By JOSEPH A. MULLER (Compt. rend., 1.899, 129, 962-964).-Each addition of one-fourth of the equivalent quantity of potash to a T. H. P.GENERAL AND PHYSICAL CHEMISTRY. 131 dilute solution of a gram-mol.of hydroferrocyanic acid gives a heat development of almost exactly 14 Cals., the total a t 18.6' being 56.18 Cals. Sensibly the same number of Cals. (14) are liberated when carbonylhydroferrocyanic acid is neutralised by thirds in dilute solution, the mean total heat evolutions being, a t 19.4' with potash, 41.91 Cals., and at about 18' with baryta, 42.29 Cals. Thus, carbonylhydroferrocyanic acid is a strong acid, and the re- placement of HCN in the molecule of hydroferrocyanic acid by the carbonyl group has no appreciable influence on the acidic properties of the remaining hydrogen atoms, Narceine. By EMILE LEROY (Compt. yend., 1899,129,1259-1261). -The heat of hydration of narceine is 6 Cal. for the dihydrated form, and, in addition, 3 Cal.are evolved when this is converted into the trihydrate. The heat of combustion is 2790.9 cal. at constant volume, and 2792.2 cal. at constant pressure. The heat of formation of the anhydrous base is 302.2 Cal,, that of the dihydrate being 308.24 Cal. The heat of neutralisation of the dihydrated form in excess of hydrochloric acid is - 4.62 Cal., whilst that of the anhydrous base is 1 -58 Cal. The hydrochloride, C2,H,70,N,HCl, crystallises, with 3H,O, from a solution containing excess of acid ; the heat of hydration of the salt is 6.76 Cal. with water, and 2.08 Cal. with ice, the heat of formation of the anhydrous salt being 21.52 Gal. The heat of forma- tion of the potassium derivative, C,,H,O,NK, is 16.7 Cal., the heat evolved on adding potassium hydroxide solutiou to an aqueous solution of the alkaloid being 11.5 Gal.Narceine is the least basic of the opium alkaloids, and, like narcotine, is neutral to litmus; the heat of formation of the potassium deri- vative indicates a distinctly acidic function, the substance being intermediate in stability between the acetates or benzoates and the phenoxides. G. T. M. Fractional Distillation under Reduced Pressure. By GIUSEPPI ODDO (Gazxettcc, 1899, 29, ii, 355-357).-The apparatus described consists of aT-piece fitted to the end of the condenser by means of a piece of rubber tubing which is slightly greased so as to allow of the T-piece being rotated. To the two branches of the latter are fitted two receivers, one being an ordinary flask, and the other an Erlenmeyer flask which is also in connection with the pump used for exhaustion, After the first fraction has been collected in one of these receivers, the T-piece is turned round so that the second receiver comes into use.If more than two fractions are required, to each branch of the T-piece another T-piece is fitted by means of a piece of greased rnbber tubing ; in this way, four fractions are obtainable. By MEYBIR WILDERMANN (Zeit. phgsilnl. Chem., 1899, 30, 508-526).-A consideration of the errors which must exist in thermometric determina- tions of freezing points. The formation of ice caps and nets is prob- ably due to the presence of variable quantities of air and organic compounds in the water ; these impurities also, although not indicated by the conductivity, may occasion variations of the freezing point, t o T.H. P. T. H. P. Determination of Freezing Points in Dilute Solutions.132 ABSTRACTS OF CHEMICAL PAPERY. the extent; of a few thousandths of a degree, Changes of external and internal pressure may also cause errors, the variation of the observed freezing point with the author's l / l O O O o thermometer being about 0*0003° per mm. of mercury. For accurate work also, the thermometer should be always kept at a temperature approximately equal to zero and not at the ordinary temperature. The effect of variations in the external temperature is also considered, but a more subtle source of error lies in the existence in the thermometer of rough place8 and dead points, which the mercury is unable to pass when Lthe actual tempera- ture is sufficiently near.Errors are also introduced owing to inaccura- cies of calibration, and accuracy is hence frequently expected beyond that possible; for example, if an accuracy of O*OO0lo is required with a l / l O O o thermometer, then the calibration should be performed with a rriercury thread of about 1 mm. in length. Other errors not due to causes inherent in the method are also considered, and the author replies briefly t o criticisms on his workl(compare Abstr., 1896, i, 352, 587). I;. M. J. Freezing Points of Mixed Crystals of Two Compounds. By H. W. BAKHUIS ROOZEBOOM (Zeit. physikal. Chem., 1899,30,385-412). -A theoretical consideration of the phenomena of solidification of mixed crystals under various conditions ; the following types are con- sidered.A. The liquid solidifies t o a continuous series of mixed crystals ; three different types of curves are obtained, namely, in the cases where (1) the freezing point for every mixture lies between those of the two constituents, (2) a maximum, and (3) a mimimum occurs. Many examples of the first case have been examined ; of the second, no case has been completely studied, but lead-thallium mixtures are probably an example, while the third type is exemplified by mixtures of mercuric bromide and iodide. The general law is deduced that in all cases the liquid phase is richer than the solid phase, in that constituent which, if added, causes a depression of the freezing point. B. When the mixed crystals form an interrupted series, two more types of curves result; (4) when the freezing point curve contains a transition point a t which the two crystal mixtures occur together, whilst a maximum or minimum may also be present-an example of this type has been found in mixtures of sodium and silver nitrates ; (5) an eutectic point occurs in the freezing point curve ; examples are mixtures of thallium and lead nitrates (Van Eijk, next page), and also of naphthalene and monochloroacetic acid (Cady, Abstr., 1899, ii, 405).When two different classes of crystals result, new types of curves are obtained closely resembling 4 and 5, and the author discusses the means of determining the type of curve indicated by experimental determinations of the freezing point. The accounts of the experimental realisation of the various types mentioned in the paper are deferred.Transition Points in Mixed Crystals, By H. W. BAKIIUIS ROOZEBOOM (Zeit. physikd. Chem., 1899, 3 0 , 41 2--429).-The possible types of curves for the transition of one set of mixed crystals t o another are considered ; the following types occur :-(1) A continuous series of mixed crystals, a, change to a continuous series, p ; the L. M. J.~ENERAL AND PHYSICAL CHEMISTRY. 133 forms of curve are analogous to types I, 2, 3 in the preceding abstract, a complication being, however, introduced when only one component undergoes a transition ; an example is the transition of mixtures of mercuric bromide and iodide. (2) A continuous series, a, change t o a discontinuous series, /3; the transition curves are here analogous t o types 4 and 5 of the freezing point curve, an example is probably the mixture of azoxyanisole and azoxyphenetole (A bstr., 1898, ii, 256) ; in this case also, transition of only one component may occur.(8) The mixed crystals form in the 'U state, and in the p state a continuous series ; examples are the systems potassium and sodium nitrates, and sodium and silver nitrates. (4) The mixed crystals form discontinuous series in both states, an example being potassium and thallium nitrates (following abstract). (5) Isodimorphous mixed crystals change into a continuous or (6) a n interrupted series of mixed crystals. Further types may occur in which the isodimorphous crystals are discontinuous, but these are not considered. L. M. J. Formation and Transition of Mixed Crystals of Potassium and Thallium Nitrates.By C. VAN EIJK (Zed. physikul. Chem., 1899, 30, 430-459).-The melting point and transition curves were completely examined in the case of mixed crystals of the above compounds. The melting points of the pure compounds a r e : potassium nitrate 339', thallium nitrate 206O, and an sutectic point occurs a t 182', the mixture containing 31 per cent, of potassium nitrate ; the law stated by Roozeboom (preceding abstracts) regarding the composition of the solid and liquid phases was verified. During the solidification of the mass, the composition of the liquid phase changes continuously and the temperature falls ; if the freezing is sufficiently slow, i t is probable that the composition of the solid would also change, pari passu, until the whole mass solidifies at a final temperature corresponding with that at which the solid of the given composition is in equilibrium with a liquid phase.In the experiments, however, the solid phase was not found to change sufficiently rapidly, SO that the final temperature is always lower than that deduced, as above, from the curves. As products of the freezing, a continuous series of rhombohedra were obtained t o 20 per cent., and a second continuous series from 50 to 100 per cent. of potassium nitrate ; for intermediate values, a conglomerate of the mixed crystals is obtained. The transition temperatures were obtained by both thermometric and dillitometric methods, as well as by the microscopical examination of the crystals. It was found that change to rhombic crystals occurs a t 129' for potassium nitrate, and at 144' for thallium nitrate.For the mixed crystals, continuous transition curves are obtained from 1/14" t o 133' on the thallium side, and from 129' t o 108-5' on the potassium side. The conglomerate has, however, two transition temperatures, the 6rst at 1334 a t which temperature it changes to a mixture of rhom- bohedra and rhombic crystals, and the second at 108.5', where the remaining rhombohedra change t o the rhombic form. Although no transition in the conglomerate occurs above 133O, the composition of the two sets of mixed crystals changes with the temperature, the per- centage of potassium nitrate being 20 and 50 per cent. a t 18Z0, 20 and134 ABSTRACTS OF CHEMICAL PAPERS. 69 per cent.a t 133", and 35 and 84 per cent. a t 1085". This systeui thus forms ."a complete example of the type 4 of transition curve deduced by Roozeboom (preceding abstracts). L. M. J. Cryoscopic Researches on the Constitution of Acid Amides. By KARL AUWERS [with A ~ A X DOHRN] (Zeit. physikd. Chern., 1899,30, 529-544).-1t has been shown that amides in naphthalene solution are generally cryoscopically abnormal (compare Abstr., 1897, ii, 476). The constitution may be either R*NH*CO*R or RN:CR'*OI€, and in the latter case the abnormality may be occasioned by the hydroxyl group and the behaviour of the thioamides should be similar to that of the thiophenols. The thiophenols examined, however, were found to be cryoscopically normal, and the thioamides to be abnormal, so that the constitution R*NH*CS*R' is most probable.As, however, the abnormality may be due to the increased acidity of the thio-compounds, t h s case was further examined. The author shows that in general a substituent causes a decrease of abnormality only when this sub- stituent and the group causing abnormality are attached to neigh- bouring carbon atoms. I n the case of substituted derivatives of benzanilide, i t was found that the compounds from ortho-substituted aniline are normal, but the derivatives of the ortho-substituted benzoic acid remain abnormal, and hence the abnormality is caused by an *NH group, that is, the previous conclusions are confirmed. Basic arnines are, however, normal, although piperidine is slightly abnormal, and it is found that the abnormality of urethane is greatly decreased by the entrance of a phenyl group.Accurate Determination of the Molecular Weight of Gases from their Density. By JOHANNES D. VAN DER WAALS (Proc. K. Akacl. Wetensch. Amsterdam, 1898, 1, 198--201).-The molecular weight of a gas is proportional to the normal density dn, which is equal to do/( 1 + a)( 1 - b), where do is the density found a t Oo under the pressure po, and a and b are the constants of van der Waals' equation. If d', be the density found at another temperature T, mathematical dis- cussion leads to the equation d,/&', = 1 - O.O0164ST,/T.(27T,lST- l), where Tk is the critical temperature of the gas. For T>27Tk/8, the correction is negative, and d,/d', has a maximum for T= 27T,/4. The condition for the observation under a pressure of II/76, without the vapour being saturated, is that 17 must not fall below a certain limit.When this limit is put at Tk/1.6, the normal density is 1 per cent. smaller than the value given by experiment. True Density of Chemical Compound and its Relation to Composition and Constitution. By INNOCENTIUS I. KANONNIKOFF (Chern. Centr., 1899, ii, 858-861 ; from J. Russ. Chern. Xoc., 31, 5.73-640).-According to the theories of Clausius and Mosotti, the ratio p2 - l/pz + 2, where p is the refractive index, is the ratio of the actual volume of the molecules to the total volume ; the true density is hence d ( p 2 + 2 / p 2 - l ) = D , and the value of this constant is the same for liquid and gaseous states. The value being, however, de- pendent on that of the refractive index, is obviously a function of wave-length and temperature, and may, if required, be corrected for L.M, J. J. C. P.GENERAL AND PHYSICAL CHEMISTRY. 135 an infinite wave-length and for zero temperature by the Cauchy dispersion formula and the expression Dt = Do( 1 + kt). The author, however, employs the values for sodium light and a temperature of from 10’ to 20’. If the true density is multiplied by the molecular weight, the product, termed the (‘ molecular density,” but of which the physical interpretation does not appear evident, is found to be an additive function. I n hydrocarbons, it is given by the expression 39Tn + (2% m)H - 4H + a.9€€- b*6H - b’s26H - c*4H, where 1% i s the number of carbon atoms, 2n+m that of the hydrogen atoms, and a, b, b’, and c the number of closed chains, ethylenic unions, naphthaleno- ethylenic unions, and acetylenic unions respectively in the molecule, the value for H being 0.967.It is stated that for a large number of compounds the values so calculated are in accord with the determina- tions. I n many cases, the “molecular density” may be a useful criterion of constitution, as the various modes of union have very diverse values, and various examples are given. By MAX REINGANUM (Chem. Cente.., 1889, ii, 955 ; from Diss. Gottinyen).-Van der Waals’ equation can be regarded only as an approximation, but any improvement sug- gested must still necessitate the law of corresponding states. The author suggests the equation ( p + a/w2))I((v - b)4/w3} = BZ’; this con- tains no more constants than van der Waals’ expression; the con- stants also are functions OF the molecular weight, and apparent and actual molecular volumes, The author states that i t gives results in good accord with previous determinations, notably, those of Young on isopentane, and the validity of the equation is proved by the co- incidence of the isothermals, and by the comparison of the predicted and found vapour pressure, expansion of liquid and vapour, and latent heat of vaporisation.The equation predicts the constant ratio between the critical and acthal molecular volumes and the con- stant ratio of the critical density to the theoretical density calculated for a perfect gas, whilst the deduced temperature coefficients of internal friction are also in agreement with the experimental results.By FRANS A. H. SCHREINEMAKERS (Zeit. physikccl. CJLem., 4899, 30, 460-480).-The theoretical aspects of such a n equilibrium system are fully considered ; in it, two pairs of the components are capable of forming two liquid layers as in the system, water-alcohol-succino- nitrile (Abstr., 1898, ii, 564), but the case is now complicated by the existence of a compound of phenol and aniline. I n such a case, by the addition of water to the compound, two liquid phases may result in which (I), with or without decomposition, the relative concentrations of the two components of the compound are unchanged, or (2) owing to decomposition, the relative concentrations vary. I n the first case, only one temperature occurs a t which the compound and the two liquid phases can exist together, but in the second a series of temperatures occur, that is, a (‘ transition interval.” This interesting case is ob- served in the system considered, the compound of phenol and aniline being in equilibrium with two liquid phases between the temperatures L.M. J. Equation of Condition. L. M. J. Equilibrium in the System, Water -Phenol-Aniline.136 ABSTRACTS OF CHEMICAL PAPERS, 18.9’ and 17.2”. curves and isothermals are given in the paper (Abstr., 1899, ii, 739). The various theoretical and determined equilibrium L. M. J, False Equilibrium, By MAX BODENSTEIN (Zeit. physikal. Chem, 1899, 30, 567--569).-A reply to Duhern’s criticisms of the author’s results (see Abstr., 1899, ii, 739). L. M. J. Condition of Substances Insoluble in Water formed in Gelatin.By CORNELIS A. LOBRY IIE BRUYN (Proc. K. Akad. vetensch. Amsterdam, 1898,1,39-42).-The exceptional phenomenon of certain substances, such as silicic acid, remaining unprecipitated in aqueous solution, is general in aqueous gelatin solution, An insoluble com- pound formed by double decomposition in aqueous solution generally remains unprecipitated when the same substances are brought together in gelatin solution, although there are grounds for believing that the double decomposition has actually taken place. Thus, Cohen has shown that when silver nitrate and potassium bromide are mixed in gelatin solution, the resulting conductivity is that due to the potassium nitrate, and not that due to the two electrolytes, silver nitrate and potassium bromide.Further, although the gelatin solution remains transparent, it takes the colour of the product formed by double de- composition, as in the cases of Prussian blue and lead iodide. Although the visible precipitation of amorphous substances is pre- vented by gelatin, crystalline, insoluble substances separate as in aqueous solution : this is the case, for example, with calcium oxalate and ammonium magnesium phosphate. J. C. P. Genesis of Dalton’s Atomic Theory. By HEINRICH DEBUS (Zeit. physikal. Chem., 1899, 30, 556--562).-A further controversial paper in reply t o Kahlbaum (Abstr., 1899, ii, 740). L. M. J. Some Anomalies in Mendel&l”s System. By THEODOR H. BEHRENS (Proc. K. Akad. Wetensch. Amsterdam, 1898, 1, 14S-151).- Ismorphism is not to be rashly used as a guide to the natural position of a n element, for the evidence is often conflicting. Itetgers, who denies isomorphism between tel.1uratea and sulphates, assigns to tellurium a place in the eighth group between ruthenium and osmium, disregarding the analogy between hydrogen telluride and sulphide, and recognising the isomorphism of K,TeCl, with K,OsCI, and K,IrClo. But, on other grounds, tellurium might be put in the fourth group, for the compounds Cs2TeCI, and Cs,SnC1, are isomorphous, and tellurium dioxide dissolves in potassium hydrogen oxalate, forming crystals like those of potassium zirconium oxalate ; further, if tellurium should be placed between ruthenium and osmium, seventeen new elements would have to be looked for in that group. With manganese, there is a similar ambiguity. The isomorphism between KMnO, and KClO, agrees with the position of manganese in the seventh group, but, on the other hand, K2Mn0,and K,SO, are isomorphous, and experiments made with manganese tetrachloride point to an analogy between manganese and tin. J. C. P.INORGANIC CHEMISTRY. 137 Relation of Physical Properties of Elements t o their Atomic Weights. By W. SANDER (Chern. Centr., 1899, ii, 955 ; from Electr. Zed., 6, 133).-Curves are given in the original paper from which the author deduces that the coefficients of linear expansion, migration velocities of ions, electrical conductivity, and electrolytic potential of metals are periodic fuaotions of their atomic weights. L. M. J,

ISSN:0368-1769    

DOI:10.1039/CA9007805125

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

129 Organic Chemistry. New Method of Preparing Unsaturated Hydrocarbons. By 1;. TSCHUGAEFF (Ber., 1899, 32, 3332--3335).-When an alkyl xanthate of the unsaturated hydrocarbon radicle C,H2m-l is sub- jected to dry distillation, it breaks up in accordance with the following equations, C,H2,-10*CS*SR = C,H2m-2 + COS + RSH and CnH2,_10*CS*SR= CnH2,n-z + CS2 + ROH. I n both reactions the unsaturated hydrocarbon is obtained, and the yield is usually very good. The dixanthate, produced by the condensation of a metallic xanthate with iodine, also breaks up in a similar manner, C,H2,_10*CS2*CS2*OC,H2m-1 = CJ12m-2 + C,H2,-1*OH + COS + CS, + S ; the yield in this case, however, is smaller and the product less pure. These two synthetical methods have been successively employed for the prepnration of menthene.Menthol, dissolved in dry toluene, is successively treated with sodium, carbon disulphide, and methyl iodide ; the xanthate thus produced, on distillation, yields rnenthene and methyl mercaptan. The hydrocarbon is purified by fractionation and distillation over sodium ;' its specific gravity and boiling point correspond with those of other preparations, but its specific rotatory power is far greater ; in menthene from the xanthate, [ a ] D varies from 114.77O to 116*06O, whilst in the specimen from the dixanthate i t is 1 1 1 . 5 6 O . The nitrosyl chloride of the most active menthene melts at 127' and gives [ a ] , , 242.5O. The menthene prepared by Urban and Kremers has a sDecific rotation of 32-77' : its nitrosvl chloride melts at 1 2 8 O and has 13-76O (compare Abstr., 1894, i,"468).G. T. M. Biochemical Oxidation of Propylene Glycol. By ANDRI~ I~LING (Compt. rend., 1899, 129, 1252-1254. Compare Abstr., 1899, i, 323)-The aldehydic substance produced by the action of the sorbose bacterium on solutions of propylene glycol is shown to be ncetol by isolating it in the form of its oxime. The amount of the glycol oxidised never exceeds 50 per cent. of the total quantity, how- ever long the fermentation is continued ; this may be due either to the paralysing effect of the acetol on the bacterium, or to the organism's preference for one of the optical forms of the glycol, or to a combination of the two causes. The unaltered propylene glycol is optically active and appears to consist of a mixture of the dextrorotatory form and the racemic compound.Le Bel, who also effected a partial resolution of propylene glycol by the action of various ferments and moulds, found that the solutions generally beuame leevorotatory. G . T. M. Cyclic Isomeric Change of Methyloctadienonol. By GEORGES L~SER (Bull. SOC. Chirn., 1899, [iii], 21, 969-973. Compare Abstr., 1899, i, 743).-Methgloctadienonol, the product of the condensation of methylheptenone with ethyl formate, has the constitution CMe,: CH*CH2*CH2*CO-CH: CH*OH, as is shown by its behaviour VOL. LXXVIII, i, I130 ABSTRACTS OF CHEMICAL PAPERS. towards methylaniline (Abstr., 1899, i, 415) and by its yielding a monoacetate, a colourless, odourless liquid boiling at 138' under 13 mm. pressure. When heated for a few minutes at 100' with five times its weight of 80 per cent.sulphuric acid, methyloctadienonol is con- verted in to the isomeric pO-oxy-P-methyl-~-octene-[-o-olne, CMe2<E3Hy2f6>cH2 9 which melts at about - 2-5O and boils without decomposition at 225-227' ; it is insoluble in cold alkalis, gives no coloration with ferric chloride, and is not acted on by chromic acid mixture, but immediately decolorises bromine or potassium permanganate solution. It forms an oxime melting at 90-91' and boiling at 150-151' under 18 mm. pressure, which yields an acetyl derivative boiling at 158-160O under 20 mm. pressure ; oxidation with 2 per cent. potass- ium permanganate solution converts it into the lactone of 7-hydroxy- isohexoic acid. The constitution which has been assigned above to the isomeride of methyloctadienonol is fully confirmed by these reactions, and also by a determination of its molecular refraction (found, 44.02 ; calculated, 43.95).Methylene Sulphate or Sulphuric Methylal. By MARCEL DEL~PINE (Compt. read., 1899, 129, 831-833).-Methylene sulphate or sulphuric methylal, CH2<O>S02 or CH,O,SO,, obtained by dis- solving trioxymethylene in fuming sulphuric acid, is a white, crystal- line, odourless, and tasteless substance, almost insoluble in water and organic solvents with the exception of acetone, from which it can be crystallised and from which it is precipitated by adding water, alcohol, ether, or chloroform. It melts a t about 155O, but even below this temperature decomposes into sulphur dioxide, carbonic oxide, sul- phuric acid, and formaldehyde; in sealed tubes at 200°, i t yields the same products together with carbon dioxide and a black, solid mC,H,O.Methylene sulphate immediately converts aldehyde into par- aldehyde ; it is but slightly affected by water or alkalis at the ordinary temperature, but at 60-70' is rapidly hydrolysed, yielding form- aldehyde and sulphuric acid. Although it has no action on alcohols in the cold, it reacts at 60-70" with methxl, ethyl, propyl, isopropyl, isobutyl, isoamyl, and benzyl alcohols, yielding the corresponding formals and acid sulphates of the various radicles. The heat of combustion of methylene sulphate (I gram) is 12865 cal. ; molecular heat of combustion at constant pressure and volume, 141 -5 Cal. Hence S(oct.) + 0, + C + H, = SO,UH, solid, develops +162*9 Cals., and the formation of the compound from sulphur trioxide and trioxymethylene develops + 18.7 Cals.This reaction is also exothermic if sulphuric acid is substituted for the oxide, owing to the heat of combination of the excess of acid with the water that is formed. Velocity and Limits of the Esteriflcation of Phosphoric Acid by Glycerol. By HENRI hfBERT and GUILLAME BELUGOU (Bull. Soc. Chim., 1899, [iii], 21, 935-939. Compare Abstr., 1899, i, 659.- When phosphoric acid and anhydrous glycerol are mixed in molecular N. L. 0 C. H. B.ORGANIC CHEMISTRY. 131 proportion, monoglycerophosphoric acid alone is formed, the coefficient of esterification reaching its maximum value almost immediately at the ordinary temperature, and then slowly diminishing, At a higher temperature (1 05'), the diminution is more rapid, a minimum value being soon reached, after which the coefficient of esterification iucreaees, and ultimately exceeds its original value.The presence of water greatly diminishes the rate of esterification, only 9-32 per cent. of the monohydrat,ed acid being transformed after 13 days a t 50'. The action of glycerol on phosphoric oxide results in the formation of each of the three glycerophosphoric acids. Acid Esters of Boric Acid. By ALFRED WOHL and C. NEUBERG (Ber., 1899,32, 3488-3492).-Hydroxychloropropionacetal, OH- CH,*CHCl*CH(OEt),, is obtained by treating acraldehydeacetal with bleaching powder and boric acid in aqueous solution (Abstr., 1898, i, 556); when an attempt is made to prepare glyceraldehyde- acetal by boiling the resulting solution with potassium carbonate, ether extracts from the product a potassium salt of the composition OK*B[O*CH( CH,*OH)* CH( OE t)2]2.By treating allyl alcohol with calcium hypobromite and boric acid, P-bromohydrin, melting a t 227-230°, was obtained in very small yield; by boiling it with aqueous potassium carbonate and boric acid, and extracting the product with ether, a potassium salt, OK*B[O*CH(CH,*OH),],, was obtained. P-Bromohydrin a-ethyl ether appears to react in a similar way ; it is made by acting on sodium allyl oxide with ethyl bromide, and treating the product with hypobromous acid. Compounds which do not contain a secondary halogen atom, such as ethyl bromide, benzyl chloride, or the chlorohydrin CH,Cl*CH(OH)*CH,*OH, do not form salts of the kind described, neither do simple secondary halogen derivatives, such a s isopropyl chloride and bromide.a-Dimethyliso crot onic (2-Dimethyl-3-butinoic) Acid. By LOUIS BOUVEAULT (Bull. SOC. Chim., 1899, [iii], 21, 1062-1065).- The action of acetaldehyde on ethyl bromoisobutyrate in the presence of zinc, according to Saytzeff and Heformatsky's process, results principally in the formation of ethyl P-~~ydl.olcy-a-dimethy~~~~tyr~t~, but symmetrical diethyl pentamethylglutarate, CHNe(CMe,*CO,Et),, is also produced. The latter boils at 170-180O under 18 mm. pressure, and has a sp. gr. 0.9953 a t 0'. Ethyl P-hydroxy-a-dimethylbutyrate is a colourless liquid which boils a t 93-94' under 18 mm. pressure and has a sp.gr. 0.9974 at 0'; i t is not affected by most dehydrating agents, but when heated at 100' with phosphorus pentachloride yields ethyl p-chloro-a-dimethylbutyrate, which boils a t about 200" and is not decomposed by alcoholic potash, and ethyl a-dirnethylisocrotonate, a colourless liquid boiling a t 144-146', which differs from the alkyl salts of up-unsaturated acids in not reacting with ethyl sodiomalonate. a-Dimethylisocrotolzic acid, obtained by hydrolysing its ethyl salt, is a colourless liquid whioh boils at 92' under 23 mm. pressure and readily combines with bromine to form a crystalline additive product melting at 91'. The chloride of this acid reacts with tetrachloroquinol to form two compounds, of the composition OH*CGCl,*CO,*C,H:, and N. L. C.F. B. 1 2132 ABSTRACTS O F CHEMICAL PAPERS C,Cl,(CO,*C,H,), respectively ; the former cryst,allises i n white needles, melts at 132', and is very soluble in neutral solvents, whilst t h e latter melts at 133-134O and is only slightly soluble in neutral solvents. N. L. Ethyl Acetoacetate. By HErmrcR GOLDSCHMIDT and LAZAR OSLAN (Rer., 1899, 32, 3390-3399).-The hydrolysis of ethyl aceto- acetate by sodium hydroxide proceeds as a reaction of the first, and not of the second, order, the velocity constant being independent of the concentration of the ester and of the base. This result can be explained if (1) ethyl acetoacetate is a strong monobasic acid and is converted almost completely into the sodium derivative by a n equivalent of sodium hydroxide, whilst (2) sodium acetoacetate possesses no marked acid properties, and (3) if the hydrolysis takes place by t h e action of the free alkali on t h e free ester and not on its sodium derivative.The last statement is supported by Fischer's observation that metallic compoiinds of esters are hydrolysed only with difficulty (Abstr., 1899, i, 262), and especially t h a t ethyl acetoacetate is hydro- lysed more slowly than ethyl dimethylacetoacetate, which does not form a metallic derivative. The neutral character of sodium aceto- acetate is shown by the fact that it does not produce any marked decrease in the velocity of hydrolysis of ethyl acetate by sodium hydroxide. The acid character of ethyl acetoacetate is shown by con- ductivity determinations which gave pI6 0.36 and plo24 3.12, p? 360, K 0.63 x 10-7 at 25'; the ester is thus a much stronger acid than phenol, and slightly stronger than o-cresol.The hydrolytic constant of ethyl sodioa.cetoacetate is calculated to be K = Z x 10-7 and the small extent of the dissociation is confirmed by cryoscopic measure- ments. T. M. L. Orientation in the Terpene Series. XXIV. By ADOLF VON though /3(-dimethyloctnne-c-oloic acid contains its hydroxyl group in the €-position relatively to the carboxyl group, it behaves like a y- or 6-hydroxy-acid and yields a lactone, P~-dirnet?~yloctane-€-olide, BAEYER (Bey,, 1899, 32, 3619-3624) [with OTTO SEUFFERT]. -A]- . - CH M~-CH;-CO brr .CH. .CHPrB>O, produced when the corresponding hydroxy- n ? acicf (Abitr., 1896, i, 217) is heated in a vacuum, distils at 128-130O under 17 mm.pressure; when cooled in a freezing mixture, it becomes solid, and as the temperature of the mass rises one portion melts, whilst the residue remains solid i n the form of tabular crystals which molt at 47'. Analysis indicates t h a t the two fractions are isomeric ; both modifications are insoluble in water and cold dilute caustic soda solution; they dissolve in the hot alkali, but are not attacked by potassium permanganate. The lactone melting a t 4'7' yields a n acid melting at 65O, whilst that of lower melting point yields an oily acid. The isomerism of the lactones and their acids depends on the pre- sence of two asymmetric carbon atoms in the molecule of the hydroxy- acid, CHMe2*CH(OH)*CH2*CH2*CHMe*CH2*C0,H ; one of these is suppressed by oxidation, and accordingly both modifications of this compound yield the same ketonic acid, CHMe2wCO*CH2*CH,*CHMe.CH,.CO,H,ORGANIC CHEMISTRY. 133 on treatment with potassium dichromate and sulphuric acid ; the ketone is identified by means of the oxime which melts a t 9'7". G. T. M. Action of Caro's Reagent on Ketones. By ADOLF VON RAEYER and VICTOR VILLIGER (Ber., 1899, 32, 3625-3633. Compare Caro, Zed. angew. Chem., I 898, 845).--MThen Caro's reagent (potassium persulphate and sulphuric acid) acts on a ketone, an oxygen atom is introduced into the molecule between the carboxyl group and one of the hydrocarbon residues; if it is assumed t h a t the first product is a peroxide, then the course of the reaction R,C<,L) - R*CO*OR is comparable with that of the Beckmann change, 0 R2C<gH --, R,CO*NHR.When menthone is treated with a mixture of persulphate and con- centrated sulphuric acid, the elactone of P[-dimet hyloctane-eoloic acid is produced (compare preceding abstract). The r-Zccctone of P-isopropylheptane-E-oloic acid, CH2*CH2*$'HMe CHpKCH2-CO--0 ' prepared from tetrahydrocarvone in a similar manner, is an oil boil- ing a t 155-156" under 21 mm. pressure. On hydrolysis, the lactone yields an uncrystallisable hydroxy-acid, the silver salt of which crystallises in white needles ; this acid, when treated with Beckmann's mixture, yields a ketonic acid identical with that obtained by direct oxidation from tetrahydrocarvone (Abstr., 1896, i, 217). Campholide is produced when a benzene solution of camphor is added to a mixture of potassium persulphate, sulphuric acid, and water (H,SO,,H,O), and is isolated by means of its additive compound with hydrogen bromide.The latter compound, bromocampholic acid, crystallises in plates and melts a t 177O. The campholide is identical with that obtained by Haller from camphoric anhydride. The corn- pomd C,,H,,O, is obtained as a bye-product in the above reaction ; it crystallises from water in plates and melts a t 189-1990". A compound having the composition of acetone peroxide is obtained from acetone and peraulphuric acid ; i t crystallises in prisms, melts at 132-133", and closely resembles the acetone peroxide obtained by Wolffenstein from acetone and hydrogen peroxide; the latter, however, melts at 94-95' (Abstr., 1895, i, 644).Terpineol, when treated with Caro's reagent, yields trihydroxy- hexahydrocymene. G. T. M. Action of Aluminium Chloride on Camphoric Anhydride. By 0. BLANC (Compt.rend., 1899,129,1019-1020. Compare Lees and Perkin, Proc., 1898, 14, 111; 1899, 15, 23; 1900, 16, 18).-When the bye- product obtained in the preparation of isolauronolic acid by the action of aluminium chloride on camphoric anhydride is distilled in a vacuum, the distillate consists of unchanged camphoric anhydride, isolauronoh acid, and an oily liquid boiling a t 140-145O under 20 mm. pressure. This oily liquid, by repeated extraction with potassium hydrogen car- bonate, is separated into an acid portion ( A ) and a neutral portion (B).i34 ABSTRACTS OF CHEMICAL PAPERS. The acid portion ( A ) boils a t 140-142" under 20 mm.pressure, and consists of a mixture of several acids of the composition C,H1402 and C,H,,O,. It was oxidised with alkaline potassium permanganate and the oxidation product distilled in steam. The residue in the flask consists of the products of oxidation of isolauronic and isolauronolic acids, and an oily, non-ketonic acid which is unsaturated and prob- ably has the composition CgH1402. The distillate consists of two saturated acids, CgHl,02; the first melts at 76-71' and forms an amide crystallising in needles and melting a t 1904 and a bromoethyl estei., boiling a t 130-1 32" under 25 mm. pressure, which, when treated with alcoholic potash, gives an m i d , CgH1402, melting at 1U8-110°, the unaide of which melts at 163O.The second acid found in the distillate is an uncrystallisable oil of high boiling point possessing a fatty acid odour; its amide is a liquid. The neutral portion ( B ) is probably the lactone of an acid, C,HI6O, ; it boils at 125-135' under 30 mm. pressure, is insoluble in cold dilute alkalis, but dissolves on warming, and on analysis gives numbers corresponding with the formula CgH1,02. By JULIUS BREDT and WILHELM JAGELKI (Annalerz, 1899, 310, 112-134. Com- pare Abstr., 1898, i, 264).-It has been shown by Etard (Abstr., 1893, i, 360) that camphene forms the additive compound CloH16,2Cr02C12 when dissolved in carbon disulphide and treated with shromyl di- chloride; treatment with water gives rise to an aldehyde, to which he ascribed the formula C,,H,,O, calling it camphenaldehyde, and this, on exposure to air, yields the corresponding acid, which was called camphenic acid.The authors, however, find that the aldehyde has the formula C,,H160, and they use the name camphenilanaldehyde ; the acid CloH,,02 is now called camphenilanic acid. The double compound, Cl0Hl6,2CrO2C1,, is a pale brown powder which is very hygroscopic, forming a green liquid when exposed t o air ; i t tastes sweet, and is somewhat soluble in ether, being insoluble in benzene, petroleum, or carbon tetrachloride. >CMe2 )CH* CHO, produced by the action of water on the double compound of camphene with chromyl dichloride, has an agreeable odour, and dissolves readily in organic solvents; it melts a t about 70°, and boils at 96"under 14 mm. pressure. >CMe2)CH*C02H, melts a t 65' and boils at 1 4 7 O under 14 mm.pressure ; the caEcizcrn and &her salts are crystalline and anhydrous. The chlwide, C,,H,,OC1, boils at 105-1 06' under 14 mm. pressure, and the methyl ester boils at 99-100' under 12 mm. pressure. Bromocamphelzilanic acid, ClOHl5O2Br, separates from petroleum in colourless crystals and melts at 145' ; the chloride, prepared by the action of bromine on camphenilanic chloride, is a white, crystalline substance, and boils at 1 6 5 O under 14 mm. pressure. Isocumphenilunic acid, C,oHl,O,, prepared by heating camphenilanic H. R. LE S. Camphenilanaldehyde and Gamphenilanic Acid. CH2*CH- CampheniEanaZde7iyde, I CH2aCMe- CH2*CH-- CH2* CMe- Camphenilanic acid, IORGANIC CHEMISTRY. 135 acid with dilute nitric acid, melts at 118O, and separates from petroleum in crystals belonging to the triclinic system ; [a : b : c = 1.8852 : 1 : 1,2155 ; a= 69O3’30’‘, It is also produced on oxidising camphenilanaldehyde with potassium perman- ganate; the caclcium salt contains 2H,O, and the silver salt resists the action of light.Hydroxycamphenilaric (campheniloloic) acid, Cl0El6O3, prepared by heating bromocamphenilanic acid with sodium carbonate, melts at 170-172‘ ; the sodium salt is not readily soluble in cold water, and the silver salt is crystalline. It is probable that camphenilanaldehyde is identical with the aldehydic substance obtained by Wagner from camphene glycol and hydrochloric acid, and hydroxycamphenilanic acid is most likely identical with the acid obtained by Wagner on oxidising camphene with potassium permanganate (compare also Jagelki, Abstr., 1899, i, 627).M. 0. F. By L ~ O N MAQUENNE (Bull. SOC. Chim., 1899, [iii], 21,1061-1062).-Azelaic acid is usually obtained by oxidising castor oil with nitric acid, but a purer product and a larger yield are more readily obtained by the action of potassium per- manganate on an alkaline solution of the crude ricinoleic acid obtained By HUGO ERDMANN (Ber., 1899, 32, 3351-3354. Compare this vol., i, 10).-The malic acid obtained from the ripe berries of €Zippopha rhamnoides (Seabuck- thorn) is identical with that isolated from mountain ash berries; their ammonium salts have the same molecular rotation (2.89-294O) Calcium malate separates from hot aqueous solutions in crystals containing 1 $H20.The berries also contain other acidic substances and mannitol, the latter being isolated in the form of its calcium derivative. G. T. M. Some Complex Salts of Tartaric and Malic Acids, and their Specific Rotatory Power. By ARTHUR ROSENHEIM and HERRMANN ITZIU (Ber., 1899, 32, 3424-3440).-The potassium, sodium, and am- monium ‘ I diberylliumtartrates,” M’,0,4Be0,2C4H,05, previously de- scribed (Abstr., 1898, ii, 71) have been examined as regards their optical activity ; the specimens prepared contained respectively 6, 9, and 9H20. The molecular rotation, [MI,, at 20’ in aqueous solution, is about 225O, 225O, and 242O respectively, and varies but little with the dilution ; it is due to a complex anion, (C,H4013Be,)” or (C4H307Be2)’,, of the nature (-C02~[C2H,:0,Be]*C0,*Be*)20 or -C02*[C,H,:02Be]*C02*Be*OH, and exceedingly stable, since dilution does not affect the rotation and so cannot produce hydrolysis.Potassium and ammonium ‘‘ mono- berylliumtartrates,” M’,0,2Be0,3C,H405 + 2H20 (loc. cit., 72), were examined in the same way (the sodium salt, with 3H20, could not be obtained sufficiently pure) ; the molecular rotation at 20° was about 126’ and 126’ respectively, and varied but little with the dilution ; it was probably due t o a stable complex anion, (C8H8OI3Be2)”, of the nature (-CO,*[CH*OH],*CO,*Be),O. By dissolving an equivalent = 99O20’, y 7 99°0’30”]. Preparation of Azelaic Acid, by the hydrolysis of the oil. N. L. Malic Acid from Hippopha Rhamnoides.136 ABSTRACTS OF CHEMICAL PAPERS. amount of beryllium hydroxide in a boiling solution of tartaric acid, a beryllium tartrate, C,H,07Be, + 7H20, was obtained ; this has, a t 20°, a molecular rotation of about 171' in 3 per cent.solution, increasing with the dilution, In all cases, the entrance of beryllium into the molecule causes a great increase in the rotatory power. Ammonium di- and moNo-beryllium racemates were also prepared ; they have the same composition as the d-tartrates ; but they are optically inactive, so that the &tartrate molecule must have been affected in the same degree 8 8 the d-molecule, and in the opposite sense, by the entrance of the beryllium. Similar observations were made in the case of malic acid. Potassium, sodium, and ammonium diberylliummalates, Mf20,4BeO,(C4H,0&0, with 5 , 7, and 4H,O respectively, were prepared by saturating boiling aqueous solutions of the alkali-hydrogen malate with freshly precipi- tated beryllium hydroxide.The molecular rotation is about - 199' at 16', - 202' at 1 6 O , and - 201' atSl3' respectively, and is due to an anion of the nature 40,. CH2* C H < ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ > C H * C H 2 Ammonium monobsrylliummalccte, (N H4),0,2Be0,2C4H40, + H2,0, pre- pared like the analogous tartrate, has a molecular rotation ot about -106'at 20'. By adding beryllium sulphate and sodium hydroxide in varying proportions to solutions of tartaric or malic acids, the molecular rotation reached a maximum when the proportions corresponded with the formation of the '' diberyllium " salt, and was then about equal t o that of the pure salt.Ethyl hydrogen tartrate gave a maximum rotation when the proportions were C,H,00,,2BeS0,,4EOH. The rotatory power of quinic and d-chlorosuccinic acids, which contain no alcoholic hydroxyl groups, is not affected by the addition of beryllium sulphate (and alkali); nor is that of dextrose. Neither magnesium, zinc, nor cadmium forms complex tartrates or malates like those formed by beryllium, nor do their salts affect the rotatory power of alkaline tartrates or malates. Action of Nitric Acid on Acids of the Fatty Series which contain the Isopropyl Group. By JULIUS BREDT and J. B. C. KERSHAW (Ber., 1899, 32, 3661-3666. Compare Abstr., 1883, 176). -The experiments of the authors have been extended to dibasic acids which have been found t o behave in a similar manner to the monobasic acids which had been previously examined.Terebic acid is converted by the continued action of nitric acid into 7-valerolactone-fly-dicarboxylic acid, CH2<~~(co2H~>CMe*C0,H, which has aiready been prepared by Rach (Abstr., 1886, 1012). The diethyl ester boils at 174-175" under 9 mm. pressure, Isopropylsuc- cinic acid (pimelic acid) is also converted by nitric acid into valero- lactonedicarboxylic acid. These two compounds therefore behave in a precisely similar manner to isohexoic acid and isohexolactone. A. H. Natural Cyclic Isomeric Change of Citronellal. By HENRI LABBB (Bull. Xoc. Chim., 1899, [iii], 21, 1023-1025. Compare Abstr., 189'3, i, 622)-Pure citronella1 is very unstable, and spon C. F. B.ORGANIC CHEMISTRY.137 taneously undergoes the same isomeric change which is effected more rapidly by the action of acids. A specimen which had been kept for two months was found to be almost entirely converted into isopulegol, which was identified by oxidising i t with chromic acid mixture, and converting the isopulegone thus formed into the mixture of two isomeric semicarbazones which is characteristic of this sub- stance. I n the presence of hydrocarbons and terpenylic alcohols, such as occur in commercial specimens, citronellal is much more stable. Formation of Barium Citryl and Citronellyl Sulphites. N. L. By HENRI LABB~ (Buh?. 8oc. chim., 1899, [iiil], 21, 1026--1027).-1n reply to the remarks of Tiemann (Abstr., 1899, i, 622), the author states that it is not contended that an accurate quantitative separation of citral from citronellal can be effected by the process described by Flatau and Labbe (Zoc.cit.). The barium hydrogen sulphite compound of citronellal is precipitated immediately to the extent of about 86 per cent. of the theoretical amount, whilst the yield of the corre- sponding citral derivative never exceeds 27-28 per cent., and in the first five minutes only amounts to 17-18 per cent. The citral com- pound, moreover, is contaminated with barium sulphite, whereas the Derivatives of the Isuretine of Formhydroxamic Acid and their Relation to Fulminic Acid. By. H. C. BIDDLE (Annalen, 1899, 310, 1-24. Compare Nef, Abstr., 1896, i, 71).-EEthylisuretine, NH,*CH:NOEt, has been described already as ethoxgformamidine (Nef, Abstr., 1895, i, 12).Benxylisuretine, NH,*CH:NO*CH,Ph, prepared from isuretine by the action of benzyl chloride and alcoholic potash, crystallises from petroleum in slender needles and melts at 58'; hot concentrated hydrochloric acid eliminates a-benzylhydroxylamine, and ni trous acid gives rise to a variety of products, including benzaldehyde, benzyl alcohol, and benzylchloro-formoxime. The pZatinichZoride crystallises in yellow, rhombic plates and melts a t 157-158'. Methyliswetine, NH,*C:H:NOMe, crystallises from light petroleum in plates and melts a t 40-40*5O. An attempt t o prepare the benzyl derivative of fulminic acid by the action o€ chloroform and alcoholic potash on a-benzylhydroxylamine gave rise t o the compound C,H,O,N, which crystallises from petroleum in colourless leaflets and melts at 86-86.5"; a mixture of benzyl alcohol and benzyl ether is also produced, along with a substance having the odour of an isonitrile.Benxylfoi.mhydroxamic acid, CH,Ph*O*NH*CHO, obtained by heat- ing a-benzylhydroxylamine with formic acid, is a viscous, colourless oil, which boils at 170" under 15 mm. pressure, when it decomposes slightly ; cold, concentrated hydrochloric acid resolves it into formic acid and a-benzylhydroxylamine hydrochloride. The silver derivative is amor- phous, and yields benzaldehyde when heated. Benxylchloro-formoximc, CH,Ph*O*N: CHCl, produced by the action of phosphorus pentachloride on benzylformhydroxamic acid, is a, citronellal derivative is precipitated in a pure state. N. L.138 ABSTRACTS OF CHEMICAL PAPERS.colourless liquid having an odour of fir-wood; it boils at 101' under 11 mm. pressure, and at 210' under atmospheric pressure. It is a stable substance, and is devoid of basic properties ; hydrochloric acid eliminates a- benzylh ydroxy lamine quantitatively. Formhydroxamic acid has been investigated by Jones (Abstr., 1898, i, 173). It displays a great tendency to dissociate into hydroxylamine and carbon monoxide, decomposing in this way when heated a few degrees above the melting point. The solution in acetone undergoes spontaneous change in the course of a few days,.yielding acetoxime. The sodium salt decomposes into ammonia and sodium carbonate. The lead salt separates from water in colourless, transparent crystals con- taining water, and explodes at 145'; when dried a t loo', it yields ammonia and lead carbonate.Chloro-formoxime benzoate, COPh*O*N:CHCl, obtained from the benzoate of formhydroxamic acid by the action of phosphorus penta- chloride, crystallises from ether in odourless needles and melts at 53.5-54-5' ; aniline converts it into benzanilide and chloro-form- oxime, the latter yielding phenylisuretine. Chloro-fownozime acetate, COMe.0-N: CHCl, prepared from the acetate of formhydroxamic acid and phosphorus pentachlaride, boils a t 60-63' under 15 mm. pressure; it has a penetrating odour resem- bling that of chloro-formoxime, and gives rise to similar physiol- ogical effects. When the purified substance is heated with a concen- trated aqueous solution of silver nitrate, i t is decomposed slowly, yielding silver fulminate, silver chloride, and acetic acid.Ethyl a-benxyloxirninoforrnic ether, CH,Ph*O*N:CH*OEt, is the more volatile of the two isomerides produced by the action of ethyl iodide on the silver salt of benzylformhydroximic acid, and boils a t 121-122' under 15 mm. pressure, having the refractive index nD 1,5105 ; alcoholic hydrochloric acid gives rise to a-benzylhydroxylamine, whilst the gas eliminates ethylic chloride. The P-modification boils at 149-150' under 15 mm. pressure, and has nD 1.5256; in chemical behaviour, it resembles the isomeride. a-Bme yloximinofwmy E acety 2 oxide, CK,Ph*O*N: CH* OAc, prepared fromacetylchloride and benzylformhydroximicacid,melts at 146-148'; the P-modification melts a t 95-96', and boils at 162-163' under 12 mm.pressure, Benxyloximinodiacetyl oxide, CH,Yh*O*N:CMe*OAc, results from a-benzylhydroxylamine and acetic anhydride ; it crystallises from petroleum in snow-white needles, and melts at 101-102°. BenzyloximinoforwyZ 6enxoyZ oqide, CH,Ph*O*N:CH*OBz, obtained from silver benzy lformhydroximate and benzoyl chloride, crystal- lises from petroleum in colourless, transparent plates, and melts a t 29.5-30.5O ; it dissolves readily in organic solvents, and is'resolved by acids into a-benzylhydroxylamine and formic and benzoic acids. It is also produced when sodium benzylformhydroxamic acid is treated with benzoyl chloride, /3-benzoyl-a-benzylhydroxylamine, CH,Ph*O*NHBz, being also formed; this crystallises in rhombic plates, and melts at 103-104O (compare Beckmann, Abstr., 1894, i, 25).M. 0. F.ORGANIC CHEMISTRY. 139 Puriflcetion of Osazones and Estimation of their Rotatory Power. By CARL NEUBERG (Ber., 1899, 32, 3384-3388).-Practi- d l y all osazones are soluble in pyridine, the solubilities of the various members differing but little ; as a rule, 1 gram of the solvent dissolves 0.25 gram of an osazone in the cold, and 0.6 gram a t the boiling point of the solvent, Most of the osazones may be purified by recrystalli- sation from a mixture of pyridine and some other suitable solvent, such as water, alcohol, benzene, carbon disulphide, &c., or even more quickly by solution in pyridine and precipitation with benzene, ether, or light petroleum, Hydrazones and hydrazides behave in a similar manner. Solutions of osazones in pyridine or in pyridine and another solvent, especially ethyl alcohol, have been examined polarimetrically. The results obtained differ, not only in amount, but in some cases also in direction, from those given when acetic acid or alcoholic solu- tions are employed. The following rotations were obtained in a 100 mm.tube by using 0.2 gram of osazone, 4 C.C. of pyridine, and 6 C.C. of ethyl alcohol. Phenylosazones of E-arabinose, + 1'10' ; xylose, - 0'15' ; rhamnose, + 1'24' ; dextrose, - 1'30' ; d-galactose, + 0'48' ; sorbinose, - 0'15' ; maltose + 1'30' ; lactobiose +, 0' ; p-bromophenylosazones of 1-arabin- ose, f 0'28' ; xylose, +, 0' ; dextrose, - O"31' ; p-bromophenglhydr- mine glycuronate I (Abstr., 1899, i, 933) gave - 7'25', from which it follows that [ a]: = - 369'.Dextrose p-bromophenylosccxone, melts a t 222' and resembles the phenylosazone ; that of xylose melts at 208', and is moderately soluble in most solvents ; l-arabinose-p-byomop?~enyZosaxone sinters at 185', melts at 196-200°, and is more readily soluble in ether than the xylose derivative. Most of the parabromophenylosazones crystallise either in the usual yellow needles or in well-developed, six-sided plates. J. J. S. By OTTO RUFF [and in part MEuSSER] (Bey., 1899, 32, 3672-3681. Compare Abstr., 1899, i, 324).-Calcium d-ara- bonate, on oxidation with hydrogen peroxide and ferric acetate, yields a mixture rich in d-erythrose, which on treatment with phenylbenzyl- hydrazine gives d-erythrosephenylbenzylhyd?.axone ; this crystallises in white needles melting at 105.5', has a specific rotation [a], - 32' at 20°, and on treatment with a solution of formaldehyde yields d-eryt hrose.d-Erythrose. ?H VH H H d-Erythrose, OH*CH,*C-C*CHO, shows mutarotation, and has an approximate maximum specific rotation [a],, - 14.5' at 20'; it reduces Fehling's solution slightly in the cold, does not ferment, and yields an osaxone which cryst,allises from benzene in the form of yellow needles melting at 164'. On reduction with sodium amalgam, it yields inactive erythritol melting a t 120' (corr.). The melting point of the natural inactive erythritol has been stated by Lamy to be 112' and by Liebermann as 126'; the author finds it to be 120'. The oxidation of calcium d-arabonate with bromine gives d-erythronic acid. This is separated by means of the strychnifie or the brzccine salt, which140 ABSTRACTS OF CHEMICAL PAPERS.melts about 215" and has a specific rot;ztion [a], - 234O at ZOO. The aqueous solution of the acid, obtained hy the decomposition o€ these salts, turns the plane of polarised light strongly t o the left, but on evaporation leaves the Zactone, which crystallises in the form of com- pact prisms melting a t 10s' and has a specific rotation [ a ] D - 73.3" at 20'. The calcium salt crystallises with 2H,O and has the specific rotation [ a ] , + 8.2' a t 20'. The phenylhydraxide forms prismatic leaflets melting at 128' and has the specific rotation [a). + 17-5" at 20". d-Erythronic acid is identical with the trihydroxybutyric acid obtained in the oxidation of laevulose (Herzfeld, Bornstein, and Winter, Abstr., 1886, 862).R. H. P. Degradation of I-Arabinose. By ALFRED WOHL (BAT., 1899,32, 3666-3672. Compare Abstr., 1893, 892, and 1898, i, 168).-The oximation and subsequent acetylation of I-arabinose yield the nitrile of I-tetracetylarabonic acid ; from this, by the action of silver oxide suspended in methyl alcohol containing a trace of ammonia, hydrogen cyanide and an ncetyl group are eliminated, leaving I-tri~cetyleryt~rose, OAc*CH,*Y-F *CHO ; this crystallises from dilute alcohol, melts at 134O, and reduces warm Fehling's solution. On treatment of the nitrile with silver oxide and ammonia, 1-erythrosediacetamide is obtained; i t crystallises from water, melts and decomposes at 210°, and has a specific rotation [ Q ] ~ - 7.9'.On hydrolysis with dilute hydro- chloric or sulphuric acid of a solution of the diacetamide, the specific rotation changes to [a], + 3 2 * 7 O , which is probably the specific rotation of I-erythrose. The sugar could not be crystallised or otherwise puri- fied, but an osaxme crystallising from benzene or water and melting at 163-164' is easily obtained. Attempts were made to purify the sugar from ammonium carbonate by evaporation in a vacuum, but by this means, 1-dierythroseimic, NH [ C H < ~ ~ ~ ~ ~ > C H * OH] is obtained, which crystallises from warm water, melts at 1 5 5 O , exhibits mutarotation, and has a maximum specific rotation [ a ] , + 136.3'. ?Ac ?Ac H H R. H. P. Resolution of Racemic Compounds into Active Com- ponents. By EMIL FLSCRER (Bey., 1889, 32, 3617--3619).-The enzyme emulsin hydrolyses the P-methylglucoside of dextrose, but has no action on its optical antipode derived from I-glucose ; a similar diflerence is observed when the a-methyl derivatives are treated with yeast enzymes; under these conditions, the racemic compounds are rendered active, one active form being decomposed whilst the other remains unaltered.The selective action of enzymes is quite analogous to the par- tial resolution of r-mandelic acid by etherification with Lmenthol (Marckwald and McKenzie, Abstr., 1899, ii, 733, and Walden, this VO~., i, 7). Both processes are similar in principle to the method involving the employment of micro-organisms, but owing to theORGANIC CHEMISTRY. 141 substitution of the living cell by a n enzyme or by some other asymmetric compound, the phenomenon now becomes a chemical one.G . T. M. Action of Acetic Anhydride on Cellulose in Presence of Sulphuric Acid. By ANTOINE P. N. FBANCHXMONT (Bec. Trav. Chim., 1899, 18, 472-476).-A reply to Skraup's note on cellulose (Abstr., 1899, i, 852). The cellulose acetate melting a t 212' is not identical with inosite hexacetate, which has the same melting point. Cellulose acetate is hydrolysed by aqueous ammonia or a n ammoniacal solution of cuprous oxide, the cellulose being recovered. It is com- pletely soluble in chloroform, the solution resembling collodion ; i t also dissolves in acetic acid, and is reprecipitated by the addition of water. T. H. P. Alkalimetry of the Amines. By A. ASTRUC (Compt. rend., 1899, 129, 1021--1023).-The amines of the aliphatic series behave as strong bases towards phenolphthalein and methyl-orange, whereas t h e amines of the aromatic series a r e weak bases, being neutral t o phenolphthalein and mono-acid towards methy 1-orange.Hjdroxyl- amine behaves as a n aromatic amine, i t s hrdrochloride in aqueous solution being neutral t o methyl-orange and acid to phenolphthalein. The addition of two aliphatic alkyl groups t o a primary aromatic amine does not increase its basicity. When a second phenyl group is introduced into a primary aromatic amine, the basicity is lowered, a s is shown by diphenylamine, which is neutral to both phenolphthalein and methyl-orange. Double Halogen Salts of Cadmium with the Methylamines and Tetramethylammonium.By C. D. RAGLAND (Amer. C'hem. J., 1899, 22, 41 7-434).-Methylanaine cccdmiochloride, (NH2Me),,2HCI,CdCl,, the only double-salt obtainable by mixing solutions of cadmium chloride and methylamine hydrochloride, forms tabular, transparent crystals with a perfect cleavage ; of the byomides, NH21\4e,HBr,CdBr2, hotv- ever, is only isolat,ed with difficulty, and forms long, flattened prisms, whilst (NH,Me),,2HBr,CdBr2 separates in large, tabular, crystalline masses ; no double iodide could be prepared. Bimethykunzine cadmioch2oride.s.-( l ) , NHMe2,HCI,CdC12, forms long prisms, darkens at 240°, and melts and decomposes a t 261-262" ; (2), NHMe,,HC1,2CdC12 + 2H20 crystallises similarly and does not melt or decompose at. 270"; (3), (NHMe2),,3HC1,2CdC12, forms flat, transpart nt prisms.All three salts are easily soluble in water. Dimethylunzine cadmiobromides.-( I ) , NHMe2,HBr,CdBr2 forms slender, white needlc s or thin prisms ; (2), (NHMeJ2,2HBr,CdBr2 crystallises in rhombo- hedral prisms ; (3), NHMe2,HBr,4CdBr2 forms short, thick, brilliant crystals. Dimethylamine cadmioiodide, NHMe,,HI,CdI,, forms tabula- , cubical crystals. Trimethylamine cadmiochZorides.- (l), NMe,,HCl,CdUl, has been de- scribed by Hiortdahl (Zeit. Xryst. Min., 1882, 6, 466) ; (Z), (NMe3),,3HC1,2CdCl, crystallises in obliquely terminated, flattened prisms, Trimeth ylamine cadnziobromides. - (1 ), N Me,,H Br, Cd Br2 H. R. LE 8.142 ABSTRACTS OF CHEMICAL PAPERS. (Hiortdahl, Zoc. cit .) ; (Z), (NMe3),,3HBr,2CdBr, forms flattened prisms terminating in pyramidal planes.Trimethylamine cadmioiodides. - (I), NMe,,HI,CdI,, forms large cubes ; (2), (NMe3),,2HI,Cd1,, crys- tallises in beautiful, rhombic prisms. TetrametT~ylammonium cudmiochloride, NMe,Cl,CdCI,, forms hex- agonal-p yramidal crys t a1 s. Cadmio bromides. - ( 1 ), NMe4Br, C dBr,, forms crystals similar to those of the corresponding double chloride, and is sparingly soluble in water ; (2), (NMe,Br),,CdBr,, crystallises in short, imperfect, flattened prisms. Cadmioiodides.-( l), NMe,T,CdT, is a crystalline powder sparingly soluble in water ; (2), (NMe,I),,CdI,, is more easily soluble, and forms transparent octahedra. Double Halogen Salts of Tin with Aliphatic Amines and with Tetramethylamrnonium. By C. G. COOK (Amer. Chem. J., 1899, 22, 435-446. Compare Slagle, Abstr., 1899, i, 39).-The stannochloride, NH,Me,HCI,SnCl,, of methylamine forms well-defined, transparent prisms, that of dimethylamine, NHMe,,HCl,SnCl,, needle- like crystals, whilst trimethylamine stamnochloride, NMe,,HCl,SnCI,, is sparingly soluble in water and crystallises in triangular plates ; Hiortdahl’s analyses (Zeit.Kryst. Min., 1882, 6, 462) of the stanni- chlorides of the three bases are confirmed. Tetramethylammonium stccnnochloride, NMe,Cl,SnCl,, is sparingly soluble in water, and from dilute solutions crystallises in needles ; it is easily oxidised by the air t o the stannichloride, ( NMe,Cl),,SnCl,, which forms measurable crystals. Ethylumine stannochloride, NH,Et,HCl,SnCl,,. forms white needles, and is rapidly oxidised by t h e air to thestannichlorzde,(NH,Et),,H,SnCl,, which crystallises in well-defined, pyramidal crystals, possessing little lustre.Trimethylamine stannochloride could not be obtained owing t o its rapidly oxidising ; specimens of the stumnichloride were prepared which, although apparently homogeneous, were in reality mixtures of the cowzpounds (NMe3),,H,SnCl, ; NMe,,HCl,SnCl,, and (NMe3),,3HCl,SnCl,. Methylamine stannobromide, NE,Me,HBr,SnBr,, forms dark-red needles,and the stccnnibromide,(NH,Me),,H,SnBr,, yellow, crystal masses of varying habit. Dimethylamine stannobromide, NHMe,, HBr,SnBr2, crystallises in beautiful, lustrous, white scales or feathers, and is spar- ingly soluble in water, whilst the stunnibromide, (NHMe2)z,H2SnBrG, f orrns transparent, hexagonal prisms with modified ends.Tyimethyl- amine stannobromide could not be prepared owing to its readily oxidising in the air t o the stunnibromide, (NMe,)z,H,SnBr,, which forms small, transparent crystals. Ethylamine stannobromide, NH,Et,HBr,SnBrz, forms yellowish- white, lustrous needles, and the stunnibromide, (NH,Et)2,H,SnBr,, bright yellow, transparent, pyramidal prisms. Triethylumine stunno- bromide could not be isolated, but the stannibromide, ( NEt,),,H,SnBr6, forms yellow, rhombic plates. Physiological Action of Methylnitramine in Relation to its Chemical Constitution. By G. BELLAAR SPRUYT (Proc. k. Akad. Wetensch,. Amsterdam, 1899, i, 321-322).-The sodium derivative of methylnitramine has no toxic action on the animal system, and in this respect resembles the nitroparaffins, but differs from the isomeric W.A. D. W. A. D.ORGANIC CHEMISTRY. 143 nitrites. The physiological behaviour of the substance supports the view of its constitution maintained by Franchimont in opposition to Hantzsch ; the former regards it as a nitro-compound (Abstr., 1895, i, 445; compare, however, Abstr., 1897, i, 8 ; 1898, i, 293), whilst the latter proposes a formula which contains the radicle :NO*OH (com- pare, however, Abstr., 1896, i, 353,673), and recalls that of the nitrites. Preparation of Ethyldichloroamine. By H. PALOMAA (Ber., 1899, 32, 3343-3344. Compare Seliwanoff, Abstr., 1893, i, 192).- Ethyldichloroamine is best prepared by adding a concentrated aqueous solution of ethylamine hydrochloride to dry bleaching powder ; the substance thus produced boils at 85-90' and may be kept under water for 18 months without undergoing decomposition.G. T. M. G, T. M. Preparation of Ethyldichloroarnine. By JOSEPH: TCHERNIAC (Bey., 1899, 32, 3582).-The author's method of preparing ethyl- dichloroamine (Abstr., 1876, i, 913) gives as good results as Palomaa's modification (preceding abstract) of this process ; the decomposition of the base on keeping is caused by light and not by the presence of water, and can be prevented by storing in red glass bottles. W. A. D. Stereochemistry of Nitrogen [Propylisobutylamine]. By WILHELM MARCKWALD (Ber., 189 9, 32,3508-35 10). -p-Toluemsulpho- propylamide dissolves readily in organic solvents and melts at 52'. p- Toluenesu~ho~o~~lisobu t y Zamide cr ys t allises from light pet role urn and melts at 59-60°.Propylisobutylamine boils a t 123' under 768 mm. pressure ; the hydrochloride melts a t 275' and sublimes at a lower temperature ; the platinichloride is orange-coloured and melts at 187-188'; the aurichloride forms yellow crystals and melts at 1 S7-1BS'. T. M. L. By ALEXANDER ELLINGER (Ber., 1899, 32, 3542-3546).-Drechsel's lysine, obtained from either caseiii o r the peptone from the self-digestion of the pancreas, gives a fairly good yield of pentamethylenediamine (cadaverine) when allowed to undergo putrefaction by the aid of rotting pancreas in an atmosphere of hydrogen. This would indicate that lysine stands in the same relationship to pentamethylenediamine that ornithine does to tetra- methylenediamine (Abstr., 1899, i, 186), and is therefore a-e-diamino- 6exoic acid, NH,* CH,* [CH,],.CH(NH,)* C0,H. Derivatives of Pyrotartaric Acid and of the Isomeric Glutaric Acid. By P. A. MEERsuRa (Bec. 5%Ccv. Chim., 1899, 18, 367-377).-Pyrotccrta& methykamide, C,H,(CO*NHMe),, prepared either from methyl pyrotartrate or from pyrotartaric chloride, is found t o have the melting point 164-165"; the value 113-115' given by Henry (Abstr., 1885, 886) is hence erroneous. Pyrotartaric dimethylamide, C,H,(CO "Me,),, prepared by the action of dimethylamine on pyrotartaric chloride, is a colourless liquid boiling at 115-120° under 0.5 to 1 mm. pressure. Constitution of Lysine. J. J. S.I44 ABSTRACTS OF CHEMICAL PAPERS, MethyZ gZutm*ate, C,H6(CO2Me),, is a colourless liquid with a faint, pleasant odour; it boils at 93.5-94.5' under 13 mm.and a t 213-5-214' under 751 *5 mm.pressure, Glutaric methylctmide, C,H,(CO *NHMe),, separates by the addition of benzene to its solution in chloroform in large needles melting a t 126'; it is very soluble in water, chloroform, or acetone, less so in benzene, and insoluble in ether or light petroleum. Glutaric dimethylamide, C3H,(CO-NMe,),, is deposited from chloro- form i n large, transparent, lozenge-shaped crystals, which are very hygroscopic ; i t melts a t 49-51', Tables, containing, however, a large number of gaps, are given of the boiling and melting points of derivatives of the acids of the oxalic acid series with odd and even numbers of carbon atoms. The chief regulari- ties shown are as follows : The boiling points of methyl oxalate and succinate differ by 32', which is also the difference between the values for methyl malonate and glutarate.On replacing a hydrogen atom by methyl in the methyl o r ethyl derivatives of these acids, a rise of 2" in the boiling point takes place in the even carbon atom series, whilst in the odd members a fall of 2' is effected. The melting points of the amides of the even terms form a descending series, whilst with the odd members the reverse is the case, The specific gravities of the methyl and ethyl derivatives diminish with an increase in mole- cular weight in both the odd and even series. By PAUL CAZENEUVE (Compt. refzd., 1899, 129, 834--836),-Parabanic acid is obtained in small quantity by boiling oxaniide with phenyl carbonate, and can be iden- tified by its physical properties, and by conversion into calcium oxalurate, and by other chemical reactions.Constitution and Synthetical Application of Mercury Ful- minate. I. Direct Aldoximation of Benzene. By ROLAND SCROLL (Be?*., 1399, 32, 3492--3501).-Mercury fulminate moistened with benzene (100 grams) is mixed with benzene (150 grams) in a conical flask of 4 litre capacity, provided with a delivery tube and a thermometer, which dips into the liquid. Aluminium hydroxide dried for 3 hours a t about 130° (15 grams), commercial crys tallised aluminium chloride, AlC11, + 6H20 (15 grams), and freshly prepared, sublimed aluminium chloride (1 20 grams) are pounded to- gether for 3 hour in a mortar provided with an india-rubber cap, through which the pestle passes.The mixture in the flask is heated to 45' in a water-bath, and then the aluminium chloride mixture is in- troduced in portions of 5-10 grams in the course of about 40 minutes, the flask being well shaken all the time. The thermometer is watched and the temperature kept a t 43-45' meanwhile, and also for 4-2 hour longer, until i t begins to fall of itself. The mixture is allowed to remain for at least 3 hours a t the ordinary temperature, pounded in a mortar with crushed ice (700 grams) and concentrated hydrochloric acid (50 c.c.), and extracted with large volumes of ether. The ether is distilled off; mercuric chloride is removed by extracting several times with saturated sodium chloride solution, the benzaldoxime is removed by extraction with 25 per cent.caustic potash, benzaldehyde Its specific gravity is 1 *09337 a t 15'/4". T. H. P. Synthesis of Parabanic Acid. C. H. B.ORGANIC CHEMISTRY. I45 with 40 per cent. sodium hydrogen sulphite solution, and benzonitrile by distillation, with or without steam ; benaamide remains. About 80 grams of the fulminate enter into the reaction, and the yield of benzaldoxime is about 70 per cent. of the theoretical. The reaction C,H, + C:N* OH = C,H,. CH:N- OH is further evidence t h a t fulminic acid is carbonyl oxime (compare Nef., Abstr., 1895, i, 10). The aldoxime is a primary product of the reaction, and so is the nitrile in a sense, resulting probably from the action on the benzene of cyanogen chloride formed from the fulminate; the aldehyde and amide are formed from these.The yield of nldoxime depends on the observance of the details; if pure aluminium chloride is used without admixture of hydroxide or hydrated chloride, the nitrile is the main product. Homologues of benzene and alkoxybenzenes react in the same way as benzene, m-dihydroxybenzene derivatives yield aldoximes with the fulminate and hydrogen chloride, without addition of alumi- nium chloride ; presumably monochloroformaldoxime is first formed. C. F. B. Action of Nitric Peroxide on Mercurydimethyl. By EUGEN BAMBERGER AND JEKS MULLER (Bey., 1899, 32, 3546--3554.)-The oxime of irninodicarboxylic acid (inainodih ydroxamic acid), N H[ C( OH) : N* OH], , is obtained when a perfectly dry ethereal solution of nitric peroxide is slowly added to an ethereal solution of mercurydimetbyl, cooled by the aid of a freezing mixture, and kept in constant agitation ; it sepa- rates a s large, colourless needles, which are extremely unstable, and can only be analysed with the greatest difficulty.It dissolves readily in water, yielding an acid solution, but is practically insoluble in ether. It decomposes when warmed by the finger, and explodes violently when dissolved in hydrochloric acid containing a little potassium chlorate in solution. Alkalis dissolve it, yielding a yellow solution smelling slightly of diazomethane, which when acidified and then shaken with ether, imparts a deep blue colour t o the ethereal layer ; when the ether is evaporated, a colourless, crystalline substance is obtained which possesses the properties of a pseudonitrole, but which has not been further investigated. Mineral acids decompose imino- dihydroxamic acid, yielding formic acid, nitrous oxide, hydroxylamine, carbon monoxide and dioxide, ammonia, and probably nitrogen.An ethereal solution of nitric peroxide reacts with an ethereal solu- tion of formoxime in one of two ways, yielding either clear, glistening plates, which decompose a t about 80°, or formoxime Izitrate, (CH,:N* OH),,HNO,, which crystallises in compact prisms melting a t about 120'. The compound decomposing a t 80' may be identical with the pseudo- nitrole derivative mentioned above. Heat of Neutralisation and Acidimetry of Cacodylic Acid. By HENRI IMBERT (Compt. rend., 1899, 129, 1244-1246) -Cacodylic acid, when dissolved in water, is neutral towards methyl-orange, but towards phenolphthalein it behaves as a monobasic acid.Its heat of neutralisation is 14.10 cals., this value corresponding with the results obtained by Belugou for the action of caustic soda on the acid salts of J. J. 5. VOL. LXXVIII. i. rn146 ABSTRACTS OF CHEMICAL PAPERS. the monoalkylphosphates ; these compounds, like cacodylic acid, are also neutral to methyl.orangs and monobasic to phenolphthalein. G. T. M. Cyclic Polymethylenes of [Russian] Petroleum. By RUDOLF WISCHIN (Chem. Zeit., 1899, 23, 916-926).-A summary and biblio- graphy of the present state of knowledge of the comnosition of Russian petroleum, and of the naphthenes, naphthylenes, terpenes, and acids of the naphthene series, which either occur in it or have been prepared synthetically.G. T. M. New Compounds of Phosphorio Oxide with Benzene. By H. GIKAN (Compt. mad., 1899, 129, 964-966. Compare Abstr., 1898, i, 407).-Further examination of the brick-red product obtained (Zoc. cit.) by heating together benzene and phosphoric oxide a t 110-120° shows it to be benxenemonodimstup~osp~~oric mid, C,H,*P2O4.OH ; i t is very deliquescent, and is acted on by water with the production of benzene and phosphoric acid. It forms a deep yellow, deliquescent ccrnmonium salt, P20,PhNH4, which is decomposed by water, yielding ammonium phosphate and benzene ; the sodium and potussiurn salts form yellow precipitates rapidly decomposed by water. At higher temperatures (200-2 1 OO), benzene and phosphoric anhy dride combine to form benxenetridimetap?bosp?horic acid, C,H,,SP,O,, = C,H,( P204* OH),, which is a yellow, deliquescent substance slightly soluble in alcohol, insoluble in benzene, ether, carbon disulphide, or chloroform, and is decomposed by water.The ammonium salt, C,H,(P,O,NH,),, is a light yellow substance. By D. F. CALHANE and P. M. WHEELER (Amel.. Chem. J., 1899, 22, 449--458).-Austen’s ‘‘ a-dibromodinitrobenzene ” (Abstr., 1876, ii, 406), on reduction with zinc dust and acetic acid, yields 3 : 6-dibromo-o-phenylenediurnine, which, on distillation with steam, is obtained in felted, slender, white needles melting at 94-95O; it cannot be crystallised from hot water, as it is thereby partially decomposed. The hydrochloride forms white, lustrous needles, and is decomposed on heating, either alone or with water ; the diacetyl derivative, C,H,Br,(NHAc),, crystallises from hot alcohol in white, thread-like, matted crystals, and melts and decomposes at 265-2439’. The base is converted by further reduction with sodium amalgam into o-phenylenediamine, and condenses with phenanthraquinone to form p-clibromop~~enccnthru~~~enaxine or p?maunt?wu- p-dibromophenoquinox~Zine,C~~H~~N~Br~, which crystallises from benzene in concentric aggregates of silky, yellow needles ; with benzil, 5 : 8-di- byorno-2 : 3-dip?~enyZquinoxaZine, C,,H,,N,Br2, crystallising in sheaf-like aggregates of needles and melting a t 215-216O, is obtained. These facts show that Austen’s dinitro-compound is 1 : 4-dibromo- 2 : 3-dinitrobenzene. T.H. P. Constitution of a-Dibromodinitrobenzene.W. A. D. Rate of Substitution of a Nitro-group by an Alkoxyl. By CORNELIS A. LOBRY DE BRUYN (Proc. K. Akad. Wetensch. Amsterdam, 1898,1, 144-148. Compare Abstr., 1899, i, 744-747j.-A discussion of results already published. G. T. M,ORGANIC CBEMISTRY. 147 Phenyl- and p-Chlorophenyl-nitromethane. By A. VAN RAALTE (Rec, Trav. Chim., 1899, 18, 378--407).-The boiling point curve of mixtures of p-chlorotoluene and p-chlorobenzyl chloride rises continuously between 158" and 2 1 5 O ; 60 that, in preparing p-chloro- benzyl chloride by the action of chlorine on boiling p-chlorotoluene, the reaction is complete when the temperature of the boiling liquid reaches 215O. p-C:hZorobenxyl iodide, U6H4C1*CH,T, prepared by the action of potassium iodide on the corresponding chloride, is soluble in ether or alcohol, and crystallises from the latter in colourless needles melting at 64", which smell something like aniseed, and strongly attack the mucous membranes of the eyes and nose.By acting on the iodide with silver nitrite,. p-cklorophenylnitromethane [p-chloro-W-nitrotoluene], CGH,ClmCH,*N02, is obtained ; this compound exists in two modifica- tions, the normal form melting at 33-34'. The iso-compound, CGH4C1*CH: NO*OH, which melts at 64O, gradually changes into the normal form, the melting point passing through R minimum of about 28'. In phenol solution, both modifications give the normal depression of freezing point ; in acetic acid, the iso-compound has the normal molecular weight, whilst in diphenylmethane the mean value obtained is 208.5 instead of 171.5. The normal modification acts like a pseudo-acid, dissolving only slowly in caustic alkali solution ; further, it gives no reaction with ferric chloride, forms a neutral aqueous solution, and a N/50 solution in a mixture of equal parts of methyl alcohol and water is a bad conductor of electricity.The iso- compound, on the other hand, acts as an acid, as it dissolves readily in sodium carbonate solution, gives a deep coloration with ferric chloride, and forms an acid aqueous solution ; it also has a high con- ductivity which, however, falls as the iso-form becomes converted into the normal compound. AcetyZbenxZiydrox~.mic acid, COPh*NH*OAc, obtained by the action of acetyl chloride on either sodium phenylnitromethane or benz- hydroxamic acid, forms small, white needles melting at 125-126'.p-Chlorobenxoylbenxhydroxccmic acid, COYh*NH*O*CO*CGH,CI, pre- pared by the action of p-chlorobenzoyl chloride on benzhydroxamic acid, separates from benzene in colourless crystals melting at 137'. p-Clilorobenxhydroxarnic acid, C,H,Cl*CO*NH*OH, crystallises in small, shining plates melting a t 168", and p-dichlorodibenxhydro~arnic acid, CGHdC1 CO NH* O*CO* C,H,Cl, when crys tallised from ace tic acid, melts at 165". Benxoyl-p-chlorobenx~ydroxccmic acid, CGH,Cl*CO*NK*O*Bz, when deposited from benzene solution, melts at 158'. T. H. P, Separation of Primary, Secondary, and Tertiary Amines by Ginsberg's Method. By WASSILY SOLONINA (Ciiem. Centr., 1899, ii, 867-868; from J. Buss. Chern. SOC., 1899, 31, 640-655.Com- pare ibid., 29, 404),-The investigation of the action of benzene- sulphonic chloride, and in some cases of p-bromobenzenesulphonic chloride and m-nitrobenzenesulphonic chloride on eleven primary amines of the fatty, and on five of the aromatic series, shows that Ginsberg's method of separating primary and secondary amines, which depends m 2148 ABSTRACTS OF CHEMICAL PAPERS. on the different solubility of the products of these reactions, is in many cases inapplicable. Of the following compounds, those of the type NHR*SO,Ph are soluble in alkalis, except where it is stated t o the contrary, whilst those of the type NR(SO,Ph), are insoluble; the compounds of both classes are usually easily soluble in hot alcohol, ether, or benzene. By the action of benzenesulphonic chloride on butglamine in presence of potassium hydroxide, benzenesulphonbutylamide, C,H,*NH*SO,Ph, and dibenxenesulphonbutylamide, C,H,-N( SO,Yh),, are formed.The former is an oil which is insoluble in water, and when treated with nitric acid of sp. gr. 1-48 forms benxenesulphonbutylnitramide, C,H,*N(N02)*S0,Ph, which crystallises in colourless plates, melts at 29', is insoluble in water or alkalis, but easily soluble in alcohol, ether, or benzene. Dibenzenesulphonbutylamide crystallises in plates, melts at 89-90', and is insoluble in water and slightly soluble in cold alcohol. pBromobenzenesuZphonbutyZamide melts at 58' and yields a nitramide which melts at 37-33'. Di-p-bromobenzenesdphonbutyl- amide melts at 116' and is slightly soluble in cold alcohol.m-Nitro- benxemsulphonbutylamide is crystalline, melts at 69-70', and by the action of nitric acid yields the nitrumide, which is crystalline, melts at 80--81', and is insoluble in water or alkalis, Di-m-nitrobenzene- sulphonbutykumide is crystalline, melts a t 136', and i s insoluble in water. By the action of benzenesulphonic chloride on propylamine, benzenesuZphonpropylumide, NHPr*SO,Ph, is formed, together with a small quantity of a compound which melts a t 65', is insoluble in alkalis, and probably consists of dibenzenesulphonpropylamide. The former forms white crystals, melts a t 36', and by the action of nitric acid yields the nitramide, which melts at 34-35'. When p-bromo- benzenesulphonic chloride acts on propylamine, di-pbromobenxene- su~honpropy~amt'de, melting at 27', is formed in small quantity together with p-bromobenxenesuZphonpropylamide, which forms white crystals, melts at 65', is insoluble i n water, and by the action of nitric acid yields the p-opylnitramide, which melts a t 44'.DibenxenesuZphon- methylamide, NMe(SO,Ph),, melts at 104-1 05'. Ethylamine under similar conditions forms only benzenesulphonethykamide. p-Bromo- benxemsuZphonethyZamide melts at 8 lo, the &i-p-bromobe7ixenesuZpho~- ethylumide at 1 3 2 O . By the action of benzenesulphonic chloride on /3-aminobutane, benxenesulphonp~eudobutylanaide, melting a t 70-5", is alone formed. p-Bromobenxenesulphonpseudobutyhmide melts at 80°. m-NitrobenxenesuZphonpseudobutylamide,C4H9 *NH SO2* C6H4*N02, melt s at 58'. Benxenesulpho~nis~~o~kam~d~ melts a t 26', and p- bromo- benzenesulphonisopropylamide a t 99.5'.The corresponding %itramides melt at 35" and 83 -83". Bertzenesulp~~onvalerylamide, prepared from /I-aminopentane, is insoluble in water and melts at 40". eAmino- a-hexylene forms only benxenesulphonhexylamide melting a t 36-5-37". Benxeneaulphonallylnmide, prepared from ally lamine, melts at 39-40'. By the action of benzenesulphonic chloride on aniline and m-xyl- idine, compounds of the typeNHR*SO,Ph soluble in alkalis are formed. When an excess of the acid chloride is used, or by the action of the chloride on the preceding compounds in presence of alkali, smallORGANIC CHEMISTRY. 149 quantities of the compounds NR(SO,Ph), are produced. Dibercxeneaulph- onanilide, NPh(SO,Ph),, forms white crystals and melts at 128-129'.The benxoyl derivative, NPhBz*SO,Ph, crystallises in needles and melts a t 112-1 13O. Benxenesulphon-m-xylide forms prismatic crystals and melts at 130-1 3 lo. Dibenxenesulphon-m-x~Z~~e, C,H,Me,*N(SO,Ph),, crystallises in small needles and melts a t 142'. Benxenesu~honhejvtylamide, C7H,,*NH*S0,Ph, differs from the pre- ceding compounds of the same type in being insoluble in alkalis. Dibenx- enesulphnheptylamide forms leaf-like crystals, melts a t 91', and is insoluble in alkalis. a-Camphylamine yields benxenesu~hon-u-c~~p~yl- umide, which is a viscous oil and is also insoluble in alkalis. Dibenxyk auZphmcamphylamide, C,oH,7(S0,Ph)2, is also formed, but could not be ifiolated. p-Bromobenzenesulphonic chloride and m-nitrobenzenesul- phonic chloride react in a similar manner to benzenesulphonic chloride.Benxenesu~horzisoundecylamide, prepared from P-aminoundecane, melts at 64-65' and is insoluble in alkalis, but soluble in alcohol, ether, or benzene. Aminomenthone yields a sulphobenzene derivative, C,,H170*NH*S0,Ph, which melts at 82-85' and is soluble in alkalis. No definite compounds could be isolated from the products of the action of benzenesulphonic chloride on diaminohexahydrocymene. Details of a crystallographic examination of dibenzenesulphonbenzyl- amide are given in the original paper. E. W. W. Behaviour of Sulphonamides of Primary Amines towardB Alkalis. By WILHELN MARCKWALD (Bey., 1899, 32, 3512-3513. Compare Abstr., 1899, i, 749, and Solonina, preceding abstract).- Benzenesulphonheptylamide does not dissolve in dilute sodium hydroxide (compare Solonina), but is nevertheless partly converted into the sparingly soluble sodium salt, which solidifies when shaken with strong sodium hydroxide, and can be recrystallised from acetone.Hinsberg's rule therefore holds good, but, as in other cases, the salt is partially hydrolysed by water. T. M. L. Fixation of Sodium Hydrogen Sulphite by Ethylene Linkings. By HENRI LABB& (Bull. 800. Chim., 1899, [iii], 21, 1077-1080).-1t would appear from Tiemann's researches on aldehydes and ketones that the fixation of sodium hydrogen sulphite by an ethylene linking generally should depend largely on the charac- teristic function of the molecule, and a series of experiments was made with various typical substances in order to ascertain whether this was the case.When styrene is boiled for 10 hours in a reflux apparatus with excess of sodium hydrogen sulphite solution, only traces of an organic salt are formed, but cinnamyl alcohol under the same con- ditions yields a notable quantity of a white, deliquescent, very soluble salt of the composition C,H,,O,SNa. Geraniol and citronellol form similar compounds of the composition C,,H,,07S,Na2 and C,,H2,0,SNa respectively; in the case of geraniol, the yield is about 15 per cent. With cinnamic acid, the reaction occurs much more readily, a large yield of the compound C,H,O,SNa, being obtained; this salt is, how- ever, difticult ta separate on account of its very sparing solubility in180 ABSTRACTS OF CHEMICAL PAPERS.alcohol. It is concluded that the fixation of sodium hydrogen sulphite by an ethylene linking takes place with great difficulty in the case of aromatic hydrocarbons with an aliphatic side-chain, but more readily in the case of alcohols, especially aliphatic alcohols of the type of geraniol, whilst with acids, probably because of their solubility, com- bination occurs with great ease. N. L. Resin Oil. By GUSTAV KRAEMER and ADOLF SPILKER (Ber., 1899, 32, 361 4).-The oil obtained by distilling colophony under pressure (Ber. 1899, 32, 2952), to which the authors assigned the formula C42H02, appears, from a determination of its molecular weight by the cryoscopic method, to have the composition C18H28, and is perhaps derived from abietic acid by the loss of 1 mol.of carbon dioxide. W. A. D. Conversion of 1 : 8- and 1 : 5DinitronaphthaIenes into Nitro- nitrosonaphthols. By PAULFRIEDLANDER(Ber., 1899,32,3528-3532. Compare Graebe, this vol., i, 24).-1f the action of sulphuric acid on dinitronaphthalene is continued until the product is completely soluble in alkali, sulphonation occurs; the sulphonic acids are con- verted on nitration into trinitronaphthols identical with those pro- duced on nitrating the nitronitrosonaphthol, which forms the chief product of the action, and are therefore 8- or 5-nitro-4-nitroso-1-naphthol- 3-sulphonic acids. 8-Nitro-4-nitroso-1-naphthol gives a 6enxoate which crystallises from xylene in yellowish-white, slightly soluble needles and melts at 194O, whilst the 5 : 4-derivative gives a similar benzoate which melts at 210'.The nitronitrosonaphthols are converted by alkaline potassium ferricyanide into the potassium salts of the cor- responding dinitronaphthols ; 4 : 5-dinitgo-1-naphtholcrystallises in straw- yellow needles and melts at 230°, whilst 4 : 8-dinitro-1-naphthol melts at 135O ; the dinitronaphthols have only feeble dyeing properties but give trinitronaphthols which resemble naph tho1 yellow in this respect . 4 : 8-Diamino-1-naphthol is oxidised by cold ferric chloride to a blue solution of the quinoneimide, but, on warming, to a red solution of g-a,ino-a-naphtha~~inone, which arystallises from acetic acid, melts and decomposes at about 180°, and dissolves in sulphuric acid to a colourless, cry s t alline salt. 1 : 3-Dinitronaphthalene is not produced in the nitration of nitro- naphthalene by nitrosulphuric acid; the 1 : 5 - and 1 : 8-dinitronaphthols can be very readily separated by crystallising from pyridine instead of extracting with acetone ; by using suitable quantities of sulphuric acid in the nitration, a similar separation can be effected, the whole of the 1 : 5-dinitronaphthalene crystallising out on cooling, whilst the 1 : 8-dinitronaphthalene remains in solution, and can be converted directly, if desired, into 1 : 3 : 8-trinitronaphthalene by adding a further amount of nitric acid.1 : 3 : 8-Trinitronaphthalene dissolves in cold sodium hydrogen sul- phite to a red solution of an additive compound, from which it is pre- cipitated unchanged by warming with acids, T. M. L,ORGANIC CHEMISTRY.151 Fittig's Reaction. By MICHEL PELLEORIN (Rec. Trav. Chirn., 1899, 18, 457-465).-By the action of sodium on a mixture of m-xylylene dibromide and bromobenzene, three definite products were obtained. 1. Diphenyl. 2. m-Dixylylene (?), CYlBHl6, slightly soluble in alcohol or ether and crystallising from the latter in hexagonal prisms melting at 131 -5" ; crgoscopic determinations in benzene gave a mean molecular weight 205.5, CI6H,, requiring the nnmber 208. It boils at 170' under 12 mm. and a t 290" under the ordinary pressure, and forms a dibromo-derivative, C1,HI,Br,, crystallising from benzene in colourless prisms which melt at 213-214'. 3. Di-m-phsnylene- diethene (?), CsH,<CH~CH>C6H,, which crystallises from a mixture of ether and alcohol in long, silky, colourless needles, melts at 19l0, boils at 260" under 1 2 mm.pressure, and is very soluble i n ether, but less so in alcohol, benzene, or carbon disulphide. I n freezing benzene, it has the mean molecular weight 200.9, the value for U,,H,, being 204. The only definite product obtained by the action of sodium on a mixture of m-bromobenzene and benzyl chloride was dibenzyl. CH'CH T. K. P. Synthesis of Picene. By T. HIRN (Ber., lf!99, 32, 3341-3343. Compare Abstr., 1892, 623, and 1895, i, 292).-Picene is a phen- anthrene of the naphthalene series and contains a linking joining the two naphthalene residues in the P/?'-position. The exact position of the dimethenyl group is, howelver, not known with certainty, and accordingly three formula for picene are possible; it may be an apa'p'-, a Ppp'p'- or an upp'p'-derivative. The first of these consti- tutions is the most probable, because the hydrocarbon is produced when aa'-dinaphthastilbene (Abstr., 1893, 272) is distilled through a red hot glass tube.The properties of the product correspond with those of picene from coal-tar, except that the xylene solution of the former is not fluorescent. Double Halogen Salts of Tin with Organic Bases. By GEORGE M. RICHARDSON and MAXWELL ADAMS (Arne?.. Chem. J., 1899, 22, 446--449).-1n addition to the compounds obtained by Slagle (Abstr., 1899, i, 39), the following have been prepared. Z'etrccniline stannichloride, (NH2Ph),,4HC1,SnC1,, is obtained in well-formed crystals. Dimethylaniline stctnnochloride, NMe,Ph,HCl,XnCl, + $H,O, corre- sponds in preparation and crystalline form with Slagle's analogous toluidine compounds.Aniline stannobromide, NH,Ph,HEr,SnBr,, forms small, white, spear-like crystals, which melt at 152O, and become oxidised on being recrystallised. Dianiline stannibvomide, (NH,Ph),,H,SnBr,, forms flat, tabular, straw-coloured crystals, whilst tetraniline stannibromide, (NH2Ph)4,4HBr,SnBrg, which is less soluble in water than the dianiline compound, separates in light-yellow, well-formed crystals, and melts and decomposes a t 274". Anilides. By FREDERICK D. CHATTAWAY, KENNEDY J. P. ORTON, and W. H. HURTLEY (Ber., 1899, 32, 3635-3638. Compare Trans., 1899, 75, 1046, and following abstract).-The following anilides have G. T. 31. W. A. D.152 ABSTRACTS OF CHEMICAL PAPERS, been obtained by the transformation of substituted nitrogen chlorides or bromides. p-ChZos.oformyZuniZide, obtained from the isomeric phenylformyl- nitrogen chloride, crystallises in white plates and melts at 102'.2 : 4-DichZor?f~myZuniZid~, prepared either from the corresponding nitrogen chloride or by formylating 2 ; 4-dichloroaniline, crystallises from alcohol in white needles melting a t 154O; the benxoyl derivative forms white prisms and melts at 115'. 2 : 4 : 6-Trichlorofo~~2yZ~n~Z~de crystallises from alcohol or chloroform in white needles and melts at 180°; the acetyl derivative is most con- veniently prepared from acetyl-2 : 4-dichlorophenylnitrogen chloride j the benxoyl derivative crystallises from alcohol in white needles melt- ing at 174O. 2 : 4-DibromoformyZaniZide forms lustrous, white needles melting at 145" ; the acetyl derivative is readily prepared from the isomeric acetyl- p-bromophenylnitrogen bromide. 2 : 4 : &Tribromoformylanilide, crystallises in white needles and melts at 221.5'; the acetyl derivative is easily obtained from acetpl-2 : 4- dibromophenyhitrogen bromide l-Chloro-2-formylnap~thulide crystwllises from benzene in prisms melting a t 136O.G. T. M. Substituted Nitrogen Bromides and their Relationship to Bromo-substituted Anilides and Anilines. By FREDERICK D. CHATTAWAY and KENNEDY J. P. ORTON (Heis., 1899, 32, 3573-3582. Compare Trans., 1899, 75, 1046).-Substituted nitrogen bromides of the type R*CO*NBrR' are readily obtained by the action of hypo- bromous acid on the corresponding anilides.They are all sulphur- yellow compounds G f low melting point, crystallising from light petroleum either in large, transparent prisms or in plates, and are characterised by the readiness with which they enter into various chemical reactions. They react with hydrobromic acid, hydrocyanic acid? potassium iodide.solution, or hydrogen peroxide, regenerating the original anilide. They are much more easily hydrolysed than the corresponding chlorides (Zoc. cit.), and are readily decomposed by alcohol, yielding the anilide, together with ethyl bromide, acetaldehyde, and ethyl acetate. When heated, all these nitrogen bromide deriva- tives undergo molecular transformation, the bromine atom migrating from the nitrogen to a carbon atom of the benzene nucleus, always in the para-position unless this is already occupied, when an ortho- derivative is formed.The authors conclude that in the ordinary bromination of an aniline or anilide the bromine becomes first attached to the nitrogen atom and then passes to the benzene nucleus. Rcetylphenylnitrogen bromide (N-bromoacetyZanil,ide, acetyZphertyZbrorn- amide), NPhBrAc, obtained by the action of hypobromous acid on a cold saturated solution of acetylanilide at 0' containing potassium hydrogen carbonate, melts at 88O, is readily soluble in chloroform, but only moderately so in light petroleum ; when kept for any length of time, it gradually becomes transformed into p-bromo- acetanilide. Acetyl-p-bromophelzylnitrogen bromide, C6H4Br*NBrAc, crystallises inORGANIC CHEMISTRY.153 six-sided plates melting at 108' ; the isomerisation is not complete even after the bromide has been kept for some months. The 2 : 4-dibromo- derivative melts at 1 loo, and is quite stable a t the ordinary temperature. The 2 : 4 : 6-tribromo-derivative melts at 123O, and when strongly heated gives up bromine and forms 2 : 4 : 6-tribromoacetylanilide. Form ylphenylnitrogen bromide, N P hBr *CHO, melts a t 88-8 9', and when allowed to remain for 24 hours is completely transformed into p-bromoformylanilide. The p-bromo-derivative melts at 1 13' ; the 2 : 4-dibromo-derivative melts a t 87' and the 2 : 4 : 6-tribromo-deriva- tive at 90'. Benxoylphenylnitrogen bromide (N-bromobenzo?llanilide, benzoylphenylbromamide), NBrPhBz, is best obtained by allowing an alcoholic solution of benzoylanilide to drop slowly into an excess of hypobromous acid containing potassium hydrogen carbonate in solution at 0'; it crystallises in small, yellow plates melting at 99', and is readily transformed into benzoyl-p-bromophenylanilide.The p-bromo-derivative melts a t 139-133" ; the 2 : 4-dibromo- derivative melts and decomposes a t 121°, and when heated for half a n hour a t 100' yields 2 : 4 : 6-tribromobenzoylanilide melting a t 198'. The 2 : 4 : 6-tdromo-derivative melts at 121'. J. J. S. Symmetrical Dinitrodixylylcarbamides and Dinaphthylcarb- amides. By HENRI VITTENET (Bull. Xoc. China., 1899, [iii], 21, 948-951).-These compounds have been prepared by methods similar to those employed for the preparation of the dinitrodiphenyl- carbamides and the dinitroditolylcarbamides (Abstr., 1899, i, 692, 81 0 ) , namely, by heating the isomeric nitroxylidines and naphthyl- amines with carbonyl chloride or phenyl carbonate.Dinitrodixylylcarbamide, CO(NH*C,H,Me,*NO,), [NH ; Me, : NO, = 4 : 1 : 3 : 51, from 5-nitro-1 : 3 : 4-m-xylidine, crystallises from anhydrous acetic acid in small, yellow needles, subliming without melting at about 300°, and is insoluble in water, benzene, ether, or chloroform, Like other compounds in which the NO, and NH, groups occupy the ortho-position with regard to each other, 5-nitro-1 : 3 : 4-m-xylidine reacts with carbonyl chloride, but not with phenyl carbonate. [NH : Me, : NO, = 4 : 1 : 3 : 61 is only obtained in very small quantity by the general methods indicated above, and is best prepared by the action of 6-nitro-1 : 3 : 4-m-xylidine on 6-nitro-1 : 3 : 4-m-xylylcarbimide in benzene solution.It crystal- lises in microscopic, white needles which sublime without melting when heated, and is insoluble in water, benzene, ether, and chloroform. a- and P-8-Dinaphthylcarbamides, prepared by this method, were found to melt at 314-315' and 309-310' respectively, not at 270' and 293O as previously stated. [Young and Clark (Trans., 1897, 71, 1200, give the melting points Dinitrodixylylcarbamide at 284-286' and 289--290'.] N. L. Aromatic Carbimides. By HENRI VITTENET (Bull. 800. Chim., 1899, [ iii], 21, 952-958).-The following new compounds have been obtained by the action of carbonyl chloride on aromatic bases, accord- ing to the general method which has been recently described (Gbstr..1899, i, 756).154 ABSTRACTS OF CHEMICAL PAPERS. 5-N~tro-m-xyZyZcarbirnide, NO,*C,H,Me,*N : CO [Mez :N : CO :NO, = 1 : 3 : 4 : 51, from 5-nitro-1 : 3 : 4-m-xylidine, crystallises in microscopic, yellow needles melting at 71-72' and is soluble in benzene, toluene, ether, chloroform, or light petroleum. Ethyl 5-nitro-m-xylylcarbcte [Me,:NH*CO,Et:NO,= 1 : 3 : 4 : 51 formed by the interaction of alcohol and the preceding compound, crystallises from 95 per cent. alcohol in small, amber-yellow prisms melting at 125-126'; it is soluble in chloroform. 6-nitro-1 : 3 : 4-m-xylidine, crystallises in large, yellow needles melting a t a few degrees above zero and distilling without decomposition a t 21 2-214' under 97 mm.pressure. Ethyl 6-nitro-l : 3 : 4-m-xylylcarbccmate, obt,ained by the action of alcohol on the preceding compound, crystallises from alcohol in large, white needles melting at 120'; it is insoluble in cold, but soluble in boiling water. p-Chlorophenylcarbimide, from p-chloroaniline and carbonyl chloride, is a white, crystalline substance which melts at 30-31' to a colour- less liquid having a very irritating odour. Ethyl p-chlorophenylcarbamate, prepared by treating the correspond- ing carbimide with alcohol, crystallises in white, silky plates melting at 68', and is very soluble in ether, benzene, or chloroform. m-Chlorophenylcurbimide, from m-chloroaniline, is a colourless liquid of irritating odour which boils a t 113-114' under 43 mm. pressure. Ethpl m-chlorophenylcarbamate, from the corresponding carbimide and alcohol, is an unstable, viscous, colourless liquid which boils at 200-201' under 46.5 mm.pressure. o-Chlorophenylcarbimide, from o-chloroaniline, is a colourless liquid boiling a t 114-115O under 43 mm. pressure and having a very irritat- ing odour. Ethyl o-chlorophenylcarbamate, from the preceding compound and alcohol, is a colourless liquid which boils at 170-172' under 42 mm. pressure. p-lodophenylcwrbimie, from piodoaniline, is a crystal line substance of agreeable odour melting a t 45-46' ; it is very unstable and quickly decomposes, yielding the corresponding carbamide. Ethyl p-iodophenylcarbamate crystallises in large, white needles melting a t 111-112O and is very soluble in ether, benzene, or chloroform. p-Methoxypheuylcarbimide, from p-anisidine, is a colourless liquid which quickly becomes yellow and decomposes ; it boils at 132-133' under 38.5 mm.pressure. Ethyl p-methoxyphenylcurbamate crystallises in large, white needles melting a t 63-64O; it is very soluble in ether, chloroform, or benzene. a-Naphthylcarbamide, from a-naphthylamine, is a brown liquid having a very irritating odour. Ethyl a-naphthylcarbamate crystal- lises in small, white needles melting at 7 9 O . This and the preceding compound have been previously obtained by Hofmann by other methods. P-NccphthyZcccl.birnide, from /3-naphthylamine, cry stallises from light 6-Xtr0-l : 3 : 4-m-xylylcurbimide, fromORGANIC CHEMISTRY. 153 petroleum in white plates melting a t 55-56O and is very soluble in ether or benzene.Ethyl /3-naphthylcarbamai?e, obtained by the action of alcohol on the corresponding carbimide crystallises from 40 per cent. alcohol in small, white needles melting at 69O; it is very soluble in ether, Characteristics of Stereoisomeric Ammonium Salts. By EDGAR WEDEKIND (Ber., 1899, 32, 3561-3569. Compare Abstr., 1899, i, 351, and Pope and Peachey, Trans,, 1839, 75, 1127)- a- (or y)-Phenylbe~~zyZmethylally~ammonium bromide is obtained by the direct com bination of benzylmethylaniline and ally1 bromide or more readily of methylallylaniline and benzyl bromide ; i t melts and de- composes not very sharply a t 161-1 63O, and dissolves readily in warm alcohol or water, but when its aqueous solution is boiled, decomposition ensues ; it crystallises in the rhombic system and is isomorphous with the a-iodide (Zoc.cit.) [a : 6 : c = 0.88888 : 1 : 0.658541. The a-chloride is obtained when the a-iodide is treated with moist silver oxide, then with concentrated hydrochloric acid, and the solution thus formed evaporated at 50-60' ; it, crystallises in large, spear-shaped, rhombic crystalsisomorphouswith the a-bromide and a-iodide, meltsat 152-1 54', and is readily soluble in most organic solvents with the exception of light petroleum and ether; it also dissolves in water, but the solution, when boiled, undergoes partial hydrolysis. The plutinichboride, (C,pH,,N),PtCl,, crystallises in minute, yellow needles and the auri- chloride forms a yellow, amorphous powder melting at 90-94'. P-Phen yl benxylmeth y Zallylammonium bromide is obtained when benzyl- allylaniline and pure methyl bromide are left in contact with one another for several months a t the ordinary winter temperature.It crystallises from a mixture of chloroform and acetone in well-developed, colourless, monoclinic plates, is specifically heavier and also melts at a lower temperature, namely, 105-107°, than the isomeric bromide. It is apparently hemihedral [a : b : c = 1.1128 : 1 : 1,3084; /3= 71'65'1. The P-chloride, obtained indirectly from either the bromide or iodide, crys- tallises in small, glistening, monoclinic prisms isomorphous with the P-bromide [a : b : c = 1.054 : 1 : 1-260 ; /? = 71'40'1. It decomposes at 113-11 6' whereas the a-chloride decomposes at 152-154O. The P-iodide (Zoo. cit.) is not isomorphous with the P-chloride and bromide ; as it crystallises in the rhombic system; it may, however, be dimor- phous.The pkatinichloride crystallises in brownish-yellow needles decomposing a t 198 -1 99' ; the P-aurichloride forms golden-yellow needles melting a t 105-107° and decomposing at about 180O. Both compounds are more soluble than the isomeric a-derivatives. benzene, chloroform, or 95 per cent. alcohol. N. L. J. J. S. Acyl Derivatives of the Aromatic Thiocarbamides : their Isomerism and Constitution. By A. HUGERSHOFF (Bey., 1899, 32, 3649--3660).-Acyl derivatives of the aromatic thiocarbamides can be prepared by dissolving the carbamide in the acyl anhydride at about 80°, and allowing the solution to remain for some time at the ordinary temperature, whereas, if the solution is heated, decomposition occurs, and thiocarbimides are produced (Werner, Trans., 189 1, 59,156 ABSTRACTS OF CHEMICAL PAPERS.396). These compounds have not the properties of thiocarbamides, since they are soluble in alkalis, and are not desulphurised by mercuric oxide. They have probably the formula NR:C(SH)-NR*COR, and this view is confirmed by the fact that the acyl derivatives of mono- substituted thiocarbamides exist in two forms, one of which behaves as a true thiocarbamide, whilst the more stable modification agrees in i t s properties with the ordinary acy1 derivatives, which the author terms isothiocarbamides. Acetyldiphenylisothiocarbamide, NPh:C(SH)*NPhAc, which has already been prepared by Deninger (Abstr., 1895,461), melts a t 96', and not a t 91' as stated by that author.Mercuric oxide converts it into the mercuric salt, (C,,H1,ON,S),Hg. Acetyldi. o-tolylisothiocarb- amide, melts at 1 0 3 O , whilst the corresponding p-tolyl compound melts a t 108O. Acetyldiphenetylisothiocarbcimide melts at 98' ; PO- pionyldiphenylisothiocarbarnide, NPh:C( SH) *NPh*COEt, me1 ts at 93*5O, whilst propionyldi-o-tolylisothiocayhamide melts at 97 *5", and the corresponding p-tolyl compound at 105". Isoualeryldiphenylisothio- carbumide melts a t 834 AcetyZphenyZthiocaybamide, NHPh*CS*NHAc, obtained by the action of acetic anhydride on phenylthiocarbamide, melts at 139', but on further heating is converted into the iso-derivative melting at 171'. Concentrated aqueous alkalis decompose it, forming acetanilide and a thiocyanate, whilst dilute alkalis dissolve it, forming a solution from which acids precipitate the tautomeric form.It undergoes the usual reaction of a thiocarbamide with mercuric oxide, acetylphenyl- carbamide being produced. The tautomeric form, NPh:C(SH)*NHAc, has already been described by Miquel (Bull. Soc. Chim., 18'75, [ ii], 25, 252). Both the forms have the same molecular weight as determined by the cryoscopic method in acetic acid solution. Acetyl-o-tolylthio- carbamide, C,H,Me*NH*CS*NHAc, melts at 140' and behaves in a similar manner t o the phenyl derivative. The corresponding iso- derivative has been described (Dixon, Trans., 1889, 55, 304). Acetyl- p-tolylthiocarbamide, melts a t 137'. AcetyZphenetylthiocarbumide melts at 137", and the corresponding iso-derivative a t 196'.A. H. [Phenylthiocarbimide] as a Reagent for the Detection of the Alcoholic Hydroxyl Group. By WILLIAM R. ORNDORFF AND F. A. RICHMOND (Amer. Chem. J., 1899, 22, 458-472).-Phenylthio- carbimide combines with aliphatic monohydroxy-alcohols to form well- defined tbiourethanes, but does not interact in so simple a manner with unsaturated or polyhydroxy-alcohols, phenols, aromatic alcohols, or fatty or aromatic acids. I n most cases, therefore, i t cannot be used as a substitute for phenylcarbimide to detect the presence of a hydroxyl group. Ethyl phenylthiocarbtamate, NHPh*CS*OEt or NPh:C(SH)*OEt, melts at 71-72", not a t 65' as stated by Hofmann (Ber., 1869, 2, 120 ; 1670, 3, 772). Methyl phenyttiziocccrbamate, NHPh*CS*OMe, or NPh :C(SH)*OMe, prepared like the ethyl derivative, separates from alcohol in white, triclinic crystals [u : b : c = 0.6065 : 1 : 0.5513 ; a = 63'19'57", p = 128'52'50", y = 103O8'48"], and melts at 97".Propgl- p~enylthiocurbamate, NHPh*CS*OPra or b;lPh;C(SH) *OPra, prepared byORGANIC CHEM&THY. 157 heating a mixture of propyl alcohol and phenylthiocarbimide for 16 hours at lOO', crystallises from absolute alcohol in white, triclinic needles and melts at 48O; if a higher temperature than 100' is used in the preparation, gaseous products together with thiocarbanilide are formed. Isopopyl phenylthiocarbamate, NHPh*CS*OPrg, or NPh:C(SH)*OPrP, prepared similarly? separates from alcohol in brilliant, colourless,monoclinic crystals, [a : b : c = 0*6777 :I : 1*8325,/3 = S7Q28'50''] and melts at 85.5'.The corresponding isobutyl compound, NHPh*CS*O*CH,Prs or NPh:C(SH)*O*CH,Prp, crystallises from alcohol, and melts a t 80.5'; the tertiwy butyl deri- vative, NHPh*CS*O*CMe,, or NPh:C(SH)*O*CMe,, melts a t the atmo- spheric temperature, but solidifies in a freezing mixture, forming long, white needles. Isoamyl p4enyZt hiocarbamate, N H P h CS* OC,H,, , or NPh*C(HS)*OC5H11, forms white crystals and melts a t about 21'. When ally1 alcohol is heated with phenylthiocarbimide, symmetrical diphenylcarbamide is formed, but no thiourethane ; in like manner, glycol and glycerol give rise only to diphenylthiocarbamide (compare Tessmer, Abstr., 1885, 774), whilst in the case of glycol chloro- hydrin, erythritol, or dextrose no action occurs.Phenol yields thio- carbanilide only, and not the corresponding thiourethane as stated by Dixon (Trans., 1890,57, 268), and Snape (Trans., 1896, 69, 98) ; with quinol, pyrogallol, and benzyl alcohol there is no action. On heating phenylthiocarbimide with acetic acid for 5 hours a t loo", symmetrical diphenylcarbamide is obtained ; with benzoic acid under similar conditions, there is no action, whilst with lactic acid, thiocarb- anilide and carbanilide alone are formed, W. A. D. Conversion of Nitrobenzene into o-Nitrophenol by means or Caustic Potash. By ALFRED WOHL (Ber., 1899, 32, 3486-3488). -When nitrobenzene is mixed with five times its weight of dry, finely- powdered potassium hydroxide, and the mixture heated in a closed vessel, in small quantities at a time, for 2 hours at 60-70" and then for 1 hour at 95', 33 per cent.of the nitrobeazene is converted into o nitrophenol. If the heating a t 95' is omitted, about 55 per cent. of the nitrobenzene is recovered unchanged, but of the rest, 45 per cent. is converted into o-nitrophenol. The air is not concerned in the oxidation, for this takes place equally in a current of hydrogen. None of the ordinary products of the reduction of nitrobenzene can be detected in the product of the reaction, C. F. B. Reactions of Phenyl Chloroacetate. By ALBERT MOREL (Bull. Soc. Chim., 1899, [iii], 2l7958-964).-Phenyl chloroacetate, obtained by heating together molecular proportions of phenol and chloroacetyl chloride, crystallises in colourless needles melting at 44-45' and is somewhat unstable, exposure to moist air slowly converting it into phenol and chloroacetic acid, It does not react with phenol at 250', and is the only product of the action of chloroacetyl chloride on phenol, even a t 200'; but when heated with ethyl alcohol or sodium ethoxide, the theoretical amount of ethyl chloroacetate is formed, with liberation of phenol.The replacement of the phenoxy-group in phenyl chloroacetate is therefore effected much more readily than is158 ABSTRACTS OF CHEMICAL PAPERS. the case with phenyl chlorocarbonate (Abstr., 1899, i, 875), whilst the chlorine atom, on the other hand, possesses great stability. The action of ammonia on phenyl chloroacetate in ethereal solution results in the formation of chloroacetamide and ammonium phenoxide.The production of phenyl aminoacetate by heating phenyl chloroacetate with alcoholic ammonia at 140°, as described by Prhvost (S. p. Chern., 1871, [ ii], 4, 379), could not be confirmed, and the formation of such a compound seems impossible in view of the reactions described above. N. L. Reactions of Phenyl Chloroacetate and Phenyl Glycollate. By ALBERT MOBEL (Bull. Xoc. Chim., 1899, [iii], 21, 964-969. Com- pare preceding abstract).-When heated with aniline (2 mols.) a t SOo, phenyl chloroacetate is converted into phenyl anilinoacetate, NHPh*CH,*CO,Ph, which crystallises in small, colourless scales melting at 52--83O, and is soluble in alcohol, ether, chloroform, benz- ene, 01: strong acids; boiling with alcohol converts it into ethy anilinoacetate, with liberation of phenol. If, however, phenyl chloro- acetate is boiled with aniline, anilinoacetoanilide is formed.Phenyl chloroacetate reacts with phenylhydrazine at 50° to form phenyl whenylhydraxinoacetate, N,H,Ph*CH,*CO,Ph, which crystallises in small, colourless scales melting at 93-94O. Pyridine slowly enters into combination with phenyl chloroacetate and yields a yellowish- white, unstable compound, CH,Cl*CO,PhlC,NH,, which is readily decomposed by water. Sodium phenoxide is without action on phenyl chloroacetate in the cold, but on heating a good yield of phenyl phen- oxyacetate is obtained ; this crystallises in slender, colourless, mono- clinic needles melting a t 58O, and is converted by boiling with alcohol into the corresponding ethyl ester, with liberation of phenol.When treated with ammonia in ethereal solution, it yields phenoxyacetitmide, whilst boiling with aniline converts it into phenoxyacetanilide. Hxcess of ammonia or of aniline a t ZOOo has no action on the second phenoxy-group, and in this respect phenyl phenoxyacetate differs greatly from diphenyl carbonate. From these results, it appears that chloroacetyl chloride, phenyl chloroacetate, and phenyl phenoxy- acetate, on the one hand, and carbonyl chloride, phenyl chlorocarbon- ate, and diphenyl carbonate, on the other, belong to two distinct classes, the first being derived from a substance of complex function, whilst the second includes derivatives of a symmetrical compound. N. L. Action of Chlorodinitrobenzene on Potassium Benzoate and on Acetamide.By OTTO KYM (Ber., 1899,352, 3539-3540). -Dinitrophenyi benzoate (Abstr., 1899, i, 647) is produced when potassium benzoate is heated with chlorodinitrobenzene at l8Oo, although no action occurs in a boiling alcoholic solution. Similarly, chlorodinitrobenzene and acetamide do not interact in alcoholic solu- tion, but when heated together at 2O0-21Oo give dinitrosniline; in presence of sodium acetate, dinitrophenol is produced. Ethers of Isonitrosoguaiacol in their Relation to the Space Isomerism of Nitrogen. By JOHN L. BRIDGE and w. C h Q E R MORQAN (Amer. Chem. J., 1899, 22, 484--488).-The authors have T. M. L.ORGANIC CHEMISTRY, 15D repeated the work ol Pfob (Abstr., 1898, i, 71) and of Rupe (;bid., i, 72) in the hope of isolating stereoisomeric forms of the ethers of isonitrosoguaiacol analogous with the stereoisomeric ethers of tolu- quinone-m-oxime (Abstr., 1899, i, 130, and this vol., i, 103); such space- isomerides do not, however, appear to exist.The berzxoyl derivative, Cl,H1,O,N, of isonitrosoguaiacol crystallises from alcohol in straw-coloured, dendritic crystals, and when heated be- gins to decompose a t 175", and melts a t 185-188O; the dibromide, CI4Hl1O4NBr2, is a yellowish-white substance which melts and decom- poses at 153-154O, and cannot be purified by crystallisation owing to decomposition occurring. ~~omoisonit~osoguu~~col, C,,Hlo04NBr, prepared by boiling the di- bromide with alcohol, crystallises from the latter in well-defined prisms and melts and decomposes a t 178". Relation between the Structure of Metaphenol [m-Hydroxy- benzyl] Haloids and their Behaviour towards Alkalis.By KARL AUWERS (Ber., 1899,32, 3588-35S7).-ThecompoundsOH*C,Br3H*CH,X (X = C1, Br, I) [CH,X : OH : Br3 = 1 : 3 : 2 : 4 : 61, OH* C6Br4* CH,Rr [ = 3 : 2: 4: 5 : 6 : 11 ; OH*C,Br,(CH,X)* CH,* OR (X = Br, I; R = H, Me, Et, Ac) [ = 4 : 3 :5 : 6 : 2 : 11 ; OH*C,Br,(CH,Br), ( = 5 : 2 : 4 : 6 : 1 ; 33; OH=C,Br,(CH,Br)* CH,*OMe 1 = 2 : 3 : 5 : 6 : 4 : I] ; OH*C,Br,(CH,* OR),, CH,Br (R = H, Me) [ = 5 : 3 : 6 : 2 : 4 : 11 ; OH* C,Br,(CHBr,)* UH:Y [Y = 0, (OMe),, (OEt),, (OAc),] [ = 5 : 3 : 4 : 6 : 1 : 21 all dissolve in cold dilute aqueous sodium hydr- oxide without appreciably decomposing after 15 minules ; but the corn- pounds OH- C,MeBr,Z* CH,Br (Z = Br,CH,* OMe) [ = 2 : 1 : 3 : 6 : 5 : 41; OH* C6MeBr3* CH2Br [ = 4 : 1 : 3 : 5 : 6 : 3 ] ; OH C,Me,Br CH,Br [=5:2:4:6 : l ] ; OH*C6Me,Rr,*CHzX (X=Cl, Br, I) [=5:2:4:3:6:1] decompose almost instantaneously under these conditions with loss of the halogen of the CH,X group.It thus appears that the presence of a methyl group in the nucleus of a m-phenol haloid renders the latter very sensitive to the action of alkalis, although if a hydrogen atom of the methyl group is replaced by a negative radicle, such as OH, OMe, OEt, or OAc, this influence is no longer exercised; those m-phenol haloids which contain two methyl groups are much more rapidly decomposed than those containing only one. Degradation of Phenols during Bromination. By KARL AUWERS and 0. ANSELMINO (Bey., 1899, 32, 3587-3597).-Although homologues of phenol yield normal substitution derivatives when heated wibh bromine in sealed tubes, they yield bromo-derivatives of the next lower homologue when treated with bromine in an open vessel, the methyl group in the p-position relative t o the hydroxgl being replaced by a bromine atom; in no case, however, has the replacement of an ortho- or meta-methyl group been observed.The alkyl ethers and acetyl derivatives of phenols behave towards bromine in like manner. It appears that the elimination of a methyl group under the conditions cited depends on atmospheric moisture, since when this is excluded normal substitution occurs ; by adding a small quantity of water or aqueous hydrobromic acid, the displacement of t~ methyl radicle is greatly accelerated. W.A. D. W. A. D.160 ABSTRACTS OF CHEMICAL PAPERS, When dibromo-+-cumenol or dibromo-phydroxy-$-cumyl bromide is left in contact with an excess of bromine for 4 hours at the ordinary temperature, it is converted into tribromo-p-xylenol [OH : Me, = 1 : 2 : 51. When q-cumenol tribromide (m.p. 128') is treated similarly, it gives C(CH,Br):CBr rise after 1; hours to the compound CH2BraC<CBr, , . CMe>'*OH (this vol., i, 162), but after 5 hours 2 : 5 : 6-tribromo-3-hydrozy-p-xyl?/l bromide alone is obtained ; this crystnllises from light petroleum in slender, lustrous needles, melts a t 118-1 19O, yields tribromo-p-xglenol (m, p. 178-179") on reduction with zinc dust and acetic acid, and is converted by the further action of bromine into an intractable resin. Pentabromo-+-cumenol [OH : Br,: (CH2Br)3 = 5 : 3 : 6 : 1 : 2 : 41 is stable towards bromine a t the ordinary temperature, but at loo', in presence of a small quantity of aqueous hydrobromic acid, yields tribromo-p- xylylene bronzide, O H * C < ~ ~ ~ ~ ~ ~ ~ ~ ~ $ W B r , which crystallises from glacial acetic acid in small, white, silky needles (+ C2H402), which slowly effloresce and then melt at 184'; it is insoluble in aqueous alkalis, and yields an acetyl derivative, CIOH7O2Br5, which crystallises from glacial acetic acid in asbestos-like fibres and melts a t 162'.Tribromo-o-xylenol [Me, : OH = 1 : 2 : 41, when left with bromine at the ordinary temperature, gives rise after 3 hours to tetrabromo-m- cresol ; the tetrabromide, OH*C,Br,Me*CH2Br [Me : CH2Br : OH = 1 : 2 : 41, and the pentabromide, OH*C,Br3(CH2Br)2 [(CH2Br2), : OH = 1 : 2 : 41, derived from o-xylenol yield, on being warmed with bromine for an hour, tetrabromo-m-hydroxybenzyl bromide (this vol., i, 162).Tribromo-mxylenol [Me, : OH = 1 : 3 : 41 probably gives rise initially to the bromide OH*C6MeBr,*CH2Br [Me : CH,Br : OH = 1 : 2 : 41, but subsequently yields tetrabromo-o-cresol (Bodroux, Abstr., 1898, i, 6 4 l ) , which can also be obtained by heating o-cresol with bromine during 4 hours at 1 00'. Tribromo-p-hydroxy-m-xylylene bromide [(CH,Br)2 : OH = 1 : 3 : 41 is stable towards bromine at the ordinary temperature, but on digesting for several hours at 100' with an excess of bromine containing aqueous hydrobromic acid, yields tetrubromo-o- h!ydroxybenxyZ bromide, which is also obtained by heating o-cresol with bromine for 8 hours at 100' ; this crystallises from glacial acetic acid or light petroleum in needles and melts at 158-159'.Tetrabromo-p-cresol is readily converted by bromine into penta- bromophenol, the acetate of which crystallises from glacial acetic acid in lustrous needles and melts at 196-197' ; whilst 3 : 5-dibromo-4- hydroxybenzyl bromide (Auwers and Daecke, this vol., i, 164) yields a mixture of tri bromo- and tetrabromo-phenol. Action of Chloroform and Alkali on 1 :3 :4Xylenol. By KARL AUWERS (Ber., 1 S99, 32, 3598-3599).-Reimer's reaction gives abnormal results with 1 : 3 : 4-xylenol as with pxmenol (Abstr., 1885, 380 ; 1886, 143 ; 1896, i, 420) ; in addition to 2-hydroxy-4 : 5-dimethy;- benxaldehyde, which crystallises from dilute alcohol in long needles or thin plates and melts a t 40-42', there is formed a considerable quantity of the cornpound C,H,oOCI,, which crystallises from light petroleum, melts at 102--103", and is derived from the aldehyde by the replace- W.A. D.ORGANIC CHEMISTRY 261 ment of an oxygen atom by two atoms of chlorine, although being insoluble in alkalis, its structure is uncertain. Oxidation Products of Phenols and Bromophenols and the Constitution of the Isomeric Tribromo-+-cumenol. By KARL AUWERS (Ber., 1899, 32, 3440 -3453).-A theoretical discussion of the compounds described in the following three abstracts. W. A. D. R. H. P. Oxidation Product of Pseudocumenol Tribromide [Tribromo- $-cumenol]. By KARL AUWERS and A.EBNER (BeT., 1899, 32, 3 45 4-3465). -On treat in g tri bromo-~-cumenol with a mixture of - nitricandaceticacids,anoxy-compound, CO<CM-,CBr>C(OH)*CH,Br, CBr'CMe is obtained, which crystallises in compact prisms melting at 1 5 8 O , on reduction yields dibromo-+-cumeool, and by acetic anhydride is con- verted into the diacetate of dibromo-p-hydroxy-+-cumyl alcohol. The corresponding ucetyl derivative, OAc*C6Me2Br,0*CH2Br, obtained by treatment with acetyl chloride, forms compact, white crystals melting at 118-1 19'. On treating the oxy-compound dissolved in methyl alcohol - C Br : CMe 0 with caustic soda and acidifying, an oxide, CO< C1Slie: C2C<bE: is precipitated ; it crystallises in long needles melting at 109-110.5', and with acetyl bromide yields an isomeric metyl derivative, C,Me,Br,O*CH,* OAc, which crystallises in white leaflets melting at 1034 The diacetate, OAc*C,Me,Br,*CH2* OAc, obtained by treating the acetyl derivative (m.p. 119") with zinc dust and acetic acid, or the acetyl derivative (m. p. 103") with sodium acetate and acetic acid, forms white leaflets melting a t 95'. With acetyl chloride, the oxide forms an additive compound, C,Me,Br,ClO*CH,* OAc, which crystallises in small needles melting at 96-98', The nzonomethyl ethe; of dibromo-p-hydroxy-+-cumylene 0-glycol, oH'fi-cBr:?*CH200Me, obtained by treating the oxy-compound CMe CBr:C*CH,*OH with methyl alcohol i n d sodium hydroxide, forms small needles melt- ing at 149' ; the corresponding monoethyl ether melts a t 11 3-1 14O. The diacetate of the methyl ether is obtained by the action of acetic anhydride, and forms yellowish prisms melting at 107-108'. 3 : 6-D ibromo-5-hydroxy-+-cu~nylene dibromide, OH*C6MeBr2(CH2Er),, prepared by the action of hydrogen bromide on the methyl ether just described, forms compact, short needles melting a t 151-152", and is insoluble in alkalis.The ucetyl derivative forms lustrous needles melting at 132-133'. If a concentrated solution of the dibromide in methyl alcohol is left for some time,the portion which can be precipitated by water is soluble in alkalis, and is the methyl ether of 3 : 6-dibromo- 5-hydroxy-J/-curnylene bromohydrin, OH*C,MeBr,(CH,Br)*CH,-OMe, which forms short needles melting at 107-108° ; on reduction, i t yields the methyl ether, OH*C,Me,Br,-CH,*OMe, melting at 92".By the continued action of methyl alcohol on the dibromide, 3 : 6- dibromo-5-hydroxy-+-cumylene dimethyl ether is obtained, crystallising in compact prisms melting a t 79-80°; it is converted by the action VOL. LXXYIII. i. 12162 ABSTRACTS OF CHEMICAL PAPERS. of hydry drogen chloride into the methyl ether of the chlorohydrin, OH*C,MeBr2(CH2C1)*CH2*OMe, which me1 ts at 93-95.5' ; on treat- ment with sodium acetate, it yields the acetyl compound, OH*C,MeBr2(CH2*OAc)*CH2*OMe, which forms white leaflets melting at 110-1 1 1'. Dibromo-m-hydroxy-$-cumyl Bromide. By KARL AUWERS and TH. MAAS (Bey., 1899,32,3466-3475. Compare Abstr., 1898, i, 343).- 3 : 6-Dibromo-5-hyd~*oxy-$-c~myZ b r ~ m i d e , C M e g ~ ~ ~ ~ . ' ~ ~ ~ C * -CMe CH2Br, prepared by treating the diacetate of 3 : 6-dibromo-5-hydroxy-~-cumyl alcohol with hydrogen bromide, crystallises in long, silky needles melting at 128', and forms an cccetyl derivative melting a t 105-106'.On boiling with alcohol, it yields the ethyl ether of 3 : 6-dibromo-5- hydroxy-$-cumyl alcohol melting at 63-64'. The acetyl derivative of the corresponding methyl derivative melts at 80-81'. The diacetate first mentioned, on reduction with sodium amalgam, yields the diacetate of 3-bromo-5-hydroxy-$-ci~myl alcohol, which forms colourless prisms melting at 65'. The monoacetate, obtained when the reduction is eBected with zinc dust and acetic acid, crystallises in small needles melting a t 104'. Both acetates, on hydrolysis, yield the 3-bromo-5-hydroxy-$-cunayl alcohol, which forms lustrous, white leaflets melting at 164'. 5-Hydroxy-$-cumyZ alcohol, prepared by the reduction of 3 : 6-dibromo-5-hydroxy-$-cumyl alcohol with sodium amalgam, crystallises in lustrous leaflets melting a t 153O, and with bromine yields 6-brorno-5-hydroxy-$-cumyZ bromide, which forms long needles melting a t 116', and with sodium acetate yields the acetyl derivative of the corresponding alcohol melting at 103'.Oxidation Products of Phenols and Bromophenols. By KARL AUWERS and J. BROICHER [and in part W. WOLFF] (Ber., 1899, 32, 3475-3486. Compare preceding abstracts and Abstr., 1898, i, 30).- The acetyl derivative, C O < ~ " , ~ ~ ~ ~ > C M e * O A c , obtained by treat- ing the oxy-compound of dibromomesitol with acetic anhydride, forms rhombohedra melting a t 94-95', The oxy-compound of 3 : 5 : 6-tri- bromo-1 : 2 : 4-xylenol forms a monoacetate melting at 11 6-1 17", and a diacetate melting at 101-102', which, on treatment with hydrogen bromide, yields o : 2 : 5 : 6-tetrabromo-1 : 3 : 4-xyZenoZ, melting at 138-139Oand forming a n acetyl derivative which melts at 110-11 1'.The constitution of the tetrabromo-compound is proved by its prepara- tion in several stages from o w : 3 : 5 : 6-pentabromo-1 : 2 : 4-xylenol. R. H. P. R. H. P. OH*fi-CBr:y*CH,*O-Me the methyl ether, CBr. CBr:C,CH,. OH , melting at 176-178' being obtained as an intermediate prodhi. o : 2 : 4 : 5 : 6-PentabromocresoZ, obtained by the action of bromine on the tetrabromo-compound, forms silky needles melting at 136-1379 The following derivatives of tribromomesitol were prepared in a similar manner t o those of tribromo-$-cumen01 (see preceding abstracts).An oxy-compound, C O < ~ ~ i ~ ~ ~ > C ( O H ) * C H , B r , which crystallisesORGANIC CHEMISTRY, 163 in prisms melting at 145-146' and forms an ucetyl derivative melt- ing at 126-127", and the corresponding oxide, which forms compact needles, melting at 118-1 19'. ww : 3 : 5 : 6-Pentabromo-1 : 2 : 4-xylenol yields a n 0x9-compound which crystallises in lustrous, monoclinic prisms melting a t 188-1 90" and forms an acetyl derivative melting at 145-146". By EDOUARD BOURGEOIS (Rec. Tmtm. Chirn., lS99,18,426--450).-The author describes improvements in the working of the two methods used for the preparation of aromatic thiols : the reduction of aromatic sulphochlorides, and the hydrolysis of aromatic derivatives of xanthogenic acid.Phenyl mercaptan, prepared by the first method, has no alliaceous odour and boils at 169.5" under 760 mm. pressure. p-Tolyl mercaptan boils at 195' under 760 mm. pressure (Vallin gave 194"). P-Naphthyl mercaptan boils under the ordinary pressure a t 288" with partial decomposition into di-P-naphthyl sulphide and hydrogen sulphide; it is slightly volatile in steam, not non-volatile as stated in Beilstein. m-Tolyl mercaptan boils a t 195.4' under 760 mm. pressure and has a specific gravity 1.06251 a t Oo/4O, Constitution of Mononitrosoorcinol. By FERDINAND HENRICH (Bey., 1899, 32, 3419-3424. Compare Abstr., 189'7, i, 446).- Nitrosoorcinol is the oxime of an orthoquinone, and not of a para- quinone as has been previously assumed ; the aminophenol formed on reducing the monomethyl ether of nitrosoorcinol readily gives an acetyl derivative, NHAc* C,H,Me(OMe)*OH, which crystallises from dilute alcohol in needles and melts a t 156-157'; when this is heated, it undergoes ortho-condensation and gives nzethoxy-p-methyltoluozccxole, R.H. P. Preparation of Aromatic Thiols. T. H. P. OMe*C,H,Me<O>CMe, N which crystallises from alcohol, melts a t 71 *5-72', and when heated under pressure with concentrated hydro- chloric acid gives aminoorcinol hydrochloride, methyl chloride, and acetic acid. This view is confirmed by a comparison of the mono- methyl ether of nitrosoorcinol with Kietaibl's two nitroso-derivatives from resorcinol monomethyl ether (Abstr., 1899, i, 343), since it closely resembles the ortho-derivative in physical and chemical pro- perties; a green h b d e modijkntion of the latter has been obtained which passes sharply into the stable yellow modification when heated to 120".Of the two possible formulae f o r nitrosoorcinol, the diortho-formula is preferred, since substitution takes place most readily in this position, and the enolic and ketonic modifications are now formulated as CH: C(oH)>C:N*OH and CNe<,H~co>C:N*OH. CH *GO CMe%H-CO T. M. L. Action of Methylene Sulphate on Benzyl Alcohol. By MARCEL DEL~PINE (Bull. Xoc. Chim., 1899, [ iii], 21, 1059-1061).- The action of methylene sulphate on benzyl alcohol at 60-65" results % 2164 ABSTRACTS OF CHEMICAL PAPERS.in the formation of dibenzylformal and benzyl hydrogen sulphate. D b benxylfownal, CH,( *O*CH,Ph),, is a colourless liquid of faint benzylic odour, boils a t about 330' and does not solidify at -23'; it is Peainified by concentrated sulphuric acid, and is converted intoo benzyl iodide by the action of fuming hydriodic acid. Benxyl hydvogen sulphate itself could not be prepared in the pure state, since its aqueous solution becomes resinified on evaporation. The barium salt, Ba(SO,* CH,Ph), + 2H,O, crystallises from water in long, colourless needles ; the anhydrous salt, obtained by cooling a solution in 80 per cent. alcohol, slowly resinifies on keeping and decomposes when heated even below 80' ; its aqueous solut.ion deposits barium sulphate when concentrated by heat.The potassium salt crystallises from alcohol in anhydrous, slender needles which are stable below 100'. The silver and lead salts under- go decomposition when their aqueous solutions are concentrated, but the greenish copper salt, which crystallises with 4H,O, is more stable. N. L. Action of Bromine on p-Hydroxybenzyl Alcohol, By KARL AUWERS and S. DAECKIC (Ber., 1899, 32, 3373-3381. Compare following abstract).-p-Hydroxybenzgl alcohol is best prepared by Hutchinson's method (Abstr., 1891, 561) and crystallises from water in large, colourless prisms or compact needles melting at 124.5-125.5' and not a t 110' as stated by Biedermann (Abstr., 1887, 38) and Hutchinson. 3 : 5-Bibromo-4-l~yds*oxybenxyl bromide, OH-C6H2Br2*CH,Br, obtained by the action of an acetic acid solution of bromine on a solution of the hydroxy-alcohol in the same solvent, crystallises from light petr- oleum in small, colourless needles melting at 149-150'; i t dissolves readily in cold ether, also in warm benzene or acetic acid, but is in- soluble in alkalis.Its constitution follows from the fact that when reduced it yields Werner's dibromo-p-cresol (Bull. SOC. Chim., 1886, [ ii], 46, 278). The ace@ derivative, OAc*C,~,Br,= CH,Br, crystal- lises from light petroleum in large crystals melting at 76-5-77*5' and is only sparingly soluble in cold methyl or ethyl alcohol. When the tri- bromide is shaken with acetone and water, it is converted into 3 : 5-di- brorno-4-hydroxybenzyyl alcohol, OH* C,H,Br,*CH,* OH, which crystallises from benzene in compact, colourless plates melting a t 11 6-1 17", and is readily soluble in ether or alcohol.The corresponding ethers, OH* C6H?Br*CH2=OR, are obtained when the tribromide is heated with the requisite alcohol. The methyl ether crystallises in glistening needles melting a t 7 1-72", and the ethyl ether in small prisms melting at 93-5-94-5'. The acetate, OH* C,H,Br,* CH,* OAc, obtained by the action of an acetic acid solution of anhydrous sodium acetate on the tribromide, crystallises from light petroleum in compact prisms melt- ing a t 114.5-1 15.5' ; it dissolves in alkalis, but rapidly undergoes decomposition when the alkali is too strong; it is also decomposed when boiled with different alcohols, yielding the corresponding ethers. The isomeric acetate, OAc*C6H,Br2-CH2* OH, is obtained when a solution of the acetyl derivative of 3 : 5-dibromo-4-hydroxybenzy l iodide in acetone is treated with moist silver oxide for several days a t the ordinary temperature, and forms a yellowish oil.The diacetate,ORGANIC CHEMISTRY. 165 OAc*C,H,Br,* CH,*OAc, crystallises in prisms melting a t 68-70' ; it may be obtained by the action of acetic anhydride on the hydroxy- benzyl alcohol or on either of the monoacetyl derivatives, and when its acetic acid solution is treated with hydrogen iodide at 80' it yields 3 : 5-dibomo-4-hydroxybenzyl iodide, which cryfitallises from benzene in yellow needles melting a t 148-149' ; when hydrogen iodide is employed at the ordinary temperature, the product is the acetyl derivative, OAc*C,H,Br,* CN,I, which crystallises in colourless needles melting at 94-95".J. J. S. Action of Bromine on m-Hydroxybenzyl Alcohol. By KARL AUWERS AND W. RICHTER (Ber., 1899, 32, 3381-3384. Compare Abstr. ,1897, i, 335, 336, and preceding abstract).-When a warm acetic acid solution of m-hydroxybenzyl alcohol, which is best obtained by von den Velden's method (Journ., 1577, ii, 338), is treated with bromine also dissolved in acetic acid, 2 : 4 : 6-trib~omo-3-?qdroxybenxyl bromide, OH*C,HBr,*CH2Br, is formed ; i t crystallises in small needles melting at 149", and dissolves readily in alkalis, and in most organic solvents except light petroleum. On reduction with zinc dust and acetic acid, i t yields Claus and Hirsch's tribromo-nt-cresol melting at 84' (Abstr., 1889, 389).I t s GccetyZ derivative crystallises in glistening needles and melts at 104@. Tribomohydroxybenxyl acetate, OH*C,I-IBr,*CH,* OA c, forms small needles melting a t 133' ; when hydrolysed with alcoholic sodium hydyxide, i t yields 2 : 4 : 6-tribromo-3-hydroxy6enxyl alcohol, melting at 130 ; this is not readily converted into its ethers by the action of different alcohols. The diacetute, OAc*C,HBr,*CH,*OAc, crystallises from a mixture of ether and light petroleum in small prisms melting at 83-84O. 2 : 4 : 6-Tribrorno-3-hydroxybenxyZ c?dwide, obtained by the action of dry hydrogen chloride on a hot acetic acid solution of the alcohol, crystallises in needles melting at 133', and the iodide, obtained by shaking an alcoholic solution of the bromide with a concentrated aqueous solution of potassium-iodide, crystalliser i n glistening, feathery needles melting at 146'.J. J. S. Tribromo-derivatives of t,b-Cumenol and Mesitol. By KARL AUWERS, F. A. TRAUN, and R. WELDE (Ber., 1899, 32, 3297-3309. Compare this vol., i, 96 ; and Abstr., 1897, i, 34 and 335 ; 1898, i, 646 ; 1899, i, 343).-The acetyl derivative, oAc* C,Me,Br,* CH,* OMe, prepared from 3 : 6-dibromo-4-hydroxy-t,b-cumyl methyl ether, crystallises from light petroleum or glacial acetic acid in white needles, melts a t 114-114-5O, and is not acted on by gaseous hydrogen chloride in boiling acetic acid solution; at 150°, or in presence of zinc chloride at loo', hydrogen chloride converts the acetate into the chloride, OH*C,Me2Br,*CH,C1, which melts at 110", and yields an acetyl deri- vative crystallising in white needles and melting at 150-150*54 Hydrogen bromidecoiiverts the acetyl derivativemelting at 114-114*5° in to clibromop-acetox~-~-cumyl bromide, OAc C,Me,Br2* C H, Br, which melts a t 161°, and on reduction with zinc dust and acetic acid yields the cccetyl derivative, OAc*C,Me,Br2, melting a t 80*5-81", derived from166 ABSTRACTS OF CHEMICAL PAPERS.dibromo-pJI-curnenol ; hydrogen iodide behaves similarly, giving rise to dibromo-pacptoxy-$-cumyl iodide, OAc*C6Me,Br,*CH,I, which crys- tallises from glacial acetic acid in felted needles, melts a t 174--175', and can also be obtained by the action of hydrogen iodide on the diacetate melting at 105-1 06c, derived from dibromo-p-hydroxy-$- cumyl alcohol. The iodide is converted by moist silver oxide into the corresponding alcohol, OAc* C6ble,Br,* CH,* OH, which melts at 122-122.5' (Auwers and Sheldon, Abstr., 1898, i, 647); this is not acted on hy boiling alcohol or aqueous acetone, but is hydrolysed by alcoholic potash t o dibromo-p-hydroxy-$-cumyl alcohol (m.p. 166'). The isomeric acetate, OH*C<CMe:CBr CBr*CMe>C*CH2- OAc (m. p. 11 4'), which is prepared by the action of sodium acetate on $-cumenol bromide and is insoluble in alkalis, is, on the other hand, hydrolysed instantaneously by alcohol or aqueous acetone, When dibromo-p- acetoxp-$-cumyl iodide is heated with silver oxide in benzene solution, it is converted into the ether, (OAc- C?Me,Br,* CK,),O (Auwers and Avery, Abstr., 1896, i, 1.50). 2 : 6-Dzb~omo-4-hydroxymesityl methyl ether, OH;* C,Me,Br,* CH,* OMe, prepared by heating mesitol tribromide with methyl alcohol.crystallises in thick, monoclinic plates, and melts at 142'; the acetyl derivative crystallises from dilute acetic acid in small plates, melts a t 109-llOo, and is converted by hydrogen iodide into 2 : 6-dibp.omo-4-acetoxymesit?/l iodide, OAc* c,Br,Me,* CH,I, which separates from glacial acetic acid or acetone in slender, silky needles, and melts a t 176-1 77'. 2 : 6-Dibromo-4-acetoxyrnesityt? alcohol, OAc*C6Br2Me,*CH,*OH, prepared by decomposing the iodide with aqueous acetone, crystallises from light petroleum in felted needles, melts a t 128O, and is converted by alcoholic potash into 2 : 6-dibromo- 4-hydroxymesityl alcohol (m. p. 186') ; with acetic anhydride, it yields the diacetate (m.p. 159-160°), whilst hydrogen bromide converts it into 2 : 6-dibromo-4-acetoxymesityl bromide, OAc-C,Me,Br,*CH,Br (m, p. 150-151'). I n the light of these results, the structure of the acetyl derivatives obtained by the action of sodium acetate on phenol bromides which are insoluble in aqueous alkali is discussed; these must be regarded as similar in structure to the corresponding phenol bromides, and therefore, like the latter, can be represented by three formulae (compare this vol., i, 96) which cannot as yet be differentiated. The phenylurethane, CH2Br- C6Me2Br2* O*CO *NHPh, formed by the action of phenylcarbimide on mesitol tribromide (compare Auwers and Allendorff, Abstr., 1899, i, 32), melts and decomposes at 257O,* and on reduction with zinc dust and acetic acid is converted into the phenyhwthane, C,Me,Br,* 0.CO ONHPh, of dibromomesitol, which can also be prepared from the latter Iny the action OF phenylcarbimide; this cannot be obtained in well-defined crystals, and melts somewhat indefinitely between 21 3Oand 21 6O- When the phenylurethane of mesitol tribromide, dissolved in xylene, is heated with aniline (2 mols.), it yields the phenyZuq*ethane, NHPh* CH,* C,Me,Br,* O*CO *NHPh, of 2 : 6-dibromo-4-hydroxymesitylnniline, which forms short, slender * !227", compare Auwers and Allendorff, loc.cit,, who give 226", and p. 3300 of original.-W. A. D.ORGANIC CHEMISTRY, 167 needles, melts at 190-194', and is easily hydrolysed by alcoholic potassium hydroxide to dibromo-phydroxymesitylaniline (m.p. 136'). The latter substance, when treated with phenylcarbimide, gives rise to a phenylurethcine which readily dissolves in aqueous alkalis, is isomeric, not identical, with the phenylurethane melting a t 190-194", and hence appears to have the constitution A - OH, C<CMe CMe >C*CH,*NPh* CO *NHPh ; CBr=CBr the phenylcarbimide, in fact, has attacked the anilino- in preference to the hydroxyl group, and with p-aminophenol a similar behaviour is observed, p-hydroxydiphenylcarbamide, OH* C,H,*NH* CO WNHPh, being formed ; this crystallises from dilute alcohol in lustrous, pearl- grey needles, melts a t 216-217', and is easily soluble in aqueous alkalis, The use of phenylcarbimide as a means of recognising the presence of a hydroxyl group in organic compounds must therefore be limited to compounds which do not contain an amino-radicle.The phenylwethane, OAc*CH,* C,Me,Br,* O*CO*NHPh, obtained by the action of phenylcarbimide on dibromo-p-hydroxymesityl acetate (m. p. 165-166'), prepared from mesitol tribromide and sodium acetate, crystallises from glacial acetic acid in short, slender needles and melts a t 163-164'. CH,Br* C,Me,Br,* O*CO*NHPb, can be obtained only with difficulty from dibromo-p-hydroxy-$-cumyl bromide, and separates from hot glacial acetic acid as a white powder melting at 225-230'. The phenylurethane, W. A. D. Dibromo-p-hydroxymesityl Alcohol. By KARL AUWERS and F. A. TRAUN (Ber., 1899, 32, 3309-3317).-4 : 6-Dibromo-2-amino-m- xylene, prepared by reducing the corresponding nitro-compound, crys- tallises from 75 per cent, alcohol in slender, felted needles, melts at 99-loo', and is converted by the diazo-reaction into 4 : 6-dibromo-2- hydroxy-m-xyhne, which crystallises from light petroleum in slender needles and melts at 132-133'; the acetate of the latter separates from alcohol or glacial acetic acid in white leaflets and melts at 79-80'. 2 : 6-Dibromo-4-hyclroxymesityZ alcohol, OH*C,Me,Br,*CH,*OH, prepared from the foregoing hydroxy-compound by the Lederer- Manasse reaction, using formaldehyde and dilute aqueous sodium hydroxide, crystallises from xylene, melts a t 1 8 6 O , and is identical with the compound melting at 191-192' formed by acting with aqueous acetone on mesitol tribromide (the bromide of dibrornoanhydro- p-hydroxymesityl alcohol, Auwers and Allendorff, Abstr.,1899, i, 32).When the hydroxy-alcohol is heated for several hours at 160-170°, it is converted into t e t ~ a b . l . o m o - p - d i ~ d r ~ x y d ~ ~ ~ ~ ~ t y ~ ethep*, (OH*C,Br,Me,*CH,),O, which is nearly insoluble in all the ordinary solvents, melts at 256') and is identical with the compound formerly stated (Auwers and Allendorff, loc. cit.) to be isomeric with the hydroxy-alcohol ; the latter conclusion was arrived at because prepara- tions melting a t 252', on being heated with benzene or xylene, appeared t o be converted into the hydroxy-alcohol melting a t 192'. It is now shown, however, that the impure hydroxy-alcohol, containing small quantities of the ether, when heated, undergoes conversion into the168 ABSTRACTS OF CHEMICAL PAPERS.latter, and melts a t 252", although the pure hydroxy-alcohol, when similarly treated, remains unchanged and melts a t 192'. The samples formerly heated with benzene or xylene and supposed to consist of the compound melting at 252", in reality consisted mostly of the hydroxy- alcohol, and the apparent regeneration of the latter is thus explained. The diacetate of the ether melts a t 229' and is identical with the compound prepared by the action of silver oxide on the acetyl derivn- tive of dibromo-p-hydroxymesityl bromide (Zoc. cit.) ; by digestion with methyl iodide and sodium methoxide, the ether yields the dimethyl derivative, O(C,Me,Br,*OMe),,. which crystallises from a mixture of absolute alcohol and benzene in slender, white needles and melts a t 205-20 6'.W. A.D. Substituted Phenyl Benzyl Ethers. By KARL AUWERS, F. A. TRAUN, and R. WELDE (Ber., 1899,32, 3317-3331).-By the action of sodium alkyloxides on acetylated hydroxybenzyl haloids of the type O A C * C < ~ ~ : CY-CY cy>C*CH,X, where X represents a halogen and Y any substituent, crystalline compounds are obtained, which the author formerly regarded as stilbene derivatives of the type O A ~ * C < ~ E ~ ~ ~:>c*cH:cH- cqCy: cy* Cy>C*OAc cy (Annaken, 1898, 301, 260), but are shown in the present paper to be substituted phenyl- benzyl ethers of the general formula R denoting the alkyl radicle. The ether, OAc*Cf,Me,Br,* CH,*O*C,Me2Br2*CH2* OEt, prepared by the action of alcoholic sodium ethoxide on dibromo-p-acetoxy-+-cumyl bromide, melts a t 175-176", and has been already described as tetra- bromodjacetoxytetramethylstil bene (Auwers and Sheldon, Annalen, 1898, 301, 272) ; the corresponding ethber, C,,H,,O,Br,, prepared from dibromo-p-acetoxymesityl bromide (Auwers and Allendorff, Abstr., 1899, i, 32) melts at 217-218'.The former of these is converted by gaseous hydrogen bromide in glacial acetic acid solution a t 80" into the ether, OAc* C17Hl,0Br,* CH,Br, which crystallises from glacial acetic acid or xylene in needles and melts at 219-221O; at looo, or more rapidly at the boiling point of acetic acid, +-cumen01 tribromide (m. p. 126') is formed. The isomeric mesitol derivative, melting a t 21 7-218', gives rise under similar conditions to the ether C20H1903Br5, which crystallises from xylene in needles and melh a t 254-255'.The ether, OAc- C17H1,0Br,* CH,I, prepared by the action of hydrogen iodide on the +-cumpI derivative melting at 1'75-176' melts and decomposes at 219-221', and cannot be crystallised from xylene or benzene without decomposition occurring ; a t 1 OO", hydrogen iodide gives rise to dibromo-p-hydroxy-11/-cumyl iodide, although hydrogen chloride, under similar conditions, is without action, and only begins to act at 1 50', when dibromo-p-hydroxy-+-cumyl chloride is formed. The methyl ether, OAc*Cl7H1,OBr4*CH2*OMe, prepared by the action of sodium methoxide on dibromo-p-acetoxy-+-cumyl bromide, crystallises from glacial acetic acid in slender needles and melts a t 202-204",ORGANIC CHEMISTRY. 169 whilst the isomeric mesityl derivative crystallises similarly, melts at 220-221', and can also be obtained by the interaction of dibromo-p- hydroxymesityl methyl ether with sodium methoxide and dibrorno-p- acetoxymesitylbromide.The latter fact shows that the action of sodium alkyloxides on acetylated hydroxybenzyl hsloids takes pIace in two stages. Hydrogen bromide converts the mesityl derivative, melting at 220-22 lo, into the bromide, OAc*C17H,,0Br4*CH2 Br, already described. The amyl ether, OAc*C,,H,,OBr,*CH,*OC,~,,, crystallises from glacial acetic acid in slender needles and melts at 146-147'; the isomeric nzesityl compound has similar properties, and melts at 163-1 64'. Hydrogen bromide interacts with these substances in the same manner as with the analogous ethyl and methyl ethers.By the action of sodium ethoxide on di bromo-p-isobutyroxy-$-cumyl bromide (Annalen, 1898, 301, ZSC), small quantities of dibromo-p- is0 but yroxy-$-cum yl ethyl ether, COPr@*O* C6Me,Br,* CH,* OE t, me1 ting a t 74-75", are formed, together with a larger proportion of the ether, COPrM3,7H140Br4*CH2*OEt, which crystallises from alcohol in white needles and melts a t 147-148' ; the mesityl derivative isomeric with the latter crystallises from glacial acetic acid in silky needles and melts a t 182-183'. The +-cumyl ether (m. p. 147-148') is converted by hydrogen bromide into the compound COPiS* CI7Hl40Br4*CH,Br, which forms slender needles and melts at 192--193' ; the isomeric nzesityl derivative melts a t 221-223', but was not obtained pure. The benaoyl derivative, OBz*C6Me2Br,* CH,Br, of dibromo-p- hydroxymesityl bromide crystallises from glacial acetic acid or petroleum in long, lustrous needles, melts at 160-161', and is con- verted by sodium ethoxide into the corresponding ether, OBz *C17H,40Br,*CH2-OEt, which crystallises from benzene or glacial acetic acid in white, felted needles, melts at 232--223', and when treated with hydrogen bromide gives rise to the corresponding bronzide, C25H2103Br5, which crystallises from xylene in white needles and melts at 234-235O.Dibromo-p-~cetoxy-+-c~~~Z dibromo-p-+-cumpZ ether, OAc*C,Me,Br,*CH,~O*C~~Le~~r,, prepased by reducing the corresponding bromide (m. p. 219-221') with zinc dust and acetic acid, crystallises from glacial acetic acid in white, felted needles, melts at 204-205', and on digestion with sodium methoxide yields dibromo-$-cumenol, methyl acetate, and dibromo-p-hydroxy-#-cumyl methyl ether ; when treated with hydrogen bromide in hot glacial acetic acid solution, the ether gives rise to a mixture of dibromo-$-cumen01 and dibromo-p-hydroxy-$-cumyl bromide.When the bromide, OAc*C,,H,,OBr,*CH,Rr, is boiled with Sodium acetate and glacial acetic acid or acetic anhydride, the corresponding acetate, OAC*C~~H,,OB~,*CH,*OAC, melting a t 204-205' is formed ; but if acetio anhydride is employed and the time of heating increased, large quantities of the diacetyl derivative (m. p. 105-106") of dibroruo-p-hydroxy-Il/-cumyl alcohol are obtained. w. a. D.1'70 ABSTRACTS OF CHEMICAL PAPERS, Hydrolysis of Benzonitrile. By CHARLES RABAUT (BUZZ.SOC. Chirn., 1899, [iii], 21, 1075--1076).-1f 10 grams of benzonitrile are dissolved in 100 C.C. of alcohol and heated in a reflux apparatus for an hour with 6 grams of potassium hydroxide, 98 per cent. of the theoretical amount of benzamide is produced, but if only 1-18 or 0.56 gram of potassium hydroxide is used, the yield is reduced to 70 or 40 per cent. respectively. With concentrated potash, the product consists almost entirely of benzoic acid. No benzamide is formed when a dilute alcoholic solution of benzonitrile is heated for an hour i n a sealed tube a t 100'. Isomeric Change of o-Amino- and o-Nitro-cinnamonitriles. B~ROBERT PSCHORR and 0. WOLFES (Ber., 1899, 32, 3399-3405. Compare A bs tr., 1 8 9 9, i, 49 1 ).-a -p-Methoxyphenyl-o-nitrocinnamo- nitrile, NO,*C,H,*CH : C(CN)*C',H,*OMe, crystallises from toluene or alcohol in minute, felted, yellow needles, melts at 162' (corr,), and sublimes without decomposition.2-Amino-3-p-meti~oxyphenylquino- line, NH,*C,NH,*C,H4*OMe, prepared by reducing the preceding compound with tin and hydrochloric acid, crystallises from alcohol in colourless needles and melts at 151--152' (corr.) ; the salts are only slightly soluble, the nitrate melts a t 207' (corr.), the hydrochloride a t 226O (corr.), and the sulphate a t 228' (corr.); the platinichloride forms yellow needles and decomposes a t 240' (corr.), and the picrate forms minute, yellow needles and melts a t 256' (corr.). 3-p-Methoxy- phenyZ-2-carbostyr?'Z, oH*C,NH,*C,H,*OMe, prepared by the action of nitrous acid on the amino-compound, or by the action of acetic anhy- dride and sulphuric acid on a-paramethoxyphenyl-o-aminocinnamic acid, crystallises from alcohol in minute, colourless needles and melts a t 259' (corr.). Frost's a-phenyl-o-nitrocinnamonitrile (Abstr., 1889, 597), on reduction, gives 2-amino-3-phenylquinoline (Pschorr, Abstr., 1899, i, 491).a-p-Nitrophenyl-o-acetaminocinnamonitrile can be converted directly by alcoholic hydrochloric acid into 2-amino-3-p-nitrophenyl- quinoline. By heating with potassium hydroxide in dilute alcoholic solution, a-phenyl-o-nitrocinnamic nitrile is converted into hydrogen cyanide and benxoykcnthrccndic acid, which can also be prepared by the action of benzoyl chloride on anthranilic acid ; it crystallises from alcohol in minute, colourless needles, melts a t 181' (corr.), and gives a monomethyl ester, which crystallises from alcohol in colourless needles and melts at 101 *5'.Similarly, a-p-methoxyphenyl-o-nitrocinnamic nitrile is converted by alcoholic potash into alzisylanthrccnilic acid, OMe*C,H,*GO*NH*C,H,*CO,H, which crystallises from alcohol in scales and melts a t 232' (corr.). By ALBXN HALLER and ALFRED GUYOT (Compt. rend., 1899, 129, 1213--1216).-The format ion of diphen ylph t halide from o-benzoylbenzoic chloride points to the existence of a tautomeric form, C,H4<ZF>0, for this com- N. L. T. M. L. Tautomerism of o-Benzoylbenzoic Acid.ORGANIC CHEMISTRY. 171 pound, With a view of ascertaining whether methyl esters corre- sponding with the two forms of the acid are capable of existence, its esterification was carried out by five different methods.The methyl ester crystallising in colourless prisms and melting at 52" was obtained in every case. G. T. ISX. Synthesis of Cyclopentane Derivatives by means of Ethyl Adipate. By Lours BOUVEAULT (Bull. SOC. Chim., 1899, [ iii 1, 21, 10 19-1 023).-Ethy 1 2-cyclopentanonecarboxylate, - - CH,* Y O c"2<CHn* CH* C0,Et' mas shown by Dieckmann (Abstr.,'1894, i, f73) to be formed by the action of sodium on ethyl adipate a t 120°, and by a modification of the original process tho author has obtained this compound in the pure state as a colourless, oily liquid, boiling at 113' under 22 mm. pressure, and having a sp. gr. 1.0976 a t 0'. The sodium and potassium salts crystallise well and are not decomposed by water; the copper salt crystallises in thin, .green plates melting at 183", and dissolves in chloroform, yielding a vioIet solution. The phenylhydmxone is an oily liquid, whilst the semicurbaxone crystallises in large, white needles melt- ing at 143".The sodium derivative of ethyl 2-cyclopentanonecarboxylate reacts with methyl iodide to form ethyl 1-methylcyclopentunonecarboxylate, which was obtained as a colourless oil, boil- CH2<CH2* CMe*CO,Et' ing a t 308' under 22 mm. pressure, and having a sp. gr. 1.0529 at 0'. This forms a white, crystalline semicwbaxone melting at 153", and differs from its lower homologue in being insoluble in alkalis. When heated with concentrated hydrochloric acid, it yields 1-methylcyclopentanone, which Montemartini obtained by heating calcium adipate ; this boils at 139', and has a sp. gr.0.7379 at 0". It forms a liquid oxime, which boils at 103" under 22 mm. pressure, and yields a crystalline benxoyl derivative melting at 63.5', and a crystalline semicarbazone which melt8 at 184' (Montemartini gives 171"). When boiled with alcoholic potash, ethyl methylcyclopentanonecarboxylate yields the potassium salt of a-methyladipic acid; if, however, a large excess of alkali is not employed, the potassium ethyl salt, C0,K*CH2*CH,* CH,* CHMe*CO,Et, Action of Potassium Hypobromite on Arnides of Hydroxy- benaoic Acids. By W. VAN DAM (Rec. Tq-av. Chim., 1899, 18, 408--425).-By the action of potassium hypobromite on salicylamide, two dibromocarboxylaminophenols are obtained, one melting at above 270' and the other at 255" (McCoy, Abstr., 1899, i, 359, gave the melting point 250°), which is not identical with the compound obtained by Jacoby by the direct bromination of carboxylaminophenol ; Jacoby's compound is found to melt at 255", not a t 243" as stated by him.The dibromocarboxylaminophenol melting at 255", obtained by McCoy and by the author, forms a methyl derivative, CH,* 70 is formed, which resists further hydrolysis. N. L. melting at 1249 a n acetyl derivative, C6H2Br2<Ni>C0, and a172 ABSTRACTS OF CHEMICAL PAPERS. barium compound, C,W2Br2<N>C0, crgstallising in white needles; it is readily soluble in acetone or alcohol, less so i n ether or water, and from its solution in caustic potash solution the potassium deriva- tive, C6H2Br2<ii>C0, is deposited in white needles.Jacoby's compound does not form salts. By the action of potassium hypobromite on m-hydroxybenzamide, s-tribromo-m-hydroxybenxavtide [CONH, : OH : Br, = 1 : 3 : 2 : 4 : 61 melting at 221' is obtained ; if excess of alkali is present, tribromo- nz-aminophenol melting at 117' is formed, the triacetyZ compound of which, OAc*C,EBr,*NAc,, melts at 136'. The action of barium hypobromite on p-hydroxybenzamide gives rise t o dibromo-p-aminophenol melting a t 191'. Under the influence of bromine and sodium methoxide, anisoyl- amide condenses to ap-anisykc6nisoylca~bamide, which melts a t 222'. The intramolecular change produced in the bromamides by the action of an alkali, by which they are converted into amides, is shown to be a reaction of the first order.Anisonitrile. By LOUIS HENRY (Rec. Trav. Chirn., 1899, 18, 466-46 7). -pMe thoxy benzonitrile and p e t hoxybenzoni trile described by Reinders and Ringer (Abstr., 1899, i, 893) have already been pre- pared (Henry, Ber., 1870, 2, 667; Pinner, Abstr., 1891, 63). OMe*C,H,*NH *CO*NH*CO*C,H,*OMe, T. H. P. T. H. P. Resolution of Racemic Amino-acids into Optically Active Components. By EMIL FISCHER (Bey., 1899, 32, 3638-3646. Compare Abstr., 1899, i, 888).-A good yield of racemic benzoyl- tyrosine is obtained from p-hydroxy-a-benzoylnminocinnamic acid by a modification of Erlenmeyer and Halsey's method (Abstr., 1898, i, 197). This compound is resolved into its active components by fractional crystnllisation from aqueous solutions of its alkaloidal salts.When brucine is employed, the first crop of crystals consists of the corresponding salt of benzoyl-Z-tyrosine. BenxoyZ-1-tyrosine crystallises in leaflets and melts at 165-166', this temperature being 30' lower than the melting point of the racemic compound ; [a], in an 8 per cent. alkaline solution at 20' is 19-25', and with a 5 per cent. solu- tion is 18.29'. I-Tyrosine is prepared by hydrolysing the benzoyl derivative with 10 per cent. hydrochloric acid ; a more concentrated acid produces racemisation. The specific rotation in 20 per cent. hydrochloric acid at 20" is -8.64', corresponding with the value - 8.48O obtained by Schultze and Bosshard for the natural product ; in 4 per cent. acid [a], is greater, that of the synthesised compound being - 1 3 * 2 O , whilst that of a specimen obtained from casein is - 12.56O; the latter result, however, does not agree with that of the above investigators, who found the rotation to be - 15.6".Natural tyrosine, when rapidly heated, melts a t 31 0-31Z0, whilst the racemic compound melts about 2' higher ; the former separates in long, flexible crystals, the latter crystallises in stout needles.ORGANIC CHEMISTRY. 173 Ben*oyl-d-tyrosine is obtained from the racemic compound by the aid of cinchonine. The alkaloid salt separates somewhat slowly in flattened needles, and is obtained pure after two crystallisations: The benxoyl derivative melts at 165.5'; in an alkaline solution La], is d-Tyrosine, dissolved in 21 per cent. hydrochloric acid, has [ alD 8.64'.A base, supposed to be d-tyrosine, has been isolated by von Lippmann from the white shoots of the sugar beet in 25 per cent. hydrochloric acid ; it gave [ Q ] ~ 6.85O. The mother liquor from the brucine salt of benzoyl-Z-tyrosine con- tains a mixture of racemic and dextro-salts ; these are converted into the corresponding tyrosines, which are treated with hydrochloric acid, when the hydrochloride of the racemic base crystallises first ; the d-tyrosine obtained from the mother liquor has a higher specific rotation than that obtained from the cinchonine salt. Coumarins. I. Behaviour of Aminophenols with Ethyl Aceto- acetate. By HANS VON PECHMANN (Ber., 1899,32, 3681-3690).- A summary and a discussion of previous results and of those enumerated in the following three abstracts.It is only m-amino- phenols which condense with ethyl acetoacetate. Coumarins. 11. 7-Dimethylamino-4methylcoumarin and Homologues. By HANS VON PECHMANN and MAX SCHAAL (Ber., 1899, 32, 3690-3696).-p-Dimethylaminophenol and ethyl aceto- acetate condense in the presence of zinc chloride to form 7-dimethyZ- amino-4-methylcoumurin, which crystallises from dilute alcohol, with 3H,O, in the form of yellowish needles melting at 143'. On fusion with alkalis, it yields traces of 2-hydroxy-4-dimethylaminoacetophenone, which forms white leaflets melting at 120°, and a compound melting at 142O, which is probably bis-dimethylaminodihydrocoumarone, C,,O,H,,Me,(NMe,),. Nitrous or nitric acid converts the 7-dimethyl- amino-4-methylcoumarin into a mononitro-derivative melting a t 159" and a &nitro-derivative melting at 230'.Bromine in chloroform - 19.59'. G. T. M. R. H. P. v CMeBr YHBr solution yields the dibromide, NMe,* C6H,<0 co , which crystallises from glacial acetic acid in white needles melting and decomposing at 210°, and on boiling with alcohol is converted into 3-bromo-7-dimethyZamino-4-nzethyZcoumarin melting at 169'. On treat- ment of this monobromo-derivative with bromine, two isomeric dibromo-derivatives are obtained, one melting at 126O, the other at 184". On dissolving the dibromide or the monobromo-derivative in alcoholic potash, 6-dirneti~ylamino-3-mothyEcoumarilic acid, NMe,. C6H,<E>C*C0,H, is obtained ; it forms grey needles melting and decomposing at 165O, and on heating yields 6-dimethyZumino-3-methyZcoumarone, which melts at 58'.wz-Dimethylaminophenol, ethyl acetoacetate, and alcohol condense in the presence of zinc chloride to form 7-dimethy2umi~o-4-methyl- 3-ethylcoumarin, which when crystallised from alcohol me1 t s at SS0, but from benzene and light petroleum at 135O.174 ABSTRACTS OF CHEMICAL PAPERS. ~-~iethylam~no-4-met~ylcoum~r~n, obtained when ni-diethylamino- phenol is used, is an oil which yields a tribromo-derivative melting at 109'. R. H. P. Coumarins. 111. 7-Amino-4Methylcoumarin. By HANS YON PECHMANN AND OTTO SCHWARZ (Ber., 1899, 32, 3696-3699).- 7-Amino-4-methylcoumarin, prepared by the condensation of m-amino- phenol and ethyl acetoacetate with zinc chloride, crystallises in fern- shaped forms, which sinter at 215' and melt at about 223'; it yields a monoacetyl derivative melting a t 270°, and a monobenxoyl derivative melting a t 249-250".- 7-Methykamino-4-methylcoumarin, obtained in a similar manner from m-methy laminophenol, crystallises from dilute alcohol, with H,O, in the form of small, yellow needles melting a t 1 2 3 O , and yields a lzztrosamine melting at 189'. On heating 'I-amino- 4-methylcoumarin with methyl iodide in a sealed tube a t loo', 4-methyZ- CMe:FH is 0- co' cou~narin-7-trimethylarnm.oniacm iodide, NMe,I- C,H,< obtained ; i t forms needles melting a t 188", and yields an insoluble platinichloride. The position of the amino-group in these coumarins is proved by the conversion of the aminocoumarin into 4-methyl- um belliferon e. Coumarins. IV. Action of m-Aminophenol on Ethyl Acetoacetate.By HANS YON PECHMANN and OTTO SCHWARZ (Bey., 1899, 32, 3699-3704).-In the condensation of m-aminophenol with ethyl acetoacetate by means of zinc chloride, in addition to 7-amino-4- methylcoumarin, varying proportions of 7 (?)-hydroxylepidone (Besthorn and Byvanck, Abstr., 1898, i, 450), 7 (?)-hydroxy-2 : 4 : 4-trimethyl- 3 : 4-dihydroquinoline, and 4 : 6 : 6 : 8-tetramethyl-6 : 7-dihydroquino- coumarin are formed. 7-Hydroxylepidone forms a rnonoacetyl derivative melting at 250-254', and a monobenzoyl derivative melting a t 288". 7 (9-Hydroxy-2 : 4 : 4-trimethyz-3 : 4-dihydropuinoline can be prepared by heating together molecular proportions of m-aminophenol and mesityl oxide ; it forms a grey, amorphous powder without a definite melting point, and on treatment with ethyl acetoacetate and an alcoholic solution of zinc chloride yields 4 : 6 : 6 : 8-tetramethyl-6 : 7-dihydroqzcino- cowmarin, which forms yellow needles melting a t 268', and on treat- ment with bromine yields 5 (?) : 10 dibromo-4 : 6 : 6 : 8-tetrcmethyl-6 : 7- dihydroquinocounaarin dibromide ; this is obtained in the form of greenish-yellow needles which melt and decompose at 204", and on treatment with alcoholic potash give 3 : 5 (3) : IO-tr&rorno-4 : 6 : 6 : 8- tetramethyl-6 : 7-dihydroquinocoumarin, which forms small, yellow needles melting and decomposing a t 191". Either of the bromine compounds on continued boiling with alcoholic potash gives 4 ('1) : 9- dibromo-3 : 5 : 5 : 7- tetramethyl-5 : 6-dihydrodibromopuinocoumariZic~~cia?, which melts and decomposes at 206", and yields a methyl ester melting at 138".Molecular proportions of m-aminophenol and ethyl acetoacetate, when heated on the water-bath for 3 hours, give ethyl m-hydroxy- phenylaminocrotonate, HO*C,H~*NH*CMe:CH*C~)2Et, which a t a tern- perature of 250-260' yields 4 : 7 (t)-dihydroxy-2-methylqzlil.lolilu j this R. H. P.ORGANIC CHEMISTRY. 175 crystallises, with H20, in the form of needles, which decompose at 300" without melting, and forms a diacetyl derivative melting at about 232". R. H. P. Derivatives of Naphthalic Acid. By FRITZ ANSELM and F. ZUCKMAYER (Ber., 1899, 32, 3283-3296).-Concentrated sulphuric acid does not act on naphthalic acid (1 : 8-naphthalenedicarboxylic acid) at a high temperature, but sulphuric acid containing 25 per cent.of anhydride gives rise a t 90-95" to the rnonosulphonic deriva- tive, SO,H*C,,H,(CO,H),, a white, deliquescent substance which melts at 198O, being converted into the anhydride ; the barium and calcium salts (each with 1H2O) and the sodium and potassium salts (each with l+H20) were prepared. On adding nitric acid (1 mol.) to naphthalic anhydride dissolved in sulphuric acid a t 5", the mononitro-derivative, NO,*C,,H,(CO),O, is obtained ; it crystallises from glacial acetic acid in slightly brownish, lustrous leaflets and melts at 249" (compare Quincke, Abstr., 1888, 843). On nitration with a mixture of sulphuric acid and 2 mols. of fuming nitric acid a t 60°, naphthalic anhydride yields the dinitro- derivative, C1,H,(NO,),(CO),O, which crystallises from toluene in yellowish-brown needles and melts at 2 14".Aminonaphthalic uizhy- dride, prepared by reducing the corresponding nitro-compound, is a yellow powder which melts above 300' and is nearly insoluble in all solvents, but the acetyl derivative, NHAc*C,,H,( CO),O, crystallises from glacial acetic acid in yellowish-white needles ; diaminonaphthalic anhydride was obtained only in the form of the tin salt. The calcium salt, Ca[S0,*C,,H4(N02)(C0,),Ca],, of nitrosulphonapht halic acid, obtained by nitrating sulphonaphthalic acid, forms stout, yellow crystals. Hydroxynuphthalic anhydride, OHo CloH5( CO),O, prepared by heat- ing sodium sulphonaphthalate with solid potassium hydroxide initially at 180°, finally at 220°, crystallises from glacial acetic acid in bright yellow, silky needles (++C,H,O,), which on drying lose the acetic acid and become lustreless ; the anhydride dissolves in alkalis to form initially a yellow salt by replacement of the hydroxylic hydrogen by the metal, but this immediately changes into a normal, colourless salt, owing t o fission of the anhydride ring; the potassium salt, C1,H,0,K2, forms beautiful, white needles. Since the hydroxy- anhydride unites with diazo-salts to form dyes, it appears probable that the hydroxyl group is not in the ortho- but in the para-position relatively to carboxyl ; the hydroxy-anhydride can also be obtained from aminonaphthalic anhydride through the diazo-reaction.Like phthalic anhydride, hydroxynaphthalic anhydride furnishes cherry- red dyes of the naph thalein and rhodamine types.Acetoxynaphthalic unhydride, OAc*CloH,(CO),O, prepared by heating the hydroxy-anhy- dride with acetic anhydride, crystallises from ethyl acetate in white leaf- lets, and melts at 21 6". ETydroxynccp~thaliinide, OH*C,,H,<~>NH, prepared by heating the anhydride with alcoholic ammonia, crystal- lises from dilute acetic acid in yellowish-green needles, and shows no definite melting point j the acetyl derivative, C,,HSO,N, forms white1 'IG ABSTRACTS OF CHEMICAL PAPERS, leaflets and melts a t 278'. naphthalimide with methyl iodide, the methyl derivative, On heating the potassium salt of hydroxy- OMe* C,,H,<~~>NMe, is formed, which separates from alcohol in yellowish-white, crystalline masses.H~d~oxy~apAthaZu.niZide, OH*Cl,H,<CO>NPh, co prepared by heating the anhydride with aniline for 4 hours a t 185', crystallises from alcohol in yellowish-white, felted needles and melts above 300' ; the acetyl derivative, OAc*C,oHS<co>NPh, forms white needles and melts a t 212'. HydroxynaphtliaZoxime, OH* C , , H 5 ~ ~ ~ 0 ~ > 0 , prepared by heating hydroxynaphthalic anhydride with alcoholic h ydroxylamine hydrochloride and sodium acetate, crystallises from alcohol in lemon- yellow, sheaf-like aggregates of needles, and has no definite melting point; it yields intensely red salts with alkalis; the potavsium salt, OH* C , , H 5 < ~ ~ ~ 0 $ 0 , forms beaut if u l needles. DiacetoxynaphthaZ- co oxime, O A c * C , , H , ~ $ ~ > O , crystallises from alcohol in long, colourless needles and melts a i 194'. On heating the potassium salt of the oxime with methyl iodide for 5 hours a t loo', the dimethyl ether, O M e * C , , H , ~ $ ~ ~ , is obtained ; it crystallises from alcohol in white, felted needles and melts a t 191O.The phenyl- hydrccxone, OH*C10H5<C,:N~~~20, forms dark yellow needles and melts at 265'. Xet~oxyrzaphthalic a?ahydrk!e, prepared by heating the hydroxy- anhydride with methyl iodide and sodium methoxide, crystallises from ethyl acetate in yellowish-white needles and melts a t 244'. Hydroxysulphonaphthalic anhydride, prepared by the action of fuming sulphuric acid (25 per cent. SO,) on hydroxynaphthalic anhydride at; 115-1 20°, crystallises from water on adding alcohol in slightly yellow sheaves of needles; the sodizcm salt crystallises similarly, and on fusion with potassium hydroxide yields the compound, - O<zE>C10H4(OH)*s02* oH4(OK)<:>O or O<~~>CloH4(S03K)~O*Cl,H4(OH)<~~0, which forms yellow crystals and is insolnble in most solvents.W. A. D. Methyl Phloroglucinolcarboxylate. By JOSEF HERZIG and FRANZ WENZEL (Ber., 1899, 32, 3541-3542. Compare Will and Albrecht, Abstr., 1884, 1335).-MethyZ pAZorogZucinolcarboxyZate, C,H,(OH),*CO,Me, is readily obtained by the action of methyl iodide on the silver salt of the acid in the absence of any solvent. It crystallises from aqueous methyl alcohol in short, white needles melting at 166-168", and is readily soluble in ether, alcohol, orORGANIC CHEMISTRY. 177 ethylic acetate.The ethyl ester may be obtained by a similar pro- cess, but does not crystallise readily. Preparation of Hydroxystyrogallol. By FRANZ SLAMA (Chem. Centr., 1899, ii, 967 ; from DiSs. Giessen., 1899, 29-34).-Sy the condensation of p-coumaric acid with gdlic acid, hydroxystyvogallol or 2 : 3 : 6-trihydroxyanthrcccourncc~.in, C,,H,O,, is formed. The properties of this substance resemble those of Jacobsen and Julius' (Abstr., 1888, 56) and of Kostanecki's (Abstr., 1888, 291) compound. The more hydroxyl groups contained in the compound, the higher is the melting point, the more intense the colour, and the less the solu- bility. Hydroxystyrogallol is less soluble than styrogallol. The former dissolves in sulphuric acid, forming a red, and in potassium hydroxide or ammonia forming a green, solution.Triucetoxystyro- gullol, C,,H,O,(OAC)~, melts a t about 250' in a vacuum, E. W. W. J. J. S. Solanthic Acid. By W. BRAUTIGAM (Chem. Centr., 1899, ii, 669 ; from Pharm, Zcit., 44, 638).--SoZanthic acid, C,HI0O!,, prepared from the flowers and stems of Heliccnthus annuus, crystallises from water, melts at 144', sublimes without decomposition, is soIuble in alcohol, ether, or water, and forms crystalline salts. The acid is probably contained in the plant in the form of the calcium salt. E. W. W. Metallic Derivatives of Salicylh ydramide. By MARCEL DELEPINE (Bull. Xoc. Chirn., 1899, [ iii 1, 21, 943--945).-Cupric rnethylsalicylimide, Cu(O°C6H4*CH:NMe),, obtained from the action of salicylaldehyde on cupric acetate and methylamine in alcoholic solution, or by adding a concentrated aqueous solution of cupric acetate to an alcoholic solution of methylsalicylimide, crystallises in long, dark green needles melting a t 157'.Cupric benzylsulicylimide, Cn(O*C,H,*CH:N* CH,Ph),, obtained in a similar manner from benzylsalicglimide, is a n olive-green, crystalline substance which melts at 204'. A crystalline salt, having most probably the compo- sition Cu~O*C,H,~CH(NMe,),],, is also yielded by dimethylamine. The formation of these compounds leads the author to conclude that the compounds which Ettling (Annulen, 1840, 35, 241) obtained by the action of salicylhydramide on ammoniacal solutions of cupric acetate and ferric tartrate, are to be considered as derivatives of salicylirnide of the type Cu(O*C6H,*CH:NR),, and not as compounds of cuprammonium and ferrammonium respectively.N. L. Preparation of Anisaldehyde. By HENRI LABS& (Bull. Soc. Chim., 1899, [iii], 21, 1076--1077).-A yield of about 70 per cent. of anisaldehyde is obtained by the following modification of Canni- zaro's original method. 1 part of anethole is mixed with 2 parts of anhydrous acetic acid and the liquid warmed, at first gently, and then more strongly, with 34 parts of nitric acid of 14' B. The insoluble oil which separates, together with a further portion which is obtained by saturating the aqueous liquid with sodium carbonate, is agitated with sodium hydrogen sulphite and the resulting crystalline mass VOL. LXXVIII. i. 0178 ABSTRACTS OF CHEMICAL PAPERS, drained, washed with alcohol and ether, and treated in the usual manner.N. L. Aldehyde-Musk. By ALBERT BAUR-THURGAU and AUUUST BIS- CHLER (Bey., 1899, 32, 3647-3648. Compare Abstr., 1898, i, 583). -Butylxylylaldehyde is best prepared by heating the corresponding glyoxylio acid with p-toluidine and treating the product with sulphuric acid; it crystallises in large tablets melting a t 60' and readily yields a n oxime, which forms white plates melting at 97-98'. Nitric acid of 95 per cent. converts the aldehyde into a mononitro-compound, which crystallises in yellow, odourless plates melting a t 66'. Nitric acid of 100 per cent., on the other hand, yields the dinitro-compound, C,,H,,O,N, Yldehyde-musk, German Patent, No. 94019), crystallising in faintly ye low tablets melting a t 112'. It yields two oximes of the same composition, CIBHl7O,N,; the one more readily soluble in alcohol is a microcrystalline powder melting a t 138-1 39', whilst the second oxime forms white plates melting a t 171'.Aldehyde-musk readily forms condensation products with various compounds ; the derivative, CI4Hl7O6N3, obtained from nitromethane melts a t 206'. Acetic anhydride converts aldehyde-musk into a diacetyl derivative, C17H2606N2, melting a t 147', which can also be obtained by converting butylxylylaldehyde into the diacetyl derivative melting at 87', and treating this with nitric acid. I n the preparation of the aldehyde from butylxylylglyoxylic acid, a second compound is obtained, which has the composition C,,H,,O. A. H. o-Nitrovanillin. By ROBERT PSCRORR and C. SUMULEANU (Bey., 1899, 32, 3405-341 3)-Acetylvanillin (Tiemann and Nagai, Abstr., 1878, 579) can be advantageously prepared by shaking a solution of vanillin in the calculated amount of alkali with an ethereal solution of acetic anhydride.o-~it?.oacetylvcLnillin, CHO* C,H,(NO,)(OMe)*OAc [I : 2 : 3 : 41, prepared by dissolving acetylvanillin in well-cooled, concentrated nitric acid, crystnllises from light petroleum in small, stout prisms, and melts at 85-87' ; the phenyZhydrcLxone crystallises in thin, reddish- brown plates and melts a t 154' (corr.). [CHO: NO, :OMe :OH= 1 : 2 : 3 :4], crystallises from alcohol in minute needles and melts at 137' (corr,) ; the phenylhydraxone crystallises from acetic acid in brick-red prisms and melts a t 161-162'. The methyl ether crystallises from dilute alcohol in long prisms, and gives a phenylhydraxone, which crystallises from acetic acid in saffron-yellow tablets and melts at 194' (corr.).o-Nitroveratric acid, NO,* C6H,(OMe),* CO,H [ = 2 : 3 : 4 : 13, was pre- pared by oxidation of o-nitrovanillin methyl ether, and found t o be identical with Matsmoto's isonitroprotocatechuic acid dimethyl ether (Abstr., 1879, 501) ; on reduction, i t gives an o-aminoveratric acid identical with that prepared by Kuhn (Abstr., 1895, i, 367) from hemipinimide, thus establishing the constitution of Matsmoto's acid, and the position of the nitro-group in the present series of compounds. The structure of the amino-acid was further established by preparation o-NitrovanilZin,ORGANIC CHEMISTRY. 170 of the acetyl derivative, and by converting it, through the nitrile, into hemipinic acid.o-Nitrovanillin methyl ether, CHO* C,H,(OMe,)*NO, [l : 3 : 4 : 61, was prepared by the action of cold nitric acid on vanillin methyl ether, and is isomeric with that prepared through the acetyl compound ; i t crystallises from alcohol in minute, yellow needles and melts at 132-13Yo (corr.) ; t h e phenylhpdrazone crystallises from acetic acid in glistening, reddish-brown, four-sided plates and melts at 2 I 6-218' (corr.). The position of the nitro-group is shown by the fact that, like the isomeride previously described, the aldehyde gives the indigo- reaction, and is therefore a derivative ol o-nitrobenzaldehyde. On oxidation, i t gives a nitroveratric acid [CO,H: (OXe)2 :NO, = 1 : 3 : 4 : 61 identical with that prepared by Tiemaon and Matsmoto by nitration of veratric acid ; the constitution of t h e latter is thus established.Condensation of Cyclic Ketones with Ethyl Succinate. T. M. L. By HANS STOBBE [AND RICHARD FIsCHER] (Be?"., 1899, 32, 3354-3356. Compare Abstr., 1899, i, 900).-When an ethereal solution of cyclo- pentanone and ethyl succinate is left i n contact with sodium ethoxide (free from alcohol) for several weeks, and is then treated with water, the ethereal solution contains ethyl succinylsuccinste, together with small quantities of indifferent substances and the aqueous alkaline solution, a mixture of sodium salts of acid esters. After acidifying, hydrolysing with barium hydroxide, and fractional separation of the barium salt thus obtained, two acids have been obtained.One of these, Cl4Hl8O4, crystallises from water, melts at 135O, and yields a sparingly soluble barium s a l t ; i t is formed by the elimination of two mob. of water from two mols. of the ketone and one of the ethyl ester. The second acid, C,H,,O,, crystallises from beuzene, water, or ether, melts and decomposes at 205--209', yields a readily soluble barium salt, and is produced from one mol. of the ketone and one of the ethyl ester. J. J. 5. Methylcyclohexanone. By OTTO WALLACH (Bey., 1899, 32, 3338---3341).-With reference to Klages' paper on methylcyclohex- anone (this vol,, i, 44), it is pointed out t h a t the constitution of this substance has been previously determined i n the author's laboratory by two independent methods.The first method is one of Oxidation, whereby methylcyclohexanone is converted into P-methyladipic acid ; the second consists in transforming the ketone into m-bromocresol. The action of bromine on methylcyclohexanone has also been inves- tigated ; crystalline bromo-substitution products, which furnish cresol and bromocresol by removal of hydrogen, and compounds with tear- exciting odours have been obtained ; the latter probably contain bromine in the side chain. The interaction between phosphorus pentachloride and methylcyclohexanone has also been studied, and the tetrahydrochlorotoluene produced has been characterised. G. T. BI. Preparation of Tetrachloro- and Tetrabromo-o-quinones from the corresponding Tetrahaloid Guaiacols and Veratroles. By H.COUSIN (Compt. Tend., 1899,129, 967--968).-When the tetra- 0 2180 ABSTRACTS OF CHEMICAL PAPERS, chloro- and tetrabromo-guaiacols or veratroles are subjected to Zincke's reaction, that is, oxidation with nitric acid, they give rise to the corresponding tetrahaloid o-quinones. The yields obtained are good when the guaiacol derivatives are used, but with the veratrole compounds they are poor, owing to fuming nitric acid being necessary for the oxidation. Tetrachloro-o-quinone gives with benzene a compound, CGCI,O, + 3C,H,, crystallising in large, red, elongated prisms, which rapidly lose the benzene in the air, leaving the tetrachloroquinone a s a violet-red powder. T. H. P. Stereochemistry of Quinoneoximes. By FRIEDRICH KEHRMANN (Annalen, 1899,310,89-111. Compare Abstr., 1899, i, 128).-[With prepared by oxidising dichlorocarvacrol with chromic acid, is volatile in steam, and crystallises from alcohol in yellow leaflets melting at 41-42O; i t separates from petroleum in crystals belonging to the rhombic system [a : b : c = 2.8449 : 1 : 1.13901.The oxime decomposes at 1 5 8 O , and separates from alcohol in crystals beIonging to the mono- clinic system [a : b : c = 1.5108 : 1 : 2.4862 ; p = 11S020']. The acetyl and benxoyl derivatives of the oxime melt a t 81-82' and 128-129O respectively. 3-Bromothymoquinone [Me:O,:Br : Pr = 1 : 2 : 5 : 3 : 41 obtained from dibromocarvacrol by oxidation, is identical with the derivative ob- tained from bromocarvacrolsulphonic acid (compare Abstr., 1890, 367) ; the crystals from petroleum belong to the monoclinic system [ a : 6 : c = 2.7130 : 1 : 1.1396 ; /3= 91'51'1. The oxinze decomposes a t 157-158O and crystallises in prisms beloaging to the monoclinic system [a : 6 : c = 2.6233 : 1 : 3.9232 ; p = 97'4'1.The ucetyl and benxoyl derivatives of the oxime melt at 75-76' and 130-131O respectively. 3-Iodothymoquinone [Me : 0, : I : Pr = 1 : 2 : 5 : 3 : 41 has been already described, and crystallises iu the monoclinic system [a : b : c 2.5257 : 1 : 1.1396 ; /3= 95O20'1. The oxirrze decomposes at 141-142°, and crystallises in the monoclinic system [a : 6 : c = 2.7031 : 1 : 3.7019 ; p= 96O2'1. The cccetyl and benxoyl derivatives of the oxime melt at 99-100" and 144' respectively. 6-Chlol.oti~yrnoqwinone [Me : 0, : Yr : 01 = 1 : 2 : 5 : 4 : 61, prepared by oxidisiag dichlorothymol, crystallises from alcohol in golden-yellow prisms, and melts at 39-40'; i t separates from petroleum in mono- clinic crystals, having the axial ratios [a : b : c = 2.2533 : 1 : 2.5796 ; p= 95O22'1.The oxime crystallises from alcohol in pale yellow prisms belonging to the monoclinic system [a : b : c = 2.1203 : 1 : 0.8713 ; p= 99"36'], and decomposes at 152". The acetyl derivative of the oxime forms rhombic crystals and melts a t 76-77" [ a : b : c = 0.5767 : 1 : 0.4777). The benzoyl derivative separates in monoclinic crystals [a: 6 : c = 1*6793:1:1*1808; /3=97'6'],and meltsat 126-127'. 6-Bromothymoquinone, which crystallises in the monoclinic system [a : b : c = 2.2284 : 1 : 2.5002 ; /3 = 94'1 1'1 and melts a t 46-41", has been already described. The oxime also crystallises in the monoclinic system [a : b : c = 1.0699 : 1 : 0.8737 ; p- 103'38'] ; the acetyl derivative 0.KRUGER].-33-Ch~O~Olhy1120~U~nOne [BE@ : 0, : c1 : PI?= 1 : 2 : 5 : 3 : 41,ORGANIC CHEMISTRY, 181 melts a t 71-72', and has the same axial ratios as the acetyl deriva- tive of 6-chlorothymoquinoneoxime, and the benxoyl derivative, which melts at 119-120°, crystallises in the monoclinic system [a : b : c = 1.6861 : 1 : 1.1873 ; p= 97'86'1. 6-Iodothymoquinone, which crystallises in the monoclinic system [a : b :c=2.0164: 1 : 0.4834 ; /3= 100°3'] and melts at 61-62', has been already described; the oxime is rhombic ( I a : b : c = 0.9067 : 1 : 0.39051 ; the acetyl derivative melts a t 67-68', and has the same axial ratios as the acetyl derivative of 6-chlorothymoquinone- oxime, and the benxoyl derivative, which melts a t 144', crystallises in the rhombic system [a : b : c = 0-6745 : 1 : 0,37991. [With M.S ~ ~ o ~ ~ ] . - C h Z o s . o n ~ t s . o t ~ ~ ~ o Z [Me : C1: OH : Pr : NO, = 1 : 2 : 3 : 4 : 61, prepared by oxidising 6-chlorothymoquinoneoxime with nitric acid, crystallises from alcohol in pale yellow, lustrous needles, and melts at 116'; it is also produced when chlorine is passed into 6-nitrothymol dissolved in glacial acetic acid. Bromonitrothymol [Me : Br : OH : Pr : NO, = 1 : 2 : 3 : 4 : 61, obtained on oxidising 6-bromothymoquinoneoxime, crystallises from alcohol in yellow prisms, and melts a t logo; it is also prepared by adding bromine to 6-nitrothymol dissolved in glacial acetic acid.The diucetyl derivative of chloroaminocarvscrol, C,,Hl80,NC1, obtained from 3-chlorothymoquinoneoxime by reduction with stannous chloride followed by acetylation, crystallises in long, lustrous needles, and melts a t 175"; it is also produced when p-nitrocarvacrol [Me : OH : Pr : NO, = 1 : 2 : 4 : 51 is chlorinated, reduced, and finally acetylated. prepared by analogous methods, crystallises in lustrous needles and melts at 157-158'. The diacetyll derivative of bromoaminocarvacrol, C1,H180,NBr7 M. 0. F. Halogen Derivatives of Anthragallol. By FRANZ SLAMA (Chem. Centr., 1899, ii, 966-967; from Diss. Giessem, 1899, 1-26).-Bg the action of halogens on anthragallol, the halogen enters into the ring which contains the hydroxyl groups in a similar manner to the forma- tion of nitro-derivatives (coinpare Bamberger and Bock, Abstr., 1897, i, 576).When bromoanthragallol is melted, or oxidised by nitric acid, benzoic acid is formed, and when melted with potassium hydroxide at 200' i t yields tetrahydroxyanthraquinone identical with Bayer and Co.% compound (German Patent, 86968), hence the formula of the halogen derivative is C,,H,Br(OH),O, or 4-chloro-1 : 2 : 3-trihydroxy- anthraquinone. When chlorine is passed into an thragallol suspended in glacial acetic acid, chloroanthragallol is formed ; this crystallises in orange-red needles, melts at 230', is soluble i n alcohol, glacial acetic acid, or xylene, and forms a green solution in aqueous potassium hydroxide ahd a red in concentrated sulphuric acid.Bromounthraga,llol, Cl4H7BrO5, melts at 212O, decomposes when distilled in a vacuum, is oxidised by nitric acid, forming benzoic acid, and is decomposed by nitrous acid. Tetra h y d roxya n t hraquinone, U, , H,O, (0 H),, prepared by heating bromosnthragallol with potassium hydroxide and a little water at 206', forms a sublimate consisting of green needles, and dis- solves in sulphuric acid or aqueous potassium hydroxide, forming a red182 ABSTRACTS OF CHEMICAL PAPERS. solution. Tetra-acetoxyanthmquinone, C,,H,O,(OAc),, crystallises in yellow needles, melts at 205O, and dissolves in boiling aqueous potassium hydroxide, forming a violet-red solution, but is insoluble in the cold. ChloroacetylcMoroanthrccguZZol, prepared by the action of chloroacetyl chloride on chloroanthragxllol, crystallises in silky, yellow needles and melts at 189-1 95' ; chZoroucetylbromoccnthrugaZZolot forms similar crystals and melts a t 197-203O.The products obtained by the action of chloroacetyl chloride are not, however, homogeneous com- pounds. When the halogen compounds are boiled with acetic anhy- dride, triacetyl derivatives are obtained, hence these compounds contain three hydroxyl groups. Chlorotriacetylccnthragarllol, CI1,H,C1O2(0Ac),, crystallises in yellow needles, melts a t lS7", and dissolves in boiling aqueous potassium hydroxide, forming a red solution, which quickly becomes green. Brornotriacetykanth~agccllol, C,,H,O,Br(OAc),, crystal- lises in yellow needles and melts a t 178'. ChZorotribe~xoylanthragalZol, C,,H,O,CI(OBz),, forms yellowish needles, melts a t 209O, and dissolves in boiling aqueous potassium hydroxide, forming a green solution.Bromot~i6en,xoyZunthraguallol, CI4H,O2Br(OBz),, forms yellow crystals, melts at 2064 is slightly soluble in glacial acetic acid or alcohol, but By LOUIS BOUVEAULT (BUZZ. Xoc. Chim., 1899, [iii], 21, 1013--1019).-An account of the author's views on the constitution of camphor and its derivatives, and the researches which have led t o their modification since 1892. Attempts to effect the synthesis of derivatives of camphoric acid have met with the same want of success as the experiments of Perkin (Trans., 1899, 75, 909). Attempts to convert ethyl isoamylacetoacetate into ethyl isolauronolate by the action of various dehydrating agents all failed.Molecular Refraction and Dispersion and Specific Rotation of Alkyl Derivatives of Camphor. By ALBIN HALLER and PAUL TH. MULLER (Con@. rend., 1899, 120, 1005-1008. Compare Abstr., 1899, i, 770, ii, 622).-The molecular refraction and dispersion, and specific rotation of the following compounds have been determined : benzylidenecaruphor, piperonylidenecamphor, cuminylcamphor, ethyl- saligenylcamphor, m-methoxybenzylcamphor and p-methoxybenzyl- camphor. The agreement between the found and calculated values (using Briihl's and Conrady's coefficients) is much closer than in the case of the compounds of camphor with aromatic aldehydes. This difference between the two values in the latter compounds is prob- ably due t o the double linking between the camphor and aldehyde groups, which is absent in the compounds enumerated above, hence the closer agreement.Pulegone and Isopulegone. By CARL D. HARRIES and GEORG ROEDER (Ber., 1899, 32, 3357-3373. Compare Beckmann and Pleissner, Abstr., 1891, 936; Semmler, 1893, i, 130; Wallach, 1896, i, 309 ; Tiemann and Schmidt, 1897, i, 198).-Pulegonehydroxylamine (Abstr., 1898, i, 573) forms an oxaZate, (Cl,H,,0,N),C204H,, which crystallises in prismatic needles melting and decomposing at 151-152'. insoluble in cold aqueous potassium hydroxide, E. w. w. Constitution of Camphor. N. L. H, R. LE S.ORGANIC CHEMISTRY. 183 With nitrous acid, the hydroxylamiae yields a white, crystalline mass, probably the nitrosamine, which is extremely unstable ; it also reacts with hydriodic acid, yielding 8-aminomenthone (compare Beckmann ahd Pleissner), the oxalate of which has been prepared; so far, the authors have not succeeded in condensing this salt with different aldehydes (compare Fischer, Abstr., 1884,53).Bispdegone, C,,H,,02, obtained by the action of aluminium amalgam on pulegone, crystallises in needles, melts at 11S-119°, and is readily soluble in benzene, ether, or acetic acid; when sodium amalgam is used in acetic acid solution, considerable quantities of menthone and oE menthol are also formed, When hydrobromopulegone is boiled with alcohol and lead hydroxide as recommended by Beckmann and Pleissner, the chief product is methylcyclohexanone (compare Wallach) ; the same product is formed when puIegone is boiled with ethyl alcohol and basic lead acetate, or when it is distilled with quinoline.When, however, the ketone is heated on the water-bath for half an hour with methyl alcohol and basic lead nitrate, a 70 per cent. yield of a-isoyulegone is obtained ; this may be separated from unaltered pulegone by treatment in ethereal solution with aluminium amalgam and subsequent distilla- tion in steam, and finally purified by conversion into its oxime melting a t 120-121"; the latter is identical with the oxime obtained by Tiemann and Schmidt. a-Tsopulegone is a colourless oil distilling a t 98-100° under 13 mm. pressure, and has a sp. gr. 0.9192 a t 19*5', and a rotatory power an -7'S', but when kept for some time iu contact with dilute sulphuric acid, i t becomes inactive ; i t s semicarb- azone, CllH190N3, crystallises from dilute alcohol in needles melting and decomposing a t 173-1'74".When an alcoholic solution of a-isopulegone is left for 24 hours in contact with baryta water, it is completely converted into ordinary dextrorotatory pulegone. According t o the authors, the isopulegone obtained by Tiemann and Schmidt's method yields a semicurbaxone melting at 183" and an oxime melting a t 143' ; they therefore term i t /3-isopulegone. Accord- ing to recent experiments by Tiemann, a mixture of the a- and /3-compounds is obtained by his method; these are probably the two inactive forms of the constitution CHMe<CBo. CH2--G'o>CH* CH, CMeZCH,, 1 1 whereas pulegone is CHMe<CH,, CH2--Co>C:CMe,, CH, J. J. 8, Camphenylone. By EDMOND E. BLAISE and G. BLANC (Compt.rend., 1899, 129, 886-889. Compare Abstr., 1899, i, 627, 629,820). -If Jagelki's formula for camphoceenic acid, and Bredt's formula for isolauronolic acid are correct, then the nitriles of these two acids on reduction should give one and the same amine. This, however, is not the case, as the following results show. Camphenylone prepared by the action of nitric acid vapours on camphene at Oo, was purified by converting it into its semicurbaxone melting at 224", which, on treatment with hydrochloric acid, gives pure camphenylone, melting a t 37O. The oxime readily sublimes and melts at 109-llOo, and on dehydration with acetyl chloride, gives camphoceenonitde, boiling a t 220-230°, and an iso-oxirne meltingIS4 ABSTRACTS OF CHEMICAL PAPERS, at 165'. Camphoceenonitrile, on reduction with sodium and absolute alcohol, gives an unsaturated base, which boils a t 204-205' and readily takes up carbon dioxide.The hydrochloride of this base is a white powder, which darkens a t 195O and decomposes a t 2 2 5 O , and when treated with potassium cyanate gives a substituted curbnmide, C,H,,*NH*CO*NH2, crystallising in micaceous plates, which melt a t 118' and are only slightly soluble in cold, but readily i n hot, benz- ene. The oxurnide, prepared by the action of ethyl oxalate on the base, forms needles which melt at 148', and are very slightly soluble in alcohol ; its pkatinichkoride is a yellow powder insoluble in alcohol and in water. From the mother liquor of the hydrochloride of the above unsaturated base, the hydrochloride of an isomei-ic base was isolated ; this boils a t 1 9 5 O , i t s hydrochloride melts at 175-176', the oxamide and substituted carbamide a t 106-107°, and the picrate at 178".The authors conclude that the trimethylcyclopentane group is not present in camphenylone and its derivatives. H. R. LE S. Ethereal Oils. By SCHIMMEL AND Co. (Chem. Centr., 1899, ii, 879-88 1 ; from Gesc/@$sber, October, 1899)-There are two kinds of commercial oil of citronella, differing only slightly in physical properties and chemical composition. The ordinary oil '' Lana Batu " contains less geraniol and citronella1 than the better oil "Maha pangiri," which is richer in compounds capable of forming acetyl derivatives. A sample of the former oil having a sp. gr. 0.908 a t 15', rotatory power - 9'36', and containing 61.1 per cent, of geraniol and citronellal, was found not only to contain campheue, dipentene, and limonene, but also two sesquiterpenes ; the one boils and decomposes at 260-270' under the ordinary pressure, and at 157' under 15 mm.pressure, has sp. gr. 0.8643 at 15', rotatory power + 1'28', and re- fractive index 1.51849 at 1 5 O , whilst the other boils at 272-275' under the ordinary pressure, a t 170-172' under 16 mm. pressure, has sp. gr. 0,912 at 15", and rotatory power +5'50'. The former terpene resinifies very easily, and this property explains the fact that, whilst many oils form clear solutions when dissolved in small quanti- ties of 80 per cent. alcohol, they give turbid solutions when treated with four or more parts of the same alcohol.The oil of citronella contained traces of linalool, about 1 per cent. of borneol and methyleugenol. Another sample of citronella oil contained 33 per cent. of geraniol, 28 of citronellal, and 8 of methyleugenol. The aqueous distillate obtained from oil of cumin contains methyl alcohol and furfuraldehyde. The yellowish colour of the former appears to depend on the presence of diacetyl; this is also the case with the methyl alcohol obtained from oil of cloves. The aqueous distillate of musk oil also contains furfuraldehyde. About 9 per cent. of damascenine was extracted from nigella oil by shaking with tartaric acid and decomposing the tartrate with sodium carbonate; this compound has a blue fluorescence, solidifies in the cold, boils a t 117' under 10 mm.pressure, and has a saponification number 277-4. From the alkaline liquid left after decomposing theORGANIC CHEMISTRY 185 tartrate, a fluorescent acid, probably an amido-acid, was isolated ; it crystallises from ether in prisms, is easily soluble in water, and forms a slightly soluble platinichloride. The presence of methoxy-groups in damascenine was confirmed. Mustard oil always contains carbon disalphide, hence the determina- tions of sulphur do not exactly correspond with the amount of allyl- thiocarbimide present. The fresh flowering plants and the roots of Vioka t~icoloor, when distilled, yield 0.00859 per cent. of a n ethereal oil, whiah consists By CHARLES TANRET and GEORGES TANRET (Bull. Xoc. Chim., 1899, [iii], 21, 1073-1075 Compare this vol., i, 78).-Rhamninase is precipitated by alcohol from the cold water extract of the fruit of Rhamnus k t e c t o r i a as a pasty mass containing 25-50 per cent.of solid matter; it is very soluble in water, and its activity does not diminish appreciably on keeping. The dry substance contains mineral salts (17 per cent.), substances coagulated by heat (53 per cent.), and galactan. A tem- perature of 70" is most favourable to the action of the enzyme, which is destroyed a t 85'. When xanthorhamnin is heated with water a t 50', a pale yellow, crystalline precipitate is gradually formed, quite different from that produced by the action o€ rhamninase. This substance is a new glucoside, which has n composition very similar t o that of xmtho- rhamnin, but differs from it in not beicg acted on by rhamninase and in yielding a larger proportion of rhamnose on hydrolysis.The solution, from which the insoluble glucoside has been deposited, contains R sub- stance, xanthorl~6mnein, which differs from xanthorhamnin in being more soluble and in having a higher rotatory power ([.ID +5" instead of + 3O.75). Schutzenberger's observations on the existence of two modifications of xiznthorhamnin are thus con firmed. mainly of methyl salicylate. x. w. w. Rhamninase and Xsnthorhamnin, N. L. Rhubarb and its Active Constituents. By ALEXANDER TSCHIRCH (Arch. Pharm., 1899, 237, 632--637).-1t is pointed out that Hesse (this vol., i, 40) is incorrectly informed as to the species of rhubarb cultivated in England for pharmaceutical purposes ; also that chrysophanic acid has lately been shown to have a purgative action, although to a less degree than alochrysin, and still less than emodin.C. F. B. Golouring Matter of Digitalis. By L. ALPHONSE ADRIAN and AUGUSTE TRILLAT (Compt. rend., 1899, 129, 889-S90).-The sub- stance CI6Hl2O4 was isolated from Digilaclis Zutea by a process analogous to that employed for the extraction of the yellow colouring matter from Artemisia absinthium (Abstr., 1899, i, 301). I t crystal- lises in beautiful, yellow needles, melts at 217--218', and dis- solves in ethyl alcohol, chloroform, or amyl alcohol ; in alkalis, it is soluble, forming solutions of a beautiful red colour. Hydrochloric acid is without action on it, and it does not form a compound with phenyl- hydrazine, neither does it give a reducing sugar.When treated with hydrochloric acid or potash, neither catechol nor phloroglucinol is186 ABSTRACTS OF CHEMICAL PAPERS. produced, which shows that the substance is not identical with the digitoflavone of Fleischer. H. R. LE S. Active Constituents of the Wallflower. By MORITZ REEB (Chem. Centr., 1899, ii, 917-918 ; fram Arch. exp. Path. Pharm., 43, 130-148. Compare Abstr., 1899, i, 378).-The physiological action of cheirsnthin resembles that of the digitalis compounds. Cheirinine, C18H35017N3, obtained from the alcoholic extract of the seeds of the wallflower, crystallises in small, colourless needles, melts at 73-74", and is soluble in warm water, alcohol, ether, chloroform, or ethyl acetate. The aqueous solution is neutral and gives precipi- tates with the ordinary alkaloidal reagents.The physiological action of cheirinine resembles that of quinine. The seeds also contain choline. E. W. W. Alkaloids of the Seeds of Lupinus Angustifolius and of Lupinus Perennis, var. Polyphyllus. By J~RGEN CALLSEN ( Amh. Pharm., 1899, 237, 566-595. Compare Siebert, Soldaini, Davis, Berend, and Gerhard, Abstr., 1892, 223; 1893, i, 739 ; 1896, i, 193; 1897, i, 174, 645, 646).-No other alkaloid, in addition t o d-lupan- ine, could be isolated from the seeds of blue and of perennial lupins ; the yield of alkaloid is seven times as great in the case of the latter plant . No new product, but only unchanged lupanine, could be isolated when lupanine was boiled with acetyl chloride, heated with fuming hydrochloric acid a t 150-180", heated with potassium permanganate and dilute sulphuric acid on the water-bath, allowed to remain with hydrogen peroxide a t the ordinary temperature and in the dark, heated on the water-bath with water and yellow mercuric oxide, or with 10 per cent.nitric acid, treated in cold alcoholic solution with metallic sodium, heated a t 200" with acetic anhydride or with dilute sulphuric acid, or on the water-bath with concentrated sulphuric acid, or at 150" with fuming hydriodic acid and amorphous phosphorus. From the product of the action of bromine on lupanine hydrochlor- ide in alcoholic solution, no alkaloid could be isolated (except un- changed lupanine) other than C,H,,ON (Davis ; Soldaini, C,H,,ON, Zoc. cit.). The platinichloride, (C,H,,ON),, H,PtCI, + 1iH,O, decom- posed at 200"; the base is a tertiary one, for it does not unite with phenylthiocarbimide, and it forms a methiodide, the pkctinichloride, corresponding with which, 2(C,H,,ONMe),Pt C1, + 6H,O, decomposes just above 200".By EDWIN S. FAUST (Chem. Centr., 1899, ii, 718-719; from Arch. exp. Path. €'harm., 43, 83-92. Compare Abstr., 1899, i, 380).-Samandarine sulphate, which has been prepared in large quantities, crystallises either in small, anhydrous needles, usually arranged in small tufts or star-shaped groups, or occasionally in large, hydrated needles. It has a specific rotatory power [a],, -53*69O, and gives a blue coloration when boiled with concentrated hydrochloric acid, When the platinichloride C. F. B. I Alkaloids from the Salamander.(~?,H,,*N,),,*,S~4~ORGANIC CHEMISTRY, 157 is dried over sulphuric acid, it loses hydrogen chloride, and forms the compound (C,,H,,ON,),PtCl,. Experiments with dogs showed that doses of 0*0007--0~0009 gram per kilogram of body weight are fatal, the symptoms of samandarine poisoning being very similar to those of rabies. The fire salamanders also contain another alkaloid, samandafidine, which appears to be present in larger quantities than sarnandarine. The sulphate, (C20H,10N2),S0,, crystallises in rhombic plates, is very slightly soluble in water or alcohol, is optically inactive, and has t h e same pharmacological action as samandarine sulphate, but to a less degree. When boiled with hydrochloric acid, i t behaves like saman- darine, and on distillation with zinc dust yields isoquinoliue. E.W. W. Behaviour of Iodoform and Chloroform with Strychnine By PERRY F. TROWBRIDGE (Arch. Phurm., 1S99, 237, 622--625).-The cornpound 3C,,H,,O,N,,CHI, (Lextreit, Abstr., 1881, 748) is formed even when 1 mol. of iodoform is allowed to react with 1 mol. of strychnine ; the two substances were allowed to remain together in chloroform solution at the ordinary temperature for a day, and the compound then precipitated with ether. When it is boiled with alcohol, another compound, 2C,,H2,O2N,,CHT3, is obtained ; this is also a reddish-brown, crystalline powder, which decomposes and melts at about 220O. When a chloroform solution of strychnine is subjected to prolonged heating at 150°, a crystalline compound, C,,H,,O,N,~HCl,CHCl,, is obtained ; this loses its chloroform partly at the ordinary tempera- ture and entirely at looo.C. F. B. By PERRY F. TROWBRIDCE (Arch. Phamn., 1899, 237, 617--622).-When strychnine and methylene iodide are heated together in methyl alcoholic solution, or allowed to remain in chloroform solution a t the ordinary tempera- ture, a white, crystalline compound, CH21*C21H,,0,N,I, is obtained ; this melts at 212O, and readily exchanges one of its iodine atoms for chlorine, &c. The corresponding chloride, CH,1*C,,H2,0,N,Cl, auri- chloride, pkutinichloride, rnercurichlorides, CH21*C,lH,,0,N,Cl,HgC12, and with 1 SHgCl,, brontide, hydrogen swlphate, hytlyogez chromate, and nitvate were prepared and analysed. Action of Iodine on Piperidine, Tetrahydroquinoline, and Tetrahydroisoquinoline.By ERNST SCHMIDT ( A ~ c h . Phcrm., 189 9, 237,561-565).-When tetrahydroquinoline is heated with iodine and alcohol in a closed vessel in the steam-bath, it is oxidised to quinoline. Tetrahydroisoquinoline, however? yields but little isoquinoline under similar circumstances, and piperidine does not yield pyridine. Action of Methylene Iodide on Strychnine. C. F. B. C. F. B. 6-Aminoquinoline and its Derivatives. By CHR. A. KNUEPPEL (Annaten, 1899, 310, 75-88. Compare Abstr., 1896, i, 391).- 6-Aminoquinoline, prepared by reducing 6-nitroquinoline in alcohol with iron borings, yields the hydvoclzloride in golden-yellow needles188 ABSTRACTS OF CHEMICAL PAPERS. melting a t 109"; the dihydrochloride is insoluble in hot alcohol and melts a t 2 5 0 O .Thionyl-6-aminoquinoZine, C,NH,*N:SO, crystallises in small, yellow needles, and melts at 64-65'; it is gradually decomposed by hot water, yielding sulphur dioxide ; 6-aminopzsinolinethionamic acid, C9NH,*NH*S0,H, melts at 124". 6-&uinyZurethane, C,NH,*NH*CO,Et, crystallises from hot alcohol in biownish plates, and melts at 168' ; the hydrochloride forms white needles, 6-AcetyZaminoquinoline, O,NH,*NHAc, crystallises from hot water in white needles melting a t 13S0, and the hydrochloride also forms needles ; the scclicykute, tartrate, and methiodide melt a t 140°, 226", and 268" respectively. 6-BenxoylccminoquinoZine, C9NH,*NHBz, crystallises in yellowish needles and melts at 169" ; the suZphate, hydroc?doridc, and nitrate are well crystallised substances.6-&uinolinehydruzine, C,NH,*NH*NH,, has not been obtained in crystalline form, but derivatives are easily obtained. The beraxylidene compound separates from water in long, reddish-yellow needles, and from alcohol in deep red cubes r n e l h g a t 203'; the semicarbaxide derivative melts a t 234O, and the pyruvic hydrazone crystallises in orange-red needles melting a t 201". 6-Axoquinoline, N2( C,N H,),, a bye-product in the preparation of 6-aminoquinoline, crystallises in lustrous, orange-red needles and melts at 248'. 6-Azoxydiquinolin.e, ClSHI00N4, prepared by heating 6-nitro- quinoline with sodium methoxide in methyl alcohol, crystallises from alcohol in dark violet needles and does not melt below 280' ; the solu- tion in sodium hydroxide is deep green, 6-AxodipuinoZine, C18H10N4, obtained when the foregoing substance is distilled with iron borings in an atmosphere of hydrogen, crystallises from xylene in yellow needles, infusible below 280".BimethyZaminobenxene-6-axoquinoline, C,NH,-N:N-C,H,*NMe,, pre- pared from diazotised 6-aminoquinoline and dirnethylaniline, crystal- lises from alcohol in lustrous, steel-blue needles. Benxene-6-diccxo- minopinoline, C,NH,*NH*N:NPh, formed on adding diazobenzene chloride to aminoquinoline, crystallises in long, orange-yellow needles, melting a t 142 ; the hydrochloride is crystalline, and the methiodide melts a t 220O. M. 0. F. 4-Hydroxycarbostyril from Anthranilic Acid. By HUGO ERDMANN (Ber., 1899, 32, 3570-3573. Compare Baeyer and Bloem, Abstr., 1883, 196, and Camps, this vol., i, 115).-4-Hydroxycarbo- styril is obtained when methyl anthranilate (Abstr., 1899, i, 621) is heated on the water-bath with ethyl acetate and metallic sodium for some three hours.The product is treated with ice-cold acetic acid and then shaken with water and ether, when the carbostyril begins to separate. The ethereal filtrate contains methyl diacetylanthranilate, NAc2*C,H,*C02Me, together with more hydroxycarbostyril. This discetyl derivative crystallises in glistening prisms melting at 180°, has a burning taste, dissolves in boiling alkalis, and is decomposed by dilute mineral acids.ORGANIC CHEMISTRY, 189 Acetylanthranilic acid melts at 185', and its methyl ester a t 101'; acetylsalicylic acid melts a t 132O, and its methyl and phenyl esters at 49' and 98' respectively.Action of Aldehydes on Quinoline Derivatives containing a Methyl or Methylene Group in Position 2 or 4. By WJLHELM KOENIGS (Ber., 1899, 32, 3599-3613).-When benzalde- hyde is heated with quinaldine (2 mols.) in presence of zinc chloride at 150-160°, a small quantity of benzylideriequinaldine (Doebner and von Miller,Abstr., 1885,1080) is formed together with a larger pro- portion of benxylidenediquinaldine, CHPh(CH,.C,NH,),, the hydro- chloride of which crystallises from absolute alcohol containing hydro- chloric acid in beautiful, colourless plates" ; the nitrate and sulphate form colourless crystals, whilst the platiniciilo~ide, with 3H,O, consists of yellow prisms and melts and decomposes a t 240'. The base IS a colourless, soft resin and cannot be obtained crystalline.When heated with benz- aldehyde in presence of zinc chloride for 7-S hours a t 160-170', i t yielde a large quantity G f resin, together with a small amount of benzylidenequinaldine, the expected tetramethylene derivative, CgNH,*CH<cHPh>CH*CgNH6, CHPh apparently not being formed. Benzylidenedilepidinc, prepared in the same manner as the corre- sponding quinaldine derivative, crystallises from alcohol i n colourless prisms and melts and decomposes indefinitely between 110' and 127' ; the hydrochloride, with 2H 0 crystallises in concentric aggregates of needles, whilst the plat$&doride, with 6H,O, forms a flocculent mass of yellow needles. Benxyl~et~iylollepidi~ie, C,NH,*CH(CH,Ph)*CH,*OH, prepared by heating benzyllepidine with 40 per cent. aqueous formaldehyde in a sealed tube for 45 hours at loo', crystnllises from benzene in colour- less, pointed prisms, and melts a t 150"; the plutinichloride forms a yellowish, crystalline mass of leaflets.The base is not further acted on by heating with formaldehyde for 9 hours at 140°, and is not changed by similar treatment with benzaldehyde for 10 hours a t 180-ZOO". When benzylquinaIdine is heated with 40 per cent. aqueous form- aldehyde €or 38 hours, benzylmethylolquinuldine, C,NH,.CH( CH,Ph )*CH,*OH, crystallising from ether in prisms or plates and melting at 11 3-1 14", is formed together with benzyldimetiiylolpuinuldine, C,NH,* C( CH, OH),*CH,Ph, which cryfitallises from alcohol in colourless prisms, melts a t 141-142", and yields a crystalline hydrochloride which sinters at 185' and meltsand decomposes at 190'; the bases were separated by means of their oxalates.Chloral condenses with benzylquinaldine in the same manner as formaldehyde, a crystalline compound me1 ting a t 173" being obtained. An attempt to obtain benzylquinaldine by the interaction of beazyl alcohol with quinaldine gave no result. Benzy lidenequinaldine doev not react with formaldehyde. * The original gives 156" and also 218" as the melting point of benzylidene diquinaldine hydrochloride. J. J. S.190 ABSTRACTS OF CHEMICAL PAPERS. Since lepidine combines with only two mols. of formaldehyde, whereas quinaldine combines with three (Abstr., 1898, i, 74 and 389), and benzyllepidine with one, although benzylquinaldine unites with two, it would appear that the benzene nucleus in the ortho-position t o the methyl radicle of lepidine exercises a stereochemical, inhibiting effect ; this hypothesis is, however, weakened by the fact that Ei-methyl- acridine, which contains two benzene nuclei adjacent to the active methyl radicle, condenses with 2 mols.of formaldehyde but 5-ethyl- acridine, in which one of the active hydrogen atoms is replaced by a methyl radicle with only one ; acridine itself does not react with fornialdehyde, yet 3-rnethyl-2-ethylquinoline condenses with one mol. of formaldehyde, and thus behaves like benzyllepidine. Met~ylol-5-methyZclcridine (5-hydrox yethyla cridine), C(CH,*CH,*OH) '(jH4<& C,H4>' the principal product obtained on heating 5-methylacridine with dilute alcoholic formaldehyde, is a yellow, amorphous substance, which melts at 115-125" and yields a hydrochloride crystallising in yellow needles ; with it there is formed a small quantity of dimethylol- 5-mthyZucridine, C,,H,,02N, which crystallises from alcohol in sulphur-yellow needles and melts at 194".Met~~yZol-5-ethylacridine, C,H4<&---- C,E4>, obtained similarly from 5-ethyl- acridine, separates from ethyl acetate in stout, yellow, lustrous crystals and melts at 183" ; the uurichloride forms yellow crystals, and the plutinichloride orange-y ellow needles which melt and decompose at 225". Although cinchonine and conchinine do not interact with form- aldehyde a t 1 30-140°, the corresponding deoxy-bases condense with 1 mol. of the aldehyde at 100"; it thus appears that the alkaloids contain the lepidine complex C,NH,*CH(OH)*C*, and the deoxy- bases the group C,NH,* CH2*C*.of methyloldeoxyconchinine darkens at 215", but does not melt at 270° ; the base is amorphous, and the other salts, with the exception of the picrute, are similar in nature. Methyloldeoxycinchonine, and its plutinichloride, C,,H,,ON,H,PtCI, + 2H,O, resemble the corresponding cinchonine derivatives. Papaverine interacts with formaldehyde at 1 OO", with elimination of 1H,O, to form methylenepapaverine, C21H,,04N, which crystallises from alcohol, on adding ether, in colourless aggregates of needles, melts at 155-156", and yields a yellow, crystalline platiuicldoride melting and decomposing between 150" and 180" ; the hydo.ochloride sinters at lOS", melts at l l O o , and decomposes at 130-140"; the hydq*obromide melts at, 110" and decomposes at 120°, whilst the picrate sinters at 100" and melts at 115".W. A. D. Amino-derivatives of a-Phenylbenzothiazole. By OTTO KYM (Ber., 1899, 32, 3532-3538. Compare Abstr., 1899, i, 647 and 943). --Dinitrophenyl thiobenxoate, C,H,(NO,),*S*COPh [S : NO, : NO, = 1 : 2 :4], can be prepared by the Schotten-Baumann method from dinitro- C (CHMe*CH,* OH) The platinichloricle, C,,H,,O,N,,H,PtCI, + 2H,O,ORGANIC CHEMISTRY. 191 phenyl mercaptan and benzoyl chloride, but more readily by mixing alcoholic solutions of chlorodinitrobenzene and potassium thiobenzoate ; it crystallises from dilute acetone in long, glistening, yellow needles, melts at 11 1-1 12', and is readily hydrolysed to dinitrophenyl mercaptan and benzoic acid ; tetranitrodiphenyl sulphide is also produced, especi- ally when the alcoholic solutions are heated.l-Phen?jZ-4-amino- benxothiaxole, NH,*C6H,<N>CPh, S prepared by reducing the pre- ceding compound by Nietzki's method (Abstr., 1897, i, 277), melts at 201-202', forms yellowish-green crystals, and gives yellow solu- tions with a greenish fluorescence, but forms a white, sparingly soluble sulphate. The acetyl derivative crystallises .from dilute alcohol in glistening, white needles, melts at 192-193', and shows a slight violet fluorescence in solution. p-Nitrothiobenxoic? acid, NO,*C,H,*CO*SH, crystallises from dilute hydrochloric acid in long, slender, yellowish-white needles and melts at 90-95' ; the disuZphide crystallises from dilute acetone in large, glisten- ing, yellowish-white leaflets, melts at 1S2-183', and is reconverted into dinitrothiobenzoic acid by warming with alcoholic potash ; the dinit~o- phen,yl estercrystallises from acetone or acetic acidinglistening, yellowish- white flakes, melts a t 139-140", and is hydrolysed by aqueous potash t o dinitrophenylmercaptan and p-nitrobenzoic acid.1-p-Aminophenyl- 4-arninohenxothiaxoZe, NH,*C6H,<i>C* C,H,*N H,, prepared by re- ducing the trinitro-ester, crystallises from dilute acetone or alcohol in long, yellow, glistening needles, melts at 237-23So, and closely resembles the corresponding oxazole, but does not form an insoluble hydrochloride, and shows a yellowish-green fluorescence in solution ; the acetyl derivative crystallises from dilute alcohol in reddish-white, glistening needles, melts a t 272--273', and shows a n intense reddish- violet fluorescence in solution.T. M. L. Methyl-o-anisidine, Methyl-o-aminophenol and their Oxida- tion Products (6-Methylphenoxazine-2 : 3-quinone). By EMIL D,TEPOLDER (Bey., 1899, 32, 3514-3528).-When o-nitroanisole is reduced with tin and hydrochloric acid, a mixture of o-anisidine and chloroanisidine [OMe : NH, : C1= 1 : 2 : 51 is produced (Herold, Abstr., 1882, 1287 ; Reverdin and Eckard, this V O ~ . , i, ZS), which is best sepa- rated by conversion into the formyl derivatives. Formyl-o-anisidine crystallises from dilute alcohol in long, colourless needles, melts a t S3*5', and dissolves in hot water and organic solvents.5-Chloro-2;foi-myZ- aminoanisole crystallises from alcohol in thin, colourless tablets, melts at 177-17So, is less soluble than the preceding compound, and is hydrolysed by boiling sodium hydroxide solution. &ethyl-o-anhidine, prepared by methylating formyl-o-anisidine, boils at 141-143' under 46-47 mm. pressure, and solidifies to long prisms which melt at 33-33-5'. Benxen~sulpl~orz-o-cclzisidine crystallises from alcohol and from hot water, and melts at 89' ; the sodium derivative is readily soluble in water, but is precipitated in white needles by strong sodium hydroxide. Benxenesulphonmethyl-o-anisidine crystallises from a mixture of ether192 ABSTRACTS OF CHEMICAL PAPERS. and light petroleum in well formed tablets and prisms, and melts at 60'.o-Methoxyphenylglycine, when purified, melts a t 153', and crystallises in white, flat needles (compare Vater, Abstr., 1884, 1144). Methyl-o-nitrosoaminophenol, OH*C6H,*NMe*N0, crystallises from dilute alcohol in needles, darkens at loo', and decomposes at 121'' dissolves readily in hot water and dilute sodium hydroxide solution, a r d gives Liebermann's reaction, but could not be converted into a paranitroso-compound . o-~:cH~~o 5-Methylphenoxaxine-2 : ~-quinone, C6H4<yv A I e*C:CH*CO , prepared by oxidising methyl-o-aminophenol with potassium ferricyanide, melts with decomposition at 212-213", separates from chloroform in dark-red crystals with a green shimmer, and gives a greenish-blue coloration with stannous chloride ; its constitution is established by hydrolysis with sodium hydroxide t o methyl-o-aminophenol and a dihydroxy-o-quinone, which passes into Nietzki and Schmidt's pdihy- droxy-pquinone ; when the latter is condensed with methyl-o-amino- phenol, a small amount of the phenoxazinequinone appears to be reproduced.5-Methylphenoxaxine-2 : 3-quinonemonoxime is a reddish- brown, micro- crystalline powder which dissolves in dilute sodium hydroxide solution, but is hydrolysed by heating with mineral acids; i t darkens at 185' and melts, with decomposition, at 200--201° ; the dioxime could not be isolated in a pure state. With o-aminophenol, the quinone gives Seidel's triphenodioxazine (Abstr., 1890, 490). With o-ptienylene- diamine, it gives N-metl~yki*iphenaxinoxazine, or, possibly, C6H4G&>C,H,<i>C6H4, which crystallises from a mixture of benzene and absolute alcohol in orange-yellow needles, melts at 250°, sublimes with partial decomposition at higher tern- peratures, dissolves in organic solvent s, giving yellow, fluorescent solutions, and in sulphuric acid with a blue coloration.With o-amino- diphenylamine and hydrochloric acid, the quinone gives N-methyltriphen- oxuxinepl~enybzonizcrn chloride, C ~ H , ~ ~ ~ C ~ H , ~ ~ ~ HN- 729), which separates in small, bronzy needles and dissolves in water or alcohol to violet-blue solutions; the azonium buse dissolves in benzene t o a reddish, fluorescent colution; the plutinichloride is a blue, microcrystalline precipitate soluble in hot water. Action of Nitrous Acid on the Leuco-base, C,,H,,N,.By AUGUSTE TRILLAT (Comnpt. rend., 1899, 129, 1242--1243).-Unsym- metrical tetramethyldiaminodiphenylethane (Abstr., 1899, i, 615), when treated with sodium nitrite in cold hydrochloric acid solution, yields p-nitrodimethy laniline. A similar result is obtained with the leuco-bases derived from methme. T. M. L. G. T. M.ORGANIC CHEMISTRY. 193 Constitution of Metallic Salipyrines (Metallic Antipyrine- salicylates). By EDOUARD BOURGEOIS (Rec. Ib*av. Chinz., 1899, 18, 451--456).-Objections are taken to Schuyten's views (this V O ~ . , i, 57) as to the structure of metallic salipyrines. History of Diazonium Salts. By EUGEN BAMBERGER (Bey., 1899, 32, 3633-3635. Compare Abstr., 1899, ii, 685 and 750).- A reply to Hantzsch (this vol., i, 126). The diazonium perbromide constitution, NPhBr,iN, for the perbromides of diazonium salts was only suggested by Hantzsch after the ammonium formula for the radicle PhN, had been substantiated.The solubility of the diazonium carbonates and the physico-chemical evidence as to the nature of the ion of diazonium salts, merely confirm the author's views on the am- monium theory of the constitution of these compounds. Action of Aromatic Nitroso-derivatives on as-Alkyl Aromatic Hydrazines. By EUGEN RAMBERGER and ARMAND STIEGELMANN (Bsr., 1899, 32, 3554-3560. Compare Abstr., 1896, i, 222).-The pro- duction of diazohydroxyaminobenzene, NPh:N*NPh*OH, from nitroso- benzene and phenylhydrazine, is probably preceded by the direct addition of the constituents to form a compound, OH*NPh*NH*NHPh, which, by the loss of two atoms of hydrogen, yields diazohydroxy- aminobenzene.This conclusion is supported by the behaviour of nitrosobenzene towards unsymmetrical phenylmethylhydrazine. When the two are brought together, the chief product is benzeneazomethyl- aniline oxide, 0:NPh:NoNMePh or O<keNMeph, and it is probably formed by the loss of two atoms of hydrogen from the direct additive compound OH*NPh*NH*NHPh. A secondary product formed in the same reaction is diazomethylaminobenzene (benzeneazomethylanilide), NPh:N*NMePh, formed by the elimination of water from the addi- tive compound. Other bye-products are also formed, mainly by the action of the hydrogen from the intermediate additive compound. The azoamine oxides, as a group, crystallise readily in yellow-coloured crystals which are very stable.They differ from azoamines (Abstr., 1898, i, 20) in that they give no coloration with naphthylamine acetate, but readily give Liebermann's reaction, When reduced, they yield diazoamines, primary and secondary aromatic amines, azo-, azoxy-, and hydrazo-compounds, hydrazine, and ammonia. Benxeneaxomst~yZaniZi~~ oxide crystallises in glistening, sulphur- yellow needles melting a t 72", and is readily soluble in most organic solvents with the exception of light petroleum. When reduced, it yields diazomethylamino benzene, aniline, methylaniline, ammonia, and unsymmetrical p hen y lme thy lhydrazine. Benxeneazodip?Leny Zamine oxide, 0: NPh: N*NPh,, obtained toget her with phenylhydroxylamine, and probably diphenylamine, by the action of nitrosobenzene on unsymmetrical diphenylhydrazine, crystal- lises in sulphur-yellow needles, melts a t 128*5--129O, and is soluble in most organic solvents, including hot light petroleum.p-B~wonLo6enxeneaxomet?~~Zanikine oxide, C6H,Br*NO: N*NMePh, cry s- tallises in brass-yellow plates melting at 77-78', and is only sparingly VOL. LxxvIII. i. T. H. P. G. T. M. NPh P194 ABSTRACTS OF CHEMICAL PAPERS. soluble in cold light petroleum. p-Brom~benxsneaxodi~~~er.lyZacmine mide is formed, together with p-bromophenylhydroxylamine and p-dibromoazoxybenzene, by the actioG of p-bromonitrosobenzene on di- phenylhydrazine ; i t crystallises in golden-yellow needles melting a t 119-1200. J. J. S. Nitro-derivatives of Azo-, Azoxy-, and Hydrazo-benzene. By ALFRED WERNER and EDMUND STIASNY (Ber., 1899, 32, 3256-3282).-The details which follow show that nearly all the results obtained by Janovsky (Abstr., 1886,794) on nitrating azobenzene are incorrect. The so-called p-nitroazobenzene melting a t 137’ (compare Gerhardt and Laurent, Annalen, 1850,75, 73 ; Klinger and Zuurdeeg, Abstr., lS90, 761) consists in reality of a mixture of this compound with p-nitro- azoxybenzene ; in the nitration, a considerable quantity of p-dinitroazo- benzene is also formed. Janovsky’s ‘‘ o-nitroazobenzene,” melting a t 127’, consists of a similar mixture, The results obtained by Zinin (Annalen, 1841, 38,222) onnitrating azoxybenzene are confirmed ; the compound melting at SS*SO, obtained by reducing o-nitroazoxybenzene with alcoholic ammonium sulphide - - (Zinin, Zoc. cit.), is benxeneuxonitrosobenzene, C,H,<?->NPh, which NO on reduction with stannous chloride and hydrochloric acid yields benzene-+-azimidobenzene, C,H,<&>NPh (m. p. 109’). N 4 : 4‘-Dinitroazobenzene melts a t 121-122’. 3 : 3’-Dinitroaxo6enx- ene, prepared by reducing 3 : 3’-dinitroazoxybenzene (m. p. 1465O, Klinger and Zuurdeeg, Zoc. cit. ; Lobry de Bruyn, Abstr., 1894, i, 573) with alcoholic ammonium sulphide, crystallises from alcohol in reddish needles and melts a t 153O; the red oil obtained by Janovsky in the nitration of azobenzene, which was supposed to be dimetanitroazo- benzene, is merely a mixture. Janovsky’s o p-dinitroazobenzene is also merely the impure 4 : 4’-dinitro-compound, and the same is true of his mp-dinitronzobenzene (m. p. 2OS0j, obtained by acting with nitric acid on p-nitroazobenzene-p-sulphonic acid ; the ‘‘ dinitroazobenzene ” melt- ing at 180’ is in reality impure 4 : 4’-dinitroazoxybenzene (infkj. 2 : 4-Dinitroazobenzene can be prepared from the synthetically oh- tained 2 : 4-dinitrohydrazobenzene as stated by Willgerodt and Ferko (Abstr., 1888, 829). 4 : 4’-Dinitroaxoxybenxelze, prepared by leaving 4 : 4’-dinitroazobenz- ene in contact with fuming nitric acid for half an hour, crystallises from benzene in stout, sulphur-yellow needles and melts at 192’. All five of Janovsky’s so-called trinitroazobenzenes are shown to be mixtures. That melting a t 11 2’ is a mixture of trinitroazoxybenzenes ; that melting a t 1 70°, obtained by nitrating p-nitroazobenzene, consists of a mixture of 0- and m-trinitroazoxybenzene (Klinger and Zuurdeeg), whilst if the nitration is more carefully regulated, 4 : 4’-dinitroazoxy- benzene (m. p. 185’) is principally formed. The trinitroazobenzene (m. p. 124’), obtained from the so-called m-dinitroazobenzene, is a mixture of trinitroazoxybenzenes ; on nitrating 4 : 4‘-dinitroazobenzene, either 4 : 4’-dinitroazoxybenzene (m. p. 185’) is obtained, or 2 : 4 : 4’-trinitro- azoxybenzene (xn. p. 135-13Go, Klinger and Zuurdeeg), althoughORGANIC CHEMISTRY. 196 Janovsky has stated that under these conditions a trinitroazobenzene melting a t 160’ is formed. The ‘‘ trinitroazobenzene ” melting at l85O, obtained by nitrating 4 : 4’-dinitroazobenzene a t a high tempera- ture, is really 4 : 4’-dinitroazoxy benzene. On energetically nitrating azobenzene, there is formed in addition to 2 : 4 : 2’-trinitroazoxybenzene (m. p. 192’ ; Klinger and Zuurdeeg, 187-188’), and 2 : 4 : 3’-trinitroazoxybenzene (m. p. 178’), a large pro- portion of 2 : 4 : 4’-trinitroazoxybenzene (m. p. 135-136’). On reduction .mi th ammonium sulphide, 4 : 4‘-dinitroazobenzene gives rise to 4 : 4-dinitrohydrazobenzene (m. p. 234’), not to Janovsky’s so- called ‘( azonitrolic ” derivative (compare Lermontoff, Abstr., 1872, 503); as this substance dissolves in alkalis yielding blue salts, Will- gerodt has assumed (Abstr., 1890,1116) it to be an “azhydroxyazo-com- pound,” NO,*C,H,*N:N*C,H;NH(OH):O. Since, however, undoubted hydrazo-compounds which are soluble in alkali can be obtained by the interaction of phenylhydrazines with dinitrochlorobenzenes, Willgerodt’s views must be rejected. The solubility or non-solubility in alkali of nitrohydrazo-compounds appears, indeed, to depend on the relative position of the nitro-groups ; thus 2 : 4 : 4‘-trinitrohydrazo- benzene (infia) forms intensely blue salts with alkalis, whilst the 2 : 4 : 2’-trinitro-compound is insoluble in alkalis, although z1 blue coloration is produced on adding these to an acetone solution of the compound ; 2 : 4 : 3’-trinitrohydrazobenzene fails to produce a coloration even in presence of acetone. Moreover, Willgerodt’s views as to the conversion of nitrohydrazo-compounds into aznitroso-compounds by loss of water are incorrect ; this decomposition is only possible with ccjmpounds which contain an ortho-nitro-group, and even with these in only a few cases, Thus although 2 : 4-dinitrohydrazobenzene in alcohoiic solution is, by adding a &op of alkali, Eonverted instttn- taneously into the compound gH*CH:?*y->NPh, with 2 : 4 : 2’-, N0;C-CH:C*NO 2 : 4 : 3’, and 2 : 4 : 4’-trinitroh<drazobenzenes no such conversion is possible. 4 : 4’-Dinitrohydrnzobenzene melts and decomposes at 234’ (compare Janovsky, Willgerodt, Zoc. cit.), and is readily oxidised to the corre- sponding azo-compound. 2 : 4-Dinitrohydrazobenzene (Willgerodt, Zoc. cit.) is converted by fuming nitric acid into 2 : 4 : 4’-trinitroazoxybenzene (m. p. 136’). 2 : 4 : 4‘-~rinitrohydraxobenxene, prepared by the inter- action of p-nitrophenylhydrazine with 1-chloro-2 : 4-dinitrobenzene, crystallises best from nitrobenzene in reddish-yellow, lustrous needles, and melts at 212-213’; it is readily converted by mercuric oxide in alcoholic or acetone solution into 2 : 4 : 4’-tl.i~itrocs~o6e~~ene, which crystallises from glacial acetic acid in red needles, melts at 172’, and by oxidation with chromic acid is converted into Klinger and Zuurdeeg’s trinitroazobenzene melting a t 135-1 36’, the constitution of which is thus established. 2 : 4 : 3’-Trinitl.ohyd~.axobenxe.ne, prepared r’rom m-nitrophenylhydrazine and 1 : chloro-2 : 4-dinitrobenzene, on oxidation with mercuric oxide, y.ields 2 : 4 : 3’-trinitroazobenzene (m. p. 172’), and with fuming nitric acid gives rise to 2 : 4 : 3’-trinitroazoxy- benzene (m. p. 178”, Klinger and Zuurdeeg). 2 : 4 : 2’-l’rinitroiiyds.~xo- benzene, prepared from o-nitrophenylhydrazine and 1 : chloro-2 : 4-cli-196 ABSTRACTS OF CHEMICAL PAPERS. nitrobenzene, crystallises from glacial acetic acid in bright yellow needles, melts at 220") and is identical with the compound obtained by Klinger and Zuurdeeg on reducing trinitroazoxybenzene (m. p. 192'), which the latter considered to be the corresponding azo-compound ; 2 : 4 : 2'-trinitroaxobenxene, prepared by its oxidation, and also by reducing the corresponding azoxy-compound with ammonium sulphide, crystallises from alcohol in reddish needles and melts at 173". Con- trary to Klinger and Zuurdeeg's statement, the hydrazo-compound melting a t 220' is readily acted on by fuming nitric acid, and converted into a substance which forms orange-red needles, melts at 220°, and is probably 2 : 4 : 2' : 4'-tetranitroazobenzene, although, owing to its explosive nature, it could not be analysed. Preparation of Carbazides. Action of Phenolic Carbonates. By PAUL CAZENEUVE and MOREAU (Compt.rend., 1899,129,1254-1257). -A mixture of hydrazine phenoxide and carbazide is produced by mixing diphenyl carbonate with an aqueous solution of hydrazine. Diphenylcarbaaide is obtained in a similar manner from phenyl- hydrazine and diphenyl carbonate or guaiacyl carbonate. Uip~enyZdimethylcal.bcrzide, CO(NH*NMePh),, prepared by heating phenylmethylhydrazine with diphenyl carbonate at 160-1 70°, forms colourless needles me1 ting at 149-1 50" PP-Dinap~~thyEcarbaxide is produced in small quantities by treating diphenylcarbonate (1 mol.) with /3-naphthylhydrazine (4 mols.) a t 100' ; the urethane, OPh*CO*NH*NH*C,,HF, obtained when a smaller propor- tion of the hydrazine (2 mols.) is employed, crystallises in pale yellow spangles. G. T. M. Formation of Methemoglobin. By RICHARD YON ZEYNEK (Chem. Centr., 1899, ii, 483-484; from Arch. A n d . Phys,, 1899, 460--490).-Spectrophotometric examination of alkaline solutions of crystallised methsmoglobin shows that this compound is optically well characterised as an individual substance. By the action of potassium f erricyanide on hsmoglobin, oxygen is liberated. The oxyhsmoglobin decomposes into hsmoglobin and oxygen ; the place of the oxygen is taken by other elements or groups which confer weak acid properties for the colour of the compound so formed, and the spectrum of its aqueous solution aro changed by the action of a small quantity of alkali. Oxygen is also liberated in the formation of methzemoglobin from oxyhaemoglobin by the action of potassium permanganate, but not by the action of sodium nitrite. W. A. D. E. W. W. Amylase. By PAUL YVON (Ann. de E'lnst. Pastew, 1899, 13, 523-528. Compare Abstr., 1895, i, 692).-By certain modifications in Lintner's method for the preparation of amylase, a better yield is obtained. H. R. LE S.

ISSN:0368-1769    

DOI:10.1039/CA9007800129

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 137 Inorganic Chemistry. Nitrosyl Chloride and its Compounds. By W. J. VAN HETEICEN (Zeit. anorg. Chem., 1899, 22, 277--3'78).--Nitrosyl chloride, when cooled in a mixture of solid carbon dioxide and alcohol, solidifies in blood-red crystals which melt at - 65'. It mixes in all proportions with liquid chlorine, and a mixture in the proportions required by the formula NOCl, does not crystallise at -80'. The compound, SnC14,2NOCI, prepared by treating stannic chloride with nitrosyl chloride and distilling off the excess, melts in a sealed tube a t 150O. The compound 2SbC15,5NOC1 melts in a sealed tube at 180°, and the compound Fe2C1,,2NOC1 at 116'. The Lower Oxides of Phosphorus. By AUGUST MICHAELIS and M. PITSCH (Annalen, 1899, 310, 45-74. Compare Abstr., 1899, ii, 285).-Phosphorus suboxide, P40, first obtained by Le Verrier, is pre- cipitated on adding an acid t o a solution of phosphorus in alcoholic potash diluted with water; it is also formed on withdrawing the elements of water from hypophosphorous acid by the action of acetic anhydride.It is an orange-red powder of sp. gr. 1.9123 at 26', but the colour depends largely upon the state of division, being sometimes pale yellow. When thoroughly dried, it is almost odourless, but a trace of moisture imparts to it the odour of phosphine ; in the former condition, also, i t may be heated in air to a comparatively high temperature without becoming ignited, but when moist it burns readily after being heated at 90' during several hours. If dried and heated in an indifferent gas, phosphorus distils over, leaving phosphoric oxide.Chlorine converts the dried oxide into phosphorus oxychloride and phosphorus pentachloride, the damp substance being oxidised to phos- phoric acid, which is also produced by the action of sodium hypo- chlorite and of warmed sulphuric acid, the latter becoming reduced to hydrogen sulphide. Concentrated nitric acid ignites the substance, which is indifferent towards hydrochloric acid. Many metals are pre- cipitated by it from solutions of their salts either in metallic form, or as phosphorus compounds. A solution of sodium or potassium hydroxide in aqueous alcohol dissolves phosphorus suboxide, forming a deep red solution which transmits only light between the C and D lines of the spectrum ; when warmed, or on standing at the ordinary temperature, this solution evolves hydrogen and phosphine, sodium hypophosphite E.C. R.138 ABSTRACTS OF CHEMICAL PAPERS. remaining dissolved. The oxide is coloured brown by ammonia, but the latter is removed on exposure t o air, and the substance regains its orange-red hue. The result of the authors’ investigation is to show that phosphorus suboxide is the only lower oxide of phosphorus existing at present, those of Gautier, Besson, and Franke being merely Le Verrier’s com- pound in an unpurified condition. An examination of these supposed oxides has been made, and is described in the paper, which gives details of the analytical methods employed [compare Chapman and Lidbury, Trans., 1899,75, 9731. M. O.F. By LUDWIG VANINO (Chern.Centr., 1899, ii, 930; from P?mrm. Cent?-.-H, 40, 63’7-668).- When sodium hydroxide solution is added to a mixture of 10 grams of a 10 per cent. solution of copper sulphate with several grams of phosphorous acid, only a faint turbidity is produced, and this disappears on further addition of the alkali. Under similar conditions, salts of the alkaline earths, cobalt, nickel, and iron (ferrous or ferric) also form clear, alkaline solutions. This property, however, is limited to those metals which form hydroxides, precipitates being formed in the case of salts of such metals as silver or mercury (mercurous or mercuric). These alkaline solutions do not usually form pre- cipitates with sodium carbonate, but often give remarkable re- actions with hydrogen sulphide or ammonium sulphide. The alkaline solution of a manganese salt is not a t first attacked by hydrogen sulphide, and a similar solution of a ferric salt also resists the action of ammonium sulphide.The copper suiphate solution is not acted on by sodium carbonate or ammonium thiocyanate, but is reduced by a trace of dextrose. Although satisfactory results have not been obtained by analysis, it is probable that in this case, as in the case of arsenious acid, salts such as CuHPO, are formed, and that these then combine with sodium phosphate to form double salts. Fluorohyperborates. By PETR G. MELIKOFF and S. LORD- KIPANIDZE (Ber., 1899,32,3349-3354. Compare Abstr., 1898, ii, 219 and 292).-Potassium jhorohyperborate, K,B,F,O,, + H,O, produced by treating an aqueous solution of potassium fluoroborate, 2KF,B,O,, with a slightly alkaline solution of hydrogen peroxide, separates on the addition of alcohol as a viscous mass which becomes crystalline on stirring ; the substance is redissolved i n water and the process re- peated, the salt being finally obtained in rhombic prisms.The follow- ing constitution, OK *BF* 0.0 * BF * 0. OK ,OK 0.BF.O O*BF* O*O:K,H,O, is assigned to the compound. The aqueous solution has an alkaline reaction and slowly evolves oxygen a t the ordinary temperature, this decomposition being accelerated by warming ; the silver salt is pro- duced as a yellow precipitate by adding silver nitrate to the solution ; it is unstable, and blackens owing t o the separation of metallic silver, oxygen being simultaneously evolved, The dry potassium salt is moderately stable ; dilute sulphuric acid liberates hydrogen peroxide, whilst the concentrated acid evolves ozonised oxygen.This salt may also be obtained by the action of hydrogen peroxide on potassium orthofluoroborate, BF(OK),. G. T. M. A General Property of Phosphorous Acid. E. W. W.INORGANIC CHEMISTRY. 139 Fluorohyperborates. By PETR G. MELIKOFF and S. LORD- Compare preceding abstract). EIPANIDZE (Ber., 1899,32,3510-3512. -The potassium salt, K2B,F,0, + H20, to which the structure O,(BF*O*OK), + H,O is assigned, is precipitated by alcohol from hydrogen peroxide solution as a crystalline powder. The ammonium salt, Am2B,F,0G + 3H0, prepared by adding hydrogen peroxide, ammonia, and alcohol to a solution of boric acid and ammonium fluoride, is a white, crystalline powder, and is moderately stable ; the aqueous solution decomposes gradually at ordinary temperatures, and rapidly on warming.T. M. L. Explosion of Potassium Chlorate. By MARCELLIN P. E. BER- THELOT (Compt., rend., 1599,129, 926-929).-Although the decomposi- tion of potassium chlorate into the chloride and oxygen is an exothermic reaction, it is not regarded as an explosive, since it does not detonate when gradually heated. If, however, the melted chlorate be allowed to fall drop by drop into a glass tube heated to redness, a sharp and rather prolonged explosion occurs as each drop comes into contact with the hot tube, a white smoke of potassium chloride being simultane- ously formed. T. H. P. Acid Iodates Containing Fluorine, and C a s i u m Fluoroper- iodate. By RUDOLPH F.WEINLAND and 0. KOPPEN (Zeit. anorg. Chem., 1899, 22, 25 6-265).-Ccesium hydrogen tetrccfEuoroiodate, CsH120,F, + 2H,O, is obtained by dissolving czesium hydrogen iodate, caesium dihydrogen iodate, or caesium dihydrogen iodate with 2 mols. iodic acid in 20-60 per cent. hydrofluoric acid, and also in smaller quantities from a solu- tion of caesium iodate in hydrofluoric acid. It crystallises from 40-60 per cent. hydrofluoric acid in thick, six-sided plates, or aggregates of thin plates, effloresces rapidly on exposure to the air, and dissolves slowly in water, yielding a strongly hydroff uoric acid solution. Rubidium hydrogen tetru$uoroiodute, with 2H20, is obtained by dis- solving rubidium fluoride (1 mol.) and iodic acid (2 mols.) in hydro- fluoric acid of a t least 40 per cent.It crystallises in plates, and is very easily converted into rubidium difluoroiodate. CaesizsmJEworoperiodate, 2CsI04,3HF + H20, obtained by dissolving caesium periodate in warm 60 per cent. hydrofluoric acid, crystallises in colourless, lustrous prisms, effloresces slowly on exposure t o the air, and is decomposed by water. Reversible Reaction between Hydrogen Chloride and Silver. By JOUNIAUX (Compt. rend., 1899, 129, 883-886. Compare Abstr., 1879, 589).-The amount of hydrogen chloride formed when silver chloride and hydrogen are heated together increases with the time of heating, and reaches a limit which is dependent on the temperature t o which the reacting substances are heated.At a temperature of 350°, equilibrium is established when the residual gas contains 75.85 per cent. of hydrogen chloride, and is attained after heating for 5 weeks, whilst at 600' the limit is reached after heating for 1 hour, and the residual gas contains 92.80 per cent. of hydrogen chloride. The action of hydrogen chloride on silver is also limited and E. C. R.140 ABSTRACTS OF CHEMICAL PAPERS. varies with the temperature. At 490', 530', and 600', equilibrium is established when the residual gas contains 94.10, 92.95, and 92-80 per cent. of hydrogen chloride respectively. The limit at which equilibrium is established i s practically independent of the amount of surface of silver chloride exposed, and for temperatures above the melting point of silver chloride this limit is quite independent of mass.H. R. LE S. Reciprocal Displacement of Metals. By ALBERT COLSON (Compt. rend,, 1899, 129, 825-827).-Experiments with silver and mercurous chloride, and silver and mercuric sulphide in sealed vacuous tubes between 150' and 300', show that the direct displace- ment of silver by mercury is, under some conditions, a reversible reaction, limited by the pressure of the mercury vapour, just as heterogeneous dissociation is limited by a gaseous pressure. Experiments with copper and cadmium sulphide or oxide gave similar, but less definite, results owing to the partial direct dissocia- tion of the two cadmium compounds below 600'. Thin films of cadmium formed by condensation of the vapour in the cool parts of the tube were violet-blue by transmitted light.C. H. B. Preparation of Monocalcium Phosphate. By L. LBON A. PRUNIER and ADOLPHE JOUVE (J. Pharrn., 1899, [ vi], 10,529-530),- If a mixture of dicalcium phosphate, Ca,H,(PO,),, and orthophosphoric acid in the proportions to form monocalcium phosphate, CaH,( PO,),, is dissolved in an equal weight of water and the solution rapidly evaporated, a deposit of dicalcium phosphate, sometimes mixed with a little of the monocalcium salt, is obtained; whereas, if the liquid is subjected to prolonged boiling, only hydrated monocalcium phosphate is formed, From these results, it is concluded that the formation of the more stable hydrated monocalcium phosphate from the anhydrous salt is only slowly effected, and this is confirmed by the fact that the pure anhydrous salt only is precipitated when alcohol is added t o the freshly prepared solution.Change of Volume during the Hardening of Hydraulic Cements. By HENRI LE CHATELIER (Compt. rend., 1899, 129, 1232--1234).-The author's experiments indicate that the apparent expansion of mortars and cements during hydration is due to the relative displacement of the solid particles, and that in reality this action is accompanied by a considerable diminution in volume. N. L. G. T. M. Action of Hydrogen Fluoride and Fluorine on Glass. By HENRI MOISSAN (Compt. rend., 1899, 129, 799--804).--Hydrogen fluoride, produced by heating carefully dried potassium hydrogen fluoride, acts at once on very carefully dried glass at the ordinary temperahre. Gaseous fluorine obtained by electrolysis, and deprived as far as possible of hydrogen fluoride by passing it over sodium fluoride, acts on glass, but if hydrogen fluoride is completely removed by subjecting the fluorine to the temperature of boiling air, or by passing the gas over dry sodium fluoride cooled in a mixture of solid carbon dioxide and acetone, the fluorine no longer acts on glass, even a t lor)', provided that it is dry and the surface is free fromINORGANIC CHEMISTRY.141 organic matter, If these conditions are satisfied, liquid iiuorine can be kept for a long time in sealed glass bulbs or tubes. The author points out that glass may retain its polish even when acted on by hydrogen fluoride, and that phosphoric oxide cannot be used for drying hydrogen fluoride, owing to the formation of phosphorus oxyfluoride a t the ordinary temperature.Activity of Manganese in Promoting the Phosphorescence of Strontium Sulphide. By Josh R. MOURELO (Compt. wnd., 1899, 129, 1236-1238. Compare Abstr., 1899, ii, 97, 98, 366, 420, and 484).-The paper contains details of the preparation of phos- phorescent strontium sulphide produced by the action of sulphur on strontium carbonateor sulphate at a red heat in the presenceof small quantities of manganous sulphate, sodium chloride and sodiumcarbonato. The effect of themanganous sulphate on the strontium sulphide is similar to that of manganous carbonate or basic bismuth nitrate; the phos- phorescence becomes more intense, lasts longer, and is attained after a shorter exposure to diEused daylight.When due to manganese, the phosphorescence has a yellowish-green colour, whilst that produced by bismuth is bluish-green, Effect of various Solvents on the Allotropic Change of Mercuric Iodide. By J. H. KASTLE and MARY E, CLARK ( h e r . Chem. J, 1899, 22, 473-484).-The authors have studied the behaviour of mercuric iodide when dissolved in the following liquida at their boiling point : ethyl bromide, propyl chloride, acetone, ethylidene chloride, ethyl iodide, ethyl acetate, alcohol, isopropyl bromide, benzene, ally1 alcohol, toluene, propionitrile, ethyl butyrate, isobutyrate and propionate, benzoic acid, phenol, benzo- nitrile, oil of winter green, propyl bromide, +-cumene, naphthalene and phenyl salicylate ; with all these solvents, except isobutyl bromide and propyl chloride, yellow solutions were obtained, and in all cases, without exception, yellow crystals separated on cooling ; the pink colour of the solutions obtained with isobutyl bromide and propy1 chloride appears to be due, not to the red modification of mercuric iodide, but ‘‘ to the formation of unstable alkyl iodides.” The fact that only yellow solutions are obtained on dissolving the red iodide in the various solvents and that the yellow modification done separates from these, appears to indicate that the transition temperature (1 28’) of mercuric iodide is lowered by the solvents dealt with, especially by those boiling at a low temperature. The question whether red mercuric iodide is insoluble in the solvents named, and only dissolves by being converted into the yellow modification, is discussed at some length.It is significant that the red modification is not obtained, but only crystals of the yellow variety, on adding a red crystal to the yellow solutions. W. A. D. Transformation Temperature of the Quadratic and Ortho- rhombic Forms of Mercuric Iodide. By D~SIRE GERNEZ (Compt. vend., 1899, 129, 1234--1236).-Yellow mercuric iodide may be kepb for a long time at the ordinary temperature, whilst the red variety persists at temperatures above that at which transformation is possible ; the former state of the iodide is termed ‘‘ crystalline superfusion3” (2. H. B. G. T. M. VOL. LXXV~II ii 10142 ABSTRACTS OF CHEMICAL PAPERS. and the latter '' crystalline superheating." On account of these retardations, it is difficult to determine the transformation temperature with exactness.When alternate layers of the two forms, placed in contact with each other, are maintained a t the same temperature, it is found that a t 127" the zones of yellow iodide slowly encroach on the red variety, whilst a t 125" this modification gradually displaces the other. The transformation temperature is therefore 126" and is the same whether the crystals are heated under atmospheric pressure or in a vacuum, Dissociation by Water of Ammonium and Potassium Mercuriodides. By MAURICE FRANFOIS (Conhpt. rend., 1899, 129, 959-962. Compare Abstr., 1899, ii, 597).-In the presence of relatively large qnantities of water, these salts suffer complete de- composition into the constituent iodides, part of the mercuric iodide being precipitated and the rest forming a saturated solution in the alkali iodide solution, By treatment of the mercuriodides with small quantities of water, as also by acting on excess of mercuric iodide with solutions of the alkali iodides, i t is found that the decomposition is limited and reversible, and obeys the laws of dissociation of salts by water j when equilibrium is attained, the liquid contains a quantity of free ammonium or potassium iodide, which is constant for a given temperature. T.H. P. Preparation of Sulphur, Chlorine, and Bromine Compounds of the Cerite Metals. By WILHELM MUTHMANN and L. ST~TZEL (Ber., 1899, 32, 3413-3419).-Didier7s method of preparing cerium and lanthanum sulphides, by passing hydrogen sulphide over the heated oxides (Abstr., 1885, 955), does not give satisfactory results unless the oxide is very finely powdered; the pure sulphides can, however, bo readily obtained if the anhydrous sulphates are used.The cerium sulphide is brownish-black to black, lanthanum sulphide is pure yellow, neodymium sulphide is olive-green, and praseodymium sulphide is chocolate-coloured. They are fairly stable in air a t the ordinary temperature, but are slowly decomposed by boiling water with evolution of hydrogen sulphide (lanthanum sulphide the most readily), and dissolve readily in dilute acids ; the four sulphides ignite readily below a red-heat and burn to a mixture of oxide and sulphate, and cerium sulphide when finely divided ignites spontaneously at the ordinary temperature. Mosander's greenish cerium oxysulphide and golden-yellow, crystalline sulphide could not be prepared.The densi- ties are La,S,, 4.9108 ; Ce&, 5.020; Pr,S,, 5*042 ; Nd,S,, 5.179 at 1 lo, increasing with the atomic weight. The chlorides are prepared by first passing hydrogen sulphide over the dry sulphates, then carbon dioxide and dry hydrogen chloride. Cerium and lanthanum chlorides are pure white, crystalline masses, neodymium chloride is rose-coloured, and praseodymium is green. They readily absorb moisture from the air, dissolve with hissing in water to a clear solution, dissolve in alcohol and are readily fusible, but only volatilise with great difficulty, For preparing large quantities of chloride containing a trace of oxide, the best method is by evapom tion and ignition of the ammonium double chloride, G.T. MIN0 RGANIC CHEMISTRY. 143 By passing hydrogen bromide over the sulphide, cerium bromide, CeBr3, was obtained as a snow-white, crystalline, soluble powder, which readily absorbed moisture from the air. Speciflc Gravity of Yttrium, Zirconium, and Erbium. By STEFAN MEYER (Moncthh., 1899, 20, 793-796).-Investigations of magnetic susceptibility have shown that the paramagnetic element yttrium occupies a position in the periodic system among a number of diamagnetic elements, and this peculiarity has led the author to determine some other characteristic constant. The specific gravity of yttrium powder was measured in a volumenometer, the powder being contained in a small tube connected through a ground stopper with the rest of the apparatus.The specific gravity was found to be 3-80 at 15'; with the atomic weight 89, the atomic volume is thus 23.6, a value corresponding with the position already assigned to yttrium in the periodic system. The abnormal magnetic behaviour of this element is therefore probably due to an admixture of some known or unknown element ; if the presence of the new element vic- torium in yttrium should be confirmed, the former must be strongly paramagnetic. The specific gravity of zirconium has been found to be 4.08, and that of erbium 4.77 a t 15'. Direct Combination of Aluminium and Nitrogen in the Electric Arc. By LEO ARONS (Chem. Cenir., 1899, ii, 643 ; from Naturw. Rundsch., 14, 453--454).-When an electric arc is produced between electrodes of platinum, zinc, copper, tin, lead, iron, or cobalt in an atmosphere of nitrogen, the surface of the metal becomes coated with a film which probably consists of nitride.I n the case of alu- minium, considerable quantities of the greyish-black nitride are formed. This nitride is insoluble in water, and when treated with potassium hydroxide solution yields ammonia. When silver electrodes are used, the appearance of the silver changes, but there is apparently no formation of nitride. The analogy between the production of nitrides and that of acetylene by means of the arc, and the importance of utilising the nitrogen of the atmosphere are pointed out. T. M. L. J. C. P. E. w. w. Double Salts of Ferric and Aluminium Fluorides with Fluorides of Bivalent Metals.By RUDOLPH F. WEINLAND and 0. KOPPEN (Zeit. anorg. Chem., 1899, 22, 266-276).-These salts are prepared by mixing a solution of aluminium or ferric hydroxide in dilute hydrofluoric acid with a solution of the carbonate or hydroxide of the bivalent metal in dilute hydrofluoric acid, and allowing the mixture to evaporate at the ordinary temperature over lime. An excess of one of the constituents and the amount of hydrofluoric acid present are immaterial. The salts can be recrystallised from dilute hydrotl uoric acid. Ferric ferrousJZuoride, FeF,,FeF, -I- 7H,O, forms yellow, rhomboidal crystals and does not effloresce over sulphuric acid. Perric nickel f l u o d e , FeF,,NiF, + 7H,O, separates in small, bright green crystals, ferric cobalt Jluoride in rose-coloured crystals, and fewic zinc JEuorirle in very small, faintly red crystals.10-2144 ABSTRACTS OF CHEMICAL PAPERS, Alumirlium fevrouscfluoride, AlF3,FeF2 + 7H20, forms small, greenish. white, rhomboidal crystals, does not oxidise on exposure to the air or effloresce when placed over sulphuric acid. The corresponding nickel salt separates in green crystals, the cobult salt in reddish-white crystals, and the einc salt in colourless crystals. Aluminium fluoride combines with copper fluoride t o Eorm three double salts. The salt, A1F,,2CuF2 + 11H,O, obtained from solutions con- taining 1 mol. aluminium fluoride to 2 or more mols. copper fluoride, crystallises in spherical aggregates of blue leaflets and does not effloresce over sulphuric acid. The sult, 2A1F,,3CuF2 + 18H,O, crystal- lises in deep blue prisms resembling feldspar from solutions containing 2 mols.aluminium fluoride to 3 mols. copper fluoride in the presence of only small quantities of hydrofluoric acid, If much acid is present, the salt, AlP3,CuF2,HF + 8H,O, is formed ; this crystallises in large, blue rhombohedra from solutions containing 1 mol. aluminium fluoride to 1 mol. or less of copper fluoride and an excess of hydrofluoric acid, and effloresces rapidly on exposure to the air with evolution of water and hydrofluoric acid. E. C. R. By VICTOR THOMAS (Compt. rend., 1899, 129, 828--831).-Nitric oxide acts violently on chromyl dichloride with abundant formation of higher nitrogen oxides, If the chromium compound is in the formof vapour, the solid product is a t first white, but afterwards becomes brown ; it is very slightly soluble in organic solvents, but dissolves readily in water with liberation of nitrogen oxides and production of a black solution containing chromic oxide, chromic acid, chlorine, and nitrogen oxides.This solid product has the composition Cr,C1507?2N02 ; when heated, it yields chromic oxide, nitrogen oxides, and chlorine, and when treated with reducing agents the nitrogen is converted into ammonia. Chromium, like tin, bismuth, and iron, can evidently form compounds containing the NO, group, which are stable even in a vacuum at the Action of Nitric Oxide on Chromyl Dichloride. ordinary temperature, but are readily decomposed by water. C. H. B. Molybdenum Disulphide. By MARCEL GUICHARD (Conzpt.rend. 1899,129,1239-1 242).-Crystalline molybdenum disulphide is readily prepared by heating a mixture of potassium carbonate, sulphur, and molybdenum dioxide or ammonium molybdate in the Perrot furnace. The amorphous sulphide is produced by heating a mixture of ammonium molybdate and sulphur in an earthenware crucible surrounded by lampblack, the operation being repeated to remove the last traces of oxygen from the product. The sulphide is not attacked by solutions of sulphur in alkaline hydrosulphides or sulphur chloride, and phos- phorus is without action on it even at high temperatures. When heated in a current of hydrogen, it is directly reduced to the metal without forming a lower sulphide. Although native molybdenite loses the whole of its sulphur at the temperature of the electric arc, it is possible in the case of the artificial product to isolate an intermediate sesy uisulphide.G. T. M. By EMILE VIaouRoux (Compt. rend., 1899, 129, 1238-1 239).-Molybdenuw~ silicide, Mo,Si3, resembles tungsten Molybdenum Silicide.INORGANIC CHEMISTRY. 145 silicide (Abstr., 1899, ii, 194), and is prepared in a similar manner by heating, in a carbon crucible in the electric furnace, a mixture of orystallised silicon and the molybdenum oxides obtained by calcining ammonium molybdate ; the crystalline product is disintegrated by electrolysis in hydrochloric acid, and the mixture of crystalline silicides is treated successively with aqua regia, caustic potash, and hydrofluoric acid ; the removal of carbon silicide is effected by means of cadmium tungatate solution, and the residue consists of molybdenum silicide mixed with more or less iron silicide.When heated in chlorine at 300°, molybdenum silicide becomes ignited, silicon tetrachloride and molybdenum perchloride being produced. Complex Inorganic Acids. VIII. Arsenoduodecitungstic Acid and Arsenoluteotungstic Acid. By FRIEDRICH KEHRMANN and E. RUTTIMANN (Zed. anorg. Chem., 1899, 285--296).-Ammonium arsenodzcodecitungstccte, 3(NH4)20,As20,,24W0, + 12H,O, obtained by adding arsenic acid to a concentrated aqueous solution of sodium tungstate, then adding hpdrochloric acid in excess and ammonium chloride, and beating to boiling, is a snow-white, crystalline powder resembling the analogous phosphorus compound. A solution of the acid is obtained by dissolving the salt in aqua regia, but decomposes on evaporation. When boiled with a 5 per cent.solution of ammonium carbonate, it is converted into the 22-acid and on adding barium chloride to the solution the barium salt, 7Ba0,As20,,22W0,, separates in small, lustrous octahedra. Ammonium arsenoluteotungstate, 3(NH4!20,As20,,18W03 + 1 4H20, obtained by heating sodium tungstate with a syrupy solution of arsenic acid and precipitating with solid ammonium chloride, crystallises in monoclinic, lemon-yellow prisms and is very soluble in cold water. When treated with ammonium carbonate, it is converted into the salt 5(NH4)20,As20,,17W03 + 8H2O, which crys- tallises in thick, white, semi-transparent crystals, and is deaomposed by boiling with water with evolution of ammonia.Potassium arsenoluteotungstate, when treated with potassium hydrogen carbonate, yields the sult 5K20,As20,,l 7W0, + 22H20, which crystallises in lustrous, white leaflets, and is not decomposed by boiling with water. By A. E. DELACROIX (Bull. 80c. Chim., 1899, ["'I, 21, 1049-1054. Compare Abstr., 1898, ii, 340).-The two soluble antimonic acids, the existence of which i n solution has previously been demonstrated, are more suitably termed tetra-antimonic and triantimonic acids instead of pyroantimonic and or t hoan timon ic acids respect ivel p. Tetra-antimonic acid is obtained, by freezing its a ueous solution, in tbe form of thin, optically active scales having t 1 e composition Sb20,,4H20, or, when dried over sulphuric acid, Sb20,,3H20 ; a further H,O is lost at 100'.It forms both monobasic and dibasic salts of the composition M,0,4Sb20, and M,O,ZSb,O, respectively. The alkali salts are soluble in water, but not in solutions of other salts, and are prepared by adding to a solution of the acid the theoretical amount of alkali hydroxide or acetate, apd freezing the liquid, when G. T. M. E. C. R. AntirnQnic Acid and AntimonsLtes,146 ABSTRACTS OF CHEMICAL PAPERS, the salts are obtained in the crystalline form; the dibasic alkali salts are precipitated in an amorphous state by adding alcohol to their solutions. The other tetra-antimonrttes are obtained by double decomposition from the metallic acetates, and are insoluble in water, The following salts have been prepared ; some of them, the dibasic sodium Falt, for instance, are decomposed by water, with the produc- tion of monobasic and dibnsic triantimonates.Na20,2Sb205 + 9H20 ; Na20,4Sb205 ; the mixed salt, Na20,4Sb205,Na20,2Sb205 + 20H20 ; K20,2Sb205 + 9H20 ; Ba0,2Sb20, + 5H20 ; Ba0,4Sb205 + 15H20 ; Cu0,2Sb205 + 9H20, a green salt which dissolves in ammonia to form a double salt crystallising in hexagonal prisms. Tetra-antimonates of silver, cadmium, mercury, nickel, and cobalt have also been obtained ; the nickel and cobalt salts form respectively red and blue double salts with ammonia. Triantimonic acid is obtained, by freezing its solution, in crystals of the composition Sb205,3H20, which lose lH20 when dried over sul- phuric acid. It forms salts of the types M,0,3Sb205,. 2M20,3Sb,0,, and 3M20,3Sb20,, besides other more complex derivatives, which are prepared by methods similar to those employed in the preparation of tetra-antimonates. The alkali salts only are soluble in water, those containing one equivalent of the base being also soluble in alcohol. The following triantimonates have been obtained : 2Na20,3Sb205 + 10H20; Na20,3Sb205+ 11H20 ; 2K,0,3Sb205 + 10H20 ; Ba0,Sb205 + 2H20 ; Ba0,3Sb20, + 5H20 ; 9Ba0,10Sb20, + 18H,O ; 2Cu0,3Sb,05 + 10H20 ; Cu0,6Sb205 + 16H20. The antimonic aaid described by 8enderens (Abstr., 1899, ii, 557) is believed t a be a mixture of tri- and tetra-antimonic acids. Sesquichlorides of Rhodium and Iridium. By EHILE LEIDIE (Compt. rend., 1899, 129, 1249-1251). -Anhydrous rhodium sesqui- chloride is most conveniently prepared by dissolving in water the crude double salt, Rh2C1,,6Pu’aC1, obtained by treating the metal with chlorine in the presence of sodium chloride, saturating the salution with hydrogen chloride, and after removing the precipitated sodium chloride, evaporating to dryness and heating the residue a t 360-440’ in a stream of chlorine or hydrochloric acid, The anhydrous chloride forms a brown powder insoluble in water and acids ; it dissolves in solutions of the alkalis, potassium cyanide, alkali tartrates, and oxalates. The double saltos of iridium sesquichloride, Ir2C1,,6KC1 + 6H20 and Ir2CI6,6NaCl+20H2O, are much more stable than the corresponding rhodium compounds, and are not completely decomposed even at 440’. The ammonium salt, Ir2C1,,6NH,C1 + 3H20, like its rhodium analogue, undergoes a complex secondary react ion and cannot be employed in obtaining the sesquichloride. Iridium sesquichloride is best produced from the double salt, IrC1,,2NH4C1; it is a dark green substapce insoluble in acids and alkalis. N. L. G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA9007805137

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mine ra lo gi c a1 Chemistry, 147 Composition of Naphtha from Grosny. By K. W. CHARITSCHKOFF (Chem. Centr., 1899, ii, 920; from J. Buss. Chem. Soc., 1899, 31, 655-658. Compare this vol, i, 74).-The naphtha of Grosny contains thiophen in the proportion of about 1 part in 10,000,000 of " benzine," and mercaptan and thio-estersare also present. The decrease in sp. gr. of the " benzine " fraction is also assumed to indicate the presence of large quantities of isoheptane (Zoc. cit.). The fractions boiling at 29-30' have a composition corresponding with that of a mixture of two isomeric pentanes. By the action of nitrosulphuric acid on the fraction boiling at 82-89', dinitrobenzene is formed, this compound being derived from tetrahydrobenzene. The Grosny naphtha contains the same compounds as American naphtha, but in different proportions.By F. 0. THIELE (Ames.. Chem. J., 1899, 22, 489-493).-Petroleum from Corsicana and from Sour Lake, Texas, was submitted to fractional distillation. The results obtained show that the Corsicana oil is closely related t o Pennsylvania oils, especially that of the Washington district, but it contains a certain amount of asphaltum, and hence care is necessary in distilling it. The greater part of the Sour Lake oil, which is a " surface oil," consists of oils excellently suited for lubricating purposes, the last fraction having a viscosity of 19' (Engler apparatus); it contains 20 per cent. of asphaltum. W. A. D. By FRANTI~EK KovBB (Juhb. J Min., 1900, i, Ref. 25 ; from Zeit. Chem.Ind. Pvag., 1898, 4 pp.). --Graphite from Klein-Tressny contains, according to two determin- ations on different samples, 39.60 and 42.35 per cent. of carbon; the remainder is ash with about 1.5 per cent. of water. Pyrolusite from Stepiinovitz occurs as nodules in red clay, which fills cavities in limestone ; analysis gives the formula E. W. W. Texas Petroleum. Analyses of Moravian Minerals. 15Mn02,.Mn0(OH),. Analyses are also given of dolomitic limestone and of a fireproof clay. L. J. S. Magnetite from near Rome. By FERRUCCIO ZAMBONINI (Jcchrb. f . &fin., 1900, i, Ref. 9 ; from Rivistcc miit. crist. itul., 1898, 21, 21-35).-A description is given of the fine crystals of magnetite occurring in lava at the quarries of Acquacetosa and Tavolato, near Rome. Analyses gave I for grains and I1 for crystals.Sp. gr. 5*04-5.11. Fe,O,. FeO. TiO,. MgO. Total. I. 69.5 28.7 0.9 0.7 99.8 11. 70.2 28.9 0.6 0.7 100.4 L. J. S. Auriferous Cobalt Ores in the Transvaal. By H. OEHMICEIEX (Ohm. Cents.., 1899, ii, 788 ; from Zed. prakt. Geol., 1899, 271-274). -Auriferous smaltite occurs as veins in diabase a t Kruis River and Laatsch Drift. L, J. S.148 ABSTRACTS OF CHEMICAL PAPERS Fluorine in Swedish Phosphorites. By J. G . ANDERSSON and X. SARLBOM (Bull. Geol. Inst. Univ. Upsala, 1899, (1898), 4, 79-87), -Analyses of phosphorites from various Swedish localities are given ; some Rhow the presence of fluorine in the proper proportion for fluor- apatite. The phosphorites occur in fossiliferous strata and have been derived from organic remains.Analyses of fossil and recent brachiopod shells show them to consist largely of calcium phosphate with some fluorine. Analyses of Moravian Minerals, By FRANTI~EK KovLii (Jahrb. f. Mirt., 1900, i, Ref. 23; from Chem. Blatter, Pray, 1899, 4 pp.).-The minerals analysed are from Wur, near Bistritz. The primitive limestone gave I for the pure white, and I1 for the grey- white, variety. L. J. 5. Insol. CaCO,. MgCO,. (Fe,hl),O,. in HC1. H,O. Total. I. 93-21 2-35 0.29 3.84 0-18 99.87 11. 92.08 3.16 0.70 3.98 0.24 100.16 A compact., white to bluish-grey substance resembling halloysite in appearance is shown by analysis I11 to be kaolinite. Melinite [?I is compact, ochre-yellow and opaque ; the fracture is earthy and the streak shining; analysis gave the results under IV, agreeing with the formula H,A lFeSi,O,.Sphene, as small honey-yellow crystals in the primitive limestone, gave V. SiO,. TiO,. A1,0,. Fe203. FeO. CaO. MgO. H,O. Total. Sp. gr. III. 45-72 - 38.80 0.29 - 0.90 0.1s 14.36 100.25 2.03 IV. 46.30 - 26.42 15.32 - 0.25 - 12.08 100.37 2.17 V. 32.55 41.58 - - 0.84 25.41 - - 100*38 3.48 L. J. S. Analyses of Moravian Minerals. By FRANTI~EK KovLG (Jahrb. f. Min., 1900, i, Ref. 24; from Roxpravg 6esk5 Akad. [Nemoirs Bohemian Acad.], ld98, 7, class 11, No. IX, Spp.).-Limonite as a botryoidal coating, from near Gross-Tressny, gave analysis I. Gymnite occurs as small veins in limestone at Gross-Tressny ; it is yellow and has a resinous lust8re; analysis I1 gives the formula Mg,Si,O,, + 5H,O. Turgite encrusts bog-iron-ore a t Rovecin near 01s; it is black and has a dark red streak ; analysis I11 (also MnO, 0.96 ; SO, trace) gives the usual formula, 2Fe20, + H,O.Vivianite occurs as dark blue aggregates of minute needles in cavities of the bog-iron-ore at Rovezin. Analysis IV (also insoluble 0*97), gives the formula 18Fe0,3Fe20,,8P,0, + 56H,O. P,O,. SiO,. Al,O,, Fe,O,, FeO. CaO. MgO. H,O. Total, Sp. gr. I. 1-32 2'43 0'17 81-73 - 0.37 - 13.75 99.77 3'172 11. - 41'17 0'18 0.76 - trace 36'32 21.46 99'89 1-972 111. 0.12 2.05 0'29 92-07 - 0.18 - 4'89 10056 4-315 IV. 28.51 - tram 12'04 32.70 traco - 25.93 99-65 3.637 Lq J, 8,MINERALOGICAL CHEMISTRY. 149 Analyses of Moravian Minerals. By FRANTI~EK KovL; (Jahrb. f . Nin., 1900, i, Ref. 24; from Zeit. Chem. Id. Pray, 1898, 4 pp.).- Whitish-grey kaolinite ('6 Steinmark ") from the graphite mines at Klein-Tressny gave I ; formula 2R"'?1Si,0g,€t"Si0, + 2H,O.Straw-yellow saponite filling cavities in the kaolinite is a plastic substance which falls to powder when exposed to the air. Anal. 11 gives the formula A1,Si3O,,9MgSiO, + 9H,O. Dull-green celadonite occurs as veins in the kaolinite. Anal. 111, formula R"',Si,O,,4R"SiO, + 5H,O. SiO,. A1,0,. Fe20S. FeO. CaO. MgO. (K,Na),O. H,O. Total. Sp. gr. I. 57-14 28.50 1'56 - 2.07 2.35 3.21 5.06 100.49 2.428 II. 51-42 7-60 0'59 - 0.43 28-15 0.24 12.07 100.50 - III. 47.52 5.14 9.01 21.33 1-77 1.14 3-18 10.~9 99 58 2.796 L. J. S. Solidiflcation of Fused Silicates under High and Normal Pressure. By C. F. W. A. OLTLING (Zeit. Kryst. Min., 1899,32,179; from Tsch.Min. Mitth., 1897, 17, 331--373).-Since natural magmas must i n most cases have solidified under high pressnres, several comparative experiments were made to observe the effect of pressure on the crystallisation of silicate fusions, I n the experiments, the following crystsllised minerals were formed : corundum, graphite, magnetite, spinel, pyroxene, plagioclase, and melilit e. L. J. S. By FERRUCCIO ZAMBONINI (Zeit. Kryst. Min., 1899, 32, 152--156).-A crystallographic description is given of olivine from the lavas, &c., of Latium. Si02. FeO. A1,0,. MgO. NiO. Total. Sp. gr. 40-39 8.81 0.35 49.73 0.19 99-40 3-41 Olivine from Latiurn. An analysis gave : L. J. S. [Mineral Analyses.] By VASILE C. EUTUREANU (Zeit. Kryst. Min., 1899, 32, 188; from Bull. SOC.Sci. Bucaresci, 1897, 6, 264-293).- The following mineral analyses are given in a petrological paper on the eruptive rocks of Suzeava : I, oligoclase from syenite ; 11, oligo- clase-andesine from miascite ; 111, orthoclase from ditroite ; IV, biotite from syenite ; V, biotite from miascite ; VI, hornblende from miascite ; VII, sodalite from ditroite. Loss on SiO, AI20,. Fe203. FeO. CaO. MgO. K20. Na,O. C1. ignition. I. 61.68 23.95 - - 5-25 0'16 1'09 6'99 - 1 '05 II. 60'28 22.40 - - 1'17 0.09 6-37 8'44 - 1 '61 V. 34.66 12.55 15'47 21.37 1'39 1-59 8'56 2'24 - 2 *62 VI. 37.19 13.38 - 29.36 10.98 3.03 2.65 2'25 - 1 '08 III. 66'23 18.12 - - 0.30 - 9.90 5'02 - 0'29 IV. 42.25 19.79 6.68 15.34 2.55 2.56 7-88 2.01 - 1.43 VII. 38.99 32.85 - - 0.80 - 0.86 24.57 0.14 1-78 L.J. S. Two New Hydrosilicates. By FERRUCCIO ZAMBONINI (Zeit. Ki-yst. Min., 1899, 32, 157-163).--M.iilZerite. This occurs as a yellowish- green coating on iron and maDganese oxides from Nontron, pep$,150 ABSTRACTS OF CHEMICAL PAPERS, Dordogne, France. It is soft, compact and opaque, and resembles nontronite (Fe,03,3Si0, + 5H,O) in appearance, but differs from this in the blowpipe reactions and in containing less water. The mean (I) of three analyses gives the formula Fe,O,SSiO, i- 2H,O. Some previous analyses of nontronite and other varieties of chloropal show con- siderable variations in composition. [The name mullerite is already in use.] This is from Saalfeld, Thuringia, and forms an aggregate of imperfect prismatic crystals and stalactitic masses. It is bluish-brown, opaque and brittle; H=3.Analysis gave the results under 11. Encrusting this mineral are small, snow-white spheres, which are shown by analysis I11 to be schrgtterite. [The name melite is likely to be confused with mellite.] SiO,. Fe,O,. Also,. CaO. hlg0. MnO. H,O. Total. Spgr. I. 48.82 35.88 4.30 - 0.35 0.63 9.66 99.64 1.97 111. 12.56 0.81 43.77 0.95 - - 41-56 99.65 2.18 Analyses of Sandstone Concretions. By CHARLES C. MOORE (Proc. Liverpool Geol. Xoc., 1898, 8, 241-265).-Analyses are given of concretions in Bunter sandstone from West Cheshire. Phyllades a n d Slates. By T. MELLARD READE and PHILIP HOLLAND (Proc. Liverpool Geol. Xoc., 1898,8,274-293).-The phyllades of the Ardennes me compared with the slates of North Wales ; several analyses of these, and of slates from other localities, are given.Melite. 11. 14.97 14.90 35.24 0.78 - - 33.75 99.64 - 1,. J. 8. L. J. S. L. J. S. Vanadium in Rocks. By J. H. L. VOGT (Chern. Centr., 1899, ii, 783 ; from Zeit. p u k t . G'eol., 1899, 274--377).-From Hillebrand's analyses (Abstr., 1899, ii, 112), the average amount of vanadium in the earth's crust is calculated to be between 0.0025 and 0.005 per cent. L. J. S. By LUDWIG MILCH (Chem. Centr., 1899, ii, 789 ; from Zeit. Deutsch. geol. Ges., 1899, 51, 62-74).-1n a paper describing the recent volcanic rocks of the Battak table-land in Cen- tral Sumatra, the following analyses by W. Herz are given : I, liparite ; 11, dacite ; 111, quartz-trachyte-andesite ; IV, trachyte-andesite. Rocks from Sumatra. SiO,. A1,0,. Fe,O,. PeO. CaO. MgO. K,O. N+O. H,O. Total. I. 71.25 14.21 0-85 0.43 2.72 0.S9 6-74 3.11 0.48 100.68 11. 66.71 15.82 0.71 0.32 3.92 2.05 2.42 7.12 1-01 100*08 111. 69.44 15.21 1-74 0.56 1.99 0.93 4-53 5.11 0.77 100.28 IV. 60.41 17.44 1.98 1.78 2.79 1.85 5-64 7.51 0.51 99.91 Meteoric Iron from Iredell, Texas. By WARREN M. FOOTE (Amer. J. Sci., 1899, [iv], 8, 415--416).-This iron, originally weighing about three pounds, was found in 1898 near Iredell, Bosque Go., Texas. It differs from other Texas irons in the fine pitting and the absence of Widmanstatten figures on an etched sur- L. J. S.PHYSIOLOGICAL CHEMISTRY. 151 face. schreibersite gave : Analysis by J. E. Whitfield of material partially freed from Ff?. Ni. CO. P. s. Total 93.75 5.51 0.52 0.20 0.06 100.04 L. J. S. Analyses of GIacial Deposits and Waters, By PHILIP HOLLAND and EDMUND DICKSON (Proc. Liverpool Geol. Soc., 1898, 8, 130--150).-Analgses are given of mud and other glacial deposits and of glacial waters from the neighbourhood of the Varanger Fjord in Arctic Norway. L, J. S.

ISSN:0368-1769    

DOI:10.1039/CA9007805147

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 151 Influence of some Alcohols of Simple or Complex Function on the Digestion of Proteids Ty Pepsin or Trypsin. By E. LABORDE (J. Phccrm., 1899, [ vi], 10, 484--488).-The influence on peptic and pancreatic digestion of the presence of 0.6 and 2 per cent. of alcohol and other substances was determined by digesting coagu- lated albumin with pepsin or trypsin for 3-4 hours at do0, estimating the albumoses and peptones produced, and comparing the results with those obtained in blank experiments carried out under similar conditions. Peptic digestion appears to be favoured by small quantities of isobutyl alcohol, glycerol, and malic acid, and also, although very slightly, by methyl alcohol, whilst ethyl and propy1 alcohols, lac tic and tartaric acids, mannitol and dextrose distinctly retard digestion. Pancreatic digestion is aided by methyl and isobutyl alcohols, glycerol and dextrose, whilst a retarding action is exhibited by ethyl and propyl aluohols, lactic, malic, and tartaric acids, and mannitol.N. L. By A. ALBU (Chew,., Centr., 1899, ii, 395 ; from Paris. Ned., 17, 505--508).--Caseon, the name given to a preparation of milk-proteid, is recommended in cases of malnuttrition. Its absorption and utilisation compare favourably with those of other proteids. By giving a high percentage of proteid in the diet, a person can hold back proteid in the body, so that a t the end of the research he is not in nitrogenous equilibrium, although the increase of body weight is not correspondingly high. Nitrogenous Metabolisni in the Cat.By LAFAYETTE B. MENDEL and ERNEST W. BROWN (Arne?*. J . Physiol., 1900, 3, 261-270).- Kynurenic acid is not excreted by the cat even during the increased proteid metabolism produced by the administration of phloridxin. The ingestion of thymus and pancreas causes a marked increase of the uric acid output as in man and dog. Excretion of allantoin is also observed after thymus and pancreas feeding or after uric acid Proteid Metabolism. W. D.H.152 ABSTRACTS OF CHEMICAL PAPERS. ingestion ; it was not observed after administration of hydrazine sulphate. The ordinary daily uric acid output per kilo. of body weight in the cat is scarcely smaller than in man and dog. Creatin- h e is ordinarily present in cat’s urine in noticeable quantity. W.D. H. Comparative Determinations of the Specific Gravity, Dry Residue, and Amount of Iron in Blood. By S. JELLINEK and SCHIFFER (Chern. Centr., 1899, ii, 721 ; from Wien klin. Woch., 12, 802--805).-0rdinary healthy blood has a sp. gr. 1*060-1°065, leaves 22-26-2394 per cent. of dry residue, and contains 0*0431-0*0527 per cent. of iron, The iron was estimated by the ferrometer. The blood of patients suffering from various diseases was also examined. The various constants of the blood of healthy beings were found to maintain a certain relationship, and in other cases the sp. gr. and percentage of dry residue seemed also to be connected. E. W. W. Cerebro-spinal Fluid. By THEODOR PANZER (Chem. C‘entr., 1889, ii, 722; from Wien klilz. Woch., 12, 805-80’7.Compare Nawratzki, Abstr., 1898, ii, 36).-The cerebro-spinal fluids of two children had sp. gr. 1.0086 and 1.00917 respectively, and were faintly alkaline; the latter contained a hexose. Both fluids contained cholesterol, neutral fat and soaps, but a1 bumoses, peptones, enzymes, and urea were not present in either. The fluid of the lower sp. gr. was found to contain 15.97 grams of solid substances, 7.34 of organic compounds, 8.63 of mineral substances, 1.404 of nitrogen, 5.99 of proteid substances (total), 4.85 of albumin, and 1.14 of globulin per litre. Hydrocele Fluid. By VERTUN (Chem. Centr., 1899, ii, 624; from Centr. Ned. Wiss., 3’7, 529--530).-A specimen of hydrocele fluid was slightly opalescent, faintly alkaline, and contained traces of sodium chloride and phosphates, and 0.04 per cent.of proteid, which was mainly albumin, with a trace of globulin. Proteoses and spermin were absent. By the addition of Florence’s potassium iodide solution, no crystals were formed ; choline, which gives Florence’s reaction as well as spermin, was therefore absent. By LAFAYETTE €3. MENDEL (Anher. J. Physiol, 1900, 3, 285--290).-The accessory thyroids in man may contain relatively and absolutely more iodine than the thyroid proper of the same individual. The observations that the thyroids of newly-born ohildren contain no iodine are confirmed. There is no satisfactory evidence to show that the carefully isolated thymus of man or animals contains iodine; traces found by others may have been due to adherent thyroidal tissue, The favourable effect of thyroid feeding in disease, like the similar effect of thymus, appears to be due not so much t o the iodine as to organic substances with which it is united.W. D. H, Normal Existence of Arsenic in Animals and its Loodisa- tion in Certain Organs. By ARMAND GAUTIER (Compt. q-elzd., 1899, 129, 929-936).-A number of organs OF different animals have been Analyses of both fluids are given. E. W. W. W. D. H. Iodine in the Thymus and Thyroid.PHYSIOLOGICAL CHEMISTRY, 153 examined for the presence of arsenic, small quantities of which were found in all the normal thyroid glands analysed ; smaller proportions of this element also exist in the thymus and brain, and traces only in the skin, 127 grams of human thyroid gland gave 0.95 mg. of arsenic.On seI;arating the nucleins from the peptones of the thyroid gland of a sheep, all the arsenic was found in the nucleins; this points to the existence of arsenical nucleins along with those containing phos- phorus. I n the following organs, arsenic could not be detected by the method of analysis employed (see this vol., ii, 168) : sheep’s, dog’s, calf’s and pig’s liver, dog’s and ox’s spleen, pig’s kidney, dog’s flesh, pig’s blood, and the human testicle. By R. NIKOLAIDES (Chem. Centr. 1899, ii, 485; from Arch. Anat. Physiol., 1899, 518-523).- Considerable importance is attached to the presence of fat in gland cells. In glands like the dog’s submaxillary gland, they are present only in the albuminous acini. They arise from protoplasm by meta- bolic action, and disappear during inanition.The Source of Milk Fat. By WILHELM CASPARI (Chem. Centr., 1899, ii, 483 ; from Arch. Anut. Pl~ys., 1899, Suppl., 267--280).-Even if it is shown that abundant proteid food increases the f a t in milk, it does not follow that the fat originates from the proteid of the food. An imrortant part of it is believed to originate from the fat of the food, Certainly iodised fats in the food pass into the milk, even though the food is poor in fat and rich in carbohydrates. Formation of Acetone in the Body. By WALDVOGEL (Chem. Cent?*., 1899, ii, 396 ; from Centr. inn. Med., 20, 729-731).-The ques- tion is undecided whether acetone comes from the proteid of the food or of the body, Administration of thyroid increases the amount of acetone, but not of uric acid, in the urine.Carbohydrates lessen the forma- tion of acetone, if given by the mouth, but not if given subcutaneously. Fat given by the mouth increases the acetone. Rabbits and dogs excrete quite different decomposition products of fat. Acetone, acetoacetic acid, and P-hydroxybutyric acid are considered to be the result of the oxidising power of the organism. The Decomposition and Formation of Uric Acid in the Body. By HUGO WIENER (Chern. Centr., 1899, ii, 2 6 2 ; from Arch. exp. Path. Phurm., 42, 374-398).--Uric acid in the body of the rabbit leads to an increase of glycocine; this might occur by oxida- tion and hydrolysis with formation of allantoin and hydantoin as intermediate substances; but the experiments on animals do not confirm this. Neither can uroxamic acid or alloxan, which are highly toxic to rabbits, be regarded as intermediate substances.Extracts of the liver of dog or pig, but not of the ox, destroy uric acid ; extracts of the kidney of ox and horse, but not of the dog, do so also. As uric acid can be destroyed in the body, the amount excreted in the urine in disease can be no measiire of the amount produced. Glycocine is formed when uric acid is destroyed by extracts of ox kidney, but not T. 13. P. Fat in Glands during Inanition. W. D. H. W. D. H. W. D. H.3 54 ABSTRACTS OF’ CHEMICAL PAPERS, in so large amount as to account for all the uric acid ; the muscles of the ox give the same result, The ‘ surviving ’ ox liver is able, not only to destroy, but also to form uric acid from xanthine derivatives.W. D. H. Fate of Proteids a f t e r their Introduction into the Clip- culation. By IMMANUEL MUNK and MAX LEWANDOWSKY (Chem. Centr., 1899, ii, 484; from Arch. Anat. Phys., 1899, Suppl., 73-88).- I n contradiction of Neumeister’s results, it was found that if caseinogen, dissolved in soda, is introduced into the blood of rabbits (2.4 grams per kilo. of body weight), all but a small fraction is kept within the body and utilised. Egg-albumin is similarly used, in rabbits to the extent of 54 and in dogs of 82 per cent, Acid albumin, alkali-albumin, and nucleo-proteid are utilisable in a corresponding way. Proteids which have been profoundly altered, for instance, casein, are not utilised. W. D. H. Fate of 8-Rydroxyquinoline ; Excretion of Ethereal Hydrogen Sulphates ; Composition of Quinosol.By E. ROST (Chem. Centr. 1899, ii, 396; from Arb. Kais. Ges. A,, 15, 288-301). -Experiments on dogs show that 8-hydroxyquinoline leaves the body a s the sulphate, and probably also as quinoline. When the amount of hydrochloric acid in the stomach is lessened, intestinal putrefaction increases, and so the amount of ethereal hydrogen sulphates in the urine rises. I n complete inanition, the amount falls, but never to zero. Quinosol appears to be a mixture of 8-hydroxy- quinoline sulphate and potassium sulphate. Chemical Reaction of the Intestinal Contents. By BEN- JAMIN MOORE and T. &J. BERGIN (Amer. J. Physiol., 1900, 3, 316--325).-The acid reaction of the intestinal contents to phenol- phthalein is probably due t o an excess of dissolved carbon dioxide.The alkaline reaction to methyl-orange, lacmoid, and litmus shows the absence of hydrochloric acid, and of all stronger organic acids, such as acetic, lactic, or butyric, which would be formed by the bacterial decomposition of carbohydrates or fats, These results were obtained by experiments on dog, sheep, and calf. Absorption of food-stuffs, at least, in the dog, can be practically completed in the small intestine. A proteolytic enzyme active in alkaline solution, and a dinstatic enzyme, also active in an alkaline solution, are present in the dog’s intestine a t this level. W. D. H. W. D. H. Cryescopg of Urine in Diagnosis and Prognosis, By H, CLAUDE and V. BALTRAZARD (Compt. rend., 1899, 129, 847-850).- If the difference between the freezing point of urine and that of water is corrected for the reduction due to soluble chlorides, and also, if necessary, for that due to sugar and albumin, the value 6 thus obtained is a measure of the number of molecules, per unit volume of urine, of other compoundls elaborated by the organism, and if this value is multiplied by the volume, V, of urine excreted in 24 hours and divided by the weight, P, in kilograms of the fixed proteids of the individual, the expression SP/P has a value which varies greatly in different cases, and may aerve as a valuable indication ofPHYSIOJ,0GIICAL CHEMISTRY.155 the beginning or progress of disease, especially in the case of maladies which affect the kidneys. By MAX CLO~TTA (Chem. Cent?.., 1899, i, 267; from Arch.exp. Path. Phccrm., 42, 453-466). -The proportion of serum-albumin t o serum-globulin in the urine in cases of albuminuria is very different from that in the blood. This is accounted for by the different permeability of mem- branes to the two proteids. Nucleo-proteid, which is stated to be absent from blood-serum, is considered to arise from the kidney tissue. W. D. H. C. H. B. Origin of the Proteids in Albuminuria. Sugar Formation in Severe Cases of Diabetes. By EMIL ROSENQVIST (Chem. Cents.., 1899, ii, 450-451 ; from Berlin kZin.Woch., 36, 61 2-617).-Partly on experimental, and partly on theoretical, grounds, the views of Seegen and Rumpf (ibid., 36, 155), that in severe cases of diabetes mellitus f a t may be a source of the sugar, is Hydroxybutyric Acid and its Relationship to Diabetic Coma.By ADOLF MAGNUS-LEVY (Chem. Centr., 1899, ii, 63-64; from A?*cJL. exp. Path. Phccrrn., 42, 149--237).-The amount of hydr- oxybutyric acid in the urine of severe cases of diabetes without coma is from 0.5 to 1 per cent. I n coma, 160 grams may be excreted daily, especially if sodium hydrogen carbonate. is administered. Diabetic coma is regarded as acid poisoning, but probably the production of the acid is the result of toxin poisoning. I n coma, as a rule, there is no rise of proteid katabolism, although doubtless the acid originates from proteid. I n urines which contain acetone, but are not diabetic, regarded as it possibility. w. I). H. as mich as 7 grams of hydroxybutyric acid may be excreted daily. W. I). H. Excretion and Detection of Glycuronic Acid in the Urine, By PAUL MAYER (Chem.Cent?*., 1899, ii, 450; from Berlin klin. Woch.,36, 59 1-593, 6 17- 6 19).-The urine of a morphine-maniac contained glycuronic acid in combination, but the compound mas not isolated. The greater number of tests for glycuronic acid are also given by pentoses, but if the orcinol test for pentoses is negative, and the urine contains glycuronic acid, a reducing substance mill be obtained after treatment with sulphuric acid Combinations of glycuronic acid do not yield a phenylhydrazine compound, but after treatment with sulphuric acid they do ; the compounds are probably numerous, varying in melting point from 135' t o 205'. Glycuronic acid also occurs in urine after the use of chloral hydrate, and in small quantities in normal urine.W. D. H. Exoretion of Alloxuric Substances in Nephritis. By CHARLES F. MARTIN (Chent. Centr., 1899, ii, 266; from Centr. in?%. Ned., 20, 625-631).-From observations on seven cases of different forms of nephritis, it is found that the total alloxuric substances excreted in the day are diminished, but the relation of the alloxuric bases t o uric acid is but little altered. W. D. H,P 56 ABSTRACTS OF CHEMICAL PAPERS, Theory of Narcosis. I. By HANS MEYER (Chem. Centr., 1899, ii, 64; from Arch. exp. Path.P/~arrn.,42,109-1 IS). 11. By PRITZ BAUM (Chem. Centr., 1899, ii, 65, from ibid., 119--137).-1n reference to Dubois’work on the action of anssthetics (Compt. rend Xoc. Biol., 1884, 583), the theory is advanced that the relative strength of these substances is de- pendent on their mechanical affinity for fatty substances (like lecithin in protoplasm), on the one hand, and to other constituents of protoplasm, especially water, on the other.I n support of this view, the second paper shows that the proportion between concentration in fat and concentration in water of a number of narcotics runs parallel with their anaesthetising activity. Physiological Action of’ Creatine and Creatinine and their Value in Nutrition. By JOHN W. MALLET (Chem. Centr., 1899, ii, 563; from Bull. No. 66, U.S. Dept. Agric.; and Chem. News, 80, 43-45, 54-56, 69-71, 77--7S).-Almost the whole of the creatine and of the creatinine given to human beings is excreted as creatinine in the urine ; the faxes contain none. These bases do not, therefore serve for the building up of proteids.They are not, how- ever, intermediate substances between proteid and urea, and it is not probable that these bases in muscle are changed even slowly into urea. This supports the view so often urged by physiologists that meat extracts have no nutritive value, The physiological action of creatine and creatinine is much weaker than commonly supposed. W. D. H. W. D. H. R61e of Leucocytes in Poisoning by Compounds of Arsenic. %y BESREDKA (Ann. de l’lnst. Pasteur, 1899, 13, 49-66, 209-224, 465--479).-The leucocytes are capable of engulfing toxic substances, among them various compounds of arsenic, arsenic trisulphide and arsenious acid being specially investigated. Leucocy tosis is one result of the injection, but the healthy state, as well as the number of the leucocytes, is important, After traversing the leucocytes, the metal is ultimately eliminated by the urine.If positive chemiotaxis and leuco- cytosis do not occur, the animal dies ; if they do, it is protected. The administration of previous small doses renders the animal immune to fatal doses. The antiamenin present in the serum is probably not a compound of arsenic. The intermediate r8Ze of the leucocytic action By JEAN DANYSZ (Ann. de I’Inst. Pasteur, 1899, 13, 156--168).-The nervous tissues fix to some extent the tetanus toxin, but this is not permanent, for in vitro, and probably in wivo, the toxin is again liberated by suitable media like physiological saline solution. The insoluble materials OF the nervous tissue possess this power t o the greatest degree, and the toxin is thus in part neutralised, but a determination of how much is rendered impossible by the fact that the soluble constituents of the tissue increase the toxic action.is, however, essential in the antagonism. w. D. H. Action of the Tetanus Toxin on Nervoussubstance. W. D. M. Furlgus Poisons which Decompose Blood, By RUDOLF KOBERT (CILem. Centr., 1899, ii, ‘981 ; from Sitxungsber. maturf. Ges. Rostock, 1899, No. 5).-Agcc&us phdloides contains a t least two poisons, con-VEGETAELE PHYSIOLOGY AND AGRICULTURE. 157 sisting of an alkaloid and a toxalbumin. When the alkaloid, which is soluble in alcohol but insoluble in ether, is administered to rabbits or cats, neither decomposition of the blood nor fatty degeneration of the organs takes place. The toxalbumin phallin has a stronger action than helvellic acid, but resembles it in dissolving the red corpuscles of the blood, dissolved oxyhsmoglobin, glycerophosphoric acid, and frag- ments of stroma also taking part in the action. By the liberation of glycerophosphoric acid, the alkalescence of the blood is decreased, the soluble hsmoglobin partially converted into methsmoglobin, and cyanose formed. A solution of phallin in 100,000 parts of water is sufficient to show the dissolving action on the red blood-corpuscles. Sections obtained from animals which had been poisoned by phallin showed many exudations of blood into the various organs. I n many cases, the blood and urine were found to contain methsmoglobin or bile-colouring matters, and in most cases the kidneys were greatly affected. Phallin could not be detected in mushrooms or other edible fungi. E. W. W.

ISSN:0368-1769    

DOI:10.1039/CA9007805151

出版商:RSC    

年代:1900

数据来源: RSC

摘要:

VEGETAELE PHYSIOLOGY AND AGRICULTURE. 15’7 Chemistry of Vegetable Physiology and Agriculture. Buchner’s Yeast Extract. By AUGUSTIN WR~BLEWSKI (Chem. Centr., 1899, ii, 672-673 ; from Centr. Fhysiol., 13, 284-297. Com- pare Abstr., 1899, ii, 170).-The extract from a pure culture of wine yeast resembles that of ordinary yeast, both in composition and properties and, like it, is capable of fermenting sugar. The ferment- ing power of the zymase of the extract obtained from a pure cul- ture of beer yeast is destroyed by the presence of formalin; 0.07 per cent. of hydroxylamine hydrochloride also exerts a slight preventive action, and larger quantities completely inhibit fermentation. From the results of experiments with pure hydrochloric acid, it is evident that the hydroxylamine hydrochloride combines with certain con- stituents of the extract, liberating hydrochloric acid, which then attacks the zymase.The extract has a denitrifying action on sugar solutions containing nitrites, and liberates nitrogen, but not carbon dioxide. Since the yeast cells are killed by even small quantities of nitrites, denitrification cannot be attributed to their action. The reduction of nitrites in soil is a purely chemical process, depending on their action on compounds analogous to amino-compounds, the action of small organisms being only of secondary importance. Nitrates are neither affected by the yeast nor its extract, and, like sodium chloride and ammonium sulphate, only hinder fermentation when present in large quantities. The addition of small quantities of neutral salts appears to increase the fermenting action of the yeast or of its extract, but large quantities of alcohol hinder fermentation, probably by pre- cipitating the proteids of the extract, VOL.LXXVIII. ii. 11158 ABSTRACTS OF CHEMICAL PAPERS. The invertin resembles the proteose and peptone-like constituents of the extract, for when the extract is saturated with ammonium sulphate only a portion of the invertin is carried down mechanically, the major portion remaining in the filtrate. Invertin may be purified by frac- tionally precipitating with acetic acid, and finally fractionally precipi- tating from the acetic acid solution by means of alcohol. The inverting action of the invertin is increased by dilute acetic acid, and even a 4 per cent.solution of the acid does not very seriously interfere with this action. A 0.28 per cent. solution of hydrochloric acid does not appreciably affect the inverting power of invertin, but the prolonged action of alcohol, or the presence of even dilute solutions of alkalis, destroys it, The properties of the zymase do not resemble those of the enzymes contained in the extract, and the former substance is more allied to protoplasm than to the group of proteoses and peptones. Zymase, unlike the enzymes, is unable to pass through an earthenware cell, and ferments only in concentrated solutions, dilution of the extract causing a rapid decrease of fermentation. Fermentation is also pro- moted by the addition of 1.5 per cent. of neutral salts. The enzymes, on the other hand, work better in dilute solutions and without the addition of salts, The effect of dilution and of the addition of neutral salts on the fermenting action of zymase appears to depend on osmotic processes.E. W. W. [A Beer Disease.] By VAN LAER (Compt. ?*end., 1900, 130, 53--56).-Beers termed by Belgian brewers ‘‘ double face ” or ‘( tweeskinde ” are quite clear by transmitted light, but by reflected light are dull brown and opalescent. Viewed from above, they appear dirty white and opsque, with a yellow fluorescence. This malady is closely connected with viscous fermentation, and seems due to a specialorganism, Bacillus &scoszcs bruxellensis, which always makes beer worts ropy; its development is promoted by the presence of nitro- genous compounds, but its effects are reduced if the liquid is thoroughly agrated.The bacillus converts carbohydrates into lac tic, acetic, and butyric acids, either by consuming them directly, or by first converting them into gummy substances. Other conditions being equal, dextrose is first attacked and then saccharose, maltose, and lactose. No invert sugar is formed. C. K. B. Reactions to Stimuli in Unicellular Organisms. By HERBERT S. JENNINGS (Amer. J. Physiol., 1900, 3, 229-260. Compare Abstr., 1899, ii, 440).-This is a continuation of previous work in which Paramcecium was used. It has been extended to Chilomonas and other flagellates, and also to numerous ciliated infusorians. The main results confirm those previously reached. Some of the results are now rather differently interpreted in accordance with modern chemical doctrines of solutions.W. D. H. Effect of Ions on Flagellated Infusoria. By WALTER E. QARREY (Amer. J. Physiol., 1900, 3, 291--315).--Ch~lomonas was the organism selected as the subject of the experiment, The effect ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. 159 chemicals is analogous to those of other stimuli like light or galvanism. Whilst inorganic acids have equal effects if the ion concentration is the same, organic acids behave differently and the effect is greater than would be expected. Bacteriological Enzymes as a Cause of Immunity and their Healing Action in Infective Diseases. By RUDOLF EMMERICH and OSKAR Low (Ghern. Centr., 1899, ii, 135; from Zeit. Nyg., 31, 1 -652-The enzymes secreted by various bacteria unite with the proteids of blood or of organs ; the compounds so formed are termed immunproteidins ; the proteid of the leucocytes which unites with the enzyme of the pathogenic bacteria is termed proteidin.The so-called agglutination is nothing but the first stage of the effect of the enzyme. There are also bacterial enzymes which are not only bactericidal, but also destroy toxins; thus pyocganase, the enzyme of Bacillus pyo- cynneus, desttroys the deadly effect of the diphtheria toxin. W. D. H. W. D. H. Changes in the Mineral Constituents of the Seed during Germination. By GUSTAVE ANDR~ (Compt. rend., 189 9, 129, 1262-1 265),-A preliminary communication dealing with observa- tions made on the variation of the mineral constituents of the Spanish bean (Phuseolus rnuZtzjZorus) from the commencement of germination to the period at which the dry weight of the seedling is again equal to that of the seed.The weight of mineral substances is trebled, but the constituents do not vary to the same extent. The quantity of phosphoric acid remains fairly constant, and there is a slight increase in the total nitrogen. As long as the plant feeds on its reserve materials, the amount of potash remains constant, but when the chlorophyllous functions develop, the weight of this constituent increases. The amounts of silica and lime present a t the end of the period under observation are respectively 400 times and 17 times as great as the original quan- tities. The analytical results are arranged in tabular form. G. T. M. Chlorophyllous Assimilation induced by Sunlight filtered through Leaves. By ED.GRIFFON (Compt. rend., 1899, 129, 1276-1 278).-Timiriazeff found that whitelight, after passing through a chlorophyll solution, loses its power of inducing chlorophyllous assimilation. The author finds that sunlight, after traversing a single leaf still induces the decomposition of carbon dioxide, but the action is con- siderably diminished, and with diffused light is almost negligible. The effect produced by sunlight after passing through two leaves is so feeble that the assimilative action is masked by respiration. These results are chiefly due to the absorption of luminous radiations by chlorophyll, but protoplasm and the colourless parts of leaves also diminish the action ; the eEect of light filtered through bleached or chlorotic leaves is approximately half that due to direct sunlight.G. T. M. 11-2160 ABSTRACTS OF CHEMICAL PAPERS. Amount of Sulphur in Plants. By SERGEI M. BOGDANOFF (Chern. Centr., 1899, ii, 489 ; from J. Buss. Phys. Chem. Soc., 31, 471 -477). -Estimation of sulphuric acid in vegetable ashes gives incorrect resnlts, as considerable loss of sulphur may take place during incineration. Liebig's method is very satisfactory, and when small amounts of potassium nitrate are employed the results are very exact . Plants contain much more sulphur than is indicated in Wolff's tables, and it is believed that the amount of sulphuric acid in soil is of practical importance. I n some Russian soils, certain crops gave considerably higher yields after mznuring with sulphates.K. H. J.M. Hydrocyanic Acid in Vicia Seeds. By F. F. BRUYNING, jun., and J. VAN HAARST (Rec. Trav. Chim., 1899, 18, 468--471).--Flour from the following species and varieties of Vicia contains hydrocyanic acid : V. sativa, ?? sativa v. dura, K sativa v. Jore alb., V. sativa v. Bernayer, V. scctiua v. Britannica, ?? canadensis, V. hirmta, and V: nngustifolia ; these hence contain amygdalin or analogous sub- stances. No hydrocyanic acid was detected i n : 7? narbonensis, 1'. co'acca, V. agrigentina, V. biennis, V. disprrna, V. pnnonicu, and v. cassubicct. 500 grams of flour from V. sativa contained 0.004 gram of hydro- cyanic acid, and after germination for three days, the quantity was 0.003 gram. I n the case of V. sativa Britannica and P.cmgustifolia, the same weight of flour yielded 0.0008 and 0.027 gram of acid re- spectivel y. T. H. P. Presence of Mannocellulose in the Ligneous Tissues of Gymnosperms. By GABRIEL BERTRAND (Compt. rend., 1899, 129, 1025-1028. Compare Abstr., 18'79, 613)-The tissues of the gymnosperms contain practically no xylan, but mannocellulose is present in considerable amount. The yield of mannose (obtained from mannocellulose by hydrolysis) from conifers is from 10-15 per cent. of the wood taken. I n the G>zetacece, a class intermediate between the gymnosperms and angiosperms, the amount of manno- cellulose is very small, and in some cases nil. Presence of Formaldehyde in Plants. By GINO POLLACCI (Chem. Centr., 1899, ii, 881-4382; from Boll. Chim. Farm., 38, 601-603).--When leaves which have been exposed to the light are macerated and distilled with water, the first portion of the distillate contains formaldehyde.This compound was detected by the violet coloration produced on adding a mixture of codeine and sulphuric acid. This mixture is extremely sensitive to formaldehyde and even more so to the polymeric formaldehyde which is formed when the aqueous solution is evaporated. Other aldehydes such as acetaldehyde, propaldehyde, butaldehyde, valeraldehyde, and benzaldehyde give a yellow, whilst vanillin and acetone form a green, coloration. The formation of a solid, white polymeride, by slowly evaporating the aqueous solution at the ordinary temperature, is also characteristic of formaldehyde. The presence of this aldehyde was also detected by H.R. LE 5.VEGETABLE PHYSIOLOGY AND AGRICULTURX. 161 the following methods. (1) An aqueous solution of aniline gives a white precipitate with formaldehyde. (2) When the distillate con- taining formaldehyde is added to a dilute solution of benzophenol and a solution of 94 per cent. sulphuric acid then poured into the mixture, a red ring is formed at the surface of contact of the liquids. (3) When a twig with green leaves which has been exposed to light is placed in an aqueous carmine solution which has been decolorised by sul- phurous acid, the leaves become violet after a time, whilst the solution itself remains colourless. Magenta decolorised by sulphurous acid gives a violet coloration with formaldehyde. (4) Ammoniacal silver nitrate solution is reduced. (5) Nessler’s reagent test-paper is turned black ; and ( 6 ) phenylmethylhydrazine gives a white precipitate with the distillate.E. W. W. The “Honey ” of Euonymus Japonica. By LSON MAQUENNE (Bull. Soc. Chim., 1899, [I iii 3, 21, 1082--1083).-The honey-like substance which is sometimes found in dry seasons at the extremities of the branches of Euonyntus Japonica is an exudation of the cell contents due to the punctures of insects; it is at first of a syrupy consistence, but soon dries to a crystalline mass. It has a marked sweet taste and is very soluble in water. When concentrated by evaporation, the solution deposits crystals of dulcitol and leaves a brownish, syrupy residue in which dextrose and saccharic acid were detected. N. L. Lotus Corniculatus.By GIUSEPPE D’ANCONA (Chem. Centy., 1899, ii, 590-591 ; from Stax. sper. agrar. ital., 32, 274-287).-Analyses of two Italian specimens of Lotus corniculcctus are given : Crude Crude Crude N-free Digestible Water. proteid. fat. fibre. extract. nitrogen. Ash. 1. 80.285 3.429 0.723 6.563 7.582 0.256 1.418 2. 76.489 3.730 0.872 8.113 8.859 0.312 1.937 The dry substance contained (1) 10,757 and (2) 11.233 per cent. of The pure ash had the following percentage composition : K20. Na,O. CaO. MgO. Fe20,+A1,0,. P2OP SO,. SiO,. C1. pentosans. 1. 21.954 7.405 24.969 5‘082 3.637 10.026 4.915 20*;81 07384 2. 21.987 6.772 23’629 4‘091 5.066 10.687 4.383 22.335 1.029 Absorption of Soluble Salts by Plants. By EM. DEMOUSSY (Ann. agyon., 1899, 25, 497-548 and 561--607).-A detailed account of experiments already described (Abstr., 1899, ii, 172 and 238), with an historical introduction.With regard to nitrates, the nature of the base has no effect on absorption by plants when supplied singly, provided that the base is not toxic ; lithium, barium, and strontium nitrates, for instance, are only taken up in very small quantities, and their injurious effect soon becomes evident. The fact that although plants absorb non-toxic metals with equal readiness, the amounts of these metals found in plants vary very greatly is attributed partly to the composition of the media in which the plant lives, and partly to the selective powers of plants. Calcium, unlike potassium, does not prevent absorption of sodium. N. H. J. M.162 ABSTRACTS OF CHEMICAL PAPERS.Plants growing in solutions containing the same amount of calcium as nitrate and as chloride respectively absorbed more calcium in the form of nitrate than as chloride, but the absorption of chlorine was greater than that *f nitrogen, owing to its greater molecular weight ; 2 mols. of nitrogen were absorbed t o 1 mol. of chlorine. N. H. J. M. Composition of the Branches of Pear Trees Removed by Regular Thinning. By NAPOLEONE PASSERINI (Uied. Centr., 1899, 28, 780-781 ; from Kicerche e. Espei.. Istituto Ay7.a~. Xcccnclicci, 1896-1 897).--Branches (without leaves) cut from pear trees mere found to have the following composition : Per cent. in pure ash. C0,in ., A . Crude crude Na,O,Cl, Water. N. ash. ash K,O. CeO. MgO. Fe,O,. P,O,. SO,. SiO,.loss. 49.29 0.506 1.748 3-3-79 15’11 6::’OO 4-51 0 4 0 4-90 2’64 1.66 7’58 I n the case of old pear trees, i t was found (average of twelve experi- ments) that 1381 kilograms of wood are cut yearly. The loss per annum is therefore as follows : N, 6-99 ; K,O, 2.40 ; CaO, 10.02 ; MgO, 0.72 ; Y,O,, 0.78, and SO,, 0.42 grams in each tree. The soil for pear trees should be comparatively rich in lime, and requires nitrogenous and potash manures. N. H. J. M. Which Meadows should be Manured with Potash as well as with Basic Slag and Superphosphate? By JULIUS NESSLER (Riecl. Centr., 1899, 28, 737-738; from Woch. L m d w . Vey. L’cden, 1899, No. 11, 139).-Level meadows, the soil of which is poor in potash but not too shallow, with much moss, &c., should receive, in autumn or winter, kainite (6-8) and basic slag (3-4 cwt.), and each subsequent year 2-3 and 3-4 cwt.respectively of basic slag and kainite. I n the case OF heavy soils, superphosphate is usually pre- ferred to basic slag, and potassium chloride (40 per cent.) is employed instead of kainite. Sloping meadows should have more potash applied to the higher than t o the lower portions, which in some cases do not require direct potash manuring. Irrigation with water from granite or gneiss geIierally renders application of potash unnecessary. The best chemical method of ascertaining whether potash is needed is t o determine the amount of potash in the hay ; the grass must be cut at the beginning of the flowering period and carefully dried. Estimating the potash in the soil takes longer and gives more uncer- tain results.Composition of Molinia coerulea and C a r e x Goodenoughii. By HEINRICH IMMMENDORFF (Bied. Cent?.., 1899, 28, 772-774 ; from Lcindw. Juhb., 1898, 27, iv, 503).-The two plants are important constituents of the herbage of peat meadows which are insuficiently drained and manured, but are not much valued as cattle-food. The composition as hay (water = 15 per cent.) is as follows : N. H. J. M. Crude Digestible N-free Crude protein. protein. Ainides. Fat. extract. fibre. Ash. 1. Nolinich C ~ ~ L ~ C L X . . . ... 6-75 4’26 0.88 2‘44 -11.28 30.96 s ’ 4 f 2. Carcx Goodwouyhii.S*OO 4’69 0.50 2.51 42’14 27’40 3.94VEGETABLE PHYSIOLOGY AND AGRICULTURE. 163 Whilst MoEinia hay is of very poor quality, the results obtained with Carex are more satisfactory, but the yield is very small. The dry substance of the two plants contained : Ash, (1) 4.196, (2) 4.64 ; K,O, (1) 1.21, (2) 1.49; CaO, (1) 0.25, (2) 0.39 ; and P,O,, (1) 0.29, (2) 0-43 per cent.Hops and Hop Soils. By JOSEPH HANAMANN and LEOPOLD UOURINSKY (Bied. Centr., 1899, 28, 778 ; from Zeit. Lccndw. Versuchs.- zcesen. Oestew., 1898, 1, 411).-During the early periods of growth, hop plants require plenty of potash, phosphoric acid, and nitrogen ; subse- quently, the plants contain nearly as much lime as potash. The leaves and tendrils are rich in lime, and in the assimilating organs 50 per cent, of the ash consists of lime, indicating considerable production of organic acids in the sap, which have to be neutralised with lime.The leaves contain much more potash, lime, magnesia, and phosphoric acid than the tendrils and stems, whilst the umbels contain the most potash and phosphoric acid. I n the original paper, analyses of the soil and of the ashes of hops at different periods of growth are given. Influence of Potash on the Development of S u g a r Beet. By JULIUS STOKLASA (Chem. Centr., 1899, ii, 490 ; from Zed. Zuckey-lnd. Biihnz., 23, 493--501).-Results of field experiments showed that potassium sulphate considerably increased the yield of roots and the percentage of sugar. Potassium chloride, in conjunction with super- phosphate and nitrate, also increased the yield of roots without in- juriously affecting the percentage of sugar. Assimilation by Sugar Beet and Estimation of Available Nutritive M a t t e r in Arable Soil.By H. WILFAWH (Chem. Centr., 1899, ii, 536-537 ; from Zed. Vey. 12iibenxuckei*-lnd., 1899, 645-652).--Whilst sugar beet grows normally when manured with nitrate, ammonium salts and blood-meal gave decidedly unsatisfactory results. Arnides were determined in the roots as a n indication of the degree of unripeness. When calcium nitrate is employed as manure, the lime is eliminated from the root, whilst with potassium nitrate the potash is retained. Deficiency of nitrogen gives rise to yellow leaves, whilst a deficiency of potash produces brown and white spots on the leaves. Tn absence of sufficient phosphoric acid, the leaves do not become yellow as stated by Stoklasa, but their growth is checked, and they have a dark green colour with black edges and spots.The results of pot experiments showed that with insufficient potash the roots contained only 4 parts of K,O t o 1000 parts of sugar, the amounts under normal conditions being 6-8 parts; with six times the necessary amount of potash, the roots were found t o contain 37 parts of K,O per 1000 of sugar. The roots are more liable to injury by nematodes in absence of potash than when a small amount of potash is applied. It is proposed t o estimate available plant constituents in soils by growing sugar beet, carrots or celery, and aaalysing the plants. N. H. J. M. N. H. J. M. N. H. J. M. N. H. J. M.164 ABSTRACTS O F CHEMICAL PAPERS Influence of the Amounts of Water and of Nutritive Substances in Soil on the Activity and Development of Potatoes. By JOHANN WILMS (Chenz.Centy., 1899, ii, 628; from J. Landw., 47,251-292).-The occasional injurious effect of Stassfurt salts on potatoes is attributed to the presence of potassium chloride. Nitrogenous substances are favourable to the developmenb of the plants and to starch production. Potash also seems favourable to starch production. Increased amounts OF moisture in the soil always diminish the percentage of starch in the tubers ; and proportions of chlorides, which are otherwise harmless, become injurious when the amount of water is large. Transpiration is increased when the per- centage of water in the soil increases, and there may be an increase, although less marked, in the actual amount of starch produced. N. H. J. M. How much Phosphoric Acid should good Arable Soil Contain 3 By AIM$ PAGNOUL (Ann.Agron., 1899, 25, 549-557)- The results of pot experiments, in which incarnate clover was grown in soils containing very little, and a good deal, of phosphoric acid respectively, with and without addition of superphosphate, indicated that 0.1 per cent., which is generally considered to be a normal amount for good soil, is too low, and that 0.15 to 0.2 per cent. is more probably the limit, a t any rate for incarnate clover, beyond which manuring with phosphates becomes unnecessary. N. H. J. M. By W. KRUGER and W. SCHNEIDEWIND (Chern. Centr., 1899, ii, 628 ; from Landw. Jalwb., 28, 579-59l).-Experiments were made on the behaviour of alinit towards free atmospheric nitrogen in nutritive solutions containing nitrogenous matters, and also towards nitrates.It is concluded that the preparation is without practical value. The microbe does not nitrify, but there was production of nitrite. Composition of Green Manure grown on Peaty and on Sandy Soils. By HEINRICH INMENDORFF (Bied. Cent?.., 1899, 28,726-7'33 ; from Landw. Jcchb., 1898, 27, 503).-The composition as regards dry matter and nitrogen of the crops grown for green manure on peat land (yellow, blue, and white lupins, serradella, grey peas, beans, rape, and white mustard) scarcely differs from that of the same plants grown in ordinary soil. I n absence, however, of inoculation, the percentage of nitrogen in the dry matter is liable to be very low. I n the case of blue lupins, for instance, the nitrogen in the dry matter was (1, inoculated) 3.26 and (2, not inoculated) 1.98 per cent. I n light, sandy soils, the moat suitable crops for green manuring are lupins and serradella (white mustard is quite unsuitable), and the composition of the plants is normal. Application of burnt lime (3,000 kilograms per hectare) was very beneficial, even in the case of lupins. Pot and field experiments were made to ascertain the amounts of organic matter and nitrogen in the above-ground growth and roots of serradella and lupins grown in peaty soil fully manured with minerals. Normal percentages of nitrogen, both in roots and in the growth Alinit. N. H. J. M. The soil did not require inoculation.ANALYTICAL CHEMISTRY. 165 above-ground, were only obtained after inoculation. Luyins yield (in the roots) more organic matter than serradella, but the latter is more nitrogenous. Crops of serradella and lupins the above-ground growth of which contain 100 and 140 kilograms of nitrogen per hectare, yield in the roots about 15 and 20 kilograms of nitrogen respectively; these amounts may undoubtedly be increased by deepening the soil. N. H. J. 31. Testing Soils for Application of Commercial Fertilisers. By H. A. WEBER (J. Amer. Chem. Xoc., 1899, 21, 1095--1099).-Five carefully selected portions of the soil are put into Wagner pots, and to four of these are added various descriptions of manure to ascertain which will answer best. The seeds of the crops required to be raised are then introduced with the usual precautions and allowed to germinate; it is not neces- sary to bring the plants to maturity; observations made during 5 or 6 weeks will give sufficient information. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9007805157

出版商:RSC    

年代:1900

数据来源: RSC