摘要:

J O U R N A L E. F. ARMSTRONG Ph.D. C. F. BAKER Ph.D. B.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. E. GOULDING B.Sc. P. HAAS B.Sc. P1i.D. W. D. HALLIBURTON M.D. B.Sc. T. A. HENRY D.Sc. L. M. JONES B.Sc. Z. KAHAN B.Sc. L. DE KONINGH. D. A. LOUIS. F.R. S. OF T. M. LOWRY D.Sc. A. MCKENZIE M.A. D.Sc. N. H. J. MILLER Ph.D. K. J. P. ORTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLEY. C. SMITH D.Sc. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. E. W. WHEELWRIGHT B.A. Ph.D M. A. WHITELEY D.Sc. G. YOUNG Ph.D. THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ON ORGANIC CHEMISTRY. H. E. ARMSTRONG Ph.D. LL.D. E. C. C. BALY. A. W. CROSSLEY D.Sc. 1’h.D. BERNARD DYER D.Sc. M. 0. FORSTER D.Sc. Ph.D. F.H.S. F.R.S. R. MELDOLA F.R.S. E. J. MILLS D.Sc. LL.D. F.R.S. S~~W.RAMSAY K.C.B.,LL.D.,F.R.S. A. SCOTT D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. JOHN WADE D.Sc. &bitom G. T. MORGAN D.Sc. J. C. CAIN D.Sc. Sub- @;bitor A. J. GREENAWAY. &3sistzrut Sub-@bitot C. H. DESCH D.Sc. Ph.D. 1906. Vol. XC. Part I. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1906.RICHARD CLAY & SONS LIMITED BREAD STREET BILL E.C. AND BUNGAY SCJFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90690FP001

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

J O U R N A L H. E. ARMSTRONG Ph.D. LL.D. E. C. C. BAI.Y. A. W. CROSSLEY D.Sc. Ph.D. BERNARD DYER D.Sc. M. 0. FOHSTER D.Sc. Ph.D. F.R.S. F. R. S. OF R. MELDOLA F.R.S. E. J. MILLS D.Sc. LL.D. F.R.S. Sir W. RAMSAY K.C. B. LL.I). ,F. R. S. A. SCOTT D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. JOHN M'ADE D.Sc. THE CHEMICAL SOCIETY. E. F. ABMSTRONG Ph.D. C. F. BAKER Ph.D. B.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. E. GOULDING B.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTOX M.D. B.Sc. T. A. HENRY D.Sc. L. M. JONES B.Sc. 2. KAHAN B.Sc. L. DE KONINGH. D. A. LOUIS. F.R.S. T. M. LOWRY D.Sc. A. MCKENZIE M.A. D.Sc. N. H. J. MILLER Ph.D. K. J. P. ORTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLEY. C. SMITH DSc. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Se. E. W. WHEELWRIGHT B.A. Ph.D. M. A. WHITELEY D.Sc. G. YOUNG Ph.D. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1906.RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90690FP003

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

JOURNALS FROM WHICH ABSTRACTS ARE MADE. All references to Journals should give the abbreviated title the year of publication lhe series the volume and the page ; thus Ber. 1901 34,2455 ; Bull. SOC. chim. 1901 [iii] 25 794 ; Gaexettn 1901 31 i 554. ABBREVIATED TITLE. Amer. Chcm. J. . . . Amer. J. Phnrm. . . Amer. J. Physiol. . . Amer. J. Sci. . . . Anal. Pis. Quiin. . . Analyst . . . . Annalen . . . Ann. Physik . . . Ann. Chim anal. . . Ann. Chim. Phys. . . Ann. Inst. Pasteur . . Ann. sci. Univ. Jmsy . Arch. ezpt. Path. Pharm. . Arch. Hygiene . . Arch. Nderland. . . . Arch. Pharna. . . . Arch. Sci. phys. nut. . . Arkiv Kern. Min. Geol . Atti R. Accad. Sci. Torino. Atti R. Acead. Lincei . Beitr. cirem. Physwl. Path. Ber. . . . . Ber. Deut. bot. Gcs. . . Ber. Deut. pharm. Ges.. Ber. Detct. physikal. Gcs. . * Bied. Zentr. . . . Bia-Cheni. J. . . . Bw-cheni. Zeitsch. . . Boll. chim. farm. . . Bull. Acd. roy. Belg. . Bull. Acad. Sci. Cracow . JOURNAL. American Chemical Journal. American Journal of Pharmacy. American Journal of Physiology. American Journal of Science. Anales de la Sociedad Espaiiola Fisica y Quimica. The Analyst. Justus Liebip’s Annelcn der Chemie. Annalen der Physik. Annales de Chimie analytique appliquke ?i l’Industrie Ariiiales de Chirnie e t de Physique. Annales de 1’Institut l’asteur. Annales scientificrues de I’Universit6 de Jassy. Archiv fur experinientelle Pathologie und Pharmako- Archiv fiir Hygiene. Archives NBerlandaises des sciences exactes e t natur- Archiv der Pharmazie. Archives des Sciences physiques e t naturellcs. Arkiv fiir Kemi Rlinei alogi och Geologi.Atti della Reale Accadeinia delle Scienze di Torino. Atti della Keale Accadernia dei Lincei. Britrjge fiir chemische Physiologie und Pathologie. Berichte der Deutschen chemischen Gesellschaft. Berich te der Dentschen botanischen Gesellschaft. Uericlite der Dentschen pharmazeutischen Gesellschaft. Berichte der Deutschen physikalischen Gesellschaft. Biedermann’s Zen tralblatt fur Agrikul turchemie und The Bio-Chemical Journal. Biochemische Zeitschrift. Bollettino chimico farmaceutico. Acad6mie royale de Belgique-Bulletin de la Classe Bulletin international de l’Acad6mie des Sciences de h l’Agriculture A la Pharmacie e t & la Biologie. logie. elles. rationellen Landwirtschafts-Betrieb. des Sciences. Cmcovie.Bull. Assoc. chim. Xucr.Dis Bull. Coll. Agr. T6kya Bull. Geol. SOC. Amer. B‘1617. hnp. Inst. . Bd1. Soe. chim. . Bitll. SOC. chiin. Belg. Bull. Xoc. franc. bfin. Bull. SOC. ind. Mulhoicse Centr. Bakt. Par. Centr. Min. . . * Chon. Zentr. . :t. . . . . . . . . Centralblatt fur Bakteriologie Parasitenkunde und . Centralblatt fiir bI ineralogie Geologie und Palaeonto- . Cheniisches Zentralblatt. Bulletin de l’dssociation des chimistes de Sucrerie e t Bulletin of the College of Agriculture Imperial Uni- Bulletin of the Geological Society of America; Bulletin of the Imperial Institute. Bulletin de la Soci6t6 chiniique de P a r k Bulletin de la Socidth chimiyue de Belgique. Bulletin de la SociBt6 franpaise de Miu6ralogie. Bulletin de la Soci6te industrielle de hlulhousc.de Distillerie. versity T6ky6. Infektionskrankheiten. logie. * Abstracts from the Zentvalblntt are mad? only in the case of papers published in journals other tbm those included in this list.JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBREVIATED TITLE. Chem News . . . Chem. 1 2 ~ . Fett-Har.z-lnd. Chem. IVeekbdnd . . Chem. Zeit. . . . Compt. rend. . . . Eqer. Stat. Record . . Gazzetta . . . . Geol. Mag. . . . . Jahrb. Min. . . . Jahrb. En. Beil.-Bd. . Jahrb. Radioaktiv. Elektro- J. Amer. Chenz. Soc. . . J. Biol. Chem. . . J. Chim. phys. . . . J. Geol. . . . . J. Hygiene . . . . J. Inst. Brewing . . J. Landw.. . . . J. Med. Research . . J. Path. Bad. . . . J. Pharm. Chim. . . J. Physical Chenz. . . J. Physiol. . . . J. Physique . . . J.pr. Chem. . . . J.Roy. Agric. Soc. . . J. Roy. SOC. New South J. Russ. Phys. Chem. SOC. . J. Xoc. Chem Ind. K. Svenska Vet-Akad.HmdZ.* Lancet. . . . . Landw. Versuehs-Stat. . L’Orosi . . . . Mem. Acead. Sci. Torino . nik. Wales. Mem. Coll. Sci. Eng. Ky6t6. Mem. Manchester Phil. Soc. Metallurgie . . . Milch. Zentr. . . . Min. Mag. . . . . Monatsh. . . . . Nuovo Cim. . . . PJliger’s Archiv. . . Pharm. Arch. . . . Pharnz. Centr-h. . . P h r m . J . . . . . Phrm. Rev. . . . Phnrm. Veekb1a.d . . Pharm. Zeit. . . . Phil. Mag.. . . . JOURNAL. Chemical News. Chemische Revue iiber die Fett- und Harz-Industrie. Chemisch Weekblad. Chemiker Zeitung. Coniptes rendus hebdomadaires des SQances de Experiment Station Record. Gazzetta chimica italiana. Geological Magazine. Neues Jahrbuch fur Mineralogie Geologie und Pal- aeontologie. Neues Jahrbuch f i r Mineralogie Geologie nnd Pal- aeontologie.Beilage-Band. Jahrbuch der Radioaktivitat und Elektronik. l’Acad6mie des Sciences. Journal of the American Chemical Society. Journal of Biological Chemistry New York. Journal de Chimie physique. Journal of Geology. Journal of 14 ygiene. Journal of the Institute of Brewing. Journal fur Landwirtschaft. Journal of Medical Research. Journal of Pathology and Bacteriology. Journal de Pharmacie et de Chimie. Journal of Physical Chemistry. Journal of Physiology. Journal de Physique. Journal fiir praktische Chemie. Journal of the Royal Agricultural Society. Journal of the Royal Society of New South Wales. Journal of the Physical and Chemical Society of Journal of the Society of Chemical Industry.Kongl. Svenska Vetenskaps-Akademiens Handlingar. The Lancet. Die landwirtschaftlichen Versuchs-Stationen L’Orosi. Rlemorie della Reale Accademia delle Scienze di Torino. Memoirs of the College of Science and Engineering Ky6t6 Imperial University. Nemoirs and Proceedings of the Manchester Literary and Philosophical Society. Met allurgie. Milchwirtschaftliches Zentralblatt. Mineralogical Magazine and Journal of the Mineral- ogical Society. Monatshefte fur Chemie und verwandte Theile anderer Wissenschaften. I1 Nuovo Cimento. Archiv fur die gesammte Physiologie des Menschen und der Thiere. Pharmaceutical Archives. Pharmazeu tische Cen tralhalle. Pharmaceutical Journal. Pharmaceutical Review. Pharmaceutisch Weekblad. Pharmazeu tisclie Zeitunrr.Russia. Philosophical Magazine rThe London Edinburgh and Dublin).JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBREVIATED TITLE. Phil. Trans. . . . Physikal. Zeitsch. . . Proc. Amer. Physiol. Soc. . Proc. Camb. Phil. Xoc. . Proc. K. Akad. Wetensch. Proc Phil. Soc. Glasgow . Proc. Physiol. SOC. . Proc. Roy. Xoc. . . Proc. Roy. SOC. Edin. . Quart. J. CTeol. SOC. . . Rec. trav. chim. . . Amsterdam. Rend Accad. Sci. Fk. Mat. Rev. de Mktallurgie . . Rev. intern. Falsi$ . . Sci. Proc. Roy. Dubl. SOC. . Xci. Trans. Boy. Dubl. SOC. Sitzungsber. K. Akad. Wiss. Sitzungsber. K. Akad. M&- Trans. Amer. Electrochem. Trans. Amer. Inst. Mining Trans. Faraday Soc. . . Trans. Nova Scotia Inst. Trans. Path Xoc. . . Trans. Roy. Xoc. Can& . Trans. Roy. Irish Acad. . Tsch.Min. Mitt. . . U.S. A . Dept. Agric. Bull. . U.S.A. Dept. Agric. Rep. . Yerh. Ges. deut. Naturforsh. Wiss. Abhancll. Phys. - Tech. Zeitsch. anal. Chem. . . Zeitsch. angew. Chem. . Zeitsch. anorg. Chm. . . Zeitsch. Bid. . . Zeitsch. Elektrochm. . . Zeitsch. Fnrb. Ind. . . Zeitsch. Kryst. Min. . . Zeitsch.. Nahr. Genzcssna. . Napoli. Berlin. chen. SOC. Eng. SCi. Aerxte Reichsanstalt. Zeitsch. 6fentl. Chem. . Zeitsch. ph ysikal. Chenz. . Zeitsch. physiol. Chem. . Zeitsch. prakt. Geol. . . Zeitsch. Ver. deut. Zicckerind. Zeituch. Zuckerind. Bohm. . JOURNAL. Philosophical Transactions of the Royal Society of Physikalische Zeitschrift. Proceedings of the American Physiological Society. Proceedings of the Cambridge Philosophical Society. Koninklijke Akadeniic van Wetenschappen te Amster- Proceedings of the Glasgow Philosophical Society. Proceedings of the Physiological Society.Proceedings of the Royal Society. Proceedings of the Royal Society of Edinburgh. Quarterly Journal of the Geological Society. Receuil cles travnux chimiaues des Pavs-Bas et de la London. dam. Proceedings (English version). Belgique. Rendiconto dell’ Accademia delle Scienze Fisiche e Matematiche-Napoli. Revue de M6tallurgie. Revue internationale des Falsifications. Scientific Proceedings of the Royal Dublin Society. Scientific Transactions of the Royal Dublin Society. Sitzungsberichte der Koniglich Preussischen Akademie Sitzungsberichte der koniglich bayerischen Akademie Transactions of the American Electrocheniical Society. Transactions of the American Institute of Mining Transactions of the Faraday Society.Transactions of the Nova Scotia Institute of Science. Transactions of the Pathological Society. Transactions of the Royal Society of Canada. Transactions of the Royal Irish Academy. Tschermak’s Mineralogische Mitteilungen. Bulletins of the Department of Agriculture U. S. A. Reports of the Department of Agriculture U.S.A. Verhandlung der Gesellschaft deutscher Naturforscher und Aerzte. Wissenschaftliche Abhandlungen der Physikalisch- Techiiischen Reichsanstalt. Zeitschrift fiir analytische Chemie. Zeitschrift fur angewandte Chemie. Zeitschrift fur anorganische Chemie. Zeitschrift fur Biologie. Zeitschri ft fur Elek trochemie. Zeitschrift fiir Farben- Industrie. Zeitschrift fur Krystallographie und Mineralogie. Zeitschrift fur Untersuchung der Nahrungs- und Zeitschrift fur offentliche Chemie. Zeitschrift fur physikalische Chemie Stochiometrie und Verwandtschaftslehre. Hoppe-Seyler’s Zeitschrift fur physiologische Chemie. Zeitschrift fur praktische Geologie. Zeitschrift des Vereins der deutschen Zucker-Industrie. Zeitschrift fur Zuckerindustrie in Bohmen. der Wissenschaften zu Berlin. der Wissenschaften zu Munchen. Engineers. Genussmittel.

ISSN:0368-1769    

DOI:10.1039/CA906900X007

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

INORGANIC CHEMIS'I'RY. 15 Inorganic Chemistry. The Demity of Chlorine Gas. FREDERICK P. TREADWELL and W. A. K. CHRISTIE (Zeit. anorg. Chem. 1905 47 446-454).-The measurements were made by a method described by Bunsen. Two bulbs of equal capacity and of approximately equal weight were filled at conatant temperature with chlorine and air respectively and the difference of weight determined; the density of air being known the density of chlorine can then be calculated readily. The chlorine prepared from potassium dichromate and hydrochloric acid and care- fully purified still contained a small proportion of air for which a correction was applied. As a mean of three determinations at 20° and 730 mm. the value 2.488 (air = 1) was found and two determinations a t 10" and 725 mm.gave the value 2.489; according to Moissan and Binet du Jassoneix (Abstr. 1904 ii 114) the density at Oo and 760 mm is 2.490. G. S. Action of Hydrochloric Acid on Potassium Chlorate. A. KOLB (Zeit. angew. Chena. 1905 18 1693-1694).-Polemica1 (compare Ditz Abstr. 1905 ii 760; Kolb and Davidson ihicl. 59). H. M. D. The System Bromine and Iodine. P. C. E. MEERUM TERWOGT (Zed. anorg. Chem. 1905 47 203-243).-The freezing-point and boiling-point curves of mixtures of bromine and iodine have been determined and vapour pressure and specific gravity measurements have been carried out chiefly with the object of deciding whether a compound IC1 exists in the solid liquid and gaseous systems. Mixtures containing 50 atom. per cent. of each element solidify at constant temperature but with mixtures in any other proportion the temperature falls a few degrees from the commencement to the completion of solidification ; this indicates according to Hoozeboom's theory the existence of a compound IC1 which when the elements are present in other than equivalent proportions separates out in mixed crystals with bromine or iodine.The boiling-point curve was constructed by finding the initial boiling points of the various mixtures and the composition of the vapour at these temperatures and then plotting the composition of the liquid both against the initial boiling points and the boiling points of the evolved vapour on the same diagram. The two curves bend towards each other when the two elements are present in equivalent proportions which may indicate the presence of ICI in a highly dissociated state.The vapour pressure curve of the .system was investigated by a static method up t o 58 atom. per cent. iodine at 50*2" and up to 80 ut,om. per cent. at 92.8"; larger proportions could not be employed owing t o the formation of mixed crystals. The pressures were plotted The boiling point of pure iodine is 188-189O.16 ABSTRACTS OF CHEMICAL PAPERS. both against composition of liquid and of vapour ; the resulting curves deviated considerably from a straight line. An attempt was made according to a method suggested by van Laar (Zeit. php&-d. Chem. 1904 47 129) to deduce from the extent of this deviation whether IC1 exists in the liquid and vapour phases and the extent of its dissociation but the results are not very conclusive.The specific gravities of liquid and solid mixtures up to 58 atom. per cent. iodine were determined and plotted against the composition. The curves (except in the change from liquid to solid) are continuous but deviate from a straight line showing contraction; this may indicate formation of IC1 or may arise from a physical cause. The author concludes that 101 is present in the solid system; its existence in the liquid and vapour systems is probable but not satisfactorily proved. G. S. Iodic Acid. ERICH GROSCHUFF (Zeit. unorg. Chem. 1905 47 331-352).-Besides iodic acid and iodine pentoxide the existence of a crystalline substance of the formula I,O,,&H,O or HI,O has been proved by dehydration of iodic acid at different temperatures and by direct determination of the transition temperature.An amorphous modification of iodic acid is also described which differs from the ordinary acid in being very hygroscopic. No hydrates of the acid could be obtained. The complete solubility curve of iodic acid at different temperatures has been determined The cryohydric point lies at - 14'; the mixture contains 72.7 per cent. of the acid. The transition tem- perature of iodic acid to the compound HI,O is at 110' ; the transition from the latter t o the pentoxide takes place between 190' and 200'. The saturated solution boils at 11 1' under atmospheric pressure. The solution saturated at 18' contains about 295 grams of the acid to 100 grams of water and has a sp. gr. of about 2.48. Strong solutions of the acid are very viscous and it readily forms supersaturated solutions.The solubility of iodic acid in solutions of nitric acid of different strengths has also been determined. Freezing-point determinations in aqueous solution show that the apparent molecular weight varies greatly with the concentration. In dilute (1 per cent.) solutions the acid is present in single molecules which are highly ionised ; in concentrated solutions on the other hand it seems to be polymerised as suggested by Rosenheim and Liebknecht (compare Abstr. 1899 ii 743). This conclusion is confirmed by the results of electrical conductivity measurements ; the degree of ionisation as calculated from freezing-point determinations agrees better with that deduced from conductivity measurements when the presence of complex molecules in concentrated solution is assumed.G. S. Application of the Partial Liquefaction of Air with Reflux Action to the Complete Separation of Air into Pure Oxygen and Pure Nitrogen. GEORGES CLAUDE (Compt. rend. 1905 141 823-826).-In a previous paper (Abstr. 1904 ii 23) the author described a method for separating the oxygen and nitrogen of air byINORGANIC CHEMISTRY. 17 partial liquefaction ; the separation was not however complete as the final products contained only 92 per cent. of oxygen and 97-98 per cent. of nitrogen respectively. The present paper contains a descrip- tion of a modification of the method whereby the separation is carried to completion. The apparatus consists essentially of a reservoir of liquid oxygen surmounted by a rectifying column ; immersed in but not communicating with the liquid oxygen are two concentric coolers each consisting of a small reservoir communicating with a series of vertical tubes The air cooled and compressed enters the inner cooler where it undergoes partial liquefaction ; the liquid phase containing about 48 per cent.of oxygen falls back into the inner reservoir the gaseous phase rich in nitrogen is partially liquefied in passing through tbe vertical tubes of the outer cooler and nearly pure liquid nitrogen collects in the outer reservoir ; by allowing the contents of the two reservoirs to percolate through the rectifying column the liquid rich in nitrogen entering the column from the top whilst the liquid rich in oxygen enters at a slightly lower level the descending liquids effect a complete rectification of the ascending gases and pure liquid oxygen collects in the large reservoir whilst pure gaseous nitrogen escapes from the top of the rectifying column.M. A. W. The Liquefaction of Air by Expansion with Performance of External Work. GEORGES CLAUDE (Compt. rend. 1905 141 762-764).-A description of a modification of the apparatus employed in producing large quantities of liquid air under pressures of 23 to 40 atmospheres (compare Compt. rend. 1902 134 1568 ; 1903 136 1659 ; Abstr. 1904 ii 23 ; preceding abstract). AT. A. W. Molecular State of Water ; its Chemical Constitution and the Relative Value of the Two Valencies of the Oxygen Atom. LOUIS HENRY (BUZZ. Acad. Boy. BeZg. 1905 377-393).-A theo- retical paper in which the author quotes evidence in favour of the mole- cular association of water the chemical identity of the two hydrogen atoms of the molecule and the consequent equality of the two valencies of the oxygen atom (compare de Forcrand Abstr.1905 ii 696). M. A. W. Formation of Hydrogen Peroxide at High Temperatures. WALTHER NERNST (Zeit. Elektrochem. 1905 11 710-713).-The formation of hydrogen peroxide cannot be observed when a mixture of steam and oxygen is passed through a hot platinum or iridium tube and then rapidly cooled. As this is possibly due t o the great velocity with which the decomposition of hydrogen peroxide takes place experiments on the rate of dscomposition were made by passing a current of air containing a known quantity of hydrogen peroxide through a heated glass tube and then cooling it rapidly.The quantity of undecomposed hydrogen peroxide was estimated by adding a solution of titanium dioxide in concentrated sulphuric acid and measuring the absorption of light a t the blue end of the spectrum by means of t h e spectro-photometer. It appears that the reaction is bimolecular 2H,0,~-2H20 + O and that its velocity constants are very nearly the VOL. SC. ii. 218 ABSTRACTS OF CHEMICAL PAPERS. same as those of the decomposition of ozone (hbstr. 1904 ii 479). Hydrogen peroxide is not formed when electric sparks pass through a mixture of oxygen and water vapour (this is evidence in favour of the view t h a t the formation of ozone is due t o ultra-violet light) ; it is formed however when sparks are passed through liquid water the rate of cooling being then sufficiently great t o prevent its complete decom- position.T. E. Chemical Oxydases acting in the Presence of Hydrogen Peroxide. G. BAUDRAN (Gompt. rend. 1905 141 891-892. Compare Abstr. 1905 ii 407,632).-Chlorittes bromates iodates and the alkali hypochlorites hypobromites hypoiodites phosphates and sulphates give a yellowish-green colour and precipitate with a 1 per cent. solutionof guaiacol in the presence of hydrogen peroxide the colour becoming red on the addition of hydrochloric or sulphuric acid ; the salts of the aliphatic and aromatic acids give a similar reaction which is accelerated by the addition of a sinall quantity of mercuric iodide solution. ill. A. W. Preparation of Colloidal Solutions of Selenium and Sulphur by Electrical Pulverisation.ERTCH MULLER and ROMWALD NOWAKOWSKI (Ber. 1905 38 3779-3’781. Compare Muller and Lucas Abstr. 1905 ii 672; Gutbier Abstr. 1902 ii 652).-A colloidal solution of selenium is prepared by the electrical pulverisation in pure water of a cathode prepared by fusing a small piece of selenium on to platinum foil. This takes several hours with a n E.H.F. of 20 volts or is effected more quickly with a greater E.5I.B’. The hydrogen selenide formed with a n i7.M.R of 20 volts is oxidised by the anodic and atmospheric oxygen; but with a n E.B.F. of 220 volts hydrogen selenide is evolved. The colloidal solution is fiery yellowish-red in thick layers or a dirty yellow i n thin layers by transmitted or yellowish-red by reflected light and deposits selenium only slowly except on the addition of a n electrolyte.A milky-white colloidal solution of sulphur having a strong odour of hydrogen sulphide is formed by the cathodic pulverisation of a sulphur-pl*ttinum electrode in pure water with a n iY.;lL.F. of 220 volts. 0. Y. Preparation of Nitrogen from the Atmosphere. GEORGE A. HULETT (J. Amer. Chenz. SOC. 1905 27 1415-1418).-The following method is described for the preparation of nitrogen from the air. I n a piece of combustion tubing of not less than 2 cm. diameter is placed a roll of copper gituze 20 cm. long followed by a layer of copper oxide of the same length. The tube is heated in a combustion furnace both the copper and copper oxide being maintained at a red heat.S i r and hydrogen are led directly into the tube and allowed to mix just before reaching the hot copper. The resulting gases are passed through solution of potassium hydroxide in order t o rerriove the carbon dioxide. For details of the method the description and diagram in the original must be consdteil. K. (2.INORGANIC CHEMISTRY. 19 Atomic Weight of Nitrogen [and Silver]. PHILIPPE A GUYE (Arch. Sci. phys. nat. 1905 [iv] 20 351-380).-A detailed account and discussion of work previously abstracted (Abstr. 1904 ii 557; 1905 ii 442 506 702). The value 14.009 for the atomic weight of nitrogen appears to be completely confirmed and the effect of this alteration is discussed. Three atomic weights are regarded as correct to 1 in 10,000 namely C = 12.002 H = 14.009 and H = 1.0076. From these the author revises the value of atomic weight of silver from the ratio Ag I AgNO the value 107.882 is obtained from Ag I CH,*CO,Ag 107.886 and from Ag I C,H50,Ag 107*888 with mean 107.885.From the ratios of Ag I NH,CL and Ag 1 C1 employ- ing Dixon and Edgar's value for chlorine 35.463 (Abstr. 1905 ii 696) the numbers 107.871 and 107.895 are obtained ; other values are Ag I Ag,S 107W34; Ag I Ago 107,928; Ag 1 Ag,P04 107.888 with a general mean of 107.885 and the author considers it certain therefore that it does not exceed 107.89. The lowering of this atomic weight will affect numerous other values L. M. J. Oxidation of Ammonia by Alkali Persulphates in Alkaline Solution. R. KEMPF (Ber. 1905 38 3972-3974. Compare Marshall Abstr.1901 ii 156).-Ttie ammonium salts contained in commercial sodium persulphate are oxidised to nitric acid (some 88 per cent.) when the solution in sodium hydroxide is kept for four days at about the ordinary temperature. When the solution is boiled a considerable portion (some 40 per cent.) is oxidised to nitrogen. J. J. S. Hydroxylamine and its Salts. W. H. Ross (Proc. Trans. Nova Scotian Inst. Sci. 1905,11,95-114).-A number of hydroxylammonium salts have been prepared and examined. Hydroxylamrnonium sulphate melts a t 163" with decomposition ; when heated above the melting point it breaks up according to the equation 3(NH,*OH),S04= (NH4),S0 + 2S0 + 2N,O + 8H,O. Hydroxylammonium chloride melts a t 157"' and the molten substance decomposes according to the equation 30H*NH3C1 = NH,Cl+ 2HC1+ N + 3€€,0. Hydroxylammonium phosphate is only moderately soluble in cold water but readily forms supersaturated solutions.When heated in a vacuum i t decomposes according to the equation 2(NH3*OH)3P0 = 6NH,*OH + H20 + H4P20,. I n an opea vessel it decomposes at 148O into ammonia water phosphoric acid ammonium phosphate and nitrous oxide. Hydroxylammonium nitrate is a viscid colourless liquid which decomposes slowly at 80° more rapidly at higher temperatures with the formation of nitric acid water ammonium nitrate nitrous and nitric oxides. It was obtained by distilling its aqueous solution under a pressure of 20 mm. and drying the distillate over phosphoric oxide. The estimation of hydroxylamine by titration with iodine in presence of disodium phosphate (compare Haga Trans.1887,51 794) was found to be unsatisfactory. The amount of iodine used increases considerably 2-220 ABSTRACTS OF' CHEMICAL PAPERS. when the quantity of diciodiumiphosphate present is increased but is almost independent of the dilution The electrical conductivity of aqueous solutions of the free base and its salts was measured. The following numbers express the equivalent conductivity\ (p x lo7) a t l S o in terms of mercury v being the volume per gram-molecule of salt. v = 2. 5. 10. 20. 50. 100. 200. 500. 1000. 2000. 5000. 10,000 Hydroxylamine ... - 0.4 0.5 0.7 0.9 1.2 1.5 1.9 2'2 - - - OH'NH3CI ......... 73.3 80.5 E6.6 90.9 95.6 96.9 101'5 104'6 107'6 109'9 111% 112'4 (VH3'0HhSOd ... - 63'6 71.6 80'5 9 2 0 97.7 103.0 109'9 113'0 115'9 118'9 120'3 OH'NE3N03 ..,... - - 106'7 112'6 119.1 122.3 124'7 127-1 129'8 131'8 134.0 138.5 (1L'Hs00R)3P04 ...- 1'3's 22.0 23.6 24.7 25.5 26'0 26.4 26'6 26'8 27'0 27'1 The nitrate has a greater conductivity than the chloride which is not what would beexpected from a comparison with the salts of the alkali metals. In all cams the conductivity of the salt solutions was found to increase with time especially with the more dilute solutions. This is due to the decomposition of the salts under the influence of the platinum black of the electrodes ; with polished electrodes the effect is considerably smaller. The base itself is oxidised even more rapidly than the salts. These phenomena necessitated special care in the determination of the conductivity data and the values for solutions of the base are only regarded as approximate.H. M. D. Density of Nitric Oxide; Atomic Weight of Nitrogen. PHILIPPE A. GUYE and CH. DAVILA (Compt. rend. 1905 141 826-82s. Compare Abstr. 1904 ii 475 557 812; 1905 ii 442 506).-Owing to the discrepancies between the values obtained for the density of nitric oxide (air = 1 ) 1 *041 (Thomson) 1.0888 (Bbrard) 1.094 (Davy) 1.188'7 (Kirwan) and 1.0388 (Lecluc) the authors have redetermined the constant using nitric oxide prepared by three distinct methods (1) decomposition of sodium nitrate or nitrite by mercury in sulphuric acid solution (2) reduction of nitric acid or sodium nitrite by ferrous sulphate or (3) decomposition of a dilute solution of sodium nitrite by sulphuric acid; it was purified by pass- ing it through concentrated sulphuric acid and subsequent repeated fractional liquefaction by means of liquid air.The mean of fourteen determinations of the weight of a litre of nitric oxide at N.T.P. is 1.3402 grams the limiting values being 1.3408 and 1.3398 respec- tively and is identical with the value recently found by Gray (Trans. 1905 87 1601) who prepared his nitric oxide by the reduction of sodium nitrite by potassium ferrocyanide and acetic acid and purified it by treatment with potassium hydroxide and final liquefaction and fractional distillation. The atomic weight of nitrogen calculated from the ratio of the densities of the gases NO/O lies between 14.010 and 14.006 (0= 1 6 ) . M. A. W. Nitrosyl Fluoride. OTTO RUFF and KURT STAUBER (Zeit.anorg. Chem. 1905 47 190-202. Compare Moissan Abstr. 1905 ii 518). -With the object of obtaining a compound of nitrogen and fluorine,INORGANIC CHEMISTRY. 21 Gore's experiments (this Journal 1869 22 391 393) with nitric and hydrofluoric acids and with nitric acid sulphuric acid and sodium fluoride were repeated and the action of nitrosylsulphuric acid on sodium fluoride was also investigated in each case with negative results. It was found however that by the action of nitrosyl chloride on silver fluoride a gaseous substance was formed which proved to have the formula NOF. The following method for preparing nitrosyl fluoride was found to give satisfactory results. A flask containing nitrosyl chloride kept at -So was attached to one end of a long platinum tube containing silver fluoride and kept at 200-250' ; the other end of the tube was connected with a small platinum flask provided with two stopcocks and cooled by liquid air.The nitrosyl chloride distilled slowly over the silver fluoride and the nitrosyl fluoride along with unaltered chloride was condensed in the platinum flask and purified by fractional distillation. Nitrosyl fluoride is a colourless gas condensable to a colourless liquid which boils a t - 5 6 O and solidifies on further cooling to a colourless mass melting at - 134O. I n the cold silicon boron red phosphorus and sodium take fire in the gas and arsenic and antimony are also immediately acted on fluorides being formed in each case and nitric oxide evolved. Lead aluminium bismuth and copper are only slowly acted on whilst iodine sulphur and carbon are not affected even on heating.Nitrosyl fluoride is decomposed by water with formation of nitrous and hydrofluoric acids; it gives brown fumes in moist air. Both in physical and chemical properties it closely resembles the nitryl fluoride NO,F isolated by Moissan but differs from the latter in its behaviour towards water and iodine. The formula NOF is confirmed by analysis and vapour density determinations. G. S. Preparation of Phosphorus Di-iodide. HOWARD W. DOUGHTY (J. Amer. Chern. Soc. 1905 27 1444-1445).-A mixture of 50 grams of iodine and 4 grams of red phosphorus in a 250 C.C. flask is heated with a free flame until completely melted. When the product has cooled to 60° 2.5 grams of yellow phosphorus are added in small pieces.By this method phosphorus di-iodide can be safely and rapidly prepared. E. G. Production of Carbon (Lampblack and Graphite) from Acetylene and Metallic Carbides. ADOLPH FRANK (Zeit. nngew. Chem. 1905 18 1733-1735).-When acetylene under a pressure of five or six atmospheres is exploded the charcoal (lampblack) obtained is contaminated with oily products resulting from the simultaneous partial condensation of the acetylene. If the acetylene is mixed with carbon monoxide or carbon dioxide in proportions given by the equations C,H + CO = 3C -I- H,O and 2C,H + CO = 5C + 2H,O these condensation products are not formed. The pressure of the mixture of acetylene and carbon monoxide before explosion should be at least six atmospheres ; with this initial pressure valne the maximum pressure developed during the explosion amounts to 40-50 atmospheres.On22 ABSTRACTS OF CHEMlCAL PAPERS. account of the high temperature developed the reaction is not complete but 85 per cent. of the theoretical quantity of carbon is obtained. The charcoal so produced has a high specific gravity-1.93 to 2.0- and its electrical conducting power is considerably greater than that of other forms of charcoal. It is very finely divided very black ancl has a high covering power. When calcium strontium or barium carbide is heated in a current of carbon monoxide or dioxide carbon separates in the form of graphite according to the equation CaC + CO = CaO + 3C. Graphite is also obtained when the carbides are heated in a current of chlorine phosphorus or arsenic but in these cases the yield is considerably less than the theoretical. The graphite obtained from calcium carbide and carbon monoxide leaves only about one per cent.of ash on combustion is very hard and has a high sp. gr. (2-2.05). It is eminently suit- able for electrotechnical and electrochemical applications. H. M. D. Attempt to Liquefy Helium. KAm OLSZEWSKI (Bull. Acad. Sci. Cracow 1905 407-411. Compare Abstr. 1897 ii 31 ; Dewar Abstr. 1901 ii 597 ; Travers Senter and Jaquerod Abstr. 1903 ii 9).--Helium obtained by heating thorianite with potassium hydro- gen sulphate contained as impurity only nitrogen which was removed completely by two coolings with liquid hydrogen. The helium so purified was cooled to -252.5' by boiling hydrogen and then to - 259' by hydrogen solidifying under 50 mm.pressure and subjected to a pressure of 180 atmospheres which was reduced slowly or suddenly to 1 atmosphere when the gas showed no signs of iique- faction or the deposit of any solid the temperature being lowered to - 271.3". The boiling point of helium is therefore below - 273.O or -+ 2' absolute. G. Y. Coloration of t h e Halogen Salts of the Alkalis and Alkaline Earths. LOTHAR WOHLER and H. KASARNOWSKI (Zeit. anorg. Chem. 1905 47 353-370. Compare Abstr. 1901 ii 166; Giesel Abstr. 1897 ii 170; Borchers and Stockem,Abstr. 1903,ii 19).-Many naturally-occurring halogen compounds such as rock-salt and fluor- spar are coloured in various ways and similar colours can be produced by exposing the colourless salts to the vapours of metals or to cathode rays.The origin of these colours has not been satisfactorily elucidated. With the object of throwing light on this question the authors heated natural blue rock-salt and colourless pieces of the same sub- stance in a stream of oxygen and found that both specimens contained about 0.016 per cent. of carbon and 0.008 per cent. of hydrogen indicating the presence of traces of organic matter. For comparison artificially coloured specimens of several halogen salts have been prepared by heating the crystals in the rapour of different metals and it was found that under these conditions the halogen salts of the alkali metals became deeply coloured in fifteen minutes and the colour did not deepen on further heating.Excess of metal could not be detected in these salts by chemical analysis so that the amount1NORGANIC CHEMISTRY 23 present must be very small. On the other hand a specimen of fluor- spar blue by transmitted and green by reflected light prepared by heating colourless crystals of the salt in calcium vapour was found on analysis to contain 2.4 per cent. of the metal in excess. Attempts to prepare coloured salts by electrolysis were not very successful ; only those parts of the fused mass which ware kept fairly cool were found to be coloured. All the coloured salts referred t o lose their colour when heated but this change takes place at a much lower temperature in the case of the naturally coloured salts. Further the latter are neutral in reaction and the colour is unaffected by water whereas the artificially coloured salts are alkaline and become decolorised on treatment with water.It seems likely that the coloration arises from different causes in the two cases ; with artificially coloured salts it is probably due to traces of metal or subchloride in solid solution in the halogen salt in the other cases to traces of organic matter. The colour does not depend on the amount of foreign substance present but chiefly on its mode of occurrence as in coloured glasses. The coloration produced by the vapours of metals and by cathode rays probably arises from the same cause. G. S. Sodium Hyposulphite. 111. ARTHUR BINZ and W. SONDAG ( B e y 1905 38 3830-3834. Compare Abstr. 1904 i 964; 1905 ii 521).-A method is described of estimating in the same solution hyposulphite sulphate thiosulphate and siilphite.By this means it is possible to follow the changes which take place on mixing the hypo- sulphite with thiosulphate. The products are sulphite and sulphide. Na,S,O + Na2S,0 + 4NaOH = 3Na,S03 + Na,S + 2H,O; in the actual experiment 1.00 mol. Ka,S,O with 0.99 mol. Na,S203 gave 2.92 mol. Na,SO and 1-00 mol. Na,S. T. M. L. Lithium Alumino-silicates Z. WEYBERG (Centr. Bin. 1905 646-655. Compare Abstr. 1905 ii 89 98 262).-By fusing kaolin (H,Al,Si,O,,H,O) with potassium chloride Gorgeu (188'7) obtained the product K,Al,Si,O?. This compound is however only obtained in the crystallised condition when an alkali carbonate is added to the mixture or when the free bases and silica are used instead of kaolin.On the other hand the more readily decomposed lithium salts when fused with kaolin give well-crystallised products. Thus by fusing kaolin with lithium chloride or lithium carbonate a white crystalline powder is obtained the crystals being orthorhombic and having the composition Li,A1,Si20,,. With lithium sulphate the cryetallised (orthorhornbic) product has the composition Li2A1,Si,0,. With lithium bromide a lithium brorno-sodalite 7Li,Al,Si20,,2LiBr crystal- lising in rhombic dodecahedra was obtained. The kaolin used in the experiments had the following composition SO,. A1,0,. H,O. Total. From South Russia ... 45.76 39.87 14.44 100.07 Meissen ......,.. 49.41 37.06 13-53 100.00 L J. 8.24 ABSTRACTS OF CHEMICAL PAPERS. Lithium Chromates. FRANS A.H. SCHREINEMAKERS (C'hewz. Centlr. 1905 ii 1486; from Ckenz. Weekblad 2 633-639. Compare Abstr. 1905 ii 8 18 820).-The only substances which can separate in a solid form from a system which consists of lithium oxide chromic acid and water at 30' are lithium hydroxide LiOH,H,O chromate Li2Cr,0,.2H,0 dichromate Li2Cr,07,2H,0 and chromic acid CrO,. Higher chromates than the dichromate cannot exist at 30°. A saturated solution of lithium hydroxide contains 7.09 per cent. ; 100 parts of water dissolve 99.94 and 130.4 parts of lithium chromate Li2Cr0 and 11 thium dichromate Li2Cr207 respectively. The solubility of the chromates of ammonium potassium sodium and lithium increases in the order given whilst for the dichromates the order of solubility is potassium ammonium lithium sodium.E. W. W. Decomposition of Ammonium Sulphate by Sulphuric Acid in the Presence of Platinum. MARCEL DEL~PINE (Compt. rend. 1905 141 886-889).-The low results obtained when the nitrogen of platinichlorides is estimated by the Kjeldahl method (compare Abstr. 18Y5 ii 290 and van Dam Abstr. 1896 ii 218) are due to the decomposition of the ammonium sulphate with loss of nitrogen for if spl.ngy platinurn or platinum foil is boiled with sulphuric acid containing ammonium sulphzlte sulphur dioxide is formed and nitrogen is evolved the quantity increasing with the duration of heating the temperature and the addition of potassium sulphate. It is probable that the platinum acts as a catalyst the sulphate being first formed and then decomposed by the ammonium sulphate according to the eqaations ( 1 ) 4H2S0 + Pt = Pt(SO,) + 250 + 4H20 ; (2) SPt(SO,) + 2(NH4).?S04 = 2N + 3Pt + 8H2S0 for the solution obtained by boiling platinum in sulphuric acid deposits platinum when heated with ammonium sulphate and further when the platinum in the above experiment is replaced by gold or iridium which is not attacked by sulphuric acid there is no loss of nitrogen.M. A. W. Separation of Constituents of Alloys. A. BOCK (Chem. Zeit. 1905 as 1199-1201).-The introduction of a third metal into a molten alloy of two metals causes a partial separation of the two constituents and a consequent loss of homogeneity in the resulting mass on solidification. The extent of the disturbance is less in thin layers of the alloy than in large blocks.The Pattinson desilverising process is attributed to the influence of the iron of the containing vessels on the molten alloy of lead and silver. The author also attributes to the iron of the mould in which they are cast the segregation observed with certain silver-copper and gold-silver alloys. P. H. Oxidations with Silver Peroxide. I. Oxidation of Oxalic Acid. R. KEMPF (Ber. 1905 38 3963-3966).-Silver peroxide is formed when solutions of silver nitrate and potassium persulphate are mixed (Marshall Trans. 1891 59 771). Such a mixhure is capable of oxidising numerous carbon compounds. Quinone yields maleic acidINORGANIC CHEMISTRY. 25 and carbon dioxide together with formic acid and carbon monoxide. Oxalic acid can be quantitatively oxidised t o carbon dioxide.A simple lecture experiment may be conducted as follows 5 C.C. of a 10 per cent. silver nitrate solution are added to a mixture of 20 grams of ammonium persulphate in 100 C.C. of 10 per cent. sulphuric acid and 100 C.C. of N-oxalic acid. A slight precipitate of silver sulphate is formed the solution becomes warm and the evolution of gas is completed in a few minutes. The active oxygen of the persulphate may be estimated by mixing with excess of standard oxalic acid solution adding dilute sulphuric acid containing a little silver sulphate and titrating the excess of oxalic acid with permanganate J. J. S. Oxidations with Silver Peroxide. 11. Formation of Nitric Acid from Ammonium Persulphate. R KEMPF (Ber. 1905 38 3966-3971. Compare Marshall Abstr. 1901 ii 156).-When silver sulphate is added to a solution of ammonium persulphate in dilute sulphuric acid a brown precipitate of silver peroxide is formed but this disappears in the course of several days pTactically no oxygen is evolved the persulphate is destroyed and nitric acid is produced.The reaction proceeds but slowly for example 0.63 gram of ammonia (as ammonium salt) required forty-eight hours. I n the absence of silver salts persulphates are not able to bring about the oxidation which must be due to silver peroxide and not to ozone Caro's acid or hydrogen peroxide. The oxidation is not quantitative. J. J. S. Electrolytic Calcium. JOSEPH H. GOODWIN (J. Amer. Chena. Suc. 1905 27 1403-1415).-A method is described for the pre- paration of calcium by the electrolysis of fused calcium chloride.A hollow cylindrical vessel of Acheson graphite is employed as the anode and an iron rod as the cathode. With a current of 163 amperes about 17.7 volts are required the current efficiency being 29.1 per cent. For details of the apparatus reference must be made to the description and diagrams in the original paper. The bright metal obtained by this method was found to contain 98.0 per cent. of calcium had a sp. gr. 1.5446 at 29.2" a specific electrical resistance of 3.43 microhms per C.C. a t Oo and a tensile strength of 612 kilograms per sq. cm. Calcium is harder than sodium lead or tin nearly as hard as aluminium but softer than zinc cadmium or magnesium E. G . Composition of Metallic Calcium. B. LARSEN (Chem. Centr. 1905 ii 1466 ; from Mitt Teechn.Gewerb.-Nus. Wien [ii] 15 244-246).-A sample of metallic calcium from the Electrochemical Works in Bitterfeld has been found to contain 99.64 per cent. of calcium 0.2 of iron 0.09 of manganese 0.06 of silica and 0.11 of calcium carbide. The metal was broken on an anvil and the man- ganese may possibly have been derived from the tool which was made of manganese steel. The pieces which weighed from 6-8 grams were quickly immersed in naphtha so that the fresh surfaces scarcely became tarnished. After removing the naphtha from the sample for analysis by means of ether the metal was dried in a stream of dry66 ABSTRACTS OF CHEMICAL PAPERS. air and finally dissolved in hydrochloric acid cooled by ice. The quantity of calcium carbide mas determined by weighing the copper acetylide formed from the acetylene which was liberated.E. W. ?V. Tarugi’s View of the Formation and Composition of Bleaching Powder. HUGO DITZ (Zeit. angew. Chem. 1905 18 1690-1 693. Compare Tarugi Abstr. 1905 ii 32).-Tarugi’s view that bleaching powder is a substance of the formula CaO,CI,,H,O corresponding with 44.09 per cent. of active chlorine is inconsistent with the analyses of different samples of bleaching powder. On the assumption of this formula the sum of the percentage numbers for the various constituents of three samples of bleaching powder examined amounts approximately to 110. The excess of this number over 100 corresponds almost exactly with 1 atom of oxygen. B. M. D. Revision of the Atomic Weight of Strontium. 11. Analysis Of Strontium Chloride.THEODORE W. RICHARDS (%it. nnorg. Chem. 1905 47 145-150).-1n a previous investigation (Abstr. 1895 ii 314) the value Sr=87*663 was found from the analysis of strontium bromide. In the present paper the analysis of the chloride by a similar method is described ; the ratio SrClz 2Ag. was found by titrating the carefully purified salt against silver dissolved in nitric acid the end-point being determined by means of the nephelometer (compare Abstr. 1904 ii 287). When the value C1=35*473 found by Richards and Wells is taken as the basis of calculation the value Sr = 87.661 is obtained as the mean of four concordant experiments in satisfactory agreement with the result obtained with the bromide whilst there is a considerable difference when the former atomic weight of chlorine is employed.The new value for chlorine is thus confirmed. The mean of the two series Sr = 87.662 (0 = 16) may be taken as the most probable value. G. S. Barium Oxide and its Hydrates the Preparation of a New Hydrate. 0. BAUER (Zeit. anorg. Ckem. 1905 47 401-420).-The compound Ba(OH),,SH,O melts at 7 8 O and begins to boil at 103’; on continued heating the temperature rises steadily to logo a t which point it remains constant for some time and crystals of a hydrate Ba(OH)2,3H,0 not previously described separate out. The new hydrate occurs in clear lustrous rhombic crystals ; chemically i t behaves in all respects like the octahydrate. Corresponding strontium and calcium compounds could not be obtained. G. S. Alloys of Cadmium and Zinc containing Lead.FRANZ NOVAK (Zeit. unorq. Chew,. 1905 47 421-445. Compare Ericson- Auren and Palmaer Abstr. 1902 ii 64; Brunner Abstr. 1904 ii 315 ; 1905 ii 235).-The investigation was undertaken with the object of determining how the properties of zinc on which its employ- ment for process blocks depend are modified by small amounts ofiNORGANIC CHEMISTRY. 27 cadmium and lead. The metal was used in the form of thin sheets rolled at 120O. The precautions taken to secure uniformity of com- position in the alloys are described. The rate of solution in acids was determined by measuring t h e hydrogen evolved and by finding the loss of weight of the plates; it was found in agreement with Spring (Abstr. 1888 WO) that the reaction velocity only attains its maximum value after some time (induction period).The rate at which zinc containing 0-1-0.8 per cent. of lead is dissolved by &/lo hydrochloric acid is lessened by the addition of cadmium up to 1 per cent. and the induction period is lengthened. On the other hand the rate of solution in 5 per cent. nitric acid is somewhat increased by addition of cadmium. Quantities of lead up to 2 per cent. (the limit of solubility of this metal in zinc) have no effect on the reaction velocity larger proportions lessen it considerably. These results find a simple explanation on the theory that the rate of solution is greatly influenced by local electric currents (compare Ericson-Auren and Palmaer Zoc. cit. ). When zinc and its cadmium alloys are heated at 270" for some time and then cooled they are attacked by acids rather more rapidly than samples which have been rolled at 120' ; this behaviour is connected with a change in the crystalline structure.per cent. of cadmium increases the hardness and breaking stress of zinc but when more than + per cent. of the former metal is present the opposite effect is produced. Photomicrographs of several of the alloys referred to are given in the paper. G. S. Addition of Determination of Atomic Weights of Rare Earths. OTTO BRILL (Zed. anorg. Chem. 1905 47 464-476. Compare Nernst and Riesenfeld Abstr. 1903 ii 57 l).-Further experinients on the rare earths have been made with Nernst's micro-balance by the method already described (Zoc. cit.). A method largely used in determining the atomic weights of rare earths is to convert the oxide into the corresponding normal sulphate or vice versd. According to Kruss (Abstr.1893 ii 283) acid sulphates are completely converted into normal sulphates by heating for some time a t 350'. To test this method oxides of several rare earths were evaporated with sulphuric acid small quantities of the resulting acid sulphates placed in the scale pan of the micro-balance and heated in an electric furnace for ten or fifteen minutes at temperatures increasing by intervals of 50° the weight being determined after each heating. A t 350° the weight did not remain constant so that as Wild has also pointed out (Abstr. 1904 ii 173) the temperature given by Kruss for conversion into the normal sulphate is too low. At 450° the conversion to normal sulphate was complete at 700" this began to decompose into basic sulphate the change being complete at 900'; at 1150° the latter was completely transformed into oxide. The basic sulphates of yttrium ytterbium erbium lanthanum and samarium thus prepared for the first time have the general formula M20,,S0 and occur in white needles From the order in which they decompose on heating the relative basic character of the oxides can be28 ABSTRACTS OF CHEMICAL PAPERS.determined ; from the weakest to the strongest base the order is Yb Er Y Sa La It is shown that atomic weights can readily be determined by heating a t 480' to form the normal sulphate then at 1150" for some minutes to form the oxide; the method is particularly useful for rapidly determining the atomic weights of fractions. G.S. Victorium and the Ultra-violet Phosphorescence of Gadolinium. GEORGES URBAIN (Compt. rend. 1905,141,954-958). -I€ the phosphorescent spectrum obtained by Crookes with different specimens of gadolinium (Abstr. 1899 ii 751; 1905 ii 250) is correctly ascribed to a new element victorium the intensity of the spectrum should be diminished by diluting the gadolinium. The author finds however that a mixture of 2.8 parts of gadolinium oxide and 97.2 parts of lime gives a phosphorescent spectrum in which the bands are very intense and similar results are obtained with mixtures of lime containing only 2/10,000 parts of gadolinium oxide ; it follows therefore that the phosphorescent spectrum given by gadolinium is a characteristic of that element itself.M. A. W. Preparation of Crystalline Crocoite and Wulfenite by the Action of Atmospheric Carbon Dioxide on Alkaline Solutions of the Lead Salts. G. CESBRO (Bull. Acad. my. Belg. 1905 327).-Many insoluble lead salts dissolve in a solution of potassium hydroxide and these solutions on slow neutralisation by atmospheric carbon dioxide deposit the lead salts in a crystalline form. Such a solution of lead chromate on exposure to the air for four months,. gave a red crystalline deposit which had the appearance and properties of crocoite. A solution of lead molybdate became turbid and blue but after some time gave a very dense grey granular powder with a metallic lustre formed of microscopic transparent tetragonal tablets F. G. C. S. Distillation of Copper.HENRI MOISSAN (Compt. mad. 1905 141 853-857. Compare Abstr. 1893 ii 507 ; 1904 ii 617; FBry Abstr. 1903 ii 293 ; KraEt and Bergfeld Abstr. 1905 ii 144).- Copper is readily distilled when heated in an electric furnace ; with a current of 300 amperes and 110 volts 77.7 per cent. of the metal is volatilised in eight minutes whilst with a current of 800 amperes and 110 volts several kilograms of copper can be distilled in a few minutes. The metallic distillate condenses on a copper cooler placed in the furnace in the form of iridescent filaments 5 to 7 mm. thick having a red to yellow colour a sp. gr. 8.16 (Kalhbaum Roth and Siedler found 8.932 Abstr. 1902 ii 259) and containing 99-76 per cent. of copper the impurities consisting of lime and graphite. The fused ingot of copper remaining in the crucible exhibits the phenomenon of '' spitting," on cooling evolving large quantities of gas and when quite cold is covered with a layer of graphite having a sp.gr. of 2-12 and consisting of 96.25 per cent. of carbon 3.36 per cent. of ash and 0.21 per ,cent. of hydrogen. A microscopicINORGANIC CHEMISTRY. 29 examination of a polished section of the ingot shows that it contains a large number of spherical cavities lined with brilliant crystals of graphite. M. A. W. Copper and Arsenic. K. FRIEDRICH (Metalltwgie 1905 2 477-.195).-The author has studied the alloys of copper and arsenic containing 0-44 per cent. of arsenic. Alloys richer in arsenic than this cannot be obtained under atmospheric pressure and the higher alloys lose most of their arsenic when heated for any length of time at 300'.The freezing-point curve shows a well-marked maximum at 70.88 per cent. As and 830° corresponding with the compound Cu3As and the existence of a compound Cu5Asq dissociating below its melting point is also indicated. Eutectic points occur at 78.5 60.6 and 52.5 per cent. of arsenic respectively the corresponding eutectic temperatures being 683' 71 lo and 603O. A transformation of unknown character was observed at 307'. The microscopic examination of sections etched with copper ammonium chloride or electrolytically in dilute nitric acid confirms the evidence of the freez- ing - poin t curve. The formation of Cu,As and CU~AS occurring in nature as algodonite and whitneyite respectively is not observed in melting together copper and arsenic and the existence of the compound Cu,As is also not confirmed.C. H. D. Commercial Guprosilicon. PAUL LEBEAU (Compt. qlend. 1905 141 889-891. Compare Vigouroux Abstr. 1896 ii 362 and Chalmot Abstr. 1896 ii 362)-A microscopical examination of the polished surface of commercial cuprosilicon shows that it contains large and small crystals of silicon embedded in a matrix of cuprosilicon ; when the uncombined silicon is removed by treatment with 10 per cent. sodium carbonate solution and the cuprosilicon dissolved in nitric acid a residue is left consisting of steel-grey crystals of ferrosilicon FeSi and these three constituents are present in the following proportions free silicon 51.11 cuprosilicon 49.97 ferrosilicon 3.49 per cent.The cuprosilicon contains 10.36 to 10.88 per cent. of silicon and has therefore the composition Cu,Si and not Cu,Si as stated by Vigouroux (Abstr. 1896 ii 362) and de Chalmot (Abstr. 1896 ii 362; 1897 ii 262). M. A. W. A Modification of Mercurous Chloride. JULIUS MEYER (Zeit. anorg. Chem. 1905 47 399-400).-When solutions of mercuric chloride and lithium sulphite are mixed the heavy white precipitate of ordinary calomel filtered off and the clear solution heated to 70-80" a new modification of mercurous chloride separates in lustrous scales. It has a sp. gr. 4.5-5 as compared with 6.5-7 for the ordinary salt ; it changes into the latter on sublimation. It shows no difference of potential when measured against ordinary mercurous chloride in a galvanic cell so that it does not seem t o be an allotropic modification of the latter. G.S.30 ABSTRACTS OF CHEMICAL PAPERS. Action of Silicon on Pure Aluminium and its Action on Impure Aluminium. Silicoaluminides. EMILE VIGOUROUX (Compt. rend. 1905 141 951-953).-Pure silicon and aluminium do not combine to form an aluminium silicide but when heated in the presence of the oxide or a salt of another metal a compound con- taining silicon aluminium and the metal or the silicoalurninide of the metal is formed. The silicoaluminides of iron nickel cobalt chromium manganese molybdenum tungsten vanadium uranium and titanium have been prepared; they are crystalline hard dense brittle and present a metallic appearance. A few are attacked by dilute acids with formation of silica but most of them resist the action of even concentrated acids with the exception of hydrofluoric acid and they are not attacked by solutions of alkali hydroxides. M.A. W. Physical and Chemical Properties of Slags. THOMAS TURNER (J. SOC. Chem. Id. 1905 24 1142-1147).-The classification of slags their physical properties the crystallisation melting points temperatures of formation and fluidity are discussed. Experiments have been undertaken to ascertain as far as possible the constitution of a typical slag A quantity of blast furnace slag weighing six tons was allowed to cool slowly and samples were taken from six positions chosen so as to represent the relative order of solidification. No evidence of the separation of calcium or aluminium silicates during the process of cooling is afforded by the analytical data for the various samples.The most noteworthy fact elucidated is that the last fluid portion which had a creamy-white colonr contained a distinctly smaller proportion of sulphur than the other samples. Apart from this elimination of sulphur from the liquid portion of the slowly cooling slag there is but little evidence of any alterationin composition. The proportion of aluminium is however highest in the parts which con- tain most sulphur and these parts have the most marked blue colour. This observation supports the view that the blua colour of the blast furnace slag is due to some form of aluminium oxysulphide. With regard to the relationship of magnesium and sulphur the sample richest in sulphur contained the smallest proportion of magnesium and vice versd.Cooling curves of the different samples were taken but these give no evidence of eutectics and do not permit of a distinction between the fluid plastic and solid states. Solidification extends over a wide temperature interval but very different values were obtained by different observers for the temperatures at which the process begins and ends. H. M. D. Volatility of Indium Oxide. JULIUS MEYER (Zed. anorg. Chern. 1905 47 281-286).-The determination of the atomic weight of indium by conversion into the oxide is inaccurate owing to the volatility of the latter at high temperatures. It is shown in the present paper however that the loss of weight on heating the oxide for several hours in a specially constructed platinum crucible at 1100" is inappreciable.I n the conversion of indium nitrate into oxide byINORGANIC CHEMISTRY. ignition a constant weight cannot be attained even a t l l O O o ; this seeins to be due to the obstinate retention of oxides of nitrogen by the oxide. The difficulty can be obviated to some extent by repeatedly treating the oxide with water and evaporating or by converting the nitrate into hydroxide with ammonia and subsequently igniting. G. S. Interaction of Hydrochloric Acid and Potassium Perman- ganate in the Presence of Various Inorganic Salts. JAMES BROWK (Zed. anory. Clzenz. 1905 47 314-330. Compare Abstr. 1905 ii 166).-Standard solutions of hydrochloric acid and of potassium permanganate were heated alone and with known amounts of various inorganic salts for a definite time at 50° a definite amount of standard oxalic acid was then added and standard permanganate run in until the red coloration was permanent.I n a former paper i t was shown that the greater amount of permanganate apparently reduced in the presence of ferric chloride is not due to the catalytic action of the salt as Wagner had supposed (Abstr. 1899 ii 275) but to oxidation of part of the oxalic acid by the chlorine evolved during the action. Corre- sponding experiments with the chlorides of cadmium chromium gold and platinum show n greater apparent reduction of permanganate in presence of these salts in agreement with Wagner but when the chlorine is removed by a current of air before adding the oxalic acid the apparent amount of reduction is not affected by the presence of cadmium and gold salts but is increased by chromium and platinum salts.The author draws the conclusion that the chlorides of the three metals first mentioned have no catalytic effect on the action the difference in tbe case of chromium being due to secondary reactions (partial oxidation to chromate) whereas platinic chloride acts as a catalyst. Since the observed differences in the majority of cases are due to the disturbing action of the evolved chlorine the latter must have less ef-fect in the presence of salts; no very satisfactory explanation of this has been found. Direct experiments show that after digestion there is less chlorine present in solutions containing salts than in the others but as no appreciable amount escapes into the air the suggestion is made that in the fqrnier case it is used up in some secondary reaction.The retarding effect of manganous salts on the reaction in question is probably due to the production of higher oxides of manganese in larger amount so that more oxalic acid is required for complete reduction. G. S. GEORGES CHARPY (Compt. rend. 1905 141 948-951).-Roozeboom's equilibrium diagrams for iron-carbon systems (Abstr. 1900 ii 728 ; 1904 ii 717) were based on the cooling curves for iron-carbon mixtures obtained by Roberts-Austen by allowing the fused mixtures to cool rapidly ; the author finds however that if in the case of mixtures containing from 2 to 4 per cent. of carbon the cooling is gradual the two main branches of the cooling curve represent respectively the separation of mixed crystals and of cementite; at 1150" (not 1050" as is usually stated) the eutectic product consisting of mixed crystals and cementite Equilibrium Diagram of Iron-carbon Alloys.32 ABSTRACTS OF CHEMICAL PAPERS solidifies and below that temperature cementite separates from the solid solution; whilst if the cooling is rapid the eutectic product which solidifies at 11 60-1 165" consists of mixed crystals and graphite mixed crystals or graphite separating above that temperature and graphite separating from the solid solution below that temperature.M. A. W. Compounds of Iron with Silicon. W. GUERTLER and GUSTAV TAMMANN (Zeit. anorg. Chern. 1905,47 163-1 79).-The authors have studied the freezing-point curve of alloys of iron and silicon and have confirmed the conclusions thus arrived at by microscopic observations and in some cases by chemical analysis.The curve falls rapidly from the freezing point of iron to a point at which 33 atom. per cent. of silicon is present; along this part of the curve mixed crystals of Fe and Fe,Si separate out in the form of cubes. The alloy containing 33 atom. per cent. silicon solidifies at a constant temperature like a pure xriatal and may be made up of saturated mixed crystals or may be a definite chemical compound of the formula Fe,Si; the latter view is the more probable since several previous investigators have isolated a compound of this formula by treating alloys poor in silicon with acids but no other case is known in which a chemical compound is the last member of a series of mixed crystals.Beyond this point the curve falls slightly until at 34.7 atom. per cent. silicon it reaches the eutectic point of mixtures of Fe,Si and a new compound FeSi at a temperature of 1235'. This descending part of the curve between 33-3 and 34.7 atom. per cent. silicon cannot be determined directly owing to the small. temperature difference (about So); its existence is deduced from the microscopic observation that the alloy containing 34.7 atom. per cent. silicon is a eutectic mixture. Beyond 34.7 per cent. silicon the curve rises to a well-defined maximum a t a temperature of 1443O when 50 atom. per cent of each element is present corresponding with the compound FeSi; along this part of the curve crystals of FeSi surrounded by masses of the eutectic mixture of Fe,Si and FeSi separate out. Beyond 50 atom.per cent. silicon the curve falls until a t 76 atom. per cent the eutectic point of FeSi and silicon is reached at a temperature of 1245"; it then rises to the melting point of silicon. Between 76 and 100 atom. per cent. silicon long crystals of this element surrounded by the eutectic Si,FeSi separate out. Hot potassium hydroxide rapidly attacks silicon slowly acts on FeSi and has practically no action on Fe,Si and iron. Hydrochloric acid on the other hand acts rapidly on iron slowly on Fe,Si and has scarcely any effect on FeSi and Si. These facts can be made use of in analysing the alloys. The hardness of these substances decreases with increasing percentage of iron. Alloys containing up to 47.5 atom.per cent silicon are magnetic whilst those containing more than 50 atom. per cent. are non-magnetic. The transition temperature of U- into /3-iron does not seem to be appreciably altered by the presence of silicon. G. S. Action of Silicon Chloride on Iron. EMILE VIGOUROUX (Cowpt rend. 1905 141 828-830).-Silicon tetrachloride is completelyINORGANIC CHEMISTRY. 33 decomposed by iron below a red heat or a t 1100' with the formation of the iron silicide Fe,Si and ferrous chloride according to the equation SiC1 + 4Fe = Fe,Si + 2FeC1,. Iron silicide Fe,Si is decomposed by chlorine with incandescence by concentrated hydrochloric acid or by aqua regia; it dissolves completely in dilute hydrofluoric acid and is not attacked by acetic or nitric acid (compare Moissan Abstr.1896 ii 173 ; Lebeau Abstr. 1900 ii 729 ; 1901 ii 317 ; and Jouve Abstr. 1902 ii 595). Attempts to prepare the higher silicide FeSi obtained by Frdmy (Em. Chirn. Art. Per.) by the action of silicon tetrachloride on iron were unsuccessful. M. A. W. The Composition of Colloidal Ferric Hydroxychloride in Relation to the Concentration of Hydrochloric Acid in the Containing Fluid. G. MALFITANO (Compt. rend. 1905 141 660-662 680-683. Compare Abstr. 1905 ii 459).-The colloid is obtained by heating a 0.5 per cent. solution of ferric chloride in an auto- clave at 100-1 15' for fifteen to thirty minutes; after dialysis and filtra- tion through collodion a solid colloidal residue is obtained. A washed preparation contained 1-57' per cent.Fe and 0.16 per cent. C1 and after dialysis a 0.01 per cent. solution of HCl. It is concluded that the amount of HCl separating depends on the quantity and composition of the colloid and is proportional t o the quantity of water and increases with rise of temperature hence the system H(Fe,O,H,),Cl tends to exist in equilibrium with the solution in which it is suspended. By the action of free hydrochloric acid on colloids of the type H(.Fe20,H6),Cl the value of n diminishes H( Fe,O,H,)Cl being the limiting value ; for instance 25 C.C. of a preparation containing (in millionths of a gram atom) 1654H(Fe20,H,),.,C1 + 76HC1 are filtered and heated with 200 C.C. containing 3464HC1 and after cooling and filtration analysis indicates 1828H( Fe,O,H,),.,,Cl + 3290HC1. From numerous similar experiments the author concludes that on increasing the concentration of HC1 the colloid approaches more nearly t o H(Fe,O,H,)Cl.When the colloid is once precipitated it may lose HCl even in a strongly acid-containing fluid. Two hundred C.C. of the colloidal solution were diluted to 1 litre containing 5 grams HC1 and heated at 130' in a Jena flask; on analysis of the total contents of the flask 13H(Pe,O,H,),,Cl+ 1016 Fe,Cl + 28456HC1 was obtained. When once the HC1 which was combined with the Fe,O,H reunites to form a molecule of HCI the stability of the compound disappears and in spite of the concentration of the solution the colloid loses HC1 and the ferric hydroxide is converted int.0 chloride. F. G. C. S. Vanadium Sesquisulphate. ARTHUR ST~HLER and HEINZ WIRTHWEIN (Ber. 1905 38 3978-3980.Compare Abstr. 1905 ii 595).-Varzadiursz hydrogen sulphute Vd,(SO,),,H,SO,,l 2H,O ob- tained by methods similar to those used for the corresponding titanium salt more especially by t h e electrolytic reduction of blue vanadyl sulphate is a green finely-crystalline silky powder and is VOL. XC. ii. 334 ABSTRACTS OF CHEMICAL PAPERS. insoluble in alcohol ether acetic acid or 60 per cent. sulphuric acid. I t s aqueous solution has a green colour. The ammonium salt Vd,(SO,),,( NH,),SO,,l 2H20 and rubidium salt have been prepared. Vanadium sesquasulphate Vd,(SO,) is obtained when the green salt is heated slowly at 180' in an atmosphere of carbon dioxide; it forms a microcrystalline powder and dissolves in hydrochloric acid t o a yellowish-brown or in dilute sulphuric acid to a green solution.J. J. S . Modifications of Antimony. ALFRED STOCK and WERNER SIEBERT (Bey. 1905 38 3837-3844).-R new black amorphous modification of antimony can be prepared either by the action of oxygen or of air on liquid antimony hydride a t about -40° or by rapid cooling of the vapour of ordinary metallic antimony. Special apparatus for these operations is described the last method consisting in distilling the metal from a porcelain tube heated electrically hy a platinum wire to about 3OOo in a good vacuum on to a surface cooled by liquid air. The black antimony has a sp. gr. 5.3 it is chemically more active than the grey form and oxidises and often catches fire in the air a t the ordinary temperature.At 400° it is converted instantly into the stable grey form and suffers the same change slowly on boiling with water ; it may be freed from antimony oxide by washing with hydrochloric acid. This has been so far prepared only in minute quantities either by the action of oxygen on antimony hydride a t - 90° or better by the interaction of antimony hgdride and chlorine dissolved in liquid ethane at - 100' in red light. The yellow modification is very unstable; it blackens above -90" even in the dark. On shaking yellow antimony with carbon disulphide at temperatures below - 50° a suspension of insoluble antimony in the colloidal state is obtained which above - 50" is in a few seconds changed into the black modification. Cohen's a-antimony is probably identical with the black antimony described above.E. F. A. Antimony also exists in a third-a yelIow modification. Melting Point of Gold and Expansion of Gases at High Temperatures. 111. ADRIEN JAQUEROD and F. Louis PERROT (Arch. Sci. phys. nat. 1905 [iv] 20 506-529).-The mean value for the melting point of gold in the authors' determinations was 1067.4' rt 1%". Previous determinations vary from 1061' to 1200" But the three most trustworthy values are 1064.3 (Holborn and Day) 1065.6" (D. Berthelot) and the authors' giving a mean of 1065.S0 or allowing a little more weight to the authors' value 1066' which they consider to be the vaIue which should be accepted for the melting point. From the experiments the relative values of the coefficients of expan- sion of the various gases employed between 0' and 1067.4' may be obtained and taking the value 0.0036643 for nitrogen the other values' are air 0,0036643 ; carbon monoxide 0.0036638 ; oxygen 0*0036652 ; carbon dioxide (1) 0*0036756 ; (2) 0.0036713 (see Abstr. 1905 ii 506 627). L. M. J.MINERALOGICAL CHEMISTRY. 35 Precipitation of Metallic #old. P. E. JAMESON (J. Amer. Chem. Xoc. 1905 27 1444).-By the following method gold can be rapidly precipitated in a convenient state for collection. A stick of potassium nitrite weighing about 5 grams is placed in a solution of 1 gram of gold chloride i n 30 C.C. of water and about 3 C.C. of con- centrated sulphuric acid are added immediately. When the reaction has ceased another piece of potassium nitrite of the same size is added and the sohiion is stirred until a clear pale blue solution is obtained. The precipitated gold collects a t the bottom of the vessel in the form of dark brown nodules which can be easily separated by decantation. E. G. Hydrated Palladium Dioxide. ITALO BELLUCCI (Zeit. a~zorg. Chem 1905 47 287-288).-A reply to Wohler and Konig’s criticism (Abstr. 1905 ii 722) regarding the author’s statements as to the composition of hydrated palladium dioxide (Gaxxefta 1905 35 i 343). G. S.

ISSN:0368-1769    

DOI:10.1039/CA9069005015

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Miner a 1 ogi c a1 C h emi stry 35 [Cubanite as a Furnace Product.] WILLIAM P. HEADDEN (Proc. Colorndo Xci. Xoc. 1905 8 39-44).-An incrnst.ation formed on an iron rabble plate of a McDougall furnace used for roasting pyritous copper ore a t Anaconda Montana showed three more or less distinct layers. The two inner layers consisted mainly of ferrous sulphide; the material of the outer layer has a bronze-yellow colour and conchoidal fracture and in composition approximates to cubanite C uFe,S,. L. J. 8. Abstraction of Oxygen from the Atmosphere by Iron. CHARLEB HENRY SMYTH jun. (J. Geol. 1905 13 319-323).-The disintegration and weathering of crystalline rocks is accompanied by the oxidation of ferrous iron to ferric iron. An attempt is made t o calculate the amount of oxygen abstracted from the atmosphere by this process during geological time.The average compositions of crystalline rocks (F. W. Clarke Abstr. 1904 ii 669) and of shales and sandstones give the following data Original crust FeO Fe,O = 1 0.75. Sediments ?? = 1 1.75. Taking Joly’s estimate of the mass of siliceous sediments as 64 x 1016 tons there must have been a total of 835x 1 O I 2 tons of oxygen absorbed by iron or 68.8 per cent. of that now present in the atmos- phere. L. J. S. Pseudomorphs of Osteolite after Calcite Grystallised Staffelite. ARTHUR SCHWANTKE (Centr. Min. 1905 641-646).- With other alteration products in a weathered basalt a t Prausnitz in 3-236 ABSTRACTS OF CHEMICAL PAPERS. Silesia are white compact masses of osteolite embedded in which are acute scalenohedral crystals with the composition -P,O 35-90 ; CO 5-85 ; CaO 53.30 = 95.05 ; the latter are pseudomorphs of osteolite after calcite.The published analyses of osteolite and staffelite are quoted and compared. Both these minerals differ from apatite in containing calcium carbonate in addition to phosphate; some fluorine is present in staffelite but none in osteolite. On a specimen of staffelite from the original locality Staff el in Hesse-Nassau were noticed some small pale green transparent crystals with the form of apatite which were found to contain carbon dioxide. Neither in the crystals nor in the botryoidal masses of typical staffelite are there any enclosures of calcite ; the carbon dioxide must therefore enter into the composition of the mineral.Staffelite and osteolite are probably identical the latter being an impure and altered variety of the former. L. J. S. Formation of Oceanic Salt Deposits. The Occurrence of Calcium Compounds up to 25'. JACOBUS H. VAN'T HOFF (Zeit. anorg. Chem. 1905 47 244-280).-A summary of work already published (see Abstr. 1904 ii 34 417 492 561 ; 1905 ii 319 464 641). G. S. Formation of Oceanic Salt Deposits. XLIV. Limit of Existence of Tachhydrite at 83'. JACOBUS H. VAN'T HOFF and J. D'ANS (Sitxwngsber. K . Akacl. Wiss. Berlin 1905 913-916. Compare van't Hoff and Lichtenstein Abstr. 1905 ii 262 641).- The diagram representing the conditions of separation of the various calcium compounds which play a part in the formation of oceanic deposiis assumes a simpler character as the temperature rises.Solubility data are recorded for the temperature of 83' above which tachhydrite CaC12,2MgCI,11ZH,0 is incapable of existence. These are contained in the following table the numbers expressing mols. of salt per 1000 mols. of water Saturation with respect t o sodium chloride and CnCI,. MgCI,. K,CI,. Calcium chloride (CaC1,,2H20! ........................ 239 0 0 Calcium chloride potassium chloride ................. 249 0 11 Calcium chloride tachhydrite .......................... 239 - 0 Calcium chloride tachhydrite carnallite ............ 239 - Tachhydrite magnesium chloride ..................... 141 45.5 0 Tachhydrite magnesium chloride carnallite ......... 141 45.5 - Calcium chloride potassium chloride carnallite ...216 27 10'5 - Na,C12. 0 3 0 *5 0.5 0.5 0 -5 0 5 0 5 H. M. D. Geological Thermometer. JACOBUS H. VAN'T HOFF (Zeit. EZektrochem. 1905 11 709-710).-The temperature at which deposits of salts such as those of Stassfurt have been formed may be inferred from the properties of the salts themselves. In general salts containing less water are formed at higher temperatures and they are able at the ordinary temperature to take up water. Glauberite CaNa,(SO,) for example combines with water and the compound melts at 29". The melting point is depressed by other salts. TheMINERALOGICAL CHEMISTRY. 37 following are the lowest temperatures at which the salts named can exist in presence of the other salts occurring with them blodite 5"; glauberite 10" ; hexahydrated magnesium sulphate 13' ; thenardite 1 4 O ; kieserite 18' ; kaliblodite 18" ; octahedral borax 34" ; langbeinite 3 7 O ; loweite 43'; van't-Hofite 46".A more accurate estimate of the temperatures at which the salts were deposited is obtained by examining the salts which can be deposited simultaneously a t a given temperature. I n this way it is shown that the following salts must have been deposited at temperatures above those given glauberite loo; langbeinite 37' ; loweite 43" ; van't-Hoffite 46'; loweite and glaserite 57' ; loweite and van't-Hoffite 60" ; kieserite and potassium chloride 7 2 O . The last appears to have been the highest temperature reached during the formation of the Stassfurt deposits. T. E. Composition of Xenotime. WALDEMAR C. BROGGER (Nyt Xag.Naturuid. Christiania 1904 42 1-'7).-Kraus and Reitinger (Abstr. 1901 ii 395) have considered xenotime (YPO,) to be an altered form of hussakite (3R20,,3P,O,,SO,). The perfectly fresh crystals of brown transparent xenotime from Aro in Norway analysed by Blom- strand in 1890 have been examined for sulphur trioxide by 0. Heidenreich but not a trace was detected. By the replacement of part of the phosphoric oxide by small and variable amounts of sulphur trioxide it appears that there may be a passage from true xenotime (YPO,) to the hussakite variety (compare Abstr. 1903 ii 553). L. J. S. [Columbite Fibroferrite Enargite Alunogen Doughtyite &c.] WILLIAM P. HEADDEN (f'roc. Colorccdo Sci. ~oc. 1906 8 55 -7O).-CoZumbite.-Analysis I is of columbite occurring as large masses with tourmaline in pegmatite a t Canon City Colorado.Analysis I1 is of similar material from Black Hills South Dakota Cb,O,. Tn,O,. WO,. SnO,. FeO. MnO. Ignition Total. Sp. gr. I 56.48 22'12 0.45 0'11 8-07 12-45 0.15 99.83 5.66 IT. 54.64 25'62 - 0.15 6'80 12'61 - 99'82 5.91 Fibroferrite.-Aggregates of greenish-white acicular crystals from Green River Utah gave the results under 111 agreeing with the formula Fe,O,,ZSO 1 OH,O so,. Fe,O,. Ca0,MgO. Na,O. H,O. Insol. Total. 111. 31-57 30'22 traces 0.59 37'06 0.10 99-54 Enwgite.-The ore at the Powers Mine Willis Gulch Gilpin Co. Colorado consists mainly of crystalline enargite (analysis IV) associated with some pyrites and chalcopyrite. Crystals are encrusted with quartz. Although lead is shown in the analysis no lead mineral was detected on the specimens S.As. Sb. Cu. Pb. Fe. Zn. Total. Sp. gr. IT. 29-35 16-17 3.77 48'40 1.83 0.30 0.19 100*01 4-4338 ABSTRACTS OF CHEMICAL PAPERS. AZzcnogen.-This occurs as large incrusting masses sometimes several hundred pounds in weight on sandstones and shales a t Doughty Springs and Alum Gulch in Delta Co. Colorado. Analysis V is of massive material (21.30 per cent. of material insoluble in water deducted); VI and VII of scaly material; VIII and IX of fibrous material. I n their content of magnesia some of these analyses show an approach to pickeringerite Insol. in SO,. AI,O,. Fe20,. CsO. MgO. Na,O. K,O. Li,O. H,O. H,O. Total. V.* 37-15 15-68 trace 0.40 0.74 trace - - 45.81 - 100'00 VI. 37'12 13.53 trace trace 2-90 1-25 0.17 trace 44.84 0.14 99-95 VII.39'18 14.17 trace 0.09 1.94 not determined 43-07 0.71 99'16 VIII. 38'90 12-51 trace trace 3.35 not determined 41-98 2-76 99'48 IX. 37'26 15-08 1-19 trace nil I:ot determined 44-84 1-37 99.74 X.? 15.00 39.51 0'45 - trace - - - 41'80 1-56 loo%? v * Also SiO (soluble in water) 0'22. .1. Also SiO 1.91 ; ZnO 0'44. Doughtyite.-This name is given tentatively to a hydrated basic aluminium sulphate which is formed abundantly as a white precipitate by the interaction of the waters (an alkaline water and one containing aluminium sulphate in solution) of the Doughty Springs Delta Co. Colorado. An air-dried sample gave results (analysis X) correspond- ing with the formula Al2(SOq),,5A1,(OH),,21H2O. Bismuthite.-Analysis ,is given of an ore sample from the Paulina Mine Nocozari Mexico consisting of an intimate mixture of bismuth- ite (Bi,S,) and micaceous hsmatite.Palladium-Description is given of a soft black material con- taining palladium 11.86 ; copper 60.21 per cent It is an artificial product of unknown origin but may possibly have been obtained from Wyoming platinum ore. L. J. S. Minerals [Stilbite Chabaeite &c.] from Gellivare Sweden. A. BYGD~N (BUZZ. Geol. Inst. Univ. Upsda 1905,6 (1902-3) 92-1 00). -In the Selets Mine at Gellivare the iron-ore is separated from the surrounding granulitic gneiss by a brecciated zone consisting of blocks of gneiss and ore embedded in a coarsely crystalline mixture of horn- blende magnetite red felspar and sometimes quartz. Cavities in this binding material contain zeolites.Analysis I is of stilbite and corresponds with the formula 2R0,ZA1203,1 3Si02,14H,0. Chabazite gave the results under I1 and 111 corresponding with the formulae R0,A1203,4Si0,,6H,0 and 2RO72A1,0,,9Si0,,1 3H20 respectively. These zeolites are often attached to a red mineral occurring as com- pact masses and as square columns which has the composition given under IV (also trace of chlorine); it is a pseudomorph of felspar (orthoclase and plagioclase) after scapolite. A crevice in the brecciated granulite of the Oskar Mine is filled with a soft soapy material which is either pale green to red (anal. V) or dark grey to violet-brown (anal. VI) in colour the two kinds being sharply separated. When dried in the air the material hardens and cracks and the air-dried material crumbles when placed in water.PHYSIOLOGICAL CHEMISTRY.39 The substance approximates t o celadonite in composition but is probably not homogeneous SiO,. A1,0,. Fe,O,.FeO. MgO. CaO. SrO. Na20.K,0. H,O. Total. Sp. gr. I. 58-22 14'68 0'22 - 0.11 7.66 - 0.51 0'44 18'22 100'06 2'14 11. 47-39 18'66 0.20 - 0.29 8'34 0.96 0'44 2.27 21.85 100'30 - 111. 49-57 17-21 0.49 - 0-46 7-74 0.61 0'30 2.27 21*15 100*10 2-09 V. 50'58 19'02 - 1.71 4.54 1'40 - 0.25 0.08 22.72 100.33 2'11 IV. 64-18 20.11 0.75 - 0.11 1.07 - 8.97 4'04 0.78 100.01 2'63-2.67 VI. 38'25 14.18 18.10 2.53 7.23 1'69 - 0.35 0.15 17.61 100.09 2.31 L. J. S. Diffusion of Barium and Strontium in Sedimentary Rocks. L. COLLOT (Compt. rend. 1905 141 832-834).-The occurrences of barytes and celestite in the sedimentary rocks of France are enumer- ated ; they are mostly in Jurassic and Cretaceous strata but celestite is found in the '' plastic clay " and green marl of Tertiary age in the Paris basin. The minerals occur as crystals lining the cavities of fossil shells and also as nodular concretions; in the latter case the barytes is sometimes partly replaced by calcite giving rise to forms which have been erroneously described as organic remains. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9069005035

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. 39 Physiological Chemistry The Feeding of the Frog’s Heart. J. MCGUIRE (Zeit. Biol. 1905 47 289-31 1).-Experiments are recorded on the isolated heart of the frog which relate to facts previously known to most physiologists ; for instance that a mixture of salt solution and blood will keep the heart beating that laked blood is toxic that potassium chloride is poisonous that carbon dioxide paralyses and that temperature and season have an influence. Bowditch’s staircase phenomenon is. due to accumulation of carbon dioxide in the resting heart and the im- provement is due to a gradual removal of that gas with successive beats; no reference is made to Waller’s theory that the phenomenon is due to the favouring action of small amounts of the same gas developed during activity.Serum which most observers find is intensely toxic is here spoken of as nutritive even when deprived of all oxygen in a vacuum. W. D. H. The Action of Carbon Dioxide on the Frog’s Heart. R. H. SALTET (Zeit. Biol. 1905 47 312-322).-This paper deals particu- larly with details of the harmful action of carbon dioxide on the heart. During action the output of the gas is not much increased as compared with the resting condition. The view advanced concerning the stair- case phenomenon is the same as in the preceding paper. It is assumed throughout that serum albumin is the main nutritive material for40 ABSTRACTS OF CHEMICAL PAPERS. cardiac and other muscle and carbon dioxide is stated t o be harmful because it renders this proteid not capable of utilisation.W. D. H. Action of Nutritive Fluids on the Heart. BERTHA FINN (Zeit. &ole 1905,47 323-334)-A somewhat similar series of observations and conclusions. Ringer’s solution is regarded as merely preservative and not nutrit,ive in any sense. W. D. H. Respiration of the Heart of Turtle and Frog. JULIA DIVINE (Zeit. Biol. 1905 47 335-378).-Another paper of the same series dealing especially with the reducing action the heart has on oxy ht-emoglobin. W. D. H. Loss of Function and Recovery of the Central Nervous System in Frogs. JULIUS RIES (Zeit. Biol. 1905 47 379-399).- The functions of the central nervous system are lost on cessation of the blood supply. No recovery occurs on subsequent perfusion with any saline solution unless mixed with protsid matter preferably obtained from serum.This and the foregoing four papers are all written with the apparent object of upholding Kronecker’s theory on t’he im- portance of serum albumin for the maintenance of the nutrition of tissues particularly those which are contractile. [No reference is made to the experiments of Locke and others which have led to a contrary conclusion.] W. D. H. Glycolysis. LEO RAPOPORT (Chem. Centr. 1905 ii 1371 ; from Zeit. Klin. Med. 5’7 208-214).-A consideration of the action of various tissues on sugar leads to the conclusion that glycolysis is due t o ferment action. W. D. H. Action of Radium Rays on the Peripheral Nerves. ADOLF BECK (BUZZ. Acad. Sci. Cracow 1906 286-289).-The author applied a box containing 10 mg. of radium bromide to the skin covering an ending of the sciatic nerve of rabbits ; in eight out of thirteen rabbits sensibility of the foot to an induction current disappeared entirely and in the remaining rabbits was diminished.No definite change in sensibility could be observed on a second application. The action of such small quantities of radium must be confined to the peripheral nerves as only the foot was affected. Little or no diminution of sensibility was observed on applying radium rays to the sciatic nerve- endings of dogs. The sensibility of the sensory nerve-endings of men was in some cases slightly increased in others slightly decreased on application of radium rays to the ulnar nerve. G. Y. Excretion of Creatinine in Man. CORNELIS A. PEKELHARING C. J. C. HOOGENHUYZE and H.VERPLOEGH (Proc. K. Akad. Wetensch. Amsterdam 1905 8 363-377).-The experiments recorded confirm Folin’s views (hbstr. 1905 ii 183 268) on the r8Ze creatinine plays in metabolism. The slight variations noticeable in the daily outputPHYSIOLOGICAL CHEMISTRY. 41 can be largely explained by the amount of creatine and creatinine in the food. The special point investigated was the influence of muscular work on the excretion. This is found to have no influence when the diet is sufficient. Creatinine is not therefore a result of energy pro- duction Only if the food given is not sufficient does an increased output of creatinine appear; that is in these circumstances the material wanted for contraction is drawn from the muscular proteids. W. D. H. Effects of Choline on Animals.E. FARQUHAR BUZZARD and RJCHARD W. ALLEN (Rev. Neurol. Psychiatry 1905 453 -461).-The repeated introduction of small doses of choline into the circulating fluids of rats and rabbits does not produce any important morbid changes in the nervous system or viscera and during life no con- vulsions or paralysis are seen. Large doses (greatly in excess of what can be produced in man by degenerative nervous diseases) lead to convulsive attacks. It is improbable that the convulsions of general paralysis or of epilepsy are due directly or solely to the presence of choline in the blood or cerebrospinal fluid (confirmatory of Mott and Halliburton but against the conclusions of Donath). W. D. H. The Pharmacology of Indaconitine and Bikhaconitine. J. THEODORE CASH and WYNDHAM R.DUNSTAN (Proc. Roy. Soc. 1905 B '7S 468-490. Compare Dunstan and Andrews Trans. 1905 8'7 1620 1636).-Indaconitine an alkaloid obtained from Aconitum chas- manthum yields on partial hydrolysis acetic acid and benzoyl-pseud- aconine; the latter substance splits up on further hydrolysis into benzoic acid and pseudaconine. Bikhaconitine from A . spicatum (A. feroa var. spicutunz) yields under the same conditions acetic acid veratric acid and a pseudaconine identical with that obtained from indaconitine. As regards physiological action these two alkaloids show a qualita- tive agreement with aconitine japaconitine and pseudaconitine dealt with in previous papers (compare Abstr. 1899 ii 42 ; 1901 ii 613). Bikhaconitine has a more powerful toxic action on cats and rabbits than indaconitine ; of the alkaloids so far examined aconitine and indaconitine are about equally poisonous japaconitine is rather more active than these but not quite so toxic as bikhaconitine whilst paeudaconitine is the most active of the series.Bikhaconitine and indaconitine are equally toxic towards frogs. The greater toxic action of bikhaconitine towards warm-blooded animals is due to its more powerful depressing effect on the respiration ; the respiratory activity of frogs is also diminished to a greater extent by the former alkaloid. The relative activity of the two alkaloids in abolishing the power possessed by nerve-muscle preparations of responding to stimuli was investigated by immersing the tissues in dilute solutions of the hydro- bromides and it was found that in this respect indaconitine is slightly more active than bikhaconitine. The pseudaconines obtained from the two alkaloids appear to be identical in physiological action and behave in all respects like the aconine from aconitine described in a former paper. G. S.42 ABSTRACTS OF CHEMICAI PAPERS. Are Toxins Ferments 3 LEO VON LIEBERMANN (Chem. Centv. 1905 ii 1370-1371 ; from Deutsch. med. Woch. 31 No. 33. Com- pare Abstr. 1904 ii 474).-From the consideration of the quantitative relationships of such toxins as abrin and ricin the conclusion is reached that the question in the title must be answered in the negative. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9069005039

出版商:RSC    

年代:1906

数据来源: RSC

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42 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Methane as Carbon-food and Source of Energy for Bacteria. N.L. SOHNGEN (Proc. K. Akad. Vetensch. Arnsterdcm 1905,8,327-331). -The fact that methane which is produced in enormous quantities in nature and is chemically so inactive occurs only in traces in the atmosphere led the author to search for living organisms capable of feeding on this hydrocarbon. These mere discovered in short rod-like bacteria provisionally called Bacillus nzethanicus which form as a slimy pink film on the surface of a culture-liquid (water 100 calcium sulphate 0.01 ammonium chloride 0.1 0 magnesium ammonium phos- phate 0.05 potassium hydrogen phosphate 0.05) impregnated with garden-soil sewage or canal-water and placed in an atmosphere of methane and oxygen a t about 30'.The methane is nearly all absorbed in a week and the presence of organic matter in the culture-liquid can be shown by oxidation with standard potassium permangsnate. A pure culture of B. methanicus is obtained by growing it on washed agar containing the necessary salts at about 30' in an atmosphere consisting of one-third methane and two-thirds oxygen. c. s. Similarity in the Action of Salts of Copper Mercury and Silver on the Lower Plants. THOMAS BOKORNY (Chenz. Zeit. 1905 29 1201-1202).-Algp are killed by salts of copper mercury and silver at dilutions of 1 in 1,000,000; all other metals require to be in much more concentrated solution to exert a .harmful effect. The germicidal action of ferrous sulphate is attributed to traces of copper sulphnte present in this substance as an impurity. P.H. Influence of Formaldehyde on the Energy of Increase the Fermentation Energy and the Duration of Generation of Different Varieties of Yeast. JULIUS HIXSCH (Chem. Centr. 1905 ii 1377-1378 ; from Allgem. Zeit. Bierbrau. J4aZxfubr. 1905).- Aldehyde stimulated the energy of incease in nearly every case. The fermentation maximum was generally reached only when the energy of increase had considerably diminished. Formaldehyde does not hinder the separation of invertin. N. H. J. M. Fermentation Process with Colophony. JEAN EFFRONT (Chem. Centr. 1905 ii 1377 ; from Mon. sci. [iv] 19 ii 721-722). -Abietic acid and colophony free from volatile acids are favourableVEGETABLE PHYSIOLOGY AND AGRICULTURE.43 to the development of the organism. I n a solution containing many yeast cells and few lactic acid bacteria the colophony settles more on the relatively greater surface of the rods than on the yeast cells and so assists the yeast in its struggle with the bacteria. I n practice an alkaline solution of colophony is added after in- troducing the yeast into the mash; very pure fermentations result and the sterilisation of the mash the addition of acid and the employment of large amounts of yeast are unnecessary. N. H. J. M. Effect of a Drug on a Simple Vital Process. HEINRICH DRESER (Zeit. Elektroclient. 1905 11 739-741).-The effect of sodium salicylate on the rate of evolution of carbon dioxide by yeast cells is studied. A small addition of sodium salicylate increases the rate further quantities produce a rapid diminution in it whilst for very large quantities the rate tends asymptotically towards a value greater than zero.The middle part of the curve can be represented by the assumption that a small addition of sodium salicylate dx produces a proportional increase dy in the rate of evolution of carbon dioxide which is proportional to the quantity of salicylate x already present or - l/y dy/dx = K.x. By putting ( x - b ) in place of x in this equation it is made t o fit the first part of the curve also. It appears probable that a part of the salicylate is absorbed by the yeast cells and becomes inactive; the constant b would represent this absorbed part. The fact that the curve does not tend towards zero as the quantity of salicylate is increased is probably due to the superposition of another phenomenon. The evolution of carbon dioxide by Buchner's enzyme is not aEected by sodium salicylate and a small residual evolution of gas will therefore be observed after all the living yeast cells have been poisoned.T. E. Assimilation of Carbon Dioxide. WALTHER LOB (Zeit. Elektro- chem. 1905 11 145-'752).-The author has attempted t o build up a sugar from carbon dioxide and water using the silent electric dis- charge in place of the natural combination of sunlight and a catalyst. The apparatus was arranged in such a way that the products formed were removed from the action of the discharge as quickly as possible. Moist carbon dioxide yields carbon monoxide and oxygen first formic acid and hydrogen peroxide are formed slowly as secondary products.I n moist carbon monoxide the main reactions are CO + H = CH,O (formaldehyde) and CO + H20 = CO + H2. Formic acid is also produced. A moist mixture of carbon dioxide and hydrogen gives formaldehyde and formic acid. Carbon monoxide and hydrogen give the same products ; the formaldehyde is however present in much larger quantity and considerable quantities of carbon dioxide are formed. When the discharge is passed through moist carbon dioxide in presence of a substance which absorbs oxygen formaldehyde and formic acid are produced in much larger quantity. Chlorophyll itself may be used as the oxygen absorber.44 ABSTRACTS OF CHEMICAL PAPERS. Moist formaldehyde vapour decomposes mainly into carbon monoxide and hydrogen but small quantities of methane are also formed Formic acid and water vapour behave similarly.From methane and carbon dioxide it is almost certain that alcohol can be synthesised and alcohol is very probably one of the intermediate products of the natural synthesis. Moist alcohol vapour alone gives a mixture of hydrocarbons carbon monoxide hydrogen and a little carbon dioxide from which further secondary products are produced. I n presence of carbon dioxide however these reactions become of secondary import- ance the main change leading to the formation of a sugar. The substance is optically inactive it reduces Pehling's solution and yields a crystalline osazone which melts at 160-164' and decomposes about 180". T.E. CH20 + ZH = CH + H20. Assimilation by Plants during Different Periods of Growth. HERMANN WILFARTH HERMANN ROMER and GUSTAV WIMMER (Landw. 'Vkrsuchs-Stat. 1905,63 1-70).-Whilst barley summer wheat peas and mustard assimilated most of their nutritive substances by the time of flowering the maximum was reached in the case of potatoes only at harvest time. With the exception of phosphoric acid more or less of the mineral constituents assimilated by barley summer wheat peas and mustard return to the soil during the ripening period. With potatoes there was no return of mineral constituents to the soil. The amount of starch increased in all the plants (except mustard) up to the ripening period. I n mustard seed the starch is replaced by fat. N. H. J. M Influence of Nutrients on the Development of Leguminous Nodules.HENRI FLAMAND (Eied. Centr. 1905 34 738-740 ; from Ing. ugric. Gembloux 1904 14 755).-Water-culture experi- ments with peas vetches and beans were made to ascertain the effect of different salts on the symbiosis as indicated by the production of nodules. The plants were inoculated from corresponding nodules when three weeks old. Potassium nitrate (1 10,000) prevented the production of nodules with sodium nitrate a larger amount (1 2000) was necessary. Peptone has only slight effect and urea no action a t all; oxamide is injurious. Potassium phosphate is more beneficial than the chloride and sulphate in the case of vetches and peas. With beans the latter salts are more baneficial. Calcium and magnesium salts are very favour- able in the case of peas and beans but some of the salts hinder the production of nodules on the roots of vetches ; only calcium sulphate is beneficial with vetches.N H. J. M. Chemotaxis of Equisetum Spermatozoids. BENGT LIDFORSS (Chern. Centr. 1905 ii 1270-1271 ; from Ber. deut. bot. Ges. 23 314-316).-The specific irritant for the spermatozoids of Equiseturn (arvense and palustre) is malic acid. The acid potassium and calciumVEGETABLE PHYSIOLOGY AND AGRICULTURE. 45 salts behave similarly to the normal malates and have a poisonous action. Free malic acid (1/1000 mol.) has a strongly attractive action whilst with stronger solutions the action is reversed. Salts of maleic acid have also a strongly attractive action. Fumaric acid and its salts have no action.N. H. J. M. Oxidising and Reducing Properties of Living Cells. I. Oxidising Power of the Absorbent Surfaces of the Roots of Flowering Plants. Af. RACIBORSKI (BUZZ. Acad. Sci. Cracow 1905 338-346).-The oxidising power of the absorbent surfaces of the roots of flowering plants in presence of atmospheric oxygen is demonstrated (1) by growing the plants in solutions of substances which when sufficiently diluted do not affect the life of the root cells and on oxidation yield coloured products either directly or on subse- quent addition of a suitable reagent or (2) by placing the sterilised germinating seeds on moistaned indicator-paper prepared from such oxidisable substances. The most suitable indicators are a-naphthyl- amine benzidine phenolphthalin and ferrous ammonium sulphate.The following substances also are oxidised Barbadoes aloes guaiacum resin phloridzin caff etannic acid pyrogallol leucomethylene-blue ursol and tetramethyl-p-phenylenediamine. I n no case was the oxidising power sufficient to liberate iodine from hydrogen iodide or its salts. I n the absence of atmospheric oxygen the oxidation of a-naphthylamine benzidine or phenolphthalin takes place slowly and to only a small extent. The oxidising power which is a function of the living cells is strictly localised being confined to the absorbent surfaces of the roots and being strongest in the region of the root hairs. G . Y. Root Secretions. DMITRI N. PRIANISCHNIKOFF (Biecl. Centr. 1905 34 741-743; from Bey. dezct. bot. Ges. 1904 22 lS4).- Millet grown in sand was found to assimilate the phosphoric acid of aluminium phosphate both dried a t 100' and ignited and of iron phosphate when merely dried but only small amounts when ignited.Similar results were obtained with vetches and mustard whilst lupins utilised ignited iron phosphate. Rye and wheat failed to develop when supplied with crude phos- phates whilst lupins produced nearly as much growth with crude phosphate as with bone phosphate. If the different behaviour of gramineous plants and lupins towards sparingly soluble phosphates can be shown to be proportional to the production of carbon dioxide by root respiration it would lend support to the assumption that the dissolving action of roots is due to carbon dioxide alone without intervention of free organic acids. N.H. J. 1111. The Preaence of Sucrose in Scammony Root. The Presence of Sucrose in the Fresh Scammony Root. PAUL REQUIER (J. Pharrn. Chim. 1905 [vi] 22 435-4325 492-494).- The dextrorotatory sugar present in the mother liquors from which crude scammonin has been precipitated (compare Abstr. 1904 i 90s)46 ABSTRACTS OF CHEMICAL PAPERS. is sucrose which in the form of barium sucrate can be separated from the other compounds present and obtained in a crystalline form by decomposing the barium compound with carbon dioxide and recrystal- lising from alcohol. One hundred grams of the dry scammony root contain 3.36 grams of sucrose. The fresh roots of scammony contain 1.872 per cent. of sucrose which is equivalent to 6.S02 per cent. of the dried root since the fresh roots lose 72.45 per cent.on drying at 105'. M. A. W. Malt Diastase. ANDREAS KLEEMANN (Lundw. Yersuchs-Stut. 1905 63 93-134).-For each kind of barley there is a definite amount of water in presence of which the greatest amount of diastase is formed. It depends however how the amount of water is added and taken up. The losses of substances due to respiration are greater the greater the amount of water absorbed during the softening and germination of the grain. The production of diastase cannot be followed with sufficient certainty by the methods hitherto available. The method employed in these experiments and found to be satisfactory is described. N. H. J. M. Effect of Improving Grapes on their Composition. G. CURYEL (Bied. Centr. 1905 34 743-744; from D.Weinluube 1904 573). -The juice of improved grapes contains more acid more sugar and more nitrogenous matter but less solid constituents especially phosphoric acid less tannin and less colour than the original grapes. N. H-. J. M. Marsh Soils. F. SCHUCHT (.I Landw. 1905 53 309-32S).- Analyses of soils from the marshes of the North Sea and especially from the mouth of the Weser (compare Zeits. ,Vc6turw. 1903 '76). N. H. J. M. Nitrogen Decompositions in the Soil. F. LOHNIS (Centr. Bakt. Par. 1905 ii 15 430-435).-The nitrogen of calcium cyanamide was very quickly converted into ammonia in April and May and its effect on the crop resembled that of ammonium salts. As regards the decomposition of bone-meal i t was found that Bacillus mycoides and Bacterium vulgare converted 39 and 28 per cent. of the total nitrogen into ammonia in three weeks.N. H. J. M. Development and Distribution of Nitrates and Total Water-soluble Salts in Field Soils. F. H. KING J. A. JEFFERY and A. R. WHITSON (20th Ann. Rep. Agr. Zxper. Stat. Univ. Wisconsin for 1902-1903 339-344).-1n soils growing maize and potatoes the nitrates in the surface soil (to one foot) increased from April to June after which owing to rapid growth and perhaps t o heavy rains as well there was a falling off. The amount of nitrates in the second foot was much less. I n a dry season the nitrates have a tendency to accuniulate near the surface. Determinations made from November 29 to April 1 showed in everyVEGETABLE PHYSIOLOGY AND AGRICULTURE. 47 case except one that the soil did not contain more nitrate a t the end of the frost than a t the end of the autumn just before the frost. Plants growing in rich soil were found to contain considerable amounts of nitrates especially the lower parts of maize stems and the vines of potatoes. Influence of the Soil on the Proteid Contents of Crops.A. R. WHITSON F. J. WELLS and A. VIVIAN (20th Awn. Rep. Agr. Expep. Stat. Univ. TVisconsin 1902-1903 345).-Pot experiments with oats maize and rape showed that the percentage of proteid increased with the amount of nitrate supplied. RICHARD HORNBERGER (Bied. Centr. 1905 34 726-727 ; from Zeit. Forst. Jagdwes. 1905 37 71. Compare Henry Abstr. 1905 ii 11 I).-After exposing leaves (oak beech acacia) and fir needles for a year to sir and rain in zinc boxes it was found that a gain of nitrogen equal to only 0.3 to 0.4 kilo- gram per hectare had taken place in two cases and that in three cases there was a far greater loss of nitrogen.Calcium Cyanamide. CONRAD VON SEELHORST and ALOYS MUTHER (J. Lumdw. 1905 53 329-356).-The results of pot experiments showed that calcium cyanamide applied to a sandy loam had a manurial value a t least equal to ammonium sulphate. Good results were also obtained with a loam. I n sand-cultures and possibIy in the case of soils very deficient in fine soil calcium cyanamide is injurious to vegetation. The poisonous action is attributed partly t o the presence of calcium carbide and partly to changes in the nitrogen of the calcium cyanamide. Addition of iron oxide to sand prevents the injurious action of calcium cyanamide. Felspar and Mica as Potassium [Manures]. DMITRI N. PRIANISCHNIKOFF (Lcmdw. Vemuchs-Stat. 1905 63 151-156).- Experiments with different plants showed that mica is better as a source of potassium than orthoclase and that the solvent action which ammonium salts show in the case of crude phosphates is not appreciable in the case of orthoclase. N. H. J. M. N. H. J. AT. Litter and Nitrogen [Fixation]. N. €I. J. M. N. H. J. M. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9069005042

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 47 Analytical Chemistry. New Burette Holder. AZARIAH T. LINCOLN (J. Arner. Chrn. Xoc. 1905 27 1442-1443).-A new form of burette holder is described which has the advantages that the burettes are always vertical and parallel can be readily put into or removed from the clamp and can be easily moved up or down. For details the description and diagram in the original must be consulted. E. G.48 ABSTRACTS OF CHEMICAL PAPERS. Ignition in a Vacuum by means of the Electric Furnace. ERNST HAAGN (Chem. Zeit. 1905 29 1209).-The author recommends a special form or" electrical furnace for crucibles constructed by Heraeus for use with a vacuum pump. With this apparatus powdered marble may be ignited to constant weight under a pressure of 40 mm.in three minutes. P. H. Modification of Winkler's Process for the Estimation of [Dissolved] Oxygen in Water. HERMANN NOLL (Zeit. angew. Chem. 1905 18 1767-1768).-1n order to allow for the presence of organic matters in waters when using his manganese method for the estimation of dissolved oxygen Winkler takes equal portions of the sample and of distilled water adds to each a certain amount of man- ganic chloride solution and then titrates both with tbiosulphate after addition of potassium iodide. The difference in the iodine is calcu- lated into oxygen and added to the amount found. Two C.C. of a 50 per cent. manganous chloride 2 C.C. of a 40 per cent. sodium hydroxide and 20 C.C. of water are shaken in a flask until the mass has become brown; 50 C.C. of hydrochloric acid are then added and the whole diluted to 300 C.C.To 100 C.C. of distilled water and also to 100 C.C. of the sample are now added 10 C.C. of a 5 per cent. solution of potassium iodide and then 25 C.C. of the above manganic chloride solution and after five minutes the iodine in both solutions is titrated. A number of experiments is given showing however that the correc- tion may as a rule be neglected as the action of iodine on organic The author has slightly modified this procedure. matters usually occurring in waters is but trifling. L. DE K. Volumetric Estimation of Sulphates with Beneidine Hydro- chloride in Presence of Thiosulphates Sulphites and Sulphides. OTTO HUBER (Chem. Zeit. 1905 29 1227-1229).-It is found that Muller and Diirke's method (Abstr.1903 ii 751) of titrating sulphates by means of benzidine hydrochloride is not directly applicable in the presence of thiosulphates sulphites and sulphides ; the following modified procedure is however recommended. By heating the mix- ture with a few drops of bromine the thiosulphate sulphite and sulphide are oxidised to sulphate; after boiling off the excess of bromine and making neutral with sodium hydroxide the hot solution is treated with benzidine hydrochloride ; this gives the total sulphate. A second portion of the solution is run into N/10 iodine acidified with hydrochloric acid the excess of iodine being titrated back by means of N/lO thiosulphate. A third portion of the solution after boiling with cadmium carbonate to precipitate the sodium sulphide is cooled made up t o 250 c.c.filtered and divided into two portions A and B of 100 C.C. each. A is again run into iodine solution and titrated back with thiosulphate which gives the amount of thiosulphate and sulphite. B after boiling for twenty-five minutes with 10 C.C. of 2N-acetic acid to destroy the sulphite and 30 C.C. of 2N-sodium acetate is treated with 1 gram of potassium chlorate and allowed to cool; titration with iodine then gives the amount of thiosulphate present ; the addition ofANALYTICAL CHEMISTRY. 49 sodium acetate prevents the t hiosulphate from being destroyed during these operations. P. H. Determination of the Strength of the Solutions employed in Nitrogen Determinations. FELIX MACH (Lundw. Veel.suchs-Stat. 1905 63 71-80).-The sodium hydroxide solution employed is rather less than N/3 and is prepared by diluting 225 C.C.of a solution of 1 part of sodium hydroxide in 2 parts of water to 10 litres and adding a little solid barium hydroxide. The sulphuric acid is prepared by diluting 200 grams of strong acid to 10 litres. The indicator is 2 C.C. of a solution of congo-red (2 grams) in 25 per cent. alcohol (1 litre). The exact strength of the solution is determined by distilling a weighed amount of amuionium sulphate (about 0.4 gram) with mag- nesium oxide and absorbing the ammonia in 20 C.C. of the acid. Hydrogen sodium carbonate (0-6-0.7 gram) is gently heated until the weight remains constant washed into 20 C.C. of the acid heated to expel the carbon dioxide and the excess of acid titrated with congo- red.Potassium tetraoxalate (0.5 gram) is dissolved in about 100 C.C. of water and directly titrated with phenolphthalein as indicator. The nitrogen value is then calculated in the usual manner. The ammonium sulphate is prepared by adding a concentrated solu- tion of the salt (previously recrystallised several times) to absolute alcohol (2 parts) ; it is then filtered washed successively with alcohol and cooled distilled water partially freed from water with filter paper and stored in a moist condition. The calcium hydrogen carbonate is prepared by passing carbon dioxide through a cold saturated solution of the carbonate. The washed precipitate is kept in a moist condition. N. H. J. M. Estimation of Mixtures of S u l p h u r i c and Nitric Acids. GEORG LUNGE and E.EERL (Zeit. angew. Chern. 1905 18 1681-1687)- The investigation of the commercial mixed acids involves the deter- mination of nitric nitrous and sulphuric acids. It is shown that the method previously recommended for the direct estimation of the sulphuric acid according to which the acid mixture is diluted with water evaporated on the water-bath and the residual acid titrated yields results which are too low in consequence of the loss of sulphuric acid in the process. The value for the nitric acid estimated by difference is consequently too high. The method of examination now recommended consists in determining (a) the total acidity ( b ) the nitrous acid from the permangsnate titre ( c ) the nitric and nitrous acids from the total nitrogen evolved in the nitrometer.The difference (c) - ( b ) represents the nitric acid ( a ) - ( c ) the sulphuric acid. An alternative method is to determine the sulphuric acid gravimetrically the nitrous acid by means of permanganate and the nitrogen by the " nitron " method of Busch (Abstr. 1905 ii 282). The nitric acid is then given by the difference in the values of the third and second determinations. H. IU D. Estimation of Nitric and Nitrous Acids. VOL. XC. ii. 4 JACOB MEISENHEIMER and FRIEDRICH HEIM (Bey. 1905,38 3834-3837).-The nitrite is de-60 ABSTRACTS OF CHEMICAL PAPERS. composed by hydrogen iodide and the nitrate subsequently by ferric chloride and hydrochloricacid and the nitric oxide gas evolved in each stage of the operation measured. The operation is carried out in an atmosphere of carbon dioxide in a suitable flask and does not take longer than an hour and a half.E. F. A. Estimation of Nitrous Acid. FRITZ RASCHIG (Bey. 1905 38 391 1-3914 Compare Meisenheimer and Heim preceding abstract).- I n solutions with which the sulphanilic acid and permanganate methods fail as for example those containing hydroxylamine the author estimates nitrous acid by addition of potassium iodide and sulphuric acid and after the lapse of at least two minutes titration of the liberated iodine with sodium thiosulphate in an atmosphere of carbon dioxide. Jf the thiosulphate titration is carried out too soon results even 10 per cent. too high are obtained probably owing to the inter- mediate formation of nitrosyl iodide NOI which decomposes slowly into nitric oxide and iodine.The estimation of nitrous acid by means of permanganate is carried out best by adding an excess of this reagent acidifying with sulphuric acid and after two minutes determining the unused permanganate with potassium iodide and thiosulphate G . Y. Estimation of Uitrate-soluble and Total Phosphoric Aoid in Basic Slag. FELIX MACH (Landw. Versuchs-Stat 1905,63,81-91).- With regard to the estimation of citrate-soluble phosphoric acid it is shown that whilst Wagner’s method generally yields satisfactory results this is not invariably the case. It is preferable to separate the silica from the extract. In determining total phosphoric acid the higher results obtained by Shenke’s modification is not due to the different relation between the citric acid and ammonia but probably to impurities present in the phosphoric acid precipitate which separates much more quickly than in the ordinary method.N. H. J. M. Estimation of Arsenious Oxide. CHARLES E. CASPARI and LEO R A. SUPPAN (Pharm Rev. 1905 23 334-338). -Three different methods are given for bringing arsenious oxide into solution previously to titration all giving equally trustworthy results. First the arsenious oxide is dissolved in warm dilute hydrochloric acid; to the solution a slight excess of sodium hydroxide is added the excess i u neutralised with N-sulphuric acid and the solution titrated with standard iodine solution after adding an excess of saturated sodium hydrogen carbonate solution. Second the arsenious oxide is dissolved in dilute sodium hydroxide solution the solution is cooled neutralised with N-sulphuric acid an excess of saturated sodium hydrogen carbonate solution is added and the titration proceeded with as usual.Third the arsenious oxide is treated with saturated sodium hydrogen carbonate solution at a boiling temperature the solution is cooled and any carbonate which may have formed is converted into hydrogen carbonate by the addition of a little N-sulphuric acid an excess of saturatedANALYTICAL CHEMISTRY. 51 sodium hydrogen carbonate solution is added and the whole titrated with iodine solution. w. P. s. Simplified Method of Elementary Analysis for Scientiflc Purposes. MAXIMILIANO DENNSTEDT (Ber. 1905 38 3729-3733. Compare Abstr. 1903 ii 103; 1905 ii 202 651).-Further details of the author’s method are given.The substance to be analgsed is placed in a boat which is weighed in a glass tube of such dimensions that it can be readily pushed into the combustion tube. This inner tube may be closed at the one end if the substance is readily volatile and also when the substance is difficult to volatilise provided carbon is not deposited during the volatilisation. An open inner tube may be used for substances such as sugar and proteids which deposit much carbon on heating. Another arrangement which gives very good results permits of oxygen being passed through the outer and inner tubes at the same time (see figure). i 0 The combustion is proceeding regularly when the contact substance glows brightly or when a small flame appears at the end of the inner tube which is pushed close up to the contact material This flame should remain in the inner tube that is it should not burn outside the rim of the inner tube.When this happens the burner under the capillary tube is to be removed and the oxygen supply increased. This double supply method may be used for most substances and permits of the regulation of the volatilisation with great ease. J. J S. Analysis of Silicates. 11. EDUARD JORDIS and WILHELM LUDEWICI (Zeit. anorg. Chm. 1905 47 180-189. Compare Abstr. 1905 ii 317 610).-The authors find that considerable loss by spirting takes place when ignited silica is treated with hydrochloric acid and water probably owing to the heat always developed when a fine powder is moistened with a liquid; this source of error is avoided by allowing the silica to cool and then moistening it with a few drops of cold water before the bulk of acid and water is added.The amount of silicic acid which passes into solution during the washing of the ignited silica on the filter depends largely on the base with which the silica has been combined; it is very small with barium and strontium silicates much greater with calcium silicate and is greatly increased by the presence of alkali metals. The colloidal silicic acid remains in solution in the filtrate even in the presence of a large excess of an alkali chloride. Kehrmann and Fliirscheim’s suggestion (Abstr. 1905 ii 411) as to the volatility of silicic acid is inaccurate ; the discrepancies observed are due to the foregoing sources of error and it is shown that when proper precautions are taken there is no appreciable loss.G. s. 4-252 ABSTRACTS OF CHEMICAL PAPERS. Simplified Method f o r Determining Potassium Sodium Calcium Magnesium and Phosphoric Acid in Hydrochloric Acid Soil Extracts. HUGO NEUBAUER (Landw. Versuchs-Stat. 1905 63 141-149).-A portion of the extract corresponding with 25 grams of soil is evaporated to dryness after adding calcium carbonate (0.5 gram) in the case of soils which do not effervesce with acid heated over a mushroom burner rubbed with a glass pestle and again heated until the organic matter is destroyed. It is then boiled with about 60 C.C. of water for half an hour diluted to 125 c.c. and filtered. The filtrate should be quite colourless and slightly alkaline.Potassium is determined in 100 c.c. as previously described (Abstr. 1900 ii 481) and also the sodium (Abstr. 1904 ii 209). The phosphoric acid is determined in the insoluble residue which is boiled for half an hour with dilute sulphuric acid (containing 5 C.C. of strong acid). The solution is diluted to 100 C.C. and precipitated with molybdate solution (100 c.c.) prepared without ammonium nitrate (Abstr. 1903 ii 102). Or the phosphoric acid may be determined preferably by von Lorenz’ method (Abstr. 1901 ii 278) in 25 C.C. of the solution (= 5 grams of soil) after adding 25 C.C. of nitric acid of sp. gr. 1.2. Calcium and magnesium are estimated in another portion of the original solution (corresponding with 25 grams of soil). After evaporating to dryness and heating as before the residue is heated with water and 2-5 grams of ammonium chloride (according to the amount of calcium) until no more ammonia is given off washed into a 125 C.C.flask and boiled with a few drops of ammonia. The cold solution is diluted to 125 c.c. filtered and the calcium and magnesium estimated in 100 C.C. by the usual methods. The method is suitable for all soils except those which contain very large amounts of sulphates. N. H. J. M. The Use of the Rotating Anode f o r the Estimation of Cadmium taken as the Chloride. CHARLES P. FLORA (Amer. J. Sci. 1905 [iv] 20 392-396).-When substituting cadmium chloride for the sulphate (Abstr. 1905 ii S59) some important differences were noted. Good results were obtained in solutions containing sulphuric acid cyanides and pyrophosphates but with phosphates such care is required that the phosphate method cannot be recommended when other methods are available.With great care fair results may be got in tho presence of urea formaldehyde and acetaldehyde. I n presence of acetates the method proved unworkable with cadmium chloride although the results had been most satisfactory in the case of the sulphate. L. DE K. Microchemical Reaction for Copper in Presence of Lead and Bismuth. PIETER A. MEERBURCI and H. FILIPPO (Chem. Centr. 1905 ii 1466; from Chem. Weekblad. 2 641-643).-The presence of 0.0001 mg. of copper can be detected by adding cesium chloride to th0 solution of the copper salt in hydrochloric acid. When a small quantity of cEsium chloride is added to a solution of a copper salt red needle-shaped or six-sided prismatic crystals (CuCl,,CsCl 4) are formed together with other colourless compounds ; the addition of a furtherANALYTl CAL CHEMISTRY.53 quantity of czesium chloride causes the separation of yellow crystals (CuCl,,ZCsCl ?) from which the red crystals may be regenerated by again increasing the quantity of cupric chloride. The long prismatic crystals cause a marked polarisation of light but the shorter ones have as a rule no such action. The presence of hydrochloric acid appears to accelerate the reaction for copper but cobalt and iron may interfere even in the presence of ammonium chloride. The iron may be removed as ferric oxide by repeatedly evaporating the solution but the cobalt cannot be separated.When a small quantity of cssium chloride is added to a solution containing cobalt reddish-brown crystals are formed and yellow or yellowish-green crystals separate on the addition of a larger quantity of cwsium chloride. Lead and bismuth have no effect on the reaction and in mixtures of these metals with copper bismuth may be detected simultaneously by Behren’s reaction and the lead finally obtained as cmium lead copper nitrite. When a large quantity of lead is present colourless highly refractive apparently rhombohedra1 crystals are sometimes formed. E. W. W. Gasometric Estimation of Copper with Hydrazine Salts. ERICH EBLER (Zeit. unorg. Chem. 1905 47 371-376).-The author finds that the oxidation of hydrazine salts by solutions of cupram- moni.um salts proceeds strictly in accordance with the equation 4(CuS0,,4NH3) + N2H,,H,S0 = 2(Cu2S0,,4NH3) + N + 2NH + 2(NH,),S04 under all conditions and on this fact has been based a method for the estimation of copper and of hydrazine compounds by measurement of the evolved nitrogen.The reacting substances are heated together without access of air in an apparatus described by Hempel and the nitrogen measured over mercury. Test analyses gave satisfactory results. Metallic salts which themselves reduce hydrazine exert a disturbing action and must be removed before the experiment ; this can be effected satisfactorily by precipitation as metal with a hydroxylamine or hydrazine salt the copper remaining in solution as the cuprammonium compound. G. S. Gasometric and Volumetric Estimation of Mercury by Hydrazine Salts and Gasometric Estimation of Hydrazine by Mercury Salts.ERICH EBLER (Zeit. nnorg. Chenz. 1905 4’7 377-385). -When mercuric salts dissolved in acetic acid containing sodium acetate are gently heated with hydrazine salts they are reduced quantitatively according t o the equation BHgCI + N2H = 4HC1+2Hg+N2. This reaction may be made use of for the estima- tion both of hydrazine and of mercuric salts by measurement of the evolved nitrogen. For this purpose the reacting substances are heated in an atmosphere of carbon dioxide the nitrogen is driven over into a Schiff’s nitrometer containing potassium hydroxide and subsequently measured over mercury. Mercuric salts in ftmmoniacal solution are also reduced completely by hydrazine salts and the reaction may be employed for the quantitative estimation of mercuric salts either by measuring the54 ABSTRACTS OF CHEMICAL PAPERS.volume of nitrogen evolved as previously described for copper (see preceding abstract) or by titrating the excess of hydrazine salt. According to the latter method ammonia is added to a weighed quantity of the mercuric salt dissolved in hydrochloric acid until t h e solution becomes clear a known excess of 1/40 normal hydrazine sulphate is added the mixture is then heated on the water-bath until the precipitate has settled allowed to cool made up to a definite volume filtered and an aliquot part titrated with iodine by the method given by Stolle (Abstr. 1903 ii 100). These methods for the estimation of mercury are also applicable t o mixtures except when substances such as silver and copper wbich are themselves reduced by hydrazine are present ; n method of removing these metals by means of hydrazine is described.G. S. Influence of the Presence of Titanium on the Estimation of Aluminium in Presence of Iron and Phosphoric Acid. HENRI PELLET and CH. FRIBOURG (Ann. Cl~inz. n n d . 1905 10 41 6-420).-Experiments still in progress showing that the processes now in use for estimating aluminium in presence of iron or phosphoric acid all give an alumina contaminated with titanium oxide should this be present in the ashes of plants &c. operated upon. The weighed alumina compound should therefore be fused with potassium hydrogen sulphate and the resulting solution tested colori- metrically with hydrogen peroxide.It is still doubtful whether the titanium occurs in the precipitate as oxide or phosphate L DE I(. Estimation of Metallic Iron in Reduced Iron. H. CORMIMB~UFF and 1;. GROSMAN (Amn. Chim. ccnal. 1905 10 430-422).-0ne gram of the sample is treated for six hours with 25 C.C. of 2iV iodine with occasional shaking. Two hundred and fifty C.C. of water are then added and the uncombined iodine titrated with 2Nsodium thiosulphate. One C.C. of iodine solution = 0.056 gram of metallic iron. L. DE K. Separation of Iron from Zinc by means of Ammonia. W. FUNK (Zeit. angew. Chem. 1905 18 1687-16S9).-The ferric iron solution is mixed with excess of ammonium chloride and then neutralised with ammonia. Sufficient ammonia is now added to fully precipitate the iron and then an excess of about thirty times the amount already used.The whole is heated to 70-SOo and the precipitate is collected and washed with a hot 5 per cent. solution of ammonium chloride. To remove the zinc completely the precipitate must be redissolved in hot dilute hydrochloric acid and reprecipitated in the same manner. The iron precipitate may then be washed ignited and weighed. Allowance must be made for any silica present. As this renders the estimation troublesome the author prefers the acetate method for the estimation The zinc may be titrated in the filtrate by the usual process. of iron in presence of zinc. L. DE K.ANALYTICAL CHEMISTRY. 55 Estimation of Tin in Copper-Tin Alloys. ARTHUR G. LEW (Analyst 1905 30 361-364).-The alloy is distilled in a current of chlorine and the volatile stannic chloride collected in receivers con- taining water.About 0- 5 gram of the finely-divided alloy is placed in a 30 C.C. distillation flask the side-tube of which is bent first up for a short distance and then down again so that any drops of liquid projected into the side-tube drain back into the flask. The flask is connected with two Volhard receivers containing water india-rubber stoppers and connections being used. The entry tube for the chlorine reaches about half-way down the bulb part of the flask ; around it and below the side-tube is wrapped a fairly tight plug of glass wool t o retain the fine spray of other chlorides carried up by the stannic chloride. The chlorine is passed through a wash-bottle containing concentrated hydrochloric acid and is then thoroughly dried before it enters the distillation flask.The latter is gently warmed when it has become filled with chlorine. The last traces of stannic chloride are removed from the flask by adding about 10 C.C. of hydrochloric acid and continuing the distillation until the bulk of the acid has been distilled off. The stannic chloride in the receivers is precipitated with hydrogen sulphide and weighed as the oxide. If antimony is present in the alloy it will distil with the tin and may be separated by the usual methods. w. P. s. Estimation of Bismuth. Separation from Copper Cadmium Mercury and Silver. ARTHUR STAEHLER and WILHELM SCHARFEN- BERG (Be?. 1905 38 3862-3869).-The precipitation of bismuth as phosphate in presence of dilute nitric acid does not yield satisfactory results as the bismuth is liable to dissolve slightly,. especially if hydrochloric acid is present.This difficulty can be overcome by precipitating in presence of phosphoric acid which dissolves the phosphates of copper cadmium silver and mercury ; lead phosphate is too sparingly soluble to be easily separated in this way. The actual precipitation is carried out by adding hot sodium phosphate to a boiling solution of the bismuth salt acidified with nitric acid in order to prevent the separation of basic salt. Analyses are given to illus- trate the separation of bismuth from chlorides from copper from cadmium from mercury and from silver. Cadmium is separated most exactly by electrolysis the electrolyte being prepared by dissolving the sulphide in nitric acid.Mercury can be separated quickly and exactly from a hot ammoniacal solution as sulphide entirely free from excess of sulphur. T. M. L. Estimation of Bismuth and Separation from the Heavy Metals as Phosphate. BEINRICH SALKOWSKI [with BERNHARD SENDHOFF] (Ber. 1905 38 3943-3944. Compare J. pr. Chem. 1868 [i] 104 172).-Bismuth is precipitated and separated quantitatively from copper cadmium mercury silver lead iron manganese cobalt nickel zinc chromium and aluminium as the phosphate in nitric acid solution which must be free from hydrochloric acid or chlorides. The precipi- tate which can be ignited without risk of reduction is weighed as56 ABSTRACTS OF CHEMICAL PAPERS. BiPO,. The insolubility of bismuth phosphate in dilute nitric acid solution may be utilised for the detection of the metal.a. Y. Temperature of Combustion of Methane in the Presence of Palladiumised Asbestos. H. G. DENHAM (J. SOC. Chem. Ind. 1905 24 (xxiii) 1202-1 205).-Different observers give widely-varying estimates of the maximum temperature at which the hydrogen in a gaseous mixture can be burnt over palladiumised asbestos without the simultaneous combustion of methane (compare Phillips Abstr. 1894 ii 393; Richardt Abstr. 1904 ii 167). The author finds that a mixture of methane and oxygen in the proportions for complete com- bustion passing over palladiumisedasbostos a t the rate of 1 C.C. per 34 sec. begins to burn a t 514-546'; a t twice the speed the tempera- ture is about 50' higher.The temperature of initial combustion rises when the proportiori of either gas is increased and is not lowered by the addition of hydrogen. Carefully prepared palladiumised asbestos gives consistent results in such combustion provided tho temperature does riot rise above 500-5509 That the action of the catalyst is not due to superficial oxidation was proved by passing oxygen over the palladiumised asbestos displacing the oxygen by nitrogen and the latter by metham; carbon dioxide was not produced a t 600'. c. s. The Iodine Value of Mineral Oils. EDMUND GRAEFE (Chem. Rev. Fett. Hum. Ind. 1905 12 296-299).-The quantity of un- saturated compounds in commercial mineral oils may be approximately estimated from the iodine value of the oil but allowance must be made for the sulphur compounds also existing in crude oils (Abstr. 1904 ii 514).In conjunction with the bromine and sulphuric acid tests tho iodine value is of use in detecting coal tar products in mineral oils. Petroleum oil remains uncoloured when carefully poured on the surface of warm sulphuric acid whilst other oils are coloured yellow or brown. American petroleum absorbs considerably more bromine than do oils from other countries. w. P. s. Detection of Methyl Alcohol in Liquids containing Ethyl Alcohol. FRANZ UTZ (Chem. Centr. 1905 ii 1 4 6 7 ; from Phccrm. Centr.-H. 46 736-737).-1n order to detect the presence of methyl alcohol in liquids which contain ethyl alcohol Kalm (D.-Am. Apoth. Zeit.) recommends the following method. 0*5-1*0 C.C. of the liquid to be tested is diluted to 5-1U C.C.with water and a red-hot copper spiral is repeatedly plunged into the solution. When 5 C.C. of milk and a solution of ferric chloride are then added and the mixture poured on to concentrated sulphuric acid a violet-blue line is formed at the zone of contact of the two layers if methyl alcohol is present in the original sample. The author finds that even when the quantity of methyl alcohol is small the formaldehyde which is formed by the oxidising action of the cupric oxide is not lost by volatilisation. Acetone gives a similar reaction but the colour is not so intense as that formed in the case of methyl alcohol. E. W. W.ANALYTICAL CHEMISTRY. 57 Detection of Methylated Spirit in Tinctures &c. ERNST SCHMIDT and RUDOLF GAZE (Arch.Pharrn. 1905 243 555-558).- Detailed directions are given for the testing of various spirits and tinctures in order to find whether they have been made with alcohol to every 100 litres of which 5 of methyl alcohol containing 30 per cent. of acetone have been added. Preparations made with methylated alcohol of this description have been put on the market lately. C. F. B. Estimation of Sugars. JULES WOLFF ( A m . Chirn. anal. 1905 10 427-431).-The amount of the precipitated cuprous oxide is estimated by dissolving it in an acid solution of ferric sulphate (free from ferrous iron) and then titrating the ferrous iron formed with Calculation of the Proportion of Lactose Hydrolysed in a Solution of this Sugar submitted to the Action of Lactase. Measurement of the Activity of Lactase.CR. PORCHER (Bull. Xoc. chirn. 1905 [iii] 33 1285-1295. Compare Porcher Abstr. 1905 ii 540 and Brachin Abstr. 1904 i 1069).-A critical dsumk of the polarimetric phenylosazone iodometric and cupric reduction methods of estimating galactose and dextrose in presence of lactose is given and it is shown that the method based on the reduction of Fehling's solution gives the best results when only small quantities of the two hexoses are present. For this reason this method is best adapted for the measurement of the hydrolytic activity of lactase towards lactose. A detailed description of the method adopted by the author in carrying out such estimations and a graphic method of calculating the results are given in the original. Polarimefric Estimation of Starch. ERICH EWERS (Zeit.ofentl. Chem. 1905 11 407-415).-Starch is completely dissolved by successive treatment with glacial acetic acid dilute hydrochloric acid and hot water and the solution obtained may be examined in the polariscope. The following conditions are necessary for the attain- ment of correct results 10 grams of the starch or starchy substance are heated in a flask with 50 C.C. of glacial acetic acid the flask being immersed in a boiling water-bath for twenty minutes. About 130 C.C. of cold water are then added and the heating continued for one hour at a temperature of 45'. I n the case of potato starch the digestion with water a t 45' must be omitted. After cooling from 2 t o 3 C.C. of saturated potassium ferrocyanide solution are added the liquid is diluted to 200 c.c.filtered and the filtrate polarised in a 200 mm. tube at a temperature of ZOO. The reading which mill be quite small (generally + 0.2 degree of the Ventxke scale) gives the amount of soluble carbohydrate in the sample. A second quantity of 10 grams of the starch is then heated with 50 C.C. of glacial acetic acid for ten minutes in a boiling water-bath. Ten C.C. of dilute hydrochloric acid (1 10) are now added and the digestion continued for exactly six minutes. The mixture is then diluted with water to a volume of 180 c.c. and heated for a further fifteen minutes except in the case of potato starch. The aolution is finally '' cleared '' with potassium permangana t e. L. DE K. T. A. H.58 ABSTRACTS OF CHEMICAL PAPERS. ferrocyanide diluted to a volume of 200 c.c.filtered and polarised. From the experiments described it is seen that all starches give approximately the same reading when the latter is calculated on the pure dry starch. For instance the following readings were obtained with various starches when treated as above wheat starch + 52.7' ; wheat flour + 52.7' ; rice starch + 52.6' ; maize starch + 52.4' ; potato starch +53*8' Yentzke when the actual readings mere calculated on the quantity of pure starch known to be present in the samples. w. P. s. Direct Estimation of Acetyl and Benzoyl Groups. RICHARD MEYER and ERNST HARTMANN (Ber. 1905 38 3956-3958. Compare R. and H. Meyer Abstr. 1896 ii 226 ; A. G. Perkin Trans. 1905 87 107 ; Sudborough and Thomas ibid. 1752).-05-0*7 gram of the substance is heated in a reflux apparatus for one hour with 5 grams of pure sodium hydroxide and 50 C.C. of methyl alcohol which has been distilled over potassium carbonate.The solution is then cooled acidified with 50 C.C. of phosphoric acid of sp. gr. 1.104 then distilled with steam and the distillate titrated with 0.1N barium hydroxide using phenolphthalein as indicator. Benzoyl groups are estimated in the same way. Attention is drawn to the fact that acid is formed when either methyl or ethyl alcohol is boiled for some time with sodium hydroxide. J. J. S. Hydrolysis of Sodium Palmitate. ROBERT CORN (Ber. 1905 38 3781-3784. Compare Zed. o f l e d . Chem. 1905 11 58; Kanitz Abstr. 1903 ii 248).-In reply to Schwarz (this vol. ii 657) the author gives experimental details to show that sodium hydroxide can be estimated accurately in aqueous solution in presence of sodium palmitate by titration of the hot solution with aqueous N/2 hydro- chloric acid with phenolphthalein as indicator and taking as the neutral point the change of colour from deep red to a light rose.The total sodium present as hydroxide and as palmitate is deter- mined by titration of the hot aqueous solution with LV/Z hydrochloric acid using methyl-orange as indicator. G. Y. Detection of Foreign Golouring Matters in Fats. GEoRa FENDLER (Chem. Rev. Fett. Rarx. Ind. 1905 12 207-209 and 237-239).-Of all the methods proposed for the detection of added colouring matters in fats and particularly in butter and margarine not one serves as a general test for each or all of the colours usually employed. The hydrochloric acid test only gives positive indications in the case of a few azo-dyes.On treating butter with a freshly- prepared ethereal solution of nitrous acid the fat is completely decolorised even if saffron marigold Orleans-yellow or Martius-yellow is present whilst turmeric aniline-yellow tropaeolin dimethyl- aminoazobenzene and certain '' butter colours " are not affected. Ex- tracting the fat by shaking with alcohol affords useful information as to the presence of foreign colours especially if the alcohol becomes strongly tinted but as nearly ail fats are soluble to a slight extent inANALYTICAL CHEMISTRY. 59 alcohol the coloration obtained must be compared with that yielded by a similar f a t known to be uncoloured.w. P. s. Behaviour of Milk towards Magenta-Sulphurous Acid Solution and the Detection of Formaldehyde in Milk. EICHHOLZ (Jfilchw. Zents.. 1905 1 499-500).-The proteids of milk have the property of giving a red coloration when treated with a solution of magenta decolorised with sodium sulphite but this property is destroyed by the addition of a trace of acid or alkali. On the other hand a solution of magenta bleached by means of sulphurous acid (Schiff’s reagent) only gives a coloration with milk when the latter contains formaldehyde. As formaldehyde after a time combines with the albumin of the milk and no longer gives a coloration with Schiff’s reagent it is better to distil the milk and apply the test to the distillate. w. P. s. Detection of Formaldehyde in Witch Hazel.WILLIAM A. PUCKNER (Amer. J. Piharm. 1905 77 501-503).-The following test is proposed as an improvement on the United States official test for the detection of formaldehyde in ‘‘ witch-hazel extract,” a preparation resembling the Liquor Hamamelidis of the B.P. One C.C. of the solution is added to 5 C.C. of a freshly-prepared solution of 0.01 gram of salicylic acid in 100 C.C. of concentrated sulphuric acid. If as little as 1 gram of formaldehyde in 10,000 C.C. is present a red coloration is produced. The quantity of salicylic acid used must not exceed the amount stated or the sensitiveness of the test will be impaired. w. P. s. Sensitive Colour Reaction for Formaldehyde Oxygenated Compounds of Nitrogen or Proteid Matters. E. VOISENET (Bull.Xoc. chim. 1905 [iii] 33 1198-1214).-When 0.1 gram of albumin is dissolved in 2 or 3 C.C. of water and to this is added a drop of a solution containing 5 per cent. of formaldehyde then on the addition OF from 6 to 9 C.C. of hydrochloric acid (4N) containing 0.01 gram of nitrous acid per litre the liquid acquires immediately a rose tint which becomes rose-violet and finally passes into an intense bluish-violet. Investigation of the conditions under which this reaction takes place shows that the colour forms most readily at a temperature of 50° that it is not produced if any one of the three substances proteid formaldehyde or nitrous acid is in excess and that hydrochloric acid may be replaced by sulphuric acid. Feeble pink colorations are produced by the action on proteid matters of hydrochloric acid containing nitrous acid in the absence of formaldehyde but these are quite distinct from the intense colours produced in presence of the aldehyde.The formation of the colour seems to be due to the interaction of the formaldehyde with the oxidation products formed by the action of nitrous acid on the scatole indole or similar substances produced by the action of hydrochloric or sulphuric acid on the proteids thus the coloration is given by most proteids by the products of pancreatic digestion of proteid and by scatole and indole but not by the products of peptic digestion,60 ABSTRACTS OF CHEMICAL PAPERS. Similarly nitrous acid may be replaced by almost any oxidising agent. Formaldehyde is the only aliphatic aldehyde which gives the coloration though similar colorations are given by some of the aromatic aldehydes.A distinct coloration is produced by solutions containing one part of formaldehyde in 10,000,000 of water. It is suggested that the reaction may be utilised for the detection of formaldehyde in food-stuffs nitrous products in sulphuric or hydro- chloric acid nitrates in water added water (containing nitrates) in milk or albumin in urine. Precise directions for the use of the reaction in these special cases are given in the original. T. A. H. Estimation of Caffeine in the Presence of Acetanilide. WILLIAM A. PUCKNEK (Yl~ccrm. lieu. 1905 23 345-350).-I)oth caffeine and acetanilide may be estimated in headache remedies by the following method. About 2.5 grams of the sample are treated with 30 C.C.of water containing 2 C.C. of Nsulphuric acid. The solution is extracted five times with chloroform using 20 C.C. each time and the extracts filtered through asbestos into a flask. The chloroform is then distilled off and the residue dried a t 100' and weighed. The residue is now dissolved in 50 C.C. of boiling water cooled and the excess of acetanilide allowed to crystitllise out. The crystals are collected on a small cotton-wool filter and mashed with about 25 C.C. of water. The filtrate and washings are treated with 1 C.C. of dilute hydrochloric acid and 25 C.C. of Nj5 iodine solution and shaken occasionally for half an hour. The precipitate of caffeine periodide is collected on an asbestos filter washed with 25 C.C. of N/10 iodine solution containing about 0.25 C.C. of hydrochloric acid and then dissolved in a solution of 2 grams of sodium sulphite in 10 C.C. of water. The filter is washed with about 15 C.C. of water and the solution and washings extracted several times with chloroform. The residue obtained on evaporating the chloroform is dried for three hours at 100" and weighed. The method yields about 99 per cent. of the caffeine actually prisent in the sample. w. P. s. Choline Periodide and the Quantitative Precipitation of Choline by Potassium Tri-iodide. VLADIMIR STAN~K (Zeit. physiol. (?]hem. 1905 46 280-285).-Choline periodide which is obtained by the addition of iodo-potassium iodide t o a solution of choline was first described by Griess and Harrow (Trans. 1885 47 298); it can be obtained in crystalline form and may be used for the estimation of choline. It is suggested that this reaction may be employed to deter- mine the amount of choline in animal and vegetable tissues. The per- iodidc has the composition C,H,,ONI,T and it may therefore be spoken of as a n enneaiodide. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9069005047

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

57 0 r g an i c C hem i s t ry. Theory of the Grignard Reactions. RICRARD ABEQG (Be?.. 1905 38 4113-4116. Compare Abstr. 1906 ii 475).-1t has been already suggested that alkyl groups are amphoteric in character ; in compounds such as ethyl chloride they have electro-positive properties and on hydrolysis yield alcohols whilst in metallic alkyl compounds such as zinc ethyl they have electro-negative properties and on hydrolysis yield hydrides (paraffins). The Grignard reactions permit of similar conclusions being drawn with reference to the electro- chemical character of other organic radicles and nine examples of different types are discussed from this point of view. Attention is called to the close analogy between the influence of electrical polarity in determining the direction of chemical change in electro- lytes and in non-electrolytes and to the fact that evidence of feeble ionisation has been obtained in the case of a few compounds generally regarded as non-electrolytes for example sugar alcohol ethyl malonate and oxonium compounds.T. M. L. Decomposition of Chloroform under the Influence of Light and Air. NICOLAAS SCHOORL and L. M. VAN DEN BERG (Chem. Centr. 1905 ii 1623 ; from Pharm. Weekblcd 42 S77-SSB).-&uantitative experiments have shown that when chloroform is decomposed by the action of light in the presence of an excess of oxygen carbon dioxide water and chlorine are formed but that when insufficient oxygen is present carbon oxychloride and hydrogen chloride are produced in molecular proportion. The latter conditions usually obtain in prac- tice.E. W. W. Readineas of Formation of Cyclic Compounds. PAVEL Iw. PETRENKO-KRITSCHENKO and,A. KONSCHIN (Annulen 1905,342,5 1-59). -After surveying the known data bearing on the Eormation of closed rings from open chains the conclusion is drawn that the readiness or better the velocity of formation of cyclic compounds from open chains depends on two factors the work necessary to bring the open chain into a cyclic position and the work required to actually close the ring. The velocities of the reaction between potassium hydroxide and various glycol monochlorohydrins and between dibromides and zinc dust are measured. The investigation of ethylene chlorohydrin tri- methylene chlorohydrin y-pentylene chlorohydrin and 6-hexylene chlorohydrin shows that there is a marked difference in the velocity of the reaction between the a-compounds and the P-compounds whilst the remainder of the substances investigated behave in much the same way.The velocity of decomposition of y-pentylene chlorohydrin is slightly greater than that of the others. The velocity of the reaction of the dibromides with zinc dust is expressed as a percentage of the material which has been decom- VOL. XC. i. f58 ABSTRACTS OF CHEMICAL PAPERS. posed in one hour ethylene dibromide 19-87 ; propylene dibromide 20.87 ; trimethylene bromide 2.02 ; y-pentylene dibromide 1-80 ; pentamethylene dibromide 1.25 ; 6-hexylene dibromide 1.92. The opinion is expressed that in the case of the compounds investi- gated unlike the acid compounds the '' tension " of the ring which is formed does not play an important part in determining the velocity of the reaction.Action of Dilute Sulphuric Acid on the Pinacone formed from Ethyl Propyl Ketone. FELIX GOLDBERGER and RUDOLF TAN- DLER (Monatsh. 1905 26 1473-1485. compare Zumpfe Abstr. 1904 i 291 ; Lieben Abstr. 1905 i 167 ; Kohn ibid.).-The pinacone obtained in a yield of 28 per cent. of the theoretical by reduction of ethyl propyl ketone with sodium and water or in poorer yield by electrolytic reduction in dilute sulphuric acid solution with a current density of 8 amperes per square decimetre boils a t 125-126' under 11 mm. or at 254-255' under the atmospheric pressure (Oechsner de Coninck A bstr. 1876 i 694). When heated with 20-30 per cent. sulphuric acid in a sealed tube a t 170-180' for six hours it yields an unsaturated hydrocarbon and an oxide.K. J. P. 0. . . I The hydrocarbon (?HMe'gPr (P) is a colourless oil which has an CHMe* CPr odour of camphor boils a t 75-76' under 11 mm. or a t 194-195" under the atmospheric pressure forms a dark resinous additive com- pound with 1 mol. of bromine in carbon disulphide solution and when oxidised with nitric acid of sp. gr. 1.5 under cooling or with alkaline permanganate solution at 60° yields carbon dioxide and an acid ; this is volatile with steam and forms a silver salt C,H702Ag The oxide C,,H,,O is a slightly yellow liquid having a burning odour which boils a t 105-106' under 11 mm. or a t 225' under atmospheric pressure and is easily soluble in ether alcohol or chloro- form.It does not form an oxime a sodium hydrogen sulphite additive compound or an acetyl derivative when boiled with acetyl chloride; it remains unchanged when boiled with sodium i n an atmosphere of hydrogen or when heated with zinc ethyl in a sealed tube a t 150' for three hours or with water under pressure a t 180-200'. It must be therefore an ay- or an a6-oxide. It is not reduced by alcohol and sodium and does not interact with magnesium ethyl iodide ; when oxidised with alkaline permanganate solution it yields a mixture of acids which forms silver butyrate and a silver salt C7H1,02 Ag crystallising in white needles. Synthesis in the s-Heptane-a6q-triol Series. JULES L. HAMONET (Compt. rend. 1905 141 1244-1245).-a~-Dirnethoxyheptane-6-ol OH*CH(CH,*CH,*CH,*OMe) prepared by the action of ethyl formate on the magnesium derivative of y-iodo-a-methoxypropane (compare Abstr.1904 i 467) is a colourless slightly odorous liquid with a very bitter taste which boils at 141-142' under 21 mm. or at 246-248' under the ordinary pressure has a sp. gr. 0.969 a t 18' and does not crystallise when cooled in a mixture of solid carbon dioxide and acetone. 6-C?iZoro-ay-dirnethoxyheptarze C7H,,Cl(OMe) prepared by the action of phosphorus trichloride on the alcohol is a colourless G. Y.ORGANIC CHEMISTRY. 59 mobile liquid with an agreeable odour boiling at 120" under 16 mrn. pressure and having a sp. gr. 1.001 at 18". a6q-Tribromoheptane C7HlaBr8 prepared by heating the alcohol with acetic acid and hydrobromic acid in sealed tubes a t loo" is a viscous liquid solidify- ing in a mixture of solid carbonic acid and acetone boiling at 184-185" under 19 min.pressure and having a sp. gr. 1.775 a t 18". a8qTri-iodoheptane C7HI3I3 obtained by the action of hydrogen iodide in the cold on the alcohol is a slightly coloured viscous liquid having a sp. gr. 2.343 at 18" which cannot be distilled without decom- posit ion. M. A. W. Halogenated Aliphatic Acids. WILHELM LOSSEN (Annalen 1905 342 112-155 157-190)..-It has been shown (Abstr. 1893 i 142) that both dibromosuccinic acid and isodibromosuccinic acid the latter more easily are converted by the action of alkali hydroxides into acetylenedicarboxylic acid a fact which is not in agreement with Wisllcenus's views as to the stereoisomerism of the two dibromosuc- cinic acids.A new series of experiments has been undertaken with the object of throwing light on this difference. [With ROBERT EICHLOFF.] -Chloro- and bromo-acetic acids were con- verted by aqueous or alkaline solutions into glycollic acid a t different temperatures and the velocity of the hydrolysis measured. The change is accelerated by raising the temperature and the velocity is greater in solutions containing molecular proportions of the acid and the base than in aqueous solutions. Increase however in the concen- tration of the alkali greatly hastens the velocity of the reaction. I n dilute solution the free acid decomposes far more rapidly than in con- centrated solution but in presence of alkali the reverse is the case. Bromoscetic acid under all conditions decomposes more rapidly than chloroacetic acid.Chloroacetic acid yields not only glycollic acid but also diglycollic acid when boiled with bases the particular reaction depending on the nature and quality of the base. Bromoacetic acid was investigated. Normal sodium hydroxide yields only glycollic acid concentrated sodium hydroxide (1 molecule of base to 1 of acid) gives also glycollic acid but 2 molecules of the concentrated base yield diglycollic acid and glycollic acid in the proportion of 1 2.8 and 3 molecules of the base gave the two acids in the proportion of 1 1.7. I t is noteworthy that potassium hydroxide in place of sodium hydroxide increases the proportion of diglycollic acid. Barium hydroxide in neutral solution converts the bromoacetic acid into glycollic acid but if two equivalents of the base are present for every equivalent of acid 76 per cent.of diglycollic acid is formed. When boiled with water both trichloro- and tribromo-acetic acids are decomposed into chloroform and carbon dioxide. If the decomposition is effected by sodium hydroxide in the proportion of 6 molecules of base to 1 of acid the reaction is represented by the equation CCl,*CO,H + CiNaOH = 3NaC1+ HC0,Na + Na2C03 + 3H,O. If less sodium hydroxide is used the two reactions occur together. and acrylic acids behaving in the manner above stated. [With EUGEN Ko~s~~.]-a-~romopropionic acid yields both lactic Barium f 260 ABSTRACTS OF CHEMICAL PAPERS. hydroxide has a somewhat different action from sodium hydroxide giving other proportions of the two acids.P-Bromopropionic acid yields hydracrylic and acrylic acids the latter forming a larger proportion of the product than in the case of a-bromopropionic acid. The decomposition also takes place more rapidly. This fact is not in agreement with Wislicenus' theory as t o the mechanism of the elimination of hydrogen haloids from organic compounds. a-Bromopropionic acid H*6-6-H should yield acrylic acid more easily than P-bromopropionic acid which has either H Br H bO,H E H Br H the configuration H.6-6-H or H*61-6-H ; the first configura- . . . . l3r CO,H H CO,H tion alone would yield acrylic acid whilst the second would give ethylene carbon dioxide and sodium bromide. act-Dibromopropionic acid gives pyruvic and a-bromoacrylic acids and the so-called acryl-colloid ; the velocity of the decomposition is affected by bases in the same way as with the foregoing substances.The proportion of a-bromoacrylic acid decreases with increasing dilution ; it crystallises in readily volatile plates melting a t 68" and is decomposed by exposure to the air or by treatment with sodium hydroxide into acetylene. The acryl-colloid is formed only in acid solution; it consists of a jelly which when dry has the composition C3nH41203n and is completely insoluble in water but soluble in alkali hydroxides. It is probably a polymeride of pyruvic acid since ether extracts from the alkaline solution after acidification a syrup which combines with phenylhydrazine yielding the phenylhydrazide of pyruvic acid. up-Dibromopropionic acid decomposes more rapidly than the aa-iso- meride yielding glyceric acid and a-bromohydracrylic acid together with small quantities of pyruvic acid or in acid solution of acryl-col- loid.According to Wislicenus' theory the aa- should decompose more rapidly than the &acid since it can exist in only one configuration namely that which mould yield bromohydracrylic acid. [With HUGO sM~L~us.]-The main product of the decomposition of a-bromobutyric acid is hydroxybutyric acid but both crotonic acid and s-dietl~yZdigE~collic (butodiglycollic) acid CO,H*CHEt*O*CHEt*CO,H are also formed. The latter is best prepared by dropping bromo- butyric acid on to solid sodium hydroxide mixing and after acidify- ing with dilute sulphuric acid separating the oily layer which consists mainly of crotonic acid and then extracting the new acid with ether and purifying in the form of the barium salt.The acid crystallises at a low temperature and melts a t 26'; it boils a t 117' under 11 mm. pressure. The normal potassium salt C,H,,O,K crystallises in hygroscopic needles whilst the potassium hydrogen salt C8H,,05K,iH,0 forms rectangular plates. The normal sodium salt C8H1205Na2 crys- tallises in leaflets or needles and the acid salt 3C8H1,O,Na,C,~:,,O,,I-I,O,ORGANIC CHEMISTRY. 61 forms needles. The amnzoniunlz salt crystallises in anhydrous needles the calcium salt C,H,,O,Ca,H,O forms microscopic prisms the barium salt C8H,,0,Ba,~H,0 prisms and the copper salt C,H,,O,Cu,H,O pale blue needles ; when anhydrous the latter is deep azure blue.The silver salt C,H,,O5Ag crystallises in quadratic prisms and the lead salt C,H,,O,Pb is amorphous. s-DietiLyldiglycollim,ide C,H120,:NH is prepared by dry distillation of the ammonium salt and is a fusible solid distilling a t 200-215°. s-Diethyldiglycollic acid can be distilled under diminished pressure but a t the ordinary pressure decomposes into carbon monoxide and propaldehyde and an acid which appears to be metameric with a-hydroxybutyric acid. When reduced with 50 per cent. hydriodic acid s-diethyldiglycollic acid yields butyric acid and hydroxybutyric acid. [With OSCAR G ~ ~ ~ a c ~ . ] - w h e n a-bromoisobutyric mid is decom- posed by treatment with water a t the ordinary temperature a process which requires eighteen months h ydroxyisobutyric acid is alone produced whereas by boiling with water S per cent.of methylacrylic acid is also formed ; 14.8 per cent. of methylacrylic acid is formed mhon 1 mol. of NNaOH is used a t B temperature of SOo and 75 per cent. when 4 mols. of 25 per cent. sodium hydroxide are employed. P-Bromoisobutyric acid yields only methylacrylic acid under all conditions. Wislicenus' theory indicates that the a-bromo-acid would yield met hylacrylic acid rather than the /I-bromo-acid. Zinc nzethylacrylkate ( C4H,02),Zn crystallises in prisms and readily polgmerises when heated. The cadmium salt forms small aggregates the sirontiunz salt needles and the lead salt prisms or plates which polymerise on heating; the copper salt is a pale blue insoluble precipitate. [With FRITZ MORSCH~CK and CARL ~o~~o.]-~romomethylacrylic acid is formed when citradibromomethylsuccinic acid is boiled with three parts of water for four hours.Both bromo- and isobromo-meth- acrylic acids are formed when a neutral solution of mesodihromo- methylsuccinic acid is warmed at 60° care being taken that the solution remains neutral. The bromo-acid separates first whilst the isobromo-acid can be extracted with ether. isoBromomethylacrylic acid crystallises in leaflets melting a t 68O. Both acids decompose on heating' into hydrogen bromide carbon dioxide and allene. When boiled for a short time the isobromomethylacrglic acid is converted into bromomethylacrylic acid but on prolonged boiling with aqueous sodium hydroxide both acids are decomposed the iso-acid more slowly into allylene.Heating of the calcium salts produces allene and allylene the iso-acid being first transformed into brornomethylacrylic acid. This change is also effected by exposure of the chloroform solution to which a trace of bromine has been added to sunlight. The silver salts of both acids are decomposed on boiling with water that of bromomethylacrylic acid yielding silver bromide silver carbon dioxide and propaldehyde. The silver salt of the iso-acid changes more rapidly than the other according t o the equation C,H,O,BrAg + H,O = CSH,,O + CO + AgBr. Permanganate oxidises both acids to acetic acid ; a similar behaviour of the two acids is also observed when reduced or electrolysed.62 ABSTRACTS OF CHEMICAL PAPERS. [With CARL Do~~o.]-Allene yields a compound with aqueous mer- curic chloride which has the composition CGH80,C1,Hg and seems to be identical with the substance obtained from allylene by Kutscheroff (Bey.1884,17,13). I n order to distinguish the two gases dependence is especially to be placed on the fact that allylene precipitates ammoniacal silver and cuprous solutions whilst allene does not. With alkaline meroury solutions allylene gives a precipitate (C,H,),Hg ; allene does not. The tetrabromide of allylene is liquid and that of allene a solid melting at 0'. Action of Cyanoacetic Acid on Crotonaldehyde. HUGO HAERDTL (Moncctsh. 1905 26 1391-1402. Compare Braun Abstr. 1896 i 594 ; Doebner Abstr. 1'300 i 536).-a-Cyanosorbic acid CHMe:CH*CH:C(CN)*CO,H is formed by heating a molecular mixture of crotonaldehyde and cyanoacetic acid in an atmosphere of carbon dioxide in a reflux apparatus in a boiling water-bath for six hours.It crystallises from water in stont yellow needles 6-8 mm. long softens and loses carbon dioxide at 150' or melts and decom- poses at 163' when quickly heated. crystallises in nodular aggregates. With bromine in chloroform solution the cyano-acid forms the additive compound C7H70,NBr2 which separates as a fine white crystalline powder and melts at 154-156". When heated in small quantities a t 150-160° until the evolution of carbon dioxide ceases the cyano-acid forms sorbortitde CHMe:CH-CH:CH.CN which when freshly distilled is a clear mobile liquid; i t boils at 50-60' under 1 2 mm. pressure and gradually decomposes in a closed vessel with formation of a brown resin.When boiled with 10-12 per cent. aqueous potassium hydr- oxide in a reflux apparatus the cyano-acid yields a brown amorphous aubeta.ice C,H,O:(?) which is soluble in pyridine or glaeial acetic acid but is insoluble in aqueous sodium carbonate and when boiled with aqueous baryta forms a barium salt (C,H,O,),Ba whilst no definite product of hydrolysis could be obtained by heating the cyano-acid with alcoholic potassium hydroxide dilute hydrochloric acid or 40 per cent. sulphuric acid. G. Y. General Method of Synthesising a/?-Trisubstituted Glycidic Esters and Ketones. GEORGES DARZENS (Compt. rend. 1905 141 766-7'68. Compare Abstr. 1905 i 11 6).-Ethyl a-chloropro- pionate readily condenses with ketones in the presence of sodium ethoxide to form the ethyl esters of the up-trisubstituted glycidic These are colourless liquids with acids of the type O< I a faint odour yielding on hydrolysis the corresponding acids which are unstable and readily break down into carbon dioxide and the corresponding ketone the latter being formed probably from an intermediate oxide by the migration of' a hydrogen atom (compare Pourneau and Tiffeneau this vol.i 20) according to the equations K. J. P. 0. The burium salt (CI7H,02N)2Ba,4H,O CRR' CMe*CO,Et'ORGAKIC CHEMISTRY. 63 I n the following table are given the boiling points of the new ethyl trisubstituted glycidates and of the ketones prepared from them together with the melting points of the semicarbazides of the latter. Melting Boiling point of point corresponding Roiling point of of semi- Ketone.ethyl glycidate. ketone. carbazide. Pressure. Pressure. - - Acetone. ... .._ .. . ... ... ... 80-82" under 20 mm. Methyl ethyl ketone ... 90-93 22 Methyl n-propyl ketone 100-102 16 Methyl n-hexyl 152 28 100-103" under 26 mm. 86-87" Methyl n-heptyl 148-150 16 101-103 15 168-169 Methyl n-nonyl 174-175 15 132-135 15 78-79 Acetophenone ... ... . . .. . 151-154 22 102-104 20 172-173 p-Tolyl methyl ketone,. 160-162 19 116-118 22 184-185 - - - - M. A. W. Preparation of Pure Ethyl Alkylmalonates. ARTHUR MICHAEL ( L p r . Chem. 1905 [ii] 72 537-554. Compare Abstr. 1905 i 564 S55).-0n adding ethyl malonate to the equivalent amount of 50 per cent. aqueous potassium hydroxide cooled to - lo" the mixture solidifies owing to the formation of ethyl potassiomalonate which rapidly decomposes to ethyl potassium malonate and alcohol.This change takes place immediately when ethyl malonate is shaken with 1 per cent. aqueous potassium hydroxide. The partial hydrolysis of ethyl ethylmalonate takes place in less than one minute with 1 per cent. in three minutes with 4 per cent. in thirty minutes with 1 2 per cent. and only to the extent of 20 per cent. in thirty minutes with 25 per cent. aqueous potassium hydr- oxide. When shaken with 25 per cent. aqueous potassium hydroxide a mixture of ethyl ethylmalonate and ethyl malonate develops heat and if extracted with ether after one minute yields 86 per cent. of the ethyl ethylmalonate in a state of purity. Ethyl diethylmalonate undergoes only slight hydrolysis when heated with 50 per cent.aqueous potassium hydroxide. The propylmalonates resemble the ethylmalonates in their stability towards alkali hydroxides whilst the methylmalonates undergo hydrolysis more easily ethyl dimethylmalonate being hydrolysed rapidly with 50 per cent. aqueous potassium hydroxide. These differences in behaviour are utilised in the detection of ethyl malonate and ethylmalonate the presence of 1 and 2 per cent. of which respectively causes the formation of a white precipitate when ethyl diethylmalonate is shaken with 50 per cent. aqueous potassium hydroxide and of ethyl diethylmalonate small percentages of which appear as drops of oil when ethyl ethylmalonate or malonate is shaken with dilute potassium hydroxide.Application of these tests to the ethyl ethylmalonates obtained by the methods used by previous authors shows that these contain varying quantities of ethyl diethylmalonate which cannot be removed by fractional distillation or by Schey's method of purification (Rec. TTCCV. chirn. 1897 16 357).64 ABSTRACTS OF CHEMICAL PAPERS. To prepare pure ethyl ethylmalonate the crude product is shaken with 25 per cent. aqueous potassium hydroxide .and the resulting oil boiled with an excess of the same reagent in a reflux apparatus. After extracting the ethyl diethylmalonate with ether the solution is again boiled with a further quantity of potassium hydroxide neutralised with hydrochloric acid and treated with calcium chloride. The calcium salt obtained in this manner yields pure ethyl ethyl- malonate which boils at 92" under 10 mm.or a t 211' (corr.) under 748 mm. pressure and has a sp. gr. 1.004 a t 20". Ethyl diethylmalonate is purified by boiling with 50 per cent. aqueous potassium hydroxide ; it boils a t 228*5-229.5° (corr.). Ethyl methylmalonate prepared by the action of methyl iodide on ethyl sodiomalonate and purified in the same manner as ethyl ethyl- malonate boils at 198.5-199' (corr.) under 765 mm. pressure. Ethyl dimethylmalonate purified by shaking with a small quantity of 25 per cent. aqueous potassium hydroxide boils at 196-196-5O (corr.) under 753 mm. pressure. Ethyl propylmalonate boils a t 225-5-226' (corr.) under '771 mm. pressiire and has a sp. gr. 0,9897 at 25'125'. Xthyl dipropylmalonate boils at 248-249' (corr.).Ethyl methylmalonate and ethylmalonate are obtained in yields of 90 and 70 per cent of the ethyl malonate used when mixtures of ethyl malonate and methyl and ethyl iodide respectively are shaken with finely-divided potassium hydroxide. Ethyl dimethylmalonate is formed in the same manner from ethyl methylmalonate. When shaken with ethyl iodide and powdered potassium hydroxide ethyl acetoacetate forms ethyl ethylacetoacetate in a yield of 70-80 per cent. of its own weight but in small yields in presence of water. The action of ethyl iodide and potassium hydroxide on ethyl ethyl- acetoacetate takes place only slowly and incompletely. G. Y. Synthesis of Dihydrocamphoric Acid. GUSTAVE BLANC (Compt. rend. 1905 141 1030-1032).-The author has confirmed the con- stitution ascribed by Martine (Abstr. 1902 i 629) to dihydro- camphoric acid namely ~-methyl-6-isopropyladipic acid (compare Perkin and Crossley Trans.1898 '73 23) by its synthesis from iso- propylsuccinic anhydride (Abstr. 1904 i 369 647 ; 1905 i 631). iso- Propylsuccinic anhydride on reduction yields a mixture of a- and P-isopropylbutyrolactones from which on treatment with phosphorus pentabromide and subsequently with alcohol a mixture of ethyl y-bromo- a- and -/I-isopropylbutyrates is obtained of which the a-isomeride condenses with ethyl sodiomethylmalonate to form a tricarboxylic ester. The corresponding free acid melts at 158" losing carbon dioxide and forming a-methyl-6-isopropyladipic acid according to the equations >O -+ C0,Et CHPrP*CH,*CH,Br -+ FHPrs*CO CH,-CH CO,Et*CHPrfi*CH,*CH,*CMe(CO,Et) -+ CO,H.CHPrWH,* CH,-CMe( CO,H) -+ CO2H*CHPr~*C,H,-CHMe*CO2H.ORGANIC CHEMISTRY.65 a-Methyl-6isopropyladipic acid has all the properties of dihydro- camphoric acid except that it is racemic ; dihydrocamphoric acid con- trary to the statement of Perkin and Crossley is optically active having [ a ] 8'30' according to measurements made by Martine a t the author's request. a-isoPropyladipic acid melting at 63' is obtained when ethyl sodiomalonate is substituted for ethyl sodiomethylmalonate in the above series of reactions. M. A. W. Iron Citrates. GIUSEPPE SIBONI (Chem. Centr. 1905 ii 1623-1624; from Boll. Ckim. Farm. 44 625-637).-Ferrous citrate prepared by boiling a solution of citric acid with iron turnings for several days and concentrating in a vacuum is sparingly soluble in water but does not crystallise readily owing to the formation of the more soluble ferric citrate.If oxidation is prevented the citrate separates out even in the presence of free citric acid (compare Martinotti and Cornelio Abstr. 1901 i 667). Ferrous citrate is very readily soluble in ammonia forming ferrous ammonium citrate (Zoc. cit.) which decomposes a t 120' and is readily oxidised in solution but is more stable in the presence of citric acid or an excess of acid ferrous citrate. Sodium ferrous citrate prepared by neutralising crystalline ferrous citrate with sodium hydroxide is more suitable for therapeutic application (compare Baroni Giorn. Farm. Chim. 53 145). Normal ferric citrate C,H,07Fe,3H,0 is obtained by digesting freshly precipitated ferric hydroxide with citric acid for twenty-four hours a t 60-65O filtering and evaporating the filtrate a t 50-60" ; an anhydrous salt separates from the aqueous solution in the form of a red powder on the addition of ether.Ferric citrate has an acid re- action and when treated with ammonia forms ammino- and ammonium salts. I The monoammino-salt 2C,H:,07Fe,NH3 forms a slightly deliquescent red powder which has an acid reaction and is not suitable for subcutaneous injection. 2C,H,07Fe 2NH3 prepared by the action of ammonia on an aqueous solution of the preceding salt or by the oxidat.ion of ferrous ammonium citrate is brown and more deliquescent than the monoammino-salt. The triam- mino-salt 2C,H,07Fe,3NH obtained by saturating a solution of ferric citrate with ammonia is neutral and better adapted for subcutaneous injection.E'erric ammonium citrcbte H,(NH,)Fe,( C6H50?)3 prepared by adding a solution of ammonia to a solution of ferric citrate forms thin yellowish-brown scales is very deliquescent and has a strong acid reaction. Ferric diammonium citrate H(NH,),Fe,( CGHR07)3 also obtained by the action of ammonia on a solution of ferric citrate forms yellowish-green scales and is very deliquescent. Ferric triammonium citrate (NH,),Fe,(C,H,O,) also separates in bright green scales and has an acid reaction. The tetra-ammonium salt prepared by neutralising a solution of ferric citrate with ammonia and evaporating at a low temperature crystallises in scales. This salt is contained in the preparation described in the German Pharmacopaeia ; the preparations of the Russian and Norwegian Pharmacopaias should contain 9.21 and 17.33 per cent.of iron respectively. The diammino-salt (NH,)3Fe?(C,H,07),,.Nq E. W. W.66 ABSTRACTS OF CHEMICAL PAPERS. Laboratory Notes. [Diisobutyl Ketone. isoNitrosobenzy1- acetone. isoButyry1- and iaovaleryl-phenylhydrazines. Erucic Acid.] GIACOMO PONZIO (Caxzettcc 1905 35 ii 394-398).- Diisobutyl ketone (valerone) CO(CH2*CHMe2)2 prepared by the action of zinc isobutyl on isovaleryl chloride boils a t 164-166" under 741 mm. pressure and gives a semicarbaxone C,,H,,ON crystallising from light petroleum in white plates melting at 115' (compare Schmidt Ber. 1872 5 600 ; Williams Trans. lS79 35 130).isoNitrosobenzylacetone can be obtained readily and in good yield by adding isoamyl nitrite and benzylacetone to alcoholic sodium ethoxide and subsequently washing the alkaline solution with ether and saturating i t with carbon dioxide. It crystallises from light petroleum in long shining needles melting at 80-81" (compare Ceresole Abstr. 1883 41). With phenylhydrazine isobutyryldinitroethane yields isobutyryl- phenylhydrazine whilst isovaleryldinitroethane gives isovalerylphenyl- hydrazine aa-dinitroethane being formed in both cases. On passing dry hydrogen bromide into a cold acetic acid solution of erucic acid the latter is converted partly into the isomeric plano- symmetric brassidic acid and partly into bromobehenic acid C22H4302Br which crystallises from alcohol in white prisms melting a t 39-40'.T. H. P. Digitoxose. HEINRICH KILIANI (Bey. 1905 38 4040-4043. Compare Abstr. 1899 i 932).-Digitoxose is considered now to have the constitution OH*CHMe*CH(OH)*CH(OH)*CH2*CH0. It is an aldehyde as on oxidation with bromine in aqueous solution and re- moval of the hydrogen bromide which is formed by means of silver oxide it yields a solution containing the Zactone of digitoxonic acid ; this when boiled with calcium carbonate forms calcium digitoxonate (C,H,,O,),Ca which is precipitated as a glutinous mass. As digitoxosecarboxylic acid also forms a lactone two of the hydroxyl groups of digitoxose must be in the /?- and y-positions whilst the &position of the third hydroxyl is shown by the conversion of calcium digitoxonate into ap-di7~ydroxygZutaric acid when it is oxidised with concentrated nitric acid under cooling with ice and finally at 35-37'".The acid is isolated in the form of its cccZcium salt C,H,O,Ca which is precipitated from its aqueous solution by means of alcohol and on liberation from this as its lactone C,H,O,. This is obtained as an oil which after some time solidifies when stirred; it commences to soften at about 115" melts a t 120" and differs from the previously known dihydroxyglutaric acids in that after cooling and resolidification it melts sharply a t 120" (compare Kiliani and Herold,Abstr. 1905 i '739; Kilianiand Loeffler ibid. 858); it is slightly dextrorotatory in 7.8 per cent. solution in a 2 dcm. tube. G. Y. Mineral Compounds which may possess the R61e like Diastase of Liquefying Malt.JULES WOLFF (Compt. rend. 1905 141 1046-1048).-Starch (25 grams) was treated with 50 C.C. of a solution containing 0.1 per cent. of potassium permanganate andORGANIC CHEMISTRY. 67 10-15 per cent. of sulphuric acid (or 6-7 per cent. of hydrochloric acid) for lfr to 3 hours washed with distilled water and dried a t 30'. The starch underwent no appreciable change in appearance or weight and when treated with malt or acids yielded the same products as ordinary starch. When however a small amount of a basic sub- stance (ammonia alkaline oxides &c.) is present and the temperature is raised to TOo it liquefies immediately. Acids neutral salts and acid phosphates have no action. When the starch treated as described is mixed with distilled water the liquid is slightly acid (to phenolphthalein).The liquefaction does not however occur exactly at the point when the acid is j u s t neutral- ised but may take place both in slightly acid and in slightly alkaline conditions. The change produced in the starch is not due to the removal of mineral salts. N. H. J. M. Liquefying and Saccharifying Actions on Starch. PAUL PETIT (Compt. rend. 1905 141 1247-1249. Compare preceding abstract).-Infusions of malt behave like guaiacol towards ferrous ferric manganous and manganic compounds. Ferric and manganic compounds of malt infusion are reduced by hydrogen. A known volume of sodium hydroxide solution is added to the infusion contain- ing the aluminium compound in an atmosphere of hydrogen. The soda is then exactly neutralised with acetic acid and tincture of guaiacol added.No colorat'ion is produced; addition of a drop of hydrogen peroxide a t once produces a strong blue colour. A solution of commercial albumin (0.25 per cent.) mas shaken with a mixture of equal parts of ferrous ferric and manganous oxides and filtered. The solution which after a time became turbid was again filtered. The clear liquid shows the same reaction with tincture of guaiacol as malt infusion and i t also liquefies starch the action being accelerated by addition of asparagine. I n presence of asparagine there is also a slight saccharification. ZDENKO H. SKRAUP [and in part E. GEINSPERGER E. VON KNAFFL-LENZ FRANZ MENTER and H. SIRK] (Monatsh. 1903,26,1415-1472).-Soluble starch was suspended in eight times its weight of acetic anhydride saturated with hydrogen chloride a t - 20'; after fourteen days at the laboratory temperature the chief product was chlorononadeca-acetylerythrodextrin ; after two months an amorphous substance having the composition of acetyl- chloromaltose ; and after four months tetra-acetylchlorodextrose.CiLlorononccdeca-cLcetylel.ythrodeztrir (C,H70,),ClAc, is soluble in benzene but insoluble in light petroleum has [.ID + 1t36*2Oo and when treated with silver acetate in glacial acetic acid solution yields the icosa-acetyl derivative ~C,H~0,)5(C,H70,)Ac, which sinters at 110' and has [ a ] D + 145.3". When hydrolysed by means of 2 f l alcoholic potassium hydroxide under cooling with snow it yields erythrodextrin having [a] + 160*S0.The product obtained on shak- ing soluble starch with acetic anhydride saturated with hydrogen chloride at 0'. for seven hours in a sealed tube at 40' is a mixture of N. H. J. M. Starch Glycogen and Cellulose.68 ABSTRACTS OF CHEMICAL PAPERS. acetylchloro-derivatives of the starch and its decomposition products. When purified by precipitation from its benzene solution by light petroleum and by ether the acetylchloro-derivative of soluble starch contains 0.268 per cent. of chlorine from which its molecular weight is calculated as 13230. It sinters at 170° becomes brown at 240-250" decomposes with evolution of a gas a t 270° does not give a coloration with iodine and when hydrolysed with 2 N alcoholic potassium hydroxide yields soluble starch. The minimum formula for soluble starch must be therefore ( C6H1005)46-50. When heated on the water-bath with silver acetate in glacial acetic acid solution the acetylchloro-derivative of soluble starch yields Pregl's triacetyl-soluble starch (Abstr.1902 i 136) and a substance which has [a]D 151" and must contain acetyl derivatives of the decomposition products of soluble starch as on hydrolysis it yields a substance which gives a violet coloration with iodine. The action of acetic anhydride saturated with hydrogen chloride at - 12" on glycogen at the laboratory temperature for twenty hours leads to the formation of an acetylchloro-compound which contains 0.15 per cent. of chlorine and has the molecular weight calculated 23630 observed about 25000. It is a white amorphous substance is readily soluble in benzene chloroform glacial acetic acid ethyl acetate or acetone and when shaken with silver acetate in glacial acetic acid solution forms the triacet9Z derivative ( C6H7O5Ac& which sin ters a t 165O becomes opaque at lSOo and melts at 240'.It has [.In + 132*34' and on hydrolysis yields a substance (C,jHIo05),oo which has [ ajD 192.1° and is more soluble than glycogen which has [ u ] ~ 196.6'. The action of acetic anhydride saturated with hydrogen chloride a t - 15' on cellulose (a) for forty-eight hours leads to the formation of a brown amorphous derivative (C,H,O,),,(OAc),o,C1 which on hydrolysis with alcoholic potassium hydroxide yields cellulose (C6H1005)34 (6) or for fourteen days leads t,o the formation of hepta- acetylchlorocellobiose which melts a t 195" and has [ + 75.21".Hepta-acetylchlorocellobiose prepared from cellobiose acetate (Skraup and Konig Abstr. 1902 i 35) melts a t 195" and has [a],+ 74.87". When warmed with silver acetate and glacial acetic acid it yields an acetate which melts a t 200° has [a] - 3045O and is not identical with cellobiose acetate which melts a t 228" and has [a],+43-64". On hydrolysis with alcoholic potassium hydroxide the acetate melting a t 200" yields a brown mass which does not deposit cellobiose on solution in water and addition of a cryhtal of that substance. G. Y. Decomposition of Nitrocellulose at Temperatures below that of Ignition. ALEXIS V. SAPOSCHNIKOFF and W. JAGELLOWITSCH (J. Buss. Phys. Chern. Soc. 1905 37 S23-S3S. Compare Abstr. 1904 i 799).-The authors have determined the velocities of decom- position a t different temperatures below that OF ignition of ordinary pyroxylin having the composition C2~H29(N0,),10 by measuring the volumes of gas evolved in definite time intervals.The volnme-time curves for temperatures from 120" to 135O are widely different in character from those obtained at 140-150° but both exhibit points ofORGANIC CHEMISTRY. 69 inflexion corresponding with maximal values of dvldt (v = volume of gas and t = time) ; the relation between these maximal velocities and the temperature is expressed by the following equations (1) between 120° and 1 3 5 O (du/dt),,,,. = - 2.22 + 0.0192T ; (2) between 135' and 150' (dv/dt),,,, = - 64.22 + 0*48T. A t 150° the decomposition of the pyroxylin is represented by the equation C2,H,,(N0,),,09 = 6'27C0 + S-5SCO + 5.37NO + 2-71N2 + 8H,O + C,,~,,H,,O,,~,N0,, and at 120' the products are 2.31C0 + 1.75CO + 2*06NO + 2-7N2 + 14*41H2O + C,B.,,H,.,0,8,16N3,5(At temperatures above 135O the solid residue contains practically no nitrogen whilst at lower temperatures about 35-30 per cent.ofy the nitrogen but very little hydrogen remains in the undecornposed matter. T. H. P. Behaviour of Vegetable and Animal Textile Fibres with Solutions of Metallic Salts. W. SCHELLENS (Arch. Pharm. 1905 243 617-627).-0ne gram of the fibre was allowed to remain for several days in 50 C.C. of the solution of the metallic salt. The total amount of salt taken up was in part merely adsorbed by the fibre ; this was removed by washing and boiling with water until the wash-water no longer gave any reaction of either constituent of the salt; the amount then remaining '' fixed " in the fibre was determined if possible (compare Zacharias Abstr.1902 i 725). The amounts are expressed as percentages of the weight of the fibre. As a rule i t is either the base or the acid of the salt that is taken up ; proportionately more is taken up out of dilute solutions as compared with strong ones and the amount taken up is greater as the extent to which the salt is hydrolysed is greater; in no case was a coloration of the fibre observed. With ferric chloride the following results were obtained in which tho numbers refer to the weight of iron fixed from solutions containing 1 and 0.1 per cent of iron respectively cotton-wool 0.112 0.112 ; filter-paper 0.23 0.123 ; precipitated cellulose 0.1 12 0.1 12 ; woolly fibre from the seeds of Eriodendron cmfructuosum 1.01 0.56 ; jute 0.56 0.44; raw silk 0.67 0.67 ; yellow Japanese silk (organsin) 0.67 0.615 ; precipitated silk 0.24 ; wool 0.84 0.36.From alco- holic ferric chloride and from aqueous ferric acetate more iron is fixed corresponding with the greater hydrolysis (Schaer Abstr. 1901 ii 603). The case of wool and ferric acetate is exceptional however less iron being fixed than from aqueous ferric chloride of equivalent strength. l\iIercury is taken up by the fibres from aqueous mercuric chloride and also from aquaous mercuric cyanide t o a smaller extent ; only a small portion is fixed however. From aqueous mercuric acetate large quantities of mercury are taken up amounting to 12.3 in the case of wool.Lead is also taken up from the aqueous nitrate; some of it is fixed in the case of Eriodendron silk and wool none in the case of cotton-wool and paper. Chromium trioxide is taken up from aqueous potassium dichromate and iodine (iodide 1) from aqueous potassium iodide. Potassium nitrate in aqueous solution is reduced to nitriteor even further; in the case of silk and wool in a 0.01 per cent.70 ABSTRACTS OF CHEMICAL PAPERS solution neither nitrate nor nitrite could be detected after eight days and in the first case the solution had become alkaline not so in the other. C. F. B. Mixed Triammine Cobalt Salts containing Ethylenediamine and Ammonia. ALFRED WERNER and AD.GRUN (Ber. 1905 38 4033-4040. Compare Werner Zeit. anorg. Chem. 1895 8 1'74; Jorgensen Abstr. 1897 ii 41 453).-17rinitrocobaltethylenediccnzine- ammine (KO,),CO(NH,)C,H,(NI~)~ is prepared by adding ethylene- diamine to a solution o'r' Erdmann's sodium tetranitrodiamminecobalt a t 60' ; it crystallises in brown leaflets or long broad feathery needles is stable towards cold hydrochloric acid but when warmed with the acid is converted into dichloi~oaqzcocobaltethylenediccminea~mine chloride [CI,(OH,)CO(NH,)C,H~(NH~)~]C~ which crystallises iu small greenish- black slightly dichroic needles dissolves in ice-cold water to form a green solution which becomes blue and on dilution red ; silver nitrate precipitates the total chlorine from the aqueous solution as silver chloride.When heated the neutral aqueous solution deposits cobalt hydroxide ; hot hydrochloric acid decomposes the chloride with formation of '' ethylenediamine chlorocobaltoate," which separates in blue leaflets. The action of sodium nitrite on the chloride leads to the formation of trinitrocobaltethylenediamineammine. The nitrate [Cl2(OH,)Co(XH3)C2H,(NH,),]NO is formed by treating the chloride with nitric acid of sp. gr. 1.4 ; it crystallises in green scales having a metallic lustre and is extremely soluble in water. Chlorodiaquocobaltet~ylenediamineu~~~~i~~e oxalate [C1(OH,),Co(NH3)C2H,(NH2)21C,0 is formed by heating t'he chloride of the dichloroaquo-compound with oxalic acid in aqueous alcoholic solution ; it crystallises in glistening blue leaflets is moderately soluble in hot wat8er when treated with hydrochloric acid in aqueous solution yields the dichloroaquochloride from which i t is formed and gives a precipitate of calcium oxalate with calcium chloride in ammoniacal solution.It forms silver chloride only slowly with silver nitrate in aqueous solution and when heated at 105' loses H,O. Chloro6romoaquocobaItethyZenediami?zeammine bs*omide [C~B~(OH,)CO(NH~)U,H,(NH,)~] Br formed by the action of hydrobromic acid of sp. gr. 1.49 on the dichloro- aquochloride crystallises in small olive-green needles sinters and loses H,O at 1 0 5 O forming a yellow crust which dissolves in water to form a yellow solution and forms a sparingly soluble iodide with aqueous potassium iodide and an easily soluble light green nitrate with concentrated nitric acid.When warmed with water and treated with an equal volume of hydrobromic acid of sp. gr. 1.49 it forms dibromoaquocobaZtet?~yZenediamineummine hromide which crystallises in small stellate aggregates of needles showing strong dichroism from bluish-black to brown forms a green powder when fiuely divided and dissolves in water to a brown solution. [ Br,( OH,)Co(NqC,H,( NH,)2]Br G. Y.ORGANIC CHEMISTRY. 71 Amides of a- and p-Aminopropionic Acids. ANTOINE P. N. FRANCHIMOKT and H. FRIEDMANN (Proc. R. Akad. Wetensch. Amster- dum 1905 8 475-477).-a-A~nino~o~ionamide NH,. CHMe* COaNH crystallises from alcohol in needles is very soluble and hygroscopic and melts at 6 2 O ; it gives a crystalline hydrochloyide a crystalline orange-red platinichtoride and a yellow picyate melting a t 199'.P-Aminopropionamide NH,*CH2*CH2.CO*NH2 is very hygroscopic and soluble but was purified by precipitating the methyl-alcoholic solu- tion with ether and forms beautiful crystals melting at 41'. Neither compound is identical with the supposed aminopropionamide isolated from urine by Baumstark in 1873. T. M. L. Configuration of Stereoisomeric Chromium Salts. PAUL PFEIFFER [with A. TRIESCHMANN] (dnnulen 1905 342 283-305. Compare Abstr. 1905 i 33).-It was shown (Zoc. cit.) that two series of isomeric chromium compounds could be obtained and converted into two corresponding series of stereoisomeric oxalates by treatment with potassium oxalate. Thus violet dichlorodiethylenediaminechromium chloride yields red crystals of an oxalate Cr,(C,O,),,SEn where En = ethylenediamine.The isomeric green salt on the other hand gives a violet compound Cr2C12(C,0,),,3En. A constitution for the red salt Cr,(C,O,),,SEn may be obtained by considering it as formed from any two of the complex ions (En,Cr)"' (En2CrC,0,)' [EnCr(C,O,),]' or rCr(C204)3]"' ; four formule are pos- sible (En,Cr)[Cr(C,O,),] (En,CrC204)[EnCr(C,04),1 and two formulze which imply a double molecular weight (En3Cr)[EnCr(C20,)2]3 and (En,CrC,O,),[ Cr( C2O4),]. Since however the red salt reacts with concentrated hydrobromic acid yielding the oxalodiethylenediaminechromiurn bromide (En2CrC20,)Br identical with the salt described by Werner and Schwarz the formulze (En,CrC20,)[EnCr(C,04),1 and ( En2CrC2O4),[Cr(C2O4)J are alone possible.I f the red salt is treated with potassium iodide the in- soluble oxalodiethylenediaminechromium iodide (En,CrC,O,)I separ- ates whilst the soluble potassium dioxaloethylenediaminechromate [EnCr(C,O,),]K remains in solution and on adding excess of potassium iodide solution is thrown down as the double salt [EnCr(C,04),]K,KI,2H20. These facts are in favour of the formula (En,CrC,04)[EnCr(C204)z] for the red salt. The red salt was then synthesised from the oxalodiethylenedi- aminechromium bromide (En2CrCz04)Br and the potassium salt [EnCr( C,O,),]K which were mixed in concentrated aqueous solution ; the red salt must therefore be called oxccZodiethyZe~ediamircechromium dioxuZoetl~y Zene~ium~nechromate. The isomeric salt (En3Cr)[Cr(C204)3] was obtained from triethylene- diaminechromium chloride (En,Cr)Cl and potassium oxalochromate [Cr(C204),]K,; it crystallised i n green lustrous leaflets with 6 or 7H,O,.and was decomposed by a concentrated solution of potass- ium iodide into the iodide (En,Cr)I and the oxalochromate [Cr(C204)31K 372 ABSTRACTS OF CHEMICAL PAPERS. The violet salt Cr,CI,( C,04),,3En has an analogous constitu- tion (En2CrC1,)[EnCr(C,04),] and is dichlorodiethylenediamine- chromium dioxaloetl~ylenediaminechrornat~. With concentrated nitric acid it yielded the green nitrate (En,CrCl,)NO and it can be synthesised from dichlorodiethylenediaminechromium chloride and potassium dioxaloethylenediaminechromate (En2CrC12)C1 + [EnCr(C,O,),]K = (En2CrC1,)[EnCr(C,0,),1 + KC1. Further the analogous violet cobalt salt (E~,COC~,)[E~C~(C,O,)~] was prepared and crystallised in leaflets.The reactions between potassium oxalate and the violet dichloro- diethylenediaminechromium salts is thus represented (En2CrC1,)* + (C,O,)" = (En,CrC,O,)' + 2Cl' ; (En,CrC,O,)' + (C204)" = [EnCr(C,O,),-J' + En ; (En,CrC,O,)' + [EnCr(C,O,),]' = ( En,CrC,O,)[EnCr( C204)J The reactions between potassium oxalate and the green dichloro- salt are on the other hand to be represented (En,CrCI,)' + 2(C2O,j" = [EnCr(C,O,),]' + 2Cl' + En ; (En,CrCl,)' + [EnCr(C,O,),]' = ( En2CrC1,)[EnCr(C20,)21. I n the case of both salts the oxalo-group replaces the chlorine of the positive ion En,CrC1 in the green salt converting it into the negative dioxalo-ion EnCr(C204) but in the case of the violet salt also giving the mono-oxalo-positive ion En,CrC,O,.It is pointed out that all these observations are in agreement with the view that the two series of salts are stereoisomeric. K J. P. 0. Resolution of Leucine into its Optically Active Components by means of its Formyl Derivative. EMIL FISCHER and OTTO WARBURG (Ber. 1905 38 3997-4005. Compare Abstr. 1900 i 646).-B'ormyZ-leucine C7HI3O3N prepared by heating leucine repeatedly with 93.5 per cent. formic acid and washing carefully so as t o remove unchanged leucine softens at about 112' and melts at 115-1 16" (corr.) ; it crystallises from water in microscopic octahedra and is converted by phosphorus pentachloride into a formyl- leucyl cldoride C,H,*CH(NH*CHO)*COCl which is a colourless indistinctly crystallme powder.B'ormylglycine CHO*NH*CH,*CO,H p.repared by the action of formic acid on aminoacetic acid crystallises from water or alcohol softens at 149' and melts and decomposes a t 153-154" (corr.). When formyl-leucine is heated with an alcoholic solution of brucine the brwine salt of formyl-d-leucine separates in a nearly pure state and on decomposing the latter with N-sodium hydroxide formyl-d- Zeucine is obtained ; it crystallises from water in long thin prisms melts at 141-144' (corr.) and has [.ID i-18.8' a t 20" in 10 per cent. alcoholic solution. B'ormyl-1-leucine prepared by decomposing the more soluble brucine salt has the same melting point as the d-form and [.ID - 18.5' at 20'. To hydrolyse the formyl-derivatives they are heated with 10 per cent. hydrochloric acid the excess of hydrochloric acid and the formic acid removed by distilling under reduced pressure and the active amino-ORGANIC CHEMISTRY.73 acid separated by adding the calculated quantity of lithium hydroxide in alcoholic solution. d-Leucine has [ a ] - 15.6" at 20° whilst 1-leucine has [.a] + 15.6" at the same temperature. These values agree fairly closely with those obtained with the active leucines prepared from the benzoyl-leucines (Fischer loc. cit. ) but a specimen of 1-leucine prepared from proteids by E. Schulze had [ a ] D + 16.9". On the other hand d- leucine obtained from the urine of a rabbit to which inactive leucine had been administered had [ a ] - 15.5" a t 20'. If the value obtained with Schulze's product corresponds with the true active leucine the products prepared from the formyl and benzoyl derivatives must con- tain about 10 per cent.of the racemic foim. W. A. D. Synthesis of Polypeptides. X. Polypeptides of the Diamino- and Hydroxyamino-acids. EMIL FISCHER and UMETARO SUZUKI (Ber. 1905 38 4173-4196. Compare Abstr. 1905 i 121).-Diamino- propionic acid dipeptide is obtained as a tough gummy mass with an alkaline reaction on heating the hydrochloride of the dimethyl ester with water at 80" ; the picyate is a citron-yellow crystalline powder which sinters at 200" and melts and decomposes a t 222" (corr.); the crystalline ?hydrochloride decomposes above 250'. Inactive Zysyl-lgsine C12H2603N4 forms a yellow crystalline picrate which sinters a t 170° melts a t 1 8 5 O (corr.) to a bright brownish-red oil and decomposes on further heating ; the hydrochloride crystallises in short twin prisms melting at about 205" (corr.). Histidine anhydride forms a picrute separating in stellar aggregates of citron-yellow flat crystals which when heated become brown at 235" (corr.) and decompose at 255" (corr.) ; the ILydrochZoride crystallises in thin colourless prisms aggregated in star-like clusters which melt and decompose at about 320" (corr.).Histidylhistidine C,,H,,O,N forms a picrate crystallising in citron- yellow prisms which melt at 165-175". Arginine methyl ester forms a citron-yellow crystalline picrate which becomes brown at 200" and melts and decomposes at about 21s' (corr.) and a nitrate crystallising in large prisms and melting a t 189' (corr.). isoSey9lisoserine methyl ester C7HI4O5N2 forms large crystals which begin to change a t 100' and are completely melted a t 180".isoXerylisoserine is a colourless powder which sinters at 220" and decomposes at a higher temperature ; its aqueous solution has an acid reaction. Serine nzetlbyl ester is a colourless strongly alkaline syrup; the hydrocldoride forms colourless transparent hexagonal plates melting a t about 114' (corr.) and decomposing above this temperature. Serine anhydride C6HI0O4N2 is obtained either as microscopic four-sided oblique plates which become brown at 265" (corr.) and decompose at 280" (corr.) or in long narrow pointed prisms melting at 226' (corr.). Xerylserine is obtained as a mixture of two isomerides; the one present in greater quantity crystallises in stellate leaflets and on heat- ing becomes brown a t 200' and decomposes at 210" (corr.).The aqueous solution is strongly acid and dissolves copper oxide to form a blue 9 VOL. xc. i.74 ABSTRACTS OF CHEMICAL PAPERS. solution. The hycZrocMorkZe of the ester crystallises in star-like aggregates of pointed needles A method of preparing arginine from edestin is described. E. F. A. Action of Carbamide on Compounds of Cyanoacetic Acid. GUSTAV FRERICHS and L. HARTWIG (J. pr. Chem. 1905 [ii] 72 489-51O).-When boiled together carbamide and ethyl cyanoacetate interact to form an ester CO<NH>C*CH2*C02Et N which crystallises from water in long colourless needles melts and decomposes at 1 6 2 O has the solubility 1:8333 in water at 2 4 O and gives a blood-red coloration with traces of aqueous ferric chloride.It has acidic properties liberates carbonic and acetic acids from their salts and in hot aqueous solution dissolves metallic zinc with evolution of hydrogen. The potassium C6H703N,K,2 H20 ammonium silver and copper (C6H70,N2),Cu,2H20 derivatives are described ; the aniline compound C6H,03N2,C6H7N crystallises in needles and melts and decomposes at 144-145' ; the m-tohidine compound crystallises in white leaflets and melts and decomposes at 143O ; the strychnine compound C6H803N2,C21H2202N2 crystallises in sheaves of flat needles and melts and decomposes at 188". The ester does not interact with benzaldehyde formaldehyde or hydroxylamine ; on hydrolysis with alcoholic potassium hydroxide or aqueous ammonia it yields carbon dioxide alcohol ammonia and acetic acid ; when heated with 25 per cent.hydrochloric acid in a reflux apparatus it yields pure ammonium chloride but when warmed with dilute nitric acid a mixture of ammonium nitrate and oxalate. With bromine in aqueous solution it forms an unstable oily additiwe compound which is soluble in ether and liberates iodine from potassium iodide. The corresponding methyl ester COGg>C*CH2*C02Me is formed by heating carbamide with methyl cyanoacetate ; it crystallises from water in colourless leaflets containing l$H20 melts a t 1 1 6 O or when anhydrous at 128O gives a red coloration with aqueous ferric chloride and is slightly more soluble than the ethyl ester which it resembles in its chemical properties. The potassium C,H,O,N,K ammonium C5H5O3N2NH and copper (C5H503N2)2Cu,~H,0 derivatives are described ; the aniline compound C,H603N,.,C6H7N cry stallises in white leaflets and melts at 120' the m-toluadzne compound C6H703N,NH4 c13H1703N89 C6H803N2Br2 c12H1503N3) forms sheaves of slender needles and melts and decomposes at 120-121° ; the strychnine compound C26H2,05N4 crystailises in flat white needles and melts and decomposes at 2119 The methyl ester forms an unstable bromine derivative similar to that obtained from the ethyl ester.G. Y.ORGANIC CHEMISTRY. 75 Mercuric Oxycyanide. KARL HOLDERMANN (Arch. Pharm. 1905 243 600-617. Compare Holdermann Abstr. 1904 i 301 and Richard J. J’harm. Chim. 1903 18 553).-Sy dissolving mercuric oxide in aqueous mercuric cyanide and cryqtallising the solution fractionally it was shown that only one oxycyanide is formed; this has the composition Hg(CN),,HgO.It is never possible to convert mercuric cyanide quantitatively into this compound ; the most con- venient method of separation is to mix the cyanide and oxide in equivalent proportions and moisten the mixture with a little water in a conical flask ; heat the mixture for four hours on the water-bath replacing the water as it evaporates ; extract the mass with boiling water (500 C.C. for 13.5 grains of cyanide and 11.5 grams of oxide); filter the solution and allow it to crystnllise; in these circum- stances about 80 per cent. of the cyanide is obtained as oxycyanide. The amount of oxide in a sample of mercuric oxycyanide can be determined very readily and accurately by adding sodium chloride t o a solution of the sample and titrating the oxide with N/10 hydro- chloric acid with methyl-orange as indicator.Commercial oxycyanide contains but a small proportion of oxide. The pure oxycyanide in aqueous solution gives no yellow coloration with potassium iodide but a n almost colourless crystalline precipitate which dissolves in excess of the aqueous potassium iodide forming a colourless solution. Its electrolytic conductivity is even less than that of mercuric cyanide. The antiseptic action ascribed t o it has been observed with very impure samples and may not belong to the pure substance a t all. Methods of analysing samples of mercuric oxycyanide and tabloids containing it and sodium hydrogen carbonate are described in detail. C.F. B. Blue Iron-cyanogen Compounds and the Cause of their Colour. 111. KARL A. HOFMANN and F. RESENSCHECK (Annalem 1905 342 364-374. Compare Abstr. 1905 i 756).-1t has been shown (Zoc. cit.) that the blue iron-cyano-compounds formed either from ferric salts and ferrocyanides or ferrous salts and ferricyanides are to be regarded as derivatives of potassium ferrocyanide in which potassium is either wholly or partly replaced by tervalent iron. The substances obtained on oxidising the compounds formed from ferrous salts and ferrocyanides do not belong to this class. The material so prepared from potassium ferroqanide and a ferrous salt in molecular proportions in acid solution is quite different from the soluble Prussian blue but identical with Williamson’s violet (Pe”( CN),jFe”’K,nH20 which is produced on oxidation of the residue (Fe”(CN),}Fe”K left in the preparation of hydrocyanic acid.A third blue cornpourLd (Fe(C“),)FeK,H,O isomeric with William- son’s violet is formed when molecular proportions of a ferrous salt and potassium ferrocyanide are brought together in neutral solution a t the ordinary temperature and then oxidised with hydrogen peroxide. It has up to the present been confused with the soluble Prussian blue; it has a greenish-blue colour in aqueous solution is stable76 ABSTRACTS OF CHEMICAL PAPERS. towards a 5 per cent. solution of ammonium carbonate but rapidly decomposed by 4 per cent. ammonia. It is completely insoluble in oxalic acid and in aqueous solution is converted by dilute sulphuric acid into an insoluble blue compound.The constitutional formula (Fe"( CN),)(Fe"'OH)KH is suggested for this compound. The cause of the colour of the iron-cyanogen compounds is discussed ; it is pointed out that the colour is associated with the presence of both bivalent and tervalent iron in the same molecule. Similarly red lead contains both bivalent and tervalent lead; and the deep indigo-blue sulphur sesquioxide although the other oxides of sulphur are colour- less also contains sulphur showing two degrees of valency. This peculiar relation between constitution and colour will be discussed in a later communication. K. J. P. 0. S o m e Derivatives of Octahydroanthracene and Perhydro- anthracene. MARCEL GODCHOT (Compt. rend. 1905,141,1028-1030.Compare Abstr. 1904 i 987 ; 1905 i 201).-Bexal~yd~*oantl~rone oxime C14Hi6:N*OH obtained by heating hexahydroanthrone and hydroxylamine acetate crystallises from alcohol in small colourless needles melting a t 1 4 3 O readily soluble in alcohol ether or light petroleum and reduced by sodium in alcoholic solution to octahydro- anthramine C,,H,?*NH a yellow liquid boiling a t 182' under 12 mm. pressure and having strongly basic properties? combining with the carbon dioxide of the air ; the hydrochloride C,,H,7*NH,,HCl forms colourless prisms decomposing without fusion at 188" and readily soluble in water or alcohol ; the piwate forms yellow needles melting at 212O readily soluble in alcohol less so in ether or light petroleum ; the ucetyl derivative Cl4Hl7* N HAc crystallises from alcohol in beautiful colourless needles melting at 183" and soluble in benzene ether or chloroform.Perhydroanthracene C14H24 prepared by reducing anthracene with hydrogen iodide and phosphorus (compare Lucas Abstr. 1888 120l) can be obtained more readily by the action of hydrogen iodide and red phosphorus on octahydroanthracene in sealed tubes at 250" or by the direct hydrogenation of octahydro- anthracene in the presence of reduced nickel at 180° a liquid hydro- carbon probably dodecahydroantlwacene CI4H2 being formed a t the same time. 31. A. W. Fluorene Compounds. FRITZ ULLMANN and R. VON WURS- TEMBERGER (Ber. 1905 38 41 05-41 lo).-9 9-Diphenyvuorene [clil.lhen~lbip?~enyZenemet?~ane] 76H4>CPh prepared by the action of bromobenzene and magnesium on methyl diphenyl-2-carboxylate crystadlises from acetic acid in colourless prisms melts at 222' (corr.) and boils without decomposition above 400'.C6H4 C H BiphenylenemethyZcarbinol[9-met?~ylJEuorene alcohol] I 4>CMeoOH CAH prepared by the action of methyl iodide and magnesiu; 0 fluorenone crystallises from benzene in glistening prisms and melts at 174.5'.ORGANIC CHEMISTRY. 77 The corresponding ethyl compound yGH4>CEt OH crystallises from light petroleum and melts at 101'. Biphenylenepropylene [9-ethylidene~%orene] y6H4>C:CHMe pre- C6H4 C J L pared by the action of acetic and hydrochloric addcon the preceding compound crystallises from acetic acid and melk a t 104'. Bipheny Zene benxylcarbino E [9- benxy Yuorene a Zcolhol] 7GH4 OH C,H4>c<CH,Ph ' separates from a mixture of benzene and light petroleum in large crystals and melts at 139O.Biphenylenephenyletliylene [9-benxylidene- fluorene] yeH4>C:CHPh separates as a yellow oil which crystallises and melts at 76'. C6H4 Bipheny Zene - a-naphth y Zcarbino I [9-a-naphth yljluorene alcohol] OH F"H">C<C 10 H ' 7 C6H4 crystallises from a mixture of benzene and light petroleum and melts at 151.5'. It is reduced by zinc and acetic acid to 6iphenyZene-a- naphthylmethane [ 9-~-naphthylJEuorene] C23H16 which separates from alcohol in colourless needles and melts a t 103.5'. Biphenylene-p- aminophenyl-a-naphthy Zmethane [9-p-arninopherql-9 -a-naphth yljluorene] prepared by the action of aniline on the FsH4>c<; C H ; *NH carbinol separates from alcohol in small white strongly electric crystals and melts at 145'.The hydrochloride C,,H,,N,HCl is a white crystalline powder and melts and decomposes at 225-5230'. CtjH 10 7 T. M. L. Acetylene Linking. FRITZ STRAUS (Annalen 1905 342 190-265).-Phenylacetylene together with copper phenylacetylide and diphenyldiacetylene are formed when copper phen ylpropiolate (CPhiC*CO,),Cu,4 H,O is heated. Solutions of sodium phenylpropiolate and cupric chloride are mixed and steam passed into the mixture when the hydrocarbon distils over. If copper phenplpropiolate is treated with pyridine 01' quinoline only copper phenylacetylide and diphenyldiacetylene are formed . Copper phenylacetylide dissolves in boiling acetic acid with an orange-yellow coloration no appreciable quantity of hydrocarbon being evolved.The solution deposits on cooling or on addition of ice-cold water the double salt CPhiCCu,CH,-CO,Cu which crystal- lises in orange-yellow leaflets ; this substance oxidises very readily its solution in organic solvents being decomposed by contact with air copper phenylacetylide being formed. If air is passed through its boiling solution in acetic acid diphenyl buteninene is formed a reaction which is thought to indicate the presence of more than one bydro- carbon radicle in the molecule of the copper compound,78 ABSTRACTS OF CEEMICAL PAPERS. Diphenyldiacetylene CPhiC*CiCPh is prepared by treating copper phenylacetylide with an aqueoiis solution of potassium ferricyanide made alkaline by potassium hydroxide or by warming copper phenyl- propiolate with pyridine ; it is crystallised from methyl alcohol and melts at 86-87'.Diphenylbuteninene CHPh:CH*CiCPh prepared by dissolving copper phenylacetylide in acetic acid in a flask from which the air has been expelled boiling and then sucking air through the mixture crystallises in colourless prisms melting a t 96.5 - - 9 7 O . The solution in acetic acid becomes blue on the addition of sulphuric acid and then forms a dichroic violet-red liquid. [With RUDOLF MULLER.]-~ chloroform or carbon disulphide solution diphenyldiacetylene yields a mixture of stereoisomeric tetra- bromides CPhBr:CBr*CBr:CPhBr from which the hydrocarbon is re- generated by reduction with zinc dust in acetone solution. It is note- worthy that more than four atoms of bromine cannot be added to the molecule.A dibromide CPhBr.:C:C:CPhBr (?) is formed as an inter- mediate product crystallising in yellow rhombs melting a t 142'. The mixture of tetrabromides melts at 120-140° and a tetrubyomide (m. p. 172') can be isolated from this mixture by cryetallisation from petroleum. When diphenyldiacetylene in acetic acid is treated with excess of bromine a tribrorno-derivative is obtained which is not as Hollemann thought; a tribromo-derivative of the diacetylene but tribromo-a- phenylnaphthalene CsH,<cph :b Br ; it crystallises in yellow CBr :CBr podules melting a t 151'. When reduced with alcohol and sodium amalgam it is converted into a-phenylnaphthalene C,,H7Ph which boils a t 192-195' under 17 mm. pressure and is oxidised by potassium dichromate and sulphuric acid to o-benzoylbenzoic acid.Reduction of the tribr;.omide with zinc dust and acetic acid yields a dibromo-a-pJienylnccpJ~thccZene C,,H,Br2Ph which forms crystals melting a t 111-111.5°. Diphenyldiacetylene is reduced by boiling in alcoholic solution with zinc dust light being carefully excluded to the labile cis-cis-diphenyl- butadiene 2>C:C*C:C<,h which crystallises in leaflets or four- sided plates melting at 70-70*5'; when exposed t o sunlight this hydrocarbon is transformed into the stable trans- trans-diphenyl- butadiene which melts at 142-145' or when pure at 150-151O. As an intermediate product in the reduction cis-diplhenylbuteninene %>C:C<gCPh is formed ; it is a yellow oil freezing a t about Oo and boiling at 187.5-188O under 12 mm.pressure ; when exposed t o sunlight it is transformed into the stable trccns-diphenylbuteninene (m. p. 97") above described. The cis-diphenylbuteninene forms with bromine a mixture of tetrabromides from which needles melting and decomposing at 205O leaflets melting at 135-136" and prisms melting and decomposing at 160' can be isolated. The two iso- merides with higher melting points are probably identical with the cornpouads obtained from trans-diphenylbuteninene. On treatment HHORGANIC CHEMISTRY. 79 with hydrogen bromide the same compound is obtained from both the cis- and trans-isomerides. cis-trans-Diphenylbutadiene ?>C C C C<Fh is prepared from HH trans-diphenylbuteninene by reduction with zinc copper couple in alcohol solution in the absence of sunlight and crystallises in leaflets melting at 150-151'.It is the most unstable of the diphenyl- butadienes and passes on transitory exposure t o light into the stable trans-trans- f orm. On bromination cis-cis-diphenylbutadiene yields in chloroform solution a mixture of tetrabromides from which two compounds can be isolated one crystallising in leaflets melting at 225' and a second crystallising in prisms melting and decomposing a t 180". trans-Diphen ylbu t eninene yields a tetra bromide CBrPh:CBr*CHBr* CHBrPh when brominated in chloroform solution which crystallises in leaflets melting and decomposing a t 197' ; a t the same time a second tetra- bromide is formed melting and decomposing at 157-158'. Hydrogen bromide converts the trans-diphenylbuteninene into diz~J~e?~?lZbutndiene dibromide Ci6Ki4Br2 which crystallises in needles melting and decomposing a t 142O and a bromodiphenylbutadiene Cl(;HL3Br which crystallises in needles melting a t 11 3.5-1 14' ; the latter monobromo- derivative is not changed by hydrogen bromide and is converted by bromine in to bromodipphenylbutadiene dibrornide C16H13Br3 crystallis- ing in needles melting at 145-147'. All the diphenylbutadiene bromides are reduced by zinc dust or the zinc copper couple to the stable trans-trans-diphenylbutadiene (m.p. 150-1 5 1"). Az-DiphenyZ6utene CH,Ph*CH:CH*CR,Ph prepared from diphenyl- butadiene crystallises in needles melting a t 45-45.5' and yields a dibromide which by heating with quinoline is converted into diphenyl- butadiene.When oxidised with potassium permanganate a t O" ,@y-di%ydroxy-a8-dipJ~enyZbutune CH,Ph-CH(OH).CH(OH)*CH,Ph is obtained as needles melting at 125'. The diphenylbutene can also be prepared by reducing with alcohol and sodium amalgam diphenyl- diacet ylene trans - dip h en yl bu t en inene truns-truns-dip hen yl bu t adiene and cis-cia-diphenylbutadiene. A2-Phenylbutene CH,Ph*CH:CHMe is formed from phenyl- butadiene by reduction with sodium amalgam and alcohol but styrene is not reduced under similar treatment. Phenylacetylene is reduced by zinc dust and alcohol to styrene and diphenylbutadiene ; with zinc dust and acetic acid diphenyldiacetylene yields a number of reduction products. Tolane is not attacked by sodium amalgam and alcohol but by zinc dust and alcohol is converted into isostilbene.When oxidised stilbene yields isohydrobenzoin and isostilbene benzoin. K. J. P. 0. Action of Ethylene Dibromide on p-Nitrosodialkylanilines 11. HENRY A. TORREY (Amer. Chern. J. 1905 34 475-481. Compare Abstr. 1 902 i 755).-Di-p-nitrosodimethylaniline-ethylene,80 ABSTRACTS OF CHEMICAL PAPERS. obtained by the action of ethylene dibromide on p-nitrosodimethyl- aniline is identical with tetramethyldiaminoglyoxime N-phenyl ether described by Pechmann and Schmitz (Abstr. 1898 i 309). When the reaction takes place in alcoholic solution tetramethyldiaminoazoxy- benzene is produced. By the action of dilute nitric acid on tetraethyl- diaminoglyoxime N-phenyl ether tetramethyldiaminoglyoxaldianil is formed which when boiled with an alcoholic solution of salicyl- aldehyde is converted into o-hydroxybenzylidene-p-aminodimethyl- aniline ; whilst by the action of benzoyl chloride benzoyl-p-amino- dimethylaniline is produced.The dianil yields a bronze-coloured picrate gives a blue precipitate with mercuric chloride and a blue coloration with dilute solutions of bromine chlorine hydrochloric acid and acyl chlorides. By the action of ethylene dibromide on p-nitrosodiethylaniline tetraethyldiaminoglyoxime N-phenyl ether (Pechmann and Schmitz Zoc. cit.) and p-nitrosodiethylaniline hydrobromide are produced. E. G. New Derivatives of Pentabasic Phosphoric Acid P( OH)5. PAUL LEMOULT (Compt. rend. 1905 141 1241-1244).-The phos- phorus alkyloxytetra-anilides of the type P(OR1)(NHR) where R1 and R represent alkyl and nryl radicles respectively (compare Abstr. 1904 i 807) condense with acetic or propionic acids to form com- pounds of the type COR1*O*P(NHR) which may be regarded as the acetates or propionates of the base OH*P(NHR),.These compounds form well-defined crystals usually containing acid of cry stallisation which they lose a t 100'; they are readily decomposed by water or alkalis to form the corresponding phosphoryltrianilides PO(NHR) and by hydrochloric acid t o form the corresponding chlorotetra- anilides. The o-tohidine-compound OAc*P(NH*C,H,Me),,AcOH forms beautiful colourless crystals melting a t 221". COEt.O*P(NH*C,H,Me),,EtCO,H forms small crystals melting a t 203'. CH,C1*CO*O*P(NH*CsH4Me) forms a confused crystalline mass. The 1 3 4-xylidine-compound OAc*P(NH*C6H,Me,),,l-5AcOH forms beautiful colourless spangles several millimetres in dimensions melting a t 2 10'.The compounds OAc*P(NHPh) and COEt-0-P(NHPh) obtained by the action of acetic or propionic acid respectively on trianilinephenylphosphimide P(NHPh),iNPh (Abstr. 1903 i 672) crystallise from a mixture of benzene and ether and melt a t 206-207' and 240' respectively. The compound The compownd M. A. W. Partial Reduction of Aromatic Dinitro- and Polynitro- derivatives by Electrolytic Methods. KURT BRAND (Bey. 1905 38 4006-401 5).-m-Nitrophenylhydroxylamine can be easily obtained by the electrolytic reduction of rn-dinitrobenzene in an approximately neutral solution ; the cathode cell consists of a porous pot containing the m-dinitrobenzeae dissolved in aqueaus alcohol with a little aceticORGANIC CHEMISTRY. 81 acid and sodium acetate.The anode liquid used is 20 per cent. sul- phuric acid. The cathode is made of silver gauze and the anode is a perforated lead plate. m-NitrophenyZ?LydroxyZumine NO,*C,H,*NH*OH prepared in this way separates from hot benzene in thick yellow crystals melts at 118-1 19" and is easily oxidised by alcoholic ferric chloride to 9%-nitronitrosobenzene (Bamberger and Hubner Abstr. 1904 i 115) ; when warmed with dilute sulphuric acid m-nitrophenylhydroxylamine is converted into 2-nitro-4-aminophenol. The substance melting at 178" described by Wohl (D.R.-P. 84138) as m-nitrophenylhydroxyl- amine seems to be a transformation product of the latter ; its nature is being investigated. On reducing m-dinitrobenzene in alkaline solution using mercury as the cathode so as to prevent the formation of a solid film on the latter and thus stopping the action m-dinitroazoxybenzene is obtained ; the yield is good and the method can be used for preparing the substance.The reduction of m-dinitrobenzene in strongly acid solution gives m-nitroaniline the yield being good. W. A. D. Hydrogenation Derivatives of Carvacrol. L ~ O N BRUNEL (Compt. Tend. 1905 141 1245-1247. Compare Abstr. 1904 i 158).-When carvacrol is directly hydrogenated in the presence of reduced nickel at 160" a mixture of two isomeric hexahydrocarvacrols (a- and P-carvacro- menthols) is produced ; they are probably the two stereoisomerides formed by the hydrogenation of an intermediate ketone the correspond- ing carvacromenthone (compare Abstr.1905 i 197 363) ; when the hydrogenation is effected at 1 15-120° P-carvacromenthol is the only product. a-Caruucromenthol is a colourless oily liquid with an odour of thyme and boils at 219'. P-Carvncromenthol an oily colourless liquid with an odour of mint boils a t 2 2 2 O does not crystallise at - lo' has a sp. gr. 0.918 a t O' and forms well-defined esters with acids. The formnte HC02*CloH19 obtained by the direct action of formic acid and the alcohol in the cold is a colourless mobile liquid with an agreeable odour like that of camphor boils a t 229O and has a sp. gr. 0.954 at 0'. The acetate OAc'CloH19 prepared by heating acetic acid and the alcohol in sealed tubes at 130° is a colourless mobile liquid with a strong odour which boils at 231.5" does not crystallise at - lo' and has a sp.gr. 0.933 at 0'. The acid succinute CO,H*C,H,* CO2*Cl0Hl9 prepared by heating the alcohol with succinic anhydride at looo crystallises from light petroleum in thin colourless odourless needles melting at 74" and soluble in dilute alkali solutions. C0,H*C,H,-C0,*C,oH,9 crystallises from alcohol in large colourless odourless crystals melting at 136' and soluble in alkali solutions. The m i d phthulate M. A. W. Action of Phosphorus Pentachloride on P-Naphthol. E. BERGER (Compt. Tend. 1905 141 1027-1028).-At temperatures below 1 30° phosphorus pentachloride reacts with P-naphthol to form P-dinaphthyl ether but when the temperature is raised to 135-140' and82 ABSTRACTS OF CHEMICAL PAPERS. the heating continued for twenty-four hours a mixture in the propor- tion 3PC1 SC,,H7*OH yields 30 per cent.of P-chloronaphthalene (compare Cleve Abstr. 1876 ii 81; Rimarenko Abstr. 1876 ii 297) together with small quantities of 1 2- 2 4- 2 6- and 2 8- dichloronaphthalenes PP-dinaphthylene oxide and di-P-nnphthyl hydrogen phosphate melting at 143'. 2 3-Dihydroxyanthracene. KASIMIR LAGODZINSKI (Annalen 1905 342 90-111. Compare this vol. ,i 98).-2 3-Dihydroxy- anthracene which has been prepared in order to procure 2 3-anthra- quinone is obtained from the dimethyl ether of hystazarin which is synthesised from veratrole. 0-3' 4'-Bimethox ybenxo ylbelzxoic acid C,H (OMe) ,*CO*C,H,*CO,H prepared by warming a carbon disulphide solution of veratrole with phthalic anhydride and aluminium chloride crystallises in colourless leaflets melting at 233' and is soluble in concentrated sulphuric acid with a blood-red coloration ; the ammonium salt forms white needles and the silver salt white crystals.The acid does not react with hydroxylamine but with phenylhydrazine yields 2-phenyl-4-veratryl- phthakazone (? o*C6H4>C*C,H,(OMe) which crystallises in yellow needles melting at 189". The dimethyl ether of hystazarin ( 2 3-dimet?~oxyanthrapuinone) M. A. W. NPh-N C,H,<CO>C,H,(OMe) co is formed when dimethoxybenzoylbenzoic acid is warmed with concentrated sulphuric acid and crystallises in golden-yellow needles melting a t 237' ; it yields a blood-red solution in sulphuric acid. Prolonged heating a t 100" with sulphuric acid con- verts the dimethyl ether into the monomethyl ether OH*C,,H,O,*OMe which crystallises in orange-yellow leaflets melting a t 236".The com- plete hydrolysis of the ether to hystazarin is best effected by heating with hydrobromic acid of sp. gr. 1.49 under pressure a t 180'. On reduction with zinc dust and 5 per cent. ammonia the dimethyl ether of hystazarin is converted into 2 3-dimethoxyanthracene C,,H,( OMe) crystallising in colourless leaflets or needles melting a t 204"; the alcoholic solution has a blue fluorescence and the solution in sulphuric acid an orange-yellow coloration ; the picrate is dark brown in colour ; in acetic acid solution it is converted into a polymeride melting a t 314O and in alcoholic solution it is oxidised to the corresponding anthra- quinone. When warmed with hydriodic acid (b.p. 127") the dimethoxy- anthracene yields 2 3-dihydroxyanthracene7 which crystallises in straw- yellow leaflets decomposing at 180-1 92'. 2 3-Diacetoxyanthracem forms pale yellow crystals melting at 155-160'. Attempts to oxidise this dihydroxyanthracene to the corresponding 2 3-dihydroxyanthraquinone were not successful. When dimethoxyanthracene is heated in acetic acid solution with hydriodic acid of sp. gr. 1.70 a compound CsoHzo04 of unknown con- stitution is formed ; it crystallises in yellow leaflets decomposing at about 260". It forms in sulphuric acid an orange-yellow solution which becomes blood-red on heating; its solution in alkali hydroxides is yellow. It can be methylated by methyl sulphate and potassiumORGANIC CHEMISTRY. 83 hydroxide and acetylated by acetic anhydride.With ether it forms the compound C30H2004 20Et2 which crystallises in greenish-yellow plates. K. J. P. 0. Aromatic Sulphine Balses. FRIEDRICH KEHRMANN and A. DUTTEN- HOFER (Ber. 1905 38 4197-41 99).-The pkatiniciiloride of diphenyl- methylsulphine (C,,H,,S),PtCl forms a yellowish-white crystalline precipitate melting a t 169.5' ; the dichromate separates as a yellow flocculent precipitate which rapidly becomes green and decomposes forming a substance crystallising in orange needles and melting at 129". Di-a-naphth ylmeth ylsulphine platinich Zoride ( C,,H,7S)2Pt Cl forms a flesh-coloured powder and melts at 162-163' ; the aurichloride is yellow and the dichromate is orange.Di-P-naphthylmethyls~~p~~ne platinichloride melts a t 136-146'. Behaviour of Esters of Organic Acids when heated with Orthophosphoric Acid. PAUL N. RAIKOW and P. TISCHKOW (Chem. Zeit. 1905,29 1268-1273).-.The combined action of heat and ortho- phosphoric acid on the methyl esters of various organic acids was studied with the object of determining whether or not the ester lost carbon dioxide leaving the methyl group attached to the rest of the molecule. The acid used was first dehydrated by heating 60 C.C. of syrupy phosphoric acid of sp. gr. 1.7 to 200' in a round-bottomed flask of 200 C.C. capacity; after cooling to below loo' a measured quantity of the ester was added and the mixture was then boiled over iron gauzo. The flask was attached to a reflux condenser the upper end of which was connected by an india-rubber tube to one limb of a U-tube containing 50 C.C.of concentrated sulphuric acid ; the other limb was connected to an apparatus for determining the amount of car- bon dioxide evolved by measuring the water which it displaced from a wide-mouthed bottle of 2 litres capacity filled with water. The boiling was continued until the evolution of gas had ceased. The gas remain- ing in the bottle was examined for carbon dioxide and carbon monoxide; the object of the U-tube with strong sulphuric acid was to absorb any dimethyl ether which might be formed. The following compounds were examined in this way. The methyl esters of benzoic 0- rn- and p-toluic 0- m and p-chlorobenzoic p-bromobenzoic o-iodo- benzoic 0- m- and p-aminobenzoic 0- m- and p-nitrobenzoic salicylic m- and p-hydroxybenzoic 2- hydroxy-3-methylbenzoic 2-hydroxy-4-methyl- benzoic 2-hydroxy-5-methylbenzoic 2 4-dihydroxybenzoic gallic anisic vanillic 3-chloro-2-nitrobenzoic 3 5-di-iodo-2-hydroxybenzoic 6-nitro- 2-hydroxybenzoic 4-nitro-Z-hydroxybenzoic phthalic isophthalic tetra- chlorophthalic 0- and p-nitrophthalic a- and /3-naphthoic p-hydroxy- naphthoic phenylacetic hydrocinnamic and cinnamic acids ; also the ethyl esters of propionic and butyric acids the phenyl esters of benzoic and salicylic acids as well as the following two free acids terephthalic and dichlorophthalic.The following conclusions are drawn from the experimental results :-(1) Except in the case of methyl p-chlorobenzoate the methyl of the ester group was never observed to replace the -C02Me group and the method is therefore of no use for the introduction of a methyl group into the benzene nucleus.(2) The methyl group was commonly split off in the form E. F. A.84 ABSTRACTS OF CHEMICAL PAPERS. of dimethyl ether ; in the case of aromatic hydroxy-acids it frequently wandered from the carboxyl group t o the phenolic hydroxyl group in the ortho- or para-position. The ethyl group was split off from the two ethyl esters examined in the form 0-f ethylene. (3) With the exception of the esters of cinnamic and o-nitrocinnamic acids no esters contain- ing the -CO,Me group attached to an aliphatic complex gave off carbon dioxide. (4) The introduction of substituting groups into benzoic acid reduces the stability of the -CO,Me group.(5) The stability of the -CO,Me group is influenced both by the nature of the substituting group and by its position in the ring. (6) The hydroxyl and the amino-groups have the greatest influence. (7) I n naphthoic acids the second benzene ring acts on the-C02Me like a substituting group but exerts a greater influence in the case of the a- than in the case of the P-acid. (8) Unlike all other substituting groups the introduction of a second -CO,Me increases the stability of the C0,Me group. P. H. The Glucoside Structure of Conjugated Glycuronic Acids. HERMANN HILDEBRANDT (Beitr. chem. Physiol. Path. 1905,7 438-454. Compare Abstr. 1901 ii 614; Neuberg and Neimann 1905 i 412).- Emulsin has no action on the glycuronic acid derivative of p-dimethyl- aminobenzoic acid ; the derivative probably has not a glucosidic structure and the following formula is suggested p-Benzobetaine does not couple with glycuronic acid in the mimal system ; the greater part is eliminated unaltered and a small portion is converted into mono- and di-methyl-p-aminobenzoic acids.The glucosides of glycerol and benzyl alcohol (E. Fischer Abstr. 1895 i 6) are hydrolysed by both emulsin and yeast. Glycuronic acid itself is decomposed by yeast or zymase volatile acids are formed and the solution loses its reducing properties. When syringinaldehyde is administered to dogs both free syringic acid and its compound with glycuronic acid are found in the urine. When syringin is injected subcutaneously in dogs Korner's gluco- syringic acid (Abstr.1889 159) and syringaglycuronic acid are found in the urine. When coniferin is administered in the same way no free vanillic acid can be found in the urine but potassium vanillinglycuronste can be isolated. Both acids are hydrolysed by emulain. This is hydrolysed by emulsin. J. J. S. Oxidation of 4Nitro-6-amino-m-xylene. GIORGIO ERRERA and RAFFAELE MALTESE (Gaxxetta 1905 35 ii 370-383).-When oxidised with potassium permanganate 4-nitro-6-diacetylamino-m-xylene yields a mixture of 4-nitro-6-aminoisophthalic acid 4-nitro-6-amino-m-toluic and 6-nitro-4-amino-m-toluic acids and their monoacetyl derivatives. 6 -Nitro- 4- acet ylamino-m-toluic acid C10H1005N2 separates from alcohol or ethyl acetate in sulphur-yellow triclinic crystals [a 6 c = 1.6623 1 1.0340 ; a= 79'40' /3= 64'4' and y = 105'33'1 melts and decomposes at 223-225".and dissolves slightly in water benzene orORGANIC CHEMISTRY. 85 xylene readily in acetic acid. The corresponding potassium salt was prepared and analysed. 4-Nitro-6-acetyZccmino-m-toZuic acid C,,H,,O,N crystallises from alcohol in pale straw-yellow plates melting and decomposing at 254-255" and is less soluble than the acid just described in all solvents except water ; its potccssium salt was analysed. 6-Nitro-4-un~ino-m-toZuic acid C8H8O4N2 separates from alcohol or ethyl acetate in shining red crystals melting and decomposing a t 239-240' and dissolves slightly in water or benzene. 4-Nitro-6-anzino-m-toZuic acid C,H,O,N crystallises from water in golden-yellow needles which on rapid heating in a capillary tube melt a t about 235"; it dissolves readily in alcohol or ethyl acetate and slightly in benzene.On heating the acid or its acetyl derivative with concentrated sulphuric acid it yields 4-nitro-o-toluidine. The methyl ester C9HIOO4N2 separates from methyl alcohol in either needles or hard crystals of a pale yellowish-grey colour and melts at 169'. 4-o-p-BinitroaniZino-6-nitro-m-toZuic m i d C,,H,,0SN4 crystallises from acetic acid in yellow needles which melt after blackening a t 298'; it is only slightly soluble in the ordinary solvents and gives red salts. 1 3 8- Trinitro-7-methyZuccridollze C,,NH,Me(NO,) prepared by heat,ing the preceding acid or its ammonium salt with sulphuric acid and subsequently pouring the mass into water separates from acetic acid in large dark brown crystals or from benzene in orange-brown needles which melt after blackening at 253' ; it dissolves slightly in alcohol and to a greater extent in xylene.T. H. P. [ Claisen's Cinnamic Acid Synthesis.] ARTHUR MICHAEL (Bey. A reply to Storiner and Kippe (Abstr. 1905 38 4137).-Polemical. 1905 i 777). J. J. S. Synthesis of Tyrosine. PETER W. LATHAM (Luncet 1905 ii 1757).-A new method of syn thesising tyrosine from hydrogen cyanide and p-hydroxybenzaldehyde is described. It is pointed out that in the body adenine an isomeride of hydrogen cyanide may take the place of the latter substance in tyrosine formation. W. D. H. Synthesis of Amino-acids of Proteid Origin. LOUIS HUGOUNENQ and ALBERT MOREL (Conzpt.rend. 1906 142 48-49. Compare Abstr. 1905 i 178 264 332).-The symmetrical p-hydrocoumaric acid derivative of carbamide CO~NH~CH(CO,H)-CH,~C,H,*OH] pre- cipitated when a slow stream of carbonyl chloride is passed into an aqueous solution of the sodium salt of tyrosine is very sparingly soluble in water more soluble in alcohol from which solution it is precipitated by water in the form of flakes resembling proteid matter. The dry powder darkens at 150" melts at 240° and gives a red colour with Millon's reagent. The p-hydrocoumaric acid derivative of phenyl- carbamide NHPh*CO*NH*CH(CO,H)*CH,*C,H,*OH prepared by the action of phenylcarbimide on the sodium salt of tyrosine is very86 ABSTRACTS OF CHEMICAL PAPERS. sparingly soluble in water can be crystallised from alcohol melts and decomposes at 194' and reacts with Millon's reagent.31. A. W. Conductivity Measurements with Organic Acids. JOSEF HANS SUSS (Monntsh. 1905 26 1331-1342. Compare Wegscheider Abstr. 1902 i 617 ; and following abstract).-With pZ = 375 nitro- opianic acid has K 0*000291 ; a week-old solution has a 20 per cent. a solution which has been heated on the water-bath for one hour a 5 per cent greater conductivity. 5-Nitro-3-aldehydobenzoic acid has KO.0100 with pz = 378. 3-Nitro- 2-aldehydobenzoic acid has K 0.000130 with px =378. Nitro- hemipinic acid [(CO,H) (OMe) NO = 1 2 3 4 61 has K 2.1 with px = 374 ; at the dilution v = 256 it shows marked dibasic dissocia- tion which is not observed with hernipinic acid a t the dilution v = 1000.The dissociation constant for the second hydrogen atom is s x 106= 208 or 218. Aminoterephthalic acid has K 0.0265 with p-ccr = 377 whilst its 1-methyl ester has K 0.00552 with puy3 =376. Methylaminotere- phthalic acid has K 0.030 with poo = 376 Acetylaminoterephthalic acid has K 0.098 with pa =375. A slightly impure specimen of 1-methyl hydrogen acetylaminoterephthalato had K 0.07 with pa = 374.4. Acetylmethylaminoterephthalic acid has h'= 0.126 with pa = 374.4. Homophthalic acid hzls K 0,0190 with pa = 376.5 ; the a-mono- methyl ester has K0.00434 with pm = 375.3 ; the P-monomethyl ester has K 0.00764 with pa = 375.3. The a-monoethyl ester has K 0.0046 with pa = 374.6 ; the /?-monoethyl ester has K 0.00708 with pa = 3 74.6. 2-Car bamidophenylace tic acid NH2*CO*CGH,*CH2.C0,H has H 0.0050 with pa = 376.has K 0.0089 with pa = 376. Phthalonic acid resembles pyruvic acid in that it is a strong acid the affinity constant of which diminishes rapidly as the dilution increases ; it has K 2.14 at the dilution v== 128 ; K 1.91 a t v = 256 ; K 1.44 at v=512; and K 1-10 at u=1024. Methyl hydrogen phthalonate CO,Me*CO*C,H,*CO,H prepared by partial hydrolysis of the dirnethyl ester as also by the action of methyl alcohol on the acid has KO.015 withpa =375*7. Phenylitaconic acid CHPh:C(C02H)*CH,*C0,H has K 0.0137 with pa = 375; it shows no distinct dibasic dissociation. Phenylacetnmide-o-carboxylic acid NH,.CO*CH,* C,H,* CO,H G. Y. Constitution of o-Aldehydo-acids in Aqueous Solution. RUDOLF WEGSCHEIDER (Monatsh. 1905 26 1231-1234.Compare Wegscheider Abstr. 1902 ii 494 ; 1903 i 562).-The affinity con- stants of o-phthalaldehydic 5-nitro-2-aldehydobenzoic 3-nitro-2-alde- hydobenzoic and nitro-opianic acids are smaller than those of the corresponding acids without the aldehyde group. These aldehydo-acids must exist in aqueous solution to a greater or less extent as the - CH(0H) pseudo-form C6H,<-CO>0 whilst opianic acid the afinity con- stant of which is ten times that calculated for the correspondingORGANIC CHEMISTRY. 87 acid without the aldehyde group must exist in aqueous solution entirely in the normal or carboxylic form. A comparison of the affinity constants of o-phthalaldehydic and opianic acids shows that methoxy-groups in the ortho- and meta-positions prevent the formation of the pseudo-form.The influence of a nitro-group in the rneta- position to the carboxyl-group on the formation of the pseudo-form is only slightly favourable if the nitro- and aldehyde-groups are in the para-position but highly favourable if these groups are in the ortho- position t o one another. G. Y. Action of Diazomethane on Aldehydo-acids and Aldehydes. HANS MEYEE (Monatsh. 1905 26 1295-1301. Compare Abstr. 1905 i 13S).--Diazomethane is estimated by shaking its solution with an equal volume of N/10 aqueous hydrochloric acid whereby it is converted into methyl chloride completely in a few seconds and titrating the excess of acid with N/10 alkali hydroxide. Opianic acid and diazomethane interact energetically to form methyl opia na t e. The action of diazomethane on bromo-opianic acid or of methyl iodide on the silver salt at the laboratory temperature leads to the formation of methyl homo-opianate C11H905Br which crystallises from benzene and melts a t 105-106°.The +-methyl ester formed by the action of thionyl chloride or of boiling methyl alcohol and sulphuric acid on the acid crystallises in needles and melts a t 109-110'. A mixture of equal amounts of the isomeric esters melts at 70" (compare Bietrzycki and Fink Abstr. 1898 i 427). The action of diazomethane on nitro-opianic acid leads to the formation of the normal ester (Wegscheider Kudy von Diibrav and Rugnov Abstr. 1904 i 59). These aldehydo-acids have therefore the normal constitution when anhydrous (compare Wegscheider preceding abstract) but whilst opianic and bromo-opianic acids give an intense blue coloration with congo-red and have therefore the normal constitution in aqueous solution nitro- opianic acid functions in aqueous solution as a $-acid as it is entirely withoiit action on the indicator (compare Lobry de Eruyn Abstr.1899 i S61). Diazomethane does not interact with benzaldehyde or heptoic alde- hyde but evolves nitrogen slowly in contact with the three nitro- benzaldehydes ; o-nitrobenzaldehyde yields a brown oil which distils apparently without change ; sn-nitrobenzddehyde yields a liquid and a solid product ; the latter crystallises in colourless needles melts at 76O forms an orange-yellow hydrazone melting at 127O on oxidation by permanganate gives m-nitrobenzoic acid but is not identical with m-nitroacetophenone as it is odourless and dissolves in boiling aqueous potassium hydroxide forming a reddish-yellow solution ; p-nitro- benzaldehyde yields two poducts melting at 62-65' and at 84" respectively.The more fusible substance C,H70,N dissolves in hot aqueous potassium hydroxide to form a rose-coloured solution changing to yellow and on oxidation yields p-nitrobenzoic acid. Diazomethane and p-chlorobenzaldehyde interact t o form a solid product which melts a t a high temperature. G . Y.88 ABSTRACTS OF CHEMICAL PAPERS. Syntheses by means of the Carboxylic Esters of Cyclic Ketones. Synthesis of Menthone from Metbylhexanone. ARTHUR KOTZ and LUDWIG HESSE (Annalen 1905 342 306-328).- Since the hydroaromatic P-ketocarboxylic acids such as cyclohexanone- o-carboxylic acid CH2<C,2.CH cH2-Co>CH*C0,H would be valuable for synthetical purposes attempts have been made to prepare such acids with readiness.Endeavours t o bring about an internal condensation of esters of dibasic acids in a manner analogous to the formation of ethyl acetoacetate or to condense cyclic ketones with ethyl carbonate led to no result. On the other hand with ethyl oxalate the ketones yielded ethyl keto-o-oxalates. Ethpl l-metluylcyclohexane-3-one-4-oxaZate is prepared from methylhexanlone and ethyl oxalate and sodium wire in the presence of light petroleum; the mixture is treated with water and the aqueous solution acidified and extracted with ether the ketonic ester being finally purified in the form of its copper salt ; it is a colourless liquid boiling at 163' under 12 mm.pressure and has a sp. gr. 1.0903 at 15'. The copper salt C22H300SC~ forms crystals melting at 153'; the semimrbazone melts a t above 245'. 1-Methyl- cyclohexccne- 3-one -4-oxalic mid prepared from the ester by hydrolysis with 10 per cent. sodium hydroxide melts and decomposes at 132'. The semicccrbaxone melts at above 245'. When the ester is warmed ~ H M e * C H * ~ * N P h * ~ O derived from with aniline a compound hexahydroindole is obtained crystallising in needles melting at 162.5'. C:NPh' CH,-CH,*C-- Ethyl l-metl~ylcyclohexune-3-one-4-carboxylate7 CH DI"<CH,- CH2'C co *,>CH-CO,Et prepared by heating the ester j;st described under reduced pressure a t 150-220° is a colourless oil boiling a t 123.5" under 13 mm.and at 165" under 100 mm. pressure and has a sp. gr. 1-05" a t 14'; the copper salt is an olive-green powder melting at 155'. With phenyl- hydrazine the ester gives a compound derived from hexahydro-1 2-benzodiazine which forms crystals melting at 243-245". With ammonia the ester yields ethyl 3-amino-1-methyl- c yclohexane- 4 -curbox ylate C H M e < ~ ~ ~ ~ ' ; ; ' ~ I > C . C O ~ E t which forms crystals melting at 67". ~ H M e . C H * ~ - ~ H CH,-CH,* C CO NPh' Ethyl 1 - dimetlqlc yclohexccne - 3-one- 1 -cccrboqlat e CHMe<CH:-C CH *CH B>CMe C0,Et prepared from ethyl methylcyclohexanonecarboxylate by treatment with sodium ethoxide and methyl iodide is an oil boiling at 120-122' under 12 mm. pressure and has a sp. gr. 1.0189 a t 19'. Zthyl l-methyl-4-isopropylcyclohexune-3-one-4-c~rboxyZate preparedORGANIC CHEMISTRY.89 in analogous manner is an oil boiling at 135-137' under 10 mm. pressure and has a sp. gr. 1.009 a t 14'. The semicarbazone melts at 144-145'. When this ester is hydrolysed by boiling alcoholic potassium hydroxide menthone is obtained melting a t 206-208' and feebly dextrorotatory ; it yields a semicarbazone melting a t 184-1 85". K. J. P. 0. Tautomerism. 111. Apparent Case of Desmotropy. PAUL RABE and DAVJD SPENCE (Awm?en 1905 342 328-355. Compare Abstr. 1901 i 33 and 1904 i 749).-The relation between the "acid " and '' neutral " forms of Hagemann's ester (Absti-. 1893 i 393) which the authors (Xbstr. 1905 i 34s) have shown to be ethyl l-methyl- cycZo-AG-hexene-5-one-2-carboxylate has been investigated.The con- ditions under which the isomerides are prepared do not point to their being tnutomeric and the tautomerism i f it exists cannot be due t o the carbonyl group but rather to the carbethoxyl group. To throw light on these phenomena ethyl phonylniethylcycZohexmonecarboxylate ine t h ylcgclo hexenonecarbox y lat e and dime t h ylcyclohexenonecnrboxylate have been prepared. I c has been found that two desmotropic isomerides do not exist but that the esters can be separated into two fractious which show a gradual difference in chemical and physical properties. The cause of these observations will be discussed later. Ethyl l-methylc~clo-A6-hexene-5-one-2-carboxylate (Zoc. cit.) boils at 157-159" under 19-21 mm. pressure and has a sp. gr. 1-0775-1*0783 a t 20'/4' and a molecnlar refraction hl 48.96-49.02.When shaken with 10 per cent. sodium hydroxide a t a low temperature two fractions are obtained ; the soluble fraction the " acid " ester boils a t 160-163' under 24 mm. pressure and has a sp. gr. 1.0701 at 2Oo/4O and Ms; 49.32 ; an insoluble fraction the " neutral " ester boils at 163' under 24 mm. pressure and has a sp. gr. 1.0856 at 20"/4' and M 4827. Both fractions are soluble in concentrated sodium hydroxide and both give a reaction with ferric chloride. Knoevenaget's ethyl 1 3-dimethylcycZo-A6-hexene-5-one-2-carboxylate behaves iu a similar manner ; the ethyl 4-hydroxy-2 6-dimethylbenzoate obtained from it by Noyes is readily hpdrolysed by alcoholic potassium hydroxide yielding 4-hydroxy-2 6-dirnet?~ylbenxoic cccid which crystal- lises in six-sided prates melting and decomposing a t 185'.Etlyl 1 -naethyZ-3 -phenylc yclo- A6-?~exene-5 -0 ri e- %car.boxylate CO,E t C H<CMe:c CPh*CH Hz>CO prepared by heating ethyl methylphenylcpclohexanolonedicarboxylate with sodium ethoxide in alcoholic solution crystallises in four-sided plates melting a t 55'; it dissolves but sparingly in 10 per cent. sodium hydroxide and only gives a colour with ferric chloride after prolonged boiling. The senaicarbccxone crys tallises in needles melting at 158-161'. K. J. P. 0. Preparation of Chloro-derivatives of Indigotin. BADISCIIE ANILIN- & SODA-FABRIK (D.R.-P. 160817).-When indigotin is chlorinated in absence of water in the dry state or in indifferent solvents the chlorine does not enter the nuclens aqd only unstable VOL.XC. i. h90 ABSTRACTS OF CHEMICAL PAPERS. products are obtained. Stable chloro-derivatives of indigotin are obtained however when indigotin is suspended in phosphorus oxy- chloride or sulphuryl chloride a little iodine being preferably added and chlorine passed through the well-cooled liquid. The product may be poured on to ice or the volatile compound removed by distillation. C. H. D. 6 6’-Dinitroindigotin. JULIUS SCHWARZ (Monatsh. 1905 26 1253-1263. Compare Baeyer Abstr. 1870 937).-5-Nit~ophenyl- ylycine-2-carboxylic acid C,,Hs06N2 is obtained in a yield of 7 0 per cent. of the theoretical by boiling five parts of 4-nitro-2-aminobenzoic acid with 10.5 parts of chloroacetic acid and 13.5 parts of sodium carbonate in aqueous solution in a reflux apparatus for eight hours.It crystallises in long slender yellow needles commences to blacken at 225O melts and decomposes a t 240-242” is readily soluble in alcohol but only moderately so in acetone light petroleum or hot water yields a reddish-brown flocculent precipitate and when heated in a tube sublimes and decomposes par tially. The potassium hydrogen salt C,H706N2K crystallises in microscopic red needles ; the silvw salt C,H,O,N,Ag is obtained as an orange voluminous precipitate. 5-Nits.oanildincetic-2-carboxyZic acid C10H1008N2 is obtained as a by-product in the preparation of 5-nitrophenylglycine-2-carboxylic acid ; it crystsllises from concentrated hydrochloric acid in long slender almost white needles melts and decomposes a t 17’74 and forms a wotassium salt as a vellow DreciDitate.1 .I A 1 3-Diacetyl-6-nitroincloxyl formed by heating 5-nitrophenylglycine-2-carboxylic acid with sodium acetate and acetic anhydride ; it crystsllises from alcohol in large yellow needles melts at 190” is almost insoluble in water but moderately soluble in alcohol ether acetone benzene or light petroleum dissolves in warm aqueous sodium carbonate to form a dark green in concen- trated sulphuric acid to form a dark blue solution and when warmed with concentrated sulphuric acid yields 6 6’-dinitroindiyotin C16H,0,N,. This is obtained in microscopic round dark blue granules is insoluble in water almost insoluble in hydrochloric or acetic acids alcohol ether benzene or light petroleum is slightly soluble in acetone and dissolves in hot aniline t o form a dark green in phenol naphthalene or hot nitrobenzene to form dark blue solutions; when heated in a glass tube it sublimes whilst on platinum foil it evolves violet vapours and detonates slightly. On reduction with zinc and hydro- chloric acid it yields 6 6’-dinitroindigo-white and on further reduction 6 6’-diaminoindigo-white which is oxidised by the atmospheric oxygen to 6 6’-diaminoindigotin.This is distinguished from 6 6’-dinitro- indigotin by its solubility in acetic acid forming a green solution. G. Y. Condensation of Epichlorohydrin with Phthalic Anhydride in Presence of Tertiary Bases. ARTHUR WEINSCHENK (Chem. Zeit. 1905 29 131 l).-When molecular proportions of epichlorohydrin and phthalic anhydride are warmed together over the water-bath in theORGANIC CHEMISTRY.91 presence of a small quantity of dimebhylaniline or dimethyltoluidine the following condensation takes place The resulting <hloromethylglycol phthalate is a iolid below 20° but between 20' and 30' it a=sumes a fatty consistency; it is insoluble i n water dissolves with difficulty in alcohol or ether and is readily soluble in epichlorohydrin. When pyridine is used as the condensing agent the reaction becomes violent and the mixture rapidly darkens. P. H. Butadiene Compounds. XII. Yellow Nitrotriphenylfulgenic Acids and their Red Fulgides. HANS STOBBE and ALBERT KULLENBERG (Ber. 1905 38 4081-4087).-Sodium a-o-nitrophenyt- 66-di;ohe.la~~uZgenate C2tH,,06NNs2 formed by the action of sodiuni ethoxide on o-nitrobenzaldehyde and ethyl yy-diphenylitaconate in absolute alcoholic solution crystallises in glistening leaflets from water or in yellow monoclinic prisms from 50 per cent.alcohol. The acid CPh,:C(CO,H)*C(CO,H):CH.C,H,.NO,,C,H,O crpstallises from alcohol in yellow needles loses C,H,;O at 105' commences to become red a t 180' and melts and evolves gas at 223-224'. The piperidine salt C,,H,70GN,2C,HI,N crystallises in yellow needles and melts and decomposes a t 201-202'. a-o-ilr;tro~?~e~zyZ-66-~ip~en?/lfulgie CPh,:y*Co>() formed N0,-C6H,* CHI C*CO by boiling the acid with acetyl chloride for four hours is obtained on slow evaporation of the solution in large pleochroic nionoclinic crystals; it crystallises from a mixture of chloroform and alcohol in blood-red leaflets from chloroform alone in yellow needles containing chloroform which is lost gradually on exposure t o air the crystals cbanging into an orange-red powder; the three modifications melt a t 207-208'.Its behaviour towards water alkali hydroxides and piperidine is the same as that of dibenzylidenesuccinic anhydride (Stobbe Naofim and Kautzsch Abstr. 1904 i 589); when oxidisetl it yields benzophenone and o-nitrobenzoic acid. a-m-Nitrophesa?/Z-66-~~p~~en~~uZge?zic acid is obtained in the form of its sodium salt C,,H,,O,NNa by digesting m-nitrobenznldehyde and ethyl yy-diphenylitaconate with sodium ethoxide in absolute alcoholic solution ; this crystallises in yellow leaflets. The acid C,,HliO,N crystallises in white leaflets or prisms from ether in yellow leaflet4 from acetic acid and melts aud decomposes a t 221-222'.The piperidine salt C,,H,70,N,2C,H,,N forms yellow needles and melts and decomposes at 177-1 78'. a-m-Nitropl~enyZ-66-dip~~en~f~ut~ide C2,Hl,05N crystallises from a mixture of chloroform and alcohol in orange-red slender needles or from benzene in stellate groups of pleochroic monoclinic prisms and melts a t 194-195'. a-p-Nitrophenyl-88-diphenylficlgenic m i d C,,H170,N from p-nitro- benzaldehyde and ethyl yy-diphenylitaconate crystallises in yellow prisms melts and decomposes at 238' and when oxidised yields benzophenone p-nitrobenzaldehyde and p-nitrobenzoic acid. The h 292 ABSTRACTS OF CHEMICAL PAPERS. sodium salt crystallises in yellow prisms; the pipwridine salt forms nodular aggregates of slender yellow needles and melts and de- composes at 181 -1 82'.a-p-Nitrophenyl-88-diphenylfulgide C,,H,,O,N crystallises in orange pleochroic monoclinic plates melting at 228O or from a mixture of benzene and chloroform in similar crystals melting at 224'. Butadiene Compounds. XIIL Aminotriphenylfulgenic Acid. HANS STOBBE and ALBERT KULLENBERG (Ber. 1905 38 4087-4090).-The a-aminophenyl-68-diphenylfulgenic acids are formed by reducing the corresponding a-nitrophenyl acids with ferrous sulphate in ammoniacal solution and precipitating the product with the calculated quantity of N-hydrochloric acid. a .o- Aminoiuhenyl-66-di~hen ylficlgenic acid G. Y. CPh, C( C0,H) C( C0,H) CH*C,H;NH2 is obtained as a yellow amorphous mass which melts and decomposes at 175-177' and is readily soluble in hydrochloric acid.The piperidine salt C,,H,,O,N 20 H ,N crystallisee in yellow needles melts and decomposes a t 192-193O and on treatment with aqueous silver nitrate forms the siZver salt C2,Hl7O4.NAg2 as a white flocculent precipitate which becomes yellow on drying. a-m- Arninophenyl-6s-dzpheizylfuIgenic acid C24H1904N crystallises in yellow monoclinic prisms melts and decomposes a t 2 2 4 O and when boiled with acetyl chloride forms a-m-acetylami?zophe?zyl-6S-diphenyZ- fulyide >0 which crystallises in slender yellow needles and melts at 215'. forms long dirty-yellow needles and melts and decomposes at a-p- Amino~l~enyZ-68-dipphenylfuIgenic acid is amorphous ; the piperidine salt forms large dark yellow crystals and melts and decomposes a t 182-183'; the copper salt C,,H1704NCu is obtained as a light brown amorphous precipitate.G. Y. Resin Acids from Conifers. V. ALBERT VESTERBERG (Ber. 1905 38 4125-4132. Compare Abstr. 1886 365 1038; 1888 294; 1904 i 151 ; Ducommun Chem. Zeit. 1885 1592).-Although d- and I-pimaric acids yield sparingly soluble crystalline ammonium salts a mixture of either acid with a large quantity of sbietic acid produces a gelatinous salt. When the two acids are in the proportions 1 10 the salt remains gelatinous for weeks but in the proportions 1 5 crystals are often observed in the course of a few days. The separation of the pimaric acid is best accomplished by the following processes (a) fractional cry stallisation of the acids from 85 per cent (vol.) alcohol until an acid is obtained which gives a crystalline ammonium salt ; ( b ) repeated cry stallisation of the sodium salt from water containing a small amount of sodium hydroxide; (c) crystallisation of the acid from alcohol or acetic acid.d-Pimaric acid has been isolated by this method from French colophony and from the resin of Pinus sylvestris. CPh, ?*CO NHAc*C,H,*CH C*CO The piperidine salt C2,H,,04N>2C HIIN 177-1 78'. J. J. S.ORGANIC CHEMISTRY. 93 Positions of the NO and NH Groups in the Mononitro- and Amino-derivatives of Piperonylaldehyde and Piperonylic Acid. EFISIO MARIEL1 ( A t t i 13. Accnd. Lincei 1905 [v] 14 ii 424-432 5 10-518).-The positions of the snbstituent uitrogen chains in the nitro- and amino-derivatives of piperonaldehyde and of the corre- sponding acid have not yet been absolutely proved (compare Abstr.1904 i 668 743 and 1023 ; 1905 i 203 889). The following are the results of the author's investigations on this subject. The oxidation of nitropiperonaldehyde yields the nitropiperonylic acid melting at 172" and already obtained by Jobst and Hesse by the nitration of piperonylic acid (Abstr. 1378 733; 1880 323). This nitro-acid or its calcium salt when decomposed by heat yields nitro- catechol methylene ether which can also be obtained by distilling an alkaline solution of nitropiperonaldehyde in a current of steam '1 he nitro-groups in nitropiperonaldehyde and in nitroca techolmethylene ether must have the same position relatively t o the other substituents as that in nitropiperorivlic acid.Reduction of the last-named com- L L 4 pound gives rise to the y-aminocatechol methylene ether (6-amino- 3 4-methylenecatechol) CH2< o*C*CH:?*NH2 I I already prepared by O-C-CH C H Rupe and von Majewski (Abstr. 1901 i 103) by van Linge (Abstr. 1897 i 618) and by Hesse (Zoc. cit.). The nitro-group in nitro- piperonylic acid must therefore occupy the 6-position with reference t o the carboxyl group the -O*CH,*O- group being in the 3 4-position. Confirmation of this conclusion has been obtained by preparing from nitropiperonylaldehydo and from nitropiperonylic acid the 4-nitro- 1 2-dihydroxy benzene described by various authors. The results given indicate that when piperonaldehyde or piperonylic acid is nitrated directly the first nitro-group introduced enters in the 6-position with respect to the aldehyde or carboxyl group in position 1 and the dioxymethylene complex in the position 3 4 and that further nitration gives rise to symmetrical tetra-substituted derivatives.The above constitution for nitropiperonaldehyde has been confirmed in an indirect manner by the recent work of Herz (Abstr. 1905 i 778). T. K. P. Tetramet*hylphloroglucinolaldehyde. JOSEF HERZIG and FRANZ WENZEL (Honatsh. 1905 26 1359-1389. Compare Abstr. 1904 i 25 1)-[ With PETER Ro~~.]-Dimethylphloroglucino~aldehyde is heated with methyl iodide and potassium hydroxide in methyl-alcoholic solution in a reflux apparatus during one day and after addition of further quantities of potassium hydroxide and methyl iodide again for one day.After distillation of the alcohol the residue is treated with water and ether when there are obtained an aqueous solution of the potassium derivative of tetramethylphloroglucinolaldehyde (1) and an ethereal solution of a condensation product (2). - ~Me,**CO*G*CHO obtained (1) Tetrametl~~~lilorogZ~inoZaZdel~ycSe CO CAIe; C* OH ' on acidification of the alkaline solution crystallisei from ether in large prisms or from methyl alcohol in colourless rectangular plates melts94 ABSTRACTS OF CHEMICAL PAPERS. at 70-71° is readily soluble in benzene but less soluble in methyl or ethyl alcohol and dissolves in aqueous potassium hydroxide to form a colourless solution which remains unchanged on prolonged warming ; it may be titrated with N/lO potassium hydroxide using phenol- phthalein as indicator. The potassium derivative OK*C,O,IsIIe,*COH forms colourless crystals and is not decomposed by carbon dioxide in aqueous solution.The oxime OH*C,O,Me,*CH:NOH crystailises from ethyl acetate in white needles commences to decompose at 189" and melts at 196' to a dark yellow mass. When heated with acetic anhydride and sodium acetate a t 160-lSO0 or when boiled with acetic anhydride only tetrarn et h ylphloroglucinolaldeh yde forms the coumarin CH:(?H which crystallises from methyl alcohol o-co ' derivative C,O,Me,< and melts a t 205-20S0. The methylether OMe*C60,Me;CH0 is formed by the action of diazomethane on tetramethylphloroglucinolaldehyde in ethereal solution ; it crystallises from alcohol and melts a t looo. When oxidised with potassium permanganate in alkaline solution the aldehyde yields a substance which crystallises in glistening scales melts and evolves gas at looo and when heated with alcohol or benzene forms carbon dioxide and the coildonsation product melting a t 2 10-2 1 2 O . [With WILHELM RExsMANN.]- ( 2 ) The condensation product (6-hydroxy-2 2' 4 4' 6'-pentoketo-3 3 3' 3':5 :5 :5':5'-octamztl'~yEtetrcc- Ii,ydrophenyZphenyzyEidenemethane) CO<CMe2*C(oH)~C.~~~C<co'cMe2~ CMe,-CO CO-CMe,' Co' is obtained on evaporation of the ethereal solution and treatment of the residue with benzene ; it is formed also together with formic acid when tetramethy lphloroglucinolaldehyde is dissolved in dilute methyl alcohol or is boiled with water or when its potassium derivative is treated with methyl sulphate.After repeated recrystallisation from a mixture of chloroform and light petroleum it forms nodular aggre- pates of white needles and melts a t 217'; it does not yield an acetyl derivative when boiled with sodium acetate and acetic anhydride. The rnethyE ether C,,H,,O,*OMe formed by the action of diazomethane on the condensation product in ethereal solution separates from alcohol in colourless crystals melts a t 163-164" and when treated with hydroxylamine hydrochloride in presence of sodium hydrogen carbonate or sodium methoxide yields a product which contains nitrogen and melts at 182'. The condensation product dissolves in aqueous potassium hydroxide to form a yellow solution which becomes colourless slowly at the laboratory temperature quickly on evaporation with formation of the potassium derivative of tetrarnethylphloroglucinolaldehyde and tetra- methylphloroglucinol melting a t 198' (m.p. 187-lSSo ; Reisch Abstr. 1899 i 803). The condemation product is again formed when the products of its hydrolysis are boiled with water containing a few drops of hydrochloric acid. The action of methyl-alcoholic potash on the methyl ether of the condensation product leads to the hydrolysis of the methoxy-group,ORGANIC CHEMISTRP. 95 and therefore t o the formation of the same decomposition products as are obtained from the hydroxy-compound. When treated with con- centrated sulphuric acid the methyl ether yields the condensation product. When reduced with zinc dust and aqueous potassium hydroxide the condensation product forms a dil~ydi.o-derivative C21H2sOz which crystallises from benzene in slender needles and melts a t 173 .It is formed also from tetrarnethplphloroglucinol by the action of (a) form- aldehyde and concentrated sulphuric acid a t 40' ; (6) of formaldehyde and potassium hydroxide in warm methyl-alcoholic solution ; or ( c ) of boiling aqueous formaldehyde. The methyl ethel. C,,H,,O,( OXe) formed by the action of diazomethane on the reduction product in ethereal solution crystallises from methyl alcohol in stout needles melts a t &lo and when boiled with hydriodic acid forms an anhydride C21.H2G05 which is formed also by the action of concen- trated sulphuric acid on the reduction product on the water-bath or by boiling this with acetic anhydride and sodium acetate ; it crystallises in needles and melts at 190'.On prolonged action of potassium hydroxide and methyl iodide on dimethylphloroglucinolaldehyde there is formed in addition to tetra- methylphloroglucinolaldehyde and its condensation product a sub- stance C,,H,,O which crystallises in glistening needles and melts at 1'73'. G. Y. Hydroxylamine Derivatives of Ketones of the Type CO(UH:CHR),. GAETANO MINUNNI and RICCARDO CIUSA ( A t t i 12. Accud. Lincei 1905 [v] 14 ii 420-424. Compare Abstr. 1905 i 245).--Attempts to determine the constitution of the base C17H,,N obtained by reducing a-dibenzylideneacetonehydroxylamineoxime (loc. cit.) by preparing its oxidation products have been unsuccessful. The compound C17H,,N,(OH) prepared by reducing disalicylideneacetone- hydroxylamineoxime gives mainly resinous products on oxidation only a small quantity of a crystalline product being obtained by treatment with potassium permanganate and sulphuric acid.~romo-a-cli~r~zz~licle~aencetonehydroxylamineoxime C,7H,,0,N,Br separates from alcohol in white crystals melting and decomposing a t 1 7 2 O and dissolves in methyl alcohol or chloroform and to a slight extent in ethyl acetate. Oxidation of a-dibenzy lideneacetonehydroxylamineoxime by means of amyl nitrite or acid potassium permanganate solution yields a small quantity of a substance C17H140N2 separating from aqueous alcohol in yellow crystals which soften at 165" melt and decompose at 176" and are soluble in almost all the organic solvents.Reduction of P-dibenzylideneacetonehydroxylamineoxime by means of sodium in amyl alcohol solution gives a n oily base the hydrochloride of which melts at 234' and the platinichloricle at 268'; the benzoyl derivative C,7H17N2.Bz of the base crystallises from a mixture of ethyl acetate and alcohol in white needles which blacken at 260° melt at 290° and dissolve readily in methyl or ethyl alcohol and to a less ex tent in carbon tetrachloride. Disa Zic?/lideneacetone?~~drox~la.nzineoxime Ci,H,GO,N,( OH)2 crystal-96 ABSTRACTS OF CHEMICAL PAPERS. lises from alcohol in hard prisms melting and decomposing at 207O and is slightly soluble in ether benzene ethyl acetate or methyl alcohol ; it dissolves in potassium hydroxide solution or in hydrochloric acid and also in sulphuric acid to which it imparts a blood-red coloration.Its tetrchenxoyl derivative C,7H1,0,N2B~4 crystallises from alcohol in hard minute prisms melting a t 1 3 5 O and dissolres readily in methyl alcohol and to a slight extent in ether benzene or ethyl acetate. On reduction with sodium and amyl alcohol it gives a compound C,7H,,N,(OH) which crystallises from alcohol in white leaflets melting and decomposing at 191' and is soluble in ether or benzene with difficulty in ethyl acetate with greater readiness and in acetic hydrochloric or sulphuric acid or potassium hydroxide solution very readily. T. H. P. Reaation between Organic Magnesium Compounds and Unsaturated Compounds. VII. Complex Products from Cinnamic Esters. ELMER P. KOHLER and GERTRUDE HERITAGE (Amer Chenz.J. 1905 34 568-580).-Phenyl a-phenylcinnarnate crystallises in needles melts at 142O is sparingly soluble in alcohol or ether moderately so in acetone or benzene and readily in chloroform. When a solution of the ester in benzene is boiled with excess of magnesium phen yl bromide trip"lenyZpropiop?~enone CHPh,*CHPh*COPh is produced which crystallises in small colourless needles melts at 1 8 2 O is readily soluble in chloroform moderately so in benzene or hot acetone and very slightly in alcohol or ether; it yields neither a hydrazone nor an oxime. When phenyl cinnamate (1 mol.) is added to a well-cooled ethereal solution of magnesium phenyl bromide (3 mols.) and the product is decomposed with cold hydrochloric acid dipbenylpropionic acid and diphenylpropiophenone are produced together with a small quantity of diphenyl.If the solution of the bromide (1 mol.) is slowly added to a cold solution of the ester (1 mol.) a substance CHPh,*CH( C0,Ph) CO*CH,* CHPh is produced which crystallises in long needles melts at 180-189° is readily soluble in chloroform or benzene moderately in ethyl acetate or hot acetone and very slightly in alcohol or ether; it is easily hydrolysed by potassium hydroxide with formation of potassium phenoxide potassium carbons t e and aate-tetraphen ylpentane- y- one CO(CH,*CHPh,) which crystallises in colourless nt edles melts a t 130° is readily soluble in ethyl acetate or chloroform and moderately so in alcohol or acetone does not combine with bromine and is not attacked by potassium permanganate.Tetraphenylpentanone oxime crystallises in needles melts a t 115-116O and when treated with phosphorus pentachloride is converted into the isomeric acid anilide which forms small lustrous prisms melts at 1 5 5 O and if heated in a sealed tube with strong hydrochloric acid yields PP-diphenyl- propionic acid and PP-diphenylethylamine. I n an earlier paper (Abstr. 1905 i 208) the effect of adding methyl cinnarnate to an excess of magnesium phenyl bromide was described.ORGANIC CHEMISTRY. 97 If on the other hand the magnesium compound is added slowly to a well-cooled solution of methyl cinnamate a nxelkp? ester CHPh,*CH( CO,Me).C'O.CH,* CH Ph corresponding with the plienyl ester obtained from phenyl cinnamute under the sitme conditions is producetl which crystallises in slender needles melts at 2 11-213° is readily soluble in chloroform or benzene moderately in acetone and very slightly so in alcohol or ether; when heated at 200' with concentrated hydrochloric acid i t is decomposed with formation OF 2 rnols.of @/I-cliphenylpropionic acid. P-Ber,xoyl- aa~~-tetrapl~enyZpntane-y-one CHPh,*CHBz.CO*CH,gCHPh which is obtained as a by-product in the preparation of the methyl ester just described and can be prepared by dropping methyl ciunamate into a boiling solution of magnesium phenyl bromide crystallises in nepdles melts at 166O is readily soluble in chloroform or acetone moderately in alcohol and sparingly so in ether. This ketone is hydrolysed by boiling alcoholic potassium hydroxide with formation of tetraphenyl- pentanone and potassium benzoate whilst aqueous potassium hydroxide converts it in to dipheuylpropiophenone and potassium diphenyl- propionate.If ethereal solutions OF methyl cinnamste and maguesium phengl bromide are boiled together for three or four hours arid the product is treated with ice-water a crystalline substcmce CHPh,. CH( CPh,* OH).CO*CH,* CHPh is obtained which melts at 153' is readily soluble in acetone or chloro- form and moderately so in alcohol and when heated alone at 270-30b0 or with concentrated hydrochloric acid at ZOOo is converted into benzophenone and tetraphenylpentanone. E. G. Soluble Preparations of o-Nitrophenyl-P-lactomethylketone. -0-Nitrophenyl-P-lactomethylketone is useful for the production of indigo-blue on the fibre but is very sparingly soluble.It dissolves however in aqueous solutions of the alkali salts of benzylaniline- sulphonic acid CH,Ph*NH.C,H,*SO,H 2 mols. of the ketone requiring at least 1 mol. of the acid for soiution. Salts of benzgl- toluidinesulphonic acids or of chlorobenzylanilinesulphonic acids and hornologues of the ketone show a similar behaviour. Derivatives of Tetrachloro-o-benzoquinone. C. LORING JACKSON and R. D. MAC LAURIN (Ber. 1905 38 4103-4105).- FARBWERKE VORM. MEISTER LUCIUS & BRCNING (D.R.-P. 160783). C. H. D. ~~eleac?~loro-o-quinoccctec~~oZ ether C,,02Cl,<o>C,C14 0 prepared by the action of tetrachlorocatechol on tetrwhloro-o- benzoquinone dissolved i n dilute acetic acid separates from benzene in deep red crystals melts a t 300° and is more soluble than the bromo-compound (Jackson and Koch Abstr.1901 i 597). It is reduced by sodium amalgam t o ILeEacl~Zorodih?/Jroxycatec~~~Z ether C,Cl,(OH),<o>C~C14 0 which crystal- lises from alcohol in colourlesa needles and melts at 290'. When condensed with aniline tetrachloro-o-benzoquinone yields a double compound ccizi~~?ze-dic~~~oro~~c6nili?Lo-o-ben~~qu~noiae C,,02CI,(NHPh),,NH,Ph,98 ABSTRACTS OF CHEMICAL PAPERS. which crystallises from benzene in long thin brown needles and melts and decomposes at 164-165'. crystallises from alcohol In glistening yellow plates and melts at 1 40-1 41'. Bichlorodiccni1ino.o- benzoquinone C,O,Cl,(NHPh) pre- pared by crystallising the aniline compound from a mixture of benzene and light petroleum separates in reddish-purple pointed needles and melts a t 194-1 95'.Chlorodiunilino-p-quinoneanil O:C,HCi(NHPh),:NPh prepared by t h e action of alcohol and aniline on the preceding compound crystallises from benzene and alcohol in broad black glistening needles and melts at 180'. 1 2-Anthraquinone. KASIMIR LAGODZINSKI (Annalen 1905 342 59-89. Compare Abstr. 1904 i 158).-1-Nitroso-2-anthroZ7 which the author regards as being in the tautomeric form O:C,,H8:N*OE can be prepared from 2-anthrol in alcoholic solution by treatment successively with an aqueous solution of zinc chloride and sodium nitrite ; the mixture is slowly heated and the zinc salt of the nitroso- anthrol separates ; it crystallises in orange needles decomposing a t 188' and gives an indigo-blue coloration with concentrated sulphuric acid.The potassium derivative C,,H,O,NK forms green arjd the sodium derivative yellowish-green leaflets. O:C,,H,:N*OEt prepared from the silver salt and ethyl iodide crystallises in golden- yellow leaflets melting at 143'. The methyl ether crystallises in similar forms melting R t 129-1 30'. l-Amino-2-a~zthroZ NH,*C,,H;OH is obtained by reducing either the nitrosomthrol with stannous chloride and hydrochloric acid or with hydrogen sulphide in alkaline solution or benzeneazo-2-anthrol with zinc dust and hydrochloric acid ; it crystallises in yellowish-green leaflets decomposing at 140-150' ; the hydrochloride and the sulphate form greenish-yellow needles; when heated with concentrated sulphuric acid a blood-red coloration is obtained. A trincetyi! derivative NAc,*C,,H,*OAc crystallises in greenish-grey leaflets melting at 165' and dissolves in alcohol solution with a blue fluorescence; on hydro- lysis with dilute alcoholic potassium hydroxide 1-c~etylamino-2- anthrol is obtained as green leaflets decomposing at 200-220°; its alcoholic solution has EL bluish-green fluorescence.1 2-Anthraquinone C,,H,O is formed when the salts of amiro- anthrol are oxidised in the cold with ferric chloride or chromic acid ; it crystallises in orange-yellow needles melting and decomposing at 185-1 go" and dissolves in sulphuric acid with a bluish-violet coloration. It condenses with o-phenylenediamine yielding 1 2- The alcohol compound c,0?c12( NHPh),,C'2H(307 T. M. L. The ethyl ether AT anthraphenmine C,,Hs<Ai >C,H which crystallises in dark yellow N leaflets melting a t 221-222O ; the hydrochloride is cherry-red and the sulphate bluish-green.When oxidised with chromic acid in acetic acid solution triacetylaminoan throl yields 1 -diacetyZamino-2-acetoxy- anthapinone C,H,<CO>C,H,( co OAc) =NAc which crystallises in paleORGANIC CHEMISTRY. 99 yellow needles melting at 1 8 9 O . On hydrolysis it is converted into 1 -amino-2-?~~drox~ar~thrccqzci~one crystdlising in dark red needles melting a t 250-251" and identical with Liebermann's a-alizarinamide. Alizarin is produced by heating the substance last mentioned under pressure with hydrochloric acid a t 250" ; the transformation is not produced by diazotisation. 1 3-Anthraqninol (Zoc. cit.) prepared from the quinone crystallises in greenish-yeilow leufiets melting and decomposing at 131" ; the alkaline solution is a t first cherry-red but soon blackens on oxidation.The diacetyll derivative forins yellow aggregates melting a t 145O and by oxidation with chromic acid is converted into diacstylalizarin. I<. J. P. 0. Chlorination of Mono- and Di-amino-derivatives of Anthra- quinone. BADISCEIE ANILIN- & SODA-FABRIK (D.R.-P. 158951. Compare Wohl this vol. i 9).-The mono- and di-amino-derivatives of anthraquinone are readily chlorinated by means of sulphuryl chloride. Thus P-aminoanthraquinone yields a monochloro-derivative 1 5 4 - aminoanthraquinone yields a tetrachloro-derivative crystallising from nitrobenzene in glistening brown needles and 2 6-diaminoanthra- quinone yields a dichloro-derivative. The solubilities of many such chloro-compounds in sulphuric acid and in organic solvents are described.C. H. D. HUGO VOSWINCKEL (Bey. 1905 38 401 5-4021).-Naphthacenediqiiinone (Gabriel and Leupold Abstr. 1598 i 4S2j dissolved in glacial acetic acid is attacked by chlorine at the ordinary temperature giving the dichloride Studies in the Naphthacene Series. co* yc1* co C,H4<C0 CCl~CO >C,H* which crystallises from nitrobenzene in rhombic crystals and melts at 175" ; with reducing agents i t gives dihydroxynaphthacenequinone (Gabriel and Leupold Zoc. cit.) and on warming with dilute aqueous sodium hydroxide the same substance is also formed but the principal product is an acid C,,H,,O perhaps co - C0,H'C,H4'c0*C~C(OH~. CO>Cf3H4* This crystallises from dilute alcohol containing hydrochloric acid in bright yellow transparent prisms melts a t lS5" and gives rz hydrazone and a red crystallirie silver salt C,,H,O,Ag,,H,O. With bromine in glacial acetic acid naphthacenediquinone gives which separates in well-formed colourless prisms and melts a t '1 98" ; a little dihydroxynaphthacenequinone is also formed.When the bromide is shaken with aqueous sodium hydroxide i t seems to yield the acid C,8Hlo06 described above but the melting point is slightly higher namely 19 go. ,CO*C,-CO,100 ABSTRACTS OF CHEMICAL PAPERS. by leaving powdered naphthacenediquinone with an aqueous suspension of bleaching powder for several days crystallises from benzene i u small orange-coloared needles melts and decomposes at about 240° and is easily reduced t o dihydroxynaphthacenequinone ; with aqueous sodiiim hydroxide the acid C1SH1006 is obtained melting at 199'.W. A. D. Preparation of Bornylenediamine. PAUL DUDEN (D.R.-P. 160 103).-Bornylenediamine (camphanediamine) is prepared by I educiDg amino- isoni troso- or isonitrwamphoroxime by means of sodium and alcohol sodium amalgam or electrolytic hydrogen. BornyEenediamine forms a waxy solid boils a t 246' and dissolves with. extreme readiness in water. The cliacetgl deiivative occurs in two stereoisomeric modifications melting at 246' and 253' respectively. C. H. D. Chemical Investigation of Resin from the Pine (Pinus obies). PETER KLASON and JOHN KOHLER (Arkiv Kern. Min. Geol. 1905 2 i No. 3 1-39).-Resin from the pine contains two isc- morphous acids a- and /3-colophonic acids C2pH309,.The acids have the normal molecular weight in freezing acetic acid and give the acid value 185.4. The separate acids have not been obtained absolutely pure so that the physical constants given below are only approximately correct. a-CoZopJ~oi2ic acid crystallises from alcohol in colourless oblique monoclinic prisms [ a b c = 1.1282 1 0,9716 ; p= 71*24'] melts at 177-182' and has [.ID - 59.41". P-Colophonic acid separates in less well-developed crys tals than the a-acid melts a t 1 68-1;33 and has [ a I + 52.2". The u~~~~~~onzizcna NH 2C20H3002 cuZciuna Ca( C,oH2902)2 and bariu912 Ba(Cl,oH,,0,),2H,0 salts of the mixed at-ids were prepartd. T. H. P. Gutta Percha and Balata. WILLIAM A.CASPARI (J. SOC. Chemz. Ind. 1905 24 1274-1278j.-Analyses of various guttns and balata purified by solution in benzene and precipitation with alcohol thrice repeated confirmed the formula (C5H& Pure gutta is of a leathery consistence and almost destitute of elasticity ; below loo" it becomes soft and can be kneaded whilst caoutchouc becomes sticky and moderately plastic bnt retains some resilience ; at higher tempera- tures the two hydrocarbons tend to approximate in behaviour. When dissolved in dry carbon tetrachloride and treated with chlorine the hydrocarbons of gutta caoutchouc or balatn yielded substances the composition of' which approximated to the formula C,,H3,C1 ; the substances when piirified by precipitation from dilute benzene or chloroform solution by means of alcohol and dried in a vacuum presented white toughish plates.Substances prepared similarly by the action of bromine gave analytical numbers leading to the formula C,,H,,Brlo ; iodine in chloroform solution yielded substances con- taining betneen 12.11 and 13.47 per cent. of iodine. Benzene solutions of gutta o r balata saturated with d i y hydrogen chloride andORGANIC CHEMISTRY. 101 precipitated with alcohol gave substances which when redissolved and again precipitated formed white leathery flakes easily soluble in benzene or in chloroform and had the composition C,oH,,,5HCl ; the behaviour of caoutchouc was found to be somewhat different. A solution of nitrogen peroxide and oxygen in benzene added to a benzene solution of the hydrocarbons produced green gelatinous precipitates of variable composition ; on adding more nitrogen peroxide yellow clots separated which had the composition C,,H,,O,N ; on subjecting these substances to the protracted action of nitrogen peroxide they produced substances which when pure were saffron- yellow powders which dissolved in acetone ethyl acetate alkalis and ammonia with a deep orange colour ; their composition is represented by the formula C,,H,,O,N,. By the action of nitric acid a substance of the formula C,,H2,0,,N was obtained. Benzene solutions of the hydrocarbons on treatment with dry nitric oxide gave substances the composition of which is represented by the formula C,,H,,O,N. The conclusion is drawn from these experiments that the hydrocarbons of gutta percha and of balata are identical whilst as regards gutta and caoutchoucs i t seems as if these were a common molecule differences in the aggregation of which caused differences in mechanical structure.P. H. Butadiene Compounds. XI. Parallel Coloured F u r y l - and Phenyl-fulgides. HANS STOBBE and RICHARD ECKERT (Ber. 1905 38 40'75-4031).-The furyl group has stronger chromophoric properties than has the phenyl group; a number of furyl and the corresponding phenyl compounds are quoted to show that where these have the same colour the former have the deeper shade. This is the case in the fulgide series the three fnryl-fulgides described below being light orange dichromate-red and reddish-brown whilst the corresponding phenyl compounds are light yellow orange-red and lemon-yellow respectively (Abstr.1905 i S57 ; this vol. i 22). a-~~i-yZ-66-di?netJ/~ulgenic (a,furfurylideneteraconic) acid CMe,:C(CO,H)~C(CO,H):CH*C,OH formed by the action of sodium ethoxide on ethyl dimethylitaconatc and furfuraldehyde in absolute alcoholic solution separates from 20 per cent. acetic acid in small slightly yellow rhombic crystals softens at 204' and melts and decomposes a t 218'. When treated with acetyl chloride cooled by a freezing mixture it yields afurpZ-66-di- methyZjidgide C12H1004 which crystallises from light petroleum in small light orange monochic prisms melts at 63' is readily soluble in ether chloroform benzene or carbon disulphide and dissolves in concentrated sulphuric acid to Eorm a yellow solution which becomes greenish-brown and finally reddish-brown changing to yellow on dilution with water.66- Diphenyl -a- furylfulgenic acid CPh, C( CO,H).C(CO,H) C Ha C,0H3 formed from f urf uraldehyde and ethyl diphenylitaconate in alcoholic sodium efhoxide solution crystallises from benzene in shimmering yellow leaflets containing C,H which is lost at 100") becomes dark at 187" and melts and decomposes at 202'. The sodium salt,102 ABSTIcACTS OF CHEMICAL PAPERS. C,,Hi40,Na,2H20,2C2H,0 crystallises from 70 per cent. alcohol in white plates. 88- Diphenyl-a-furylfulgide C22H1404 formed by pouring cold acetyl chloride on to the dicarboxylic acid crystallises from carbon disulphide in dark red prisms which lose CS on exposure to air ;. when free from carbon disulphide it is dichromate-red melts at 156O is easily soluble in chloroform or .benzene and dissolves in concentrated sulphuric acid to form a green solution which becomes brown and on dilution with water deposits a greenish-blue flocculent precipitate.&Dif urylfulgenic acid (dif urfurylidenesuccinic acid) C40H3*CH C(C0,H) *C( C0,H) :CH*C,OH is obtained by treating a mixture of 3 mols. of furfuraldehyde and 1 mol. of ethyl succinate in alcoholic solution with 2 mols. of sodium ethoxide in a yield of 15 per cent. of the theoretical; it melts at 227-228" (217-225' Fichter and Scheoermann Abstr. 1901 i 479 ; 185-187' Titherley and Spencer Trans. 1904 85 190). a8-Difurylf ulgide (dif urfurylidenesuccinic anhydride) forms brown- ish-red rhombic crystals softens at 197' and melts at 204O (187' Wherley and Spencer Zoc. cit.p. 188). Diphenyl-o-phenoxylenedihydroanthracene. FRITZ ULLMANN aud JACOB TSCHERNIAK (Bey. 1905 38 41 10-41 11).-2'-2Zyd~o- Jluorangldipphen ylcartino I O<~~>CH*C6H,*CPh,* OK prepared by the action of bromobenzene and magnesium on methyl hydro- fluoranate (Meyer Abstr. 1895 i 291) O<CFK4>C H*C,H,*CO,Me separates from benzene iu colourless crystals and melts at 196'. By the action of acetic and sulphuric acids it is converted into 10 10-dipphenyl- 1 ; 9-o-p?~enoxylenedihydronnt?waceney which sepa- rates in colourless crystals and melts a t 325'. T. MI. L Salts of the Alkaloid Cinchonamine. BERNARD F. HOWARD and F. PERRY (J. SOC. Chen?,. Ind. 1905 24 1281--1283).-The cinchonamine used in the investigation was obtained from a sample of the crude nitrate which had been precipitated from the alkaloid of the bark of 12emijicc.Puvdeiana. The crude salt was twice recrystallised from water and converted into the hydrochloride jn which form it wcx several times recrystallised ; on precipitating the base and recrystallising it from acetone it was obtained as a perfectly white crydtaliine product. Cinchonamine hydrochloride C,,H,,ON,,HCI crystallises from t h e acid solution in soft almost white glistening laminze. A hot saturated neutral solution of the hydrochloride cooled to 27' deposits cubical crystals of a monohydrated salt. A dihydrochloride could not be obtained. The hydrobromide was prepared in a manner exactly similar t o t h e hydrochloride and was found to be anhydrous ; it is very slightly soluble in cold water. The hydriodide prepared by double decomposition of a salt of cinchonamine with potassium iodide or by boiling the alkaloid with 5 per cent.hydriodic acid crystallises in shining slightly yellow plates; on exposure to dry air it loses hydro- G. Y. C K 6 4 (&H,*FH-y,H CPh,*C,H3 -0ORGANIC CHEMISTRY. 103 gen iodide; it is almost insoluble in cold water but is fairly soluble a t higher temperatures. The platinichloride forms a very insoluble semicrystalline yellow solid. The salicylate prepared by neutralising a warm solution of salicylic acid with cinchonamine forms a resinous mass which crystallises from dilute aqueous solutions in thick colour- less prisms which are very readily soluble in acetone. The sulphate was obtained by neutralising an alcoholic solution of the alkaloid with dilute sulphuric acid a t a temperature just below the boiling point of alcohol; on rendering the neutral solution just acid and cooling it was deposited in small needles ; it is extremely soluble in water and is practically insoluble in absolute alcohol ; it is very soluble in pyridine and crystallises from i t with one molecule of the solvent.The acid sulphate C,,H240N2,H2S04 is best prepared by dissolving the sulphate in a small quantity of water a t the temperature of the boiling water-bath and stirring in a molecular quantity of dilute sulphuric acid ; on slow evaporation in a vacuum the solution deposits large truncated octahedra. The picrate obtained as a yellow amorphous powder by adding a cold aqueous solution of picric acid to the hydrochloride melts at 54' and contains &H20.Solubilit<y curves are given for the haloid salts. P. H. Nicotine and its Specific Rotation. I. FLORIAN RATZ. (Monatsh. 1905 26 1241-1252).-The author has purified two samples of nicotine of different origins by fractional distillation under 20 mm. pressure and obtained two fractions having [.ID - 163.19" and - 166.77' at Z O O respectively. The specific rotation of these fractions was not altered by further fractional distillation but on con- version of each into the zincochloride fractional cry stallisation of this and liberation and fractional distillation of the base two specimens of pure nicotine were obtained. This boils at 246.2' under 719.8 mm. pressure and has the sp.gr. 1.00924-1*00925 at 2Oo/4O and La] - 169.22" to - 169.54" a t 20". Nicotine zincochZoTide C,,H,,N,,2HC'l,ZnC12,H20 is soluble in two parts of water or 4-4.5 parts of 60 per cent. alcohol or in 0.1 or 0.35 part of the boiling solvents respectively. A table is given showing the sp. gr. and the specific rotation of nicotine as found by a number of authors. The different figures obtained previously must be due to the presence in varying amounts of an impurity which is removed only partly by fractional distillation ; the nature of this the author proposes to investigate. G. Y. Scopolamine and Scopoline. ERNST ScHmDT (Arch. Plbarm. 1905,243,559-583. Compare Abstr. 1892,1255 ; 1895 i 158 ; 1898 i 499 ; 1903 i 5l).-Numerous attempts to obtain reactions which would correspond with the presence of ketonic oxygen in scopoline C8H1?02N gave no positive result.Further it was not found possible to reduce scopoline in either acid neutral or alkaline solution ; neither could a compound with hydrocyanic acid be obtained; nor was a benzylidene derivative formed when scopoline and benznldehyde were allowed to remain in acetic acid solution saturated with hydrogen104 ABSTRACTS OF CHEMICAL PAPERS. chloride as happens with substances which contain a CH,*CO group (Willstiitter Abstr. 1898 i 160). By methylating scopoline (Luboldt Abstr. 1898 i 499) a small quantity was obtained of a crystalline methylscopolim which melted a t 69-70"; it was analysed in the form of its awrichloride which melts at 154O. When scopoline is allowed to remain with hydrogen peroxide it yields a product which melts and deconiposes at 122' and forms ft crystalline hydrochloride C8H,,0,N,HC1 ; probably this product is an oxide the NMe group having been converted into NMeO. Scopoline is oxidised but very slowly by a boiling solution of chromic and sulphuric acids ; the products are scopoligenine C,H1102N pyridine methosulphate methylamine and carbon dioxide.[With RUDOLF Gaz~.]-Bromine either in chloroform solution or in the form of vapour converts scopoline partially into scopoligenine ; in the latter case a eniall quantity was also obtained of a substance melt- ing a t 1 10-1 13* .probably a bromo-derivative of scopoline. Scopoligenine yields unsaturated hydrocarbons and pyridine when it is heated with zinc dust in a current of hydrogen gas.When hydrobronioscopoline hydrobromide is boiled with phosphorus tribromide and the product reduced with zinc and dilute sulphuric acid hydroscopolidine is formed; this was analysed in the form of its aurichloride U,H,,N HAuCl which melts at 204-206'. The uuric?doride of hydroscopoline C,H,,U,N HAuCl which is obtained by reducing hydrobromoscopoline (Abstr. 1905 i 51) meIts at 200-201'. New varieties of the platinichloride and anrichloride of scopoline respectively anhydrous and with H,O are described; these melt practi- cally at the same temperature as the salts known already. cgH1s02N HAuC147 Hydriodoscopoline hydriodide melts at 196'. C. F. B. Modern Theories of Double Linkings and the Constitutional Formula of Pyrrole. GIACOMO CIAMICTAN (Guxxetta 1905 35 ii 384-39 S).-The author discusses the various formuh which have been proposed for pyrrole in which as he has already pointed out (Abstr.1893 i 602) two valencies of the nitrogen atom exist in a latent condition. On the basis of Thiele's theory of partial valencies he supposes that in thiophen pyrrole and furan the partial valencies of the group -CH:CH*CH:CH- are more or less satisfied by the latent valencies of the sulphur nitrogen and oxygen respectively the extent of t h i s neutralisation being greatest with sulphur and least with oxygen (see also Abstr. 1905 i SO). T. H. P. Compounds of Copper Salts with Pyridine and Quinoline. PAUL PFEIFFER and V. PIMMER (Zeit. anorg. Chern. 1905,48 98-1 11). -The following additive compounds of copper nitrate and pyridine have been prepared.Cu(N03),,2C,H,N a light blue powder ; Cu(N03),,3C,H,N azure- blue crystals ; CU(NO,)~,~C,H,N violet plates ; Cu(N03),,6C H,N small cobalt-blue crystals. The tetra- pyridine compound is readily formed from its components ; with excess of the base it forms the hexapyridine compound whereas it yields theORGANIC CHEMISTRY. 105 di- and tri-pyridine compounds when heated carefully. The compounds Cu(N0,),,2C5HSN,2H20 and Cu(N0,),,6C,H5N,3H,0 have also been prepared ; the former occurs in light blue plates whilst the latter has a violet-blue colour. Diquinoline cup& nitrate Cu( NO,),,2 C9H7F prepared directly froin its components crystallises in transparent indigo-blue needles. Dippidine cupric bromide CuBr2,2C,H,N prepared from its com- ponents occurs in green needles; with excess of the base it yields hexapyridine cupric bromide CuBr2,6C,H5N as a blue crystalline mass.Ppridinium cupric bromide Cu(C,H,N),Br4 prepared by dissolving the dipyridine additive compound in hydrobromic acid forms lustrous reddish-black prismatic crystals ; the corresponding quinolinium com- pound Cu(C,H,N),Er4,3H,0 prepared by a similar method crystallises in black plates. G. S. Aminoacetals and Aminoaldehydes. 11. ALFRED WOHL (Ber. 1905 38 4154-4157. Compare Abstr. 1901 i 513).-A summary of the results contained in the three following abstracts. Amino- aldehydes and their substitution derivatives are best purified in the form of their platinichlorides ; the free aldehydes very readily undergo condensation and in only a few cases have they been obtained pure by reducing to a minimum the decomposing action of heat alkali and water .c. s. ALFRED WOHL KURT SCHAFER and A. 'J'mEm (Ber. 1905 38 415$-4161).-yy-Amino- bntyraldehyde diethylacetal is conveniently obtained by the interaction of /3-chloropropaldehyde diethylacetal sodium ethoxide and dry hydrogen cyanide in alcoholic solution a t 118-1 22" for two days the product being subsequently reduced with sodium and absolute alcohol. y-A~2ino6ul?/raZde?,?/da NH,*CH,*CH,*CH;CHO obtained by the de- composition of the acetal by a dilute solution of oxalic acid forms a syrup which still contains oxnlic acid. is an unstable crystalline substanc'e. y -.Aminobutyraldehyde and Pyrrolidine. The platinichloride (C,H,ON),,H,Pq y-~o~mylccminobutyru?de7~~de diethylucetal CHO*NH*CH2*CH,*CH,*CH(OEt),~ prepared from ethyl formafe and the acetal base bolls at 170" under 14 mm.pressure and is soluble in water or the usual organic solvents. y- Form~laminobzcI?/rccldeT~yde CRO*KH*CH,*C H,-CH,*CHO is ob- tained in an impure state by the decomposition of the acetal with oxalic acid. The plutinicldoride (C5H,0,N)2,H2PtCl melts and de- composes a t 176". 3 3 obtained by the action of benzenesulphonic chloride on an aqueous- alcoholic solution of y-nminobutyraldehyde diethylacetal and treatment of the oil so protliicetl with a 5 per cent. alcoholic potash is a crystal- line substance which melts a t 76-78" and distils without decomposi- tion. It is insoluble in water but dissoIves in ordinary organic solvents ; i t is reduced to pyrrolidine by sodium and hot amyl alcohol.c. s. VOL. XC. i. i106; ABSTRACTS OF CHEMICAL PAPERS. Hydrogenated Pyridine-aldehydes. ALFRED WOHL FV . HERTZ- BERG and M. S. LOSANITSCH (Ber. 1905 38 4161-4169).-/3-Inrino- dipropaldehyde tebraethylacetal NH[CH,*CH,*CH(O Et)2j2 obtained by heating under preesure P-chloropropaldehyde diethylacetal ( 1 part) with a cold saturated solution of ammonia in alcohol (6 parts) a t 118-120' for not more than nine hours is a colourless viscous liquid inclining t o yellow ; it boils at 157' under 1.5 mm. pressure has a basic odour is somewhat soluble in water dissolves in the ordinary organic solvents and has a sp. gr. 0,9466 at 15'. Dilute oxalic hydrochloric or sulphuric acid hydrolyses it t o the extent of SS per cent.Cold con- centrated hydrochloric acid causes the formation of a syrup which was identified as A"-tetml~?/di.o~?lrid~ne-3-ddeiLyde in the form of the hydro- chloride of i t s nitrop~~en?lEhydraxorLe HC1 rH-UH,-fi.CH N,H- C,H,*N 0 CH,*CH;CH a hygroscopic reddish-yellow substance which sinters at 173.5' and melts with decomposition at 251'. 9 P-Et~~yliminodipropaldehyde tetrnethylucetal NEt[CH,*CH,*CH(OEt),1 obtained from ethylamine jind P-chloropropaldehyde diethylacetnl in benzene solution a t 135-140' is a colourless viscous oil which boils at 159' under 13 mm. pressure; it is sparingly soluble in water and is miscible with the ordinary organic Folvents. The platinicldoride (U H 3504N)2.H,PtCI separates from dilute alcohol in yellow octa- hedral crystals which melt and decompose at 92-93' (corr.).1- Etli~l-~~-tetrah~d~opyridine-3-ulclel~~lde h ydrocldode C,NH,Et BCHO HC1 is obtained from the acetitl by the action of cold concentrated hydro- chloric acid. I t separates from dilute alcohol in long colourless crystals which melt at 208' (corr.) shows reducing properties and gives n reddish-brown coloration with concentrated siilphuric acid and phenol or P-naphthol. The platiniclJoride forms yellow cubes which melt and decompose at 190". The hjdrocltloride of the nitrophenyl- hydrazone separates from dilute alcohol in reddish-yellow hygroscopic needles which melt and decompose at 263'. The hydrochloride of the oxime forms long colourless needles which melt at 248-249' (corr.).The free oxinze which is not produced by mixiog i t s components is obtained from the hydrochloride by the action of potassium carbonate ; it crystallises in white scales and melts at 134' (corr.). The acetate of the oxime obtained by the action of acetic anhydride and sodium acetate on the hydrochloride boils a t 102-105° under 0.1 mm. pressure. Thionyl chloride converts the hydrochloride of the oxime into the IqdroclJokIe of the nitrile C,N H,Et*CN,HCI which separates from dilute alcohol in white needles melting at 265-266" (cow.). prol)arecl I>y the action of 11;drogen clilo~ide on the liydrochloricle of 1 -ethyl-A3-teirahydi~opyriclline-3-aldehyde dissolved in absolute alcohol is a colourless oil which boils a t 79-'80' under 0.05 mm. pressure. I t sOIiG ANIC CHEMISTRY.107 reduction by .?odium and absolute alcohol produces 1 -etlb&ipe?*idi?ze- 3-ccldelqde diethykccetcd which is a colourless oil boiling at 63-65" under 0.04 mm. pressure. c. s. Free Aminoaldehydes. ALFRED WOHL and M. S. LOSANITSCH (Uer. 1905 38 4170-41 72).-l-~th~Z-~~-tetral~~/dropyridirte-3-alde- Ityde obtained from its hydrochloride (see preceding abstract) by the action of solid potassium carbonate is a colourless oily liquid with a basic stupefying odonr ; it boils at 52-44' under 0.06 mm. pressure has an alkaline reaction and reducing properties and is resinified by potassium hydroxide. l-Et?'?lZ~)~~~eridilae-3-aZde?~?lde is obtained in small quantity from the corresponding acetal (Zoc. cit.) by the action of strong hydrochloric acid with subsequent addition of potassium carbonate to the cold diluted solution. It is a colourless oil which boils at 40' under 0.2 mm.pressure ; i t has a burning taste fumes with hydrochloric acid and reduces Fehling's solution. I n contact with air it becomes resinous and insoluble in water. The PZatinicldoride crystallises in octahedra. p- Eth~l~cmi~~zo;u~opciZdehyde diethylacetal NHEt CH,* CH,*CH( OEt) is a by-product in the preparation of the tertiary base (Zoc. cit.). It is a colourless mobile oil with a basic odour and strongly alkaline reaction. It boils at 82*5-83*5' under 13 mm. pressure. When decomposed by strong hydrochloric acid it yields the hydrochloride of the aminoaldehyde C5H,,0N,HC1 which melts at 265-265-5' (corr.) and reduces solutions of silver salts. p- Ethylaminopropddel~yde (NHEt*CH,*CH,*CHO) is obtained from the hydrochloride by the action of potassium carbonate as a slightly yellow oil which reduces solutions of silver salts but not Fehling's solution answers to Schiff's test and forms with hydro- chloric acid a hydrochloride identical with that from which it is pre- pared.The free aldehyde is remarkably stable retaining its properties unchanged after being heated in a vacuum to 180". c. d. Reciprocal Stereochemical Influences. HANS MEYER (Monatsl'. 1905 26 1303-131O).-Two similar or dissimilar groups which influence each other so that they act as if only one group were present the author terms '' conjugated groups." Typical examples of sub- stances containing '' conjugated groups " are the 2- and 4-aminopyr- idines and the 2- and 4-aminoquinolines in which the two basic groups influence each other so that salts are formed with only 1 mol.of hydrochloric acid. On treatment with nitrous acid these bases behave as stable aliphatic amines. In 4-aminonicotinic acid the carboxyl group and in 4-aminolut- idinic acid one of the two carboxyl groups is partially neutralised by the 'i conjugated groups '' j these acids are therefore pseudo-betaines (Abstr. 1904 25 490). On the other hand in the 3-aminopyridines 7-aminoquinoline and 5- and 8-aminoisoquinoline the tertiary nitrogen and the amino-group have no stereochemical influence on each other and these bases form i B10s ABSTRACTS OF CHEMICAL PAPERS. salts with 2 mols. of hydrochloric acid and when diazotised behave as aromatic amines.Similarly whilst the 3-hydroxypyridines react normally the 2- and 4-hydroxypyridines (2- and 4-pyridones) and the 2- and 4-hydroxy- quinolines do not give the typical reactions. Thus the 2- and 4- pyridones do not yield nitroso-derivatives cannot be acetylated do not react normally wiih phenylcarbimide (Goldschmidt and Meissler Abstr. 1890 i 499) and have only feeble salt-forming properties. Claus has shown that on bromination of carbostyril the " conjugated group" exerts no directive influence (Abstr. 1896 i 449). G. Y. Action of Diazomethane on Pyridones and Hydroxy- pyridinecarboxylic Acids. HANS MEYER (Monatsh. 1905? 26 131 1-1329. Compare preceding abstract).-Whilst 2-pyridone is converted into 2-methoxypyridine only slowly and partially by the action of diazornethane this reagent interacts energetically with 3-hydroxypyridine which must be a true hy droxy-compound forming 3-methoxypyridine ; this yields a mercurichloride which crystallises in slender colourless needles and melts at 1 lo' and a platinichloricle which is obtained in yellowish-red crystals and melts at 182'.The action of diazomethane on 4-pyridone leads to the formation of a mixture of 4-methoxypyridine and 1-methyl-4-pyridone. 4-Methoxy- pyridine mercurichloride crystallises in colourless needles and melts at 191'. Carbostyril interacts with diazomethane to form 2-methoxy- quinoline and not the N-methyl derivative. The action of methyl iodide on 6-hydroxynicotinic acid in aqueous alkaline solut,ion leads to the formation of 6-keto-1-methyl-1 2-di- hydropyridine-3-carboxylic acid which melts at 238-239' (compare von Pechmann and Welsh Trans.1885 47 150; Abstr. 1885 174). This differs from all 1 -methylpyridinecarboxylic acids investigated previously as owing to the negative influence of the keto-group on the methylimico-group it does not form the betaine and can be titrated with h'/lO potassium hydroxide. When treated with diazomethane it yields the methyl ester which crystallises in long glistening needles and melts at 1313". The action of diazomethane on 6-hydroxynicotinic acid leads to the formation of a mixture of derivatives consisting of 88.5 per cent. of methyl 6-keto-1-methyl-1 2-dihydropyridine-3-carboxylate and 11.5 per cent. of methyl 6-metlzoxynicotinate OMe*C,NH,*CO,Me which crystallises in soft needles and melts at 122O whereas diazornethane and methyl 6-hydroxynicotinate interact to form methyl 6-keto-1- methyl- 1 2 -dihydropyr.idine-3-car boxylate only.Methyl 2-hydroxycinchonate is formed from the acid by the action of thionyl chloride or sulphuric acid and methyl alcohol or together with methyl 2-methoxycinchonate by the action of diazomethane. It crystallises in glistening colourless needles me1 ts at 242' sublimes at 240-250" and distils apparently without change Jfetlh) 2-methoxy- cinc?~oizate crystallises in needles melts at 120° and has an odour of orange blossoms. When boiled with 2 per cent. aqueous sodium hydroxide propionyliscctin which is formed by boiling isatin with propionic anhydride and melts a t 1 41° yields 2-hy droxy-S-methyl-ORGANIC CHEMISTRY.109 cinchonic acid OH*C,NH,Me*C02H ; this separates from water in colourless crystals melts a t 315-31 7" and when treated with thionyl chloride and methyl alcohol or with diazomethane yields methyl 2-~ydrox~-3-nzeth?/lcinc;cLolzccte which crystallises in long slender needles and melts a t 174-175'. Prolonged treatment with diazo- methane had no further action on the methyl ester. Chelidamic acid interacts energeticdly with diazomethane forming the dimethyl ester OH*G',NH,(CO,Me) which crystallises in long needles melts a t 125" and is only sparingly soluble in ether. The author discusses the constitution of comenamic acid (compare Lapworth and Collie Trans. lS97 71 843 ; Yeratoner Abstr. 1902 i 493) and concludes that it is 4 5-dihpdroxypyridine-2-calk,oxylic acid.It cloes not interact with thionyl chloride (compare Abstr. 1902 i 31) but when treated with diazomethane yields rnet?qZ ~-~~~ldroxy-~-met~~ox~p/pyr~dilze-~-carboxy~c6te melting a t 1 1 8 O . Formation from Furfuraldehyde of Colouring Matters derived from Pyridine. WILHELM KONZG (J. pr. Chew,. 1905 [ii] 72 555-562. Compare Abstr. 1904 i 449 S17; Zincke Heuser and Rloller Abstr. 1904 j 921 ; Zincke and Miihlhausen this vol. i 33).-'L'he hydrobromide of a-hydroxyglutaconaldehyde- dianilide NHPh*CH:CH*CH C( OH) CH (0 H)*NHPh,HBr is formed by heating aniline with furfuraldehyde in alcoholic solution on the water-bath and after cooling adding hydrobromic acid of sp. gr. 1.48 diluted with alcobol. It crystallises from acetic acid in prisms which have a deep blue lustre melts at 164-165O and dyes silk and tannin mordanted cotton-wool deep red or unmordan ted cotton-wool rose-red.When heated with nitrobenzene a t 150" it decomposes into aniline and 3-hy droxy-1-pheny lpyridinium bromide which crystal lises in mhi te needles containing H20 and melts a t 129" (compare Zincke and Muhl- hausen Zoc. cit.). The picrate CI7HIBOSN4 crystallises in slender yellow needles and melts at 219'. The hydrobromide of a-hydroxyglutaconaldehydedi-p-phenetidide C,,H,60,N,,H Br formed from p-phenetidine and furfuraldehyde by the bame method as the dianilide crystallises in glistening blue prisms melts a t 157-15So and dyes silk and unruordanted cotton- wool the rhodamine colour but not fast.The free bc6se is obtained as a yellow oily mass. When heated with nit'robenzene it yields 3-hydroxy- 1 -p-et~~oxyphen?lZpyriin~~nz bromide C,,H,,O,N Br H,O which crystallises in colourless iridescent leaflets and melts a t 167--168O. The picmte forms yellow needles and melts a t 207". Dyes derived from Furfuraldehyde. WALTER DIECKMANN nrid LUDWIG BECK [and in part BRUNO SZELINSKI] (Ber. 1905 38 4122-4135. Compare Zincke and Miihlhausen this vol. i 3 3 ; Kiini g abstract). - H y drox ygl u taconalcle h y ded ian ilid e hydrobromide N HPh*CH:CH*CH:C(OH)*C H:NPh,HBr,H20 pre- pared either by the action of aniline and aniline hydrobromide on furfuraldehyde or by the action of aniline and cyanogen bromide on 3-hydroxypyridine melts and decomposes at 166" and is converted by heating with alcohol and hydrochloric acid into 3-hydroxy-1-phenyl- pyridinium chloride OH*C,NH4PhBr which melts and decomposes a t G.Y. G. Y. preceding110 ABSTRACTS OF CHEMICAL PAPERS. 210° and yields a picrate melting and decomposing at 218-221' and a platinichloride melting and decomposing at 199' ; the identity of the two preparations is thus fully demonstrated. Similar evidence was obtained in the case of the p-chloroaniline derivatives. Hyd~*ox~glutaconaldehydedi-p-chloroaniZide hydrochloride C,H,Cl~?JH~CH:CH*Cl~:C(OH)~CH:N~C,H,Cl,HCl resembles the dianilide hydrochloride and melts' and decomposes a t 167'. 3-Rydroxy- 1 - p - chlorophen y lp yr id inium chloride OH- C 5N H,C1* C,H,Cl cry st all is es from water in long colourless needles and melts and decompo"ses a t 221'.The pZutinichloride crystallises from hot water in orange- yellow needles and melts and decomposes at 217'. T. M. L. Action of o-Nitrobenzaldehyde on Dimethylaniline in Presence of Hydrochloric Acid. THEODOR ZINCKE and WILHELM PRENNTZELL (Ber. 1905 38 41 16-4122).-o-Nitrobenzaldehyde and dimethylaniline which yield a triphenylmethane compound when acted on by zinc chloride give when acted on by concentrated hydrochloric acid at 11 O-115° a compozmd C,,H,,ON,Cl which is formulated as an anthranil derivative but might possibly be an acridone compound C,H,c1<:!>c6H,*NMe ; it crystallises from hot alcohol in yellow needles from acetone in stout reddish-yellow needlw and melts at 162-163° ; its dilute alcoholic and ethereal solutions show a very strong fluorescence similar to that of fluorescein ; concentrated solutions are yellow ; it is stable towards alkali hydroxides and does not lose chlorine but has slight basic properties.The hydrochloride forms colourless flakes the nitrate and sulphate solourless needles; the platirzichloride (C,,€I,,ON2C1),,H,PtC1 crystallises in minute yellow scales is insoluble in water and decomposes above 200" ; the methiodide C,,H,,ON,Cl,BleI crystallises from hot alcohol in glistening scales melts at 184' liberating methyl iodide and fluoresces in alcoholic solution. Reduction by means of zinc and acetic acid gives a compound formulated as 5-ch1?oro-2-umino-4'-dimeth~luminobenxopl~enone NH,*C,H,Cl COO C,H,*NMe which crystallises in minute yellow needles and melts a t 185".The hydrochloride crystallises from dilnte hydrochloric acid in colourless glistening tablets but is decomposed by water or alcohol. The acetyl derivative crystallises from dilute alcohol in yellow glistening needles and melts at 132O. The ketone is reduced by hydrogen iodide and phosphorus a t 19 0-200' to 2 4'-diaminodiphenylmethane (Stadel Abstr. 1895 i 233) which crystallises from ether in transparent tablets melts a t SS-S9O and is readily converted into diphenyl- methane. The hydrochloride crystallises in small colourless needles. The acetyl derivative separates from alcohol in white tabular crystals melting a t 20So or in small glistening needles melting at 218'; only the latter modification is described by Stadel. T. M. L.ORGANIC CHEMISTRY.111 Phenylhydrazine as a Reducing Agent in Organic GIUSEPPE PLANCHER (Gaxxetta 1905 35 ii 460-463). A reply to Odd0 and Puxeddu (Abstr. 1905 i 842). T. 11. P. Chemistry. -Polemical. Phenylethylidenehydrazine. GEORG LOCKEMANN and OTTO LIESCHE (Annulen 1905 342 14-50).-Ptrenylethylidenehydr- azine that is acetaldehydephenylhydrazone was used in the preparation of acmldehyde as a means of recognising acet- aldehyde (Abstr. 1905 i 570). It has been shown by Fischer (hbstr. 1896 i 361) to exist in two or three mutually convertible isomeric forms. A list is given of the phenylhydrazones of aldehydes or ketones or ketonic acids of osazones of diketones and other simi1:tr hydrazones which exhibit isomerism. This isomerism has been variously regarded as a structural or steric isomerism but the explanation given by Hantzseh and based on the latter type of isomerism is regarded as the most adequate.The conditions under which the two forms of the acetaldehyde- phenylhydrazone are stable have been investigated. Fischer (Zoc. cit.) obtained a p-form (m. p. 63-65") which was transformed by alcoholic sodium hydroxide into the a-form melting at 98-101"; the latter then passed slowly into a third variety melting a t 80". It is now found that this substance exists in two modifications; the stable a-variety melts a t 9S-l0lo whilst the labile p-fo?.rn melts a t 57". The P-hydrazone gradually changes into the a-form but the trans- formation is hastened by the action of bases such as sodium hydroxide or ammonia and also by various salts.Crystallisation from alkaline 75 per cent. alcohol is the most efYectual method. The change from the a- into the p-form also takes place in certain solvents but is momentarily effected by treatment with aqueous sulphurous acid. Tho depression of the freezing .point of the a- modification does not appear to be due to cz conversion into a third form but to decomposition oxidation &c. Fischer's isomeride (m. p. 63-65') is probably an amorphous mixture of the a- and P-hydrazones. X cetaldehydephenylhydrazone is prepared by adding molten phenyl- hydrazine to an ice-cold solution of acetaldehyde in light petroleum. The product which is white can only be kept in an atmosphere free from alkaline or acid vapours; i t melts usually a t 51-57' although higher melting points ( 9 P ) have been observed. 011 crystallisation from 75 per cent.alcohol containing a trace of sodium hydroxide prismatic crystals of the a-modification are obtained. The p m( dification is obtained by adding aqueous sulphurous acid either to a 75 per cent. alcoholic solution of the a-hydrazone or by moistenivg the crystals. The use of a stronger acid hydrochloric or nitric brings about the transformation but a t the same time causes some decomposition. Carbon dioxide attacks the a-modification slowly but does not convert it into the p-form. Even in a com- pletely neutral medium such as air the @-modification becomes coloured and the melting point rises. Indifferent solvents cause the transformation of either form into the other but in no case can a complete transformation be effected by simple112 ABSTRACTS OF CHEMICAL PAPERS.recrystallisation. The melting point of the p-form may be somewhat raised by recrystallisation or that of the a-form somewhat lowered. Both isomerides show the same behaviour towards benzoyl chloride. Dibenzoylphenylhydrazine (m. p. 177-1 78') is formed when an aqueous suspension of the hydrazone is treated with benzoy 1 chloride and sodium hydroxide ; a t the same time tribenxoylphenyl~ydraxilze C27H2,0,N2 is formed; it can be prepared by repeated treatment oE phenylhydrazine with benzoyl chloride in ethereal solution in the presence of sodium hydroxide and crystallises in rhombic plates melting at 200-201°. Both the a- and /3-hydrazones yield the same p- benxoyl-P-phenyl- a-ethylidenehpdraxine CHMe N *NPhBz when the benzoylation is carried out in pyridine solution; it crystallises in rectangular plates or cubes melting at 89-90° and is reduced by zinc dust and acetic acid to benzanilide. I t does not condense under the action of phosphoric oxide or zinc chloride to a diphenylpyrazole.It is thought that the isomerism of acetaldehydephenylhydrazone is not explicable from a stereochemical standpoint but rather is better accounted for as a case of tautomerism. Diphenylhydraeine Hydrazobenzene and Beneylaniline and Miscibility of the last two with Azobeneene Stilbene and Dibenzyl in the Solid State. F. M. JAEGER (Proc. K. Akad. N'etenach. Amsterdam 1905 8 466-474).-The following crystallographic constants were determined as-diphenylhydrazine triclinic [a b c = 0.7698 1 0,5986 ; hydrazo- benzene rhombic [a b c = 0.9787 1 1.24971 ; benzylaniline mono- clinic [u b c = 2.1076 1 1.6423 ; p = 76'36.5'1.Bruni and Gorni (Abstr. 1899 ii 407 732) and Garelli and Calzolari (Abstr. 1899 ii 732 ; 1900 ii 65) have concluded from freezing-point observations that mixed crystals are formed bet ween dibenzyl stilbene tolane and azobenzene the groups -CH,*CH,_ -CH:CH- -CiC and -N:N- being capable of mutual replacement in an isomorphous series a conclusion which has been confirmed by the crystallographic measurements of Boeris (Atti Soc. ItaZ. Sci. MiZano 1900 39 111-123). It has therefore been suggested that if two aromatic substances can form mixed crystals their hydro-products can do the same.This conclusion is contradicted by the marked contrast between hy drazobenzene (rhombic) and azo benzene (monoclinic) which are not isomorphous do not form mixed crystals and give the normal V-shaped melting-point curve ; the group -NH *NH- must therefore be excluded from the above series. Benzylaniline containing the mixed group -CH,*NH- might be expected to fall in with the rest of the series ; actually although not isomorphous with azobenzene a rearrangement of the indices gives very similar values for a b and for p but different values for c b ; the ielatiouship is therefore morphotropic but not isomorphous. Action of Nessler's Solution on Antipyrine Pyramidone Antifebrin and Exalgin. PAUL N. RAIKOW and CHB. KULUMOW (Chem. CeiLtr. 1905 ii 1595; from Oesterr. CILenL.Zeit. [ii] 8 445-448. Compare Schuyten Abstr. 1898 i 452 ; Ville and Astre Abstr. 1900 i 363 4ll).-The author has succeeded in preparing K. J. P. 0. a = 89'24' p = 137'28.5'. y = 90O4.5'1 ; T. M. L.ORGANIC CHEMISTRY. 113 mercuric iodide compounds of antipyrine pyramidone antifebrin and exalgin by using alkaline solutions of mercuric iodide. " Antipyine oil" forms a bright yellow somewhat viscous liquid and has a sp. gr. 1.3518 a t 19" ; it is readily soluble in alcohol or acetone less so in water and insoluble in ether carbon disulphide chloroform or alkalis. The aqueous solution is alkaline. The com- pomd is decomposed when treated with water which has not been distilled or by boiling the solntion in distilled water a white precipitate being formed in each case ; hydrochloric and sulphuric acids also give precipitates.Antipyrine oil is not volatile and is decomposed when strongly heated. With concentrated sulphuric acid i t gives a red coloiation and on warming the mixture small red crystals are forrued and iodine liberated. By the action of hydrogen sulphide silver nitrate and a n excess of silver nitrate on a solution of the oil in acetone mercuric sulphide mercuric iodide and silver iodide are formed respectively ; when heated with acetic acid a compound Hg[N(I)<ggIXE] 1 is formed which crystallises in pale yellow prismatic crystals mhts a t 133" and is decomposed by repeated crystallisation from glacial acetic acid. It is soluble in acetone chlotoform or glacial acetic acid but insoluble in cold water ether or carbon disulphide.When heated with water i t becomes deep yellow but regains its original colour on cooling ; the warm aqueous solution is neutral. 9 The compound H g 1 * ~ ~ [ 2 ~ ~ > C * N H l l l e I (?) formed by the action of Nessler's reagent on dimethylaminoantipyrine ( pyramidone) crystallises from acetic acid in sulphur-yellow ueedles and melts a t 170-172°; i t is readily soluble in acetone or hot acetic acid sparingly so in water arid insoluble in ether chloroform or benzene. The aqueous solution is neutral to litmus. Acetanilide (antifebrin) is only partially attacked by Nessler's reagent a yellow mercuric iodide compound being formed which is insoluble in ether chloroform or alcohol and is decomposed by water with liberation of mercuric iodide.The yellow oil " exalgin oil," HgI*NPhMeI*COMe or Hg,(NPhlMe*COMe),,BHI obtained by the action of Nessler's reagent on ruethylacetanilicle (exalgin) gradually becomes darker ; i t is mihcible with a small quantity of water. By the action of a large quantity of water on the oil yellow mercuric iodide is formed m d the liquid becomes opaque; after a time however red mercuric iodide separates out and the liquid regains its transparency and becomes almost colourless. When water or' ether is added to a solution of the oil in acetic acid red mercuric iodide is formed. The oil is insoluble in carbon disulphide and is partially decomposed by light petroleum regenerating its components ; by the action of concentiated sulphuric Pyrimidines ; 2 5-Diamino-6-oxypyrimidine.XII. TREAT L;. JOHNSON and CARL 0. JOHNS (Anaer. Chem. J. 1905 34 554-56S).- or nitric acid exalgin and iodine are formed. E. w. w. 5 -,\.itw-B-cunaino- 6-oxypyrimidine NH<Co.C(No2)>CH C(NH,) :N- obtained by114 ABSTRACTS OF CHEMICAL PAPERS. the nitration of 2-amino-6-oxypyrimidine (isocytosine) (Wheeler and Johnson Abstr. 1903 i 526) crystallises in groups of yellow micro- scopic prisms becomes brown at about 280" does not decompose below 300° and is insoluble in the usual organic solvents; when heated for four hours at 190-200° with dilute sulphuric acid i t is converted into nitrouracil. When 5-uitro-9-amino-6-oxypyrimidirie is reduced with aluminium amalgam in preseiice of ammonia 3 5-diusnino-6-oxypyim- idine NH<Co. C(NH C(KGp)>CH,H,O )-N is produced which crystallises in large radiating prisms is very soluble in water and is probably identical with the diamino-oxypyrimidine obtained by Kutscher (Abstr.1903 i 668) from the nucleic acid of yeast. The anhydrous base decomposes a t about 2 4 5 O aod has no definite melting point. The picrate hydrochloride nitrute and siclphate are described. When 2 5-diamioo-6-oxypyrimidine is heated with 20 per cent. sulphuric acid for three hours a t 130-140° in a sealed tube it is partially con- verted into 2-umino-5 6-dioxypyrimicline which crystallises from water in groups of microscopic prisms and does not decompose below 300'; its picrate is described. 2 5-Diamino-6-oxypyrimidine may also be prepared by heating 5-bromo-2-amino-6-oxypyrimidine with concentrated solution of ammonia or by the action of alcoholic ammonia on 5.amino-6-oxy- 2-ethylthiolpyrimidine.When an aqueous solution of guanidine is heated with ethyl sodioformylhippurate 2-arnino-6-oxy-5-benzo~lumi?zo- - _ _ pprimidine hydrochloride N H < ~ & ~ ~ d & B ~ > C H H C l is produced which crystallises from hot water in microscopic needles and decom- poses at about 275O. By the action of benzaldehyde on 3-amino-6-oxy- pyrimidine 6-oxy-2-benxylidenec6m~nopyr~m~dine C(N:CHPh) :N is obtained which forms yellow crystals decomposes a t 238 -242O and is very stable towards nitric acid. When a solution of 2-amino-6-oxy- pyrimidine in acetic acid is treated with sodium nitrite a substance is formed which crystallises in microscopic prisms is very soluble in water turns brown a t about 280° does not melt below 300° and is probably an acetate of 2-amino-6-oxypyrimidine. NH<CO-CH>CH E.G. New General Method of Syn thesising Pyrazole Derivatives. GAETANO MINUNNI [in part with G. VASSALLO RICCARDO CIUSA and GUIDO LAZZARINI] (Atti R. Accad. i%zcei 1905 [v] 14 ii 414-420). -On heating a mixture of equal quantities of bonzaldehydephenyl- hydrazone and ethyl acetoacetate at 195-205O a substunce C21H,602N2 is obtained which crystallises from alcohol ir white nacreous laminae melting a t 140-140.5° and is soluble in ether light petroleum or amyl alcohol and very readily so in ethyl acetate benzene or chloroform. It dissolves in cold concentrn ted sulphuric acid imparting t o it a n inteose red coloration and when boiled with concentrated potassium hydroxide solution is converted into a substance which separates from alcohol in white crystals melting a t 11 2 -1 13".With bromine in chloroform solution it gives a compound which crystallisesORGANIC CHEMISTRY 115 from alcohol in long white needles melting a t 160° and contains 20.5 per cent. of bromine. Later attempts to prepare the substance C,,K,,O,N from other samples of ethyl acetoacetate have proved fruitless and its constitution has not been determined. The condensation of benzaldehydephenylhydrazone and ethyl aceto- acetate in presence of zinc chloride yields ethyl 1 3-diphenyl-5- methylpyrazole-4-carboxylate ( I h o r r and Blank Abstr. 1885 810). Similarly the condensation of sixlicylaldehydephenylhy drazone with ethyl acetoacetate in presence of ziuc chloride leads first t o the formation of ethyl 1-phenyl-3-hydroxyphenyl-5-methylpyrazole-4- carboxylnte which loses one mol.of ethyl alcohol giving the lactone of 1 -phenyl-3-hydroxyphenyl-5-methylpyrazole-4-carboxylic acid N=-Y*C,H By alcoholic potassium hydroxide solution this lactone is transformed into the acid which is readily reconverted into the lactone by heating or by the action of acid chlorides. The phenylhydrazone of m-(or p - ) - nitrobenzaldehyde when condensed with ethyl acetoacetate in presence of zinc chloride yields ethyl l-phenyl-3-~n-(or p-)nitrophenyl-5- met h ylp yrazole- 4-carbox yla t e. endoIminotriazoles. 11. MAX BUSCH and GUSTAV MEHRTENS (Bey. 1905 38 4049-406s. Compare Abstr. 1905 i 307).-The action of aldehydes on triarylsminoguanidines leads to the formation of aminodihydrotriazoles >C*NHR which are decomposed by mineral acids and on oxidation yield endoiminotriazoles which are formed also by the action of acetic and benzoic acids on triarylamino- gFanidines in presence of phosphorus pentachloride but not of the acids alone ; they form sparingly soluble nitrates.With alkyl haloids the endoiminotriazoles form additive compounds NPh<C~e:C-cO>O' T. H. P. P;;IR-N CHR-ER N=y- I TR ?NRyA.lkX which yield csrbinol bases NR* C EL-/ YR-N OH*CR*NR >C*NR*Alk and when heated with potassium hydroxide are decomposed with rupture of the cyclic nucIeus. 3-Anilino-1 4-diphenyl-4 5-dihydro-1 2 4-triuxoZe C,N,H,Ph,*NHPh formed by the action of formaldehyde on triphenylaminoguanidine in boiling alcoholic solution crystallises in stout white glistening needles melts at 128" is easily soluble in chloroform ether benzene or hot alcohol and yields formaldehyde when heated with dilute sulphuric acid.When oxidised with alcoholic ferric chloride or sodium nitrite in alcoholic-acetic acid solution i t yields 1 4-diphenyl- 3 5-endoanilodihydrotriazole which the author terms '' nitron." This forms a picrate C,,H,,07N7 which crystallises in sheaves of small needles and melts at 257--258' and a diddoride C2,H,,N,,2HCl which cryst,alliees in glistening white leaflets and commences t o116 ABSTRACTS OF CHEMICAL PAPERS. N=C- N€'h-CH-/ decompose at 160'. The methiodide I (?Ph 'NPk,Mel formed by heating nitron with an excess of methyl iodide in a reflux apparatus fitted with a mercury valve crystallises from alcohol in yellow plates or from water in glistening needles melts a t 31 1-2 13" and has the conductivity p272 = 85 a t 25".The aqueous solution of the methiodide becomes neutral immediately on addition of sodium hydroxide but in dilute alcoholic solution the isomeric change from the strongly alkaline ammonium base first formed into the carbinol base takes place more slowly and is represented by the gradually diminishing alkalinity of the solution. The action of sodium hydroxide leads further t o the hydrolysis of the carbinol base and formation of a red axo-compound which on reduction with hydrogen sulphide yields anilinodiphenyZmet?~?lZguanidine NHPh*NH*C(NPh)*NMePh ; this crystallises in sheaves of needles melts a t 96-97" is readily soluble in benzene or ether and is oxiclised in alcoholic solution by the air becoming red.The cccrbinol base (5-~~ydroxy-3-rnet?~~ZccniZi~zo-l ; 4-diphenyl-4 ; 5- N>C*NMe€'h is prepared by dihydro-l ; 2 4-triaxole) treating the methiodide with aqueous ammonia; it forms a yellow powder melts a t 65O is readily soluble in alcohol ether or benzene and on treatment with nitric acid in dilute acetic acid solution forms the rnethonitl.de C2,H1,N4*N0 which crystallises in glistening clear flat needles and melts a t 1 60°. "'l'he rrzethopicrcnte Cz1H19N4,CGH207N formed by the action of picric acid on the carbinol base in dilute acetic acid solution or on the methiodide in alcoholic solution crystallises in long glistening needles and melts a t 193".YPh- CH(OH)*NPh The additive compound of nitron and benzyl chloride C27H23N4C1,H20 crystallises in clear thick tetragonal plates sinters slightly a t 1 80° melts at 210° is readily soluble in alcohol or warm water forming neutral solutions has the conductivity plo = 60 a t 25" and exhibits the same behaviour as the methiodide on treatment with alkali hydroxides. The hydrochloride C,7Hz3N,Cl,HCI crystallises in colour- lees needles softens a t 150° and melts and decomposes a t 160'; the nitrate C27H,303N5 crystallises in white needles sinters a t 209O and decomposes hucldenly a t a few degrees higher. The cavbinol base (5-hydroxy-3-henxylanilino-1 ; 4-diphenyl-4 ; 5-ditqdro-l 2 ; 4-triaxole) Cz7Hz4ON4 formed by the action of aqueous ammonia on the chloride crystallises in glistening transparent short tetragonal prisms melts at 153q is only sparingly soluble in alcohol ether o r benzene and on treatment with alcoholic hydrogen chloride is converted into a mixture of the benzyl chloride additive compound and its hydrochloride.N HPh* N H- C (NPh)-NPh* CH2Ph formed by the action of sodium hydroxide on the benzyl chloride additive compound crystallises in nodular aggregates of needles melts Amilinodipheny Zbenxylguanidine,ORGANIC CHEMISTRY. 117 at 153" and is oxidised on expmure t o the air with formation of the red axo-compound. 3-Anilino-1 4-diz3?~en?/l-5-nzetl~yl-4 5-dihydro-1 2 4-t?iuzoZe C,N,HMePh;NHPh formed from triphenylaminoguanidine and acetaldehyde crystallises from alcohol in glistening white leaflets melts at 131° is readily soluble in chloroform ether or benzene and on oxidation yields 1 4- diz3l~en?/Z-5-?izetl~~l-~ 5-endoanilo-4 5-dihydro-1 2 4-triazole 1 $Ph 'NPh.which is formed also by boiling triphenylaminoguanidine with acetyl cliloride in a retlux apparatus. It crystallises in moss-like aggregates of yellow needles melts at 245-346O is moderately soluble in methyl alcohol acetone or chloroform forms e a d y soluble salts and is decomposed by alcoholic alkali hydroxides forming acetic acid and triphenylaminoguanidine. The pZatinichZoride (C,lH,,N,),,H,PtCI, forms microcrystdine leaflets and melts at 180-1 S lo. 1 4-Dip?~enyZ-5-etl~yZ-3 5-endoani/o-4 5-dihydro-I. 2 4-triuxoZe formed by heating triphenylaminoguanidine with propic nic chloride at 120' and finally at 140" crystallises from dilute alco 101 in long brown rectangular plates melts at 229-230° i s moder ttely soluble in boiling benzene or chloroform and readily so in dilute siilphuric or acetic acids.N=C- BlPh*CMe- / C@?"N4 3-Adino-1 4 5-triplLeizyZ-4 5-dilqdro-l 3 4-triaxoZe C,N,HPh,*NHPh formed from triphenylaminoguanidine and benzaldehyde crystallises from alcohol in colourless needles melts at 165" is readily soluble in chloroform etlizr or benzene yields an odour of benzalclehyde and when oxidised with sodium nitrite i n acetic acid solution yields 1 4 5- triphenyl-3 5-endoanilo-4 5-dihydro-1 2 4-triazole \ X=C- I I k p h ,NPh NPh-bPh- which is forrn ecl also by heating triphenylaminoguanidine with benzoic chloride a t 130' or by boiling the gnanidine with benzoic acid and phosphorus pentachloride.It crystallises from alcohol in glistening dark yellow flat needles melts at 231-2.32° and forms a n additive compound with benzoic chloride C,,H,,ON,Cl which crystallises from ether in colourless needles melts and decomposes with forma- tion of benzoic chloride at about 262" and when dissolved in alcohol yields triphcnyle~ado,znilodihydrotriazole hydrochloride and ethyl benzoate or benzainide when trentc d with nlcoholic ammonia. The nit?*ate C2GH20N4 Hilu'O. cryst:~llihes froiii boiling water in colourless needles aiicl inelts nbovc 270" ; the Iiydrochloride forms dieeves of colourleqs flat needleq and melts at 270'. The nzethiodide C2,H2,N,,MeT crystallises from its ethereal-alcoholic solu- tion in colourless needles melts at 231" and is readily soluble i n alcohol or chloroform.118 ABSTRACTS OF CHEMICAL PAPERS.5-Hydroxy-3-methylanilino-1 4 ; 5-t~iphenyl-4 5-dil~ydro-1 ; 2 4-tri- axole OH*C,NgPh,*NMePh formed by the action of potassium hydroxide on the methiodide in ice-cooled absolute alcoholic solution cry stallises from a mixture of light petroleum and chloroform in yellow hexagonal leaflets melts a t 1 5 8 O is readily soluble in chloroform and when treated with dilute hydrochloric acid yields the methochloride C,7H,,N,CI which crystallises in spherical aggregates of white needles and melts above 265'. Anilinophenyl-p-tolylguanidine NHPh*NH.C(NPh)*NH.C7H7 formed from phenylhydrazine and carbodiphenylimide crystallises in spherical aggregates of needles melts a t 184-1 85O and condenses with formaldehyde t o form 3-anilino-2-~~~enyZ-4-p-tol?/l-4 ; 5-dihydro-1 ; 2 4- triazole C H20N4 which crystallises in colourless needles and melts at 148O.On oxidation with sodium nitrite i t yields a l-phen?/l-$-p- tolyl-3 ; 5-endoanilo-4 ; 5-dihydro-l 2 4-t&xoZe 1 $Ph N*C7H7 NPh*C H-/ mbich crystallises from a mixture of chloroform and light petroleum in dark yellow needles and melts a t 210O. C,,H,,N formed from formaldehyde and p - toluidinodipheoylguanidine crystal- lises from alcohol in glistening leaflets melts a t 123O is easily soluble in benzene 01- chloroform and on oxidation with nitrous acid yields 4- pl~enyl-1-p-tobyl-3 5-endoanilo-4 ; 5-dihydro-l ; 3 ; 4-triaxoZe "==C \ N = C- 3-Anilino-4-pl~e~zl/l-l -p-tolyl-4 5-Jihydro-l 2 d-t~iaxole I -\ I T P h )NPh N (C,H,)* C H - which crystallises in matted; glistening light yellow needles and melts a t 222'.3-Tolzcidino-I-phen?/l-4-p-toly1-4 ; 5-dihydro-l 2 4-tricmole C,,H,,N formed from formaldehyde and anilinoditolylguanidine crystallises in matted long white needles melts at 132O and on oxidation yields 1- phenyl-4-p- tolyl-3 5-endotohido-4 ?-di?tydro-l 2 4-triccxole (-12aH,,N which forms glistening yellow needles melts a t 170° and is readily soluble in chloroform. It has been found that as a test for nitrates nitron is even more delicate than was stated previously (Abstr. 1905 ii 28%). G. Y. Synthetical Bases from 4-Aminoantipyrine.MAX LUFT (Bey. Compare Knorr and Stolz Abstr. lS97 i 1905 38 4044-4049. 1 12).-Dinntip~lryEethyZelzediamine formed when 2 mols. of 4-nminonntipyrino arc heated with 1 mol. of ethylene dibromide i n alcoholic solution on the water-bath and 20 per cent. aqueous sodium hydroxide is added until the mixture is alkaline. It separates from a mixture of chloroform and ether as a colourless flocculent powder melts a t 54O is extremely hygroscopic absorbsORGANIC CHEMISTRY. 119 carbon dioxide from the atmosphere and is precipitated unchanged on addition of alkali hydroxides to its acid solutions. The platinichloride C,,H,80,N,H,,PtCl forms orange needles and decomposes at 20G-208'; the picrate crystallises in yellow needles and melts at 182' ; the mei.curic?Zoridee is insoluble in water and decomposes at 70 -72".Biantipyn$d iet?ylenediamine ( 1 4-diant ipyryZpiperaxine) Ph-C0 CH,*CH CO-YP1-1 NMw CMe ~c"<C€I"*Ca >N*cGCMe.NMe' formed by the act'ion of an excessYof ediylene dibromide on antipyrine or on diantipyrylethylenediamine at l20-13O0 crystallises from alcohol in colourless nacreous rhombic plates or needles me1)us at 2 6 2 O is only sparingly soluble or is inqoluble in all solvents and is very stable towards alkali hydroxides. crystallises in colourless needles and melts at 24s' ; the hydrobromide melts a t 237' ; the pZntinicMoride C~,H300,",,H,PtCI forms yellow needles becomes grey at loo" and decomposes at about 145"; the mercuricldoride melts a t 2 3 1 O . The hydroclJoride C ~ H ~ O @ N ~ ~ H C ~ rPh-CO C H,*CH NMe-C Me " 0 1 -Antippyllpiperidine >'"<(JH .CH >CH formed O O by heatiug 4-aminoantipyrine with a€-dibromopentane at loo" crystal- lises from ether in colourless needles has an odour of piperidine melts a t 144" is soluble in alcohol ether benzene or dilute acids and is stable towards alkali hydroxides.The hydrocldoride is deliquescent ; the hydriodide Cl,H210N3,HI crystallises in glistening yellow needles and decomposes with evolution of a gas at 215"; the picrate forms glistening yellow prisms and melts and decomposes a t 198'; the pkatinichloride C3,H,,0,N,,H,PtC1 forms plates and melts and decomposes at 208-2 10" ; the mercurichZoi*ide crystallises in white rhombic plates and melts and decomposes at 204"; the methiodide is obtained as a brown oil which solidifies t o a yellow mass; it melts a t 206" and decomposes when warmed with water.1 - Antipyrp Ztetrahydro- 1 4-oxaxine (antipyrykn2.orphoZi92e) >OY YPh-CO UH,*CH NNe CMe 9 C €3 r) is obtaiaed by digestion of 4-aminoantipyrine with ethylene oxide or ethylene bromohydrin in aqueous solution in R sealed tube for two days at the laboratory temperature and then for fourteeti hours a t 60° and heating the yellow oily product with 50 per cent. sulphuric acid at 125-135" under pressure. The intermediately formed hy droxy ethyl- and d i h y droxj e th yl-aminoan t ipyrine could not be isoliited. The morpholine derivative crystallises in rosettes of long colourless needles has an aromatic odour melts at 157" and is soluble in alcohol ether benzene or dilute acids. crystallises i n yellow plates and iiielts a t l i 2 O ; the while crystalline wercurich,Zoride me1 t s and decorriposes at 201' ; thc msthiodide C,,H,90,N,,MeI crystallises in colourless needles melts at 134" and decouiposes when warmed with water.'The picrate C1,T3190,N3 c(j'3307N3 G. Y.120 ABSTRACTS OF CHEMICAL PAPERS. Action of Sulphur Dioxide on nt-Toluenediazonium Chloride and Benzenediazonium Sulphate. JULIUS TROGER W. H ILLE and P. VASTERLING (J. pr. Chem. 1905 [ii] 72 511-535. Compare Abstr. 1904 i llS).-The red sulphonic acid formed by the action of sulphur dioxide on diazotised m-toluidine is considered now to have the constitution C,H,*N,*C,H,*NH*NH.SO,H. It yields sulphuric acid when hydrolysed with aqueous hydrochloric acid and potassium sulphite with dilute potassium hydroxide whilst reduction with stannous chloride and hydrochloric acid leads to the formation of sulphuric acid ammonia m-toluidine and a tolylenediamine.The potassium salt is oxidi$ed by mercuric oxide in aqueous solution with formation of the potassium salt C7H,*N,*C,H,*N,*S0,K which does not give a red coloration on acidification and is reduced to the original sulphonate by ammonium sulphide. The colourless sulphonic acid Cl4HI4O3N4S forms stable silver barium and calcium salts whereas the red sulphonic acid reduces warm ammoniacxl silver solutions . The action of nitrous acid on the red sulphonic acid leads to the formation of a derivative C,H,*N,*C,H,-N (P) which forms short dark red prisms or small orange-red crystals and melts at 65'.The sulphonic acid condenses with salicylaldeh yde in presence of sulphuric acid to form the sulphate OH*C6H4*CH(C7H,*N2 C7H,-NH*NH,),,H2S0 which is obtained in microscopic needles having a green sheen and dissolves in water to form a violet-blue solution. The hydroc?doride C,,H,,ON,,HCl and the nitrute C3,H,,0N,,HN0 formed by con- densation of the sulphonic acid with salicylaldehyde in presence of hydrochloric and nitric acids respectively have similar properties. The action of ammonia on the salts of the condensation product leads to the formation of an orange-red crystalline substance ~H'NH*C6H4>CH*C7H,."N.NH,. which melts a t 130" and forms dark-coloured crystalline salts with strong acids. The red sulphonic acid forms similar condensation products with other fatty and aromatic aJdehydes and with ketones.When a current of sulphur dioxide is passed through a cooled aqueous solution of benzenediazonium sulphate for one day the sulphonic cccid N,Ph*C,H,.NH*NH*SC),H is formed as a voluminous red mass (compare Koeaigs Abstr. 1878 219). It crystallises in micro- scopic dark red needles decomposes when dried a t looo and when re- duced with stannous chloride and hydrochloric acid yields sulphuric acid ammonia aniline and p-phen ylenediamine. When treated with sulphuric acid and sodium nitrite in alcoholic solution i t forms the substance N,Ph*C H *N3 which crystallises in small bronze leaflets and melts a t 9029ib. The potassium salt C,2H,,0.3N,SK forms reddish- yellow crystals dissolves in water forming a yellow solution which becomes red on addition of mineral acids tmt not of carbon dioxide or hydrogen sulphide and when oxidisetl with mercuric oxide yields the potassium salt N,Ph*C,H,*N,*SO,K from which it is again formed by reduction with ammonium sulphide.The colourless sulphonic acid C,,H1,O,N,S forms stable barium calcium and silver salts. 7H(j*N,* C7H6 G. Y.ORGANIC CHEMISTRY. 121 Azo-dye from 3 4-Dichloroaniline. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 1607SS).-The diazonium compound of 3 4- dichloroaniline combines with sodium P-naphthol-3 6-disulphonate to yield a red azo-dye which forms sparingly soluble metallic lakes remarkably stable towards light. The lakes of the corresponding azo- compounds from 3 4- and 2 5-dichloroanilines are so unstable towards light as to be practically useless.C. H. D. Yellow Disazo-dyes. FARBENFABRIKEN VORM. FRIEDR. BAYER C!G Co. (D.R.-P. 160674 and 160675).-Tbe tetra-azotised solutionsof benziciine- 2 2’-disulphonic and 3 3’-tolidine-2 2’-disulphonic acids combine with 2 mols. of l-phenyl-3-methyl-5-pyrazolone to form yellow disuzo- compounds which dye wool. Similar dyes are obtained when the same tetrazo-compounds are combined with 2 mols. of methylindole or with 1 mol. of methylindole and 1 mol. of l-phenyl-3-methyl-5- pyrazolone. C. H. D. o-Hydroxyazo-dyes. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 160536. Compare hbstr. 1905 i 250).-The formation of diazosulphonates in the treatment of diazotised a- and P-naphthyl- arninedi- or poly-sulphonic acids with alkali acetates or carbonates is avoided by adding chlorine or alkali hypochlorites as well as the salt used to fix the acid thus destroying any sulphites formed.Thus a diazotised solution of P-naphthylamine-1 5-disulphonate is neutralised with sodium carbonate and an alkaline solution of sodium hypochlorite added. The temperature may rise to 35’. Combination with P-naphthol then takes place in the usual manner. C. H. D. Hydrolysis of Egg-albumin. A. ADENSAMEH. and PH. HOERNES (Monutsh. 1905 26 1217-1230. Compare Skraup Abstr. 1904 i 954).-Using Skraup’s method the authors have isolated from the products of the hydrolysis of egg-albumin d-alanine leucine amino- valeric acid and a mixture of substances which crystallises in micro- scopic plates or needles melts in a sealed capillary tube at 280° has [ alD + 30.1 96O and contains probably aminovaleric acid and isoleucine ; it forms a copper salt which is readily soluble in methyl alcohol.The copper salts obtained from the filtrate from the phosphotung- states were fractionally crys tallised and made alkaline. The liberated ammonia was removed by distillation in a vacuum and the residue shaken with naphthalene-P-sulphonic chloride when the only product obtained was naphthalene-6-sulphonainide. No glycine pyrrolicline-2-carboxylic caseanic or caseic acids could be detected amongst the products of hydrolysis and if present they must be so only in extremely small quantities. G . Y. Colloidal Solutions. The Globulins. WILLIAM I;. HARDY (J. Physiol. 1905 33 25 1-337.Compare Abstr. 1903 ii 469).-This paper deals with the behaviour of globulins to acids alkalis and salts and the properties of the solutions considered as cases of colloidal solution. Globulins are amphoteric electrolytes ; the globulin salts iouise in solution therefore in an electric field the entire mass of proteicl VOL. XC. i. k122 ABSTRACTS OF CHEMICAL PAPERS. moves. A method for the direct measurement of the specific velocity of globulin ions is described. Among the many other points raised for which the original paper must be consulted the complete absence of “ionic ” globulin from blood serum is noted. It is probable that the globulin is formed in serum by the decomposition of a more com- plex proteid. W. D. H. Globulins. J. MELLANBY (J. Plzysiol. 1905 33 335-373).- Solution of globulin by a neutral salt is due to forces exerted by its free ions.Ions with equal valencies whether positive or negative are equally efficient and the efficiencies of ions of different valencies are directly proportional to the squares of their valencies. The amount of globulin dissolved by a given percentage of neutral salt is directly proportional to the strength of the original globulin suspension. The precipitation of globulin by neutral salts depends on a molecular combination between the salt and globulin the compound so formed being stable only in excess of the combining salt. Precipitation by salts of the heavy metals depends on the formation of a stable com- pound. Solution of globulin by acids or alkalis is of the nature of chemical combination.The relative solvent efficiencies of acids or alkalis are of the same order as their chemical avidities. W. D. H. The Group of Organic Acids containing Nitrogen and Sulphur which is present in Normal Human Urine. STANIS- LAUS BONDZY~SKI ST. DOMBROWSKI and KAZIMIERZ PANEK (Zeit. physiol. Chein. 1905 46 83-124. Compare Abstr. 1898 i 501; 1902 i 847).-nZZo0xyproteic acid is precipitated by the addition of lead acetate and the excess of lead removed by means of sodium carbonate. The addition of mercuric acetate and acetic acid precipitates a new acid antioxypoteic acid in the form of its mercuric salt and when the filtrate from this is neutmlised with sodium carbonate a precipitate of‘ the mercury salt of oxyproteic acid is obtained.The 6cwiurn and silver salts of the new acid have been analysed and the values calculs~ted therefrom for the acid are C 43.21 H 4.91 N 24.4 S 0.61 and 0 26-33 per cent. It gives a precipitate with phosphotungstic acid which is soluble in an excess or in water and from this precipitate the barium salt may be obtained without precipitation with mercuric wetate. The sodium and potassium salts dissolve readily in water and yield emulsions with alcohol. The alkali-earth salts also dissolve readily in water but are precipitated as white powders on the addition of alcohol. It gives neither the biuret nor the Millon reaction but gives both Ehrlich’s and Prieclenwald’s diazo-reactions. To obtain a good yield of oxyproteic acid it is advisable to remove the acetic acid and acetates before precipitating antioxy- and oxy-proteic acids with mercuric acetate ; if however the pure antioxyproteic acid is required the removal of the acetates is not recommended as when these are absent a considerable quantity of the oxyproteic acid is pre- cipitated with the antioxy-acid.Oxyproteic acid has the composition C 39.62 H 5-66 N 18.08 S 1.12 and 0 35.54 per cent. The acid is dextrorotatory.ORGANIC CHEMISTRY. 123 The acid previously described as dlooxyproteic acid was not pure as acids free from sulphur and nitrogen are removed when the colourless mercuric salt is decomposed with hydrogen sulphide and extracted with ether. The composition of the pure allo-acid is C 41.33 H 5.70 N 13.55 S 2.19 and 0 37.23 per cent. The salts are less soluble in alcohol than those of the other oxyproteic acids.These salts are often coloured by a substance which is comparatively rich in sulphur and appears to be identical with urochrome. Thiele’s uroferric acid (Abstr. 1904 i 452) closely resembles but does not appear to bc identical with cdlooxyproteic acid J. J. S. Action of Lactic Acid on Casein and Paracasein. 0. LAXA (kIiZchw. Zentr 1905 1 538-547).-Casein combines with lactic acid t o form a number of lactates. The latter are soluble in water except those which contain less than 1 per cent. of lactic acid. By dialysis a lactate containing from 1.4 to 1.9 per cent. of lactic acid is produced whilst by ‘‘ salting out ” a solution of casein in lactic acid :t lactate with 7.5 per cent. of acid is obtained. To term the insoluble litctates ‘‘ mono-lactates ” and the solable lactates “ cli-lactates ” is therefore inconclusive.The casein lxctates contain a proportionately small percentage of phosphorus from 0.45 to 0.48 per cent. The lactic acid produced by bacteria in the milk converts the phosphates present into acid phosphates and a t the same time combines with the casein forming soluble and insoluble lactates. The soluble lactates however are precipitated subsequently by the mineral salts present and the whole milk curdles. Impregnation of casein with calcium lactate renders the former exceedingly plastic. Paracasein is very probably a coinpound of casein with calcium phosphates. Acids con vert i t into casein and it yields the same lactates as casein. w. P. s. Amount of Glycine and Alanine from Casein.ZDENICO H. SKRAUP (Monatsh. 1905 26 1343-1349. Conipare Abst,r. 1905 i 619).-Details are given of the method by which d-slanine and glycine have been obtained from casein. I t is considered that the composition of casein varies and that the appearance of glycine amongst the products of the hydrolysis of commercial casein purified by Hammarsten’s method is not due to the presence of an impurity. G. Y. Kyrines. ZDENHO H. SKRAUP and RUDOLF ZWERGER (Xonatsl~. 1905 26 1403-1414. Compare Skraup Abstr. 1905 i 398; Siegfried Abstr. 1903 i 586 ; 1905 i 104).-When casein is heated on the water-bath for one hour with an equal weigbt of concentrated hydrochloric acid the mixture dissolves completely in an equal volume of water and if the resulting solution is further heated its lm-0- rotatory power changes to clextro-rotatory becoming constant in about forty-eight hours; a t the same time the behaviour of the solution t o phosphotungstic acid changes the precipitates formed a t first are resinous but those obtained after about forty-two hours’ heating on the water-bath consist of short prisms and contain nitrogen124 ABSTRACTS OF CHEMICAL PAPERS.and carbon in the atomic proportion 1 2.6 which was found by Siegfried for his caseinokyrine. The basic syrup obtained on treatment of the crystalline phosphotungstate with bnryta forms a double salt with cadmium iodide containing nitrogen and carbon in the atomic proportion 1 2.6 a double salt with potassium iodide containing nitrogen and carbon in the atomic proportion 1 2-4 and a derivative with naphthalene-P-sulphonic chloride in which the proportion is 1 2.2.The basic syrup (30 grams) yields 21 grams of lysine picrate 0.5 gram of arginine nitrate and 1.5 grams of crude histidine from which 0.2 gram of the crystalline hydrochloride is obtained. G. Y. Gelatin. 11. ZDENKO H. SKRAUP and F. HECKEL (ikfonutsh. 1905 26 1351-135s. Compare Abstr. 1905 i 398 619).-Gelatin was hydrolysed by heating with hydrcchloric acid and the product evaporated in a vacuum and esterified by treatment with absolute alcohol and hydrogen chloride. After removal of ethyl aminoacetate hydrochloride the filtrate was extracted with ether and the residual solution precipitated with phosphotungstic acid in three fractions. The final filtrate after removal of the phosphotungstic acid yielded a small amount of glutamic acid.The second phospho tungstate precipitate yielded lysine and arginine. The third precipitate mas crystallised from water when three fractions were obtained ; the least soluble part yielded an uncrystallisable syrup ; the moderately soluble fraction yielded a mixture of d-alanine and glycine whilst the most soluble part yielded almost pure glycine. d-Alanine and glycine are separated by repeated fractional crystal- lisation alternately of the copper salts and of the acids. G. Y. Jecorin. J. MEINERTZ (Zed physioE. Chern. 1905,46,376-382),- Manasse states that Drechsel’s jecorin yields on decomposition the same products as lecithin with dextrose in addition. Ring regards it as a mixture of various compounds of lecithin of which lecithin-dextrose is an abundant one.I n the present research jecorin was prepared from liver by Drechsel’s method treated with dilute hydrochloric acid and dialysed ; the dialysable substances are the reducing substance a nitrogenous material and inorganic matter containing calcium and phosphoric acid ; the residue was without reducing action and showed all the properties of lecithin. W. D. H. The Chromogen of the so-called Scatole-red contained in Normal Human Urine. J. PII. STAAL (Zeit. physiol. Chern. 1905 46 236-263).-Normal human urine when mixed with hydrochloric acid and a few drops of potassium nitrite solution yields in addition t o indigo-red a dye which is insoluble in chloroform and diEers spectro- scopically from indigo-red.A close examination of this dye proves i t to be identical with Pl’encki and Sieber’s urorosein (Abstr. 1883 101). The chromogen which gives rise to this dye may be extracted by Stokvis’ method (Ned. lrijdsch. Gem 1901 i 961). The ethyl acetate extract may be freed from indican by shaking with water and when mixed with magnesium carbonate yields a rnugnesiurn derivative which may be isolated by removing the ethyl acetate and extracting theORGANIC CHEMISTRY. 125 residue with 90 per cent. alcohol. It is a brownish-yellow amorphous powder soluble in wa,ter alcohol acids or alkalis but insoluble in ether chloroform or acetone. With hydrochloric acid and a few drops of potassium nitrite solution it yields the stable red dye which may be extracted with nmyl alcohol.The composition of the magnesium compound is Mg 10.26 C 46.59 €1 4.98 and N 3.35 per cent. It is not a “coupled” sulphnric or glycuronic acid and is not a scatole derivative as this base is not formed when the compound is reduced distilled o r fermented by bacteria. When heated with sulphuric acid,!it yields acetic and hippuric acids. J. J. S. Preparation and Analysis of Nucleic Acids. XI. Nucleic Acid from the Mammary Glands of the Cow. *JOHN A. MANDEL and PHOEBUS A. LEVENE (Zeit. plqsiol. Chem. 1905 46 155-158. Compare Abstr. 1900 i 572 ; 1‘301 i 299 623 ; 1902 i 668 779 ; 1904 i 126 ; 1905 i 105 847).--The copper salt of the nncleic acid gave the following analytical data C = 31.34 H = 4.07 N = 14-65 P=S-48 Cu=7*00 per cent.When hydrolysed with 2 per cent. sulphuric acid 100 grams yield guanine 1.05 and adenine picrate 4.56 grams. With 25 per cent. sulphuric acid thymine 5 grams and cytosine picrate 10 grams are obtained. When distilled with hydrochloric acid the acid yields furf uraldehyde and with concentrated sulphuric acid I~evulic acid. J. J. S. Nucleic Acids of the Thymus. 111. HERMANN STEUDEL (Zeit. physiol. Chein. 1905 46 332-336. Compare Abstr. 1904 i S37).- When hydrolysed with acids nucleic acid yields both purine and pyrimidine bases among other substances. The relationship between these is doubtful. If a reducing agent is added to the acid ased in hydrolysis much of the purine bases is destroyed but there is no cor- responding increase in the pyrimidine bases If the hydrolysis is carried out with sulphuric acid so energetically as to destroy all the purine bases the same negative result regarding pjrimidine bases is obtained.Cytosine and thymine are present but in smaller amount than in experiiiients where the hydrolysis was not carried so far. W. D. H. Catalysis and Enzyme Action. C. HUGH NEILSON (Anzer. J. Pl~ysiol. 1906 15 148--158).-Further evidence is adduced which shows the similarity between the action of enzymes and that of nietallic catalysts. Platiniim black and manganese dioxide act in the same way on salicin and amygdalin as emulsin does. W. D. H. Physico-chemical Nature and Activity of Enzymes. LUIGI MARINO and G. SEBICANO (Guxxettcc 1905 35 ii 407-417).-The authors have prepared carefully purified specimens of emulsin and msltase which were white a,nd dissolved in water giving solutions having a faint reddish-yellow or brownish-red colour according to the concentration.If a drop of a very concentrated solution of ernulsin126 ABSTRACTS OF CHEMICAL PAPERS. is added to a very large quantity of water the latter becomes milky but as more emulsin is added the amount remaining in solution gradually increases. The authors compare this phenomenon with that observed with readily hydrolysable inorganic salts. The deposited emulsin has the same composition as that in solution and exhibits similar behaviour. A t temperatures above about 30° the emulsin solutions remain clear however great the quantity of added water may be. Maltase exhibits similar comportment but the temperature above which its solutions remain clear on dilution with water is lower than with emulsin.Rmulsin has the following percentage composition carbon 43.68 ; hydrogen 7.62 ; and nitrogen 13.64 that of mnltase being carbon 43.48 ; hydrogen 6.87 ; and nitrogen 6.80. On exposing an 18-20 per cent. emulsin solution to the action of sunlight in absence of oxygen it was found that the activity of the enzyme decreased and increased in a periodic manner. The following are the relative amounts of salicin decomposed by a constant quantity of the emulsin solution after exposure to sunlight for different periods at first 93.6 ; after six days 70.2; after eleven days 15.1 ; after sixteen days 28.0 ; after twenty-one days 35-0 ; after twenty-six days 38.5 ; and after sixty days less than 10.6.After such exposure to sunlight the emulsin has the same chemical composition and the same physical properties as the original enzyme. Emulsin solutions exposed to only the heat rays or only the light rays of the sunlight underwent no change. The weak sunlight of the end of October exerts no influence on the activity of emulsin solutions. Maltase exhibits the same behaviour as emulsin when its solutions are acted on by sunlight. Solutions of emulsin and maltase of equal concentration have the same refractive index specific rotatory power and specific conductivity. Studies on Enzyme Action. Lipase. HENRY E. ARMSTRONG (Proc. Koy. Xoc. 1905 B 76 606-60S).-In the experiments on castor oil ground castor oil seed was employed; in the experiments on other esters the oil was first removed by means of ether.The observations of Connstein and his co- workers that ricinus lipase is effective only in presence of acid and that it acts preferentially on the natural fats are confirmed. Ethyl mandelate is not much affected by ricinus lipase whereas it is readily attacked by animal lipase (compare Dakin Abstr. 1904 i 10'71). Attempts to prepare an extract containing an enzyme were un- successful. U7hen the material free from fat is digested with the amount of sulphuric acid in presence of which hydrolysis of fatty oil is rapidly effected the enzyme is destroyed. Nuclease. FRITZ SACHS (Zed. plqsiol. C'hem. 1905 46 337-353). -The experiments recorded support the theory that ferments exist which are capable of cleaving nuclein with the liberation of nuclein bases.Such ferments are found in the extracts of many tissues but especial attention is directed in the present research to the iiuclease of the pancreatic juice; this is not identical with trypsin but is destroyed by tryptic action. T. H. P. G. S . W. U. H.ORGANIC CHEMISTRY. 127 Papain-digestion. FRIEDRICH KUTSCHER and LOHMANN (Zeit. physiol. Chew,. 1905 46 383-386).-Contrary to Mendel's statement (Abstr. 1901 i 355) it is found that abundant quantities of crystal- line cleavage products are obtained by the action of papain on proteids. They resemble those obtained by the use of trypsin. Tetra- and penta-methylenediamines which are characteristic of the prolonged action of pepsin could not be prepared. W. D. H. Action of Rennin.I. H. REICHEL and KARL SPIRO (Beitr. chem. Physiol. Path. 1905 '7 485-507).-The experiments relate mainly to reaction velocity and show that within quite wide limits the amount of enzyme and the time of curdling are inversely proportional. The influence of calcium salts follows an equally simple law. The effect of other snbstances was also studied. W. D. H. Ferment Action and Ferment Loss. 11. H. REICHEL and KARL SPIRO (Beitr. chem. Physiol. Path. 1905 7 479-484. Compare Abstr. 1904 i 1071).-In milk the loss of the enzyme rennin is related to the amount of calcium salts present. I n specimens con- taining such salts the loss increases and in those in which the calcium percentage is kept constant the amount lost rises with higher con- centrations of rennin and is relatively greater than in those poor in calcium salts.Magnesium chloride acts in a similar way but not so markedly. Potassium thiocyanate increases the loss slightly ; glycerol and urea increase i t greatly but possibly in some cases an injurious effect on the ferment has here to be dealt with and not merely a division of the amount of ferment between curd and whey. W. D. H. Studies on Enzyme Action. VII. The Synthetic Action of Acids contrasted with that of Enzymes. Synthesis of Maltose and isoMaltose. E. FRANKLAND ARMSTRONG (Proc. Roy. Soc. 1905 B 76 592-599. Compare Trans. 1903,83 1305 ; Abstr. 1904 i 956-958 1070 ; 1905 i 746).-When dextrose is condensed by means of hydrochloric acid (compare Fischer Abstr. 1891 412; 1896 119) both maltose aud its isomeride isomaltose are produced. To detecb isomaltose the acid was removed by means of lead carbonate and the filtered solution fermented with Xucclmrontpes intermedians to get rid of unaltered dextrose; from the resulting solution an osazone was obtained which behaved in all respects like the osazone of isomaltose obtained by E. Fischer. I n testing for maltose the dextrose was removed from another portion of the solution by fermenting with S. Mu~*x&anu which contains no maltase and the maltose confirmed by observing the rotatory power of the solution by preparation of the osazone and by its behaviour towards maltase. I n the former case isomaltose was produced but the solution was not tested for maltose; with emulsin maltose was formed but probably not isomaltose. The theory of condensation by acids and enzymes is discussed. Dextrose was also condensed by means of maltase and emulsin. The investigation of these points is being continued.128 ABSTRACTS OF CHEMICAL PAPERS. With acids both isomerides are t o be expected since the condensation is '' uncontrolled," but with enzymes owing to their selective action the process is probably controlled. Experiment shows as in the above examples that a n enzyme favours the production of a sugar isomeric with that which it can hydrolyse; the question as to how the control of the enzyme is exerted so as to produce this result is considered. G. S. Studies on Enzyme Action. VIII. The Mechanism of Fermentation. E. FRANKLAND ARMSTHONG (Proc. Roy. Soc. 1905 B 76 600-605. Compare preceding abstract).-The action of twenty typical pure yeasts prepared by Hansen's methods on dextrose mannose lwulose and galactose has been investigated. Whereas the three first-mentioned sugars were fermented apparently with equal readiness by all the yeasts about half of the latter had no action on galactose a result which is in accordance with previous observations. This inability to ferment galactose has nothing to do with the absence of hydrolysing enzymes since i t was observed with yeasts contain- ing invertase maltase and lactase respectively. Further dextrose mannose and lzevulose were readily fermented by yeasts which do not contain any enzyme capable of inducing the hydrolysis of bioses. Prom these results it is clear that the processes of enzymo-hydrolysis and of fermentation differ in some essential respects although for reasons given in a previous paper (Abstr. 1904 i 957) i t is probable that they are cognate phenomena. It is pointed out that the three hexoses which behave alike have a common enolic form and the change to this is probably the initial stage in fermentation. The mechanism of the fermentation of galactose seems to be different from that of the other three sugars. G. S. Diphenylsilicone and Benzylsilicon Compounds. WALTHER DILTHEY [and FRITZ EDUARDOFF] (Bey. 1905 38 4132-4136. Com- pare Abstr. 1904 i 132 464).-The gelatinous diphenylsilicone (diphenyl silicoketoue) becomes crystalline when rubbed with a few drops of acetic anhydride. It separates from chloroform and light petroleum in clear flat prisms melting a t 188' and readily soluble in ether benzene or chloroform. Both the gelatinous and the crystalline compounds are trimolecular probably O<siph5.0 Si Dibenx?/ZsiZicoZ Si(CH,Ph),(OH) crystal1i;es from a mixture of benzene and light petroleum melts at 76O and dissolves readily in ether benzene or chloroform. The yield is small. FribenzyZsiZicoZ Si(CH,Ph),*OH is obtained when a larger quantity of magnesium benzyl chloride is used ; it crystallises from alcohol in long colourless needles and melts a t 106". SiPh - 0 ~ Ph,. J. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9069000057

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

61 General and Physical Chemistry. Supposed Relationship between Molecular Size and Rota- tory Power in Solutions. THOMAS S. PATTERSON (Bey. 1905 38 4090-4101. Compare Walden Abstr. 1905 ii 130).-Walden states that there is a relationship between the molecular weight of a compound in solution and its rotatory power. The figures quoted for ethyl tartrate are invalidated by differences in the temperature at which experiments were made in different solvents and doubt is also cast on the validity of the molecular weight determinations on account of excessive concentration of the solutions. The most striking adverse evidence is found in the case of solutions of ethyl tartrate in benzene where in spite of a very great change of molecular weight the rotatory power is the same at 5 and at 25 per cent.concentrations ; in aqueous solutions on the other hand the molecular weight remains consbant but the rotatory power varies widely. Several other examples are quoted which go to show that the relationship postulated by Walden does not exist. T. M. L. Solubility and Specific Rotatory Power of Carbohydrates and certain Organic Acids and Bases in Pyridine and other Solvents. JOSEPH GE~CARD HOLTY (J. Pl~ysicul Chem. 1905 9 764-779).-The author’s experiments were performed chiefly with pyridine solutions for which the following solubilities are given laevulose 18.49 ; malic acid 14.6 ; dextrose 7.62 ; sucrose 6-45 ; galactose 5.45 ; erythritol 2.50 ; lactose 2-18 ; strychnine 1.23 ; mannitol 0.47. Propyl tartrate was found to be miscible with pyridine. The specific rotation of lacbose was less in pyridine than in aqueous solution and decreased with dilution.For dextrose and galactose the rotation was greater than for the equally concentrated aqueous solution. For lzevulose the laevorotntion was much less than that of the aqueous solution the values for a 7% per cent. solution being pyridine - 36.8 ; water - 87.3. The laevorotations of mannitol and malic acid are considerably greater than those of the aqueous solution values for a 7.6 per cent. solution being respectively -26.9 and -2.07 in the case of malic acid. Strychnine gave a lzvorotatory solution of higher specific rotation than the corresponding solution in chloroform. For a 6.45 per cent. solution of sucrose the specific rotation was 82.97 and the value increases slightly with dilution.From his inability to verify it experimentally the author considers that the theory of a greater solubility for small than for large particles is not true in the case of pyridine solutions of sucrose. L. M. J. Action of Alkaline Uranyl Salts on the Rotatory Power of Sugars and other Optically-active Hydroxyl Compounds. HERMANN GROSSMANN (Zeit. Fer. deut. 2ucker.-lnd. 1905 1058-1073). -Lzvulose and mannitol react readily with alkaline uranyl solutions VOL. XC ii 562 ABSTRACTS OF CHEMICAL PAPERS. forming intensely golden-yellow alkaline liquids the rotations of which differ considerably from the true rotations of the optically-active compounds. Complex compounds in which the alcoholic hydrogen atoms are replaced by the uranyl-residue are here formed.The addition of 1 mol. of uranyl salt t o 1 mol. of laevulose or mannitol changes the direction of the rotation. Dextrose galactose lactose and rhamnose also exhibit similar changes in rotation but the direction of the latter is not reversed. Sucrose is slowly transformed into l ~ v o - rotatory alkali-uranyl compounds but no change of the sugar molecule appears to take place here. The optical activity of mannitol is accentuated by a number of compounds for instance boric molybdic and uranic acids. The increase in the rotation of tartaric acid by uranyl nitrate and sodium hydroxide observed by Walden (Bey. 1897 30 28S9) is not a reaction occurring in alkaline solution but requires the presence of hydrogen ions so that the hydrogen atoms of the hydroxyl groups are probably not replaced by uranyl-residues.Saccharic acid exhibits on the whole similar behaviour its direction of rotation being reversed. T. H. P. Spectrum Analysis of the Light emitted by Crystals of Radium Bromide. F. HIMSTEDT and G. MEYER (Chenz. Centr. 1905 ii 1661 ; from P/~ysikaZ. Zeit. 6 688-689. Compare Sir William and Lady Huggins Abstr. 1904 ii 4).-In order to examine the spectra of the light emitted by radium bromide three crystals were arranged in front of the collimator tube of a quartz spectrograph in such a way that they did not touch each other. The whole apparatus was enclosed in an opaque air-tight case which was filled with dry air hydrogen or carbon dioxide. After an exposure of seven to ten days the photograph showed three continuous spectra extending from 460pp to 337pp.The blackest portion reached to 380pp and when the case was filled with air the nitrogen bands in this region were only faintly visible. Beyond 380pp however the nitrogen bands could be identified with certainty and were distinctly apparent in the spaces which separated the spectra. The nitrogen line 3 15*9pp extended with equal intensity from the bottom to the top of the plate. The nitrogen in the atmosphere near the crystals must therefore have been rendered luminous. The presence of traces of moisture was found to decrease the intensity of the light considerably. When an atmosphere of dry hydrogen or carbon dioxide was used the three continuous spectra extended to 310pp and did not show any traces of bands or lines in the intervening spaces.The strongest fluorescence was observed in an atmosphere of carbon dioxide. The wave-lengths of the nitrogen light are the same in the case of radium bromide and of radiotellurium. E. W. W. Some Phosphorescence Spectra indioating the Existence of New Elements. Sir WILLIAM CROOKES (Chem. News 1905 92 273-274).-8ub-fractionation has yielded earths in which certain groups of unassigned lines and bands of the phosphorescent spectra grow fainter or stronger independently of both other unassignedGENERAL AND PHYSICAL CHEMISTRY. 63 groups and of groups of lines assigned to known elements. provisionally regarded as indicating new elements. Radium in Sweden. JOHN LANDIN (Arkiv Kern Min. Geol. 1905 2 i No. 2 1-7).-The author has demonstrated the presence of radium in culm by preparing from it barium sulphate and testing the action of the latter on a photographic plate.The alum schists of Billinge answer t o the same test and like culm also contain uranium. The quantity of radium in these minerals is howevey too small to be of industrial importance. Hjelmite crystals slowly KNUT ANGSTROM (Chem. Cewty. 1905 ii 1575 ; from Yhysikal. &it. 6 685-688).-Since the quantity of heat emitted by radium does not decrease to an appreciable extent in a year and is not dependent on the nature of the surrounding medium the energy lost in the form of a- p- and y-rays can only be a very small proportion of the total energy (compare Yaschen Abstr. 1904 ii 798). Measurements have been made by an electrical compensation method in which an equal quantity of heat was generated electrically and balanced against a sensitive thermo-element.86.5 mg. of radium bromide were used. Lead copper and aluminium calorimeters were used the results differing by not more than 2 per cent. When about 1/7 of the y-rays which passed through the aluminium calorimeter were absorbed by a cylinder of lead the quantity of heat imparted to the cylinder was not equal to 1 per cent. of the quantity liberated in the calorimeter; the energy of the p- and y-rays citnnot therefore be equal to more than a few parts per 100 of the total energy emitted by the radium. The mean value of the quantity of heat given out by 1 gram of radium bromide per minute from September These are D.A. L. blacken a photographic plate. T. H. P. Emission of Heat by Radium. 1903 to January 1905 was 1.136 cals. E. w. w. Relative Absorption of the Rays of Radium and Polonium. E. RIECKE [with RETSCHINSKY and WIGGER] (Chena. Centr. 1905 ii 1574-1575 ; from Physikal. Zeit. 6 685-685),-The results of determinations of the coeilicients of absorption of the rays of radium and polonium should give a clue to the nature of the radiation. If for instance the radiation is effected by means of corpuscles then the absorption-coefficient cannot be constant since the absorption depends on the collision of the particles with the molecules of the absorbing substance whilst on the other hand constant values should be obtained if the energy is transmitted by waves. Although however the absorption-coefficient of the a-rays of radium in air has been found t o be constant the deflection of the rays in a magnetic or electric field appears to indicate a corpuscular structure.Experiments on the a-rays of polonium in which Marckwald's arrangement of a copper rod covered with radiotellurium was employed have shown that the absorption- coefficient is not constant. The velocity of the rays is decreased by collision of the particles with the molecules of the air whilst the abgorption is increased. The results of experiments on the absorption of the y-rays emitted by radium bromide in lead have proved that the 5-264 ABSTRACTS OF CHEMICAL PAPERS. rays are not homogeneous ; their nature is not affected by the absorp- tion. When a lead plate of sufficient thickness is used only those rays which have the lowest absorption-coefficient (0.25) remain.The theory of the identity of the y-rays with the Rontgen rays is supported by the fact that the absorption-coefficient of the ‘‘ residual ” rays in mercury lead copper iron zinc aluminium and sulphur is propor- tional to the sp. gr. of the substance (k/d = 0.0021). E. W. W. Radioactivity of Products of Etna. GIOVANNITROVATO CASTORINA (Nuovo Cim. 1905 [v] 10 198-202).-ln general the products of Etna are radioactive the following series being in order of increasing activity rock sand sandy tufa clay and clayey soil mud soil and pozzolane or soil coloured by the lava The activity of the soil is influenced by heating by chemical reactions or by absorption of wator.T. H. P. A. E. Nordenskiold’s Investigations on the Radioactivity of certain Swsdish and Norwegian Minerals. HJALMAR SJOGREN (Arkiv K e r n . illin. Geol. 1905,2 i No. 4 1-5).-The author gives an account of A. E. Nordenskiold’s researches on the radioactivity of Swedish and Norwegian minerals which in order OF their activity are as follows cleveite from Raade ; uraninite from Johanngeorgen- stadt ; oraugite and yellow thorite from Svinor ; nohlite from Noh1 ; fergusonite from Sandoen and orangite from Brevig ; euxenite from Morefjiir ; Eschynite from Hitter0 ; xenotime from Sandoen ; monazite from Raade and fergusonite from Ytterby ; malacon from Kammerfors. Columbite from Moss ixiolite from Skogbole and hjelrnite from Nya Kgrarfvet showed no action on a sensitive plate even after ninety-six hours’ exposure.The paper is accompanied by photographs illustrating the actions of the different minerals. T. H. P. Abnormal Anodic Polarisation produced by Fluorine Chlorine and Bromine Ions. ERICH MULLER and ALFRED SCHELLER (Zeit. anorg. Chem. 1905 48 112-128. Compare Abstr. 1904 ii 250 811 812. Skirrow Abstr. 1903 ii 69).-It has already been shown by Miiller and others that the addition of indifferent ions often causes increased polarisation at the anode (Zoc. c i t . ) ; in the present paper the effect of fluorine chlorine and bromine ions on the anode potential during the electrolysis of sulphuric acid is described. Experiments were made with a series of mixtures of normal sulphuric acid and normal solutions of the halogen acids with different current densities and a t various temperatures and the results are represented by curves the potentials being plotted as ordinates against the com- position of the mixtures as abscissae.With hydrochloric acid at the ordinary temperature the curves show maxima at about 2.5 per cent. of the acid; the greater the cur- rent density the greater is the rise in potential and the more distinct the maximum. With very small current densities the only effect of chlorine ions is to lower the potential. Increasing the temperatureGENERAT AND PHYSICAL CHEMISTRT. 65 has the same effect as lessening the current density ; thus the chlorine ion has a powerful polarising action a t 0" which quite disappears at 70". The bromine ion has a similar but less powerfnl action ; only mix- tures containing less than 10 per cent.of the acid show increased potential whereas stronger solutions lower i t very considerably. Hydrofluoric acid increases the anode potential in all concentrations ; in this case as well the effect decreases with rise of temperature. It is pointed out that the above results are very similar to those obtained in investigating the decomposition potentials of the halogen acids (compare Luther and Brislee Abstr. 1903 ii 708). The author suggests that the phenomena observed are due to the formation of the lower halogen oxyacids and shows that this theory accounts for the results obtained with chlorinc and bromine ions. G. S. Mechanism of the Production and the Nature of Cathodic Pulverisations. CH. MAURAIN (Compt.rend. 1905,141 1223-1225). -When a plate of glass or mica is placed opposite or inclined to the cathode inside a tube containing a rarefied gas the film of cathodic material which is deposited on it is most abundant at the edges that is at those parts of the plate farthest removed from the cathode. When the VrZcuiim tube is placed between the poles of an electro-magnet in such a position that the cathode is normal to the magnetic field the cathodic film deposited on the malls on the tube is most abundant in the trace of the luminescent plane and in a plane at right angles to it. Prom the results of these and similar experiments t,he author draws the conclusion that the cathodic pulverisations are formed of fairly large pnrticles torn from the cathode by the impact of the a-rays projected iii all directions and carrying variable electrical charges the e / m being illrich smaller than in the case of the particles forming the cathode rays.MI. A. W. Chemical Composition of the Nickel Oxide Electrode in the Jungner Edison Accumulator. JULIAN ZEDNER (Zed. EZekh*ociienz. 1905 11 809-S13).-If nickelic oxide be prepared in any way and pasted on to a platinum wire the potential difference between the wire and zinc amalgam i n a solution of potassium hydroxide is the same 2s if the nickelic oxide were not present. A nickel oxide accumulator plate gives a larger potential difference and nickelic oxide deposited electrolytically in various ways on platinum gives the same result as the accumulator plate. The negative result obtained with the pasted oxide is probably due to its extremely smnll conductivity.Quantities of nickelic oxide sugcient for analysis were obtained by electrolysing a solution of nickel sulphate and sodium acetate with a rapidly rotating anode and adding dilute alkali hydroxide solution gradually so as to maintain the solution constantly neutral. The substances obtained had compositions varying between those represented by the formulae Ni20,.H20 and Ni203,11H,0 according to the method of drying. Exact measurements of the E.N.P. of the cell Zn I Zn(OK) + KO€€ I Ni,O showed that this oxide is ideri t ical with that formed in the nccumu1;itor. T. F A66 ABSTRACTS OF CHEMICAL PAPERS. Lead Peroxide as Anode in the Electrolytic Oxidation of Chromium Sulphate to Chromic Acid.ERICH MULLER and MAX SOLLER (Zeit. Elektrochem. 1905 11 863-872).-Chrome alum dissolved in 3-sulphuric acid is not appreciably oxidised t o chromic acid when an anode of smooth platinum is used. Traces of a salt of lead in the solution are precipitated a t the anode as lead peroxide and bring about considerable oxidation. ,Small quantities of chlorine ions also favour the change. The oxidation takes place a t a platinised platinum anode to about one-third the extent observed under similar conditions with a lead peroxide anode. With a lead peroxide anode the oxidation takes place almost quantitatively in fairly concentrated solutions of chrome alum when the current density is not too high (about 0.005 ampere per sq. cm. is suitable). The difference in the behaviour of the platinum and lead peroxide anodes is not due to the latter having a higher anodic potential (the reverse is rather the case) but appears to depend on a catalytic action of lead peroxide which is capable of producing the oxidation purely chemically.T. E. Conductivity and Viscosity of Solutions of certain Salts in Mixtures of Acetone with Methyl Alcohol Ethyl Alcohol and Water. HARRY C. JONES and EUGENE C. BINGHAM (Amer. Chern. J. 1905 34 481-554. Compare Jones and Carroll Abstr. 1905 ii 73).-A study has been made of the relations between the viscosities and conductivities of lithium nitrate potassium iodide and calcium nitrate in mixtures of acetone with methyl alcohol ethyl alcohol and water. Determinations have been made of the conductivity a t 0" and 25" of solutions of these salts of various concentrations in methyl alcohol acetone ethyl alcohol water and mixtures of acetone with methyl alcohol ethyl alcohol or water containing 25 50 or 75 per cent.of acetone. The results of the experiments are tabulated and plotted as curves. The temperature-coeflicients have been calculated in all cases. The viscosities a t 0' of acetone methyl alcohol ethyl alcohol and mixtures of methyl alcohol and acetone and of ethyl alcohol and acetone have been determined. 'Determinations have also been made of the viscosity a t Oo and 25' of water a mixture of water with 25 per cent. of acetone and solutions of calcium nitrate in the following solvents acetone methyl alcohol and mixtures of acetone with water methyl alcohol or ethyl alcohol containing 25 50 or 75 per cent.of acetone. The viscosity fluidity and density of the various solutions are given in tabular form. Com- parisons of the temperature-coefficients of conductivity and fluidity in these mixtures show that they vary in the same manner but that the former are uniformly smaller than the latter. The conductivities of the salt solutions in mixtures of acetone and water exhibited the minimum in conductivity which has been observed previously and which is shown to be intimately connected with the minimum in fluidity. I n the mixtures of acetone and alcohols the fluidities are in accordance with the law of averages and the fluidity curve is nearly a straight line whence it is concluded that acetone and these alcohols do not form complex molecular aggregates when mixed.The fluidities are also plotted as curves.GENERAL AND PHYSICAL CHEMISTRY. 67 The curves for the conductivity of potassium iodide in the various mixtures are nearly straight lines a t all dilutions and are very similar t o the corresponding fluidity curves. Lithium nitrate a.nd calcium nitrate in mixtures of acetone with methyl or ethyl alcohol show a deviation from the fluidity curves and exhibit a pronounced maximum in conductivity. After a consideration of t.he various factors which could influence the conductivity i t was concluded that the observed maximum is due to a change in the dimensions of the atmospheres about the ions (compare Kohlrausch Abstr. 1903 ii 403). The conclusion of Dutoit and Friderich (Abstr. 1899 ii 351) and of Jones and Carroll (Zoc.cit.) that conductivity is directly proportional to the dissociation and inversely proportional to the viscosity is incomplete since it does not allow for possible changes in the size of the ionic spheres. The conductivities of lithium nitrate and calcium nitrate in mixtures of acetone and water also shorn a tendency towards a maximum. This tendency to form a maximum in conductivity increases from potassium iodide through calcium nitrate to lithium nitrate and it is considered that this may be connected with the velocities of migration of the ions. E. G. Can an Element form both Positive and Negative Ions? MAX LE BLANC (Zeit. Elektrochem. 1905,11,813-818).-Both sulphur and selenium (in the form of a thin film on a platinum wire) when used as cathodes in potassium hydroxide solution go into solution in the form of polysulphide or polyselenide ions SZ” or Se,” the largest values of x observed being 5 and 4.4 respectively.Used as anodes no action was observed at all. Telluioium as cathode in a1 kaline solutions dissolves readily; in very concentrated solutions of potassium hydroxide the dust observed by Miiller and Lucas (Bbstr. 1905 ii 672) is not formed. Its formation is more probahly due to the dissociation of polytelluride ions T e l Z T e ” + Te in dilute solutions. At a tellu- rium anode in potassium hydroxide there is no vkible change but tellurium goes into solution w i t h the valency 3.9 ; it therefore gives off the ions Te”” which tben react with hyclroxyl ions to form the ions TeO,”.T. E. Experimental Study of the Three Parts of an Electrolytic Cell and their Relationships. G. HOSTELET (Zeit. Elektrochem. 1905 11 889-904).-In determining decomposition points by Glaser’s method (Abstr. 1899 ii 78) the author found difficulty in interpret- ing the results owing to variations in the resistance of the system and in the potential of the constant electrode. H e has therefore worked out a method in which the falls of potential between the anode arid the electrolyte between the cathode and the electrolyte and in the elec- trolyte itself are all separately and simultaneously determined. The method is applied to the study of the electrolysis of potassium chloride with a platinum anode and a cathode of mercury. T. E. Theory of Electrolytic Dissociation taking account of the Electrical Energy.R. MALMSTROM (Zeit. Elektrochem. 1905 11 797-809).-In addition to the ordinary attractions between the68 ARSTRACTS OF CHEMICAL PAPERS. various molecules in the solution of an electrolyte there are forces due t o the attractions and repulsions of the electric charges on the ions. Assuming these electrical forces t o be superposed on the ordinary attractive forces the free energy of a dissolved electrolyte is calculated and from this an equation for the equilibrium between the ions and undissociated molecules is obtained. This is found t o be in rather better agreement with measurements of conductivity than any of the equations proposed previously. It is suggested that owing to electro-striction the dielectric constant of the solution must be a function of the concentration and that a better agreement might be obta,ined by taking this into account.T. E. Theory of Electrolytic Dissociation. LOUIS KAHLENBERCr (f'hd. Compare Abstr. 1905 ii 139)- Mag. 1905 [vi] 10 662-664. A reply to Jones' criticism (Phil. Mag. 1906 [vi] 10 157). J. C. P. Accurate Measurement of Ionic Velocities. ROBERT B. DENISON and BERTRAM D. STEELE (Proc. Roy. Sac. 1905 76 A 556-557).-An apparatns has been devised for measuring the velocities of ions without using gelatin or other partitions during the experi- ment. The apparatus consists of two reservoirs each provided with a special electrode vessel and of a measuring tube of known cross-section in which the solution to be examined is placed.One of the reservoirs contains a solution of B salt with a less mobile cation than the cation under observation the other a solution of a salt with a less mobile anion than that of the salt under investigation. The measuring tube is provided at each end with parchment-paper partitions which facilitate the formation of a sharp electrolytic margin between the measured and the indicator solutions and these partitions are so arranged that they can be removed after the margins have been formed. Experiments have been made at dilutions down to 0.02 normal. The calculated transport numbers agree very well with those obtained by Hittorf's method and the measured average ionic velocities confirm in a remarkable manner those calculated from conductivity data.H. M. D. Mobility of Ions of Salt Vapours. GEORGES MOREAU (Compt. rend. 1905 141 1225-1227. Compare Abstr. 1903 ii 125 196 ; 1904 ii 536; 1905 ii 9).-The author has measured between the temperatures of 170' and 15" the mobility (k) of the ions in air which has been bubbled through solutions of potassium salts of different con- centrations and then passed through a tube heated to redness. From the values of k thus obtained the sizes of the ions for different tempera- tures and concentrations are calculated with the results that at the higher temperatures the ions have a diameter five to fifteen times that of the molecule and appear to consist of an electrically charged nucleus surrounded by two t o seven layers of molecules whilst at the l o ~ e r temperatures the number of layers is increased to ten t o twenty.M. A. W.GENERAL AND PHYSICAL CHEMISTRY. 69 Electrical Conductivity of Dilute Solutions of Sulphuric Acid. W. C. DAMPIER WHETRANI (Proc. Boy. SOC. 1905 76 A 577-583).-The equivalent conductivity of solutions of strong acids and alkali hydroxides increases with dilution but reaches a maximum a t 0.001 to 0.0005 gram-equivalent per litre and falls rapidly with further increase in dilution. The effect of traces of impurities on the equivalent conductivity of sulphuric acid in dilute solution has been examined by measuring the variation of the conductivity with the con- centration in four solvents (1) good quality redistilled water and the same containing (2) a trace of carbon dioxide (3) a trace of potassium chloride and (4) the same water freed as far as possible from volatile impurities by repeated boiling under diminished pressure.I n each case the conductivity of the solvent was subtracted from that of the solution. The results shorn that the conductivity of sulphuric acid in dilute solution is not affected by addition of a trace of potassium chloride or by boiling under diminished pressure but that it is appreciably diminished in presence of a litt,le carbon dioxide and in this case the maximum conductivity is reached at a higher concentru- tion. The abnormally low conductivity of dilute solutions cannot however be wholly attributed to the presence of carbon dioxide in the water used as solvent. H. M. D. Transit of-Ions in the Electric Arc. A. A. CAMPBELL SWINTON (Proc.Roy. SOC. 1905 76 A 553-556).-An experiment has been devised to show t h a t the current in the electric arc is cayried by positive and negative ions emitted by the electrodes. A small hole was bored axially through one of the carbon electrodes which was 6xed rigidly a t the end of a brass tube and an insulated Faraday cylinder w t s supported within the brass tube so that its aperture was in line with and immediately behind the aperture in the carbon electrode. With a current of three amperes and about 50 volts the Earaday tube remained unchanged in atmospheric air but when the apparatus was enclosed in a glass vessel and the pressure reduced the Faraday cylinder acquired the same charge as the opposite carbon electrode. The effect increased with the degree of exhaustion of the containing vessel ancl correspond- ing with the greater mobility of the negative ions the galvanometer deflection for a given degree of exhaustion was greater when the opposite carbon electrode was made the negative pole.H. M. D. Magnetisation and Magnetic Change of Length in Ferro- magnetic Metals and Alloys at Temperatures ranging from - 186' to + 1200". KOTARO HONDA and Su~ru SHIMIZU ( P l d . May. 1905 [vi] 10 642-661).-The papercontains n large number of data bearing on the magnetisation of Swedish iron nickel annealed cobalt and various nickel steels. The results obtained are in general harmony with those of earlier observers such as Osmond and Dumas. J. C. P. Coexistence of Paramagnetism and Diamagnetism in the same Crystal. GEORGES MESLIN (Conzpt.inend. 1905 141 1006-1008. Compare Compt. re?ziJ. 1905 140 i6S3).-A small70 ABSTRACTS OF CHEMICAL PAPERS. cube cut from a crystal of pyrrotite in such a way that its faces are parallel with or perpendicular to the magnetic plane exhibits para- magnetism when placed in a magnetic field in such a position that the magnetic plane passes through the axis of the electro-magnet whilst in a direction a t right angles to this it exhibits diamagnetism. By immersing the cube in a concentrated solution of ferric chloride its paramagnetic susceptibility is diminished and its diamagnetic sus- ceptibility is increased. M. A. W. Magnetic Compounds of Non-magnetic Elements. EDGAR WEDEKIND (Zeit. Elektrochem. 1905 11 850-861).-The manganese borides previously described (Abstr.1905 ii 322) are found to be strongly magnetic ; they also possess considerable permanent magnetism. Compounds of manganese with antimony and bismuth are also magnetic ; manganese arsenide however is not magnetic but becomes magnetic when heated in the air. The phosphides carbides and sulphides of manganese prepared by the alumino- thermic process are also magnetisable whilst the silicide is not so. T. E. Specific Heats of Gases. SILVIO LUSSANA (Nuovo Cirn. 1905 [v] 10 192-195).-The author points out that although in their paper on the specific heats of gases a t high temperatures Holborn and Austin (Abstr. 1905 ii 228) affirm that it is impossible to state with certainty that the specific heats of the simple gases increase as the temperature rises yet all their results exhibit such an increase the mean value of which is 3 per cent.whilst the accuracy of their measurements is about +_ 1 per cent. The author's investigations on this subject extending over a number of years lead to the conclusions that for all gases the specific heat a t constant pressure (1) increases with the pressure up to a. certain limiting value and then diminishes the maximum corresponding with a pressure which is lower as the gas deviates more from Boyle's law and (2) increases or diminishes with the temperature according 5s the latter is near t o or far from the temperature of liquefaction of the gas ; the temperature variation of the specific heat increases with the pressure. T. H.. P. Latent Heat of Fusion of Ice. ANATOLE LEDUC (Compt.rend. 1906 142 46-48).-There is a difference of nearly 1 per cent. between Bunsen's value (S0.03) for the latent heat of fusion of ice and the value (79.25) found by Laprovostaye and Desains and confirmed by Regnault and the difference is still of the same order if the numbers are corrected for the variation of the specific heat of water taking 1.004 as the specific heat of water a t 0" according to the results obtained by Callendar and Barnes. If however the author's value 0-9176 for the specific volume of ice a t 0' is substituted for the value found by Bunsen 0.9 1674 Bunsen's value for the latent heat of fusion of ice becomes 79.15 and the author considers that 79.3 is the most probable value for t h i s constant. M. A. IT.GENERAL AND PHYSICAL CHEMISTRY.71 Connection between Depression of Freezing Point and Latent Heat of Fusion. KARL DRUCKER (Zeit. Elektrochem. 1905 11 904-905).-Goebel (Abstr. 1905 ii 679) has calculated the latent heat of fusion of ice a t temperatures below zero from the vapour pressures of ice and water. The author points out that a very small inaccuracy in the formula representing the vapour pressures makes a very large error in the heats of fusion calculated. Goebel’s results differ enormously from Pettersson’s direct determinations. If the latter are used to calculate the vapour pressures of ice numbers are obtained in good agreement with the experimental numbers. Hence the correction of the freezing-point depressions given by Goebel is much too large. He has also erroneously taken the concentrations in gram-molecules per litre of solution instead of per kilogram of water which partially compensates the first error.Solvent and Ionising Properties of Ethylene Cyanide (Succinonitrile). GIUSEPPE ‘ BRUNI and ANTONIO MANUELLI (Zeit. Elektrochem. 1905 11 860-862).-The molecular depression of the freezing point of succinonitrile is 182.6 from which the molecular latent heat of fusion is calculated to be 0.94 cal. which is the smallest value yet observed for any organic compound. Ethylene bromide and chloride give abnormally small depressions of freezing point when dissolved in succinonitrile which is doubtless due to the formation of solid solutions. Compounds containing amino- or hydroxyl groups give small depressions probably owing to molecular association.The high dielectric constant of succinonitrile points to considerable dis- sociating power. The freezing points of solutions of potassium and tetraethylammonium iodides were determined and values of i calcu- lated which lie between 1-26 and 1.3 for potassium iodide and 1.78 and 1-89 for tetraethylammonium iodide. The latter solutions conduct well. The anhydrous chlorides of copper manganese cobalt and nickel are insoluble in succinonitrile. Critical Temperature of Solutions in Liquid Carbon Dioxide. ERNST H. EUCIINER (Chem. Centr. 1905 ii 1618-1619 ; from Chem. Weekblad 2 691-694).-The results of experiments on solutions of p-dichlorobenzene tribromomethane p-dibromobenzene o-chloronitro- benzene naphthalene and 1 3-dichloro-5-nitrobenzene in liquid carbon dioxide have shown that van’t Hoff’s law holds approximately in these cases the molecular rise of the critical temperature being almost constant.The results may however be more accurately expressed by means of van Laar’s hypothesis in which the rise per gram-molecule per cent. is not only dependent on the critical tempera- ture of the solvent but also on therelationship of the critical temperature of the dissolved substance to that of the solvent and on the ratio T of the critical pressures. Since as a rule T = 1 6 = O(O - a) in which 8 = l/Tk.(dT,/d,) and 5“k =critical temperature of the solvent. T. E. T. E. E. W. W. Relative Vapour Tensions of the Three Modifications of Carbon ANDREAS SMITS (Ber. 1905 38 4027-4033. Compare Schenck and Heller Abstr.1905 ii 619).-The equilibrium constant72 ABSTRACTS OF CHEMICAL PAPERS. of the reaction CO2+C,2CO is X = p ~ ~ ~ / p c o p c where p c is the partial vapour pressure of the carbon that is the maximum vapour pressure of the solid carbon at the given temperature. As this increases so do the values of K,pc and p2co/pco in the equation Klpe =p‘co/pco,. The equilibrium constant for the reaction Fe + CO t FeO + CO is AT= ( ~ ~ ~ ~ . ~ ~ ~ o ) / ( p ~ o / p ~ ~ ) ; if the differences in the solubilities of the three modifications of carbon in iron are neglected may be considered as constant and the equation may be written K2=pco/pco,. If the sum of the partial vapour pressures CO + C02 = P then P = k,pc( 1 + k2)/k,2 which differs from Schenck and Heller’s equation by the presence of pc (Zoc.cit.) and the greater the vapour pressure of the modification of carbon the greater is the equilibrium pressure P. If pc p’c a n d p ” ~ are the ‘a our pressures of the three modifications,then P P’ P”=pc :p’c :p”c. h e author discusses the work of Schenck and Heller from a theoretical point of view and concludes that the equilibrium pressures measured by them are not trustworthy. If however these are assumed to be correct the vapour pressures of the diamond amorphous carbon and graphite are in the proportions pc :p‘c :pNc = 3.7 1.8 1 at 500”; 4.1 2.4 1 a t 550O; 5.2 4.1 1 at 600”; and 5-4 4.2 1 a t 641O. G. Y. Distillation in High Vacua by means of Dewar’s Air Absorption Method and a Shortened MacLeod Vacuum Gauge. ALFRED WOHL and M.S. LOSANITSCH (Rer. 1905 38 4149-4154. Compare Pischer and Harries Abstr. 1902 ii 491 ; Erdmann 1904 ii 20).-The apparatus t o which is attached an absorption vessel containing 20-30 grams of extracted blood charcoal is evacuated by means of an ordinary water pump and the receiver and absorption vessel are then cooled by liquid air. Pressures of 0.006-0.008 mm. can thus be attained within thirty minutes. It is not necessary that the apparatus shall be absolutely air-tight as small amounts of air which enter are absorbed by the charcoal. The same cooled charcoal (25-30 grams) may be used for several distil- lations provided the apparatus is exhausted before being attached to the absorption vessel. For measuring high vacua a MacLeod apparatus shortened in much the same manner as suggested by Stlock (Abstr.1905 ii 514) for the Topler mercury pump is recommended. J. J. S. Distillation of Liquids which are Mutually Insoluble. C. VON RECHENBERG and W. WEIPSWANGE (J. prakt. Chem. 1905 [ ii] 72 47S-4SS).-Experiments on the weights of the two components of a non-miscible liquid mixture which distil over are not in accord with the conclusions of Charabot and Kocherolles (Abstr. 1904 ii 234). The authors’ results are however in accord with their deductions that the weights of the components are proportional to the products of their molecular weights and partial pressures. If the vapour mixture is saturated with respect to both components then the partial pressure for each component is the normal vapour pressure corresponding with the temperature of the vapour.I f the vapour mixture is unsaturatedGENERAL AND PHYSICAL CHEMISTRY. 73 with respect to one component the unsaturated vapour has the pressure equal to the difference between the pressure of the mixed vapour and the vapour pressure of the saturated component a t the temperature of the mixed vapour. Progressive Dissociation of Dibasic Acids. 11. RUDOLF WEGSCHEIDER (Moncctsh. 1905 26 1235-1239. Compare Abstr. 1902 ii 643).-In the case of sparingly soluble dibasic acids or of those which have a high value for the dissociation constant s of the second hydrogen atom it is necessary to calculate both dissociation constants from the results of the same experiments which may be done if approximate values for the two constants are known or can be guessed.A maximum value for k the dissociation constant of the first hydrogen atom is obtained according to Ostwald’s law of dilution from the conductivity in the most concentrated solution. is substituted for g1 in the equations L. Ill. J. If the value (I) - 2g2(zK+ Po0 (1) and (2) previously given then (11) - 2SVVK + 17.4) + ?( 1 - 1/1 - 8SVP(L + 4 . 4 - P ’) g = 4(Z + I - p a ) L2SV(l + Z2J + p] ’ in which g is a function oh the known constants I and pa of the experimentally determined values v and p and of the unknown constant s and (111) F(kls) = Kvp \‘pa - p + g2[2(E! + ZZA) - per 1) - [ p - 2g2(Zli + EZa4)][p - 2g,(E + E - pa ) J = 0 where F is a function of k and s. If the approximate value of k and the values of g calculated by equation (11) from the results of a number of experiments with assistance of the approximate value of s are substituted in equation (HI) as many values of 3’ are obtained and the values of k and s must be altered until in each case P-0.I f k+6k s+Ss are the correct values for the two constants k and s then (IV) O = P 6P SF ( k + 6k,s + 6s) = F(k,s) + -as + -6k ; from these are obtained two 6s 6k equations by means of which 6k and 6s may be calculated. Equations are given also for the adjustment of s and k in case of more than two observations. The method of calculation is illustrated in the case of 4-acetyl- aminoisophthalic acid. G. Y. Dissociation of Electrolytes. CARL HENSGEN ( J . prakt. Chem. 1905 [ii] 72 345-477).-1t has been shown previously that con- centration differences exist in a salt solution not entirely a t the same temperature.This case is first investigated for a solution of copper sulphate the upper layer of which was kept a t a temperature of about 98” whilst the lower was maintained at the ordinary temperature. It was found that not only was the concentration different for the two layers but also that the ratio CuO SO was not unity and was greatest for the highest layer. Numerous expressions have at different times been proposed to connect the sp. gr. of a solution with its chemical composition; these are fully considered and found by the author to be unsatisfactory for solutions of copper sulphate and it is74 ABSTRACTS OF CHEMICAL PAPERS. found that the ratio CuO SO varies within wide limits.Numerous tables showing this ratio a t different temperatures and ooneentrations are given in the paper and fullF discussed. The author considers that his results indicate that solutions of normal salts are the liquid phases of a heterogeneous equilibrium system brought about by the chemical action of the water and dependent on temperature &c. The general idea associated with the term solution of a normal salt namely the complete passage of the solid normal salt into the solution main- taining throughout the same proportion of its components regarded as base and acid is not consistent with the actual conditions. The molecular contents of normal salts in solution are therefore not calculable. Crystallisation of normal salts takes place only in solutions which do not contain acid and base in the same proportions as those of the precipitated salt.It is evident that these conclusions are not in accord with ordinary chemical views of solution and they and their consequences are discussed a t considerahle length by the author in the paper (compare Abstr. 1901 ii 540). KAKL DRUCKER (Zeit. Elektrochem. 1905 11,845).-The author assumes that the surface tension of a binary mixture may be expressed on the analogy of van der Waals' molecular attraction constant by l / y =L l/y,x2 + 1/y2( 1 - x ) ~ + l / ~ . ~ ( 1 - x)x. The formula is applicable to mixtures of non-associating substances ; yIm2 becomes constant in mixtures of acetic acid and benzene or carbon tetrachloride when the molecular weight of acetic acid is taken as double its formula weight ; in mixtures of water with alcohols or fatty acids constancy of yl.a is obtained by trebling or quadrupling the molecular weight of water.T. E. L. M. J. Molecular Weight of the Solvent in Binary Mixtures. Origin of the Formation of Layers in Solutions observed by A. Sinding-Larsen. C. CHRISTIANSEN (Chem. Centr. 1905 ii 161'7 ; from Overs. K. Danske Vidensk. SeZsk. Forh. 1905 307-315).- Sinding-Larsen (Ann. Fiqsik 1903 [ iv] 9 1186) observed that when solutions of sodium chloride in which the concentration was not uniform were heated sharply defined layers were formed and attri- buted the cause to surface tension and the formation of hydrates. Experiments on water water and toluene and with various solutions have shown however that layers may be formed by heating the liquids on one side and cooling them on the other.The formation of layers is due to movement of the liquid and to differences of temperature and is in no way dependent on the formation of hydrates. The surface of contact between two layers of different concentrations can only remain. sharply defined when the liquid is in motion and although the mixture of the layers is thereby delayed it is not entirely prevented. An electrolytic method of causing two layers of sulphuric acid solu- tions t o circulate is also described in the original paper. E. w. w. Limiting States of some Dissolved Chromic Salts. ALBERT COLSON (Compt. rend. 1905 141 1024-1027. Compare Abstr. 1905 ii 94 255 460 592).-When a solution of the normal green chromicGENERAL AND PHYSICAL CHEMISTRY.75 sulphate Cr,(S0J3 is exposed to sunlight the colour becomes turquoise-blue the density increases (compare Boisbaudran Abstr. 1875,427,730) and the heat of decomposition by potassium hydroxide diminishes t o a limiting value reached more rapidly in dilute than in more concentrated solutions as is shown in the following table Heat of decomposition [Cr,(SO,),:GKOH]. Duration of r- h . to sunlight. 1/10 ntol. per litre. 3/10 mol. per litre. exposure Solntions of Solutions of 0 57,300 cal. 57,200 cal. 10 days (May) - 56,100 28 9 9 48 7 50,400 84 7 50,100 52,200 165 9 50,100 to 50,000 cal. 51,800 51,600 - I The change in density corresponds with a contraction of 1 mol. H20 per 1 mol. Cr2(S04)3 and the turquoise-blue solution probably contains the hydrated sulphate S04<dr:so cr(0H)'s04H of which the heat of decomposition by potassium hydroxide is 50,000 cal.and not an equilibrium mixture of the green and violet chromic sulphates of which the heat of decomposition would be (57,200 + 45,000)/2 cal. or 51,100 cal. A solution of the violet chromic acetate OCr,(OAc) in excess of acetic acid becomes green on exposure to sunlight and cryoscopic and thermochemical measurements indicate that the tetra-acetate has combined with acetic acid to form the penta-acetate OH-Cr,(OAc) which however cannot be isolated for on evaporating the green solution to dryness it decomposes into the two salts Cr(OAc) and OH* Cr(OAc),. M. A. W. Abnormal Increase of Solubility with Organic Substances. DANIEL STROMHOLM ( A ~ k i v Kern.Hin. Geol. 1905,2 i No. 7 1-9).- The author has examined the influence of the addition of small quantities of water on the solubility in ether of benzoic acid p-nitro- benzoic acid picric acid acetanilide quinol phloretin methyl terephthalate benzil P-naphthaquinone phthalimide a-nitro- naphthalene p-nitroaniline P-naphthylamine benzyl sulphoxide sulphonal benzy 1 sulphide azobenzene and phenanthrene. The presence of water in excess causes the solubility in ether to increase by the following percentage proportions benzoic acid 80 ; quinol 296 ; a-nitronaphthalene 10-5 ; methyl terephthalate 16.7 ; benzil 19 ; P-naphthaquinone 43; P-naphthylamine 33.3; p-nitrobenzoic acid 161 ; picric acid 573; acetanilide 5 17; p-nitroaniline 127; phthalimide 47.7; benzyl sulphoxide 92.2 ; and sulphonal 30.3.With benzyl sulphide azo- benzene and phenanthrene the increases in solubility are inappreciable. Augmentation of the solubility hence occurs with all the acid substances examined and with all non-acid compounds containing amino-groups. Hydroxyl compounds carboxylic acids and phenols apptar to be very greatly influenced.76 ABSTRACTS OF CHEMICAL PAPERS. I n the cases of mercuric chloride and iodine the author has previously shown (Abstr. 1903 ii 547 and 644) that the increase of solubility caused by addition of water is due to the existence of hydrates of these substances in solution. This is probably also the case with the above-mentioned compounds. T. H. P. Partition of some Organic Acids between Two Solvents. WALTER HERZ and MARTIN LEWY (Zeit.EZektrochern. 1905 11 $1 S-S20).-The partition of acetic chloroacetic and picric acids between water on the one hand and chloroform bromoform carbon disulphide and carbon tetrachloride on the other hand is studied. The results point to the existence of double molecules in the more dilate solutions and of more complex molecules in the more concentrated solutions. T. E. Passivity of Metals. WOLF J. MULLER (Zeit. E’lektrochem. 1905 11,8a3-824). -The author’s theory of passivity was incorrectly stated by Ruer (Abstr. 1905 ii 755). T. E. Passivity. CARL FREDENHAGEN (Zeit. Elektrochem. 1 905 1 I 857-S60).-With special reference to Rner’s recent work (Abstr. 1905 ii 795) the author maintains the view that passivity is better explained by assuming a protecting layer of gas (Abstr.1903 ii 353) than by assuming a skin of oxide. The gas theory is capable of accounting for cathodic as well as anodic passivity. The protecting layer of gas may exist as a solid solution as a surface film or in some intermediate condition. T. E. Rate of the Reaction between Arsenious Acid and Iodine in Acid Solution ; Rate of the Reverse Reaction ; and the Equilibrium between them. (11.) J. R. ROEBUCK (J. Physical Chem. 1905 9 727-763. See Abstr. 1903 ii 14).-It has been shown previously that the velocity of the reverse reaction is given by dx/dt = (arsenic acid)(pot. iodide)a(sulphuric acid)@ where a and /3 approach unity in dilute solution. The investigation of this was extended and the values a and /3 found to increase considerably with increasing concentration values as high as 2.4 and 3.7 being obtained. Where the concentration of iodide (C) and acid (D) considerably exceeds that of the arsenic acid the expression may be written dzldt=K5CDV-3(E-x) and it was found that the value of K5 increases as equilibrium approaches and also when clxldt is decreased by decreasing (E - x).The author considers that these anomalous results may be explained by the supposition that the reaction pro- ceeds in two stages namely (1) H + I + H3As0 = H3As0,HI and (2) H,AsO,HI = H,AsO + HIO the reaction of the first proceeding with a measurable velocity. The author extends his determination of the direct rate to near the equilibrium point and from the reaction velocities in the neighbourhood of the equilibrium calculates the eq ui- librium constant which agrees well with that directly determined the two values being 1.4 x lo5 and 1.5 x lo5.The temperature-coefficient + -GENERAL AND PHYSICAL CHER.IlSTR1’. 77 between 10’ and 0” for the equilibrium constant was found to be 1 41 and that calculated from the coefficients of the direct and reverse velocities was 1-43. Experiments were also made with hydriodic acid in p!ace of sulphuric acid and results in accord with theory were also obtained. L. M. J. Affinity Constants of Amino-acids. RUDOLF WEGSCHEIDER (Monatsh. 1905 26 1365-1276. Compare Abstr. 1902 ii 494 ; Walker Abstr. 1904 ii 309 ; 1905 ii 1 3S).-The observed ‘‘ acid ” dissociation constant K of an amino-acid is less than the constant k Calculated from simple stoichiometric relations for those acids which obey Ostwald’s law of dilution or by means of Walker’s constant for the ‘‘ acid ” dissociation of amphoteric electrolytes which do not obey the law of dilution if an intramolecular salt is formed or if the amino- group forms with water an ammonium hydroxide which is less negative but is greater if the ammonium hydroxide is more negative than the amino-group. I f A’ k” .. . are the true constants of the “acid ” dissociation of different acids having an amino-group in the same position relatively to the carboxyl and x’ x” . . . . are the dissociation constants of the corresponding acids with hydrogen in the place of the amino-group then (1) kl’/xl’ = ~iN/xl“ = . . . . -f wheref is the factor representing the influence of the amino-group. I n a dibasic acid which has x1 and x2 the dissociation constants of the two carboxyl groups where fl andf are the factors representing the influence of the two arnino-groups which are usually in different positions.As the observed constant (3) li’=k,P for monobasic acids and it follows from (1) and (3) that (4) -F=fp’=fp”=. . . dibasic acids A’= Flzl + F2x2. (2) kl =fix1 +A?% r / x t = T / X ” . . = F k1P =flPIxl +f2Paxs =!fix1 +fiX,)P. For From (Z) (3) and (4) it follows that As in this equation f and x can be realised only if p = p = p2 p must be the same for all amino-acids the affinity constants of which can be calculated by means of the same factor for the influence of the amino- group irrespective of the position of the amino-group relatively to the carboxyl. observed for acetylaminoterephthalic acid 0.098 f o r 1-methyl hydrogen 3-acetylnminoterephthalate 0.07 and for 4-acetyl- aminoisophthalic acid 0.079 agree moderately well with the constants calculated 0,084 0.066 and 0.069 respectively with the aid of Ostwald’s factors for the influence of the group NHAc* in o- m- and p a c e tylam inoben zoic acids.The P-anilino-fatty acids which are weak acids give no constant factors whereas the stronger a-anilino-acids give only small variations from the mean factors for the anilino-group 2.1 for the p-toluidino- group 0.63 and for the o-toluidino-group 3.3. For the introduction of the acetylanilino-group -NPhAc into the a-position of acetic proyionic and butyric acids the factors are 14 9.4 and 7.3 ; for the introduction of the o-acetyltoluidino-group The constants VOL.XC. ii. G78 ABSTRACT8 OF CHEMICAL PAPERS. into the a-position of the same acids the factors are 12 7.8 and 6.2 ; and for the introduction of the p-acetyltoluidino-group into the a-position of acetic propionic butyric and isobutyric acids the factors are 12 7.8 7.2 and 6.6 respectively. These factors are highest for the introduction of the groups into a methyl lowest for introduction into a methenyl group. The factors for the influence of the amino-group in the ortho- meta- and para-positions obtained from the three aminobenzoic acids 0.17 0.27 and 0.20 respectively are much smaller than the factors obtained from 5-nitro-3-aminobenzoic acid which gives f(NH2,m) = 0.6 1 from 1 -methyl hydrogen 3-aminoterephthalate which gives and from aminoterephthalic acid which gives f(NH,,o) = 0.33 and f(NH,,m) = 1-38.The amino-group appears in some cases as a nega- tive substituent and it may be that in all other cases the smallness of the factor is due to salt formation. f( NH,,o) = 0.33 G. Y. Theory of Dyeing. IV. Lakes. WILHELM BILTZ [with KURT UTESCHER] (Bey. 1905 38 4143-4149. Compare Abstr. 1904 ii 392 ; 1905 ii 807 808).-Experiments have been made by dyeing precipitated metallic hydroxides with alizarin and similar dyes. The results are arranged as curves in which the concentration of the dye- bath is plotted against the number of grams of dye taken up by one gram of hydroxide. With ferric hydroxide and an alkaline solution of alizarin the curve points to the formittion of a definite compound of 1 mol.of hydroxide with 3 mols. of dye. The curve also indicates a certain amount of a d sorption. With chromic hydroxide and alizarin-red SW the curve indicates adsorption and not chemical combination. I n the case of ferric hydroxide the quantity of dye taken up depends to a large extent on the nature of the hydroxide; when gelatinous some ten times as much dye is absorbed as when in the granular s t ate. Experiments with ferric hydroxide and alizarin in ammoniacal or alcoholic solution with the same hydroxide and aqueous solutions of acid alizarin-blue and with aluminium hydroxide and alcoholic gallein solution gave no very definite results. [Construction of the Periodic System.] AUGUSTO PICCINI (G'uzzettu 1905 35 ii 417-42 l).-The author criticises adversely the periodic system of the elements deduced by Werner (Abstr. 1905 ii 308). T. H. P. J. J. S. An Automatic Steam Generator and Superheater. JOHANNES THIELE (Zeit. ancd. Chem. 1905 44 767-768).-The apparatus consists of a vertical boiler having a conical opening down its centre. In this opening is placed a cylindrical vessel. The water is boiled by a buruer under the boiler and the steam passes through a pipe into the upper part of the cylindrical vessel. The burner is now placed under the latter from which the superheated steam'is withdrawn by a pipeINORGANIC CHEMISTRY. 79 reaching to the bottom of the vessel. The burner is regulated by a specially constructed thermostat which by means of a aide-tube is not brought into action until the water in the boiler is at a boiling temperature. w. P. s. New Apparatus for the Extraction of Liquids. EFISIO llrlAmLr (Chenz. Centr. 1905 ii 1569 ; from La Sccrdegm Scmituria 1). -An apparatus is described which only differs from a Soxhlet extraction cyliuder in the following respects. The tube which conveys the vapour of the solvent from the flask is not sealed on to the side of the cylinder but is connected with another tube which passes through the cork and reaches to the bottom of the cylinder. The siphon tube is lengthened YO that it terminates near the bottom of the flask. I n another form a small tubulns is attached to the bottom of the cylinder through which a tube passes t o the bottom of the flask reaching to a convenieut height in the cylinder and being straight or bent in the upper portion into a U form. The vaponr of the solvent passes through a tube fitted in the cork of the flask and coonected with the extraction cylinder as described above. E. w. w.

ISSN:0368-1769    

DOI:10.1039/CA9069005061

出版商:RSC    

年代:1906

数据来源: RSC