摘要:

J O U R N A L H. BRERETON BAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. F. G. DONNAN M.A. Ph.D. F.R.S. BZRNAHD DYER D.Sc. F. It. S. OF T. M. LOWRY D.Sc. W. H. PERKIN Sc.D. LL.D. F.R.S. J. C. PHILIP D.Sc. Ph.D. F. B. POWEP. Ph.D. LL.D. A. SCOTT M.A. D.Sc. F.R.S. G. SENTEK D.Sc. Ph.D. THE CHEMICAL SOCIETY ABSTRACTS OF PAPERS E. F. ARMWRONG I’h.D. D.Sc. F. BARROW M.Sc. Ph.D. H. W. BYWATEKS D.Sc. Ph.D. R. J. CALDWELL D.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DESCH D.Sc. P1i.D. W. H. GLOVEI~ Ph.l>. W. GODDEN B.So. E. GOULDING D.Sc. W. D. HALLIBUKTON M.D. F.R.S. ‘1’. A. HENRY D.Sc. H. R. HUTCHINSON P1i.D. J,. DE KONINGH. G. D. LANDER D.Sc. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. G. F. MORRELL Ph.D. D.Sc. T. H. POPE B.Sc. T. SLATER PI:ICE D.Sc. Pl1.D. E. H. RODD D.Sc. 8. B. SCIIRYVER DSc. Ph.D. W. P. SKEKTCIILY. F. SODDY M.A. F.R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STAXFORD hl.Sc. Ph.D. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B.A. J. 0. WITHERS Ph.D. H. WREN M.A. I).Sc. P1i.D. 0. SMITH D.Sc. 1914. Vol. CVI. Part I. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 1914.PRI~TED IN GREAT BKITA~N BY RICHARD CLAY & SONS LIMITED BRUNSWICK W. STAMFORD ST. S.E. AND BMOAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91406FP001

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

J O U R N A L €1. BREKETON RAKER M.A. D.Sc. J. N. COLLIE Ph.D. F.R.S. A. W. CI:OSSI,F,Y T).Sc. Ph.D. F.R.S. F. G. DOXNAN M.A. PIi.D. F.R.S. BERNARDYER D.SC. M. 0. FoitsrEn D.Ec I’li.D. F.R.S. P.R.S. OF ‘1’. M. LOWRY D.Sc. lv. k1. PERKIN sC.l). LI,.D. F.B.S. J. C. PHILIP D.Sc. Ph.D. F. R. POWRR Ph.D. LL. D. A. SCOTT K A . D.Sc. F.R.S. G. QENTER D.Sc. Ph.D. S. SMILES D.Sc. THE CHEMICAL SOCIETY.PRIXTED IN GREAT BRITAIN BY RICHARD CLAY & SONS LIMlTEf> BRUNSWICK ST. STAAIFORD ST. S.E. AND BUNOAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91406FP003

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii. 46 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Surface Tension and Molecular Complexity of Chlorine. E. MARCHAND (J. Chim. I'hys. 1913 11 573-576).-The surface tension of chlorine has been measured by the method of capillary rise in narrow tubes at temperatures from Oo to 50° and from the results the values of the constant K of the Eotviis formula have been calculated. It is shown that the value of K lies betwesn 2.07 a t Oo and 2.14 at 50° and consequently liquid chlorine is to be regarded as a non-associated liquid. R E N ~ DUBRISAY (Compt. v d . 1913 157 1150-1163).-8 study of the neutralisation of periodic acid by a method already described aad applied to chromic acid (compare A. 1913 ii 388 712). The results which are set out in tables and curves show that periodic acid in solution behavea as a tribasic acid.J. F. S. The Neutraliraation of Periodic Acid W. G. Melting Point of Oxygen. TAD ESTBEICHER (Zeitsch. physikat. Chum. 1913 86 432-434).-The author shows from some resultsINORGANIC CHEMISTRY. ii. 47 previously published (A 1904 ii 477) that in accord with Wahl's suggestion (A. 1913 ii 208) the melting point -227O is most probably the transition temperature of the one modification of solid oxygen into the other. The melting points at different pressures are extrapolated and found to be 0.46 mm. -221*8O 0.87 mm. -219*9O and 1-12 mm. -219.1O. It is shown also that the heat of change of one form of solid oxygen into the other is probably less than that of sulphur which has a value of 2.5H per gram. J. F. S.Revision of the Density of Oxygen Density of the Air at Geneva F. 0. GERMANN (Compt. rend. 1913 157 926-929).- The author has determined the density of oxygen as prepared by heating recrystallised potaesium permanganate and subjecting the gas to liquefaction and subsequent fractional distillation. As a mean of fifteen determinations he finds the weight of a normal litre of oxygen to be 1.42905. I n four of the determinations the oxygen was passed over platinised asbestos a t 400° prior to measuring the density. Two diagrams are given showing the arrangement of the apparatus used. This apparatus has also been used to determine the density of the air a t Geneva in March on two different dates. The mean value found was 1.2930 for a normal litre of air (compare Guye Kovacs and Wourtzel A.1912 ii 636). W. G. The Solubility of Atmospheric Oxygen in Water. TOR CARLSON (Zeitsch. angew. Chem. 1913 26 713-714).-The author has collected the most trustworth7 data obtained by previous investi- gators and also made fresh experiments himself using a modification of Winkler's method with respect to the solubility of atmospheric oxygen irG water at temperatures varying from Oo to 25O. From the results obtained a table is given showing the solubility for every degree between Oo and 25O (a) at 760 mm. ( b ) at (760-0 mm. where f is the vapour pressure of water at the particular tempera- ture. T. 8. P. Formation of Ozone at Various Pressures. H. VON WARTEN- BERG and L. NAIR (Zeitsch. Elektrochem. 1913 19 879-881).-The formation of ozone by a silent discharge has been studied at 8 series of pressures.It is shown that there is a point between 0.5 and 1.0 atmospheres where the formation is a t a maximum. The experiments were continued up to 5 atmospheres pressure and so arranged that the molecules of the gas were always under the influence of the discharge for the same time. Preparation of Sulphur and Sulphates by Heating Sulphites under Pressure. FARBENFABRIKEN VORY. FRIEDR. BAYER & Co. (D.R.-P. 265167).-Sulphur and sulphates can be obtained by heating a mixture of a sulphite and a hydrogen sulphite under pressure when the following reaction occurs 2NaHS0 + Na,SO,= 2N%80 + S + H,O ; for example 150 parts of ammonium hydrogen sulphite 90 p&a J. F. S.ii. 48 ABSTRACTS OF CHEMICAL PAPERS.of ammonium sulphite and 200 parts of water are heated in an autoclave a t 150° for a few hours. J. C. C . The Alloy of Selenium and Iodine. ERNST BECKMANN and ERICH GR~NTHAL (Zeihch. anorg. Chem. 1913 84 97-102. Com- pare Beckmann 2nd Hanslian A. 1913 ii 402; Pellini and Pedrina A. 1908 ii 833).-The tendency to undercooling and t'he difficulty of making cryoscopic observations increase with the con- centration of the selenium. A eutectic point is found a t 50 atomic% and 58O. The eutectic mixture retains iodine even after extraction with solvents until colourless but a t 100-llOo all the iodine can be removed by heat. (2. H. D. The Existence of Compounds of Selenium and Iodine. ERNST BECKYANN and OTTO FAUST (Zeitsch. anorg. Chem. 1913 84 103-112. Compare preceding abstract).-The question whether the dissociation of selenium when dissolved in iodine is to be explained by the formation of loose compounds is not readily answered by thermal analysis on account of the liability to under- cooling.Dilatometric experiments with sulphuric acid ae filling liquid show that the volume change of the eutectic on melting may be calculated from that of the components by the mixture rule. This is also true of the specific volumes whilst the expansion in the formation of the tellurium compound TeI is ten times the experi- mental error. The electrical conductivity shows the eutectic to be a mixture of crystalline iodine and amorphous selenium. Tellurium iodide shows an entirely different behaviour. The molecular weight of selenium Sel0 in methylene iodide is not changed by the presence of iodine 12.The cause of the disso- ciation of selenium in iodine solution must therefore be physical not chemical. C. H. D. Nitrogen Hexoxide and Nitrogen isoTetroxide. F. RASCUIG (Zeitsch. anorg. Chent. 1913 84 115-120. Compare A. 1912 ii 346; Muller ibid. 753).-A reply to Miiller's criticisms as to the point a t which the analysis of the residual solid after the oxygen has evaporated should be made. On washing with liquid nitrogen a dull blue residue is obtained having the composition NO or N,O,. This is nitrogen isotetroxide. The hexoxide is perhaps only stable in presence of an excess of liquid oxygen. C. H. D. The Action of Carbon Dioxide on Boron Sulphide. N. D. COSTEANU (Compt. rend. 1913 157 934-935.Compare A. 1913 ii 694).-Carbon dioxide reacts with boron sulphide in the same way as with silicon sulphide (compare loc. cit.) giving rise to boric anhydride carbon monoxide and sulphur B2S3+ 3@0,=B203+ 3CO + 3s. The reaction commences at 300° and is increased by prolonging the heating and by rise in temperature but is never very rapid being hindered by the formation of a layer of boric anhydride. w. a.INORGANIC CHEMISTRY. ii. 49 The Action of Carbonyl Chloride on the Natural Phosphates and Silicates. J. BARLOT and ED. CHAUVENET (Compt. yend. 1913 157 1153-1155. Compare A. 1911 ii 602).-Carbonyl chloride will attack numerous natural phosphates such as vivianite pyro- morphite uranite and monazite and natural silicates such as thorite gadolinite cerite and zircon yielding in each case the anhydrous metallic chloride.The phosphates are attacked a t tem- peratures between 300° and 500° whilst the silicates require temperatures above 1000° emerald not being decomposed a t 1400O. This reaction forms a ready method of analysis of such minerals and also of preparing anhydrous metallic chlorides from these minerals. W G. Corrosion of Metals by Water. A. T. STUART (J. Ind. Eng. Chem. 1913 5 905-906).-Experirnents carried out with raw and filtered peaty waters showed that although the waters attacked iron t o the same extent in the case of the raw waters a large proportion of the metal removed by corrosion remained in solution possibly in a colloidal state whilst the filtered waters deposited Solubility of M6tale in Water.VICENTE M. ~SNARDI ( A n d . Xoc. Quirn. Argentina 1913 1 214-221).-The course of solution was traced by electrical-conductivity determinations plates of metal 4 cm. long by 2 cm. wide being placed in contact with 70 C.C. of twice distilled water for ten twenty and thirty days a t 18-22O and for one two and three hours at looo. Tin and silver are the least soluble. Copper is more soluble than lead although the latter is more corroded. The solution of lead is proportional t o the time. In the case of zinc the solubility rises very rapidly after twenty days. Tendency of Haloids and Other Salts of the Same Metals to Combine. Fluorides Chlorides and Carbonates. M. AMADOKI ( A t t i R. Accad. Liizcei 1913 [v] 22 ii 366-372. Com- pare A. 1913 ii 216).-The paper deals with the thermal analysis of the systems NaF-Na&O KF-&C03 NaCl-Na&Os and Sodium fluoride and sodium carbonate do not form any com- pound and are not miscible in the solid state.There is an eutectic corresponding with 39 mo1. % of sodium fluoride and 690O. I n the system KF-K,CO the curve of crystallisation of the carbonate descends to an eutectic a t 688O (about 46 mol. % KF) and that of the fluoride to an eutectic a t 682O (about 60 mol. % KF). Mixtures containing 46-60 mol. % KF solidify between these temperatures a compound KF,K,CO being formed which gives with the components two eutectics which melt almost a t the same temperature as itself. Sodium chloride and sodium carbonate do not form compounds and are practically immiscible in the solid state.There is an eutectic at 636O and 59 mol. % NaCI. a ferruginous sediment. w. P. s. G. D. L. KCl-KZCO3. VOL. CVI. ii. 4ii. 50 ABSTRACTS OF CHEMICAL PAPERS. The systam KC1-K2COs is analogous to the preceding; the eutectic temperature is 636O corresponding with 65 mol. % KCl. R. V. S. Crystalline Form of CEsium and Rubidium Nitrates. A. DUFFOUR (Budl. SOC. f r a y . Mi?&. 1913 36 136-143).-Crystals of msium nitrate crystallised from a solution containing also casium dichromate are of two habits on0 as a hexagons1 prism terminated by a hexagonal pyramid and much resembling crystals of quartz; the other as pseudo-cubic forms. The system is rhombohedral with the rhombohedral angle 89O54/ and this pseudo-cubic form is further emphasised by twinning. Rubidium nitrate is orthorhombic with a b c = 0.5789 1 0.7108 the angles here also being very near to those of cubic crystals.The two salta ar0 isomorphous and form mixed crystals. I n both salts the double refraction is feeble and a t a lower temperature it disappears altogether t b crystals then being truly cubic. There is thus a passage from the orthe rhombic through the rhombohedral to the cubic form. Ammonium Peroxide. P. MEL~KOV (Ber. 1913 46 3899).- A correction to the communication of D'Ans and Wedig (A 1913 ii 1051). The compound NH40,H of these two authors is identical with the compound (NR&O2,HzO2 prepared by Melikov and Pissarievski. T. S. P. L. J. S. The Hydrates of Silver Fluoride. A. GUNTZ and A. A. GUNTZ jun. (Compt. rend. 1913 157 977-981).-A reply t o Vanino and Sachs (compare A.1911 ii 884) and a study of the conditions governing the formation of the various hydrates of silver fluoride. Their formation is dependent on the temperature the content of the solution with respect t o hydrofluoric acid and is also a function of the nature of the saturated solution for a metastable or stable phase at the given temperature. The starting material was prepared by saturating concentrated hydrofluoric acid with freshly precipi- tated silver hydroxide concentrating on a water-bath filtering hot and cooling. The crystals obtained were collected and dissolved in distilled water. On evaporating in a vacuum a t loo a neutral solution containing 120 grams of silver fluoride in 100 grams of water and suitably seeding the liquid colourless transparent voluminous crystals of the hydrate AgF,4H20 m.p. 18*5O were obtained having at 1 3 O a heat of solution -4.93 cal. Below 1 8 * 5 O this is the only hydrate stable in neutral solution. A solution containing 170 grams of silver fluoride allowed to crystallise between 18O and 38O gives deliquescent prisms of a hydrate AgF,2H20 m. p. 42O decomposing t o the anhydrous fluoride. Its heat of solution is -1.5 cal. at. loo. The presence of hydrofluoric acid lowers the transition temperature of AgF,4H20 to AgF,2H20 5.5% of acid lowering it t o Oo. On evaporating a neutral saturated solution of silver fluoride at 26-36O hard highly refractive slightly yellow deliquescent crystals are obtained of a hydrate AgF,H,O. The heat of solution of this hydrate is +0*85 cal. a tINORGANIC CHEMISTRY.ii. 51 loo. By repeating this crystallisation a t the ordinaq temperature there is formed round each nucleus of the monohydrate volumin- ous colourless rosettes of a hydrate 3AgF,5H20. Both the latter forms are unstable in the presence of crystals of AgF,2H20 giving this hydrate and anhydrous silver fluoride. Each of these hydrates dried in a vacuum over sulphuric acid yields the anhydrous fluoride in an amorphous form. This can be obtained crystalline in the form of ruby-red cubes by evaporation in a vacuum of a solution of silver fluoride containing 5% of hydro- fluoric acid. It has heat of solution 4.3 ca.1. at 16O. Supersaturated solutions of the above hydrates attack silver more or less rapidly according to the temperature giving crystalline silver subfluoride Ag2F.W. G. Preparation of Metallic Chlorides and Sulphates in a Solid Soluble Colloidal Condition. LADISLAUS KARCZAU (D.R.-P. 263286).-Metallic chlorides or sulphates in a dry colloidal condi- tion can be prepared by the action of thionyl chloride sulphuryl chloride or chlorosulphonic acid on the metallic salts of organic carboxylic acids ; when calcium salicylate is warmed with thionyl chloride the mixture divides into two separable layers the under one consisting of colloidal calcium chloride which can be finally isolated by the addition of ether and dried in a vacuum. F. M. G. M. A Formation of Calcium Carbono-phosphate of the Paleo- lithic Age. P. TEILHARD DE CHARDIN (Conzpt. rend. 1913 157 1077-1079).-An account of a deposit of calcium phosphate in the grotto of Castillo (near Santander) exposed by excavations. The phosphate is found covering corroded calcite and appears to be localised ic a region of persistent dampness.Analyses are quoted showing its composition and examination of the deposit shows the similarity both in site and mineralogical character between these phosphates and t-hose of Quercy (compare Lacroix A. 1910 ii 622) and also the possibility of fixing a date for the commencement of the formation of these phosphates. Crystallographic and Thermal Investigation of t h e Ternary System Barium Chloride Potassium Chloride and Sodium Chloride. HANS GENSKY (Juhrb. Min. BeiZ.-Rd. 1913,36,513-558). -The author has made a detailed examination of the quilibrium relationships characteristic of the above ternary system by means of cooling curves f o r liquid mixtures containing the three chlorides in different proportions and by the investigation of the crystallo- graphic structures presented by the solid products.The data obtained for the three pairs of binary systems indicate that barium chloride and potassium chloride form a compound of the formula BaCl2,2KC1. The melting points recorded itre potassium chloride 7 7 5 O ; barium chloride 9 5 5 O ; BaC?12,2KC1 6630. The eutectic temperatures are 660° for BaC12,2KC1 + KCl and 6 5 2 O for BaC12,2KCl+ BaCI,. At 930° the singly refracting modification W. G. 4-2ii. 52 ABSTRACTS OF CHEMICAL PAPERS. of barium chloride which crystallism out at 9 5 5 O is transformed into a doubly refracting form.This is the usual monoclinic modification stable at ordinary temperatures. Barium chloride and sodium chloride yield freezing-point curves which intersect a t a point corresponding with 39 mols. % of barium chloride and a temperature of 654O. Potassium chloride and sodium chloride form mixed crystals and and freezing-point curve exhibits a minimum at about 50 mols. % of each constituent the temperature of the minimum being 660O. On cooling the mixed crystals they give rise to mixtures of potassium and sodium chloride at temperatures between 300° and 400O. The data obtained in the investigation of mixtures containing all three chlorides indicate the existence of a ternary eutectic a t about 540G. At this temperature the co-existing solid phases are barium chloride the compound BaC12,2KC1 and mixed crystals containing potassium and sodium chloride which represent the limiting mixture for the sodium chloride end of the series.The limiting mixed crystals rich in potassium chloride are resorbed a t a temperature higher than the eutectic. H. M. D. Allotropy of Cadmium. ERNST COHEN and W. D. HELDERMAN (Proc. K. Akad. JVetensch. Amsterdam 1913 16 485-489).-When cadmium is heated for a considerable time a t 70-looo in contact with a solution of cadmium sulphate its density diminishes to a small but mbasurable extent. Observations with a dilatometer containing 360 grams of cadmium which had been previously heated for twenty-four hours in contact with a solution of cadmium sulphate have shown that this change in the density is due to an enantiotropic transformation wh'ich occurs a t 64.9O.The observation affords an explanation of the disintegration which was found by Matthiessen and Bose t o occur in cadmium wires heated ,at 80°. H. M. D. An hydrous Sulphates VII. Cadmium Sulphate with Lithium Sodium and Potassium Sulphates. G. CALCAGNI and I). MAROTTA ( A t t i 12. Accad. Lincei 1913 [v] 22 ij 373-379).-The m. p. of cadmium sulphate is 1000° but there is a marked thermal effect a t 820° indicating a transformation at this temperature. Cadmium sulphate and lithium sulpliate beh'ave like the other sulphahes of bivalent metals hitherto described ; there is an eutectic a t 5 5 1 O (45% C'dSO,). The reactions which occur between the solid components of the system CdS0,-Na,SO are very complicated and numerous and the diagram of the system differs entirely from that given for it by Le Chatelier (Ann.des Mines 1897 [ix] 11 209). Three compounds are formed namely CdSO,,SNa,SO (at 351°) CdSO,,Na,SO a t (551°) and 3CdS04,Na2S0 (at 7 4 6 O ) . The com- pound CdS04,Na2S04 shows a transformation a t about 496O and the compound 3CdS04,Na,S0 has a transformation point a t about 456O. R. V. S.INORGANIC CHEMISTRY. ii. 53 The Behaviour of Lead Carbonate Basic Lead Carbonate and Lead Sulphate in Aqueous Solutions of Alkali Carboa- ates. FRIEDRICH AUERBACH and HANS PICK ( A d . Kuis. Gesundh. Amt. 1913 45 113-165. CompRre Pleissner A. 1908 ii 40; Herz A. 1911 ii 972).-In connexion with the fate of lead paints in the human body the behaviour of lead carbonate basic lead carbonate (white lead) and lead sulphate towards solutions of the alkali carbonates has been investigated. Lead carbonate is transformed into basic lead carbonate by solutions of potassium carbonate whilst the basic carbonate is changed to the normal carbonate by the action of potassium hydrogen carbonate.These two reactions lead to the equilibrium expressed by the equation 3PbC0 + K2C0 + 2H20 L= 2PbC03,Pb(OH)2 + 2KHC0,. The ratio of the potassium carbonate to the potassium hydrogen carbonate concentration is displaced in the direction of higher carbonate concentration as the total alkali concentration increases and in the direction of higher hydrogen carbonate concentration with increasing temperature. The two lead carbonates behave similarly towards solutions of sodium carbonate and sodium hydrogen carbonate as long as the total sodium concentration does not exceed 0.077.N. Above this concentration a double salt basic sodium lead carbonate NaPb2(C03)2-OH is formed the stability of which increases with increasing sodium concentration. This salt is quite different in appearance from the normal and basic lead carbonates being greyish-yellow in colour.The conditions necessary f o r its formation and decomposition were thoroughly investigated. By experiments carried out a t 18O and 37O using solutions in which the total sodium concentration varied up to 0*25W the existence domains of the two lead carbonates and of the double salt were ascertained and the constants calculated for the equilibria expressed hy the equations 2PbCO,,Pb(OH) + 2HC03’ t 3PbC0 + CO,” + 2H20 ; 3[NaPb2(C03)2-OH] + R 2 0 z 2[2PbC03,Pb(OH),] + HC03’+ CO,/’ -J- 3Na’.The constants had respectively the approximate values 32.5 12 and 0.05 a t 18O the concentrations of the substances on the right- hand side of the above equation being in the numerator. From these results the dissociation pressure of carbon dioxide in the change from normal to basic lead :arbonate was calculated t o be about 0.1 mm. Hg a t 18O. Also from these results the authors were able to devise methods for the preparation of pure basic lead carbonate and pure hasic sodium lead carbonate. Solutions of sodium carbonate and hydrogen carbonate which also contain varying quantities of sodium sulphate behave qualitatively towards normal and basic lead carbonate in the same way as sulphate-free solutions ; quantitatively the equilibrium con- centrations are altered in a regular manner.The formation of lead carbonate and a solution of sodium ZPbCO + Na’ + CO,” + H,O NaPb,(CO,),*OH +- HCO,! ;ii. 54 ABSTRACTS OF CHEMICAL PAPERS. sulphate by the action of a solution of sodium carbonate on lead sulphate is not a direct reaction. Basic lead carbonate is first formed and then basic sodium leaci carbonate which in the presence of sufficient lead sulphate is transformed into normal lead carbonate. Lead sulphate and sodium hydrogen carbonate interact according to the equation PbSO + 2NaHC03c PbCO + Na2S04 + CO + H,O from which it follows that lead carbonate suspended in a solution of sodium sulphate can be transformed into lead sulphate by the action of carbon dioxide under pressure.From the various equilibrium constants ascertained in the above experiments the following solubility products (at 18O) were calcu- lated [Pb"j[CO,//] = 10-13; [Pb"]3[C03~~]2[0H1]2= 3*5 x [Pb"]2[Na'][C03'~]2[OH~]=10-~1. T. S. P. The Behaviour of Lead Chromate and Basic Lead Chromate in Aqueous Solutions of Alkali Carbonates. FRIEDRICH AUERBACX and HANS PICK (Arb. Kais. Gemmdh.-Amt. 1913 45 166-190. Compare Lehmann Arch. Hyg. 1893 16 315; Golblum and Stoffella A. 1910 ii 698).-The authors have investi- gated the behaviour of lead chromate basic lead chromate and lead carbonate towards dilute solutions of sodium carbonate sodium hydrogen carbonate sodium chromate and mixtures of the same.I n dilute solutions of sodium carbonate the following equilibrium is formed 2PbCr0 + 2Na2C0 + H,O With increasing dilution and rise in temperature the equilibrium is displaced towards the right-hand side of the above equation. When the equilibrium is approached from the side of the basic lead chromate exactly the same results are not obtained as from the side of the normal lead chromate but this point was not further investigated. PbO,PbCrO + 2NaHC0 + Na,CrO,. The reversible reaction expressed by the equation PbCrO + Na2C0 Z? iPbCO + Nat2Cr04 only takes place in the presence of considerable quantities of hydrogen carbonate in solution otherwise basic lead chromate is formed. The existence domains of the two lead chromates and of lead carbonate in solutions in which the total sodium concentration was 0.05N and O*lN were ascertained a t 18O; the equilibrium constants for the following reactions 2PbCr0 + 2C0," + H20 PbO,PbCrO + CrO," + ZHCO,' ; SPbCO + CrO," + H,O PbO,PbCrO + 2HC0,' ; PbCrO + CO," 2 PbCO + CrO," were found to be respectively 0.057 1-95 and 0.23 the concen- trations of the substances on the right-hand side of the equations being in the numerator.Lead chromate enters into reversible reaction with a solution of sodium hydrogen carbonate according to the equation P bCrO + 2NaHC0 .- PbCO + Na,CrO + CO + H,O ;INORGANIC CHEMISTRY. ii. 55 equilibrium .is attained a t c much lower pressure of carbon dioxide than is the case with lead sulphate (compare preceding abstract) The following solubility products a t 1 8 O were calculated from the various equilibrium constants [Pb”] [CrO,”] = 2 x 10-14; [Pb”]2[Cr04”] [OH’]z= 6 x 10-35 (compare Beck and Stegmuller A 1910 ii 1067).T. S. P. The Amount of Lead given up by Sparingly Soluble Lead Salts to Solutions containing Sodium Hydrogen Carbonate. FRIEDRICH AUERBACH and HANS PICK (Arb. Rais. Gtsundh-Amt. 1913 45 191-196).-Dilute solutions 0-02N and 0*1N of sodium hydrogen carbonate which may also contain sodium chloride and free carbon dioxide dissolve only 0.3-0.4 mg. of lead per litre when shaken up a t 37O with lead carbonate lead chromate or basic lead chromate. It follows that injurious quantities of lead cannot be dissolved from the above compounds by the action of the pancreatic and intestinal juices in the human body. T.S. P. Alkaline Cuprothiosulphates. PIERRE DUTOIT (J. Chirn. Phgs 1913 11 650-673).-The author has studied the titration of copper salts (nitrate and sulphate) by thiosulphates (sodium potassium and calcium) making use of electrical conductivity electric potential and lowering of the freezing point of the solutions to determine the end points. The titrations are carried out in both ways that is adding the copper salt to the thiosulphate solution and by adding the thiosulphate to the copper salt. It is shown that by all methods the titration is complete when 0.9 mol. of a copper salt has been added to 2 mols. of the thio- sulphate or when 2.2 mols. of thiosulphate has been added t o 1 mol. of the copper salt.The author isolates from these reactions the salt 4CuS,0,,3Na,S,03,9H,0 which is the least soluble product formed. In the titrations two inflexion points are noted in the precipitation curves; the first is held to correspond with the formation of the complex Cu,S2O,,9M,S,O and the second to the complex Cu,S20,,5M,S,0,. I f the titration is carried out very slowly it is possible to get producks of the formula Cu,S203,M2S,0,. In these salts the copper is shown t o exist in the anion complex. J. F. S. The Chemical and Physical Nature of Colloidal Hydrous Aluminate Silicates. R. GANS (Centr. Him. 1913 699-712 72&-741).-Aluminate silicates with the composition 3-4 mol. SiO 1 mol. A1,0 1 mol. base (CaO MgO K20 Na,O) are pre- pared by the action of a solmion of alkali aluminate on silicic acid but not by the interaction of alkali silicate and aluminium hydroxide.They are colloidal and very readily dissociated and resemble the zeolitic silicate of soils and the artificial product called permutite. Detailed arguments are given in favour of regarding them as definite chemical compounds rather than as adsorption compounds. L. J. S.ii. 56 ABSTRACTS OF CHEMICAL PAPERS Hypereutectic Alloys of Iron and Carbon. H. HANEMANN (Zeitsch. anorg. Chem. 1913 84 1-23).-The investigation of Wittorf (A. 1912 ii 259) leads to the assumption of several iron carbides Fe,C Fe,C FeC and possibly FeC,. The experiments are open to the objection that the optical examination of the surface in contact with carbon vapour did not give the correct temperature of the molten mass.In the present experiments electrolytic iron and sugar charcoal are fused together stirred with a carbon rod and cast in iron chills after observing the temperature by an optical pyrorueter. The cementite contents obtained by analysing the chilled specimens give points which lie between the curves found by Wittorf and by Ruff (A. 1911 ii 897). The higher the temperature the less accurate is the determination of these points but the assumption of distinct breaks in the curve does not seem to be justified. On quenching from temperatures of 1400O and upwards graphite is always present as a primary product and not as a product of the decomposition of cementite. Microscopical examination shows that the cementite in quenched specimens crystallises radially from the centre indicating that it is formed during cooling.The mechanical separation of- crystais f?om the mother liquor at' a very high temperature as in Wittorf's experiments cannot be used to determine the composition of the solid phase as the separation is always imperfect. Mixtures of molten iron and carbon become very viscous above 1700° and heating to 2500O does not reduce the viscosity. A t 2500O a quenched specimen contains nearly 14% of carbon mostly as graphite entangled in the highly viscous liquid. During cooling the liquid becomes less viscous a t 1700O. Ruff's conclusion that the solubility of carbon again diminishes a t very high temperatures is not confirmed. The dendrites described by Wittorf as a carbide Fe,C are shown to be austenite ils they are converted into martensite by cooling in liquid air and into pearlits by annealing.The supposed carbides FeC and FeC are both regarded as graphite. After treatment with nitric acid the residual carbon is convertible into graphitic oxide and does not contain amorphous carbon as it would do if derived from a carbide. Influence of ailicon on the Solubility of Carbon in Iron. GEORQES CHARPY and ANDRI~ CORNU (Compt. rend. 1913 157 901-903. Compare A. 1913 ii 602).-The authors have deter- mined the solubility of carbon in samples of f erro-silicon containing varying amounts of silicon a t temperatures varying from 600° to 1000°. The results show that silicon causes a gradual diminution in the solubility of carbon in iron the solubility becoming prac- tically nil a t 900° if the silicon content is above 4% and a t 10000 if the silicon content exceeds 7%.At lower temperatures 2% of silicon suffices. W. G. Some Hydrothermal Syntheses. PAUL NIGGLI (Zeitsch. ano9.g. Chem. 1913 84 31-55. Compare Morey and Niugli A. 1913 ii 861).-A principal difficulty in hydrothermal syntheses is the C. H. D.INORGANIC CHEMISTRY. ii. 57 low velocity of reaction when amorphous (labile) substances are present. Such syntheses aim a t the formation of those minerals which can exist a t high temperatures in contact with aqueous solutions. Pressure is only used to maintain the system in the required condition. The products generally result from partial reactions in the amorphous mass and so may contain metastable crystals.The present preliminary syztheses do not therefore necessarily indicate the true stable phases. The apparatus used is that of Baur (A. 1911 ii 991). The materials used are amorphous silica potassium aluminate and silicate and aluminium and ferric hydroxides. The minerals identified are hzmatite potassium zegirite orthoclase and potassium nepheline hydrate. Potassium-aegirite I<,0,Fe203,4Si02 or KFeSi,O is not found in nature whilst its sodium analogue has not yet been obtained synthetically. Another product not definitely identified may be an anhydrous potassium nepheline. Amorphous material is always present. A t 450° hsmatite is obtained together with aluminium felspar free from iron. The presence of hzmatite in natural felspars is not to be attributed to alteration but to separation during cooling from an originally isomdrphous mixture in which ferric iron replaces alumina.The conversion of minerals in eruptive rocks into analcite zeolites and muscovite corresponds with the hydrothermal changes during cooling. Hzmatite occurs in good six-sided leaflets. C. H. D. Alterability and Instability of Cobaltarnmines. NILRATAN DHAR (Zeitsch. anoyg. Chem. 1913 84 224-226).-Great care must bs exercised in the preparation of the cobaltammines. The use of rather more dilute ammonia in the preparation of dinitro- tetramminecobalt chloride than is prescribed in text-books leads to the formation of trinitrotriamminecobalt chloride whilst an increase in the proportions of ammonia and ammonium chloride leads to the formation of nitropenta-amminecobalt chloride.Carb ona totetra-ammineco balt nitrate [Co ( NH3),C0,]N0,,~H20 is slowly decomposed by boiling with water. C. H. D. Ternary Alloys of Nickel-Gold-Silver. P. DE CESARIS (Ganxettn 1913 43 ii 609-620).-These alloys have been investigated by methods similar to those used for nickel-copper-silver alloys (A. 1913 ii 1061) similar results being obtained. The mutual solubilities of nickel and gold a t the eutectic tem- perature are somewhat higher than the values given by Levin (A. 1905 ii 532) gold dissolving about 8% of nickel and the latter about 20% of gold. The space-diagram is described and reproductions of micro- photographs given. T. H. P. The Neutralisation of Chromic Acid. L. MARGAILLAN (Compt. rend. 1913 157 994-995).-h study of the neutralisation of chromic acid by sodium hydroxide the acidity of the solutionii.58 ABSTRACTS OF CHEMICAL PAPERS. being measured by determining the E.M.F. of a ile in which intervenes the half element h j drogenised platinum psolution the other half being mercury 1 calomel I NI10-HCI. The curves given show by sudden alteration in direction the two acid functions of chromic acid; these two points on tlic curves correspond with the end points obtained with helianthine and phenolphthalein as indicators respectively. W. G. 180- and Hetero-poly-salts. IX. Molybdo-phosphites -hypophosphites and -hypophosphates. A RTHUR ROSENHEIM WALTER WEINBERG and JAKOB PINSKER (Zeitsch. anorg. Chem. 1913 84 217-223. Compare A. 1913 i 413).-The oxygen atoms of the alkylarsinic acids are replaceable by MOO or Mo207 residues and the more alkylated the acid the smaller the number of molybdic residues taken k t o the compound.Alkylphosphinic acids are difficult to prepare but phosphorous and hypophosphorous acids may be regarded as derived from them by the replacement of alkyl by hydrogen. An acid solution of ammonium molybdate is precipitated by phosphorous acid and the yellow crystalline precipitate which has the composition (NH,),[HP(Mo~O~)~],~H,O may be used as a delicate test f o r phosphorous acid. The sodium salt N~,[HP(Mo,O~)~],~IH,O is slightly more soluble. It loses all its water a t l l O o . Conductivity measurements show the absence of an acid salt and the salts must be regarded as containing the anion [pr0207)3]." The acid like phosphorous acid is dibasic.The potassium salt is R,[HP(MO,O,)~,~ 1H20 and the yuanidiitium salt Corresponding tungsten compounds have not been obtained the tungsten salts being tribasic as Na3[P(W207)31,1 6H,O. Guaiiidinium molybdoarsenite (CN3H,)3[As(Mo207),],H20 has a similar constitution. A mixturd of sodium hypophosphite (1 mol.) and sodium molybdate (4 mols.) gives precipitates with ammonium potassium or guanidinium chloride. The ammonium salt has the composition NH,[H2P(Mo207)2],6H,0 and these salts may be regarded as derived from the hypophosphite anion PzJ' by replacement of oxygen atoms by molybdic acid residues. Sodium hypophosphate NaHP03,2H,0 (1 mol.) sodium hydroxide (1 mol.) and molybdic acid (6 mols.) yield a yellow crystalline sodium salt Na,[P(Mo20,),],8H,0.PAUL PASCAL (Compt. rend. 1913 157 932-934).-A large number of uranyl salts can be converted into complex salts by the addition of the corresponding alkali salts and according to the acid radicle they possess one of two con- stitutions M,[U02X6] and M,[UO,X,]. The first type where the bivalent radicle UO possesses the maximum index of co-ordination is always very stable resisting hydrolysis and having the reactions of uranium completely masked. (CN3H6)2[HP(M0207)31* C. H. D. Complex Salts of Uranium.IKORGANIC CHEMISTRY. ii. 59 The second type behaves in dilute solution as a double salt and to check dissociation a large excess of the corresponding alkali salt is often necessary. The author has studied the pyrophosphates and the cyanates. On dissolving uranyl pyrophosphate in sodium pyrophosphate solution the freezing point rises to a maximum corresponding with 3Na,P207,(U0,)2P207 and then descends to a minimum a t 2Na4P207,(U0,)2P20T up to which stage the characteristic reactions of uranyl salts are not obtainable.If this solution is evaporated and the gummy residue treated with alcohol a very soluble hygre scopic powder is obtained having the constitution Nad (UO,) 2(P207)31 6H2*. From a solution of sodium pyrophosphate saturated with uranyl pyrophosphate there is precipitated by alcohol a yellow powder Na6U0,[(U02)2(P207)3J,~zH20 which rapidly passes into Na,(UO,),P,O,,H,O insoluble in water. A mixture of alcoholic solutions of potassium and uranyl cyanates gives a microcrystalline precipitate having the constitu- tion K,[UO,( CNO),] very soluble in water gradually dissolving in this solvent to yield an anhydrous orange-yellow double salt KCN0,2U02(CNO),. An excess of alkali cyanate added to the preceding solution gives a golden-yellow precipitate of a double salt.KCNO,UO,(CNO) whilst an excess of uranyl cyanate in slightly alcoholic solution precipitates anhydrous uranyl cyanate as a golden-yellow powder UO,(CNO),. The Isomerism of t h e Stannic Acide. 111. WERNER MECKLENBURG (Zeitsch. nnorg. Chem 1913 84 121-143. Compare A. 1912 ii 355).-The peptonisation of a stannic acid preparation does not depend directly on the size of its primary particles. Readily peptonised prepara-tions are obtained by using nitric acid containing hydrochloric acid. The greater the concentration of the nitric and the less that of the hydrochloric acid the more completely gelatinised is the precipitate.Hydrochloric acid also lessens the oxidation causing the product to contain stannous as well as stannic compounds but in more concentrated solutions the quantity of stannous compound formed is less. If a solution containing stannous salts is heated on the water-bath complete oxidation to the stannk condition takes place violently. The p r e cipitate has sometimes a crystalline appearance but cannot be recognised as crystalline under the microscope. The peptonising action of the reagents examined on the same stannic acid precipitate decreases in the order 22\THC1-+ 22%HC1 -+ 2NHN0 -+ alcohol -+ NH,SO -+ water -j. ether. The preparations have not shown any considerable change in four years.The colloidal solutions obtained by peptonisation have been examined by Tyndall’s method. Hydrochloric acid favours the formation of fine particles. The precipitate contains adsorbed hydrochloric acid. The protective action of this electrolyte closely resembles that of a protective colloid. Alkali hydroxide is also a protective electrolyte. C. H. D. W. G.ii. 60 ABSTRACTS OF CHEMICAL PAPERS. Zirconium Hypophosphite a Zirconium Salt Sensitive to Light. 0. HAUSER and H. HERZFELD (Zeilsch. anorg. Chew. 1913 84 92-94).-Zirconium phosphate Zr(PO,),,H,O is readily obtained by precipitation. Zirconium hypophosphite Zr(OPH20),,H,0 is obtained by add- ing hypophosphorous acid t o a solution of zirconium nitrate until the precipitate has completely redissolved and then adding alcohol.It forms colourless highly refracting crystals which become deep violet very rapidly in direct sudight or in the course of several weeks in diffused daylight without any other perceptible change. C. H. D. Organosols of Metals of t h e Platinum Group. CONRAD AYBERGER (Rolloid-Zeitsch. 1913 13 310-313 Compare A. 19 12 ii 1053 1059).-The preparation of organosols of metallic palladium and platinum is described in which lanolin plays the part of a protective colloid. The lanolin is impregnated with aqueous solutions of salts of bivalent platinum or palladium and the resulting paste triturated with the calculated quantity of alkali metal hydroxide or carbonate. The hydroxides of the platinum metals are then reduced by addition of hydrazine hydrate. On treatment with light petroleum or chloroform the palladium or platinum dissolves together with the lanolin and the colloidal metals can be precipitated from these solutions by the addition of alcohol. Since only a portion of the lanolin separates out on the addition of alcohol this process serves for the concentration of the metal in the preparation. The pasty black substances which are obtained in this way dissolve very readily in chloroform and carbon tetrachloride and are also readily soluble in ethyl ether light petroleum liquid paraffin and fatty oils. The liquid organosols appear to be quite transparent when examined in a very thin layer a. M. u. Organosols of the Hydroxides of Bivalent Platinum and Palladium. CONRAD AMBERCER (Kolloid-Zeitsch. 19 13 13 313-317. Compare preceding abstract) .-Colloidal hydroxides of platinum and palladium in admixture with lanolin as protective colloid have been prepared by the method described in the previous paper. I n thi,s case the addition of hydrazine hydrate is omitted. The pasty substances obtained are readily soluble in light petroleum and other organic liquids which dissolve lanolin. The solution of palladium hydroxide in liquid paraffin has found therapeutic application in the treatment of obesity. The preparation of a palladium oleate organosol is also described. The only modification of the process consists in the substitution of potassium oleate for the hydroxide or carbonate. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9140605046

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

hf INERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 61 Water and the Volcanic Gases. ARTHUR L. DAY and E. S. SHEPHERD (Compt. rend. 1913 157 958-961).-A study of the volcanic gases collected from the crater of Kilauea during the summer of 1912. Contrary to the results recorded by Brun (com- pare Recherches exhalaison volcaihique 191 l) the authors obtained abundant evidence of the presence of water in these gases by inserting a collecting tube into crevices in the lava behind the flames and withdrawing a sample by means of a pump. The gases collected consisted mainly of carbon dioxide and sulphur dioxide with small quantities of carbon monoxide hydrogen and nitrogen. The water condensed in the sample tube was found to contain fluorine chlorine sodium potassium calcium iron and aluminium in the form of dissolved salts and free sulphur but no titanium.W. G. Conclusions to be Drawn from the AnaIysis of the Gases from t h e Crater of Kilauea. ARTEUR L. DAY and E. 5. SHEPHERD (Compt. rend. 191 3 157 1027-1030. Compare preceding abstract). -In the gases as collected analysis reveals the presence of gases which are unable to co-exist a t a temperature equal t o or above 1000°. Consequently reactions will take place particularly a t the surface with the development of heat and the authors have found temperature variations of as much as 115O. The gases exhaled undoubtedly contain water 300 cx. having been condensed in the experimental tubes. The visible volcanic cloud is constituted essentially by free sulphur and not by chlorides and contains both sulphur dioxide and sulphur trioxide.The analyses of the gases show that the chlorine content is less than 0.02%. The nitrogen collected contains no argon this being further proof of the absence of atmospheric contamination W. G. Bournonite from St. Kreue Aleace. Huao BUCEIN~ ( ~ U i t t Geol. Londesanst. Elsass-Lothringen 19 13 8 201-21 3).-Crynt allo- graphic descriptions are given of bournonite and xanthoconite from St. Kreuz near Markirch. Analysis by L. Durr of the bournonite gave Pb. Cu. Sb. S . Total. Sp. g ~ . 43'35 12.86 24.53 19-17 99'91 5.81 L. J. S. Dolomite (variety Miemite) from Croatia. FR. TU~AN (Jalwb. Min.. 1913 ii Rd. 377-378; from SOC. Sci. Nat. Croat. 1913 25 194).-The rniemite variety of dolomite (anal. I) long known from Curoatia occurs as small veins in serpentine and trachyte a t Mount Fruska.The pisolitea measure up to 5 cm. across and have polyhedral outlines; in cross- It is pale green with a pisolitic structure.ii. 62 ABSTRACTS OF CHEMICAL PAPERS. sectio,n they show a concentric structure and usually a nucleus of decomposed dacite but in one instance of magnesite (anal. 11). Occasionally the mineral occurs as masses with a banded struc- ture 111. SiO,. A1,0,. Fe,O FeO. NiO. MuO. CizO. QO. CO,. HoO. Total. 1. 0.28 0.18 - 3'17 0.23 0.12 30.01 17.63 47.58 - 99'20 11. 0.59 0.01 3.62 1.03 - trace 6'04 39'80 48.71 0.63 100'63 111. 2'53 0.38 - 1'21 trace trace 29.58 20'28 45.56 - 99'54 L. J. S. Cerussite from 0 tavi German South-West Africa. HEDWIG DUBIGK (Diss. Munster i.W. 1913 ; JaJleb. Mi%. Bd.-Bd. 1913 36 214-246).-A brief account is given of the deposits of copper and lead ores in the Otavi Mountains. Beautifully crystallised speci- mens of cerussite from Tsumeb show associated malachite and chessylite on a matrix of aplite and. cellular dolomite. The axial ratios of the crystals are a b c = 0.610160 1 0'723182. Refrac- tive indices (Na-light) a = 1.80258 The optic axial angle increases with the temperature 2E(Na) a t 2 5 O being 17O50/ and a t 180° the value is 22O45/. Analysis of pure crystals gave 1'110. CO,. Insol. Total. 83.27 16.64 0'24 100-15 = 2.07420 y = 207618. L. J. S. Natural Chilean Aluminium Sulpbate. ATILIO A. BADO (Anal. SOC. Quim. Argentina 1913 1 129 -13O).-Keramohalite or alunogen occurring as a white fibrous mass soluble in water gave on analysis Al,O,.CaO. Na,O. SO,. H,O. Total. 17.76 0.05 0.04 37.38 44.77 100'00 agreeing with the formula Al,0(S0,),,12H20. G. D. L. Yukonite a New Hydrous Arsenate of Iron and Calcium from Yukon Canada. JOSEPH B. TYRRELL and RICHARD P. D. GRAHAM ( Y r m s . Boy. SOC. Ca?zudct 1913 [3] 7 sect. 4).-The mineral described occurs as small irregular masses with oxidised galena in a quartz-vein near Tagish Lake in the southern portion of Yukon territory. It is brownish-black resinous and amorphous breaking with a smooth conchoidal fracture thus resembling pitticite in appearance. It is very brittle and under water it breaks up with a crackling noise giving off a considerable quantity of gas which consists mainly of carbon dioxide.Whilst immersed in water D increases from 2.65 t o 2.86. Ths mineral is complefxly soluble in hydrochIoric acid and it fuses readily to a black magnetic globule giving off fumes of arsenic oxide. About half of the total water is lost in a vacuum or a t looo whilst the remainder is expelled only at a high temperature together with some amenic oxide. The f ollo wing analysis corresponds with 2Ca,A~08,3Fe2,As,08,5Fe,(0H)6,23H,0,MINERALOGICAL CHEMISTRY. ii. 63 or nearly (C~,Fq,)As20,~Fe2(OH),,5H,0. This composition is similar to that of arseniosiderite with the addition of water. CaO. Fe,O,. Rs,O,. H,O. Total. 10.07 36'26 33-94 20.28 100.55 Coating the yukonite is a yellow ochreous material of apparently the same composition and embedded in this are small green fibres of symplesite.L. J. S. GIOVANNI D' ACIIIARDI (Jahd. Min. 1913 ii fief. 381 ; from Proc. Verb. soc. l'oscana sci. flat. 1912 Reprint 5 pp.).-Radially-fibrous anthophyllite with a silky lustre and salmon colour is found in quantity in the magnesite mine a t San Piero in Campo. It exhibits all the characters of an ortho- rhombic amphibole. Analysis agrees with (Mg,Fe)SiO,. Anthophgllite from Elba. H,O H,O SiO,. Al,O,. FeO. MgO. Na,O. (at 160*). (ign.). Total. Sp. gr. 58.75 1-27 5-60 31.53 0.51 0 2 5 1.70 99.61 2.95 L. J. S. Tremolite from Elba. PIERO ALOISI (Jahrb. Min. 1913 ii Ref. 382 ; from Yroc. Verb. Soc. Toscana Sci. Nat. 1912 Reprint 4 pp.).- Fibrous to columnar tremolite fills crevices in peridotite on Monte Perone. Analysis gave SiO,. A1,0,. FeO.CaO. BIg0. Ns,O. K,O. H,O. Total. 54'21 0.74 2.22 13-56 24'86 1.10 0'35 2.54 99-58 L. J. S. Magnesia-Tourmalines. KARL EECU'HT (Diss. Beidelberg 19 13 1-75) ; ERNST A. WULFING and KARL BECHT (Sitz.-Ber. Heidelberger Akad. Wiss. 1913 A Abh. 20 1-lo).-Determinations were made of the crystallographic and optical constants of a number of brown magnesia-tourmahes. Analyses by M. Dittrich are given of the following I yellowish-brown from Macomb New York; 11 dark brown from Post Stmjo East Africa; 111 pale brown from Ceylon; IV medium brown from Ceylon; V dark brown from Ceylon B,03 FiO> Ti203 AI2O3. FezOJ. FeO. MgO. CaO. Sa2O. LitO. KzO. H2O. F. Total. 81). gr. 111. [11'36] 35 46 - 2 9 . 3 - 0 46 14.04 2 1 3 0'23 11.d. 0 20 3.55 11 d. 100'00 3'059 IV. [l0*57] 36-51 11.d.30.00 - 0.74 12.64 3'91 0.72 n d. 0 5 t 4.17 n d. 100'00 3.059 V. 11'47 35'15 3'43 25'30 1%; 5'21 10.16 3'07 0'53 0'15 0.28 2 SS 0'12 100'22 3'142 I. 10.23 37.05 0'56 2S.61 d.44 1'31 13-66 2.97 1-43 - 0.31 3'05 1'23 loo's9 3.066 11. 11'11 36'98 0'02 325'7 - 3.55 9.50 0.26 1 1 2 - n.19 20s 0.14 99.31 3.055 The composition is expressed as the isomorphous mixing of the three molecules Sil2B6A1,,Na,H& Si,,B6A1,,Fe,H,06 vd Si,2B,A~,,Mg,2H606 (A. 191 3 ii 7 18). Tables ar0 given showing the variation of the crystallographic and optical constants with the density of the chemical composition. J o n ~ R. SCRIVENOR (Min. Mi. 1913 17 51-52).-The samples examined have the form of a pale green sand obtained as a concentrate from the Yong Choon district in province Kwang Tung.Mixed with it are small quanti- ties of malachite calcite quartz etc. The grains are optically L. J. 8. Calcium-iron Garnet from China.ii. 64 ABSTRACTS OF CHEMICAL PAPERS. isotropic and occasionally show cubic forms. The mineral is attacked by cold hydrochloric acid and when powdered it is readily and completely decomposed by hot acid. Analysis of a cleaned sample gave Loss on SiO,. Fe,O,. AI,O,. CnO. MgO. ignition. Total. Sp. gr. 40.26 28'62 2.61 28.29 trace 0.94 100.72 3'69 proving the mineral to be andradite but the fact that it is so readily decomposed by acid before ignition is remarkable for a garnet. L. J. S. Hodgkinsonite a New Mineral from Franklin Furnace New Jersey. C. PALACHE and W. T. SCHALLEB (J. Washington Acad. Sci. 1913 3 474-478).-This occurs together with bnrytes and native copper in films and thin seams in the granular willemite- franklinite ore.It is bright pink t o pale reddish-brown with a vitreous lustre and white streak. D 3-91 H nearly 5. The crystals are monoclinic (a b c = 1.539 1 1.1165 ; p =84O33&') with an acute pyramidal habit and a perfect basal cleavage. The optic axial plane is parallel to the plane of symmetry and the mean refractive index is 1-73. The mineral decrepitates when heated and fuses to a brown enamel; no water is lost a t l l O o . It is readily soluble in acid yielding gelatinous silica. Analysis gives the formula SRO,SiO,,H,O or nearly Mn0,2Zn0,Si02,H20 or Mn(ZnOH),Si@,. SiO,. MnO. ZnO. CaO. MgO. H,O. Total. 19-86 20'68 52.93 0.93 0.04 5.77 100'21 L.J. S. Presence of Manganese Cobalt and Nickel in Coloured Clays. L. AZEMA (Bull. SOC. fiunq. M'in -1913 36 133-135).- The minerals examined include montmorillonite from Bordes (A 1913 ii 784) and other French localities and from Branchville Connecticut ; also delanouite dubuissonite and landevanite. All these contain traces of manganese and with the exception of monb morillonite from Branchville and landevanite also traces of cobalt and-nickel. These coloured clays usually occur in proximity to deposits of manganese ores. Psilomelane from various French localities was found t o contain besides cobalt also appreciable traces of nickel. L. J. S. Meteoric Stones of Baroti India and Wittekrantz South Africa,. GEORGE T. PRIOR (Min. Mag. 1913 17 22-32).-A meteorite fell a t Baroti Bilaspur district Punjab on September 15th 1910 and several fragments of the stone the largest weighing 4$ lbs.were collected. D 3.54. A few chondrules are visible. From analyses of the portions of the powdered stone attracted and unattracted by a magnetic comb the bulk-analysis I is deduced. A partial analysis of the soluble silicate in the unattracted portionMINERALOGICAL CHEMISTRY. ii. 65 gave 3Mg,Si0,1FqSi04 as the composition of the olivine. mineral composition is under Ia The Metallic. FeS. A Fe. S. SiO,. TiO,. A1,0,. Fe,O,. Cr,O,. I. 8-13 0.75 0.03 4.32 2'47 39.68 0'16 2'40 0'44 0'18 11. 7.65 0.75 0.02 2.20 1'26 41'12 0.17 2-54 0.48 0'36 FeO. MnO. CaO. MgO. Na,O. K,O. P,O,. H,O. Total. t I. 13.93 trace 1.79 24.71 0.91 0.04 0.25 0.17 100'42 11.14-51 0.15 2'12 25.40 1.16 0'14 0.16 0.16 100.35 Magnet- Chrom- Apat- Oli- Troil- Nickel- Pelspar. ite. Ilmenite. ite. ite? Bronzite. vine. ite. iron. Water. Ia. 10.25 0.63 0.31 0.27 0-56 30-38 42-12 6.79 8.91 0.17 IIa. 11.95 0.70 0.32 0.52 0.37 26-89 47'42 3'46 8-42 0.16 The meteoric stone of Wittekrantz Beaufort West Cape Colony fell on December 9th 1880 and fragments weighing 44 lbs. and 113 grams were preserved. D 3.49. Chondrules are few. Bulk- analysis (combined result of the analyses of the attracted and unab tracted portions) under 11 and the mineral composition under IIu. The olivine has the composition 3Mg2Si04,Fe@0,. The Remarkable Similarity in Chemical and Mineral Compoaition of Chondritic Meteoric Stones. GEORGE T. PRIOR (Min. Mag 1913 17 33-38).-The close similarity between the Baroti and Wittekrantz meteorites (preceding abstract) suggested a comparison with other chondritic meteoric stones and the resulb of previously-published analyses of forty-one such stones are tabu- lated. The mineral composition approximates in all cases to the following mean value L.J. S. Rickel-iron Olivine Bronzite (with (with (with Felspar Chromite. Fe :Ni=lO 1). Troilite. Mg Pe=3 1). Mg Fe=4 1). (oligoclase). etc. 9 6 44 30 10 1"1 Although so similar in ehemical and mineral composition these stones have been assigned to a number of different groups in the Brezina and quantitative rock classifications (A. 1912 ii 361) the differences in the latter case being due to errors in analysis more especially with regard to the allotment of the iron as metal as oxide or as sulphide. L. J. 5. Mineral Water from Deutsch- Jassnik Moravia. M. GLASER (T~lch. Illin. Petr. Mitt. 1912 [i.e. 19131 31 659-662).-Detailed analyses arc given of the water from two springs. They show 1.3056 and 2.8801 grams Ca(HCO& 22.6984 and 24.1074 grams free carbon dioxide respectively together with small amounts of other substances in 10,000 grams of water. L. J. S. VOL. CVI. ii. 5

ISSN:0368-1769    

DOI:10.1039/CA9140605061

出版商:RSC    

年代:1914

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ii. 66 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. The Foundations of Acidimetry and Alkalimetry. A. THIEL (Ber. Deut. Pharm. G‘es. 1913 23 578-596).-A criticism of the views put forward by Crato (A. 1913 ii 665). The author also gives an account of the interpretation which is afforded by the ionic theory of the behaviour of indicators in the volumetric estima- tion of acids and bases. H. M. D. Physico-chemical Volumetric Analyses. DoMINaA c. LANZA (Anal. Soc. Quina. AvgeFntinCt 1913 1 200-214).-The c3urse of neutralisation is followed by means of memurements of conduc- tivity. Figures are quoted for a mixture of hydrochloric and acetic acids sulphuric acid zinc chloride and morphine hydro- chloride. G. D. L. Pyro-analysis of Drugs. L. ROSENTHALER (Ber. Deut. Phacrm. Ges.1913 23 577. Compare A 1911 ii 948).-A piece of appar- atus for use in this method is described. The drug is placed a t the bottom of a tesbtube and covered with a layer of glass-wool; a tube slightly smaller in diameter than the test-tube is inserted in the latter the lower end of the tube resting on the layer of glass- wool whilst the upper end is connected with an exhaust pump. A piece of rubber tubing slipped over the tube f o m an air-tight joint between the mouth of the test-tube and the tube. The sublimate formed collects in the tube when the air is exhausted from the apparatus. w. P. s. o-Tolidine as a Reagent for the Colorimetric Estimation of Small Quantities of Free Chlorine. J. W. ELLMS and S. J. HAUSER (J. Ifid. Eng. Cham. 1913 5 914-917).-A hydrochloric acid solution of o-tolidine yields a yellow coloration with small quantities of free chlorine and the reaction may be used for the estimation of the latter in water which has been treated with the gas.The coloration develops in about three minutes is permanent for a t least thirty minutes and is not affected by the presence of the salts usually present in drinking waters. One hundred C.C. of the water are treated with 1 C.C. of a 0.1% o-tolidine solution in 10% hydrochloric acid and after five minutes the coloration obtained is compared with that produced by known quantities of chlorine under similar conditions. The coloration may be obtained in as small a quantity of chlorine as 0.005 part per million. w. P. s. Estimation of Chlorine i n the Blood.H. ROG~E and C . FRITBCH (Biochem. Zeitsch. 1913 58 175-176~.-Polemical. A reply to Bang’s criticisms of the authors’ method (A. 1913 ii 872). 8. B. 8.ANALYTICAL CHEMISTRY. ii. 67 Iodometric Estimation of Iodine Present as Iodide. ERICH MULLER and GUSTAV WEGELIN (Zeitsch. anuz. Chew. 1913 53 20-28).-When excess of potassium iodate is added to an acid solution of an iodide the iodine liberated conglomerates and is difficult to titrate. By the following device accurate results can be obtained. The solution to be tested is placed in a stoppered bottle 10 C.C. of 10% sulphuric acid are added and the liquid is covered with a layer of benzene. After adding excess of potassium iodate and thorough shaking a solution of 4 grams of anhydrous borax iu water is added and finally 3 grams of potassium iodide (not strictly necessary however).The iodine is now titrated by means of AT / 10-arsenious acid with constant ehaking. Thiosulphate should not be employed. L. DE I(. Estimation of the Sulphates in Wine by a Physico- chemical Volumetric Method. PAUL DUTOIT and MARCEL DUBOUX (BUZZ. SOC. chim 1913 [iv] 13 1068-1074).-A reply to Bruno and Turquand d’Auzay (compare Bull. SOC. chim. 1913 [iv] 13 24) in which the authors reaffirm the accuracy of their physicochemical volumetric method for estimating sulphates in wines by the; use of barium hydroxide (compare A. 1908 ii 781 892). W. G. Estimation of Total Sulphurous Acid in Wine. L. L ~ Y (Ann. FuZttiJ 19 13 6 595).-The method depends on the oxidation of sulphur dioxide by hydrogen peroxide.Fifty C.C. of the wine are mixed in a stoppered flask with 2 grams of barium peroxide; after eighteen hours’ contact hydrochloric acid is run in until bubbles of gas are no longer evolved ammonium chloride is added the mixture boiled and the barium sulphate collected ignited and weighed. The quantity of sulphate present in the wine is estimated in a separate portion of the sample and the difference between the two estimations is calculated into sulphur dioxide. W. P. 8. New Method for the Volumetric Estimation of Thiosulphate in the Presence of Sulphite. J. BODNAR (&itsoh. anal. Chm. 1913 53 37-41).-The process is based on the fact that thio- sulphates when treated with silver nitrate yield in the end silver sulphide and free sulphuric acid. After removing the excess of silver by means of sodium chloride the acidity can be determined by standard alkali.Sulphites do not interfere. L. DE K Detection and Estimation of Minute Traces of Selenious Acid. JULIUS MEYER and WILHELM VON GARN (Zeitsch. anal. Chem. 1913 53 29-33. Compare A 1913 ii 948).-1nto two cylinders are put 5 C.C. of the solution to be tested and 5 C.C. of a solution of selenious acid of approximately the same strength respectively ; 70 C.C. of water are added also a drop of gum arabic and 5 C.C. of 5-2ii. 68 ABSTRACTS OF CHEMICAL PAPERS. 5% hydrochloric acid and then the whole is diluted to 99 C.C. After adding to each tube 1 C.C. of potassium iodide solution and stirring vigorously the colo,rations which are due to iodine and to colloidal selenium are after five minutes compared in a Krum colorimeter.Addition of starch solutions may be useful. L. DE K. Comparison of the Kjeldahl-Gunning-Arnold Method with the Kjeldahl and Gunning Methods of Estimating Nitrogen. T. C. TRESCOT (J. Ind. Eng. Chem. 1913 5 914-915).--The Kjeldahl-Gunning-Arnold method was found to yield more trust- worthy resulta than the Kjeldahl or Gunning methods. W. P. s. Apparatus for Use in the Estimation of Nitrogen in Soils by Kjeldabl’s Method. ALBERT HUTIN (Ann. Chim. anal. 1913 18 426-428).-0wing to the small quantity of nitrogen present in soils a relatively large portion of the sample must be taken for the estimation and the insoluble substances (sand etc.) remain- ing after the digestion cause difficulties to arise in the subsequent distillation of the ammonia.It is therefore recommended that t8he acid digestion mixture should be transferred to a flask and steam-distilled after the addition of sodium hydroxide. The flask is closed with a rubber stopper through which pass the stem of a tapped funnel a tube for the introduction of superheated steam a delivery tube which is connected with a condenser and a tube reaching to the bottom of the flask; the outer end of the latter tube is connected with a pump so that the contents of the flask may be withdrawn a t the end of the distillation. w. P. s. Apparatus for Use in the Distillation of Ammonia in Kjeldahl’s Method. EMM. POZZI-ESCOT (Bull. Assoc. Chim. Sucr. Dist. 1913 31 235-236).-A description of a still-head is given ; it consists of an elongated bulb provided with a stem which passes through the stopper of the distillation flask.This stem extends upwards into the bulb itself and is then bent downwards in the form of a spiral. The vapours from the flask pass through the spiral then enter the bulb and leave the latter by a tube a t the top. Any alkaline spray escaping from the flask is effectually collected a t the lower part of the bulb and returns with other condensed liquid to the flask a narrow tube leading from the bottom of the bulb and passing down the centre of thO stem being provided for this purpose. w. P. s. Iodometric Estimation of Arsenic in Iron and in Iron Ores after Precipitation with Hypophosphorous Acid. L. BRANDT (Chern. Zeit. 1913 37 1445-1447 147 1-1472 1496 -14969.- Of ores 10 grams are mixed with 8 grains of potassium chlorate and 60 C.C.of strong hydrochloric acid and the whole is heated until all but some siliceous matter is dissolved. After diluting with water the filtrate is made up t o about 120 C.C. Of iron or steel samples 10 grams are dissolved in dilute nitric acid and thenANALYTICAL CHEMISTRY. ii. 69 evaporated to dryness with addition of sulphuric acid ; the residue is then dissolved in about 125 C.C. of dilute hydrochloric acid. In either case the solution is heated to boiling and the iron reduced by adding sodium hypophosphite which then also yields a deposit of metallic arsenic. For iron ores 20 grams and for iron or steels 40 grams will suffice. Towards the end another 35 C.C. of hydrochloric acid are also added.After washing the filter and contents are removed and treated with 15 C.C. (or less) of a solution containing 6 grams of potassium iodate and 30 grams of potassium iodide in 500 C.C. Owing to a trace of free iodine always present the arsenic dissolves slowly a t first more rapidly afterwards with liberation of iodine which must then be a t once titrated with tliiosulphate. I n the circumstances 1 atom of Method of Forming Realgar and its Influence on the Separation of Arsenic from Tin. H. CABON and D. RAQUET (An92. Chim. unal. 1913 18 432-434).-When a mixture of stannous sulphide and arsenic trisulpliide is boiled with hydrochloric acid the stannous sulphide is converted into stannous chloride whilst the arsenic trisulphidc is reduced to the disulphide and remains insoluble; the disulphide is also insoluble in ammonia. In the case of a precipitate containing tin antimony arsenic and gold sulphides it is recommended that the tin and antimony sulphides should be separated by boiling the mixture with hydrochloric acid; the insoluble portion is then oxidised with nitric acid when the arsenic is obtained in solution whilst the gold sulphide still remains insoluble.w. P. s. The Dehydration and Recovery of Silica in Analysis. F. A. GOOCH F. C. RECKERT and S. 8. KUZIRIAN (Amsr. J. Sci. 1913 [iv] 36 598-604).-After a large number of experiments the authors recommend drying the silica as recovered by evaporation on the steam-bath a t a temperature of l l O o before attempting to remove the soluble salts with dilute hydrochloric acid.Half an hour's ignition over a Bunsen burner is then sufficient to drive off the last traces of water. Should there be a further tendency to lose weight when heated over the blast this is not caused by water not yet expelled but by alkali compounds which should be removed by the usual treatment with sulphuric and Elementary Analysis of Substances containing Nitrogen. WALTER EICHHORN (Ch6WZ. Zd. 1913 37 1465).-Tf the copper spiral used in elementary analyses is reduced in a current of hydrogen and allowed to cool in that gas it retains sufficient hydrogen to affect seriously the analytical results. Allowing the spiral to cool in a stream of nitrogen does not improve matters much; it is necessary to heat strongly in nitrogen after the reduction with hydrogen is complete and then to allow to cool in nitrogen in order to obtain good results.The precipitate is collected on an asbestos filter. iocline=l atom of arsenic. L. DE K. hydrofluoric acids and allowed for. L. DE K. T. S. P.ii. 70 ABSTRACTS OF CHEMICAL PAPERS. Thioacetic Acid as a Reagent. NAZARIO ALVAREZ (Anal. SOC. Quim. Argentinu 19 13 1 122-1 28).-A solution of ammonium thioacetate is used as a source of hydrogen sulphide. The author claims that the nascent agent is more effective than the gas. I n applying it the thioacetate is added t o a solution of the metal salts in excess of hydrochloric acid. G. D. L. Thioacetic Acid,as a Reagent. Action on Salts of Rare Metals. NAZARIO ALVAREZ (Anal. SOC. Quim. Argentina 19 13 1 223-230).-Ammonium thioacetate in t,he presence of hydro- chloric acid may replace hydrogen sulphide in its action on vanadic molybdic tungstic selenious and telluric acids and on thallous sulphate palladium chloride ruthenium chlorate and sodium iridio-chloride.G. D. L. A Simple Process for Nitrating Sodium Hydroxide Solu- tions. ERNST ALTMANN (Chem. Zeit. 1913 37 1465).-The total alkali present hydroxide and carbonate is estimated by titrating the hot solution with standard sulphuric acid using phenol- phthalein as indicator. The amount of sodium hydroxide present is estimated by titration after precipitating the carbonate with barium chloride. T. S. P. Flame Reactions of the Alkali and Alkaline-earth Metals. LUDWIG KOPA (Chem. Zed. 1913 37 1506).-The author recommends a rod of graphite in place of the ordinary platinum wire for use in flame reactions (compare Kopa A.1913 ii 722; Wedekind A 1912 ii 382; 1913 ii 578). The graphite is most readily obtained from an ordinary lead pencil; i t does not break when quenched in cold water . T. S. P. Titration of Calcium and Magnesium in the Same Solution. PAUL J. Fox (J. Ind. Eng. Chem. 1913 5,910-913).-The solution containing the calcium and magnesium is treated while hot with oxalic acid and ammonia is added slowly until the solution is slightly alkaline in reaction. Ammonium arsenate is then added to the hot solution followed by ammonia until the ammonium magnesium amenate commences t o precipitate. After cooling an excess of ammonia is added and the precipitate is collected after fifteen hours and washed with dilute ammonia. The precipitate is now rinsed into a flask with water and dilute sulphuric acid; the acid solution is heated and titrated with standardised potassium permanganate solution.The mixture is then cooled 25 C.C. of diluted sulphuric acid (1 1) and 5 grams of potassium iodide are added and the solution is titrated with thiosulphate solution until the coloration is light yellow; i t is then placed in the dark for KONRAD SCHENK (Chern. Zeit. 1913 37 1464).-The bronze is dissolved in nitric acid and the tin estimated as dioxide the impurities in which are determined about five minutes and the titration completed. w. P. 8. The Rapid Analysis of Bronzes.ANALYTICAL CHEMISTRY. ii. 71 in the usual way by fusion with sodium carbonate and sulphur etc.Copper and lead are estimated in the filtrate by the usual electro- lytic rapid methods after which the iron and any aluminium are precipitated as hydroxides. The filtrate from the iron is evaporated to dryness after the addition of a few C.C. of sodium hydroxide in order t o re-move ammonium salts and the residue again evaporated with concentrated sulphuric acid to remove nitric acid. The residue is dissolved in water a large excess of sodium hydroxide added and the zinc estimated electrolytically using a rotating cathode. T. S. P. Microchemical Detection of Aluminium. F. RATHGEN (Zeitsch. anal. Che?n. 1913 53 33-37).-A particle of the alumina material is heated in a small platinum crucible with && C.C. of crystallised ammonium fluoride and 4-5 drops of strong sulphuric acid and the whole is very gradually evaporated to dryness and then heated for a moment to redness.When cold the mass is detached if necessary with the aid of a drop of water and then examined under the microscope. Aluminium is easily recognised by the colourless corundum-like hexagons which however may bO slightly coloured by iron or chromium. Four micro-illustrations are Estimation of Alumina in Bauxite. W. TRAUTMANN (Zeitsch. angew. Chem. 1913 26 702-703).-0*5 Gram of the finely powdered substance is fused in an open nickel crucikle with an excess of sodium peroxide and a little hydroxide. The fusion is dissolved in a little water diluted to about 500 c.c. and filtered into a litre flask. The undissolved mass is ignited and again fused with the soda mixture then dissolved in 20 C.C.of water and without filtering added t o the main solution. When cold the liquid is diluted up to the mark and after shaking portions of 100 C.C. are filtered off. The solution is supersaturated with hydrochloric acid and then boiled with a slight excess of ammonia. The precipitate after being washed once with water containing a little ammonia and ammonium nitrate is rinsed from the filter and redissolved in nitric acid and then again precipitated by ammonia using the same filter for collecting the alumina. After washing with the above liquid the precipitate is a t once heated in a platinum crucible until the ash is white. I n order to free it from traces of silica it is heated with 2 C.C. of hydrofluoric and 15 drops of sulphuric acid and after expelling the acids heated over the blow- pipe so as to render the alumina non-hygroscopic and to remove Use of Diphenylcarbohydraeide as Indicator in the Titration of Iron by the Dichromate Method.L. BRANDT (Zeitsch. anal. Chern. 191 3 53 1-20).-The solution of ferric chloride containing large excess of hydrochloric acid is reduced in the ordinary manner with stannous chloride the excess of which is then removed by mercuric chloride. After adding the usual solution of manganese sulphate containing free sulphuric acid and also phosphoric acid 5 C.G. of the above indicator are added and the liquid titrated with given. L. DE E. the last traces of sulphuric acid. L. DE K.ii. 72 ABSTRACTS OF CIIEMICAL PAPERS. standard potassium dichromate until the colour reddish-violet at first gradually passes into a pure green.The indicator is prepared by dissolving 0.1 gram of s-diphenyl- carbohydrazide in 35 C.C. of concentrated acetic acid and diluting up to 100 c.c.; the solution does not keep well rarely more than Colorimetric Estimation of Small Quantities of Manganese in Water. L. HARTWIG and H. SCHELLBACH (Zeitsch. N a b . Ganussm. 1913 26 439-442).-A method depending on the oxidation of the manganese by ammonium persulphate in the presence of silver nitrate is recommended as being more rapid than a similar method described by Schowalter (A. 1913 ii 880) and more trustworthy than that proposed by Haas (ibid. ii 437). Fifty c.c. or more of the water are treated with 0.5 C.C. of nitric acid evaporated to above one-half the original volume ; after cooling a quantity of silver nitrate more than sufficient to precipitate the chlorides is added followed by 10 C.C.of a 10% ammonium persulphate solution. The mixture is heated on a water-bath until the silver chloride has settled completely then heated t o boiling cooled and the coloration obtained compared with that exhibited by known quantities of permanganate diluted with a solution prepared by boiling for twenty minutes 2 litres of water after the addition of 40 grams of ammonium persulphate and 1 2 C.C. of a 1% silver nitrate solution. w. P. s. Estimation of Manganese Vanadium and Titanium in the Presence of One Another in Pig-iron and Steel. C. W. WRIGHT (Chew. News 1913. 108 248-249).-A quantity of 1-1 grams of the sample is dissolved in 35 C.C.of nitric acid D 1.2 the solution is filtered and the filtrate is heated after the addition of sodium bismuthate; sulphurous acid is then added the solution is cooled treated with an excess of sodium bismuthate and filtered the filter and residue being washed with 3% nitric acid. An excess of N/l0-ferrous sulphate solution is added to the filtrate followed by the addition of N/ZO-permanganate solution. As long as there is an excess of ferrous sulphate the permanganate solution introduced a t the rate of 2 or 3 drops per second is decolorised immediately but when the oxidation of the vanadium commences there is a dis- tinct retardation in the disappearance of the pink coloration. The reading is now taken and the titration is continued until a permanent pink colour is obtained; in case of doubt the operation may be repeated any number of times by again adding ferrous sulphate and titrating with permanganate solution.The quantities of manganese and vanadium present are then found by calculation. The solution is now transferred to a graduated cylinder hydrogen peroxide is added and the coloration obtained is compared with a standard prepared by similarly treating pig-iron or steel free from titanium or vanadium and adding to the solution a quantity of vanadium exactly equal to that found in the sample hydrogen peroxide and a definite volume of a standard titanium solution. a week. L. DE K. w. P. s.ANALYTICAL CHEMISTRY. ii. 73 The Estimation of Chromium as Chromic Oxide.G. ROTHAUG (Zettsch. anwg. Chem. 1913 84 165-189).-Precipitation of chromic salts with ammonia and ignition of the precipitate yield high results. The precipitate must be ignited a t first in a closed crucible as it becomes incandescent with violent projection of particles a t 420-680° a,ccording to the coarseness of the material. The average excess of weight found starting with pure chromic sulphate solution is 0.75% Cr. Ammonium sulphide gives a mean excess of 1*60% and potassium iodide and iodate + 1.02% Cr. The results are the same whether hard glass or platinum vessels are used. The error is lessened by shortening the preliminary heating to thirty seconds and then transferring to an electric furnace but chromic acid is always formed to a small extent.Washing the precipit’ate extracts chromic acid and repeated ignition followed by washing yields f urtlier quantities of chromic acid. Alkalis and lime are shown to be absent and the solutioii contains a chromic chromate. The formation of this compound is a maximum a t 300° and is observable even at looo. The quantity produced falls rapidly to 400° and very gradually after that point. The reaction is 5Cr,03+ 9 0 ~ C I - ~ ( C ~ O ~ ) ~ and it is probable that solid solutions are formed. The chromic acid in the washings may be estimated by Moulin’s colorimetric method with diphenylcarbazide (A. 1904 ii 368) whilst the same method applied after oxidation with hydrogen peroxide gives the total chromium. The composition of the chromic chromate Cr2(Cr0& has been determined in this way.Ignition of the hydroxide in hydrogen gives completely accurate results. C. H. D. Sensitive Reaction of Molybdenum and Tungsten in Presence of Mercury. Em. POZZI-ESCOT (Bull. SOC. chim. 1913 [iv] 13 1042).-In the author’s previous note on this subject (A. 1913 ii 532) the words tungstate and molybdate should be interchanged whenever they occur. T. A. H. Eetimation of Titanium by Titration. EDMUND KNECHT (Zeitsch. ungew. Chern. 1913 26 734-735).-A claim for priority over Neumann and Murphy (A 1913 ii 1079); compare Knecht (A* 1907 ii 654) and Hibbert (A. 1909 ii 351). Apparatus for the Melting Points of Substances of Indefinite Melting Point. A. P. BJERREGAARD (J. I d . Eng. Chcm. 1913 5 938-940).-The apparatus consists of a block of iron having one face inclined a t an angle of 45O to the horizontal.A number of grooves 0.5 in. wide and 0.25 in. in depth are provided down this face and samples of the material to be tested are pressed into the upper part of the grooves; two step-like cuts are made across the tops of the ridges between the grooves the material filling the upper step. Heat is applied to the bottom of the block and is so regulated that the temperature of the block as determined by a thermometer inserted in a mercury cup a t the top is raised T. S. P.ii. 7’4 ABSTRACTS OF CHEMTCAL PAPEHS. 100 in about every 100 seconds. The inclined face is covered with a glass plate. The temperature a t which the material is liquid enough to flow from the upper t o the lower step-like cut is taken as the melting point.The apparatus may be used for such sub- An Anomalous Reaction of Resorcinol. EDWIN P. HICKS (J. Amer. Chew. Soc. 1913 35 1891-1893).-From the author’s experiments it appears that the commonly accepted idea that resorcinol can be titrated as a dibasic acid with alkali hydroxides using Poirrier’s blue as an indicator is erroneous. If an aqueous solution of resorcinol is titrated with a standard solution of alkali hydroxide neutrality to the indicator is attained when a 1-14 molecular proportion of the alkali has been added; after keeping for ten to fifteen minutes the alkali in the neutralised solution can be titrated back with a mineral acid the liberated resorcinol being without effect on the indicator. Even when resorcinol is kept in 0.1 molar solution for three hours with a decimolecular proportion of alkali hydroxide the solution is found to be alkaline to the indicator and the whole of the alkali can be titrated before acidity is restored. The author inclines to the view that alkali induces in resorcinol a change t o some non-phenolic and possibly tautorneric substance ; extraction of the solutions with ether yielded nothing but ordinary resorcinol.cH<Co-CH;>CO CH*CH stances as pitch asphaltum etc. w. P. s. It is suggested that the ketonic formula possibly represents the less acidic substance. Modiffcation of the Fehliag-Soxhlet Volumetric Method. OTTORINO CARLETTI (Boll. chim. farm. 1913 52 747-748).-The end-point in the titration of reducing sugars by this method may be accurately determined by taking advantage of the fact that cuprous potassium cyanide does not react with phenolphthalin whilst cupric potassium cyanide gives with it a red coloration.The phenolphthalin reagent is made by mixing phenolphthalein (1 gram) potassium hydroxide (10 grams) zinc dust (5 grams) and water (100 c.c.) and boiling until decolorised. In the titration the sugar solution is run into Fehling solution and when reduction is almost complete a drop of the liquid is withdrawn mixed with a drop of the phenolphthalin reagent and the mixture treated with two or three drops of potassium cyanide (10%). When the end of the titration is reached this test will show no coloration whilst as long as cupric salt is present a red coloration will be obtained. D. F. T. R. V. S.Influence of the Metals Present in Urine on the Velocity of the Reducing Tests for Dextrose. GERTRUD WOKER and ELTSABETH BELENCKI (Pfliiger’s Archiv 191 3 155 45-67).-The presence of mercury in urine retards the Nylander test for dextrose and affects also other tests. Serum preparations containing mercury behave very irregularly. The indication of dextrose in urine by the usual reduction methods is affected also by the presence ofANALYTICAL CHEMISTRY. ii. 75 arsenic iron potassium iodide and salicylic acid. The effect on the different methods is not quantitatively the same. Urine is considered to contain two substances the one accelerating the inter- action of dextrose with methyleneblue bismuth nitrate or mercuric chloride the other retarding the reaction with alkaline copper sulphate or silver nitrate.The velocity of reduction of dextrose is in either case a function of the urine concentration. E. F. A. Velocity of Reduction of Methylene-blue by Dextrose and Laevulose and its Application to Urine Analysis. ,J. F. MUSTEX and GERTRUD WOKER (Pfliiger's Archiv 1913 155 92-96).-1n presence of alkali hydroxides methylene-blue is much more rapidly reduced by lzvulose than by dextrose and a met'hod is based on this difference for detecting and discriminating between these two sugars in urine. E. F. A. Gabriel Bertrand's Method of' Sugar Estimation. M. ROSE- BLATT (Biochem. Zeitsch. 1913 57 335-336).-A reply to Sonntag (A. 1913 ii 800). The Micro-method of Sugar Estimation. IVAR BANG (Riochem. Zeitsch. 1913 57 300-312).-The author has introduced certairi modifications into the method previously described by him (A.1913 ii 446). He employs 1 C.C. of the copper solution instead of 3 c.c. and he has reduced the amount of acid used in the coagulation of the protein which can be effectively done by substi- tuting hydrochloric f o r acetic acid. The solution now employed for coagulating the blood is made up of the following mixture 1360 C.C. saturated potassium chloride solution + 640 C.C. water + 1.5 C.C. 25% hydrochloric acid. N/200-Iodine solution can now be used for titration and this is made from 5 C.C. N/l0-hydrochloric acid + 1-2 C.C. 20A potassium iodate solution + 2 grams potassium iodide+water up to 100 C.C. I n summer this solution should be titrated every twenty-four hours.An improved pincette for holding the flask during the reduction process is also described. Titration with the iodine solution is carried out until the blue starch colour remains permanent for thirty to sixty seconds. Various other new details are given b y t h e author. I n the micro-method the results of blood sugar analyses are usually slightly higher than those obtained by the macro-method. This can be accounted for by the fact that the solution containing the sugar decolorism a small amount of iodine before reduction by the copper solution. This amount is nearly constant. A subtraction of 0.015% from the total gives the correct result. Detection of Sucrose in Urine. ADOLF JOLLES (Biochem. Zeitsch. 1913 57 420422).-The author has previously shown that dextrose solutions on treatment with alkali are rendered optically inactive.The estimation of the change in the polarisation after such treatment will give a measure of the amount of dextrose present. Change of polarisation produced by inversion will give S. B. S. S. B. S.ii. 76 ABSTRACTS OF CHEMICAL PAPERS. the measure of the sucrose present. By employing both methods of treatment sucrose can be detected with certainty in the presence of dextrose. S. B. S. HANNS STIEGLER (J. Landw. 1913 6 1,399-426).-The amount of substance employed varies from 1.5 to 3 grams according to the amount of fibre present. The finely-powdered substance is added to 20 C.C. of water in a 300 Soxhlet milk-sterilising bottle treated with 60 C.C. of hydro- chloric acid (D 1-19> well shaken and left for ten minutes.Boiling water (to 200 c.c.) is then added and the flask immersed in boiling water for an hour a slow cdrrent of air being drawn through it all the time. When the heating is completed the residue is allowed to settle and the acid liquid drawn off through a tube closed with a plug of glass-wool. The latter is then removed from the tube and placed in the bottle containing the residue. This is next neutralised treated with 50 C.C. of potassium hydroxide solution (5%) and boiling water (to 200 C.C. as before) and again heated for half an hour in a water-bath. The hot solution is filtered through a porce- lain Gooch crucible with a disc of ignited asbestos paper covered with ignited and washed asbestos. The fibre and the glass-wool are washed successively with hot water (500 c.c.) and alcohol and then left in contact with ether for about half an hour.After filtering off the ether the crucible is heated for two hours at 100-105° weighed ignited and again weighed. Titrimetric Estimation of Potassium Xanthate. BROR HOLMBERG (Be?.. 191 3 46 3853-3859).-The estimation depends on the fact tohat free xanthic acid rapidly decomposes in solution into carbon disulphide and alcohol. The xanthate solution is treated with an excess of standard hydrochloric acid the mixture allowed to remain about ten minutes until the decomposition of the xanthic acid is complete and the excess of free mineral acid titrated with alkali. A volumetric method for the estimation of mercury depending on the formation of an insoluble mercuric xanthate is also described; the solution of the mercury salt (which must be present in the mercuric condition) is treated with potassium xanthate and the excess of the latter determined in the manner just described.The estimation can be carried out in the presence of chlorides bromides and sulphates but if iodides are present the mercuric xanthate must be filtered off before the excess of potassium xanthate is determined. It is claimed that mercury can be estimated in this manner more rapidly and more conveniently than by any other method. The author confirms the observations of previous workers that aqueous solutions of potassium xanthate are not very stable but finds that the sclid salt can be kept in a dry atmosphere without undergoing change. F.B. Estimation of Lactic Acid in Wine. THEODOR ROETTGEN (Zeitsch. Nahr. Gcnusem. 1913 26 437-439. Compare A. 1911 ii 942 ; 1912 ii 1005).-Results of experiments on the estimation New Method for Estimating Crude Fibre. N. H. J. M.ANALYTICAL CHEMISTRY. ii. ’77 of lactic acid i n wine and in the dry residue of the same show that the dry residue (total solids) of wine contains the whole of the lactic acid and is practically free from volatile acids. Compara- tive estimatio,ns of lactic acid by the methods described by Kunz and Moslinger showed that the processes are equally trustworthy. w. P. s. Estimation of Hydroxybutyric Acid. PHILIP A. SHAFFER and W. MCKIM MARRIOTT (J. Biol. Chem. 1913 16 265-280).-The method of estimating hydroxybutyric acid by oxidising it to acetone with chromic acid gives uniformly about 90% of the theo- retical values; the values must therefore be corrected by an addition of 1076 of the amount formed.The results obtained by the oxidation method were compared with those obtained by Black’s ether extraction method. A procedure for the isolation and purification of hydroxybutyric acid in the form of calcium zinc hydroxybutyrate CaZn(C,H,03)4 m. p. 200° (decornp.) is described. W. D. H. ErJtimation of P-Hydroxybutyric Acid in Blood and Tissues. W. MCKIM UARRIOTT ( J . Biol. Chem. 1913 16,293-298).-Shaffer’s method is applicable to blood and tissues provided proteins are removed (by sodium acetate) ; paired glycuronic acids dextrose and protein remnants are then precipitated by basic lead acetate and ammonia.Full details of distillation etc. both for large and small quantities of blood are given. By applying the nephelometer f o r the ec;timation of acetone occurring as such or as acetoacetic acid or to that obtained by oxidation of 8-hydroxybutyric acid it is possible to make a complete analysis with only 2-5 C.C. of blood. W. D. H. General Method for the Estimation of Fixed Acids in Vegetable Substanoes. EMM. POZZI-ESCOT (BUZZ Assoc. CAim. Sucr. Dist. 1913 31 225-230).-Oxalic tartaric lactic citric malic and succiuic acids may be estimated in the presence of each other by means of the following method which is a combination of processes described previously by the author (compare A. 1908 ii 740 904 993 1078). Oxalic A cid.-The solution containing the mixed acids is neutralised with ammonia ammonium chloride and acetic acid are added and the oxalic acid is precipitated as calcium oxalate or as barium oxalate; the oxalate is separated dissolved re-precipitated and then titrated with permanganab solution in the usual way.The filtrates from the oxalate precipitate are mixed treated with sulphuric acid t o remove calcium or barium salts and then diluted t o a definite volume. The solution is used for the estimation of the other acids. Tartaric Acid-This acid is precipitated from a portion of the solution as magnesium tartrate aft.er the addition of 50% of alcohol to the solution; the precipitate is collected washed with alcohol ignited and the tartaric acid calculated from the weight of magnesia obtained. Lmtic Acid.- Another portion of the solution is treated with a large excess ofii.78 ABSTRACTS OF CHEMICAL PAPERS. an alcoholic barium bromide solution and alcohol when all the acids are precipitated with the exception of lactic acid. After filtration the solution may be evaporated acidified with sulphuric acid and titrated first to neutrality to Congo-red and then to phenolphthalein the latter titration giving the quantity of lactic acid. Or,_the solution is evaporated to dryness the residue calcined and the resulting barium carbonate titrated. Citric A cid-The barium precipitate obtained in the separation of the lactic acid is freed from barium by means of sulphuric acid and then treated with an excem of lead acetate in acetic acid solution when lead citrate and tartrate together with lead sulphate are precipitated whilst lead malate and succinate remain in solution.After the lead has been removed from the precipitate as sulphide the citric and tartaric acids are precipitated as their barium salts the latter being collected ignited and the barium carbonate titrated. The quantity of tartaric acid found previouslg is deducted from the result to give the citric acid. Malic and Succinic Acids.-The solution containing the lead salts of these acids is treated with hydrogen sulphide the lead sulphide is separated and in one-half of the solution the two acids are estimated together by double titra- tion whilst the succinic acid is estimated in the other half of the solution by precipitation as its barium salt after the malic acid has been oxidised with permanganate (compare A.1908 ii 993). w. P. s. Reaction of Nopic Acid (Reaction Characteristic of Oxalic Acid). BERNABB DORRONSORO and OBDULIO FERNANDEZ (Anal. Pis. Quim. 1913 11 441-443).-The coloration with resorcinol and sulphuric acid supposed by Fernsndez to be caused by nopic acid derived by oxidation of the terpenes by means of alkaline permanganate (A. 1910 ii 1119) is shown to be due to oxalic acid the sodium salt obtained in the oxidation being that of oxalic and not of nopic acid. G. D. L. Modification of Jonescu’s Test for the Detection of Benzoic Acid. P. FLEURY (J. Pharm. Chim. 1913 [vii] 8 460-461).- This test which depends on the conversion of benzoic acid into salicylic acid by the action of hydrogen peroxide is very sensitive when carried out in the following way To 10 C.C.of an aqueous benzoic acid solution are added successively three drops each of dilute ferric chloride solution dilute hydrogen peroxide soIution and 3% ferrous sulphate solution. A violet coloration commences to appear in about thirty seconds and reaches its maximum in about ten minutes; a distinct coloration is obtained with 0.2 mg. of benzoic acid. The mixture should not be heated as the oxida- tion of the benzoic acid then proceeds too far and the character- istic violet coloration is not obtained. w. P. s. Detection of Vegetable Fats in Animal Fats. If. KLOSTER- MANN (zeilsch. A?ah. Genussrn. 1913 26 433-437).-A method of isolating cholesterol and phytosterol by means of digitonin (com-ANALYTICAL CHEMISTRY.ii. 79 pare A 1913 ii 885) is described. One hundred grams of the fat are saponified with alcoholic potassium hydroxide solution and after dilution the fatty acids are separated by the addition of hydrochloric acid; 250 C.C. of ether are then added the ethereal solution of the fatty acids is separated from the aqueous portion and washed three times with water. The ethereal solution is mixed with 250 C.C. of light petroleum and 25 grams of sodium chloride shaken filtered and the filtrate is treated with 1 gram of digitonin dissolved in 20 C.C. of alcohol. After thirty minutes the crystals which separate are collected washed with ether dried and boiled with acetic anhydride until completely dissolved. The excess of acetic anhydride is evaporated the residue dissolved in 50 C.C. of alcohol and 25 C.C.of water are added slowly to the solution. The crystalline precipitate is collected washed with 70% alcohol dis- solved in ether the solution is evaporated to dryness and the residue is crystallised twice from alcohol the M. p. being then determined. Pure lard yields crystals m. p. l l O o whilst in the case of lard containing 2.5% of rape oil the crystals have m. p. 1 1 8 O . Butter gives crystals having m. p. 113O which is raised fo 115O when the butter contains 2.5% of cocoanut oil. The crystals obtained from pure rape oil or cocoanut oil have m. p. 126-128O. w. P. s. Estimation of Acetone. W. MCKIM MARRIOTT (J. Biol. Chem. 1913 16 281-288).-The Messinger method (A. 1889 90) gives correct results. The Scott-Wilson method gives accurate results only when certain modifications of the original procedure are made; it is applicable to very minute quantities of acetone.In distilling a very dilute acetone solution all the acetone may be collected in the distillate within ten minutes W. D. H. Nephelometric Estimation of Minute Amounts of Acetone. W MCKIM MARRIOTT (J. Biol. Chem. 1913 16 289-292).-When the quantity of acetone is too small for estimation by the Scott- Wilson method as for example in small amounts of blood the estimation may be accurately made nephelometrically ; the opales- cence observed is produced by adding the acetone to a silver- mercury cyanide solution K. PECHE (Ber. Deut. Bot. Ges. 1913 31 45S-462).-When sections of the rind of white or better black radish are placed in a solution of potassium myronate (10% or less) saturated with barium chloride white globules presumably of barium sulphate are deposited on some of the protein cells; with strontium chloride the precipitate is granular whilst with calcium chloride well-formed needles of calcium sulphate are formed after some time both in and outside the sections.The sulphates are produced by the joint action of the glucoside and the alkaline earth. On the assumption that the ally1 group of the mustard oil is the only substance present which reacts with osmic acid (tannins have not been detected and the presence of fats and oils in the rind of W. D. H. Microchemical Detection of Myrosin.ii. 80 ABSTRACTS OF CHEMICAL PAPERS. radish is improbable) the glucoside may be localised by slightly heating a washed ssction in 1% osmic acid.11. Estimation of Amino-nitrogen in t h e Tissues. DONALD D. VAN SLYKE ( J . Biol. Chern. 1913 16 187-196).-The amino-acids are extracted from the tissues with hot water. Uncoagulated proteins are precipitated by alcohol ; alcohol and ammonia (present in the extract) are removed by concentration in a vacuum and the amino-nitrogen estimated by nitrous acid. The action is rapid and is only slightly increased after hydrolysis with hydrochloric acid; this indicates that the bulk of the amino-acids are free. N. H. J. M. The Fate of Protein Digestion Producte in the Body. W. D. H. Estimation of Amino-acid-Nitrogen in Urine. 8. R. RENEDICT and J. R. MURLIN (J. Biol. Chm. 1913 16 385-388).-The method previously published by the authors f o r modifying the form- aldehyde titration gives low results and it was found that certain amino-acids are in part removed by the preliminary treatment with lead.The procedure now recommended consists in adding phosphotungstic acid to dilute urine; three hours later the clear fluid is poured off and phenolphthalein and barium hydroxide added until it turns pink; after an hour it is filtered and the filtrate neutralised ; it is then titrated with neutral formaldehyde to a deep red colour. The result is corrected by deducting the amount of *V/ 10-sodium hydroxide necessary to produce the same colour in an equal quantity of water free from carbon dioxide with the same mount of formaldehyde. OTTO MAYEB (Zeitsch. angcw,. Chem. 1913 26 639-640; Pharm. Zerztr.-h. 1913 54 1205-1208).-The author recommends that in the examination of urines for albumin the following reactions should be carried out in the cold; (a) a mucin test ( b ) a protein test with a slight modification of Jolles's reagent. For quick approximate estimations 5-10 C.C. of urine are floated in a conical glas? on the same volume of a reagent made by dissolving 5 grams of mercuric chloride 5 grams of citric acid and 40 grams of salt in 500 C.C. of water. At the end of 1.5 minutes a well-defined white ring appears a t the junction of the liquids when 0.001% of albumin is present. Stronger urines are diluted after preliminary tests until the same time is required for the development of the ring. Estimation of Protein in Urine by the Centrifugal Method. CASIMTR STRZYZO~VSRI (Zeitsch. physiol. Chenz. 1913 88 25-3'7).- I n estimating the amount of protein in urine after adding Esbach's reagent and centrifugalising the depth of the precipitate varies with the temperature and with the specific gravity of the urine. The method may be made exact by the use of a standard centrifuge standard sedimenting tubes a constant temperature and by bring- ing up the specific gravity of the urine to a standard level (D 1.030); this is best done by the addition of zinc sulphate. W. D. H. A Delicate Test for Albumin in Urine. J. C. W. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9140605066

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii 81 General and Physical Chemistry. Refractive Index of Gas Mixtures. S. VALENTINER and 0. ZIMMER (Bar. Deut. phys~kal. Ges. 1913. 15 13()1-131ti).-The authors have measured. the refractive indices of mixtures contain- ing hydrogen and carbon dioxide and also hydrogen helium and neon. I n the latter mixtures the proportion of helium to neon was constant a mixture of these two gases containing 27.8% of helium being used in the preparation of the gases submitted to investiga- tion. The refractivity data were obtained with the aid of a Zeiss interferometer. The results indicate that the refractivity of mixtures of hydrogen and carbon dioxide is slightly less than that calculated according t o the mixture rule. I n the case of the mixtures of hydrogen helium and neon the deviations from the mixture rule values are within the limits of possible experimental error.H. M. D. Mixed Liquid Crystals. PAUL GAUBERT (Compt. rend. 191 3 157 1446-1448. Compare A. 1911 ii 949; 1912 i i 109 510).-'l'he author has extended his study of the variation in birefraction of an optically negative crystalline liquid on addition of a substance giving optically positive liquid crystals to mixtures of substances capable of mixing in all proportions. The two substances studied were cholesteryl propionate and ethyl anisylideneaminocinnamate the results are shown in a table and graphs the measurements being made'at looo f o r the rays B C D 3 P. The rotatory power is found tot increase considerably with the birefraction of the mixture. W. G. Spectroheliographic Investigation of the Arc Light.OTTO OLDENBERG (Zeitsch. wias. Photochem. 191.3 13 133-172).-8n apparatus is described by means of wllich the author has obtained monochromatic reproductions of the arc light on photographic plates. By impregnating the carbons with metallic salts it was possible to examine the behaviour of well-known series lineB and bands. In the case of sodium the photographic records show that the principal and second subordinate series of lines are mainly emitted by the periphera.1 layers of the arc whilst the first subordinate series is due to emission from layers nearer the axis. Lithium behaves similarly to sodium but the observations with aluminium magnesium and calcium indicate that these behave quite differently from the alkali metals.The monochromatic reproductions show further that there are two distinct types of bands. I n the case of the carbon and cyanogen bands the intensity diminishes from the centre to t h s edge of the arc whilst all the other bands examined are characterised by greater intensity at the edge of the arc. I n view of the very VOL. CVI. ii. 6ii. 82 ABSTRACTS OF CHEMICAL PAPERS. considerable difference between the monochromatic pliotograplis of bands and lines it is suggested that this method may be made use of in doubtful cases to determine the character of a particular emission. H. M. D. Influence of the Constituents of the Crystal on the Form of the Spectrum in the X-Ray Spectrometer. W. H. BRAGG (Proc. Roy. Soc. 1914 [A] 89 430-438).-1t has been observed that the relative intensities of the different parts of an X-ray spectrum may be altered very considerably by changing the crystal which is employed in the spectrometer and an account is given of experi- ments which have been made to determine the origin of this effect.According to the observations of Barkla every metal emits characteristic rays which can only be excited by rays character- istic of metals which are of higher atomic weight. These observa- tions have also shown that homogeneous X-rays are strongly absorbed by any substance in which they can excite the rays characteristic of that suhstance. As a consequence of these rela- tions the connexion between the atomic weight of an absorbing screen and its power of absorbing X-rays of given quality exhibits marked discontinuities and it is shown that the operation of this factor through the absorbing action of the atoms of which the crystal is composed gives rise to the variations in the relative intensities of the different parts of the spectrum.H. M. D. A Seoond Spectrum of Neon. THOMAS RALPH MERTON (Proc. Boy. Xoc. 1914 [A] 89 447-451).-A comparison has been made of the spectra obtained with a weak discharge from an induction coil and with the same discharge when a small Leyden jar and a spark-gap of about 2 mm. were introduced into the circuit. I n the mom refrangible region the jar-discharge spectrum was found to consist of a large number of lines which are not present in the ordinary neon spectrum whilst the strongest of the ordinary neon lines were only just visible.The wavelengths of most of these lines were measured from photographs taken with the grating spectrograph but some of the lines in the green are so feeble that it was found necessary to obtain photographic records with very long exposure on the prism spectrograph. The wave-length data agree with those recorded by Liveing and Dewar (A. 1901 ii 213) although about 50% of the Lines given by these authors have not been observed. The experiments indicate that neon like argon krypton and xenon is capable of giving two different spectra according to the manner in which it is electricdly excited. H. M. D. The Band Spectrum of Aluminium and its Presence in the Flame Spectra of Certain Minerals. ARNAUD DE GRAMONT (Compt. rend. 1913 157 1364-1368).-The author has discovered a sixth absorption band in the spectrum of aluminium much more refrangible and much weaker than the other five. It lies between h 4330.5 and h 4462.6 becoming degraded towards the red.Work-GENERAL AND PHYSICAL CHEMISTRY. ii. 83 ing with an oxy-acetylene flame the author finds that in the case of pure substances the true aluminium spectrum is only obtained when using the metal itself or its haloids the oxygen compounds not giving the spectrum as described. He has also studied a large number of minerals and examined them carefully for halogens and finds that for them the above rule does not hold good but that the spectrum is more probably controlled by the constitution of the mineral. W. G. Absorption of Inorganic Salts in tbe Ultra-violet. T. RETSCHINSKY (Ann.Yhysik 1913 [iv]. 42 1580-1588).-The ultra- violet absorption of lithium chloride lithium bromide sodium chloride sodium bromide sodium iodide and potassium iodide has been examined in aqueous solutions of varying concentration. All these salts show a strong absorption maximum in the extreme ultr% violet beyond h=220 pp. I n the case of lithium bromide there is also a weaker absorption band between 255 and 280 pp and some evidence of a further band a t about 300pp.. The former band is much less clearly marked in the cam of sodium bromide but both salts behave the same in regard t o the limiting wave-length of ultra-violet transmission. The chlorides and bromides conform to Beer's law but slight deviations have been found in the ca50 of the iodides in that the absorption increases with the concentration of the solution when the product of this concentration and of the thickness of the absorbing layer remains constant.The absorption curve is shifted towards greater wave-lengths when the temperature is raised to looo in the case of sodium chloride lithium bromide sodium bromide and potassium iodide but no shift is observed with lithium chloride. When the limiting absorption of the dissolved salts is compared with that found for the molten salts (A. 1908 ii 910) it is found that the straight lines which represent the influence of temperature in the case of the molten salts pass through the points which corre- spond with the limiting absorption in aqueous solution at 20° and looo. I n making this comparison the concentrations of the solutions were chosen so as to give the same number of absorbing molecules in the two cases.H. M. D. Absorption Spectra of Nickel Derivatives of Primary Aliphatic Nitroamines. A. P. N. FRANCHIMONT and H. J. BACKER (Rec. trav. chim. 1913 32 321-324. Compare T. 1912 101 2256 ; A. 1913 i 833).-'l'he nickel derivatives of methyl- and ethyl- nitroarnines have been prepared and their absorption spectra compared with that of nickel nitrate. The amine derivatives are prepared by treating freshly precipitated nickel hydroxide with aqueous solutions of methyl- and ethyl-nitroamines respectively. It is shown that the colour of the nickel nitroamines resembles that of nickel nitrate much more than the colour of the corresponding derivatives of copper and cobalt resembles that of their nitrates.Nickel methylnitroamine crystallises with 6H,O and possesses a bluish-green colour ; i t loses its water on remaining over sulphuric 6-2ii. 84 ABSTRACTS OF CHEMICAL PAPERS. acid and becomes intensely green. The anhydrous salt is more easily soluble in water than the crystallised salt. All three salta in N/Z-solution have maxima of absorption at l/h=2850 and ca. 1/h=2000 whilst t h e nitrate has a third band at 3810. The absorption curves for the methyl- and ethyl-nitroamine derivatives coincide over practically their whole length and the absorption is compleb in the ultra-violet. Spectrographic Examination of the Colour of Picrylalkyl- nitroarnines with Alkalis. A. P. N. FHANCHIMONT and H. J. BACKER (Rev. trwv. chim. 191 3 32 325-333).-The ahwrption spectra of alcoholic solutions of picrylmethylamine and picryl- methylnitroamine have been examined both alone and in the presence of potassium hydroxide.A solution N/5000 of picryl- methylamine exhibits two absorption bands with their heads a t 1/h=2390 and 2875; there is a maximum of transmission a t 2600 and a t 3490. On adding a slight excess of potassium hydroxide both bands persist but the head of the first is shifted to l/h=2420. Picrylmethylnitroamine exhibits general absorption but on the addition of alkali two bands appear a t 1/h=1975 and 2350. On allowing the alkaline solution to remain for twenty-four hours the character of the absorption spectrum is entirely changed and on measurement is found to be that of potassium picrate thus show- ing that picrylmethylnitroamine is hydrolysed by a slight excess of potassium hydroxide in cold solution according t o the equation C,H,(NO,),*NMe*NO + H,O = C,H,(NO,),-OH + NHMeONO,.N / 200-Solutions of picrylmethylamiiie and picrylmethylnitroamine have about the same colour but on dilution the colour of the picrylmethylamine is only slightly diminished whilst that of picryl- methylnitroamine e'ntirely disappears. Selective Absorption of Ketones. GEORGE GERALD HENDERSON and ISIDOR MORRIS HEILBRON (Proc. Roy. SOC. 1914 [AJ 89,414-418). -It is suggested that selective absorption of ultra-violet rays by ketones is caused by intramolecular vibrations due to the alternate forination and breaking down of unstable ring systems and that the momentary formation of these is effected through the agency of free partial valencies which make their appearance on the atoms of the compound under certain conditions.I n the case of acetone the two alternating phases may be represented by the formulz J. F. S. J. F. S. 1 ; CH~*C-CH -+ 1 f- O.-..-.H O H i . . and the selective absorption is attributed t o the' ele&ronic disturb- ances which accompany this intramolecular oscillation. The semicarbazones of acetone and its homologues exhibit only general absorption and this is also in agreement with the above hypothesis if it is assumed that the attraction between hydrogen and nitrogen is not sufficiently strong t o cause the appearance of free partial valencies.GENERAL AND PHYSICAL CHEMISTRY. ii. 85 The theory can be extended to other groups of ketones of which diacetyl [dimethyl diketone] and acetylacetone may be taken as examples.H. M. D. Absorption of the Ultra-violet Rays by Alkaloids of the Morphine Group and by Phenanthrene. M. GOMPEL and VICTOR BENRI (Compt. rend. 1913 157 1422-1425).-A study of the ultra-violet absorption spectra of phenanthrene morphine codeine and apomorphine with a view to throwing some light on their relative constitutions. The absorption curve of phenanthrene can be divided into three regions (1) between A 3800 and 3050 in which region E. varies between 200 and 600 and there are five absorption bands; (2) between A 2990 and 2700 where E. varies between 2000 and 10,000 and there are two absorption bands one strong (A 2925) and the other weak (A 2810); and (3) the region between ~ 2 7 0 0 and 2144 where E varies between 10,000 and 135,000 and there is a very intense band at ~ 2 5 0 3 .Morphine and codeine present almost identical absorption curves having one single broad absorption band a t h 2850 where ~.=1600. The curve then passes to a minimum a t h2620 and finally rises steadily to h 2195 where E. = 20,000. The curve for apomorphine resembles that of phenanthrene much more closely except that the intense band a t A2503 is missing. The authors therefore suggest that this band is produced by the double linking between the carbon atoms 9 and 10 this being missing in apomorphine. apollorphine can be detected spectrographically a t a dilution of 0.01 mg. per c.c. whilst for morphine and codeine the extract must contain a t least 0.1 mg.per C.C. W. G. Photographic Determination of the Fluorescence Spectra of the Chlorophyll Pigments. CH. DHBR~ (Compt. rend. 1914 158 64-67).-An examination of the fluorescence spectra of a- and P-chlorophyll carotin and the xanthophylls. Both a- and &chlorophyll show only one band of fluorescence the axis of which is very slightly displaced towards the red as compared with that of the corresponding absorption band this displacement being greater in the case of the f?- than the a-variety. I n the case of carotin a slight green fluorescence is obtained the band of which is distinct from ~ = 5 0 0 p p to 560 pp. The xanthophylls show no visible fluorescence. The examination was made of solutions of the pigments in anhydrous ethyl ether and photographs are given for a- and &chlorophyll.W. G. Infiuepce of Intramolecular Relative Vibration on the Intensity of the Absorption and Fluorescence of Valency Electrons. J. STARK and P. LIPP (Zeitsch. physikal. Chem. 1913 86 36-50).-A theoretical paper in which the general statement is deduced If of two substances A and B each containing similar atoms with similarly bound valency electrons the number of colli sions between the valency electrons with atom groups or otherii. 86 ABSTRACTS OF CHEMICAL PAPERS. molecules is greater in the case of B than that of A then the absorption bands of B due to the valency electrons will be stronger than those in the case of A and the fluorescence of A will be stronger than that of B. I n other words an increase in the number of collisions between valency electrons and atom groups or molecules increases the light absorption and weakens the fluores- cence.The fluorescence and absorption spectra of a number of substances are considered on the basis of the above statement and shown to be in accord with it. Deductions from the Valency Theory IV. Intramolecular Oscillations. J. STARK (Zeit~ch. physikal. Chem. 191 3 86 51-60. Compare preceding abstract).-A theoretical paper which con- siders intramolecular vibrations on the basis of ths Stark valency hypothesis and Planck’s radiation theory. It is shown that in an aggregate of a large number of molecules only very few valency electrons oscillate about their position of rest and that the larger number of the valency electrons have no vibration of their own apart from that of the atoms to which they are attached.At moderate temperature the valency electrons can only be made to oscillate of themselves by the absorption of light energy of the same frequency as the oscillation. If these oscillations are not damped by intramolecular collisions they take on a large ampli- tude which makes itself visible in fluorescence. It is shown that in an aggregate of molecules a portion of the atoms possess a marked thermal vibrational energy a t ordinary temperatures. The results of these deductions are applied to various chemical processes such as tautamerism. E. TALBOT PARIS and ALFRED W. PORT~R (Phil. Mag. 1914 [vi] 27 91-95),- A comparison has been made between the rotations of the plane of polarisation produced by a long column of a solution of sucrose when the light was emitted (1) from a constant source (2) from an intermittent source in the form of a platinum-mercury spark.Special’ experiments showed that the duration of the spark was less than 3 x 10-6 second. The means of several observations show that the rotations differ by less than one minute in 500° which is within the limit of experimental error. The result shows that the incident light has no directive action on the molecules of sucrose in the solution. H. M. D. J. F. S. J. F. S. Experiment on Rotatory Polarisation in Liquids. Non-influence of Oxygen on Certain Photochemical Re- actions. MARCEL BOLL and VICTOR HENRI (Cornpt. rend. 1914.158 32-34).-A criticism of Bodenstein’s theory (compare A.1913 ii 1039) explaining the disagreement of certain phot~chemical reactions with Einstein’s law of photochemical equivalence (compare J. Phys. 1913 3 277). The authors show that this theory does not apply t o the hydrolysis of the chloroplatinic acids (compare A. 1913 ii 745) or the decomposition of oxalic acid in the presence of uranyl nitrate (compare A. 1913 ii 652) these two reactions not being retarded by oxygen. W. G.GENERAL AND PHYSICAL CHEMISTRY. ii. 87 The 7-Rays of Polonium Radium and Radioactinium. A. S. RUSSELL and J. CHADWICK (Phil. Mag. 1914 [vi] 27 112-125).- Ionium radio-thorium polonium radium and radioactinium expel in addition to a-rays it minute quantity of y-radiation and this is probably generally true of all a-ray-giving substances.For these y-rays to be detected the quantity of substance required is such that it must give off as many a-particles per second as 1 mg. of radium. Ionium and polonium emit a still smaller amount of &radiation also of intensity about 10% of that of the y-radiation. A detailed account is given of the separation of polonium radium-D and -E from old radium in a form suitable for experi- ment. I n the final stage the active material is volatilised either in air or hydrogen in a porcelain tube on to a surface kept cool by contact with an inner tube in which water circulates. Polonium is volstilised in air a t 900° but to volatilise radium-E a tempera- ture above l l O O o is required although in hydrogen 900° suffices. For polonium the y-radiation emitted is of one type with p / d =215(cm.)-I which comes from the polonium itself indepen- dently of the material on which it is supported.But on copper although not on aluminium platinum or lead a characteristic radiation is excited in addition which is probably in the L series. From radium the intensity of the y-rays measured through I mm. of aluminium was from 1 to 1.5% of that of the radium in equili- brium with its short-lived products. In addition to the known soft 8-rays some hard &rays with p(Al,cm.-l) = 20 were observed which were probably due to the radium itself and not to its products. Their intensity was some 4% of that of the soft P-rays and 2.5 times that of the y-rays. I n the latter three types were recognised with ,u/d(cm.)-l in aluminium 130 6 and 0.1 respec- tively.For radioactinium two types of y-rays with p l d about 8 and 0.1 were found. This y-radiation contributes about 25% of the total y-radistion of actinium in equilibrium with its products. Results given in a previous preliminary communication on a new product in the actinium series are withdrawn. F. S. &Rays from Gases. NORMAN CAMPBELL (Phil. Mug 1914 [vi] 27 83-91) .-The theory is considered of conduction through an ionised gas when the pressure is so low that the free path of the electrons liberated is not small compared with the distance between the electrodes and the number of ions made in the gas is not large compared with the number of &rays liberated from the electrodes. The view taken is based on the work of Franck and Hertz (A. 1313 ii 548) that an electron colliding with a molecule of helium or hydrogen is reflected with little loss of energy and that with a molecule of oxygen or other element with strong affinity for the electron probably the electron is not reflected but adheres to the molecule.Some earlier measurements in air and hydrogen are considered in light of the theory and although not capable of quantitative explanation they are in general accord with it and show that the &rays from ionised gams are probably emitted withii. 88 ABSTRACTS OF CHEMICAL PBPERS. velocities of the same order of magnitude as those emitted from metals. F. S. rhe Ionisation in Various Compounds of Carbon Hydrogen and 0~ygei1 ~y kiomogaeous A-Radiation. H. MOORE (Phil. J4fig. 1914 [.I] 27 177-r87).-A long c~ Ilndrical ctrauiber of aluminium lined lnternaliy with paper to minimise the ionisation (chiefly corpuscular) due t o the radiation from the walls was filled with a mixture of hydrogen and the vapour of various liquids -inethyl formate ethyl ether ethyl formate methyl acetate benzene ethyl acetate ethyl alcohol-at their saturation pressure at Oo.The secondary X-radiation from copper was employed as the ionising radiation. It was found impossible to obtain any “ atomic ionisation ” values which would satisfy the results ; the values for an atom of carbon and for an atom of oxygen (that for hydrogen being negligible) obtained from one pair of compounds gave errors as great as 25% when applied t o the others. It was €ound that the discrepancy is due t o the different ionisation produced by a corpuscle liberated from the molecule or atom of the gas or vapour when absorbed by different gases.Further experiments showed that the real “ atomic ” effect is the liberation of these corpuscles from the atoms of the X-rays. The absorption of the X-rays resulting in the liberation of corpuscles is atomic and is the same for a given atom whether in combination or not. The ionisation produced however is a secondary effect the ionisa- tion resulting by the absorption of the liberated corpuscular radia- tion in the gas being dependent on the chemica.1 nature of the gas. Knowing the ‘ I corpuscular factor,” the ionisation in the various gases and vapours could be calculated from the composition of the gas from fixed values for the atomic corpuscular radiations of oxygen and carbon in most cases with good agreement with the experimental results F.S. Registration of the Emanation Content of the Underground Air a t Potsdam by the Benndorf Electrometer. K. KAHLER (Phyysikal. ZeitacJt. 1914 15 27-31).-A zinc cylinder 1.5 metres deep and 0.45 metre in diameter open a t the bottom was sunk into the earth and an inner electrode connected with the recording electrometer. A continuous register of the leak due to emanation in the cylinder was taken from late summer 1910 t o early summer 1912. It was found t h a t the vertical movements of the air includ- ing the changes of barometric pressure had the greatest effect on the emanation content of the air and on the escape of emanation from the ground.Sunshine also favoured the’ escape of emanation. The daily variations have no influence on atmospheric conductivity but possibly the yearly variation has an influence. F. S. A Determination of the Variation with Altitude of the Radium Emanation Content of the Atmosphere. J. R. WRIGHT and 0. F. SMITH (PhysikaZ. Zeitsch. 1914 15 31-39).-These measurements were carried out by the cocoanut charcoal methodGENERAL AND PHYSICAL CHEMISTRY. ii. 89 in Manila for two places one 5 metres and the other 2460 metres above sea-level on Mount Pauai. The individual measurements of the emanation content varied widely in accordance with the changes in meteorological conditions. Rainy weather and high wind velocities lowered whilst settled weather with low wind veloci- ties favoured the emanation content. For the low station the mean content was 82.5 x 10-12 curie per cubic metre about four times greater than the mean content 19.2 x 10-12 curie per cubic metre on the mountain.An Alleged Separation of the Radium-D from the Lead in Active Lead by means of Grignard's Reaction. CEARLES STAEHLING (Compt. rend. I 9 13 15 7 14 :30-1432).-The a u t bor has repeated the work of Hofmann and Wolfl (compare A. 1907 ii 5'2l) and has been unable to obtain any evidence in support of their views his results being entirely negative. FREDERICK SODDY (Phil. Jfug. 1914 [vi] 27 215-221).-The effects observed by Antonov (A. 1911 ii 844; 1914 ii 17) of an abnormal decay of the soft P-rays of uranium-X have been obtained from all uranium-X preparations however chemically separated in which the time of re-accumulation of the uranium-X from the uranium was short.The barium sul- phate method of separation which Antonov found gave uranium-X free from uranium-P and decaying normally gave decay curves identical with those of the other preparations. The conclusion is formed that i f uranium-P has an existence separate from that of uranium-X it must be isotop'c with it that is occupies the same place in the periodic table and is chemically identical with it. This requires that both uranium-X and -P should be formed from either uranium-Z or -ZI in a dual change in which in both modes a-rays are expelled and that initially the slope of the soft &ray recovery curve of pure uranium preparations must be considerably steeper than that due to uranium-X alone.Under conditions when the a-rays of uranium are completely absorbed the soft P-rays produce only one-tenth of the effect of the hard &rays and the point is difficult to establish. Evidence of the increased slope in the recovery curve was obtained however which although slight witis of the right order of magnitude. The whole of the results are in agreement with the view that uranium-P is the parent of actinium in a branch series starting from either uranium-Z or uranium-ZZ claiming some 8% of the atoms on the assumption that the atoms of uranium-X and uranium-P produce equal ionisa- tions on disintegration. Since however the product of uranium-P in group IV by a &ray change must be in group V a further a-ray change must occur before actinium in group 111 can be produced. Attempts to detect an a-radiation from uranium-X and -P separ- ated as rapidly as possible from uranium were negative.Dependence of the Photo-electricity of Metals on the [Sur- rounding] Gas. GEORG PAECH (Ann. Physik 1914 [iv] 43,135-164). -The dependence of the photo-electric activity of platinum F. S. W. G. The Existence of Uranium-Y. F. S.ii. 90 ABSTRACTS OF CHEMICAL PAPERS. on the nature of the surrounding gaseous medium has been examined in a similar manner to that which was adopted by Ullmann in a previous series of experiments on the photo-electric behaviour of zinc ( A m . Physik 1910 [iv] 32 1 4 8 ) . I n both cases the surrounding gas has a considerable influence on the photo- electric activity and from the data obtained with hydrogen air carbon dioxide and water vap.our i t is evident that the activity of the two metals is similarly affected by a given change in the surrounding gas.From observations in which small quantities of the vapours of methyl alcohol acetone chloroform benzene and water were admixed with air it has been found that the photo-electric effect is much larger than in pure dry air and that the difference increases with the dielectric constant of the admixed vapour. Other experiments were made in which the metal was in contact with pure ammonia methyl ether and ethylene vapours. With ammonia the photo-electric effect was five times with methyl ether 2.5 times and with ethylene 1.8 times as great as with dry air.These results also support the view that the photo-electric effect is influenced by the nature of the gas which is in contact with the active metal. H. M. D. Relation between the Conductance and the Viscosity of Electrolytic Solutions and its Bearing on the Theory of these Solutions. CHARLES A. KRAUS (J. Arner. Chem. Soc. 1914 36 35-65).-A study has been made of the conditions under which corrections for viscosity may be applied to conductivity values and the results are interpreted in the light of the ionic theory. The influence of a change in viscosity on the speed of an ion in a solution varies with the nature of the process by means of which the viscosity change is brought about. I n general such a change is effected by (1) a change in concentration due either to the addition of a new substance or of a further amount of one already present in solution; (2) a change in pressure; o r (3) a change in temperature.Consideration is given t.o the relation between the change of ionic velocity and the change of viscosity as brought about in each of these three different ways and the results obtained are based on the figures recorded by various workers in this field. It is shown that in t h O case of aqueous solutions exhibiting negative viscosity the conductivity may be corrected for viscosity in direct proportion to the fluidity change and that the same is probably true for viscosity change due t o external pressure. Corrections f o r viscosity cannot as a rule be made in the case of aqueous solutions exhibiting a positive viscosity although some- times correction may perhaps be effected by considering the influ- ence of viscosity on the individual ions.The change in the true transference numbers of electrolytes with concentration is due t o the different effect of viscosity on the speed of the two ions. The viscosity change due t o change in concentra- tion in non-aqueous solutions is positive and much greater than i t is in water for inorganic electrolytee. The velocity of the ions inii. 91 GENERAL AND PHYSICAL CHEMISTRY non-aqueous solutions changes much less than the fluidity of the solutions although at high concentrations a marked influence results. Correction for viscosity is not possible in these caws and up to N-concentrations is in many citses unnecessary. It is pointed out that' the influence of viscosity on the speed of the ions depends on the relative dimensions of the ions and molecules to which viscosity change is due.The characteristic relations observed in aqueous solutions are partly due to the complexity of the liquid water molecules. A t higher temperatures the velocities of different ions in aqueous solutions tend to reach a common limit indicating that the ions are becoming of approximately the same size. The dimensional changes observed cannot be accounted for on the assumption that the larger ions become smaller at higher temperatures but it is suggested that ~ J S the temperature rises the smaller ions increase in size owing to increasing hydration. It is shown that the view that the high speed of the hydrogen and hydroxyl ions is related to the fact that these ions are ions of the solvent itself is erroneous.Electrical Conductivity in Hydrocarbons their Halogenated Derivatives Esters and Bases. Part I. (cont.). P. WALDEN (Bull. Acad. Sci. St. PStersbourg 1913 987-996).-Further conductivity measurements have been made (compare this vol. ii 21) of solu- tions of various' substituted ammonium salts in aniline quinoline methylaniline acetic acid sulphuryl chloride ethyl f ormate methyl acetate and methyl benzoate. Consideration of the results obtained and of those previously described (Zoc. cit.) leads to the following conclusions. Beginning with benzene to1 uene and carbon tetrachloride which have dielectric constants of 2-2-2.3 all solvents are capable of giving salt solutions with measurable electrical conductivity and must be regarded as ionising media.The magnitude of the molecular conductivity depends essentially on (1) the nature of the electrolyte binary salts especially giving conducting solutions and (2) the concentration of the electrolyte; which with faintly ionising solvents must be relatively great in order that the conduc- tivity may be appreciable. In correspondence with the slight ionising power and extremely low dielectric constants of these media the ionic concentration and the molecular conductivity are only small. I n passing from the more concentrated (V equal to or less than 1) to the more dilute of these salt solutions the conductivity curve follows one of three courses according to the nature of the solvent (1) the molar conductivity A first rism to a maximum generally a t V=1-2 and t.hen falls rapidly no minimum having been yet observed; (2) A attains a maximum and then a minimum and subsequently increases again ; the dilution corresponding with the minimal or transition point varies with different solvents and the value of the minimum ranges from about 30 to 500; (3) A shows continual increase.With tetraisoamyl- or tehrapropyl-ammonium iodide case (1) is realised with solvents having dielectric constants of E. G.ii. 92 ABSTRACTS OF CHEMICAL PAPERS. about 2 case (2) when E lies between 4.95 (chloroform) and 8-10 (dichloromethane ethyl bromide quinoline s-dichloroethane) and (3) when E is greater than 9 or 10. With another binary salt having a lower ionising tendency than the above iodides for instance tripropylammonium chloride the typical curve (2) may be observed when the value of E for the solvent is greater than 9.Curve (Z) showing successively an increase a decrease and an increase of tlhs conductivity represents the general or typical form. The lengths of its first and second branches depend on the choice of solvent and solute. I n some circumstances the minimum may approach the maximum so closely that branch 2 virtually disappears and branch 3 becomes a continuation of branch 1,so that the curve exhibits no apparent maximum or minimum. Comparison of the values of A (V=20 t=25O) for tetraisoamyl- ammoaium iodide in the different solvents with the dielectric constants and viscosities of the latter shows that in general (1) in solvents with approximately equal values of 7 the greatest molecular conductivity corresponds with the greatest dielectric constant ; (2) in solvents with approximately equal dielectric con- stants the molecular conductivity is the greater the smaller the viscosity of the solvent; (3) the molecular conductivity is there- fore a function of the dielectric constant E and of the fluidity f(l!v) that is h = F ( ~ f ) .The value of the minimum shows similar dependence. Solutions of good salt-like electrolytes in solvents of high ionising power obey the Nernst-Thomson law according to which the extent of the electrolytic dissociation increases with the dielectric constant of the solvent ; further the molecular conductivity increases with the fluidity.Hence with such solvents the dependence of the molecular conductivity on the viscosity and the dielectric constant is similar to that holding with those of low ionising properties. Between the latter which are often termed insulators and solvents which readily ionise electrolytes there is then no fundamental difference. T. H. P. Some Solvents with Small Dielectric Constants. A . SACH- ANOV and J. PRSCHEBOROVSKI (Zeitsch. Elektrochew. 1914. 20 39-41). -It was previously shown (Sachanov A. 1912 ii 730) that solvents with small dielectric constants bring about a decreased molecular conductivity of the dissolved substance on dilution. With the object of testing this point further the conductivity of a number of salts in solutions of o-toluidine (DC 6-0) benzylamine (DC 5*2) chloroform (DC 4*7) bromal (DC 7*5) a-bromobutyric acid DC 7.2) and isobutyric acid (DC 2.6) were determined The speci B c conductivities of these solvents are less than 1 x 10-7.The molecular conductivities of solutions in these solvents decrease on dilution and it is shown that the relationship AvnBlh =constant holds for all concentrations; in the case of dilute solutions where H = h (approx.) the expression becomes hvn= const. where A is the molecular conductivity v the dilution and n a constant H the viscosity of the solution and h that of the solvent. I n the casesGENERAL AND PHYSICAL CHEMTSTRT. 93 examined the value found for this expression is very constant. The authors' expression is compared with a similar expression of Kraus and Bray (A.1913 ii 914) which is shown to reduce t o the same form. J. F. S. Calculation of the Electrical Conductivity in Very Dilute Aqueous Solutions. SVANTE AHRHENIUS (Medd. K. Vet. Nobelinstitwt 1913 2 No. 42 l-l2).-The author discusses the question of the correction which must be applied to the conductivity values for dilute aqueous solutions in order to eliminate the influence of the solvent. On the assumption that the conductivity of the solvent is due to carbonic acid it is shown that the methods usually adopted in the case of acids and salts are theoretically justified provided that the acids are stronger than acetic acid and that the salts in question are salts of strong acids. On the other hand if the salts ar4 salts of weak acids the correction to be applied is less than that represented by the conductivity of the solvent.The theoretical correction depends as a first approximation on the value of k / c where k is the ionisation-coefficient of the acid and c is the concentration of the salt and a table is given in which the correction is expressed in terms of the actual conductivity of the solvent such numbers being recorded for a series of values of k / c . By reference t o the conductivity measuremenh of Kohlrausch and Maltby for very dilute solutions of sodium chloride and sodium nitrate it is shown that the variation of the conductivity a t the highest dilutions is in agreement with the requirements of the mass law. F o r both salts the ionisation-coefficient k = u2/ (1 - u)u is equal to 0.024 and the view is expressed that a t sufficiently great dilutions the ionisation of all electrolytes is in accord with the law of mass action.H. M. D. Amnity Measurements in Aqueous Alcoholic Solutions. H. EULER and I(. BLOMDAHL ( A ~ k i v . Kern. Min. Geol. 1913 4 No. 40 l-8).-The authors have determined the affinity constants of phenol and guaiacol in 80.4 aqueous-alcoholic solution by measure- ments of the conductivities of solutions of their ammonium salts (compare Euler and Bolin A 1909 ii 374; Hagglund A. 1912 ii 120 910). The values are respectively 3-1 x 10-12 and 2.4 x 10-12 corresponding with the fact that the dihydroxybenzenm are very little more dissociated than phenol (Euler and Bolin The ratio of tho dissociation constants of the compounds salicylic acid acetic acid pnitrophenol and phenol in water to that in 80% alcohol varies between 15 and 77; experiments with phosphoric acid indicated that its dissociation is affected in a similar way probably to a greater extent by alcohol.loc. cit.). T. S. P. Dissociation Constants of Organic Acids. JAMES KENDALL (Medd. K. Vet. Nobelinrrtitzct 1913 2 No. 38 1-27).-A general formula for the ionisation of acids has been given in a previous paper (T. 1912 101 1275) and further measurements of theii. 94 ABSTRACTS OF CHEMICAL PAPERS. electrical conductivity of acids have been made in order to test the formula more completely. The acids previously examined have been investigated in more concentrated solutions and measurements have also been made for salicylic acid and some of its derivatives.The results obtained afford further confirmation of the view that the ionisation constant is subjected to the influence of two disturb- ing factors clne of which (the total concentration influence) causes the constant to diminish as the concentration increases whilst the other (thc ionic concentration influence) gives rise to an increase in the constant with increasing concentration. I n the case of very dilute solutions of salicylic acid and its derivatives it is found that the ionisation constant increases to a small extent with increasing dilution. This property is character- istic of dibasic acids and it is supposed that the proximity of the carboxyl group to the phenolic group increases the strength of the latter to such an extent that the acid behaves as a weak dibasic a,cid.I n agree'ment with this it is found that salicylic acid and its derivatives cannot be titrated a t all sharply with phenolphthalein as an indicator. m2/ (1 - m)q= L + c(1- m ) / m is not apparent but the presence of the expression (1 - m ) as a factor on the right-hand side of the equation seems to point t o the activity of the non-ionised acid aB being the cause of the variation in the constant. It is also shown that the author's equation may be regarded as a special form of the general equation put forward by Bray and Krczus (A 1913 ii 914). The theoretical significance of the equation H. M. D. Piezochernical Studies. XII. The Influence of Pressure 03 ABnity. 111. G. TLMOFEEV (Zeitsch. physikal. Chem. 1913 86 113-128. Compare A.1905 ii 678; 1911 ii 15).-The influence of pressure on the E.M.K. of the elements (a) Ag-AgC1-KC1 0-1N-HgCl-Hg ; ( b ) 7% Zn amalgam-35-037L ZnClz solution-AgC1-Ag; ( c ) 7% Zn amalgam-65*59% ZnC1 solution-AgCl-Ag ; (d) 7% Zn amal- gam-65-59 ZnC1 solution-HgC1-Hg has been determined over a range of pressure 1-1500 atmospheres and a t 25O. The influence of pressure can be represented by the expression in which E and E represent the E.M.F. at pressures 7r and 1 atmosphere respectively and v1 and v2 the volumes of reacting substances before and after the change. E - E ~ = T ( v ~ - v ~ ) J. F. S. Calibration Tables for Copper-constantan and Platinum- platinrhodium Thermoelements. L. H. ADAMS (J. Amer. Chern. Xoc. 1914 36 65-72).-0wing t o the fact that thermo-elements are becoming more extensively used for measuring high temperatures two tables have been conetructed with the object of obviating trouble in converting micro-volts into degrees.Each table gives the temperature and temperature-difference for every 100 micro-GENERAL AND PHYSICAL CHEMISTRP. ii. 95 volts the cold junction being maintained a t Oo. The table for each of the two elements is intended for use in conjunction with a deviation curve determined by calibration of the particular element with three or more of certain fixed points given at the foot of each table. E. G. Behaviour of Wehnelt Electrodes in Different Gases. KARL FREDENHAGEN (Physikal. Zeitsclh. 1914 15 19-27. Compare Gehrts A. 1913 ii 1005).-The influence of oxygen nitrogen and hydrogen on the efficiency of the Wehnelt cathode has been investigated by measurements a t 9 4 5 O 1085O and 1235O and in a few cases a t 1340O. The results obtained are presented in the form of curves which show the connexion between the current and the applied potential up to 200 volts.In all cases the current-potential curves were determined for different pressures of the gas present. These curves indicate that nitrogen diminishes the efficiency of the oxide electrode but has little influence on the variation of the effect with temperature. I n presence of oxygen the efficiency of the electrode is found to be diminished t o a very much greater extent and at the same time the temperaturecoefficient of the effect is reduced especially a t the higher oxygen pressures. I n contrast with the behaviour of nitrogen and oxygen hydrogen is found to increase the activity of the electrode and in this case the currentcpotential curves for the different temperatures lie very close together.A few experiments have also been made with methane coal-gas and cyanogen. The two former behave like hydrogen whilst cyanogeu reduces the activity of the electrode to a much greater extent than oxygen. The change produced by the cyanogen in the oxide electrode is permanent and the activity is not restored even when the electrode is strongly heated in an atmosphere of oxygen. It is supposed that the change is due to the formation of calcium cyanamide. The observations are interpreted in terms of the theory of the Wehnelt electrode which has been put forward in a previous paper (Zoc.cit.). H. M. D. [Electrodes of the Third Type. J FRIEDRICH AUERBACH (Zeitsch. pl~yaikcd. Chem. 1914 86 243-246).-A criticism of the methods employed by Spencer (A 1913 ii 596) in the calculation of the ionic solubility product L = [Cu"] [I03/]2 for cupric iodate. It is shown that the agreement between the values obtained from different combinations of electrodes is determined by algebraic relationships. From Spencer's data (compare also A. 1912 ii 1129) the author finds L = 1.47 x 10-7. In view of the magnitude of the solubility of cupric iodate it is not permissible to calculate this solubility directly from the ionic solubility product. E. M. D. A Scheme for the Dissociation of Ternary Electrolytes. RUD. WEGSCHEIDER (Zeitsch. Elektrochent. 192 4 20 18).-Polemical against Drucker (A 1913 ii 1015).The author shows thatii. 96 ABSTRACTS OF CHEMICAL PAPERS. Drucker’s statements are too wide if he applies the generally adopted meaning to the word “electrolyte,” but if the term ‘ I electrolyte ” is distinguished from the term “ half-electrolyte ” the conclusions arrived a t by Drucker are tenable. J. F. S. The Electrolytic Deposition of Alloys and their Metallo- graphical and Mechanical Investigation. I. Alloys of Nickel and Iron Deposited at the Ordinary Temperature. R. KREMANN C. TH. SUCEY and R. MAAS (~ki’onarsh. 1913 34 175‘i-lS~~9).-All the experiments were made using a current density of one ampere per sq. dcm. a t the cathode. Iron .may be deposited from solutions of a ferric salt (0-5-M ferric ammonium sulphate) the current yield being 3*9% if it is assumed that the Fe”’-ions are directly deposited.If nickel sulphate (0.6-Jf solution) is also present in solution the current yield is increased agreeing with the assumption that in the simul- taneous deposition of two metals which form solid solutions the deposition of these metals is facilitated by the mutual depolarising effect of the metals. I n all the following experiments the electrolyte consisted of a solution of ferrous and nickel sulphates in varying proportions. It was found that the ratio (R,) of nickel to iron in the alloy was considerably smaller than the ratio (R2) of the metals in ths solution; also R gradually increased with R,. The character of the deposit depended on the nature of the cathode; with a carbon cathode the deposits were smooth and adherent whilst with iron cathodes they were irregular and scaly; in all cases they were brittle owing to occlusion of hydrogen.When a combined nickel- iron anode was used chiefly iron went into solution. A slight alteration of the current density had scarcely any influence on the composition of the deposit. The addition of potassium oxalate to the electrolyte increased the ratio R in a,ccordance with the fact that nickel forms more highly complex ions with oxalate-ions than does iron. Attempts to coat sheet iron with adherent deposits of an iron- nickel alloy from a neutral electrolyte were unsuccessful owing to the fornation of large quantities of a cathode sludge and to the fact that the expansions of sheet iron and the alloy deposited are different.The alloy was also very brittle because of its hydrogen content and in different experiments carried out under the same conditions the composition of the alloy varied. The formation of the cathode sludge could be prevented by the addition of sulphuric acid to the electrolyte but in solutions 0*2N with respect to the acid no deposition of metal took place. I n the last seriea of experiments citric acid was added to the electrolyte. It was found that the acid was used up during the electrolysis and a t the same time the alloy deposited contained carbon which varied from 0.5 to 1.1%; the higher the concentra- tion of the citric acid the greater the carbon content of the alloy. With increase in value of the ratio R the carbon content of the alloy increased to a maximum and then fell.When the concen-GENEBAT ASD PHYSICAT CHEMISTRT. ii 9 i tration of the citric acid was kept constant the ratio R iiicreased with t-he ratio R although not in proportion. The addition of citric acid to the electrolyte almost completely did away with the formation of cathode sludge and it was possible to deposit alloys 4-5 mm. in thickness on a carbon anode; the alloys were brittle. The metallographic investigation of the alloys deposited showed that they were' analogous in structure to and in some cases identical with alloys prepared by thermal method@. In some cases structures similar to those occurring in meteorites were observed. A structure whicn was characteristic of the electrolytic alloys consisted of concentric layerings (sphmolites).The cross-section of the deposits had a distinctly lamellar appearance which only disappeared on heating to a white heat. The hardness of the various electrolytic alloys wils measured by the sclerometric method. Both nickel and iron when deposited from acid baths are softer than when deposited from neutral baths. The alloys obtained from acid baths are harder than would corre- spond with the rule of mixtures. The authors are of the opinion that the hardnew of the electrolytic deposit depends on the fineness of the structure and not on the presence of hydrogen; the finer the structure the harder the alloy. T. S. P. Magnetic Properties of the Alkali Metals in Combination. PAUL PASCAL (Compt. rend. 1914 158 37-39).-By measuring the molecular-coefficients of magnetisation of the haloid salts and the nitrates sulphntes and carbonates of the alkali metals knowing the values of the part contributed by the acidic ions the author has calculated the atomic coefficients of magnetisation of these metals.The values obtained increase with increase in atomic weight. By plotting the logarithms of these coefficients against the atomic weights he finds that the points for lithium sodium and potass- ium lie on a straight line and for potassium rubidium and czesium on another straight line. Comparing these figures with those obtained for hydrogen and silver hydrogen comes on the first line and silver on the second line. W. G. The Shape of Molecules. T. SVEDBERG ( A ~ k i v Kern.Alin. Geob. 1913 4 No. 39 1-5).-1t has been shown by Cotton and Mouton (compare A. 1913 ii 4) that certain isotropic substances for example nitrobenzene become doubly refracting in a strong magnetic field. This is probably due to incomplete orientation of the molecules but hitherto i t has not been possible to detect any variation of the electrical conductivity of such substances according as the conductivity is measured along or across the lines of magnetic force. Such a variation should occur if the molecules show geometrical dissymmetry since the resistance to migration should vary with the orientation of the molecule. The author has found that such a variation takes place in the conductivity of anisaldazine. This substance forms an anisotropic liquid (liquid crystals) between 165O and 180° and in a magnetic VOL.CVI. ii. 7ii. 98 ABSTRACTS OF CHEMICAL PAPERS. field behaves as a strongly doubly refrating uniaxial crystal the optical axis of which is parallel with the magnetic lines of force (compare Wartenberg A.. 1911 ii 952; Mauguin A. 1912 ii 630). Since the amount of ionisation and consequently the conduc- tivity of anisaldazine is very small an electrometric method of measurement had to be used for determining the conductivity. The results showed (1) that the conductivity in a magnetic field is smaller than the ordinary conductivity; (2) that with the cell used the relative increase in resistance at right angles to the magnetic lines of force is about three times greater than parallel to the same; (3) that in a field of about 4500 Gauss the relative increase in resistance t o the magnetic lines of form is of the order of 4%; (4) that the influence of the magnetic field is closely connected with the anisotropic condition of the anisaldazine since it does not exist above 180° or below 165O.T. S. P. ETpansion of Mixtures of Garbon Disulphide and Acetone. J. VECINO Y VARONA (Anal. Pis. Quirn. 1913 11 498-515).-The density a€ Oo and refractive index a t 14'58O of acetone were found to be 0.81229 and 1.43528 and of carbon disulphids 1.29217 and 1.63149 respectively. The coefficients of expansion of acetone and carbon disulphide were determined as 148.1 x 10-6 and 117.53 x 10-5 respectively. Mixture of these liquids is attended by expansion in contra- distinction to the usual rule and similarly the thermal expansion does not follow the rule of mixtures possibly on account of the formation of molecular compounds. G.D. L. Convenient Method for Calibrating Thermometers by means of Floating Equilibrium. THEODO~ZE W. RICHARDS and JOHN W. SHIPLEY (J. Amev. Chem. Soc. 1914 36 1-lo).-In an earlier paper (A. 1912 ii 599) it was shown that the (' floating equilibrium " of a suitable solid float is exceedingly sensitive and that the " floating equilibrium temperature " is almost a linear function of the concen- trations. It was also shown that this method can be used t o analyse solutions and to calibrate thermometers. The present paper deals with the application of this process to the standardisation of thermometers and experiments are described which consist in determining the temperatures at which different aqueous solutions of sodium sulphate attain exactly the density of a given float.By plotting the floating equilibrium temperatures against the percentage composition of the solutions an almost linear curve is obtained and it is pointed out that this curve when once established will serve for the calibration of any thermometer a t any time. The method is also serviceable for determining the coefficients of expansion of liquids with known floats or the coefi- cients of expansion of floats with known liquids. E. G. Electrical Contact Vapour-pressure Thermoregulator. ALEX. L. FEII.D (J. Am#. Chem,. Soc. 1914 36 72-76) -A new form ofGENERAL AND PHYSICAT CIIEMISTRT. ii. 99 vapour-pressure thermoregulator is described which is not affected by changes of atmospheric pressure.It consists essentially of an upright U-tube closed a t both ends. One side of the tube contains a volatile liquid the b. p. of which is near the desired temperature of the bath. Above the liquid is its saturated vapour with or without admixture of air or other gas. The pressure exerted by the vapour or the vapour and gas supports a column of mercury which maken and breaks an electrical contact on the other side of the U-tube. This contact is made in an atmosphere of dry carbon dioxide. This thermoregulator is light easily adjustable and has an observed sensitiveness of 0.01-0*005°. It is adapted for use in liquid baths is not affected by agitation of the liquid and rapidly adjusts itself to changes of temperature of the bath.The regulator is therefore particularly adapted for the accurate control of the temperature of an ordinary thermostat. Speciflc Heat. 0. D. OSGOOD (Zeitsch. RZektrocIwtn. 1914 20 37).-A mathematical paper in which the application of a curve found in a thermodynamical investigation of the mass action equilibrium constant is shown in connexion with a heat loss as indicated from the magnetic hysteresis curves. Speciflc Haat of Solids. 11. H. VON JUPTNER (Zeitsch. Elektro- chsm. 1914,20 10-18. Compare A. 1913 ii 921).-A msthematicrtl paper in which an expression is evolved by means of which the atomic heat of solid substances between the temperatures T = Pv' and I1=O.394/3v' can be calculated. An expression of the form E.G. J. F. S. is deduced for the mean atomic heat of solids between T=Pd and higher temperatures. A series of tables are given by means of which the true and mean atomic heats and heat capacities between 1'=0.394Pvr and any higher temperature may be calculated. It is shown that the heat capacity a t temperatures below T = 0*394Pvr is so small that i t for most purposes may be neglected. ALBERT WIGAND (Zeitscli Elekti-ochem. 1914 20 38-39).-The specific heat of the two forms of tin have been redetermined by the author and it is shown that grey tin has a smaller value than white tin. This is in accord with the measurements of Bronsted (A. 1912 ii 897). The previous valum for grey tin obtained by Wigand (A. 1907 ii 70) are shown to be due to the presence of oxide.These results are discussed in connexion with the van't Hoff- Thomsen rules and the Richarz rule the latter of which states that in the case of allotropic substances the form with the higher specific heat has the smaller density. This rule is not followed in the case of tin. J. F. S. An Invereion Point for Liquid Carbon Dioxide in Regard to the Joule-Thomson Effect. ALFRED W. PORTER (Proc. Koy. SOC. 1914 [ A ] 89,3'77-378).-According to the experiments of Jenkin and J. F. S. Specific Heat of Grey Tin and the Richarz Rule. 7-2ii. 100 ARSTRACTS OF CHEMICAL PAPERS. Pye (A. 1913 ii 753) the Joule-Thomson effect for liquid carbon dioxide shows a change in sign a t -ZOO to -3OO. Assuming that the change in pressure may be treated as a differential it is shown that the inversion point must correspond with a minimum (or maximum) value of v/!P where t~ is the specific volume at To (absolute).Three sets of experimental data corresponding with a mean pressure of 500 .pounds per ,square inch concur in giving a minimum value of v / T a t about -24O which agrees fairly closely with the result of direct observation. The result is of special interest in that it implies that liquid carbon dioxide in this region behaves approximately like a perfect gas its volume being nearly proportional t o the absolute temperature. Latent Heat of Fusion of Ice. H. C. DICKINSON D. R. HARPER and N. 5. OSBORNE (Chem. Zentr. 1913 ii 2025 ; from J. Franklin Inst. 1913 176 453-454).-The latent heat of fnsion of ice has been determined (I) by allowing a mass of 100-200 grams to melt in a calorimeter and (2) by measurement of the energy in form of an electric current necessary to fuse a mass of about 500 grams placed in a calorimeter.As mean of ninety-two experiments performed with a great variety of samples of ice the number 79.63 cal. per gram is found. Occurrence of an Upper Critical Point of Mixing at the Go-existence of Two Mixed Crystal Phases. A. S m ~ s a n d C. A. LOBRY DIG BRUYN (Proc. K. Akud. Wetensch. Arnstwdum 1913 16 557-564).-The freezing-point and melting-point curves for binary mixtures of potassium and sod;um chlorides are continuous and exhibit a minimum at about 664O. During the cooling of a solidified mixture of the two salts changes occur whereby the homogeneous isomorphous mixture is converted into two co-existing mixed crystal phases.These phases are identical in composition at 407O but as the temperahwe falls they diverge t o an increasing extent until at the ordinary temperature the one consists of practically pure potassium chloride and the other of pure sodium chloride. This mixture affords therefore an instance of an upper critical mixing point. I n order to ascertain whether the observed phenomena are due t o the formation of a compound experiments have been made with two mixtures containing respectively 20 and 60 mols. % of potassium chloride. The two mixtures were melted and allowed to cool the rate of cooling between 37OC and 340° being very slow. The mix- tures were then powdered and agitated with a little water for two hours a t 25O the saturated solutions obtained being then analysed.The analyses show that the same solution was obtained for both solid mixtures and from this the conclusion is drawn that the phe- nomena of mixing in the! solid state are not due t o the formation of a compound of the two salts. G. WYROUBOFF ( A r m . Chim. Ph,ys. 1913 [viii] 30 633-634. Compare A. 1909 ii 740).-A reply to Cornec (compare A. 1913 ii 840). H. M. D. H. W. H. M. D. The Basicity of Acids. W. G.GENERAL AND PHYSICAL CHEMISTRY. ii. 101 Properties of Liquids as Functions of the Critical Constants. JAMES KEP~DALL (Medd. K. Vet. Nobelinstitut 1913 2 No. 29 1-28).-1t is shown that the heat of vaporisation and the specific volume can be expressed as simple functions of the critical con- stants and by reference to the experimental data of Young (A. 1910 ii 271) the validity of these relations is demonstrated for the ordinary range of temperatures.For the heat of vaporisation the equation obtained is &=k(T,-T)@ in which Q is the latent heat T the temperature T the critical temperature L a constant characteristic of the liquid under exam- ination and n a constant which has the same value 0.386 for all normal liquids. By combination of this equation with Trouton’s rule i t assumes the form MQ = 20*7T(1 - 7’/ T,)n in which M is the molecular weight of the liquid. For the specific volume of liquids the equation obtained is JT- $x=kl( T - T$ in which d is the density of the liquid at TO d the critical density and k1 a constant which depends on the nature of the liquid.The variation of the density of the saturated vapour with the tempera- ture is reprwented by a similar formula in which D is the density of the saturated vapour a t temperature T and k is a constant characteristic of the substance. The densities of liquids a t absolute zero have been calculated from the first of these two equations and it is found that the values obtained in this way are in good agreement with those found by Guldberg by extrapolation. The ratio of the density a t absolute zero to that a t the critical temperature is approximately the same for all normal liquids with an average value of 3.75 which is identical with the value obtained by Guldberg. With the aid of this relation d,!d = 3.75 the equation connecting the specific volume of the liquid with the temperature may be simplified in which case it reduces to the form $/d/d,-1=0*553(1 -T/T,)+ and this equation is found to be approximately satisfied by all normal liquids.By combination of the above equations with that of Mills for the heat of vaporisation the relation is obtained in which P is the vapour pressure V the volume of 1 gram of saturated vapour ’u that of 1 gram of liquid and p is a constant charactenstic of the liquid. According to this the equation Q = k( T - T)O.s*6 is an interpolation formula in which the exponent has a value intermediate to the values which are charac- teristic of the second and third terms of the previous equation. At low temperatures this equation assumes the form I n this equation the condition d&,/dT = 0 is satisfied if the relation- ship kipM/3T,t=R holds.This is found to be the case for normal liquids. H. M. D. yx - yo= kL( 7; - T,& Q =O*O431833P(V -v) + k,p(T,- T)*+ kZp(Tc- T)+ Q = R T I M + k ( T - T ) 8 + f/. J d,.ii. 102 ABSTRACTS OF CHEMICAL PAPERS. Heat of Vaporisation of Associated Liquids. JAMES KENDALL (Medd. K. Vet. Nobezinstitut 1913 2 No. 36 l-l4).-The formula for the heat of vaporisation of normal liquids given in a previous paper (preceding abstract) has been applied to a number of associated liquids. I n the case of normal liquids the value of n in the equation &,=k(T,-T)rh is equal to 0.386 but it is found that the exponent must have its value changed if a formula of this type is to afford values in agreement with those derived from experi- ment.I f the heats of vaporisation of water acetic acid and methyl ethyl and propyl alcohols are plotted against the temperature (TC-L") it is found that water approximates most nearly to the normal type whilst acetic acid is the most abnormal. The alcohols occupy an intermediate position. An explanation of the difference in behaviour is put forward in which the changes in molecular complexity on vaporisation and the accompanying heat changes are taken into consideration. H. M. D. New Relations between the Physical Properties of Liquids. DANIEL TYREH (J. Physical Chem. 1913 17 717-736).-A large number of empirical relations have been found connecting the latent heat of vaporisation surface tension density and other physical properties of liquid substances. From an examination of these relations by reference to the data for a number of chemically dissimilar substances it appe,ars that the three following equations are satisfied within the limits of experimental error.I n these equations I is the internal heat of vaporisation dl the density of the liquid d that of th4 saturated vapour T the absolute temperature T the critical temperature T the boiling point d8 the density of the liquid a t T y the surface tension m the molecular weight C (71.. . constants which are independent of temperature but vary with the nature of the liquid k k f . . . constants which are inde- pendent both of the temperature and the nature of the liquid. The three relations in question are y+=Vdl+(d$- d,3) where C'=kT,+/m+. d,a) and ydsa /Z(& -&)? = k'.(TG- T)dt/Z(dl-d,))- =Cff=kffm/d, holds equally well provided the temperature is not less than 6OC below the critical temperature and the relation ml= kf f f J T,(T,-T) has a similar validity if the temperature is more than 80° removed from the critical temperature. The other relations given by the author are approximate in character and the divergences met with when these are applied to actual data cannot be accounted for on the basis of experimental error. H. M. D. Relation between the Boiling Point and Composition of a Mixture of Ethyl Iodide and Ethyl Alcohol. SARAT CHANDRA JANA and JITENDRA NATH SEN GUPTA (J. Amel.. Chcm. ACoc. 1914. 36 115-118).-A study has been made of the b. p.'s of mixtures of ethyl iodide and ethyl alcohol and it has been found that these are much lower than the b.p. of either of the two components. A ml = C( T - T)+/ (d+ + d$) The equation :GENERAL AND PHYSICAL CHEMISTRY. ii. 103 mixture containing 26.69% of ethyl iodide has b. p. 7 0 0 2 ~ . As the proportion of ethyl iodide is increased the b. p. gradually falls until a minimum is reached with a mixture consisting of 87% of ethyl iodide and 13% of ethyl alcohol. This mixture distils a t 61-2O as a homogeneous liquid. On further increasing the proportion of ethyl iodide the b. p. rises again; when 97.63% of ethyl iodide is present the b. p. is 64*0°. The results of the investigation are plotted as a curve. General Cornparkon of Vapour Pressures. J. M. CRAFTS (Compt. rend. 1913 157 1403-1405).-By means of the formula T - TI = (TI1 - T/ll)C where T and TI are the boiling points of any substance at pressures P and PI and T N and TI1’ are the boiling points of a standard substance a t the same pressures C being a constant it is pomible in most cases to calculate all other vapour pressures of a substance.I n the case of hydrogen chlorine water alcohols and acids the formula needs to be modified t o where c is another constant. The standard substance used is naphthalene and a table is given showing the results for a considerable number of substances and giving the values of C and c. The value of t l - t increases by unity from zero for each 20° difference between TI1 and TI11 for nap h t-h alene. Cheaard’s Tube for Fractionation by Adiabatic Condensa- tion. E. HILDT (BUZZ.SOC. chim. 1914 fiv] 15 37-41).-The E. C. T - TI = (TI1 - T”’)[C ~ ( $ 1 - t ) ] W. G. apparatus is shown in the diagram. Partial condensation takes place in the spiral S owing according to the author to the cooling of the vapour brought about by the work done in expand- ing against the external pressure. The liquid thus condensed isii. 1104 ABSTRACTS OF CHEMICAL PAPERS. returned by the tubes 0 Of 0'1 etc. to the tube L and hence to the flask. Using this apparatus the first four fractions of 40 C.C. obtained in the distillation of 1500 C.C. of a 12*50/ alcohol con&sted of 91% alcohol. T. S. P. The Temperature of Sublimation. J. JOLY (Phil. M G ~ . 1914 [vi] 27 1-14. Compare A. 1913 ii 556).-Further experiments have been made to determine the approximate temperature a t which sublimation occurs when different minerals are heated t o a gradually increasing temperature in contact with air.The new obsmvations have reference t o minerals containing antimony arsenic sulphur tellurium bismuth selenium and lead and it is shown that the temperature of sublimation may be utilised in the classificatiori of the members of these different groups. H. M. D. Laboratory Apparatus for the Continuous Evaporation of Large Volumes of Liquid in a Vacuum. WILLIAM A. DAVIS ( J . Ayric. Xci. 1913 5 434-436).-8 simple appamtus is described with sketch by means of which large volumes of alcoholic plant extracts which are liable to froth can be evaporated continuously and the distillate recovered if desired in fractions. When once started the distillation can be left to itself except when the liquid in the flask has to be renewed.The apparatus consists of an ordinary distilling flask the side- tube of which is bent upwards and passes into a short wide tube which serves as a froth trap. The latter is connected with the top of an upright condenser the lower end of which is fitted to a cylindrical funnel (with tap) which is connected below with a pump flask and above with a large reservoir t o ensure a steady vacuum. The vacuum is obtained by means of an ordinary water- pump a safety valve (Hutchinson A. 1911 ii 933) being inserted between the pump and the apparatus. N. H. J. M. Heat of Formation of Hydrogen from Hydrogen Atoms. IRVING LANGMUIR (PhiE. Mag. 1914 [vi]. 27 188-189. Compfire A.1912 ii 826).-Further measurements of the loss of heat from electrically-heated tungsten wires in hydrogen a t pressures ranging from 1 t o 760 mm. have shown that the value of 130,000 cal. for the heat of formation of hydrogen molecules from hydrogen atoms is much too large. The new experimental evidence indicates a value of 75,000 t o 80,000 caI. which is much closer t o the value calculated by Bohr from his theory of the constitution of atoms and molecules (A. 1913 ii 689 943 1045). H. M. D. The Determination of Heat of Formation from Electro- motive Force [Measurementsl. LUISE WOLFF (Zeilsch. E/&trochem. 1914 20 19-22).-The electromotive force and temperature- coefficients of the E.M.F. have been meaaured for the cells (I) Ag I AgCl 1 nHCl1 C1,1 Pt (2) Hgl HgCII nHC11 C1 I Pt (3) Ag.] AgC'l I nHCl I HgCl1 Hg,GENERAL AND PHYSICAL CHEMISTRY.ii. 105 and from the values obtained the heat of formation of silver chloride and mercurous chloride and the heat of reaction of the change 2Ag + Hg2C1 = 2Hg -+ 2AgC1 have been calculated. The chlorine electrode was fed by chlorine largely mixed with air to reduce the secondary reactions. The heat of formation of silver chloride is found to be 30612 cal. Hg,C1 31827 cal. and the heat of the reaction between silver and calomel -2.1324 cal. A com- parative table is given of the corresponding values found by Halla Thomsen Bronsted Korev and Braune. J. F. S. The Heat of Formation of Some Compounds of Cupric Chloride with Ammonium Chloride. A. BOUZAT and ED. CHAUVENET (Compt.rend. 1914 158 40-42).-The authors have determined the hects of solution of anhydrous cupric ammonium chloride CuC1,,2NH4C1 and the hydrate with 2H20 obtained in the blue or the green form. The' anhydrous double chloride is best prepared by warming the hydrate in an atmosphere of hydrogen chloride and chlorine or heating it at looo in a current of dry chlorine. W. G. Thermochemical Studies of Diazo- and Azo-compounds. VI. Diazo-derivatives of t h e Three Nitroanilines. V. SVENTO- SLAVSKI (J. Buss. Phgs. Chsrn. Soc. 2913 45 1789-1765. Compare A. 1910 ii 691).-The heat of diazotisation of m-nitroaniline NO,*C,H,*NH,(diss.) + HCl(diss.) + HNO,(diss.) = 2H20(liq.) + NO,*C,H,*N,Cl( diss.) in aqueous hydrochloric acid is +24-19 Cal. and in acetic acid + 16.75 Cal.The heat of the reaction N0,*c6H4*N2C'l(diss.) + 2NaOH(diss.) = N0,*C6H,*N,-ONa(diss.) + NaCl(diss.) + H,O(liq.) has been measured in three ways (1) starting from the anti-cjalt + 11-20 Cal. ; (2) starting from the amine + 11-04 Cal. ; (3) starting from the diazonium chloride + 11-58 Cal. The agreement between these numbers in conjunction with the fact that the last method excludes the possibility of the formation of traces of symdiazo-salt demonstrates that the action of sodium hydroxide even in dilute solution on m-nitrobenzenediazonium chloride consists in the quantitative isomerisation of the m-nitrobenzenediazonium into the anti-diazo-salt. Measurements of the amounts of heat developed in the coupling of m-nitrobenzenediazonium chloride with @-naphthol show that the process proceeds quantitatively independently of whether the &naphthol or the diazonium salt is in excess.The value +18.89 Cal. previously given (A. 1910 ii 691) for the heat of diazotisation of pnitroaniline is incorrect owing to an error in the calcizlation of the amount of sodium hydroxide used in one of the control experiments. I n aqueous solution the value for the reaction N02*C,H4*NH2,HCl(diss.) + €INO,(diss.) = N02-C6H,*N,Cl(diss.) + 2H,Oii. 106 ABSTRACTS OF CHEMICAL PAPERS. is now found to be +19-722 Cal. in aqueous solution and +18*36 Cal. in acetic acid or allowing for the heat of solution of p-nitro- aniline in acetic acid namely -4.47 Cal. (Zoc. cit.) +13.89 Cal. The heat of the reaction II\To,*c,H40Nz~~(d~s.) + 2NaOH(diss.) = N02*C,H,*N,*ONa(diss.) + NaCl(diss.) + H%O(liq.) is + 13.77 Cal.or if the sodium hydroxide is taken in large excess + 14,724 Cal. so that the salt NO,*C,H,*N,*ONa undergoes hydro- lysis but to an extent inconsiderable in comparison with that shown by salts of cis-diazo-compounds. The heat of the reaction is 6.513 Cal. and that of N0,*C,H4*NzC'1(diss.) + NaOH(diss.) = ~ O * C ~ ~ N ~ ~ ~ ( s o l i d ) + NaOH(diss.) = N0,°C,H4*~2*O13[(solid) + NaCl(diss.) NO,*C,H,*N,*ONa(diss.) + H,O + 6.991 Cal.; the sum of these two values + 13'50 Cal. agrees satis- factorily with the number given above +13*77 Cal. Hence the product NO,*C,H,*N,*OH ,precipitated by the action of thO first molecule of sodium hydroxide does not undergo any subsequent profound change but these results are insufficient t o show that it5 N*OH ' structure is that of a trans-diazonium hydroxide since i t might equally well be the nitrosoarnine NO,*C,H,*NH*NO.But if it is assumed that the heat of solution of the precipitate differs little from that of the nitroaniline 3-74 Cal. the heat of the reaction NO,. C,,Hp*# NO,-C,&*N,*OH(diss.) + NaOH(diss.) = NO,*C,H,*N,-ONa( diss.) + H,O(liq.) will be 3-74 + 6-99 = 10.73 Cal. ; and the heat of the same reaction taking place under such conditions that the compound undoubtedly has the structure of a trans-diazo-hydroxide has already been determined to be +10*37 Cal. (Zoc. cit.). Comparison of the heats of solution of pnitrobenzenediazonium chloride in 12.7% hydro- chloric acid - 1.363 Cal. and in water - 3.00 Cal. indicates hydro- lysis in the aqueous solution.The tram-salt NO,*C,H,*N,*ONa after repeated crystallisation from 95% alcohol contains 2H,O and not lH,O as was stated by Schraube and Schmidt (A. 1894 i 237). Its transformation in 12.7% hydrochloric acid into diazonium salt N0,*C,H4~Nz*ONa(diss.) + 2HCl(diss.) = NO,-C,H,*N,Cl(diss.) + NaCl(diss.) + H,O(liq.) is accompanied by the development of 15-48 Cal. and from this the heat of the reaction NO,*C,R,*N,Cl(diss.) + 2NaOH(diss.) = N02*C,H4*N,*ONa(diss.) + NaCl(diss.) + H,O(liq.) is + 11.92 Cal. The difference between the latter number and that determined above +13*77 Cal. is owing to hydrolysis and decom- position of the tram-salt at the beginning of the reaction to the unevenness of the process of isomerisation and to the difficulty experienced in making use of concentrated hydrochloric acid as a calorimetric liquid; 13'77 Cal.is the more probable value andGENER.AL AND PHYSICAL CHEMISTRY. ii. 107 13.63 Cal. instead of 15.48 Gal. for the reverse change. effect of the reaction The heat NO,*C,H,-N,Cl(diss.) + P-C,,H,*ONa(diss.) = Na C1 (diss. ) + NO,* C,H,* N C,,H,* OH( solid) is +38*69 Cal. which should differ from 26.21 Cal. the heat developed by the same reaction in 95% acetic acid by approximately the heat of neutralisation of acetic acid namely 13.30 Cal.; the actual difference is 12.48 Cal. With o-nitroaniline the following results were obtained NO,-C,H,*NH,,HCl(diss.) + HNO,(diss.) = NO,-C,H,~N,Cl(diss.) + 2H,O(liq.) + 18.66 Cal. NO,*C,H,*N,Cl(diss.) + ZH,O(liq.) + 13.07 Cal.or in acetic acid N0,*C,H4-NH,(solid) + HNO,(diss.) + HCl(dies.) = For the isomerisation of the diazonium salt into tram-diazo-salt by the action of excess of sodium hydroxide the amount of heat developed +13*78 Cal. agrees exactly with that found with the corresponding para-derivative. These resulk in conjunction with some of those previously obtained show that for aniline p-toluidine a-naphthylamine and m- and pnitroanilines the sum of the heats of diazotisation isomer- isation into diazo-hydroxide and coupling is constant 48.44-49.35 Cal. For o-toluidine benzidine and dianisidine the heat of neutralisation by hydrochloric acid necessary to the calculation is unknown. T. H. P. Thermochemical Studies of Diazo- and Azo-compounds. VII. Supplementary Data for Diazobenzenesulphonic Acid.V. SVENTOSLAVSRI and A. MANOSZON ( J . Rugs. Phys. Chem. hbc. 1913 45 1765-1770).-The following reactions have been investigated (1) Using excess of the nitrite S03H*C,&*NH2(diss.) + NaNO,(diss.) = SO,Na~C,H,=N,=OH(diss.) + H,O(liq.) + 16.20 Cal. Using excess of the sulphanilic acid rnSO,H*C,H,*NH,(diss.) + NaNO,(diss.) = SO,Na*C,R,*NH,(diss.) + c,H,i<r (diss.) + 2H,O + so (m - 2)SO,H*C,H,*NH,(diss.) + 20.51 Cal. which gives SO,'H=C,H,*NH,(diss.) + HNO,(diss.) = so c6H,< I '(dim.) + 2-0 4- 20.31 Gal. N2 The agreement of these results with those previously obtained (A. 1910 ii 588) shows that the process proceeds quantitatively independently of whether the nitrite or the sulphanilic acid is in excess and thatl tho process of diazotisation proceeds in one and the same direction in both cases.80 (2) C,H,< 1 '"(diss.) + NaOH(diss.) = SOsNa*C,H,*N,*OH(diss.) + 5.65 Cal. *2ii. 108 ABSTRACTS O F CHEMICAL PAPERS. and C6H4<~03(diw.) + 2NaOH(diss.) = hence SO3Na-C,H4*N,*OH(diss.) + NaOH(diss.) = If a large excess of sodium hydroxide is used the heat of formation of the pseudo-salt S03Na*C6H4*N,*ONa is 6-18 Cal. the mean between this value and 4-50 Cal. approximating closely to the value 5-46 Cal. previously given (Zoc. cit.). Simple Form of Micro-balance for Determining the Den- sities of Small Quantities of Gases. F. W. ASTON (Yroc. Roy. SOC. 1914 [ A ] 89 439-446).-A simple form of quartz microlbalance (compare Steele and Grant A. 1909 ii 876) is described in which a small quartz bulb of about 0.3 C.C.capacity fused to the end of one arm is balanced by a fixed counterpoise consisting of a piece of quartz rod attached to the end of the other arm. With this arrangement the pressure necessary to bring the beam to zero affords a meaaure of the density of the gas in the balance case. This consists of a cell. about 3 mm. wide made of thick glass plates accommodation for the bulb being provided by an attached glass tube which is closed by a glass plug pushed in as far as possible without actually touching the bulb itself. The case is connected by a short capillary tube to the gas-admission apparatus and pump through one stop-cock ard to tho manometer through another. The total volume of the balance case manometer and tubes through which the gm is admitted is only a few c.c.so that the quantity of gas necessary for measurements a t a pressure of about 100 mm. of mercury is only about 0.5 C.C. In making measurements with the micro-balance the gas of which the density is required is admitted into the balance case and manometer and the pressure is raised until the bulb rises and the knob at the extremity of the counterpoise appears on the field of a fixed reading microscope. The pressure is then carefully adjusted until the knob reaches some definite arbitrary zero when the pressure is read off. The gas is now pumped out and the operation repeated with a gas of known density. The ratio of the densities is then given by the inverse ratio of the pressures. The determination can be performed in a few minutes with an accuracy of 0.1%.It is suggested that the instrument may conveniently be applied to the measurement of pressure in gases of known density. N S03Na*C,H4-N2*ONa(diss.) + H,O(liq.) + 10.15 Cal. ; S03Na*C,H4*N2*ONa(diss.) + H20(liq.) + 4.50 Cal. T. H. P. H. M. D. The Relationships between the Go-volume b and the Critical Constants. L. GAY (Compt. rend. 1914 158 34-36).- The author has determined the values of the ratios B,/b and RB/nb (compare A. 1913 ii 1027) for a number of other substances in- organic and organic gaseous and liquid. For the ratio RB/.lrb the inorganic substances give values con-GENERAL AND PHYSICAL CHEMISTRY. ii. 109 cordant with that already found namely 13.84 (Zoc. cit.). The alcohols aniline benzonitrile and water however give results dif- fering somewhat widely and this the author conslders is due to their polymerisation.The ratio V,/b for which the value 3-65 had previously been obtained needs t o be increased to 3.95 for the difficultly liquefiable gases such as nitrogen and argon. The other substances give values closely approximating to 3-65. W. G. Pieaometric Analysis. JEAN TIMMERMANS (Bull. Acctd. Roy. Belg. 1913 810-83O).-A method of studying the changes which occur in condensed systems is described. This depends on the observation of the changes in volume which take place when the compressed system is allowed to return very slowly t o the condition which it assumes under ordinary atmospheric pressure the temperature being maintained constant during the process. If the pressure readings are plotted against time piezometric curves are obtained which are in many ways analogous to the well-known cooling curves of thermal analysis.The nature of the piezometric curves which are to be expected for the various types of changes which occur in one or two com- ponent systems is examined and discussed in detail. H. M. D. Viscosity of Binary Mixtures. JAMES KENDALL (Medd. K. Vet. Nobelinst. 1913 2 No. 25 1-16).-1t is shown that tlhe viscosity of binary mixtures of non-associating chemically indif- f erent liquids can be satisfactorily represented by the formula 11 =qlnl . q2n2 o r logy=n,logq + n210gq2 in which 7 is the viscosity of the mixture n1 and n2 the molar fractions of the two components in the mixture and ql and q2 the viscosities of these components. The formula has been applied to the observations of Thorpe and Rodger Linebarger Dunstan and Getman and it is found that the average percentage deviation between the calculated and ob- served viscosity is smaller than that afforded by any of the formulz which have been previously put forward.I n the case of dilute solutions the viscosity q may be expressed in terms of that of the solvent qo by the formula y = A s . T ~ in which A is a constant and x the molar concentration of the solute with reference to a fixed weight of solvent. This formula may be derived from the previous formula by assuming that one of the components of the mixture is present in large excess. It is shown that the viscosities of aqueous solutions of sucrose and carbamide and of benzene solutions of octyl hydrogen phthalates can be satis- factorily represented by the second formula over very considerable ranges of concentration.It should be noted that the above logarithmic forrnuh only differ from those put forward by Arrhenius (A. 1888 236) in the manner in which the composition of the binary mixture is expressed. H. M. D.ii. 110 ABSTRACTS OF CHEMICAL PAPERS. Viecosity of Calcium Ghloride Solutions. FREDERICK SIM EON (Phil. May. 1914 [vi] 27 95-100).-The viscosity of a series of concentrated aqueous solutions of calcium chloride has been meas- ured a t 1 5 O and 20°. The liquid was made t o pass a t constant pressure through a horizontal tube about 30 cm. long and 0.4 mm. in diameter. Curves are drawn connecting the viscosity with the concentration and it is found that these curves are not in agree- ment with Tucker’s recent measurements (A.1913 ii 3’78) of the fluidity a t 16’77O. The curve representing Tucker’s data intersects the author’s curve for 20° a t a high concentration. H. M. D. Is Poiseuille’s Law Valid for Suspensions. M. KOTHMANN (PJluyer’rr Archie 1914 155 318-348).-X form oE viscometer is described by means of which it is possible to make continuous measurements of the rate of flow of a liquid through a capillary tube when the driving pressure is increased a t a steady rate. One end of the horizontal capillary is attached to a wider glass tube serving as reservoir whilst the other end is connected t o a second glass tube of uniform diameter and also perfectly cylindrical.The position of the liquid meniscus in this tube affords a measure of the volume of the liquid which has passed through the capillary. This position is recorded on a photographic- film which moves with cbnstant speed in a direction perpendicular to the capillary tube. In the case of a liquid which obeys Poiseuille’s law the record obtained on the film for the movement of the liquid in the wider horizontal tube will be represented by a parabolic curve. This result was actually obtained in experiments with a mixture of glycerol and water. A parabolic curve was also obtained with frog’s blood and with dog’s blood (diluted wit.h serum in the ratio 1 10) when a capillary tube of a diameter equal to 465p wits em- ployed. I n both these cases quite different curves were obtained however when a tube of much smaller diameter (loop,) was used.The evaluation of these curves by a graphic method indicates that the viscosity diminishes as the pressure increases. The rate of diminution of the viscosity with increasing pressure is much greater in the case of the frog’s blood which fact is doubtless connected with the much larger size of the corpuscles. In the matter of the number of the corpuscles the two liquids were practically identical the dilution of the dog’s blood with serum in the above-mentioned ratio being such as to make the liquids strictly comparable in this respect. The experiments indicate that Poiseuille’s law is not valid for liquid suspensions moving through narrow capillary tubes. For such liquids the viscosity depends on the driving pressure and also on the ratio of the diameter of the suspended particles to the diameter of the capillary. From an examination of the available observations relating to the circulation of blood in the living organism the author arrives a t the conclusion that this does not occur in accordance with the Poiseuille’s law.H. M. D.GENERAL AND PHYSICAT CHEMISTRY. ii. 111 The Laws of Absorption of Garbon Monoxide by Blood in vitro. MAURICE NTCLOUX ( C m p t . rend. 1913 157 1425-1428. Compare A. 1913 ii 1071; and Douglas Haldane and Haldane A. 1912 i 591).-The percentage of hzemoglobin combined with carbon monoxide in blood placed in contact with a mixture of carbon monoxide and oxygen can be determined by the equation y = lOOz/z(l- K ) + IOOK where y is the percentage of haemoglobin combined with the carbon monoxide and x the percentage of carbon monoxide in the gaseous mixture referred to their respective pres- sures in the mixture and K is a constant.The author has verified this law in the case of pig’s blood and has obtained very concordant values for K on varying the values of z. Haemoglobin in blood therefore when in contact with mixtures of carbon monoxide and oxygen combines with the two gases in proportions defined by their respective pressures in the mixture and regulated by the law of mass action. The same holds good if air is substituted for oxygen it being necessary then to consider only the oxygen. in the air. W. G. Adsorption from Solutiona. A. M. WILLIAMB (Medd. K Vet. Nobelinstitut 1913 2 No.27 1-23).-Experiments have been made on the adsorption of acetic acid by blood charcoal from aqueous solutions and on the adsorption of acetic acid and water from the vapour in contact with acetic acid solutions of varying concen- tra tion. It is pointed out that both solute and solvent may be adsorbed and when this occurs the methods usually adopted f o r the measure- ment of the adsorption lead to erroneous conclusions for neither the volume of the solution nor its mass can be regarded as constant. It is therefore suggested that the concentration of the solution should be referred t o a constant weight of solvent. In cases where the adsorption equilibrium is the same indepen- dently of whether adsorption takes place from solution or from the vapour phase in contact with it it is shown that the amounts of solvent and solute adsorbed may be calculated.In terms of this double adsorption it is possible t o give a simple explanation of the phenomena of ‘‘ negative ” and Observations a t great dilutions seem to show that the value of n in the exponential adsorption equation a=kcn becomes a whole number or a simple fraction. anomalous ” adsorption. H. M. D. Utilisation of Diffusion Processes in the Preparation of Pure Substances. JOHN JOHNSTON (J. AM. Chem. Soc. 1914 36 16-19).-The formation of large particles of slightly soluble sub- stances can be secured by causing the separation of the substance to proceed very slowly and by so selecting the temperature and composition of the medium as to have the substance as soluble as possible.The simplest way of carrying out such a process is to fill with a suitable liquid a large vessel a t the opposite sides of which are placed two small evaporating dishes containing the solid sub- stances. The vessel is protected from violent fluctuations of tem-ii. 112 ABSTRACTS OF CHEMICAL PAPERS. perature in order t o prevent the disturbing effect of convection. By this means large hexagonal prisms of calcium hydroxide can be obtained from calcium chloride and sodium hydroxide a t the ordinary temperature. Large crystals of barium sulphate have been obtained in a similar manner a t looo which were practically free from the impurity occluded by this salt when precipitated in the usual way. Another method is described in which solutions of the interacting substances are placed in flasks provided with syphon tubes which dip into the main mass of liquid.Each solution is transferred very slowly since air is only admitted into each flask through a second tube which is drawn ou,t to a very fine capillary. The crystals obtained in this way are of great purity and are theref ore very suitable for the determination of physico-chemical constants. E. G. Molecular Gomplexes in Solutions and the Distribution of Certain Substances bet ween Benzene and Water. F. BUBANOVI~' (Medd. K. Vet. Nobelinstitut 1913 2 No. 33 l-BS).-Ry means of measurements of the changes which occur in the freezing points of solutions of ethyl alcohol acetic acid and chloral hydrate in benz- ene when successive small quantities of water are added to the solutions it has been found that each of these substances forms hydrates by combination with the added water.From these data and the molecular association of the three substances in anhydrous benzene solution i t has been found possible to deduce approxi- mately the composition of the hydrates. The calculations indicate that ethyl alcohol in the more dilute solutions forms the hydrate GEtOH,H,O whilst in solutions which contain a larger proportion of alcohol the hydrate 8EtOH,H,O appears to be formed. I n the case of acetic acid and chloral hydrate the complex molecules formed correspond with the formulze 4CH3*C0,H,H,0 and 4CC13*CH( OH),,H,O. The solubility of water in benzene solutions of the above three substances has also been determined.The results show that the increase in the solubility is proportional to the square of the quan- tity of ethyl alcohol associated with a definite quantity of benzene whilst the increase of the solubility in the case of acetic acid and chloral hydrate solutions is proportional t o the first power of the quantities of these substances. Other experiments have been made on the ratio of distribution of alcohol acetic acid and chloral hydrate between benzene and water. These show that all three substances form complex mole- cules in the benzene solution. H. M. D. Solubility of Crystals on Different Faces. J. LEBRUN (Bull. Acad. Roy. BeZq. 1913. 953-979).-A solution of sodium nitrate (containing 48.55 grams of _salt per 100 c.c.) dissolved from the faces ( l o l l ) (OOOl) and (1210) of a crystal of sodium nitrate 11.8 10.8 and 10.7 mg.per sq. cm. per minute respectively. A solution of magnesium sulphate (33.10 grams MgSO per 100 c.c.)GENERAL AND PHYSICAL CHEMISTRY. ii. 113 dissolved from the faces (OOl) (OlO) (110) and (111) of a crystal of magnesium sulphate (MgS0,,7H20) 3.7 3.5 3.5 and 3.7 mg. per sq. cm. per minute respectively. The amount of material in mg. per sq. cm. per day dissolved from different faces of a quartz crystal by hydrofluoric acid of concentration I (9.718 grams) and I1 (20.169 grams HF per 100 C.C. of solution) is as follows I. 11. Base (0001) ....................... 7 -2 18-76 Prism of second order (1 120) ... 1.15 4-37 Prisiri of first order (iOT0) ...... 1-17 4'41 Direct rhombohedron (1011) ...0.97 3 *7 Fused quartz ........................ - 70.0 L. J. S. Solubility Differences on Grystal Surfaces. ALBERT RITZEL (Zeitsch. ph?ysikaZ. Chem. 1913 86 106-108).-Polemical against Kuessner (A. 1913 ii 932; compare also Ritzel A 1911 ii 488). J. F. S. Modifications of the Form of Crystals of Some Substanoes Artificially Goloured during their Growth. PAUL GAUBERT (Compt. rmad. 1913 157 1531-1533. Compare A 1906 ii 152 343; 1910 ii 4 ; Marc A. 1911 ii 193 258).-Colouring matters dissolved in aqueous solutions of various salts from which crys- tallisation is proceeding enter regularly into the crystals during the growth not only modifying their faces bue also causing the formation of macles. W. G. Retger's Rule as a Criterion of Isomorphism. W. STORTEN- BEKER (Rec.t m w . chim. 1913 32 210-225).-A theoretical paper in which the various means of testing isomorphism are discussed. It is shown that there is nothing or a t most very little in modern work which is incompatible with the view that the properties of isomorphous mixtures are a continuoue linear function of the com- position; this is most markedly seen in the case of the specific volume of isomorphous mixtures. The Action of Hydroxyl Ions on Clays and Kaolins. 11. PAUL ROELANU (Bioci~em. Zeitsch. 1913 58 202-204. Compare A. 1912 ii 1150; 1913 ii 412).-Very small hydroxyl ion concentra- tions have no influence on the sedimentation of kaolin emulsions. I f the concentration is increased the sedimentation effect is also increased up to a certain maximum point.Increase of the hydroxyl concentration above this point generally slowly diminishes the sedimentation. S. B. S. J. F. S. Equilibrium in Ternary Systems. X. F. A. H. SCHREINE- MAKERS (Proc. K . Akad. Wetensch. Amstwdurtt 1913 16 540-552. Compare A. 1913 ii 851; this vol. ii 41).-A theoretical paper in which the author discusses the nature of the equilibria in ternary systems characterised by constancy of both temperature and pres- sure. H. M. D. \TOT,. CVI ii 8ii. 114 ABSTRACTS OF CHEMICAL PAPERS. Equilibria in the System Sulphuric Acid Ammonium Sulphate and Lithium Sulphate at 30". G. C. A. VAN DORP (Zeitrrch. physikccl. Chem. 1913 86 109-112. Compare Dorp A. 1910 ii 698; and Schreinemakers and Cocheret A. 1906 ii 424; 1907 ii 23).-The equilibrium relations of the four-phase system water sulphuric acid ammonium sulphate and lithium sulphate have been determined and the results plotted on a projected spatial co-ordinate system.The following hitherto unknown compounds were isolated (NH,)2S04,3Li,S04,4H2804 ; 2(NH,)2S04 2Li2SO4,4H,SO ; and 3(NH,)2S04,Li2S04,4H,S0 J. F. S. Neutral Salt Action. BOHDAN DE SZYSZKOWSKI (Medd. K. Vet. Nobelinstitut 1913 2 No. 41 1-55. Compare A 1907 ii 238; 1908 ii 761; 1910 ii 703).-The experiments described were carried out in order to determine the influence of strong electro- lyt,es on the affinity constants of weak acids. It is shown that this influence may be calculated from observations on the distribution of the acids between benzene and water containing varying amounts of a strong electrolyte.The acids used were benzoic and salicylic with sodium chloride as the electrolyte and the concentration of this was varied from 0.1 to 1N. If the values of the affinity constants of the acid are plotted as a function of the sodium chloride concentration the curve for benz- oic acid is found to rise from 6.0 x in pure water t o a maximum value of 8 . 2 ~ 10-5 a t about 0*5N. As the concentration of the sodium chloride is further increased the affinity constant falls and in 1N-solution its value is only 4.1 x 10-5. I n the case of salicylic acid a similar type of curve is obtained the affinity constant increasing from 1 . 0 2 ~ 10-3 in water t o a maximum value of about 1-65 x in 0.25N-solution then falling to 1-00 x 10-3 in 1N-sodium chloride solution.The results obtained for a pp-ticular concentration of the strong electrolyte are independent of the concentration of the acid and this fact affords strong support to the interpretation which is placed on the experimental data. I n order to account for the maximum in the value of the affinity constant a t a definite salt concentration it is supposed that the ionisation of the acid is subjected to the influence of two opposite factors. On the one hand the ions tend to increase the ionisation of the weak acid whilst the undissociated salt molecules tend tlo reduce the ionisation. The maximum affinity constant can obviously be explained on the basis of this hypothesis for the action of the ions will preponderate in the more dilute salt solutions and that of the undissociated molecules will be the more important in more concentrated solutions. Measurements of the solubility of benzoic and salicylic acids in water containing variable amounts of sodium chloride have given results which support the above view.I n this connexion it may be noted thatl the solubility of salicylic acid in 0-1N-sodium chloride solution is somewhat greater than it is in pure water. The later portions of the paper are concerned with the explana-GENERAL AND PHYSICAL CHEMISTRY. ii. 115 tion of the deviations from the mass law which are exhibited by strong electrolytes and the view is expressed that such deviations are merely due to effects comparable with that which has been examined by the author. When it is possible to apply the necessary correction for such neutral salt effects i t will probably be found that the mass law is applicable to the ionisation of all electrolytes.H. M. D. The Combustion of Gaseous Mixtures and the Velocities of Reaction. TAFFANEL (Compt. rend. 1914 158 42-45).- A mathematical discussion of results already published (compare A. 1913 ii 1039). W. G. Influence of Hydrogen Ion and of Neutral Salts on Colour Changes and Reaction Velocities among Dyes of the Triphenylmethane Series. H. C. BIDDLE (J. Anror. Chetrh. Soc. 1914 36 84-104).--It has been shown in an earlier paper (A. 1913 ii 312) that the action of an excess of an acid on a rosaniline dye or its carbinol base leads to an equilibrium between the coloured and the colourless forms which is largely dependent on the concen- tration of the hydrogen ions of the acid.A further study of this change has proved that the velocity of the reaction leading to this equilibrium is a function of the diminishing concentration of the H' ion. The rate of the reaction differs from that of the co_nversion of the cinchona alkaloids into their toxins (Biddle and Rosenstein A. 1913,- ii 492) in being independent of the nature of the acid and being consequently a function of the molecular concentrabion of the acid. The velocity increases as the temperature rires the rate of increase becoming greater with diminishing concentration of the H' ion. Neutral salts increase or decrease the rate of the reaction in presence of a weak acid in accordance with their effect in diminishing or increasing the degree of dissociation of such an acid.The neutral salt effect gives rise to a change of colour and a diminution of the velocity of the reaction corresponding precisely with the results produced by an increasing concentration of the H' ion. It has been found that within certain limited ranges the rate of reaction may be used as a dynamic method for determining the concentration of the H' ion. E. G. Expression of the Velocities of Transformation of Physico- chemical Systems as a Function of the Affinity. R. MARCELIN (Ccin7pt. rend. 1913 157 1419-1422. Compare A 1911 ii 27).- A mathematical discussion of such expressions in the case of dif- fusion,. evaporation sublimation and solution based on the hypo- thesis that a physico-chemical complex in process of transformation is constituted by two systems which evolve in opposite senses; the progressive system increases in mass whilst the regressive system diminishes.The observed velocity u is the resultant of the velocities of these systems. W. G . 8-2ii. 116 ABSTRACTS OF CHEMICAL PAPERS. Reactions of Vibriolysine. SVANTE ARRHENIUS [with THORVALD MADSEN and YUTAKA ‘rEHUUCEI] (Meclcl. h’. Vet. Nobelinstitut 1913 2 No. 39 1-39).-Experiments have been made to determine the nature of the processes which are involved in the absorption of vibriolysin by blood corpuscles coagulated serum-albumin and animal charcoal and also in its neutralisation by anti-vibriolysin. I n the case of the blood corpuscles the rate of absorption can be represented by the formula for a unimolecular reaction an equi- librium condition being reached in which the concentration of the vibriolysin in the corpuscles is 286 times that in the surrounding solution.The ratio of distribution in the equilibrium condition has been found to remain constant when the concentration is varied in the ratio 1 25. The velocity of absorption increases very rapidly with the temperature the velocity becoming 4.7 times as great for a rise of loo. The dynamic experiments with charcoal show that vibriolysin is decomposed by this substance and the data would appear to in- dicate that each particle of carbon is only capable of decomposing a definite quantity of the lysin per unit of time. I n many respects the change offers a close resemblance to reactions in which enzymes are involved.The influence of temperature on the change is relatively small a rise of temperature of loo increasing the velocity only in the ratio 1 1.5. The neutralisation of vibriolysin by anti-vibriolysin takes place in accordance with the formula for a bimolecular reaction if the concentrations of the reacting substances are reckoned from the equilibrium condition. This behaviour is closely similar to that which has been observed in the neutralisation of tetanolysin. With regard to the absorption of the lysin in coagulated serum- albumin it is found that the process leads to a condition of equi- librium and that the rate of change is approximately in agreement with the bimolecular formula. The amount absorbed in the equi- librium condition is proportional to the square-root of the concen- tration of the surrounding solution and it seems probable therefore that the phenomenon is one of absorption. It differs therefore completely from the changes which are involved in the absorption of vibriolysin by blood corpuscles and in the neutralisation by anti- vibriolysin.Although the decomposition of the lysin is the chief characteristic in the action of animal charcoal it is possible that the decomposition is preceded by adsorption. The Influence of Foreign Substances on the Activity of Catalysts. 111. Platinum a s Hydrogen Carrier. C. PAAL and E. WINDISCH (Ber. 1913 46 4010-4016).-1n continuation of previous experiments (compare A. 1913 ii 1043) the catalytic behaviour of platinum deposited on various metal powders and insoluble’ compounds has been investigated ; the particular reaction used wae the reduction of cotton-seed oil by hydrogen.The platinised metals were prepared by shaking the metal powder with an aqueous solution of chloroplatinic acid; in the case of magnesium an aqueous-alcoholic solution was used. The products H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 117 were washed with water alcohol and ether excepting platinised magnesium where washing with water was omitted and then dried in a vacuum. The amount of platinum deposited was 2.5% of thO weight of the metal. The compounds were coated with 2.5% of platinum by suspending them in an alkaline solution of chloro- platinic acid and subsequent reduction with hydrazine. Only magnesium and nickel have no effect on the catalytic activity of the platinum ; aluminium cobalt and bismuth diminish the activity very considerably whilst iron copper zinc silver tin and lead do away with it completely.Magnesium oxide and carbonate have no effect whereas basic lead carbonate and basic bismuth nitrate make the platinum passive. Gatalytic Esteriflcation by the Wet Method. E. BODROUX (Compt. rend. 191 3 157 1428-1 430).-A theoretical discussiou of the nature of the action in the catalytic esterification of acids by means of inorganic acids (compare this vol. i lo). The author suggests that an intermediate additive compound is formed by the organic and inorganic acids as follows T. S. P. /OH \X R*CO,H + HX = ft*C-OH where HX represents an inorganic acid. Size and Constitution of the Atoms. ADOLF HEYDWEILLER (Ann.Physik 1913 [iv] 42 1273-1286. Compare A. 1913 ii 645 9l'9).-Tbe diameters of molecules can be calculated from the mean free path in the gaseous condition and also from the molecular refractivity. A comparison of the results obtained in the cme of the monatomic inert gases shows that satisfactory agree- ment is obtained only i n thO case of xenon. With falling atomic weight the divergence between the numbers increases and in the case of helium the ratio of the values reaches 1 - 5 l . The values obtained for the diameters of the molecules of hydrogen and chlorine from viscosity data are respectively 2.176 and 3.693 x The diameters of the hydrogen and chlorine ions as deduced from refractivity data are 1.663 x 10-8 cm. and 2.765 x 10-8 cm. respectively.The ratio of the numbers for hydrogen is 0.764 and for chlorine 0.749. On the assumption that the hydrogen (or chlorine) atoms fuse together to form a spherical molecule the ratio of the atomic to the molecular diameter would be 0.794. If on the other hand the atoms remain isolated the ratio of the atomic to the effective molecular diameter would be 0.774. Both these numbers are in fair agreement with the above ratios for hydrogen and chlorine and afford support f o r the author's view that atomic dimensions can be accurately calcu- lated from refractivity data. The constitution of the atom is discussed in reference to the author's steric theory (Zoc. c i t . ) and evidence is obtained which suggesh that the number of eiectrons in the atom is about a hundred timw as large as the steric number.According to this,. the hydrogen atom would contain about 500 electrons. H. M. D. W. G. cm.ii. 118 A 13STLtACTS OF CHEMICAL PAPERS. Theory of the Electrical and Chemical Forces in the Atom. A. BYK (Ann. Physik 1913 [iv] 42 1417-1453).-A theoretical paper in which the author discusses the constitution of the atom and the nature of the forces which come into play in atomic systems. The theory is applied in the calculation of molecular dimensions values being obtained for the diameters of the molecules of the alkali metals the halogens and compounds of carbon sulphur and chlorine which are in accordance with those derived from experimental data. The heats of dissociation of chlorine bromine iodine sulphur and phosphorus are also deduced from a formula in which electro-magnetic data only are involved the values obtained being in all cases in fair agreement with the thermal data recorded in the literature.A further conclusion to which the author’s theory leads is that the forces operating within the atom give rise to a definite atomic configuration in the case of the atoms of carbon compounds and complex inorganic compounds but that such a condition of atomic equilibrium is not characteristic of the atoms of electrolytes. H. M. D. Calculations of Frequency and Certain Relations between Elastic and Thermal Constants of Solid Elements. C. E. BLOM (Ann. Physik 1913 [iv] 42 1397-1416).-The various formule which have been put forward for calculating the frequen- cies of atomic vibration are compared by reference to the values obtained for a large number of metals.The values are not in agreement and it is not possible to decide which of the formulae gives the best results. The formula comparison suggests that. the quantities 1 / E T,/ V R,/3aV and C,,/3aB are proportional to one another E being the compressibility T the absolute melting temperature V the atomic volume R the gas constant C the atomic heat at constant volume and a the coefficient of linear expansion. If this propor- tionality is assumed a number of relations can be shown to hold between 3he elastic and thermal constaats ; these relations have been obtained previously in some cases empirically and in others by theoretical deduction. The atomic frequencies show a periodic variation with the atomic weight a relation which is not surprising in view of the periodic connexion between the elastic properties and the atomic weight and of the fact that the atomic frequencies are closely related to the cohesive forcm.Although the frequency formulze are not in general applicable to compounds certain relations which these formulae suggest are to be found between the elastic and thermal properties in certain cases. For oxides of the type RO i t is shown that there is a parallelism between the hardness and the atomic heat. H. M. D. Linking of Atoms particularly those of Carbon. A. F. HOLLEMAN (Em. f m v . chim.. 1913 32 175-183).-The author evolves a theory of the linking of atoms which combines some ofGENERAL AND PHYSICAL CHEMISTRY. ii. 119 the views of Werner with those of Stark.Making use of Stark’s idea of valency electrons it is shown how the linkings can move their relative positions on the surface of the atoms. The hype thesis is made use of to explain the Walden inversion racemisation and the Baeyer strain theory. It is shown that easy formation of double linkings cannot be directly explained on the present hypo thesis. The theory is examined in the case of other atoms; the positions of the valency electrons a t opposite ends of a diameter of the oxygen atom ar0 regarded as producing a strain in the carbonyl group which explains the ease with which the carboxyl group enters into combination. The isomerism of oximes is explained if the quinquevalent character of nitrogen is admitted. The equilibrium positions of the valency electrons for elements of valencies one to six are deduced.J. F. S. Mechanical Processes of Combination. NATHANIEL T. BACON (J. Physical Chem. 1913 17 762-768).-A theoretical paper in which an attempt is made to explain certain reactions between gases and solids by the assumption that condensed layers of gas molecules are formed a t the surface of the solid in consequence of the imperfect elasticity of the molecules. P. DE KEEN (Bull. Acad. Roy. BeZg. 1913 667-679).-The author con- siders that the electron theory does not furnish any satisfactory explanation of the behaviour of elemente of variable valency. H. M. D. The Electron Theory and the Conception of Valence. H. M. D. Automatic Mercury Pump. G. P. PAMFIL (J. Chim. P h w 1913 11 801-804).-A description of a mercury pump the auto- matic action of which is maintained by the use of a water-pump. The reservoir into which the gases from the apparatus to be exhausted expand and from which they are then expelled by the mercury is relatively large so that the rate of exhaustion is rapid.The pump contains an arrangement for collecting the exhausted gases for analysis. T. S. P. Simple Stirring Arrangement for Test-tubes. H. E. SCEAUMBURG (Chern. Zed. 1913 37 1581).-h bulb the diameter of which is about 1 mm. less than the internal diameter of a te& tube is blown on the end of a piece of glass tubing. I f this is immersed in the liquid in the test-tube and then moved rapidly up and down taking care that the bulb does not come above the surface of the liquid it acts as a very efficient stirrer. T. S. P. An Electric Vacuum Oven for High Temperatures. JOHANNES WOLF and ERICH MULLER (Zeitsch,. Elektrochem. 191 4 20 1-4).-An electric oven is described which by the use of carbon resistance tubes gives a temperature of 2850O. ThO energy con- sumption for this temperature is 15 kilowatts a quantity about 30% less than that consumed by other ovens of the same type.ii. 120 ABSTRACTS OF CHEMICAL PAPERS. The furnace is fitted with an arrangement for removing the experimental substance whilst i t is a t its highest temperature. J. F. S. A Rapid Apparatus for Ether Extractions. J. J. L. ZWJKKER (Pharm. Weakblad 1914 51 21-23)-A new simple form of ether- extractmion apparatus in which the extraction vessel is immersed in a condenser the ether vapour is carried by a bent tube to the lower end of it and the condensed ether rises through the liquid to be extracted and passes through a side-tube back into the heating flask. A. J. W. A New Form of Extraction Apparatus and Reflux Con- denser. PROBODHA CHUNDRA CHATTOPADHYAY (J. Soc. Chem Ind. 1913 32 1145-1146).-The extractor consists of an outer glass jacket and an inner glass tube (thimble) of smaller diameter. The latter is provided with a series of holes at the top and with some near the middle; there is also a very small hole a t the bottom of the thimble to allow the liquid to drain away completely when the extraction is finished. There is no syphon tube as in the Soxhlet apparatus. The substance to be extracted is placed directly into the thimble or else in a fat-free paper thimble which is then placed in the glass thimble. During the extraction the liquid overflows continuously through the holes near the middle of the thimble. I n the reflux condenser the inner tube consists of a series of four bulbs with flat spirals interposed between the second and third and between the third and fourth bulbs. The advantage of this arrangement is that a central draught which is a drawback even with double surf ace condensers is prevented. A. W. DAVISON (J. Phyrrical Chem. 1913 17 737-754).-The paper contains an account of a series of experiments on the dyeing of wool and cotton which were undertaken with the special object of collecting data which might be utilised in devising lecture experiments to illustrate the theory of dyeing. The experiments were made with basic and acid dyes and the behaviour of these in alkaline neutral and acid solution was compared. Other observations have reference to the influence of the addition of sodium sulphate and the behaviour of lakes. T. S. P. Experiments in Dyeing. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9140605081

出版商:RSC    

年代:1914

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PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 101 The Composition of the Air in the Tracheal System of Insects. AUGUST KROGH (Skand. Arch. PhysioZ. 1913 29 29-36). -The tracheal system in the hind legs of the grasshopper can be rapidly and extensively ventilated by the respiratory movements of the insect. About 20% of the contained air can be renewed by one breath. The oxygen percentage of the air of the hind legs is high during rest (16%) but after exhausting muscular exercise it is reduced t o 576. The percentage of carbon dioxide is always much lower than the oxygen deficit and a large part of the carbon dioside formed in the tissues must be carried away by other means than through the trachea=. Saline Perfusion of the Respiratory Centre in Frogs; the Effect of Calcium Chloride and Potassium Chloride.I). R. HOOKER (.I. P~~TWUXCO~. expt. Z'hr. 1913 4 443-451).-M7h 11 the respiratory centre is perfused with a suitable salt solution i t continues active for several hours. If the salt solution contains balanced quantities of calcium and potassium removal of the potassium depresses and of the calcium excites the centre. Increase of potassium depresses and decrease excites. Increase of calcium excites and decrease depresses. W. D. H. TAT. D. H.i. 102 ABSTRACTS OF CHEMICAL PAPERS. Chemical and Morphological Investigations on the Im- portance of Cholesterol in the Organism. IV. The Cholesterol Content of the Blood of Difierent Animals and t h e Influence of Cholesterol Intake especially with the Food. L. WACKEJX and W.~ H I J E C K (Arch. mpt. Path. Pharm. 1913 74 416-441).- Simple shaking of fluids (blood bile etc.) with ether chloroform etc. for the purpose of extracting lipoids is not free from error for the other colloid constituents of the fluid are affected. Cholesterol in the blood is contained in the corpuscles in the free state; the white corpuscles contain five times the amount of that in the red corpuscles. The blood fluid contains cholesterol partly free partly as esters. Defibrination does not affect the cholesterol. The relationship of the free to the combined cholesterol varies in the animals used (rabbit calf dog horse) from 1 1.7 t o 1 3.3. It is affected by nutrition muscular work breathing and other factors. By feeding on free cholesterol the amount of free cholesterol in the blood serum is increased but that in ester form is still more increased; it may reach twenty-two times the normal.The same result follows subcutaneous administration ; the corpuscles are but little affected. I n growing animals cholesterol accelerates growth leading especially to deposition of fat. The suprarenal cortex is richer in cholesterol and other lipoids. The same is true f o r other organs (liver kidney spleen etc.) Continued adminis- tration leads t o disorders of the alimentary canal and to arterial sclerosis. W. D. H. Chemical and Morphological Investigations on t h e Im- portance of Cholesterol i n the Organism. V. The Cholesterol Content of t b e Blood of t h e Dogfish (Scyllium catulus) under the Influence of Dyspncea. W. HUECK (Arch.expt. Path. Pham. 191 3 74 443-449).-The blood-plasma of Scyllium contains very little lipoid (0*05%) and about half of this 0*02% is cholesterol. The red corpuscles contain only free cholesterol (0.08%) ; the plasma contains free cholesterol (0.01 5%) and cholesterol esters (0.005%). I n narcosis and in the dyspneic condition which follows exposure to air the cholesterol esters of the blood quickly rise to tenfold the normal amount and the free cholesterol is doubled. W. D. H. Chemical and Morphological Investigations on the Im- portance of Cholesterol in t h e Organism. VI. The Influence of Muscular Work on t h e Cholesterol Content of t h e Blood and Supra.rena1 Bodies. EDWIN PICARD (Arch. w p t . Pnth. Pharm. 1913 74 450-460).-1n dogs muscular work affects the amount of cholesterol in the blood and in the suprarenal cortex in opposite directions.If the work is prolonged and increasing the cholesterol esters of the cortex fall and of the blood rise. I n short with rapid muscular exercise the amount iiicreases in the cortex and slightly falls in the blood. W. D. H. The Permeability of Blood-corpuscles for Dextrose. P. GYORGY (Riochen?. Zeitsch. 191 3 57 441-455).-1t baB been shownPHYSIOLOGICAL CHEMISTRY. i. 103 by Rona and others that the blood-corpuscles of sheep are impermeable to dextrose whereas those of dog and man are permeable. Experiments were carried out with the corpuscles of sheep to ascertain whether they could be made permeable either by alteration of the hydrogen ion concentration of the artificial medium in which the corpuscles were suspended by means of regulators (phosphate carbonate o r acetate mixtures) or by the addition of sugar to the whole blood in the presence of hzemolytics (present in quantities below those necessary t o produce hzemolysis) and in the presence of various salts such as those of calcium or aluminium.The results obtained were however negative. S. B. S. The Behaviour of the Maltase of the Blood-serumof Fed and Fasting Animals. T. KUMAGAI (Bioclmn. Zeitsch. 19 13 5 7 375-379) .-The hydrolysis of maltose by the blood-serum obtained from fasting dogs takes place more rapidly than by that from fed animals. Quantities of serum which when obtained from fed animals are inactive produce distinct hydrolytic action when obtained from fasting animals.The results confirm those previously obtained by Kusumoto (A. 1909 ii 69). S. B. S. The Gastric Secretion at Birth. ALFRED F. HEM (Amer. J. Dis. Children 1913. 6 264-276).-New-born infants secrete a good deal of hydrochloric acid before any food is given; it was found in fifty-one out of fifty-two cases. The amount is variable. The gastric juice in unfed new-born children also contains pepsin rennin and lipase. W. D. H. Pancreatic Enzymes in Infants. I. ALFRED F. HESS (dmer. J. Dis. cfddven 1912 4 205-218).-1n infants it is easy to obtain the duodenal contents by a long catheter ; the pancreatic juice aspirated off in this way contains all the normal enzymes but the total secretion is very scanty during the first week of life. Amylase increases in amount with age so also does the total juice. Even in marasmic children the amouo5 secreted although thin is abundant and contains all the enzymes although i t is weak in lipase.I n these children the gastric juice is scanty. W. D. H. Pancreatic Enzymes in Infants. 11. In Acute Intestinal Indigestion. ALFRED F. HEW (8naer. J. Dis. Children 1913 5 268-2 72).-In acute indigestion (alimentary toxEmia) the lipase of the pancreatic juice is deficient although the other two enzymes are present in considerable amount. This is not a general charac- teristic of all febrile conditions. The lack of lipase may be related t o fat intolerance which is often seen in this condition. W. D. H. Fermentation Processes in t b e Digestive Tract of Ruminants and Pjgs. J. MARKOFF (Biochem.Zeitsch. 191 3 57 1-69).-The partly digested food was removed from the first stomach of oxeni 104 ABSTRACTS OF CHEMICAL PAPERS. by means of a stomach-pump described and figured and trans- ferred to the lower bulb of a modified Pfluger gas pump. The gastric contents thus obtained were then allowed to ferment and the gases produced were removed and submitted t o analysis in a modified Haldane gas apparatus. The details of the method are fully described and the apparatus is figured in the text. The carbon dioxide methane and hydrogen produced by fermentation were estimated and also the amount of carbon dioxide which is produced by the direct treatment of the gastric juice with acids. This is derived from the carbofiates secreted in the saliva which in the case of oxen is large in amount.Attention is incidentally called t o the fact that diastase is not present in this saliva. The addition of sugar causes increased production of carbon dioxide due to the formation of organic acids of about the same molecular weight as butyric acid. The contents of the other parts of the alimentary tract than the first stomach of freshly killed animals (oxen and pigs) were also removed and submitted to fermentation by the above-described methods. I n this way the fermentation in different parts of the alimentary tract was examined after ingestion of different kinds of food and the losses of energy value of the food-stuff s owing t o fermentation was thereby determined. The results are illustrated by a large number of gas analyses which are mainly of technical inksrest.S. B. S. The Fate of Protein Digestion Products in the Body. YII. The Absorption of Amiao-acids from the Blood by the Tissues. ~JONALD D. VAN SLYKE and GUSTAVE M. MEYEP ( J . B;ol. Chem. 1913 16 197-212).-The disappearance of amino-acids from the circulation after intravenous injection is rapid and due to their absorption by the tissues without undergoing any immediate change. I n the muscles there is a saturation point beyond which the acids are not absorbed (75 t o 80 mg. per 100 grams); the capacity of internal organs is greater (125 to 150). The removal from the blood is never complete; after a fast of several days the blood still contains O*OOS-O.OOS%. A t this point the amino- acids of the blood are in equilibrium with those of the tissues.Transference from organ 60 organ or from mother to fetus may occur. The process is not wholly osmotic because normally the con- centration of amino-acids in the tissues is five t o ten times greater than in the bhod. Probably the tissues adsorb the acids mechani- cally or else a loose compound is formed between the tissue-proteins and the acids. W. D. H. The Fate of Protein Digestion Products in the Body. IV. The LZICUS of Chemical Transformation of Absorbed Amino- acids DOXALD I). VAN SLYKE and GUSTAVE 311 MEYER (J. B i d . Ch~m. 1913 16 213-230).-Not only are amino-acids injected into the blood a.bsorbed by the tissues but absorbed amino-acids disappear rapidly from the liver. The amino-nitrogen of the liver may be doubled after injection of amino-acids into the blood but in two hours it returns t o normal; in the muscles there is in this time noPHYSIOLOGICAT CHEMISTRY.i. 105 appreciable fall ; the disappearance from kidney intestine pancreas and spleen is also less rapid than from the liver. The decrease in the liver is accompanied by an increase of urea in the blood. This supports the view so long held that the liver is the main organ where catabolism of protein digestion products takes place. The liver being so ready t o get rid of absorbed amino-acids maintains indefinitely its power to remove these substances from the circu- lation; and i t is only when the entrance is unnaturally rapid as in injection experiments or when the liver is degenerated that this organ is unable t o cope with the supply; the kidney then assists by excreting them unchanged.Each tissue is probably able to synthesi-se its own proteins from the amino-acids which it absorbs from the blood. W. D. H. The Fate of Protein Digestion Products in the Body. V. The Effects of Feeding and Fasting on the Amino-acid Content of the Tissues. DONALD D. VAN SLYKE and GUSTAVE M. RIEYER (J. Bid. Clronz. 1913 16 331-234).-The amino acids not only serve as tissue-building material but also occur as inter- mediate breakdown products of the tissue proteins. Starvation therefore would not necessarily mean a disappearance of the tissue amino-acids; i t might even increase the amount. This view is supported by experiments on dogs in various degrees of inanition; male dogs only mere used t o avoid complications due t o pregnancy.The failure t o increase the free amino-acid content of the tissues by high protein feeding indicates furthermore that when nitrogen is retained in the organism it is not t o an appreciable extent stored in the state of digestion-products but as body protein. W. D. H. Endogenous Metabolism of the Pig. I. The Effects of Acid and Basic Salts and of Free Mineral Acids on the Endogenous Nitrogen Metabolism. E. V. MCCOLLUM and D. R. HOACL~ND (J. R i d . Chem.. 1!?13 16 299-316).-D4t t are presented which show that the endogenous metabolism of the pig reaches its lowest level when the animal has an abundant supply of carbo- hydrates together with a salt mixture of an alkaline character. The total output of nitrogen derived from endogenous sources can be greatly increased without changing the output of creatinine.The additional nitrogen excreted on an acid diet is in the form of ammonia. The pig is not able to use the nitrogen of the urea fraction to neutralise the acids of the food but draws additional nitrogen from the tissues for the production of ammonia. W. D. H. Endogenous Metabolism of the Pig. 11. The Influence of Fat Feeding on the Endogenous Nitrogen Metabolism. E. V. Blr:CoLr,unr and D R. HOAOLAND (.7 Biol. Chom. 19 I 3 16 3 17-320)- If fat is given as the sole source of energy there is no sustained rise in the nitrogen output of pigs which have been reduced to their lowest level of nitrogen metabolism by long-continued feedingi. 106 ABSTRACTS OF CHEMICAL PAPERS. on starch; but i t may lead to a considerable elimination of creatine.The total creatine + creatinine may be greatly increased without a corresponding rise in the total nitrogen output. The possibility of the acid or basic character of the ration influencing creatine production is suggested. Endogenous Metabolism of the Pig. 111. The Influence of Benzoic Acid on the Endogenous Nitrogen Metaboliem. E. V. MCCOLLUM and D. R. HOAGLAND (J. Biol. Chem. 1913 16 321-326). A good deal of the nitrogen wh'ch appears as urea in pigs reduced to the lowest level of endogenous protein metabolism may be converted into glycine when benzoic acid is given and excreted as hippuric acid. Benzoic acid does not raise the total nitrogen excreted unless very large quantities are given ; the urea-nitrogen may then be less than 20% of the total; it causes no change in the creatinine output.Endogenous protein metabolism presents two types; one can be stimulated by acids leading to the production of ammonia or by benzoic acid leading to the production 07 lzippuric acid ; the other measured by creatinine remains unaffected. W. D. H. W. D. H. Formation of Sugar from Fat. RUDOLF ROUBITSCHEK (Pfiiigeds Archiv 1913 155 68-73).-Adrenaline does not cause glycosurin in the case of dogs completely free from glycogen. Glycosuria sets in immediately however when the liver is enabled to make glycogen from the glycerol component of an oil. It is requisite that the oil shall have passed through the intestine and given up its glycerol component. E. F. A. The Diet and Metabolism of Eekimos.AUGUST KROGH aud MAXIE K~oatr (Meddelelser om Groodand 1913,51 Reprint. 52 pp).- The normal diet of Eskimos contains an excessive amount of protein (280 grams) and much fat (135 grams) while the quantity of carbohydrate is very small (54 grams) of which more than half is the glycogen of the meat eaten. This diet has no injurious effects whatever; the people are capable of prolonged work and have great endurance towards cold and other hardships. Uric acid diseases are very rare if they occur at all. The large quantities of seal meat are well absorbed and utilised. The loss of nitrogen in the faxes amounts to 3 to 5 grams per day. Details are given of the composition of the urine in diffeIent parts of the day and of the respiratory exchanges. The " specific dynamic action " of the protein works out as 8.6 5% of the calorific value of the protein catabolised.The dietary habits of the Eskimos are very like those of the carnivora and these people are able t o retain a large amount of protein for a certain period exceeding twenty-four hours and t o utilise it as a source of energy with very little loss. Metabolism Studies on Cold-blooded Animals. 11. The Blood and Urine of Fish. W. DENIS (J. Bio2. Chem. 1913 16 389-393) .-The non-protein nitrogen urea ammonia uric acid W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 107 and creatinine wem estimated by the methods of Folin and his colleagues and the results stated f o r numerous fish in a table. In elasmobranch fishes the urea in the blood is high but in teleosts i t is lower than in mammals.The ammonia fraction of the blood is high. Uric acid is present in elasmobranch blood in the merest traces but in teleostean blood in moderate amount; the amount in the urine is small in both classes. The analysis of one composite specimen of urine from the goose fish (Lophius piscatorius) is given ; this is a representative teleost ; the most noteworthy points are the large amount of undetermined nitrogen and the creatinine is almost entirely replaced by creatine. It is possible that in fishes nitrogenous waste may be eliminated by some organ other than the kidney. W. D. H. Studies on Growth. I. Growth on Vitamine-containing and Vitamine-free Foods. CASIMIR FUNK (Zeitsch. phwsiob. Chwm. 1913 88 352-356).-Young chickens were fed on various diets and their growth watched.Those fed on ordinary chicken food grew normally; on polished rice they died quickly from beri-beri. On unpolished rice they did not develop disease but did not grow. On unpolished rice plus yeast they grey comparatively slowly; on unpolished rice plus sarcoma tumour (Rous) they grew more slowly still. I n each batch some of the birds were inoculated with the tumour; the inoculated specimens grew more rapidly. From the last-named observations no conclusions are drawn a t present ; but from the others the conclusion is drawn that the vitamine which prevents beri-beri is a different one from that which stimulates growth. The chemistry of the ‘‘ growth vitamine ” is not yet known. It is suggested that the vitamine undergoes metabolic changes in such organs as the pituitary gland.W. D. H. The Influence of Butter-fat on Growth. THOMAS B. OSBORNE LAFAYETTE B. MENDEL EDNA L. FERRY and ALFRED J. WAKEMAN (J. Rid. Chem. 1913 16 423-437).-The growth-promoting ‘‘ vitamine ” of milk is found in the butter-fat fraction ; its chemical nature is not known. The experiments were made on rats. W. D. H. Parentera1 Nutrition by Intravenous Injection. V. HENRIQUES and A. C. ANDERSEN (Zeitsch. phqaiol. Chem. 1913 88 357-369).- A method is described by which it is possible to keep animals (goats) alive for a considerable time by intravenous injections of a nutritive mixture. The mixture is composed of almost completely cleaved flesh (about 15% of the nitrogen in peptide form) dextrose sodium acetate and salts. The animals put on nitrogen.Protein synthesis is therefore possible without the digested protein producb passing through the intestinal wall. W. D. H. The Lipoids of Ancient Egyptian Brains. W. MAIR (J. Path. Ract. 1913 17 179-184).-Whereas fresh brain contains noi. 108 ABSTRACTS OF CHEMICAL PAPERS cholesteryl esters but only free cholesterol the brains of mummies 3000-4000 B.c. and even of Copts 500 A.D. contain esters. Thus the free cholesterol in recent brains amounts to 11.3%; of the Coptic brain the total cholesterol is 8*4% of which 8 is in ester form. I n the brains 3000 to 500 B.c. the total is from 0.68 to 0*83% and that as ester from 0.43 t o 0.5. I n ancient brain (4000 B.c.) the little cholesterol present (0.04%) is all in the form of esters.Details are also given of nitrogen phosphorus ash etc. The Coptic bodies were packed in salt before burial; the older ones not. The effect of time on chemical reactions is probably the same as the effect of heating. Preparation and Saponiflcation of Cholesteryl Esters. W. MAIR (J. Path. Bact. 19 13 17 185-1 90).-Chnlestjeryl esters occiir in areas of brain softening; these are saponifiable by boiling for four hours in a N/5-barium hydroxide solution in 90% methyl alcohol. The lipoids in ancient Coptic brains are not saponifiable in this way. Various esters were therefore examined; those with lower fatty acids are saponifiable; those with higher fatty acids are not saponifiable by this method. Lauric palmitic and stearic acids however form two kinds of ester with cholesterol; if prepared from the chloride the ester is not saponifiable; if prepared from the fatty acid the ester is saponifiable by the method mentioned and differs in melting point solubilities and crystalline characters from the other.The esters in necrotic brain are either those of the latter class or are eaters of lower acids. W. D. H. W. D. H. The Relationship between the Protein and Total Nitrogen and the Hydrogen Ion Concentration in the Cerebrospinal Fluid. AXEL BISGAARD (Biachom. 2-itsch. 1913 58 1-65).-The protein can be conveniently estimated by the method of Roberts and Brandberg according t o which the maximum dilution of the liquid which is still capable of giving a turbidity with nitric acid (Heller’s test) is ascertained. The author gives the experimental details of the process.A similar method can be applied when ammonium sulphate is used instead of nitric acid. The physio- logical limits of the ammonium sulphate reaction lie between the numbers 0 and 2 (dilutions) whereas those of the nitric acid reaction lie between 6 and 20. I n cases of dementia para7yticn there is an increase of total protein in the solution accompanied by an increased percentage of protein precipitable by half-saturated ammonium sulphate. These increases are absent in cases of cerebral tumour cerebral syphilis and acute meningitis. Formalin forms compounds with the proteins and alters the reaction of the liquid t o nitric acid and ammonium sulphate. The total nitrogen was estimated in small quantities in the liquid by a combination of the methods of Kjeldahl and Nessler which arc described in detail by the author.The protein nitrogen calculated from the nitric acid reaction amounts t o from 10 t o 207L of the total. The physiological limits of total nitrogen lie between 0.01 and 0.025%. The residual nitrogen is seldom less than 0.009%. I n organicPHYSIOLOGICAL CHEMISTRY. i. 109 diseases of the central nervous system the relationship between protein and total nitrogen increases. The hydrogen ion concen- tration of the cerebrospinal fluid exceeds the value p = 8-10. The Phosphatides of the Heart and Other Organs. S. B. S. HUGH MACLEAN (Biochem. Lef,tsch. 19 13 57 132-142).-1t has been the custom hitherto in the extraction of lipoids from the heart and other tissues to extract first with ether and then with alcohol and i t has been generally assumed that the two extracts yield different lipoids.It is now shown by the author that this double extraction is unnecessary as the alcohol and ether both extract the same lipoids. The alcoholic extract is however contaminated with other sub- stances from which the lipoids cannot be extracted by the methods ordinarily employed (solution in ether and precipitation from this solution by alcohol acetone etc.). The alcoholic extract can be purified by suspending it in water and carefully adding acetone. The lecithin then separates leaving the nitrogenous impurities in the water. I n addition. to lecithin and cruorin the heart muscle contains traces of a diarninomonophosphatide similar in properties to the substance described by Stern and Thierfelder and by Thudichum.A similar product has been obtained by the author and by Dunham and Jacobson from the kidneys. The substance from the heart muscle may be derived from the nervous tissue contained therein. S. B. S. The Perfused Heart. I. Anaesthetics and Inorganic Saltrs. W. BURRIDGE (Quart. J expt. PIqsiol 1913 7 145-166).- Anzesthetics produce three kinds of contraction in the frog’s ventricle ; their depressing action is antagonised by calcium salts; depression of initiation and conduction are similarly antagonised. Damage to the sarcoplasm is believed to underlie an action of anaesthetics which results in increased amplitude of contraction. W. D. H. Tbe Perfused Heart. 11. Action of Acids and Alkalis. W.RURRTDGE (Quart. J. expt. Physiol. 1913 7 l67-lS3).-Alkalis produce in small concentration a type of ventricular contraction which depends on the calcium salts in the perfusing medium; greater concentrations cause “ alkali-rigor.’’ Acids also produce two types of contraction; certain organic acids cause a slowly developing rigor which destroys the contractile material ; inorganic acids produce a quickly developing contraction. The action of lactic acid is intermediate. Acids act probably by altering the permeability of cell membranes t o calcium or potassium salts. This can be neutralised by a phosphate but not by a bicarbonate. W. D. H. The ‘( Spontaneous ” Evolution of Hydrogen Sulphide from the Liver and from White of Egg and the Nature of the Thiol Group. MAX HAUBDIANN (biochen~.Zeitsch. 19 13 58 65-91) .-Fresh minced liver either after warming or treatmenti. 110 ABSTRACTS OF CHEMICAL PAPERS. with alcohol (SO-100%) or phenol (4-go%) evolves “ spon- taneously ” hydrogen sulphide the evolution lasting for several days. This evolution is dependent on the thiol group present in the liver which can be detected by the sodium nitroprusside reaction. Other animal organs and yeast give a similar reaction and hydrogen sulphide evolution. “ Natural ” egg-white does not evolve this gas as it contains no thiol group. Two reactions appear to explain the hydrogen sulphide evolution (a) the formation of polysulphides from potassium sulphide solutions especially on addition of phenol; ( b ) egg-white after treatment with poly- sulphides and coagulation by alcohol and phenol also evolves hydrogen sulphide.As a pre-existing thiol group is absent in egg- white Heffler’s hypothesis for the explanation of hydrogen sulphide on addition of sulphur is not sufficient. S. B. S. Urea Formation in the Liver. A Study of the Urea- forming Function by Perfusion with Fluids Containing (a) Ammonium Carbonate and (b) Glycine. CYHUS H. FISKE and HOWARD T. KARSNER (J. Biol. Cheni. 1913 16 399-418).-The surviving liver is able t o convert ammonium carbonate perfused through it partly into urea. Whether any is converted into amino-acids has not been determined. The perfusion of the liver of the cat or rabbit with homologous defibrinated blood containing as much as 44 mg. of nitrogen as glycine per 100 C.C.leads to no increase of urea. W. D. H. Nitrogenous Constituents of Dried Cod (Gadus Brandtii). K . YOSHIMURA and M. KANAI (Zeitsch. physiol. Chem. 1913 88 346-351).-0ne thousand grams of dried cod containing 17% of water yielded the following creatinine 1-40 grams; betaine (as chloride) 0.44 gram ; rnethylguanidine (as picrate) 0.7 gram ; taurine 13 grams; alanine 0.5 gram; and a little glutamic acid. Creatine and choline were absent. E. F. A. Carbon Metabolism. The Physiological and Pathological Signiflcance of the Labile Carbon of the Urine. ENRICO REALE (Biochcm. Zeitsch. 1913 57 143-155).-The C/N ratio of tho urine is markedly increased after administration of carbohydrates. The procentual relationship of the carbon t o hydrogen in the three persons investigated was increased on an average by 11.28%.With a normal person on standard diet the administration of 100 grams of dextrose increased the relationship by a average number of l2*32% where?s tEe isodynamic quantity of fat caused an increase of only 6.3%. When the bread of a standard diet is replaced by meat there is a diminution of the C/N ratio. The effect of diet on the labile carbon (that is carbon of the urine which can be oxidised by hydrogen peroxide) is still more marked. Whereas the labile carbon on a standard diet is 6% of the total the administration of dextrose causes a rise to 12%. The administration of fat causes however a diminution of this number to 4.58%. After a meatPHYSIOLOGICAL CHEMISTRY. i. 111 diet the amount of labile carbon in the urine on the second day was practically negligible.Thyroid administration caused a diminution of the percentage of labile carbon t o 2.76% of the total. Even the administration of 100 grams of dextrose under the influence of thyroid medication did not bring the percentage of labile carbon up to the normal. The presence of labile carbon in the urine appears to indicate incomplete ntilisation of the carbo- hydrates. S. B. S. The Influence of Drugs on Uric Acid Excretion. 1%. ABL (AYCIL. ex@ Path. Pharrn. 1913 74 119 -163).-Di~uinution iu the excretion of uric acid is brought about by calcium salts barium sulphate bism-uth subnitrate and uzara ; increase of the action of atophan by calcium saits barium sulphate uzara and atropine. Increase of uric acid excretion is produced by mustard arsenic colchicin thorium-X sulphur santonin glycerol choline chloral hydrate neurine strontium piperazine and other drugs.Important factors in producing an effect are solubility ease of absorption and local action in the alimentary canal. There is a parallelism between the flow of blood in the portal system the secretion of the digestive glands and the output of uric acid. Isolation of Carrotene from Ox Gallstones. HANS FISCHER and HEINRICH ROSE (Zeitsch. physio!. Chem. 191 3 88 33 1 -333).- A yellowish-red microcrystalline powder separates from the ethereal extract of ox gallstones. This is identified as carrotene m. p. 178-180O. It is considered to be derived from the food of the animal and not to have been formed in the body. The Formation of Dextrose from Propionic Acid in Diabetes mellitue.ISIUOE GREENWALD (J. Biol. Chcnt. 19 13 16 375-378).-Ringer showed that in phloridzinised dogs the administration of propionic acid is followed by the elimination of '' extra dextrose '' equal in amount to that capable of being formed by propionic acid if all three carbon atoms are used. I n the present observations on severe cases of human diabetes the same is true but there is as a rule no rise .in the excretion of the acetone group of substances. Membranes and Narcosis. The Colloidal Theory of Narcosis. S. LOEWE (Biochem. Zeitech. 1913 57 161-260).- The author reviews a t length the conception of the cell membrane as a polyphasic gel-like structure in which the hydrophil colloid is the carrier of the properties influencing the selective permeability and in which lipoids exist as an essential component.The phenomenon of narcosis produces a change in this system and it is assumed that the action of the narcotic consists in changing the hydrophil lipoid constituent of the colloid into a hydrophobe condition without loss of its water of combination. This causes a change in the permeability of the membrane and an injury to its normal functions indicated by a weakeqing of the bioelectric differences of potential and the loss of selective per- W. D. H. E. F. A. W. D. H.i. 112 AHYTLtACTS OF CHEMICAL PAPERS. meability. To test this theory experimentally the changes of conductivity of the membrane under influence of various narcotics was investigated. It was assumed that the colloid particles which can adsorb the narcotic become surrounded by a non-conducting layer and are thus no longer effective as regards permeability for electrolytes.If now the hydrophil previously partly-conducting particles become non-conducting the adzition of narcotics should result in a decrease in the conductivity of the membrane. A method is described for preparing membranes from colloids. A parchment membrane is covered with the lipoid solution in organic solvents and the solvent allowed to evaporate. By an arrangement the apparatus f o r which is figured in the text this membrane is clamped between two parchment papers which cover the ends of two bent tubes the whole system forming a U-tube. Salt solutions are placed in each limb and the mn,mbr;;tne is allowed to imbibe water.Electrodes a t accurately known distmces apart are introduced into each limb and the influence of Lhe addition of narcotics on the con- ductivity can then be investigated. It can hardly be said however that the results of experiment confirm thO theory. The author draws attention t o the great difficulties of the experimental method employed and t o the great possibilities of error. S. B. S. The Relation between Non-protein Nitrogen Retention and Phenolsulphonphthalein Excretion in Experimental Uranium Nephritis. C. FROTHINGHAM R. FITZ OTTO FOLIN and W. DENXS (Arch. int. Med. 1913 12 245-258).-Tn iiranium-nephritis in rabbits the excretions of phenolsulphonphthalein in the urine and non-protein nitrogen and urea of the blood vary from the normal and return t o the nornial as the nephritis heals.The degree of variation is parallel to the amount of kidney injury. During the attack the urinary phenolsulphonphthalein drops and the non- protein nitrogen and urea of the blood increase. I n these experi- ments both the uranium nitrate and the phenolsulphonphthalein were administered subcutaneously. W. D. H. The Action of Univalent Alcohols on the Surviving Mam- malian Heart. YAS. KUNO (Arch. oxpt. Path. Ylimrm. 1913 74 399-415).-From experiments on the rabbit's heart perfused with Locke's solution to which alcohol was added the following con- clusions are drawn; the action of alcohols on the heart increases with the rise in their boiling points; the effect is never stimulating but always the reverse.The alcohols dilate the coronary blood- vessels. If a heart is perfused with an akohoiic solution and then brought back to its former condition Ey Locke's solution each successive perfusion with the alcohol produces a smaller effect. W. D. El. The Capacity of Carbohydrates to Act as Antigens. T. KUMAGAI (Biochem. Zeftwh. 1913 57 380-4 I3).-'l!he author confirms the results of Weinland according to whom the repeated subcutaneous in jectioii of sucrose in large quantities into young dogs causes invertase to appear in the serum after 12-15 days.PHYSIOLOGICAL CHEMISTRY. i. 113 He was however unable to confirm Abderhalden and Kapfberger’s statement (A. 1910 ii 1093) that injections of small quantities of sucrose into fully-grown dogs produces invertase in the serum after a very short interval.On the other hand he confirms the results of Abderhalden and Brahm (A. 1910 ii 319) who produced this result when large quantities of sugar were injected. The results of the latter investigators were not however constant but i t is now shown that a constant result can be obtained if a definite interval of some days is allowed t o elapse before the serum is investigated. A new property of the antiserum produced by the sucrose ‘‘ antigen” was also discovered namely that i t acts also on dextrose and lzvulose. The former is converted first into a lzvorotatory and then into a dextrorotatory substance which latter product is also obtained by the action of the antiserum on lavulose. These conversion products have been obtained pure (the details are not given in this paper); the dextrose is first converted into lavulose and the latter is converted into a dextrorotatory di- saccharide.The sucrose immune serum also acts on lactose and the dextrose thereby prodaced is also converted into lzvulose (and finally a disaccharide). It also hydrolyses soluble starch much more energetically than a normal serum. The serum when perfectly fresh is somewhat inert. On being kept at room temperature for four hours i t becomes very active. The fresh serum appears therefore to contain a pro-amylase. Sucrose -immune serum loses its activity as regards sucrose and its hydrolysis products on keeping but the activity can be restored by the addition of normal serum. The immune serum produces a precipitate with soluble starch.The immune serum can be produced by the methods both of active and passive immunisation. If the serum of an animal which has been immunised by the injecticin of sucrose is injected into another animal (even of a- different species) the serum of the latter rapidly acquires the properties of an immune serum. When starch maltose and dextrose are injected into animals (employed as antigens) the only effect observed is a larger or smaller increase in the amount of amylase in the serum. When on the other hand lzvulose lactose o r galactose is employed as antigen not only is there an increase in the amylase but the immune serum contains invertase and is capable of converting dextrose into lzvulose and the latter into a disaccharide. The results indicate that the production of amylase depends on different factors t o that of invertase for the former is increased in the serum after injection of dextrose lzvulose and d-galactose and all the polysaccharides which yield these sugars on hydrolysis whereas the latter is produced only after injection of lzvulose galadose and the disaccharides from which they can be produced.It is probable that the immunisation takes place in stages the polysaccharide being first hydrolysed yielding laevulose or galactose both of which are then converted into a new sugar (both yielding the same product) which is the immediately acting antigen. S. B. S. VOL. CVI. i. ii. 114 ABSTRACTS OF CHEMICAL PAPERS. Antagonism of the Properties of Uuanine and Adrenaline. DESQREZ and DORI EANS (Compt.vend. 1913. 157 946-947).- Subcutaneous injection of guanine previous to similar injection of adrenaline diminished the toxicity of the latter to a certain extent in that the injected rabbit or guinea-pig survived the control animal receiving no guanine often by several hours. Similarly guanine very noticeably reduced the glycosuria ordinarily produced by adrenaline. W. G. Lipoid Anaphylaxis. FREDERICK P. WILSON (J. Path. Bact. 1913 17 163-l68).-The attempts to sensitise guinea pigs to various lipoids gave negative results. The possible presence of minute amounts of protein with the lipoids may be the cause of apparently positive results. The [Physiologicd Action of] Aromatic Mercury Gom- pounds. 111. FERDINAND BLUMENTHAL and KURT OPPENHEIM (Biochem. Zeitsch.1913 57 261-296. C4irnr)ar-e A. 1911 ii 51 7 1017).-The toxicity of the various salicylmercury com- pounds in which the mercury is directly attached to a carbon atom was investigated. Asarol the double salt of sodium hydroxy- mercurisalicylate OH*Hg*C,H,(OH)*CY),Na with sodium mono- hydroxybutyrate is the most poisonous to rabbits and rats. Then follows mercurysalicyl OH*C,H,<EF/O dissolved in diethylene- diamine; then follow embarin and then en6so1 a combination of rnercurysalicyl with arsenic. The percentage of mercury in the two latter compounds is less than in the others. The toxicity of the following compounds was also ascertained-sodium hydroxy- mercurinitrobenzoate sodium hydroxymercuriacetylaminobenzoate (toxynone) NHAc*C,H,(Hg*OH)*CO,Na mercuric chloride mercuric paminobenzoate mercuric chloride mercurous chloride mercuric o-aminobenzoate mercuric paranucleate mercuric potassium nitrite and mercuric potassium thiocyanate.Various methods of administration were employed. The results are chiefly of therapeutic interest. It was found that the chief organs con- cerned in the excretion of mercury were the kidneys and intestine and these show the chief anatomical changes in animals poisoned by mercury. S. B. S. The Effect of Asymmetric Nitrogen Atoms on Physiological Activity. P. P. LA1i)LAw (.I. Phnwnacol. mpt. Thpr.. 191:j 4 461-469).-An asymmetric nitrogen atom may exercise a profound influence on physiological activity. I n the case of the Zcanadine methochlorides the P-salt is twelve times as active as the a-salt.I n the d-isomerides the &variety is only three times as active as the a-salt. In both cases the lworotatory salt is weaker than the dextrorotatory salt but not in equal degree. The differences may possibly be connected with differences in solubility. The Influence of the Subsidiary Alkaloids of Opium on t h e Action of Morphine. WALTHER STRAUB (B~ochom. Zrituch. 19 13 57 156-160).-8 reply to certain criticisms of h-leissner (A. 1913 i 1279). S. B. S. W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 11.5 The Action of Codeine and Thebaine on the Intestine J. PAL and E. POPPER (Biochom. Zeitsch 19 I S 57 492-49 i ).-Ttte authors have shown that the opium alkaloids can be divided into two classes in respect to their action on the intestine. The chief effect of the one class (the phenanthrene group) which includes codeine and thebaine is t o excite the wall of the intestine increas- ing its tonus and peristaltic action.This action is illustrated by four tracings. The results are not in accordance with those obtained by Meissner (A. 1913 i 1279). I n the case of thebaine it is suggested tha-t the alkaloid used by Meismer was contaminated with papaverine which belongs t o the second group of opium alkaloids and exerts an antagonising action to thebaine. No explanation can be offered to explain the discrepancy of the results obtained with codeine. S. B. S. The Influence of 2-Phenylcinchonic Acid (Atophan) on Uric Acid Elimination. UTTO FOLIN and HENRY LYMAN (J. Phn~macol. e y p t . l’her. 19 13 4 539-546). - The s t tern s r l t i n ~ d v hy rere! t clinical observers that atophan increases the excretion of uric acid is confirmed.This is supplemented by estimations of the uric acid in the blood by the Folin-Denis method. Four cases of gout and one of albuminuria were utilised; the uric acid of the urine rose and that of the blood sank. The increased output is due to elimina- tion of accumulated uric acid in the blood due to kidney ineffi- ciency. A rise in other nitrogenous excreta occurred in some cases but not in all. I n a sixth case (severe gout) there was not a high amount. of uric acid in the blood during the greater part of the course of the disease; but later on it rose and then atophan produced the usual result. The drug acts on the kidneys and does not “mobilise” deposited urates.I n a healthy man the drug caused an increase in the urine and a drop in the blood uric acid. W. D. H. The Constituents and Effects of Strophanthua Drugs. EWALD HESSEL (Chem. Zentr 1913 ii 869-870 ; fr I r n Sitzwnysbor. A b h a d l . n n . t w f (7’es. Rmtock. 1913. 5. pp. 43. Cloutpale Siehurg A. 1913 i 640).-The hzmolytic action and toxicity of sodium g-strophantate and allied products is described. The crude sodium salt contains what is probably a cholesteride which nullifies the activity of the substance. On purification through the medium of the lead or barium salt the hzmolytic action becomes evident. J. C. W. Action of Protovercttrine and Aconitine on the Neuro- murcular Apparatus of the Frog. (Mws) MARJORY AlACNAUGFITON (Quart. J . expt.Ph.yl/siol. 191 3. 7 131-1 4 4 ) . - - T h ~ action of proto- veratrine on nerve closely resembles that of yohimbine so that it exhibits fatigue after action and recovery on rest. Protovera- trine fatigue is however most lasting and there is no “snap reflex,” and no Wedensky effect.” The action of aconitine on nerve resembles that of protoveratrine. If the protoveratrine is applied to the muscle the myoneural i 2i. 116 ABSTRACTS OF CHEMICAL PAPERS. junction is affected and stimulation through the nerve produces rapid and permanent fatigue ; aconitine is without this action. W. D. H. The Toxic Action of Products obtained from the Animals of the same Speciee. FRIEDRICH SIMON (Biachem Z~itsch. 1913 57 337-374).-Livers of rabbits were allowed t o autolyse o r were treated with pepsin or trypsin the products of digestion were treated with alcohol and the precipitated powder was then dried. The effects of the administration to rabbits of the various prepara- tions thus obtained was investigated. The temperature changes and the onset of albuminuria were regarded as symptoms of toxic effect. The toxic effects were however in no case very marked nor could they be considered as constant. The products were also injected into rats. Relatively large doses of digestion products produced short-lasting convulsions or increase in rapidity of respiration lasting for some hours. The Tolerance Shown by Elasmobranch Fish towards Certain Nephrotoxic Agents. W. DENIS (J. B i d Chew&. 19 13 16 395-398).-1n the dog fish large doses of uranium nitrate and potassium chromate cause little or no accumulation of waste nitro- genous products. The elimination of these substances by the kidneys is normally small and the animals are apparently able t o utilise the liver or perhaps the intestine as an excretory organ. S. B. S. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9140600101

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

i. 116 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Oxidation of Manganous Carbonate by Microbes. M. W. BEYERINCK (I’YOC. K. Akad. Wetensch. Amstadant 1913 16 397-401). -When two pieces of filter paper with a little manganous carbon- ate between them and moistened with a dilute solution of ammonium chloride and potassium phosphate are infected with garden soil and kept at about 2 5 O dark brown or black spots of a manganic compound will appear on them after some days. The characteristic reactions of the manganic compound thus produced are the sudden decomposition of hydrogen peroxide and the oxida- tion of hydriodic acid. An examination of the related microbes shows that bacteria and various species of mould are the cause of the oxidation. Pure cultures of the bacteria were obtained on agar plates con- taining 0.05-0*1% of manganous lactate.Small capsulated colonies appear which after being crushed prove to consist of delicate quickly-moving rodlets whilst the brown wall of the capsula again gives the usual manganic reactions. The mould species are readily grown on agar plates containing nothing but manganous carbonate and some mineral salts; on pure agar without manganous carbonate they also develop but lessVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 11 7 quickly so that the carbonate evidently serves as a food and not only as a catalyst. These moulds belong to very different groups of the fungi and consist of species of the genera Botrytes Sporo- cylbe Trichocladium and in particular of Mycogone two of which Yapulosporn inaiigatiica and Sporocyb e clinrtoikoon are fully described.Oxidation appears t o occur as well within as without the mycelium. It could not be brought about by oxydase or peroxy- dase of difierent origin. The statemenb found in many textbooks that manganous carbon- ate is readily oxidised on exposure to air appears to require some modification since the author has been able to preserve an aqueous suspension of this substance for years without taking any special precautions whilst the manganous carbonate agar plates continue unchanged for months with free access of air. The Behaviour of Certain Bacteria towards d-Glucosamine. KURT MEYER (Biochern. Zeitsch. 1913 57. 297-299).-The behaviour of various species of bacteria grown in Barsiekov’s medium with addition of glucosamine was investigated.It was ascertained whether acid was formed or gas evolved. The results obtained were similar to those when dextrose was employed instead of glucosamine. The differences of behaviour towards the two substances are not sufficient to be of diagnostic value. A So-called Biochemical Variation of the Bulgarian Lactic Ferment. F. D U C H ~ ~ E K (Compt. rend. 1913 157 1095-1097).- An explanation of the differences observed by Bertrand and Effront in the biochemical behaviour of the lactic ferment. The author shows that the two workers were dealing with quite different material. Bertrand’s pure lactic ferment decomposes only lactose and some of the hexoses causing coagulation of the milk by the acidity produced whilst Eff ront’s commercial sample contained a proteolytic ferment and but a very feeble form of the Bulgarian ferment proper.He has studied both these forms and gives an account of the variations in their properties and as a result does not agree with Effront that there is a biochemical variation of the Bulgarian ferment. W. G. Bacterial and Enzymic Changee in Milk and Cream at Oo. M. E. PENNIKOTON J. S. HEPBURN E Q. ST. JOHN E. WITMEB M. 0. STAFFORD and J. I. BURRELL (J. Biol. Chorn. 1913. 16 331-368).-Milk and cream kept at freezing point undergo changes such as proteolysis lactic acid fermentation and libera- tion of fatty acids. The enzymes responsible for these and other changes are mainly secreted by bacteria which accommodate them- selves to the low temperature and proliferate. Micrococcus uuran- t i a c u s (Cohn) and M .ova7is (Escherich) which belong to the group of acid-formers were the predominant organisms found. W. D. H. The Rate and Magnitude of the Increase of Yeast in Wort. TOR CARLSON (Biochem. Zeitseh. 1913 57 31 3-334).-The yeast formed in the wort was measured by centrifugalising in tubes H. W. S. B. S.i. 118 ABSTRACTS OF CHEMICAL PAPERS. terminating in graduated capillaries until the amount of sediment formed is constant. The relationship between the time of sedi- mentation and the speed of the centrifuge was determined experi- mentally. Ths rate of growth of yeast was plotted on a curve. At the commencement the rate of increase is an exponential function of the time. Afterwards however the foodstuff in the wort com- mences appreciably to diminish and this is accompanied by a diminution of the rate of increase in the yeast until finally the curve (representing this rate) runs nearly parallel with the abscissa (representing the time).The rate of growth may be fairly well expressed by the equation where ym represents the maximum amount of yeast which can be formed in a given wort and yz and yl the amounh formed at the end and beginning of the time t. In a current of air the rate is increased by about 12% and in a current of nitrogen by 25% whereas in a current of oxygen it is diminished by about 15%. Alcohol also diminishes the rate and in the presence of 12% the growth practically ceases. The relationship between the amount of yeast formed and the dilution of the wort was also investigated as the maximum of amount formed is not in the most concentrated yeast The relationship between the dilution (u) and the amount may be represented by the equation where Y represents the limiting value.alcohol formed determines in this case the magnitude of the crop. A- = 1 / A t * l%(Y - Y J Y 2 l (Y - Y2)Yj 9 = 1 y.. IYX) yo0 - Yo0 h The concentration of the S. B. S. Fermentations with Yeast in Absence of Sugar. XIII. The R61e of the Aldehyde Formation in the Fermentation of Sugars Bnd the So-celled Auto-fermentation. C. NEUBERG and JOH. KEHB (Riochem. Zeitsch. 1913 58. 158 -17O).-AlJet~pd~ has been fouiid as a fermentation product and i t is theoretically possible that it is an essential intermediary product (the equations being given in the text).The authors draw the conclusion however that this is not the case. The chief reason for this is that the quantities formed are extremely small even when their amount is increased by the addition of zinc chloride and there is no evidence that even these minimal quantities are formed from the sugars. Furthermore they do not regard the experimental evidence as satisfactory which tends t o show that acetaldehyde can be reduced t o alcohol by the yeast'. S. B. S. Influence of Mercury on Alcoholic Fermentation. P. NOTTIN (Compt. w r p d . . 191 3. 157 10W-l008~.-The phenctmenon observed by Lindet and Ammann (compare A. 1913 i 144) with respect to the action of mercury on alcoholic fermentation is due essentially t o mechanical action.The retardation of the fermentation is due to the formation OF mercury salts by the more or less prolonged contact of the metal with the naturally acid must. The increase in production of yeast is due to the action of the mercury in destroyingVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 119 the supersaturation with respect to carbonic acid thus allowing the yeast to breathe and vegetate better. Apart from these effects th3 metal and its salts seem to be without marked action on the zymase or on its selective power. W. G. Influence of Metals on the Development of Aspergillus niger Cultivated on Raulin’s Liquid. M. BORNAND (Centr. Bakt. Pur 1913 [it]. 39 488-496).-As~~or~i/Zus niger has been grown on Raulin’s liquid contained in capsules of the metals silver alumin- ium copper iron tin lead zinc nickel and in a glass capsule with a layer of mercury.Control cultures were carried on in glass capsules. I n the case of silver contrary t o the results obtained by Cadur and Thiry (compare Compt. rend. SOC. Biol. 1913 487) and Clement (ibid. 1913 749) the author finds that this metal produces a retardation in the development but does not prevent sporulation which is however much weaker than in the control. It is not possible to accustom Aspergillus niger to develop in a normal manner on aaulin’s liquid in a silver capsule. With the other metals the development of the mould was checked except in the case of aluminium and platinum mercury entirely inhibiting development even after ten days. In no case was sporulation complete.The metals which were most active in checking develop- ment. were found to be most readily attacked and dissolved by Raulin’s liquid the exception being mercury which however vaporises slowly. I n the case of copper the mycelium is green and vermiculated (compare Sauton Ann. Inst. Pastezcr 1911 27 923) but when re-sown on Raulin’s liquid in a glass vessel it develops normally and sporulates completely. It is not possible to obtain a normal development of Aspergillus niger by replacing the salts of iron and zinc in Raulin’s liquid by the metals themselves in the form of containing vessels. W. G. The Substitution of Zinc by Various Chemical Elements in the Culture of Aspergillue niger [ Sterigmatocystis nigra] The Case of Cadmium and Glucinum. M. JAVILLIER (Chem. Zentr.1913 ii 603; from B d . Sci. Phrcrmacol. 1913. 20. 321-337. Compare A 1913 i 236 326; Lepierre A. 1913 i 326 327).- The author reaffirms his statement that cadmium and glucinum unlike zinc do not further the growth of Aspergillzcs. After four days the mycelium is by no means so heavy with cadmium salts as with zinc salts of the same concentration. I n time however the same weight may be reached but i t is due t o the formation of spores a t the expense of the mycelium in the case of zinc cadmium having an adverse effect on sporulation. During four days glucinum salts give no greater growth than a culture without zinc and even after some time the weight of mycelium is never so great as with zinc. J. C. W. Gomparative Influence of Zinc. Cadmium and Glucinum on the Growth of Some Hyphomycetes.M. JAVILLIER and (Mme.) H. TSCHERNORUTZKP (Compt. Tend. 1913 157 1173-1176).-Threei. 120 ABSTRACTS OF CHEMICAL PAPERS. different types of Hyphomycetes have been grown on Raulin’s liquid containing no zinc cadmium or glucinum and on similar liquid to which one of these metals has been added in the form of salts a t dilutions varying from 1 in 100,000,000 t o 1 in 5000. The results show that in all three cases examined zinc has a marked superiority as 3 biological catalyst even in minute quantities. Cadmium is similar in its action t o zinc but has greater toxicity. Glucinum is almost completely inactive. W. G. Influence of Radioactive Emanations on Vegetation. J. STOKLASA and V. ZDOBNWKY (Compt. rend. 1913 157 1082-1084.Compare A. 1913 i 1421).-Plants have been grown under the following conditions and thus submitted t o the influence of radium emanation (1) Culture in Knopp’s nutritive solution made either with artificially radioactive water or with naturally radioactive water; (2) in pots filled with earth and watered with artificially radioactive water; (3) culture in large vessels (85 litres capacity) the air being rendered radiohctive by emanation. I n all cases radioactive emanation in small quantities exerted a f avourable influence on the development of the plant the mechanism of gaseous exchamges flowering f ertilisation and markedly on the crop weight. Large quantities of emanation on the other hand arrest growth. The chlorophyll is altered and plasmolysis occurs. The experiments were conducted with various species of plants giving in some cases an increase in the dry weight of the crop amounting to 164%.W. G. J. PARNAS ( C h m . Zen&. 1913 ii 1314 ; from Naburwiss. 1913 1 819-820).-An adverse criticism of Baur’s view that oxalic acid is the primary product in the assimilation of carbon dioxide by plants (compare A. 1908 ii 780; A. 1913 i 443). Photochemical Processes in the Diurnal Disappearance of Acids in Succulents. H. A. SPOEHR (Biocham. Zeitsch. 1913 57 95-111).-Attention is called to the well-known fact that juices of plants are more acid in the morning and that the acidity for the most part disappears on exposure t o light. Experimental evidence is brought forward to show that this disappearance is not due t o the action of ferments as i t also takes place in the heated juices after their exposure t o light.It is shown furthermore that certain plant acids especially dibasic acids readily undergo decom- position (but only in the presence of air) when exposed t o ultra- violet light- in quartz vessels. Malic and tartaric acids lose two molecules of carbon dioxide under these conditions and the alcohols thus formed are oxidised further to acetaldehyde and acetic acid. The latter acid also undergoes decomposition yielding formaldehyde and formic acid. The last-named acid yields carbon dioxide as final oxidation product. Acetaldehyde under conditions of light- oxidation can give rise to oxalic acid. Under the conditions of light-oxidation therefore the ordinary plant acids can give rise to The Genesis of Carbohydrates.J. C. W.VEGETABLE PHYSIOLOGY AND AGRTCULTURE. i. 121 volatile oxidation products. The discovery of formaldehyde as product of light-oxidation of acisls throws some doubt on the significance of Baeyer's hypothesis according to which the aldehyde is a direct photochemical product of carbon dioxide as it can be produced from plant acids. Distribution of Organic BaBes Particularly Adenine and Choline in the Vegetable Kingdom. K. YOSHIMURA (Zeitsch. phgsiol. Chem. 1913 88 334-345).-The flowers of Chrysanthcmurn sinense contain adenine choline arid a little etachydrine ; the leaves contain adenine a little choline and some stachydrine. The latter are remarkable in containing nearly 3% of calcium oxide calculated on the dried material.Young material of Chrysanthemum coromrium contains adenine and a little choline but no betaine. Ai.temisia vulgcrris and rice gluten contain both adenine and choline but no betaine. M o m s a1 ba contains adenine choline and trigonelline. New Tannin Reaction and its Relation to Anthocyanin. KUNO PECHE (Be).. deut. botan. Ges. 1913. 31 462-471).-When sections of the leaf or rind of Prwzzis laurocerasus are quickly heated in a mixture of equal parts of potassium hydroxide (20%) and formaldehyde a bluish-green coloration is produced in the cells with tannins which give a green coloration with ferric chloride. The colour is changed t o red by acids. The colours resemble the anthocyanins except as regards solubility. A soluble pigment was obtained from the sap of Mespilus germaniccr.The formaIdehyde only acts in preserving the phenolic hydroxyl from oxidation. I n the Rosaceze the pigments produced in this manner are only formed from tannins which give a green coloration with ferric chloride. It was also shown that in the Rosaceze the anthocyanins are formed from the same group of tannoids. Experimental Production of an Anthocyanin Identical with that which is Formed in Red Leaves in the Autumn Starting with a Compound Extracted from Green Leaves RAOUL COMBES (Compt. rend.. 1913 157 1003-1005. Compare A. 1909 ii 426; 1911 ii 1125).-The author has isolated from the green leaves of A nzpelopsis hederacea a substance crystallising in rosettes of brownish-yellow needles (loc. c i t . ) which when dissolved in alcohol acidified with hydrochloric acid is reduced by nascent hydrogen generated by sodium amalgam giving a compound crystallising ir purple needles and identical in its behaviour and properties with the natural anthocyanin extracted from red leaves.This supports the view that the anthocyan pigments in leaves are formed as a resnlt of the modification of a continuous phenomenon which takes place in the leaf organs during the whole of their existence. W. G. Constituents of Aloes. F. TUTIN and W. J. S. NAUNTON (PAarm. Jouwa. 1913 [iv] 37 836).-The primary object of this S. B. S. E. F. A. N. H. J. M.i. 122 ABSTRACTS OF CHEMICAL PAPERS. investigation was to ascertain whether aloes contain any anthra- quinone derivatives other than aloe-emodin but no such compounds were found.I n addition to aloe-eniodin the following substances were identi- fied in CuraTao aloes salicylic acid ( 1 ) ; a fatty acid m. p. 75-78O; cinnamic and pcoumaric acids. According t o Tschirch and Hoffbauer (A. 1905 i 913) Curagao aloes contains cinnamic acid but no pcoumaric acid. A small amount of glucosidic material is also present which after hydrolysis yielded d-phenylglucosazone ; no pentose could be detected. F. B. The Araliaceze Family with Special Reference to the Glucosides and Oxydases of the Leaves of Polyscias nodosa Forst and Hedera Helix L. A. W. VAN DER HAAR (Pharm. Weekblad 1913 50 1350-1359 1381-1393 1413-1427).-An investigation of the substances present in the leaves of the East Indian Polyscias nodosa Forst and the European Hedera Helix.The leaves of Polyscias ?iodosa were extracted with light petroleum ether 95% alcohol 50% alcohol and finally with water. The light petroleum extracted a vegetable wax (a niyricyl ester) and chlorophyll; the ether chlorophyll and a trace of tannin; the 95% alcohol a trace of saponin and of tannin much chlorophyll but no alkaloids; the 50% alcohol much saponin reducing carbo- hydrates a trace of tannin and of acids but no alkaloids; the water peroxydases and other enzymes. The saponins were extracted with 95% alcohol precipitated by ether dialysed in aqueous solution extracted with methyl alcohol after evaporation and purified by means of magnesium oxide. Two individuals were isolated from the product Polyscias a-saponin C,,H,,O, and Polyscias A-saponin C,,H,20,0 homologous com- pounds belonging to Kobert's series C,LH2n-8010. Intermediate homologues may have been present but were not isolated.The saponins thus obtained are white amorphous products which begin t o decompose a t 200° and carbonise a t 225O. With con- centrated sulpliuric acid they give the usual violet coloration addition of water t'o the mixture precipitating a crystalline sub- stance m. p. 230-234O (uncorr.). On fusion with potassium hydroxide the products were a crystalline subsfairce m. p. 150-152O which gives a faint red coloration with ferric chloride; and acetic formic and butyric acids. Concentrated nitric acid converted the saponins into picric acid and benzoic acid. They can be salted out by means of ammonium sulphate. They yield a hepta-acetyl derivative m.p. 155-160° so that the formulze of the liomologues Inversion of these saponins with dilute mineral acids yields equi- molecular proportions of a sapogenin arabinose and dextrose along with traces of methylpentoses. Po!7/scins sapogeni?z C26H4404 forms rhombic prisms m. p. 324O ru]k* +75*58O in pyridine. It gives the characteristic violet coloration with sulphuric acid and its pro- perties indicate the presence of a lactone ring but the absence are C22H2903(OH)7 and C,,H,,q,(OH),.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 123 of hydroxyl methoxyl and ethoxyl groups and also of double linkings. It exhibits great stability towards oxidisers. Its formula C 0 iuay be written C2,Hta02<b . A t 300°/60 mm. it yields two sublimates one light in colour and the other darker.The second has m. p. 327O. A detailed account of the physiologic_al action of the various products is given. The leaves of Hedera Helix L. contain two kinds of glucosides soluble or insoluble in water. The soluble are denoted by A and the insoluble comprise t'he amorphous or y the crystalline or P and a-hederirb m. p. 256-257O. On inversion the A-glucosides yield an insoluble fission-product. It forms small colourless needles [a]iO +9*6S0 in alcohol. The substance has an acidic character. It dissolves in concentrated sulphuric acid to an orange solution which becomes bright cherry-red and finally colourless as a violet precipitate is deposited. After inversion it reduces Fehling's solution but not before. It is inverted with difficulty the products being an insoluble product and a soluble sugar.It forms a pentn-acetyl derivative m. p. ca. 155O and contains one methoxyl group so that its formula may be written The insoluble product of the inversion of a-hederin by 5% sulphuric acid is a-hederagenin C31H5004 m. p. 325-326O [a] +81*2O in pyridine. I n concentrated sulphuric acid it dis- solves t o a colourless solution which changes through yellow and orange to violet indicating it t o be the reacting substance in the sulphuric acid test for a-hederin. It has one lactone ring forms a diacetyl derivative m. p. l l O o and a dibenzoyl derivative but does not contain a methoxyl group Its formula may be written The formula of a-hederin is possibly C31H5004. C,,H,,O,(OH),(OCH,). fln On distillation with zinc duit in a current of hydrogen a-hederagenin yields water and a greenish-yellow fluorescent oil which contains a sesquit erpene C15H24 which is optically inactive and volatile with steam.The non-volatile residue is a semi-solid yellow flu or escent SZG b s t a n c e. The insoluble inversion product of a-hederin contains arabinose and rhamnose. These sugars are also present along with a-hedera- genin in the inversion produ3t obtained from the mother liquor of the extraction of a-hederin. Existence of Maltam in Cereals. ZENON WrERzcHnwsm (Biorhem. Zeitsch. 191 3 57 125-1 31).-All the Cerwds examined were repeatedly extracted with water until the diastase content was removed and the action of the solid residue on starch and maltose solution was investigated.All kinds were found to contain a maltase especially millet maize and buckwheat. I n all the grains it was not found possible to extract quantitatively the diastase. I n those kinds in which the diastase could be quantitatively A. J. W.i. 124 ABSTRACTS OF CHEMICAL PAPERS. removed it was found that starch was present during the whole fermentative process. The ferment acts therefore like the one already described by the author in maize (A. 1913 i 1255) in directly degrading the starch into dextrose without the inter- mediate stages of dextrin formation. From certain of the grains small quantities of the maltase can be extracted by water. The dry powder has however more powerful enzymatic properties than aqueous extracts. S. B. S. The Digestibility of the Nitrogenous Substances in Cocoa Beans and Pods.5. GOY (Biochem. Zeitsch. 1913 58 137-147).- The digestibility of the proteins of the beans by pepsin varies greatly according to their origin and method of roasting. The percentage of digestible protein varied between 25 and 63. The percentage of digestible proteins of the pod varied between 3.6 and 29. S. B. S. Arsenic and Manganese in Some Sea-water Plants. HENRI B~ARCELET (Chsm. Zentr. 1913 ii 1412-1413; from Bull. Sci. Phnrmaco!. 191 3 20 480-412).-colo~.irnetric estimations of manganese by means of silver nitrate and potassium persulphate show that marine plants contain unevenly distributed quantities of that metal (1.5 t o 36.3 mg. per 100 grams of dry material). The quantity of manganese bears no relation t o the amount of arsenic present.Marine grasses contain more of these elements in the chlorophyll-bearing parts than in the roots. Composition of Oil-seeds of Two Symphonia spp. from Eastern Madagascar. ALEXANDRE H~BERT (Bull. Soc. chim. 19 13 [iv] 13 1039-1042).-The seeds of S. Zaecis yield 35*2% and those of S. Louueli 40*0% of a semi-solid yellow fat having the following constants (where two figures are given the first is for the fat of S. Zctezyis and the second f o r that of S. LouveZi) Dii 0.872 0-879; ni. p. 15-16O; acid number 8.4; saponification number 189 ; Reichert value 1.65 ; Hehner value 94.3 94.1 ; iodine value 66.7 67.6; m. p. of fatty acids 42*5O 43O; saturated fatty acids 40% 35%; unsaturated fatty acids 60% 65%. The saturated fatty acids in both cases appear to consist of a mixture of margaric arachidic lauric and decoic acids.T. A. H. Production of Alcohol by Wheat Germs. S. KOSTYTSCHEV and A. SCHELOUMOV (Bw. deut. bot. Get?. 1913 31 422-431).-No alcohol is produced by living wheat germs when aerated; even in presence of toluene very little alcohol is formed (CO EtOH= 100 3). When aeration is deficient considerable amounts of alcohol may be formed (CO EtOH = 100 50). Further experiments with wheat germs incapable of germination showed that alcohol is produced in considerable amounts even when thoroughly aerated. Nuclear Degeneration Caused by Uranium in Vegetable Cells. C. ACQUA ( A t t i R. Accad. Lincei 1913 [v] 22 ii 390-392). -When plants are grown in solutions containing traces of uranyl J.C. W. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 125 nitrate root growth is rapidly arrested owing to the penetration of uranium into the nuclei of the meristem. It can be seen there in the form of a yellow substance probably the yellow oxide. The chromatin of these nuclei is found t o have disappeared so that karyokinetic division is no longer possible. R. V. S. The Influence of Iron in the Development of Barley and the Specificity of its Action. J. WOLFF (Conipt. rend. 1913 157 1022-1024. Compare Ma& Ruot and Lemoigne A. 1912 ii 1088).-Working with aseptic solutions and carefully purified barley seeds free from all moulds and bacteria the author has shown that ferrous sulphate to the extent of 0.4 gram per litre has a very favourable influence on the growth- of the barley plant.I n one case the dry weight ratios of iron-free t o iron-containing media were as 45 160. Neither chromium nor nickel can replace the iron. Njckel even in small amounts checks all development of the plant whilst chromium a t the rate of 0.01 gram in 500 C.C. of culture liquid first caused extraordinary root development and then the plants became chlorotic and died. The Influence of Salts Common in Alkali Soils on the Growth of the Rice Plant. I(. MIYAKE ( J . Biol. Chem. 1913 16 235--264).-Alkali salts may have both toxic and stimulant effects on the growth of rice seedlings according t o their concentrations; the toxic concentrations of magnesium sulphate and chloride calcium chloride and carbonate are greater than N/100 while sodium sulphate and sodium hydrogen carbonate are greater than Nj50.The greatest stimulation was observed with the salts in the following concentrations magnesium sulphate 500 ; magnesium chloride and calcium chloride iV/ 1000 t o N/5000 ; sodium chloride N / 10 t o T / l O O ; sodium carbonate and sodium hydrogen carbonate N/100 to N/500. Two salts however in toxic concentrations lead t o loss of poisonous effects; this is due to the ions formed on dissociation. Bivalent cations are markedly antagonised by uni- valent cations although the reverse does not hold; the antagonism of anions is less marked. The curve of antagonism between sodium and potassium shows two maxima. The antagonistic action of calcium on other metallic ions is most important; barium and strontium can replace it.W. D. H. Decomposition of Proteins in the Seedlings of Kentucky Tobacco. F. TRAETTA-MOSCA (Gazzetta 1913 43 ii 445-452). -The seedlings of the tobacco plant contain proteolytic ferments and among the products of their action the author has identified lysine histidine arginine glutamine leucine and aspartic acid. Clioline was also found. W. G. R. V. S . Presence of Barium and Arsenic in Italian Manufactured Tobaccos. R. SPALLINO (Gaxzetta 19 13 43 ii 475-481).- These tobaccos all contain barium the quantity varying from 0.019 to 0*036% calculated as sulphate obtainable from the driedi. 126 ABSTRACTS OF CHEMICAL PAPERS. material. A proportion amounting t o 0*003-0*009% is in a state soluble in water. Seven tobaccos examined contained 0*08-1*02 mg.of arsenic per 100 grams of dry material. R. V. S. Humic Acids. 111. Composition of Sphagna and their Power of Absorbing Bases. Influence of Locality and Importance of the Sirlgle Nutrients. EUQEN GULLY ( B L ~ . Zo?slr. 1913 42 652-655 ; from M i t t . K . Buyr. NoorkultuTamt. 1913 Heft. 5).-Numerous analyses of Sphagna of different origin showed that more food is taken up than is required for growth the amounts varying with the different varieties. The composition of the living and the dead portions of Sphagita differ considerably the dead portions containing less potassium phosphoric acid and nitrogen than the living portions; the amount. of calcium remains the same in some varieties. The predominance of Sphagna is caused partly by deficient nutritive matter especially potassium.As a rule the absorptive power for bases is somewhat higher in dead than in living peat mosa. N. H. J. M. Soil Solution and the Mineral Constituents of the Soil. ALFRFD DANIEL HALL W I N I F R E D E L S I E BHENCHLEY,md LILIAN MARIN0 UBDERWOOD (Ph7l. l’mws. 1913 [ B ] 204 179-200) -Water culture experiments are described in which wheat and barley were grown in extracts of soil from differently manured plots of the permanent wheat and barley experimental fields a t Rothamsted ; nitrogen was supplied in the form of sodium nitrate. The results showed that the growth varied with the different extracts and that the yields corresponded with the average yields of the plots themselves. The relative composition of the extracts was found to be similar t o that of the soils as judged either by the total or citric acid soluble plant food they contain.Further experiments in which the soil extracts were compared with artificial nutrient solutions showed that the former gave better results than the latter owing perhaps to the presence of nitrogen compounds of special value in the earlier stages of growth. Notwithstanding the sixty years’ growth of wheat and barley on the respective fields no evidence of any soluble toxin was obtained. The weights of wheat and barley were almost exactly the same whether grown in extracts from wheat or barley soil; and boiling the extracts had no effect. Further experiments are described in which barley was grown in solutions containing dihydrogen potassium phosphate magnesium and calcium sulphates and sodium chloride (each 0.5 gram) potassium nitrate (I gram) and ferric chloride (0.04 gram per litre) and in the same solutions diluted to 1/5 1/10 and 1/20 respectively.From the commencement the growth proceeded in the order of the concentration and the final yield in the strongest solution was about twice that of the next and six times that of the lowest. The results were confirmed by sand culture experi- ments in which the solutions of different strengths were allowed to percolate through the sand.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 127 Finally experiments were made in which water cultures were compared with cultures in coarse sand fine sand silt and kaolin ; and on the effect of aeration in water cultures. I n sand cultures containing 20% of nutritive solution it was found that there was no retardation of growth due t o slow diffusion although with that amount of water the sand could readily be crumbled.The yield was better than in water cultures supplying the same amounts of nutrients. Similar results were obtained when the nutritive solutions were placed in porous cylinders in the sand in which the plants were growing so that the solutions had to pass through the porous cell before reaching the roots. I n all these experiments the results depended on the concentration of the solutions. Comparing coarse and fine sand with salt and kaolin the coarse sand gave much the best results; water cultures next; then kaolin silt and fine sand. Very striking results were obtained in water cultures with barley and lupines. The solutions were (1) not aerated ; (2) aerated daily; and (3) aerated continuously.Cont,inuous aeration nearly doubled the yield as compared with no aeration and the conclusion is drawn that the superiority of sand cultures over ordinary water cultures is due to the better aeration. N. H. J. M. Displacement of the Potash Contained in Certain Felspathic Rocks by Some Substances Used as Fertilisers. a. A N D R ~ (Co~npt. rend 1913 157 856-858).-An exairnindtion of the effect of such salts as sodium nitrate calcium phosphate etc. commonly used as fertflisers on a felspar steadily ground in a mortar with aqueous solutions of these salts for 130 hours. The amounts of potassium oxide thus rendered soluble vary with the salts used.Ammonium sulphate (1% solution) gives the highest figure rendering 7.38% of the total K,O in the felspar soluble. Sodium chloride and sodium nitrate have the same effect rendering 3.25% soluble. Sparingly soluble calcium carbonate and phosphate only have a slight effect while the more soluble superphosphate is much more active. W. G. Contribution to the Study of Clays. A . MUNTZ and H. GAUDECHON (Cowpt. vend. 1913 157 968-974). -A study of the sedimentation of clays. Clay suspensions of definite concentrations were le'ft for the clay to settle over varying periods of time in jars 30 cm. high holding one litre of liquid. The liquid was siphoned off in four equal fractions and the amount of clay left in each and in the deposit determined. The top fraction loses its fine particles most readily having a t the end of six days lost 84% of its total clay in suspension.I f in addition t o the gravitational effect an electrical effect is introduced i t is found that the fine particles which are most stable under the action of gravity are the most rapidly deposited under the influence of the electrical fields produced by the insertion of two electrodes of a circuit. Clays of different origin show different rates of disappearancei. 128 ABSTRACTS OF CHEMICAL PAPERS. of the clay from the top 250 C.C. of liquid and the author suggests that this might form a method of identifying and classifying clays. W. G. Occurrence of Arsenic in Soils. JOSEPH E. GREAVES (Biocliem. hU. 1913 2 519-523).-Some virgin soils coritviu arsetlic frorri the decay of rocks.Many cultivated soils contain a larger quantity but there is no uniform relationship of the total arsenic to that which is soluble in water. The same is true when arsenic is added to the soil. Lead arsenate is regarded as the safest of the arsenical insecticides. W. D. H. Presence of Araenic as a Normal Constituent of Soil. GINO ZUCCBRI (Gaznetta 1913 43 ii 398-403).-Samples of unmanured soil from twenty different localities all contained arsenic the quantities found in 100 grams of soil varying from 0-187 to 6.000 mg. Composition of Rain-water Collected in the Hebrides and in Iceland. NORMAN H. J. MILLER ( J . Scot. Met. Soc. 1913 16 141-158).-Estimations of ammonia nitrates and chlorides in monthly samples of rain-water collected a t the Butt of Lewis lroin December 1908 t o November 1912 and a t Vifilsstadir Iceland from November 1911 to September 1912 (the October sample being lost). Also for several months a t other places in the Hebrides and west coast of Scotland. The average amounts of nitrogen per acre per annum a t the Butt of Lewis (1) and the amounts a t Vifilsstadir (2) calculated from the eleven months are as follows R. V. S. N . per rnillioi~. - N. per acre (lb.). A c - Rain fa1 1. As As A s As Inches. anii n on ia. nitrates. aminon ia. nit rates. Total . 1. 39-70 0.036 0.032 0'311 0.289 0 600 2. 38-34 0.091 0 030 0'808 0 263 1.065 The amounts of ammonia per acre a t the Butt of Lewis are the lowest hitherto recorded and the Iceland results are the next lowest with exception of New Zealand and Madras. The nitrates are also very much lower than the great majority of results pre- viously obtained. Rain-water collected a t Shillay (Mcnach Islands) and at Barra- head contained considerably more ammonia and nitrates than was found a t the Butt of Lewis. The results so far obtained indicate that the total nitrogen a t the two places is about 1.8 and 2'2 lb. respectively per acre per annum or about half the amount found a t Rothamsted. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9140600116

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii. 120 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Preservation of Hydrogen Peroxide by means of Acet- aoilide. A. M. CLOVEH (Bmev. J. Phavrn,. 19 13,85,538-545) -The investigation has been undertaken with the object of determining the justification for using acetanilide as a preservative for com-INORGANIC CHEMISTRY. ii. 121 mercial hydrogen peroxide solutions since it has been claimed that the usual instability of the latter is due to the presence of certain impurities introduced in the course of manufacture and that if these impurities could be eliminated a stable product would result. The gradual decomposition of hydrogen peroxide solution in the presence of hydrochloric sulphuric phosphoric or boric acid a t different concentrations has been studied whilst the effect of various salts (sodium chloride potassium chloride calcium chloride sodium silicate ferric chloride and aluminium sulphate) alone and with acetanilide on solutions of hydrogen peroxide which have been made N / 100 in hydrochloric sulphuric and phosphoric acids respectively has been investigated. The author is led to the conclusion that pure hydrogen peroxide is a very unstable substance and that its stability is greatly in- creased by the addition of small amounts of acid.Addition of salts of the alkali and alkaline-earth metals does not appear to have any marked effect. Of the acids used phosphoric acid gave the best results a t all concentrations but the best preserved solution had lost nearly 30% in strength after seven months. I n the presence of both acids and salts the decomposition in those solutions containing acetanilide is only a small fraction of that in the corresponding solutions which do not contain the preservative.As to the mineral impurities the salts of the alkali and alkaline-earth metals and all other salts used except those of copper and iron appear to have no influence whatever on the stability of the solutions when acetanilide is used. Traces of copper and iron have a very deteriorating effect but this is prevented to a great extent by acetanilide. H. w. Ignition of a Glowing Splint of Wood in Oxygen Mix- tures. P ANEMA (Chem. Weekblud 1913 10 1056).-A mixtnre of air and oxygen containing 30% of the latter does not ignite a glowing splint 3f wood. Ignition of Glowing Match-Sticks and the Extinction of Their Flame in Mixtures of Oxygen and Nitrogen.W. P. JORISSEN (Cham. Weekbhd 1913 10 1057. Compare preceding abstract).-The ignition limit is 28-29% of oxygen by volume and the extinction limit about 1676 of oxygen by volume. A. J. W. A. J. W. A Third Form of Sulphur. 111. A. H. W. ATEN (Zeitsch. physihl. Chum. 1913 86 1-35. Compare A .. 191 3 ii 580).-The third form of sulphur S has been further investigated. A method is devised by means of which the quantity of S may be estimated in a mixture of SA S and S,. The transformation of S into S is investigated and it is shown that the change S -+ S is at first very rapid but the velocity quickly decreases and becomes extremely small when there is only a small quantity of S present. The relative quantities of Sh S and S present in sulphur which has been heated to various temperatures are determined. The amount of .S is a t a maximum in sulphur which has been heabd to 180° and a t this point the amount present is 6.5% The quantityii.1%2 ABSTRACTS OF CHEMICAL PAPERS. of S increases as the temperature increases up to 445O the greatest rate of increase being between 170° and 180O. SA decreases as the temperature increases; a t 180° the composition is given by Sr = 6*5% S = 20*4% and S h = 73.1%. The influence of the cata- lysts sulphur dioxide ammonia and iodine on the equilibria S t S Z Sh is studied and i t is shown that ammonia increases the transformation of S more than it does that of S,. The change S,-+S takes place a t the same rate in the presence of iodine as i t does in the absence of iodine.The hard and soft varieties of S are considered together with S and evidence advanced t o show that S is in all probability contained in the soft variety of S which is really a mixture of S Sh and S containing very little SA. A number of properties of sulphur for example coefficient of ex- pansion and viscosity are considered and it is shown that the changes in these properties with temperature are more easily ex- plained when three modifications of sulphur are admitted than when two only are considered. A table of the composition of various forms of solid sulphur is given; in most cases the quantity of S is extremely small but S is found in sulphur which has been melted but not in that which has been crystallised.J. F. S. The Change of Sulphites into Sulphates. EMILE SAILLARD (Z+?itsch. Vev. deut. Zuckerind. 191 3 1035-1 043. Compare Titnff A . 1904 ii 113; Lange A. 1912 ii 550).-The change of sulphites into sulphates is retarded in sucrose solutions the amount of retard- ation being the greater the greater the concentration of the sucrose. Rise in temperature increases the velocity of change. Nitr- ogenous substances for example asparagine aspartic acid glutamic acid and potassium lactate also exert a retarding action whilst sodium chloride has no effect. T. S. P. Invert sugar has approximately the same effect as sucrose. Active Nitrogen. ERICH TIEDR and EMIL DOMCHE (Ber. 1913 46 4095-4103).-1n a previous communication (A. 1913 ii 210) Tiede has stated that when pure nitrogen is used the active modi- fication of Strutt cannot be obtained; this has been disputed by Koenig and Elod (A.1913 ii 316) and by Strutt (A. 1913 ii 316 696). The authors now give an account of experiments in support of the statement of Tiede. I n the preliminary experiments the apparatus was made com- pletely of glass no rubber joints being used; the various connexions were either fused together or else cemented with marine glue. Taps were made tight. with mercury in order to prevent the use of any fat and mercury vapour was prevented from diffusing into the apparatus by the interposition of vessels filled with gold leaf and cooled in liquid air. The nitrogen used was freed from oxygen by a combination of the copper method with that of Gehlhoff (A.1911 ii 487) and moisture and carbon dioxide were removed by appropriate absorbents. All parts of the apparatus were freed from adsorbed gases by heating during exhaustion. Under theseI PIT ( ) llGANIC C H EM ISTRY. ii. 123 conditioiis when it was certain that all oxygen had been removed the phenomena described by Strutt could not be observed. The final experiments were made with a smaller apparatus com- pletely of glass which contained fused on to it two glass tubes containing respectively barium azoimide and silver oxide from the former of which pure nitrogen is readily obtained by heating at 170°. After all parts of the apparatus had been freed from gas by repeated heating and exhausting the barium azoimide being main- tained a t 120° it was filled with pure nitrogen from the azoimide.There were then no signs of Strutt’s phenomenon but if the silver oxide were heated in order to add oxygen to the contents of the apparatus the characteristic glow was observed. The apparatus could then be cleaned from oxygen filled with pure nitrogen and again there would be no sign of Strutt’s phenomenon. The authors therefore conclude that the phenomena observed with so-called “active nitrogeu” are due to traces of oxygen in the nitrogen. T. S. P. Oxidation of Nitrogen during Electric Discharge. FRANZ FISCHER (Bey. 1913 46 4103).-The arithor maintains his opinion that the oxidation of nitrogen during electric discharges is pre- ceded by an activation of the oxygen (compare Fischer and Hene A. 1913 ii 132 317). The views of Koenig and Elod (A.1913 ii 1049) are invalidated by the recent communication of Tiede and Domcke (compare preceding abstract). T. S. Y. Combustion of Air in the Voltaic Arc. A. GOHBOV and V. The authors criticise the manner in which the results of Saposhni- kov Gudima and Kutovski (A. 1913 ii 950) are expressed the hourly volumes of air passing through the furnace being referred to varying numbers of kilowatts whereas the important point is not the absolute volume of air traversing the furnace per unit of time but a magnitude indicating the amount of energy applied to such volume of air. Calculation from the results given by the above authors shows good agreement with the formulae elaborated by the present authors (A. 1913 ii 950). MITKEVITSCH (tJ. KUS8. P/L:oS. Cht?m..L ~ O C . . 1913 45 16!n-1697).- T. H. P. Reduction of Hydronitric Acid [Azoimide]. 11. Structures of the Trinitride Radicle. J. W. TURRENTINE (J. Amsr. Chenr. Soc. 1914 36 23-35. Compare A. 1912 ii 448).-Further evidence is adduced in favour of the formula. H*N:NiN for azoimide (compare Turrentine and Moore A. 1912 ii 449). It is shown that Fischer’s interpretation of the reaction yielding diazobenzeneimide (A. 1878 305) on which is based the conception of the cyclic structure of the trinitride radicle is erroneous. It is pointed out that this reaction is essentially an oxidation of hydrazine and that Browne and Shetterly (A. 1907 ii 863; 1908 ii 373; 1909 ii 233 658) in their study of the oxidation of hydrazine have failed to observe any reaction analogous to that proposed by Fischer.E. G.ii. 124 ' ABSTRAC'I'S OF CHEMICAL PAPERS. The Intermediate Formation of Nitrogen Trioxide by the Action of Oxygen on Nitric Oxide. Behaviour of Nitrogen Trioxide towards Potassium Hydroxide. GABRIEL KLINGER (Zeitsch. angew. Chem. 1914 2 7 7-8).-Both RA schig and Lunge have shown that a mixture of nitric oxide and nitrogen dioxide dissolves in concentrated sulphuric acid quantitatively as if it were the compound N,O whereas sodium hydroxide dissolves only about 85% of the mixture relatively more of the dioxide dissolving than of nitric oxide. Raschig (A. 1905 ii 700) gives an explanation of this which postulates the existence of the compound N,O in the gaseous mixture whereas Lunge (A. 1906 ii 438) gives a different explanation and denies the existence of nitrogen trioxide.The author points out that both explanations are unsatisfactory and that it is probable that water is the disturbing factor when sodium hydroxide is used. Nitrogen trioxide would give nitrous acid with even traces of water and this would be further oxidised to nitric acid by the excess of nitrogen trioxide with evolution of nitric oxide and thus cause the observed discrepancies. I n support of this theory it is found that dry nitrogen trioxide is quantitatively absorbed by dry potassium hydroxide (compare A. 1913 ii 619). The question as to whether nitrogen trioxide is formed as an intermediate product when a mixture of nitric oxide and nitrogen dioxide is acted on by dry potassium hydroxide can be decided by measuring the ratio of the contraction which takes place to the volume of nitric oxide taken when a known mixture of nitric oxide with excess of oxygen is treated with the dry hydroxide.Experi- ments which were carried out agreed quantitatively with the inter- mediate formation of nitrogen trioxide which was then absorbed by the potassium hydroxide giving potassium nitrite. The Reaction of Metals and Alloys with Nitric Acid. J. H. STANSBIE (J. Soc. Chem. Ind. 1913 32 1135-1136).-Nitric acid dissolves copper silver mercury and bismuth much more rapidly when the metals remain a t rest in the acid than when they are rapidly rotated or the acid is stirred owing to the fact that in the former case nitrous acid accumulates in the neighbourhood of the metal (compare A. 1913 ii 982).Similar results are obtained with alloys of copper and zinc as long as they contain more than 48% of copper the alloy dis- solving as a whole. Below this percentage of copper the zinc either dissolves faster in proportion than the copper or precipitates that metal from solution with the result that more copper dissolves in the stirred solutions than in the solutions a t . rest. A neutral solution of copper nitrate has no corrosive action on alloys con- taining more than 80% of copper. T. s. P. T. S. P. The Action of Garbonyl Chloride on Phosphates and Oxides. J. RIBAN (Compt. . r e d . 1913 157 1432-1433. Compare A. 1883 287).-A claim for priority over Barlot and Chauvenet (compare this vol. ii 49). W. G.INORGANIC CHEMISTRY. ii. 125 Preparation of Solid Alkali Perborates from Boric Acid and Alkali Peroxides without the Use of Water 80 Solvent.CHEMISCHE FABRIK REISHOLZ (D.R.-P. 262144) -Boric acid is mixcltl with the amount of ice necessary for hydration and the alkali peroxide is added. Examples are given of the preparation of sodium perborates of the formulae Na,B,0,,2NaB03,10H20 NaB03,4H20 and Na,B,08,10H20. Experimental Demonstration of the Variability of the Molecule and the Atom. P. DE HEEN (Bull. Acud. ~ o y . ndg.. 1913 680-694).-Observations are described which seem to show that the sensitiveness of silver chloride to light can be varied by the action of reagents although the physical condition of the chloride remains constant. If the silver salt is triturated with a very concentrated solution of potassium hydroxide washed with water and boiled with nitric acid it is found that the residuai silver chloride is very much more sensitive to light than the original silver salt.A similar effect is obtained if the silver chloride is spread in a thin layer over the surface of a platinum cathode and subjected to the action of a current f o r several days. I f on the other hand the silver salt is subjected to the action of the current a t the surface of the anode its photo-sensitiveness is found to diminish. I n this case the action is less rapid and the current must be passed for a t least ten days. I n another series of experiments a quantity of silver chloride was divided into three portions one of which was subjected t o the action of the current a t the cathode the second portion to the anodic action of the current whilst the third was unacted on.The three portions of silver chloride were then reduced to metal and the three samples of metallic silver re-converted into chloride by dissolving in nitric acid and precipitating with hydrochloric acid. The silver chloride obtained from the first sample of silver was found t o be much less sensitive and that from the second sample much more sensitive to light than the chloride prepared from the third sample of silver. The above facts are supposed to show that the silver chloride molecule can be modified by suitable treatment and that the dif- ferent forms of silver salt are to be regarded as derived from silver atoms which are not identical. I n other words the experiments afford evidence of transmutation of normal silver into its meta- elements.H. M. D. New Compounds of Nitrogen and Hydrogen with the Alkaline-earth Metals. F. W. DAFERT and R. MIKLAUZ (Monatdh. 1913 34 1685-1712).-The calcium used by the authors in their experiments was obtained pure by distilling the commercial article in an apparatus similar to that used by Guntz in the preparation of strontium (A. 1910 ii 1064); the strontium and barium were obtained by distilling a mixture of the respective oxides with the equivalent quantity of aluminium powder (compare Guntz A. 1906 ii 669; 1910 ii 1064). J. C. C.ii. 126 AESTRACTS O F CHEMlCAL PAPERS. The pure nitrides and hydrides of calcium strontium and barium are readily obtained by heating the respective metals in the pure gases.When the nitrides are heated in a current of hydrogen compounds having the formula= M//,N,H are formed (compare A. 1909 ii 8821 but only the calcium and strontium compounds could be obtained pure since the barium compound even a t relatively low temperature reacts with hydrogen in accordance with the equation Ba,N,H + H = 3BaH + N,. When hydrogen is passed over heated barium nitride or more correctly over the impure compound Ba,N,H ammonia is formed. The barium hydride which is thereby produced is readily trans- formed back to the nitride by the action of nitrogen so that a process is given for the fixation of atmospheric nitrogen. When a mixture of equal volumes of hydrogen and nitrogen is passed over the heated alkaline-earth metals or over their hydrides or nitrides imides M'INH are produced which similarly t o lithium imide (A.1912 ii 253) darken on exposure to the light. Calciumlimide is most easily prepared but it has not been obtained pure; the formation of barium iinide is incomplete. The following table giving the temperatures a t which reaction occurs with the various gases shows that the tendency of the alkaline-earth metals to combine with nitrogen and hydrogen increases with the atomic weight? whilst the tendency of the nitrides to combine with hydrogen decreases with increase in atomic weight of the metal. Ca ......... 410" 300" Cn,N .......... 230" Ba ........ 260 170 Ra,N,.. . . . . . . . 300 N. H. H. Sr ........ 380 21 5 Sr,N ........... 270 T. S. P. Formation of Magnesium Barium and Strontium Com- pounds Analagous t o Apatite and Wagnerite.HANS WINTER (Diss. Leipzig 1913 1-46),-The phosphates and halogen salts were fused together in an electric oven and the equilibrium diagrams are given for several pairs. Barium chloride (m. p. 958O D 3.789) is optically biaxial and positive whilst barium fluoride (m. p. 1289O) strontium chloride (m. p. 874O D 3*054) and strontium fluoride (m. p. 1400O) are all cubic in crystallisation. These do not form mixed crystals but the double salts BaCl,,BaF (m. p. 1008O D 5.931) and SrCl,,SrF2 (m. p. 962O D 4.616) both of which are tetragonal and optically negative. Magnesium fluoride and phosphate yield wagnerite MgF2,Mg3P,08 and only doubt- fully a compound corresponding with apatite (magnesium-fluor- apatite). The barium and strontium compounds corresponding with wagnerite were not obtained but the four apatites of the composition BaC1,,3Ba,P,08 BaF2,3Ba3P208 SrCI2,3Sr3P,O and SrF2,3Sr3P,0 ; these were obtained in a crystallised condition and their melting points density and refractive indices determined.L. J. S.IN( 1RGANIC CHEMISTRY. ii. 127 Allotropy of Zinc. ERNST COHEN and W. D. HELDERMAN (Proc. K Akad. Wetensch. Amsterdam 191 3 16 565-568).-Experi- ments are described which show that zinc which has been obtained by rapid cooling of the liquid metal undergoes slow changes in respect of its density. The molten metal was poured into a cylinder of asbestos paper cooled by a mixture of solid carbon dioxide and alcohol. The density of the solid was then found to be 7.130 a t 25O.After heating for a fortnight a t looo in a solution of zinc sulphate the density was found tyo be only 7.102. These observations show that ordinary zinc is in a metastable condition and that the modification which is formed a t high temperatures changes only very slowly into that which is stable at the ordinary temperature. The stable form was probably obtained in an almost pure condition by Kahlbaum Roth and Siedler (A. 1902 ii 259). H. M. D. Atomic Weight of Oadmium by the Investigation of Cadmium Chloride and Cadmium Bromide. ELTON L. QUINN aod GEORGE A. HULETT (J. Physical Chew. 1913 17 780-798).- Weighed quantities of the carefully purified chloride or bromide were converted into sulphate by evaporating solutions of the salts to dryness after the addition of the calculated quantity of sulph- uric acid.The cadmium sulphate was then dissolved and subjected to electrolysis in an amalgamated platinum crucible which served as the cathode. As shown by previous experiments (Perdue and Hulett A. 1911 ii 433) this method can be applied very con- veniently i n the case of metals like cadmium which are readily . soluble in mercury and sufficient evidence has already been obtained that the electrolytic method affords very exact results in the estima- tion of cadmium (compare also A. 1911 ii 397). The results obtained with the chloride give for the atomic weight of cadmium 112.32 +0.01 whilst the bromide results lead to the value 112.26 +0*005. The mean of these is 112.29 which agrees very well with the value 112.30 obtained by Perdue and Hulett (Zoc.cit.) from the analysis of cadmium sulphate and also with the results obtained by Laird and Hulett in their work on the cadmium coulometer (Trans. Amer. Electrochem. SOC. 1912 22 385) which lead t o the value 112.31. The authors consider that these observations show that the atomic weight of cadmium is nearer 112.3 than the value of 112.4 which is accepted as the most probable value according to previous measurements. H. M. D. Cadmium. MANUEL VERES (Compt. rend. 1914. 158 39-40)- Using the methods of Lepierre and Lachaud (compare A. 1892 943 1282) and Klobb (compare A. 1892 941 1399) the author has prepared a new double salt of cadmium sulphate and ammonium sulphate having the constitution 2CdS04,(NH4),S04. It is ob- tained in microscopic crystals yellow when hot white when cold.It is v0ry hygroscopic and has D22 3-11. It is very soluble in water and from its solution on evaporation crystals of CdSO4,(N€&),S0,,6H,Oii. 123 ABSTRACTS OF CHEMICAL PAPERS are deposited. The salt 2CdS04,(NH,),S0 is decomposed by warming with concentrated sulphuric acid at looo giving anhydrous cadmium sulphate in rhombic crystals. W. G . Egyptian-Blue. A P. LAURIE W. F. P. MCLINTOCK and F. D. MILES (Proc. Roy. Soc. 1914 A 89 418-429).-Experimerits have been made to determine the nature and conditiolns of formation of Egyptian-blue. Acco'rding to Fouqu6 (BUZZ. SOC. Mines 12 36; Compt. rend. 1889 108 325) this substance is a crystalline double silicate of copper and calcium of the formula Ca0,Cu0,4Si02.That the substance is really crystalline in character has been shown by the examination of a number of samples of real Egyptian- blue between crossed nicols. I n order to ascertain the conditions under which the compound is formed a mixture containing 36 grams of quartz sand 4 of fusion mixture 8.6 of copper carbonate and 7.2 of calcium carbonate was heated for several hours in an electric resistance furnace a t temperatura ranging from 760° t o over 900°. These experiments show that the temperature should be kept between narrow limits (830-900O) if the blue compound is to be obtained. The mixture may however be heated to the temperature of the oxyhydrogen blow-pipe provided that the mass is subsequently maintained for a considerable time at about 850O.If the tempera- ture is too high or too law the product is an olive-green glass. Further experimenta show that the formation of the blue com- pound is not dependent on the presence of sodium or potassium carbonate or other alkali salts although if these are absent the mass is so infusible that reaction takes place with great difficulty. On the other hand if the amount of fusion mixture is increased very much above that correspondipg with the mixture referred to above the calcium copper silicate does not crystallise out of the mass but remains in solution as a green glass. From analyses of Egyptian-blue prepared by the authors i t appears that in presence of an alkali a little of the copper and calcium is replaced by the alkali metals. Apart from this the analyses are found to correspond with the formula Ca0,Cu0,4Si02.H. M. D. Polymorphism of Mercuric Iodide. MEINHARD HASSELBLATT (Zeitsch. physikal. Chem. 1913 86 61-64).-Polemical against Smits (A. 1910 ii 400). Mercuric Oxide. GUY B. TAYLOR and GEORGE A . HULETT (J. Physicatl Chm. 1913 17 755 -761).-Mercuric oxide waR prepared by heating carefully purified mercury in an atmosphere of oxygen at about 420° and a pressure of 2-3 atmospheres. The apparatus was arranged so that fresh supplies of oxygen could be admitted from time t o time. It was found possible to obtain from 10 to 15 grams of the oxide in thel course of an experiment which lasted from five to Beven days. The oxide was finally freed from all J. F. S.Ih’ ORGAXIC CHEMISTRY. ii. 12:) trac;es of unconibined metal by heating to 400° iu a rapid current of oxygen a t atmospheric pressure.The pure mercuric oxide obtained in this way was reduced to metal by heating with pure finely divided iron the temperature being maintained a t 275-300O for two to three hours and then at about 600° for twenty-four to thirty-six hours. During the last half-hour the protruding end of the tube was cooled in ice and the globule of condensed mercury transferred to a porcelain crucible and weighed. Nine analyses of the oxide were made according to this method the results agreeing exceedingly well with one another and giving for the mean value of the percentage of mercury in the oxide 92.6053 k 0*0008. This corresponds with an atomic-weight value for mercury of 200-37 k0-025. This value is considerably smaller than that recently obtained by Easley and Brann (A.1909 ii 1013; 1910 ii 957; 1912 ii 257) from the analysis of mercuric chloride and bromide namely? 200.62. I f the higher value is correct the lower value might be explained by the presence of a small quantity of a higher oxide. The authors consider however that the discrepancy calls for a further investigation of the atomic weight of mercury. H. M. D. The Alloys of Cerium with Silicon and Bismuth. RUDOLF VOGEL (Zeitsch. anorg. Chem. 1913 84 323-339).-The fact that cerium combines with lead and tin with development of heat forming several compounds indicates that it does not belong to the same chemical family of the fourth group. It is now found that it combines with silicon at high temperatures with great violence.It has not been found possible to prepare alloys con- taining more than 70% of cerium as combination does not take place until 1400° and the heat developed brings about the destruc- tion of the containing vessel or if carbon crucibles are used there is a considerable production of cerium carbide in which case the alloys rapidly disintegrate in air. Solid silicon floats on molten cerium and a t a sufficiently high temperature combines explo- sively. Between 0 and 70% Ce the freezing-point curve has two branches intersecting at l24Oo and 53% Ce. The eutectic times indicate that the maximum on the curve must be at 83% Ce corresponding with a compound CeSi melting above 1500O. This compound forms yellow rounded crystallites and the eutectic has a distinct lamellar structure.Free silicon crystallises in needles which are harder than the compound. The alloys are brittle very stable in air and are not pyrophoric. Cerium and bismuth combine with great development of heat. Porcelain tubes are rapidly corroded but carbon tubes may be used and the alloys are not seriously contaminated with carbide. The thermal effects are ofteri small and the micro-structure has been largely employed in determining the form of the diagram. The sections must be polished with wet alumina but they oxidise very rapidly and the polished surfaces cannot be preserved. VOL. CVI. ii. 9ii. 130 ABSTRACTS OF CHEMICAL PAPERS. Four compounds are fornied BiCS Bi,Ce BiCe and BizCe. The compound Bi,Ce melts a t 1630° and appears as a maximum on the freezing-point curve.It crystallises in polygonal grains. BiCe is formed at 1400° and is softer than Bi,Ce,. It forms a eutectic with cerium a t 757O. BiCe is formed a t 1525O and Bi&e a t 882O whilst the second eutectic point practically coincides with the melting point of bismuth. All the alloys are more readily attacked by water than cerium. Between 25 and 75% Bi the action of water may even raise the alloys to incandescence. C. H. D. The Resolution of Ytterbium into its Elements. C. AUER VON WELSBACH (Monatsh. 1913 34 1713-1728).-1n the resolution of ytterbium into its elements (compare A. 1908 ii 591) the fractionation proceeds at first very slowly but after a large number (ZOO) crf fractionations have been carried out there is a very marked increase in the rate of fractionation.This increase could be ascribed to the existence of an unknown element occurring between the elements aldebaranium and cassiopeium but the spectroscopic examination afforded no definite evidence in this direction. The cause of the increased rate of fractionation is therefore a t present inexplicable. The atomic weights of aldebaranium and cassiopeium have been determined by a new method. The respective hydrated sulphates 3X2(SO4),,8H2Oy were dried in a platinum crucible in a vacuum desiccator; heating on a water-bath is not permissible in the case of cassiopeium sulphate. They were then dehydrated by careful heating an excess of oxalic acid added and the crucible twethirds filled with water. The crucible and its contents were then heated on a water-bath t o dissolve the excess of oxalic acid after which the insoluble oxalates were collected washed and then converted into oxide. Any salt.remaining in the mother liquor and washings was precipitated by making use of the fact that the ammonium oxalates of these metals are insoluble in a saturated solution of ammonium hydrogen oxalate and allowed for. The results gave Cp = 175.00 Ad = 173'00. T. S. P. The Perchlorates of Aluminium Chromium and Mag- nesium. R. F. WEINLAND and FR. ENSGRARER (Zeitsclh. anorg. Chem. 1913 84 368-372).-AZumirtium percchlorate [ Al(€€20)61(C104)q is ft derivative of the hexa-aquo-base and thus completely resembles the ferric compound (this vol. ii 132). Its solution yields with sodium perchlorate a crystalline sodium aluminotetraperchlorate [A1(C104),]Na,12H,0 which loses 6H20 over sulphuric acid. Chromium yields two perchiEorates of the hexa-aquo-base [Cr(H,0),]C10,)3 and [Cr(H,O),!(C!10,),,3R,O but no sodium chromiDerchlorate.Both of theae salts are bluish-preen. Mag&iam perchJornte [Mg(H,O),](ClO,) is al& a hexa-aquo- salt. C. H. D.INORGANIC CHEMISTRY. ii. 131 The Critical Ranges of Pure Iron. H. c'. H. CARPENTER (J. Iron Sted Inst. 1913 i 315 -326).-Electrolytic iron sheet contain- ing 99.967% of iron gives cooling curves which are consistent with the view that the critical point Ar is merely the retarded termina- tion of Br3. The point -4c is only faintly marked on the heating curves when dissolved gas has been removed. The results support the view of Benedicks (A. 1913 ii 599) that P-iron is a solid solution of y-iron in a-iron (compare Miiller A.1909 ii 485; Burgess and Crowe 9. 1913 ii 711). C. H. D. The Tenacity Deformation and Fracture of Soft Steel at High Temperatures. WALTER ROSENHAIN and J. C. W. HUMFREY (J. fron Steel Inst. 2913 i 219-271. Compare A. 1910 ii 128).- Tensile tests with strips of soft steel in a very high vacuum indicate that the tenacity falls rapidly with increasing temperature from 600° to 730O; there is then a break in the curve and the tenacity passes through a minimum between 800° and 900° an entirely distinct curve starting from a relatively high tenacity at 900') and then falling gradually representing the y-phase. The first break is considered to represent the a+/3 change.The influence of size of crystal grain and rate of loading on the resulta has also been determined and the results are regarded as supporting the " amorphous cement " theory of the constitution of metals (Rosen- liain and Ewen A 1913 ii 119). C. H. D. Influence of Sulphur on the Stability of Iron Carbide in the Presence of Silicon. W. H. HATFIELD (J. I T O ~ Steel Inat. 1913 i 139-156).-Sulphur increases the stability of iron carbide (cementite) a t high temperatures entering in small quantity into the carbide. The influence of sulphur is not purely mechanical through the formation of sulphide films. Its influence in cast iron is neutralised by the presence of manganese which forms an insoluble sulphide and of silicon possibly owing to the formation of a silicon sulphide although such a compound was not actually isolated.C. H. D. The Rusting of Iron in Water. W. A. BRADBURY (Chem. News 1913 108 307-308).-Two flasks were filled with well-boiled Manchester tap-water some coils of bright iron binding wire added and the flasks securely corked. No rusting took place whereas rusting readily occurred in unboiled tap-water. I f rusting takes place according to the equation Fe + 2H,C03 = Fe(HCO,) + H the ferrous hydrogen carbonate then being oxidised by oxygen present hydrogen should be evolved. It was found however that no hydrogen was liberated when rusting took place in ordinary tap-water. This could be accounted for by the nascent hydrogen liberated being oxidised by the oxygen present in the water or else by the hydrogen remaining dissolved in the water.This was tested by using water into which carbon dioxide had been passed for fifteen minutes. At first no hydrogen was evolved; the iron 9-2ii. 131 ABSTRACTS OF CHE3lIC.A J d PAPERS. reiuained quite bright but ferrous iron was present ill solutiorJ. After some days hydrogen was evolved but the iron remained quite bright. Apparently no hydrogen was evolved until all the oxygen present in the water had been reduced; owing to the removal of this oxygen no rust could form although a large quantity of iron was present in solution as ferrous bicarbonate. These experiments confirm the view that rusting is due t o dissolved oxygen and carbonic acid present in the water. Contrary to what is usually supposed to be the case magnesium chloride was found not to have a deleterious effect on iron.T. S. P. New Method for the Preparation of Colloidal Ferric Hydroxide. 'hEoDoRE C'OHEN (J Amer. Chern soc. 1914 36 19-23).-Experiments are described which show that a colloidal solution of ferric hydroxide can be obtained by the hydrolysis of a ferric nitrate solution which takes place in a nitric acid solution containing copper; for example if 3 grams of iron filings contain- ing copper as an impurity are added to 10 C.C. of concentrated nitric acid and the solution is diluted filtered and dialysed a deep red liquid is obtained from which on treatment with a little sulphuric acid or with the electric current ferric hydroxide separates. A similar solution can be prepared by boiling a solution of ferric nitrate with copper filings or with zinc dust.R. DE FORCRAND (Compt. rend. 1914 158 20-23).-A btudy of the hepta- tetra- and mono- hydrates of ferrous sulphate and the anhydrous salt. The hepta- hydrate can be obtained perfectly pure and dry by powdering an ordinary sample and repeatedly pressing it between folds of filter- paper. It neither oxidises effloresces nor deliquesces. It has heat of solution -4.323 Cal. a t 13.5O. The tetrahydrate has heat of solution t1.599 Cal. a t 13*5O the monohydrate +7.538 Cal. at 13.5O and the anhydrous salt +14.901 Cal. at +13*5O. From these results the author calculates for the monohydrate a b. p. 300° for the tetrahydrate b. I>. 118'5O and for tho lieptahydrate 118.3O. E. G. Ferrous Sulphate and Its Hydrates. The product thus obtained is quite stable in air a t 1 5 O .W. G. Salts of Ferri-phosphoric -sulphuric and -perchloric Acids. R. F. WETNLAND and FIR. ENSGRABER (Zeifsch. anorg. C h m 1913 84 340-367).-An ammonium ferriphosphate has been obtained by Cohen (A. 1907 ii 552) and there is other evidence of a series of complex salts. Either ferric hydroxide or ferric chloride is mixed with an excess of phosphoric acid and the complex alkali salts may then be obt'ained by the addition of alkali hydr- oxide phosphate or chloride. Definite proportions must be used and the solutions must be heated for a t least twenty-four hours otherwise the products although well crystallised are not homo- geneous. Sodium f erridiphosphate [Fe(PO,),1R,Na,H2O is obtained in pale pink crystals by heating a solution of ferric hydroxide inINORGANIC CHEMISTRY. ii.133 phosphoric acid with sodium hydroxide (Fe P Na = 1 24 8) for three days on the water-bath. After six months a t the ordinary temperature i t is obtained with 3H,O. The corresponding am- monium salt [Fe(PO,),]H,-NH consists of pale pink microscopic hexagonal crystals. By using less ammonia an acid ammonium salt [Fe(P0,),H3],NH,,7H,0 may be prepared in light red micro- scopic crystals. The pyridinium salt [Fe(PO,),]H,C,NH is white. Sodium ferritriphosphate [Fe(PO4),]H,Na,H2O is obtained when sodium phosphate o r chloride is added to the solution of ferric phosphate instead of sodium hydroxide. Thus a mixture in the proportions (Fe P NaCl= 1 6 4) yields the salt after heating for twenty-four hours on the water-bath.It is a very pale red crys- talline powder. A mixed ammonium ferri-di- and tri-phosplutte 3[ Fe( P04),]H,,[Fe( PO,),]H 1 *5NH3,1 OH20 crystallises in the course of six months With a large excess of ammonium chloride and a deficiency of phosphoric acid an entirely different salt of unknown constitution is obtained as a greenish-yellow microcrys- talline powder. It has the empirical composition 2FePO4,NH,,4H,O. All of these compounds are very 'sparingly soluble in water. It has not been found possible to prepare corresponding potassium salts. Ferric phosphate prepared by heating molecular proportions of ferric chloride or acetate with phosphoric acid for two days on the water-bath is a pink microcrystalline powder and may be regarded as ferric ferridiphosphate [Fe(P04),1Fe,5H,0.It is very sparingly soluble in water and dilute acids whilst the phosphates of variable composition obtained by precipitating ferric solutions with alkali phosphates dissolve readily in dilute acids. Ammonium ferridisulphate [Fe(SO,),]NH obtained on heating a solution of ferric ammonium asluin with sulphuric acid for twenty- four hours is a white microcrystalline powder sparingly soluble in water and depositing ferric hydroxide rapidly on heating. The potassium salt [Fe(SO,),]K,H,O and the pyridinium salt have similar properties. Trisodium ferritm'sulphate [Fe(SO,),]Na,,SH,O is a white crys- talline salt as is the previously known ferridisulphuric acid [ Fe( S04)2]H,4H,O- Sodium f erritetraperchlorate [Fe(C1O4),]Na,6H,O forms large pink hygroscopic crystals.Ferric perchlorate Fe(C10,),6H20 is to be regarded as a hexa-aquo-salt [Fe(H,O),](ClO,),. [Fe(S0*)2]H,C,NH,,2H20 C. H. D. Rinmann's Green. A RVID HEDVALL (Arkiu. Kern. illin. Geol. 1913 5 No. 6 1-27).-!Che author's further investigations (com- pare A. 1912 ii 846) show that Rinmann's green is not a definite substance but rather a series of solid solutions of the components zinc oxide and cobalt oxide since its composition may vary con- siderably. The series of mixed crystals is isodimorphic since zincii. 134 ABSTRACTS OF CHEMICAL PAPERS. oxide is hexagonal and cobalt oxide generally regular although in one case the latter oxide has probably been obtained in hexagonal crystals. T. S. P. Chromic Oxide Jellies.E. H. BUNCE and L. S. FINCH (J. Physical Chew. 1913 17 769-779) -Experiments have bwn made to determine the conditions of formation of chromic oxide jellies. If a sufficient amount of sodium acetate is added to a solution of chromic sulphate or chloride the subsequent addition of a suitable amount of alkali metal hydroxide or ammonia causes gelatinisa- tion. The chromic oxide jelly is violet if prepared by the addition of ammonia or of a slight excess of alkali metal hydroxide. If this is added in larger quantity the jelly is green in colour. The con- centrations of the chromic salt and sodium acetate may be varied within fairly wide limits without interfering with the formation of the jelly. If after the addition of sodium acetate the solution is heated the time required for gelatinisation is found to diminish appreciably.Apart from this prolonged heating of the solution has no effect on the subsequent gelatinisation provided acetic acid is not driven off during the process. Chromic oxide jellies dissolve in hydro- chloric acid but are reformed when the solution is neutralised if sufficient sodium acetate is present. The addition of sodium or potassium chloride has no appreciable influence on the gelatinisa- tion but this is prevented by the freezing or stirring of the solutions. Chromic oxide jellies can also be obtained by adding sodium or potassium hydroxide to a solution of chrome alum but not by the addition of ammonia. The addition of sodium acetate to the chrome alum solution appears to be without influence on the result.Although jellies are obtained by the addition of potassium hydr- oxide to solutions of chromic acetate and chrome alum this is not the case when the alkali is added to solutions of chromic nitrate chloride or sulphate. The acetate method of preparing jellies gives no result in the case of salts of manganese aluminium copper and cadmium. H. M. I). Chromic Silicofluoride. Its TraneformationR. Fluopenta- nquochromic Silicofluoride. A. RECOURA (Compt. rend. 191 3 157 1525-1528. Compare A. 1913 ii 603).-In explanation of the fact that the normal ferric silicofluoride is decomposed as formed giving the compound Fe2F,,2SiF the author expresses the view that ferric fluoride itself is really a complex t o be represented by (Fe2F?)F4 and thus the double compound prepared is a true silicofluoride (F%F2)(SiF4),. I n support of this he shows that the latter compound reacts with potassium chloride t o give potass- ium silicofluoride and a compoicnd (Fe,F,)Cl in which the fluorine is masked.I n the case of chroniiuu1 the silicofluoride Cr2F,(SiF& is obtained in solution although i t is not possible to isolate it as the violet solution spontaneously and gradually turns bluish-green andINORGAPilC CHEMISTRY. ii. 135 from i t a green solid can be isolated to which the author assigns the constitution (CrF,5H20)SiF6 and compares i t with the two silicofluorides - (CrC1,5NH3)SiF6 and (CrCl,H,0,4NH3)SiF6 pTe- pared by Jorgensen. The violet solution immediately after its preparation reacts normally with potassium chloride giving potassium silicofluoride and chromic chloride but on remain- ing it reacts to give potassium silicofluoride and the com- pound (Cr2F2)C14 from which the fluorine cannot be precipitated by addition of barium chloride.The compound (CrF,5H20) SiF is perfectly stable when kept in a desiccator even in a vacuum but on exposure to air it slowly loses silicon fluoride ultimately yielding a green chromic fluoride Cr,F,,7H20. Aluminium silicofluoride gives analogous results. Metastability of Metals Prepared by an Electrolytic Method. ERNST COHEN and W. D. HELDERMAN (Chem. Weekblad 1914 11 83-84).-At 1 8 O grey tin is converted into the white modification. The white modificatlon is also deposited by electrolysis of a solution of a tin salt a t -2OO. The Action of the Silent Electric Discharge on a Mixture of Hydrogen and Titanium Tetrachloride Vapour.11. A Poly- morphic Titanium Trichloride. F. BOCK and L. MOSER (I?lonntsh. 1913 34 1825-1849).-1n a previous communication (A. 1913 ii 9) a brown substance was described which was considered to be a polymorphic form of ordinary violet titanium trichloride. I n the present communication the authors describe an improved apparatus f o r preparing and handling this substance. The change from brown to violet trichloride is not reversible; the heating curve of the brown modification the temperature being gradually raised above that a t which transformation takes place did not differ appreciably from that of the cooling curve of the violet modification thereby formed. The heats of solution in water of various known mixtures of the brown and violet trichlorides with titanium tetrachloride were determined as also the heat of solution of pure titanium tetra- chloride.From the results the following figures were obtained (TiCl,,aq.) 59030 cal. ; (brown TiCl,,aq.) 48150-48837 cal. ; (violet TiCl,,aq.) 44287-45800 cal. These figures are taken to prove that the brown and violet titanium trichlorides are mono- tropic modifications. T. s. P. H A N ~ BUCHTALA ( J . pr. Chern. 1913 [ii] 88 '771-'785).-hn account of the prepara- tion of a number of thallous borates. ThJaZZous tetraborate Tl,B40 prepared by dissolving thallous carbonate (1 mol.) and boric acid (1-4 mols.) in water crystallises with 2H,O. It is also obtained together with the hexnborate T12B60,,,3H20 when the carbonate is fused with boric acid (6 mols.) and the product crystallised from water; if the fusion is carried out with a greater excess of boric acid (8 mols.) a mixture of tho hexaborate and decaborate T12B,,0,,,8H,0 is produced. W. G. A. J. W. Compounds of Thorium with Boric Acid.ii. 136 ABSTRACTS OF CHEMICAL PAPERS. Thallozis octaborate T12B,0,,,4H,0 and thallous dodecaborate T12B,,01~,7H20 are prepared by dissolving thallous carbonate in an excess of aqueous boric acid (10 mols.); the last-named borate also crystallises with 5H20 in twinned monoclinic crystals (a b c = 1.556 1 1.920. 11 = 945?0°). ThaZEoiLs perborate is obtained as a white powder by the addition of 30:h hydrogen peroxide to an aqneous solution of any of the preceding borates. It shows the usual reactions of a per-salt and decomposes explosively when rapidly heated. The amount of oxygen liberated by hating the perborate with water corresponds with the formula I >O; the aqueous solution on evaporation yields a red thdious metaborate which becomes blackish-red on exposure t o air and crystallises from water in radially-arranged colourless wodge-shaped crystals of the corn- position Tl,B,O,,H,O. F. B. TlO*B-O*O TIWB*O*O

ISSN:0368-1769    

DOI:10.1039/CA9140605120

出版商:RSC    

年代:1914

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129 Organic Chemistry. Preparation O f Isoprene. BADISCHE ANILIN- 8 SODA-FABRIK (D. R.-P. 268100 268101).-Isoprene is obtained by applying the process described in the chief patent (255519 A 1913 i 438) which consists in heating the substances there mentioned to a high tempera- ture under diminished pressure in the presence of catalysts to methyl- butenyl acetate (1st patent) or methylbutenyl ether (2nd patent). J. C. C. Preparation of Isoprene. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 268102).-Instend of as-dimethylallene as described in the chief patent (A. 1913 i l) isopropylacetylene is dropped on to strongly heated aluminium oxide under a presgure of 40-50 mm. J. C. C. Preparation of Erythrene. FARBENFABRIKEN VORM. FBIEDR. BAYER & Co. (D.R.P. 262553 2628S4).-Erythrene can be obtained by submitting cyclopentane or 1-methylcyclopentane-3-01 or other homologues and derivatives of cyclopentane to pyrogenic decomposition. The second patent states that cycZohexano1 can also be used.J. C. C Preparation of E r y t h r e n e a n d Other Unsaturated Gom- pounds ALBERT GERLACR and RUDOLF KOETSCHAU (D.R.-P. 267079 267080).-The pyrogenic decomposition of oleic acid or oils fats and waxes derived from the acids of the oleic series is advantageously carried out by means of an electrically heated metallic spiral placed inside the reaction vessel the latter being externally heated to the boiling point of the contents. The second patent mentions that such substances as wool fat cholesterol etc. may be used in this process for obtaining erythrene and the other unsaturated hydrocarbons which are also produced.J. C. 0. Catalytic Decomposition of Alkylidenehydrazines. Investi- gation of the Hydrocarbons from Gitral and Citronellal. Compare A 1913 i 1161).-The hydrocarbon b. p. 164-165'/ 755 mm. obtained from citralhydrazone (A. 1911 i 1027) has been prepared in larger quantity from unpurified citral and subjected t o further investigation. It is found to be a mixture of two isomerides the one present in larger quantity (119 grams) being (1) the limonene modification CH2:CMe*CH2*CH2*CH,-CMe:CHMe b. p. 162-163'/ 760 mm. DiO 0.7677 n 1.4422. When this hydrocarbon is converted by means of fuming hydrobromic acid into the dibromo-derivative C,,H,,Br and the latter either distilled with aniline or boiled in a reflux apparatus with alcoholic potassium hydroxide the linaloolene obtained by Semmler by the action of sodium on linalool ('g Die N.KISHNER (J. RU58. PhyS. Chem. SOC. 1913 45 1779-1787. VOL. CVI. i. 1;i. 130 ABSTRACTS OF CHEMICAL PAPERS. Aetheriachen Ole," I 527) is formed ; when alkali is used for decomposing the dibromo-compound the unsaturated alcohol C,,H,,*OH b. p. 190-195O is also obtained. Reduction of the limonene modification by Sabatier and Senderens' method yields inactive /3[-dimethyl- octane CHMe,*CH,*CH,*CH,*CHMeEt b. p. 158-159*5"/776 mm. (157*4-158'/748 mm.) DF 0.7287 (0.7281) n 1.4100 (1.4097). Similar reduction of the linaloolene obtained above does not yield this same dimethyloctane but an isomeride b. p. 161-162'/772 mm. Dfo 0-7399 m 1.4146.CMe, (YH*CH,*CH,*CMe CHMe obtained in smaller quantity (25 grams) has b. p. 163-165'/760 mm. DF 0.7699 n 1.4439 and yields acetone and other products on oxidation with permanganate. An optically active /I[-dimethyloctane was previously obtained (A 1911 i 1087) by reducing with hydriodic acid in a sealed tube the hydrocarbon C,,H, formed when citronellaldehydehydrazone is distilled with fused potassium hydroxide. As this method of reduction of ten leads to partial racemisation Sabatier and Senderens' method was employed the resulting hydrocarbon having the proper- ties b. p. 159.5'/753 mm. Di0 0.7308 n 1.4106 [a] +6*43' which are changed after purification with fuming nitric acid t o b. p. 160-161'17'72 mm Di0 0.7301 nD 1.4109 [a]D + 6-21'. Combination of the hydrocarbon C10H2 with hydrogen bromide and distillation of the bromo-derivative C10H27Br with quinoline yields a hydrocarbon CI0H2 which has slightly different physical constants and on reduc- tion by Sabatier and Senderens' method gives the hydrocarbon C10H2 b.p. 159*5-160'/760 mm. DF 0.7293 nD 1.4115 [a] +6*97'. For the dihydromyrcene obtained by Semmler (A. 1901 i 732) the author suggests the formula CH,:C~e*CH,*CH,*CH,*CEt:CH,. (2) The terpinolene modification T. H. P. Simultaneous Oxidation of Saturated and Unsaturated Hydrocarbons by means of Potassium Permanganate. N. KISHNER (J. Russ. Phys. Chem. Xoc. 1913 45 1788-1792).-The results of the author's previous experiments on the purification of saturated hydrocarbons by treatment with potassium permangaaate raise the question Does admixture of an unsaturated hydrocarbon influence the stability of a saturated hydrocarbon as regards its oxidisability? In other words is the oxidation of a mixture of a saturated and an unsaturated hydrocarbon to be regarded as a coupled or induced reaction ? Various experiments have been made with P[-dimethyloctane the unsaturated hydrocarbon C10H22 b.p. 161-163'/772 mm. (preceding abstract) the hydrocarbon C,,H (Zoc. cit.) and d-P[-dimethyloctane (Zoc. cit.) in order to ascertain whether they are oxidised more readily in presence of menthene than alone. The results show that the unsaturated hydrocarbon does not occasion considerable increase in the rapidity with which the saturated hydrocarbon oxidises. This reaction shows complete analogy to the coupled or induced oxidations investigated by Schilov (A.1903 ii 276). The oxidation of different saturated hydrocarbons is influenced inORGANIC CHEMISTRY. i. 131 the above manner t o different extents. PS-Dimethyloctane contains two tertiary hydrogen atoms and these undergo oxidation far more readily than those of other hydrocarbon radicles such as the methyl or methylene group ; this circumstance explains the results obtained by Nametkin (A. 1913 i 1285) with mixtures of propane or cyclopropane with an unsaturated hydrocarbon and it is probsble that a mixture of isobutane with propylene would exhibit different behaviour. When the products of oxidation of a mixture of P[-dimethyloctane with menthene are distilled a distinct odour of tertiary alcohols is per- ceptible indicating that the initial stage of the oxidation of the dimethyloctane consists in hydroxylation of the tertiary hydrogen.T. H. P. Influence of Constitution on the Rotatwy Power of Optically Active Substances. VII. Optically Active Hydro- carbons from Citronellel. H. RUPE and ALPEO~US JBGE~ (AnnaZun 1914 402 149-186. Compare A 1913 i 884).-Continuing the investigation of the influence of certain radicles on the rotatory power of optically active substances the authors have selected ci tronellaldehyde as a very suitable material for their purpose because it coctsins only one centre of optical activity and by the introduction of alkyl and aryl groups by the Grignard reaction is readily converted into secondary alcohols from which unsaturated hydrocarbons are obtained by the loss of water.Semmler's hypothesis that citronella1 reacts sometimes according to the " limonene " formula CH,:CMe*[CH2],*CHM~*CH0 at other times according to the '( terpinolene " formula CMe,:CH*[CH,],*CHMe*CH,*CHO is even if true without weight in so far as the authors' purpose is concerned because the double linking in both formulz is so widely removed from the centre of optical activity as to be without appre- ciable influence on the rotatory power. Quite different is the case of the double linking produced in the unsaturated hydrocarbons when these are obtained from the secondary alcohols by the (indirect) elimination of water. This double linking can occupy different positions (in suitable substances) and since i t is within the sphere of influence of the asymmetric carbon the determination of its exact position is a matter of prime importance. /3[-Dirnethyl-A"-nonen-B-ol (Rupe and Splittgerber A 1907 i 7 1 l ) P[-dlmethyl-Af-decen-O-ol (Austerwell and Cochin A 1910 i 572) pi- dirnethy Z-AF-undecem#-ol CMe, CH*CH,*CH,*CHMe*CH,*CHPra*OH b.p. 124'19 mm. and 1u-ctimethyl-AaL-undecadien-6-01 CISle,:CH*CH,*CH,*CHMe-CH2*CH(OH)~CH2-CH :CH b. p. 123-124O/lO mm. are obtained in the usual manner from citronella1 and magnesium methyl ethyl propyl and ally1 bromides respectively. These carbinols are converted by phosphorus tri bromide at 100-105° into tho corresponding bromides from which hydrogau bromide is then eliminated by boiling with pyridine or better alcoholic sodium ethoxide.pt- Rimethgl- AFV-nonndiene CMe,:CH*CHI,*CH2*CHRlu*CH:C KRle k 2i. 132 ABSTRACTS OF CHEMICAL PAPERS. bas b. p. 61-62'/9 mm. Di0 0.7730 [a]:' -8*12' [a] - 10*37' [a] - 12*29' and [a] - 16.17'. By treatment in glacial acetic acid with 6-8% unpurified ozone and subsequent decomposition by water on the water- bath the dimethylnonadiene yields 6-acetyl-a-methyt- oaleric acid CH,Ac*CH,*CH,*CHMe*CO,H (isolated as the semi- carbazone C,HI7O,N m. p. 129-1 30° colourless needles) and a-methylglutaric acid (and possibly also a little P-methyladipic acid). The formation of these two acids not only proves that the new double linking in the dimethyloonadiene is as near as possible to the asymmetric carbon atom but also is evidence in favour of Semmler's hypothesis that citronellaldehyde reacts in two forms (v.supra). P1-Dimetnyl-APe-decadiene CMe,:CH*C H,gCH,*CHMe*CH,*CH:CHl\le has b. p. 81-82'/9 mm. Dt0 0.7813 and [a] - 6.64'. The position of the new double linking is proved by the decomposition of the ozonide by hot water whereby c-cccetyl-p-methylhexoic acid (isolated as the semicarbazone C,,H,,O,N m. p. 135-1 36') and P-methyladipic acid are obtained (again evidence of Semmler's hypothesis). &- Dimethyl-APe-undecadiene CMe,:CH*CH,*CH;CHMe* CH,* CH:C KEt has b. p. 9@-91'/8 mm. Dao 0.7873 [a]:' -5*22' [a] -6-6So [a] - 7-98' [a]? - 10*55' and n 1,44614 n 1.44903 np 1,45602 ny 1.46215. The position of the new double linking is determined by the value of [a] which is practically identical with that of the dimethyldecadiene. The abnormally high value of [a] of the dimethyl- nonadiene must be due to the presence of the double linking in the immediate neighbourhood of the asymmetric carbon atom.The molecular refractions of the three hydrocarbons nre very nearly normal. &-D~rnethyl-AaYL whdecatrians C Me, CH * CH CH,. C HMe* CH,* C H CH C H CH bas b. p. 94-95'18 mm. D?," 0.8005 [a]Zo - 7-87" - 10-12' - 12.34' - 16.92' for the C D E and F lines and 2' 1.46887,1*47261 1.48216 1.49040 for the a D p and y lines. The presence of the conjugated double linking is indicated by the pronounced exaltations of the specific arid the molecular refractions. The molecular rotation is considerably greater t ban that of the dimethylundecadiene ; also it is noteworthy that a comparison of the specific rotatory powers of the dimethyl- nonadiene and the dimethylundecatriene shows that the double linking in the immediate neighbourhood of the asymmetric carbon atom has the same effect 011 the rotatory power as the conjugated double linking at a greater distance The interaction of citronellaldehyde and a n excess of magnesium cyclohexyl bromide in ether leads t o the forma tion of O-cyclohexyl-P[-di- methyl-AP-octen-8-ol CMe,:CH*CH2*CH2*CHMe*CH2*CH(OH)~C6Hl b.p. 166-167'/10 mm. ; by-products are isopulegol and probably cyclohexane and decahydrodiphenyl (isopulegol is a1 so obtained as a by-product in the preparation of ~:-ddmrnthy~-AaL-undecadien-6-o1 unless a large excess of ally1 bromide is employed). The brornido obtained from the carbinol is converted by boiling pyridine into yy-dimethyl- Aac-octadienyZcyclohexane CMe,:CH*CH,*CH,*CHMe* CH C H*C,H 11ORGANIC CHEMISTRY.i. 133 2>CH,) b e p. (or CMe,:CH-CH,*CH,-CHDle.CH2-CH:C<cH2,cH2 CX,*CH 142-143"/9 mm. D:00.8468 [a] - 5-03' [a] - 6*40' and [a] - 7-65'. The alternative formula is necessary because the decomposition of the ozonide by water yields adipic and cyclohexanecarboxylic acids. The adipic acid is produced from the intermediately formed cyclohexanone ; the authors show that by treatment with ozone i n carbon tetrachloride and subsequent decomposition by water cyclohexanone is converted into adipic acid. The specific rotatory power of the dimethylocta- dienylcyclohexane despite the position of the double linking in the immediate neighbourhood of the asymmetric carbon atom is almost the same as those of the dimethyldecadiene and dimethylundecadiene. Apparently therefore the influence of a saturated hydroaromatic group on the rotatory power is smaller than t h a t of a n alkyl group.I n comparison with the preceding dimethyloctadienylcyclohexane yq-dimethyl-Aa~-octadienylbenzene (Klages and Sautter A. 1906 i 489) has -a very high rotatory power [a] -63.24'. This is evidently due to the conjugated double linking i n the immediate neighbourhood of the asymmetric carbon atom because its product of reduction CMe,:CH-CH,=CH,-CHMe*CH2*CH,Ph has [a]. - 7*26' and moreover when the conjugated double linking is situated further away from th6 centre of optical activity the rotatory power is quite small.CMe,:CH*CH,*CH,*CHMe*CH,*CH,Ph b. p. 17S-179'/9 mm. obtained in 20% yield from citronellaldehyde and magnesium benzyl chloride (the main product SO% yield is a-phen y l- O-beizz y l- %dime th y Inonan- p-ol CH,Ph*CMe2* CH,*CH,*CH,* CHMe*CH,*CH( OH)*CH,Ph b. p 243-244"/9 mm) is converted through the bromide into 68-dameth yl- Aa?-nonctdienylbenxene CMe,:CH*CH,*CH,*CHNe*CH,*CHPh b. p. 159-160'/9 mm. Uy 0.8894 [a] -3*33' and n 1.51360 nD 1.51770 np 1.52960 and ny 1.53964 Thus l-phe~~~Z-P~-dimet~~yl- A p-nonen- 8-01 K - Phenyl-pc dirnethy LAP-decen-9-0 I? CMe,:CH*CH,-CH,-CHMe-CH,*CH(OH)*CH,-CH,Ph b. p. 188-189"/9 mm. obtained from citronellaldehyde and magnesium P-phenylethgl bromide is converted through the bromide into €1-dimethy E - h@-decudienyl benzene CMe, CH*CH,*CH,*CHMe CH,*CH:CH*CH,Ph b.p. 163-164"/9 mm. DSo 0-8852 - 4-54' - 5-76' - 6*84O - 8.90' for the C D E and F lines and n 1.50375 n 1.50766 nzp 1.51768 and lyly 1.52629. c. s. Preparation of Ally1 Alcohol. A. KOEHLER (Bull. Sod. chim. 1913 [iv] 13 1103-1105. Compare Chattaway T. 1013 105 15l).-The author has increased the yield of ally1 alcohol from 20% to 32% by replacing the oxalic acid with formic acid in its preparation. One hundred grams of glycerol are heated with 80 grams of formic acid for one hour on a water-bath and the product fractionally distilled and collected in three fractions (1) up to 200' (2) 200-260° (3) residue. The saponification index of fraction (2) is determined,i. 134 ABSTRACTS OF CHEMICAL PAPERS. and it is then carefully poured on t o twice the calculated quantity of Eolid potassium hydroxide.The whole is boiled for one hour allowed to cool and the top layer docanted and dried over anhydrous potassium carbonate. The intermediate product is monoformin. W. G . Preparation of Chlorohydrins. HENRY V. WALKER (D.R.-P. 267205).-Chlorohydrins are obtained by treating gas-naphtha (which contains about 40% of olefines and 60% of paraffins) with R mixture of a1 kali hydrogen carbonate and hypochlorite solutions J. C. C. Preparation of Monochlorobutylene Glycol Ether. FARBEN- FABRIKEN VORM. FRJEDR. BAYER & Co. (11.R.-P. 262832).-ChZoro- tutylene glycol ether [y-chlorobutyl y-hyh-ozybusyl ether] CH,*CHCI *CH,*CH,*O*CH,* CH,*CH( OH')* CH3 R colourless liquid b. p. 82-8G0/18 mm. is prepared by treating butylene ay-glycol with concentrated hydrochloric acid.It may be used for the preparation of erythrene. J. C. C. Preparation of True Acetylenic Derivatives s t a r t i n g with Dipropargyl. LESPJEAU (Gompt. Tend. 1913 157 1439-1440).- J n the preparation of the dimethyl ether of the glycol (Aac-octadi- inene-a0-diol) OH*CH,*CiC*CH,*CH,*CiC*CH,*OH from the di- magnesium derivative of dipropargyl (compare A 1910 i 535) there is always produced a t the same time an appreciable quantity of rl-metl~oxy-AaE-he;nlndi-inene CH i C* CH,*CH,* Ci C*CH,*OM e b. p. 67*5O/ 11 mrn. D1"' 0.9156 n1,5" 1,50125. The fact that this is a true acetylenic derivative is shown by the following properties. With aqueous silver nitrate folution i t gives a precipitate soluble in warm water crystallising out in slender needles on cooling. With cuprous chloride i t gives a yellow precipitate which with iodine yields aapE~-~~enIniodo-rl-methoxy- AcGeptadiene CI,:CL*CH,*CH,*CI:CI*CH2*OMe m.p. 95". Finally the ether reacts with magnesium ethyl bromide giving a magnesium derivative which with chloromethyl ether yields the dimetbyl ether of AP~-octadi-inene-aO-diol. This * magnesium derivative also reacts with carbon dioxide giving y-metAoxy-Aac-lieptadi- inene-a-carboxyZic acid CO,H*CiC*CH,*CH,*CiC*CH,*OMe m. p. 46-47". W. G. Ar-Acetylenic Glycols and the Ketohydrofurans Derived from them. GEORGES DUPONT (Ann China. Phys. 1913 [viii] 30 4S5-587).-A rdeum6 of work already published (ccmpare A. 1909 i 545; 1910 i 85 379 456; 1911 i 173 554 804; 1912 i 290 483; 1913 j 696 and Iotsitch J.Russ. Phyn Chern. SOC. 1902 34 239 242 ; 1903 35 430 1269 ; 1906 38 252 656). The following new ccmpounds are described 817-Dip?.o~yZ-b~-dec;nene-Gr]-diol OH*CPr,*CiC*CPr,*OH m. p. 1204 which on hydrogenation yields sr]-d.zj?rop?lldecan-677-dio2 m. p. 82-84' and aas6-telrccivhenyZ-A.8-butinene-a8-diol OH*CPh,*CiC*CPh,.OH m. p. 193". C€T,.CH:CMe*CiC.CMe:CH~CH y [ - D imetlr yloctn- APC- diene- A8-inene,ORGANIC CHEMISTRY. i. 135 a liquid with an agreeable odour b. p. 170' m. p. - 45" nD 1.4977 D22 0,807 1. 8rj-Dipropyldeca- Am-diene- Ae-inene CH,*CH2*CH :CPr* Ci C*CPr:CH*CH2*CH a yeliow liquid b. p. 125-127'118 mm. IZ 1,4890 D19 0.81313 on hydrogenation yielding 8y-dipropyldecane b. p. 125-1 27'118 mm. Dipropyl Ae-decinene-6q-diol does not give the corresponding hydro- ?ZD 1,4450 D 1.7887. furan with mercuric sulphate but an internal anAydride C*CPr C-CPr I l l >o b.p. 137"/18 mm. n 1,4747 D23 0.8404. On hydrogenation i t yields 3-kelo-2 2 5 5-tetrapropylhydrofuran) b. p. 132'118 mm. n 1.4498 D 0.8203. Similarly acetylenedicrotonaldehyde (compare A 191 1 i 804 b. p. 105'/20 mm. n 1.5802 C-CH*CH:CHMe C*CH* CH C El Me gives the compound 111 >O D20 0.9548. W. G. Products Obtained by the Action of Bromine on Ether by Schutzenberger McIntosh and the Author. V. V. TSCHELINCEV ( J . Russ. Phys. Chem. Soc. 1913 45 1845-1860).- Criticism of Arbuzov's results and conclusions (compare A. 1913 i 815). T. H. P. Dimethyl Phosphates of the Rare Earths. J. C. MORGAN and C. JAMES (J. Amer.Chem. Soc. 1914 36 10-16; Chem. News 1914 109 13-15).-Tn order to determine the value of dimethylphosphoric acid for the separation of the rare earths a study has been made of the following salts. The solubilities are expressed as parts of the anhydrous salt per 100 parts of water. Yttrium dimethyl phosphate long white needles solubility 2.80 a t 25' and about 0.55 a t 95". La2( Me2P0,)6,4H,0 white hexagonal crystals solubility 103.7 a t 25'. Cerous dimethyl p?iosphate Ce,(Me2P0,)o,H,0 white hexagonal plates solubility 79.6 a t 25" and about 65 a t 95". Praseodymium dimethyl phosphate green hexagonal crystals solubility 64.1 a t 25'. Neodymium dimethy2 phosphate Nd2( Me,PO,) lilac-coloured hexagonal plates solu- bility 56.1 at 25' and 22.3 a t 95'. Sumarium dimethyl phosphate cream-coloured hexagonal prisms solubility 35.2 at 25" and about 10.8 at 95".Gadolinium dimethyl phosphate long white needles solubility 23.0 a t 25' and 6.7 a t 95'. Erbium dimethyl phosphate long needles solubility 1.78 a t 25". Ytterbium dimethyl phosphate long white needles solubility 1.2 a t 25" and 0.25 at 95". Fractionation experiments were made by preparing a solution of the rare earths in dimethylphosphoric acid gradually raising the tempera- ture and collecting the precipitates ; additional fractions were obtained by evaporation of the mother liquor. I n the case of a material Lanthanum dimethyl phosphate,i. 136 ABSTRACTS OF CHEMICAL PAPERS. containing gadolinium with just sufficient terbium to colour the oxide orange-brown the gadolinium collected in the most soluble fraction and the terbium in the least soluble. Similar experiments with other mixtures of rare earths showed that the rate of separation by this method is much greater than by other methods.Lanthanum cerium praseodymium and neodymium are left in the mother liquor. Samarium europium and gadolinium are much less soluble than these but more soluble than terbium dysprosium and holmium. Erbium thulium yttrium and ytterbium collect in the least soluble f ractione. Some difficulty is encountered in the application of this method owing t o the fact that the dimethyl phosphates gradually decompose with formation of a gelatinous precipitate which renders filtration troublesome. E. G. Preparation of Methylbutenyl Esters. BADISCHE ANILIN- & SODA-FA BRIK (D.R.-P.26 755 3) .-When @y- or /3&dibrorno-@-methyl- butane is boiled with acetic acid and sodium acetate mixtures of the corresponding methylbutenyt acetates are obtained. 3 . C. 0. Decomposition of Hydroxy-acids by Soda-Lime. LEONARD CARPENTER (Chem. News 1914 109 5)-When sodium lactate intimately mixed with soda-lime is destructively distilled in an iron tube under reduced pressure at a temperature just below redness a product is obtained which consists of an aqueous solution of acetone and a brown oily layer composed mainly of mesityl oxide. It appears t h a t ethyl alcohol if formed is immediately oxidieed probably to acetic acid which then loses water and carbou dioxide giving acetone. The same product was also obtained by the action of soda-lime on citric acid.J.t is t o be noted also that very little charring occurs during heating. H. W. Influence of the Position of the Oxygen Atom in t h e Chain on the Velocity of Hydrolysis of Esters. M. H. PALOMAA (Chem. Zentr. 1913 ii 1956-1960; from Ann. Acud. Sci. Fennicae 1913 [A] 4 No. 2 1-104. Compare A . 1913 i 6).-The rate of hydrolysis of esters of hydroxy- and alkosy-acids of mono- esters and ether-esters of glycols of esters of ketonic acids and keto- alcohols by 0.1 N- and 0*2N-h~drochloric acid at 25O has been determined in comparison with the rates of hydrolysis of esters of fatty acids. The constants are calculated from the formula for a reaction of the first order k= 1 / 0 - 4 3 4 3 t . log U / ( U - z) The results show that a reaction minimum occurs at a definite median position of the oxygen atom in the chain which since it occurs when the oxygen atom is in the @-position to the ester group suggests the possibility of intramolecular ring formation substances being thereby produced which have a more saturated character than open chain compounds and thus yield with greater difficulty the additive products which are initially formed in the hydrolysis of esters byORGANIC CHEMISTRY.i. 137 acids. indicated by the dotted lines The following formulae are suggested partial valencies being H25+-3O H,Y-O n 2 c 7 ,yo Hz?-7? \,(,,,' \ ;/' \,!,/' \\ p' H,C /OR' H,C ' h O R ' Meh / O R MeC /COR OK 6 R 0 0 Esters of Ether esters of Est.crs of Ester of alkoxy-acids. ethylene glycol. acetoacetic acid.acetone alcohol. The following substances are described Ethyl glycollate b. p. 15S0 DF 1.0869 ; methyl methoxyacetate b. p. 131-131~4' Di5 1.0578; methyl ethoxyacetate b. p. 144-5-145' Di5 1.0112 ; ethyl ethoxy- acetate b. p. 158'/752 mm. DY 0.9754 ; methyl n-propoxyacetate b. p. 16 1 *5-162O Di5 0,9867 ; ethyl n-propoxyacetate b. p. 174-1 74*5'/ 764 mm. Di5 0.9551 ; methyl n-butoxyacetate b. p. 180-180*5°/ 765 mm. Di5 0.9675 ; methyl isohutoxyacetate b. p. 1715-172.5'/ 767 mm. DY 0.3605; methyl a-methoxypropionate b. p. 129*5'/752 mm. Di5 1.0108 ; methyE y-methoxybutyrate (from y-methoxybutyric acid and methyl alcohol in the presence of phosphoric acid) b. p. 162*5-163'5"/ 767 mm. Di5 0.9879 ; methyl yethoxybutyrate b. p. 175*5'/760 mm. Di5 0,9622 ; methyl 6-methoxyvalei.ate b.p. 184*5-185*5O/767 mm. Di5 0.9741 ; n-propoxymethyl acetate CH;CO,*CH,OPr (from chloro- methylpropyl ether and potassium acetate) b. p. 150-151*5'/759 mm. Di5 0,952 1 ; methoxymethyl propionate C,H;CO,*CH,*OMe b. p. 134.7-135.5@/752 mm. Di5 1.0024 ; ethoxymetliyl propionate b. p. 149-5-150 5@/75.5 mm. DY 0.9709 ; n-propoxyrnethyl propionate b p. 166-1 68' Dy 0.9484 ; P-hydi*oxyethyl formate H*CO,( CH,),*OH (from ethylene glycol and 95% formic acid) b. p. 179-150.5'/766 mm. Di5 1.1989 ; P-methoxyethyl formate (from methoxyetbylene glycol and formic acid) b. p. 131-131*5'/767 mm. Di5 1.0484 ; P-ethoxyethyl formate b. p. 141-0-14 1*7'/748 mm. Di5 1.0013 ; ,B-n-popoxyethyZ formate b. p. 157-159'/766 mm. D:" 0.9762 ; P-ethoxysthyl acetate (from ethylene glycol monomethyl ether and acetyl chloride in the presence of pyridine) b.p. 156-1565O/761 mm. Di5 0.9810; P-ethoxyethyl n-butyrate b. p. 188' Di5 0.9438 ; y-hydroxypropgl formate (trimethylene glycol foymate) (from trimethylene glycol and formic acid) b. p. 195-197'/757 mm. D'4" 1.1405 ; y-rnetlioxypropyZ formate b. p. 146-1 47@/767 mm. Uy 1.0057 ;. y-ethoxypopyl formate b. p. 157.5-159'/742 mm. Di5 0.9731 ; tramethylene glycol mono- n-propyl ether b. p. 170-1 72" Ui5 0,9076 ; y-propoxypropyl formate (from previous compound and formic acid) b. p. 174-5-1 76' ; y-hydroxy- propyl acetate (from trimethylene glycol and glacial acetic acid) b. p. 202*5-204" ; y-met?ioxypropyl acetate (from trimethylene glycol mono- methyl ether and acetyl chloride in the presence of pyridine) b.p. 162-163*5O/762 mm. DF 0.9803 ; y-ethoxypropyl acetate b. p. 174.5-1 75*5' D:" 0.9567 ; cccetylpropyl acetate CH,-CO,*CIT,*CH,* CO-CH (fiwm acetylpropgl alcohol and acetic anhydride) lo. p. 2 1 I -213' 11:" 1.0217. H. W.i. 135 ABSTRACTS OF CHEMICAL PAPERS. A c t i o n of Dimethylamine on tbe Two Chlorohydroxyiso- butyric Acids and their Derivatives. E. FOURNEAU and M. TIFFENEAU (BuZl. SOC. cliim. 1914 Liv] 15 19-26).-1t is known that the two isomeric iodohydrins derived from styrene namely OH*CHPh*CH,Il and CHIPh*CH,*OH (Tiffeneau and Fourneau A. 1913 i 1337)) as also the two chlorolactic acids react with dimethyl- amine yielding the same product ; for example in the former case OH*CHPh*CH,*NMe,. In the present investigation i t is shown that even where one of the positions affected is a tertiary one a similar behaviour is observed.When ethyl p-chloro-a-hydroxyisobutyrate is heated wi t h fused sodium acetate at 1 90-200' ethyl a-hydroxy-p-acetoxyisobutyrata OAc*CH,*CMe(OH)*CO,Et D! 1.135 b. p. 226-2229' is obtained. The following compounds can be prepared in R similar manner Propyl a-h ydvox y-P-acetox yisobutyrate Dj 1.001 b. p. 244-245'1770 mm. Propyl u-hydroxy-P-valeroxyiso- butyrate b. p. 272'. Ethyl a-h3droxy-P-benzoyloxyisobutyrate m. p. 35' b. p. 175-1 7 6'11 8 mni. Propyl a-hydroxy-P-benzoyloxyisobutyrate Di 1,1457 b. p. 205-208O/29 mm. Ethyl a-hydroxy-P-salicyloxgiso- butyrate rectangular prisms m. p. 52' b. p. 197'/16 mm. Yropyl a-hydrotzy-P-salicyloxyisobutyrate b. p. 200°/1 7 mm.By the gradual addition of thionyl chloride to a mixture of the substance with pyridine at 0') propyl a-hydroxy -P-acetoxyisobutyrate can be converted in to prop91 a-chloro-~-acetoxyisobutyrate OA c*CH,*CClMe*CO,*C,H b. p. 147-150'/50 mm. Bthyl a-chloro-P-acetoxyisobutyrate D8 1.1686 b. p. 2 16-2 17'/760 mm. and propyl a-chloro-P-benxoyloxyisobutyrute b. p. 198-200' are obtainable i n a similar manner. These immediately preceding esters are hydrolysable by boiling with five times their weight of 10% hydrochloric acid with formation of a-c~~Zoro-P-hydroxyisobutyric acid hygroscopic rectangular prisms m. p. 77" soluble in most solvents; its ethyl ester obtained by the action of alcohol containing a little sulphuric acid has b. p. 201-202'. When heated at looo for ten hours with dimethylamine in benzene solution ethyl a-chloro-P-hydroxyisobutyrate is converted into the ethyl ester b.p. 192-1 94') of P-dimethylamino-a-bydroxyisobutyric acid which is produced by hydrolysis of the ester with water ; this acid m. p. 173-174" is identical with that previously described (Fourneau A. 1909 i 210); the ester gives a benzoyl derivative m. p. 140' (compare Fournesu Zoc. cit.) of which the hyds.ochloride and picrate form hygroscopic prismatic needles m. p. 140-141' and elongated lamellae m. p. 127O respectively. Ethyl a-chloro-p-acetoxyisobutyrate and propyl a-chloro-P-benzoyl- oxyisobutyrate also slowly react with dimethylamine in benzene solution the former at loo' and the latter at 125-130'. The product is again the dimethylamino-ester just described but in the experiment with the former of the two esters the main product was accompanied by a small quantity of a n acid substance m.p. 130° and possibly ~-dimethylarnino-a-acetox~isobutyric acid,ORGANIC CHEMISTRY. i. 139 Thus a-chloro-P-hydroxy- and ~~chloro-~-hydroxy-isobutyric acid derivatives yield the same product with dimethylamine. D. F. T. Double Aluminium Oxalates. W. STORTENBEKER (Rec. trav. Chim. 1913 32 226-243. C'ompare Wyrouboff and Rosenheim Zeitsch. anorg. Chem. 1909 63 121).-The author has examined and described a number of double alumino-oxalates of sodium ammonium and rubidium together with mixed crystals of these substances. It is shown that mixed crystals and compounds of the same substances can be obtained and also that chemical compounds may be accompanied by mixed crystals which have the same crystalline form.The most probable interpretation of the last fact is that mixtures are formed of the compound and the simple salt which crystallise with the same amount of water of crystallisation and in the same form. J. F. S. Stereochemistry of the Halogenosuccinic Acids. 11. BROR HOLMBERG (J. p r . Chem. 1913 [iiJ 88 553-603).-1n the previous paper (A 1913 i 824) the author has shown that measurements of the rate of formation of bromine ions from I-bromosuccinic acid in neutral solution did not give concordant values for a unimolecular reaction and pointed out that this was probably due to the reconver- sion of the P-propiolactonecarboxylic acid under the influence of the bromide formed in the reaction into the bromo-acid.This view has been confirmed in the case of the decomposition of sodium I-bromo- succinate by removing the bromide almost as fast as i t is formed by the gradual addition of silver nitrate when concordant values for a reaction of the first order were obtained. According t o Senter ('I!. 1910 97 346; 1911 99 95 1049) the presence of silver bromide exerts an accelerating influence on the hydrolysis of the bromo-derivatives of fatty acids. The behaviour of I-bromosuccinic acid in the presence of silver ralts has been investi- gated by the author but no accelerating influence could be observed. Further the presence of silver salts during the decomposition of sodium I-bromosuccinate has no influence on the configuration of the resulting malic acid the sign of rotation of the latter being determined by the reaction of the solution in which the hydrolysis of the inter- mediately-formed P-propiolactonecarboxplic acid takes place ; in acid solution the lactone is hydrolysed to I-malic acid and in alkaline solution to the d-acid.Attempts have also been made to isolate the lactonic acid formed by the decomposition of sodium E-bromosuccinate in neutral solution but hitherto the compound has been obtained only as a syrup. An aqueous solution of the sodium salt of the lactonic acid is readily obtained by removing the malate and unchanged bromosuccinate from the solution resulting from the decomposition of the sodium salt of I - bromo-acid by precipitation with silver nitrate.The sodium salt reacts with sodium chloride bromide and iodide in aqueous solution to form the salts of the corresponding I-halogeno-i. 140 ABSTRACTS OF CHEMICAL PAPERS. succinic acids ; with ammonia i t yields almost pure d-P-malamic acid which is hydrolysed by hydrochloric acid to d-malic acid. In neutral solution the lactonic acid is moderately stable but is readily hydrolysed in acid or alkaline solution t o I- and d-malic acids respectively ; the salts with the common metals are soluble in water. The transformation of I-bromosuccinic acid into propiolactone- carboxylic acid and reconversion of the latter into the Lbromo-acid is accompanied by very little racemisation and the author therefore assumes that these reactions take place without change of corifiguration ; I-bromosuccinic acid must therefore have the same configuration as the d-lactouic acid t o which it gives rise Further since change of configuration is unlikely to occur when substitution is not effected at the asymmetric atom the conclusion is drawn that d-/3-malamic acid obtained from the d-lactone has the same configuration as the I-bromo-acid. The author considers that d-malic acid corresponds with the d-lactone and that the hydrolysis of the latter is accompanied by configurative change only in acid solution.The racemisation of I-bromosuccinic acid by sodium bromide and hydrobromic acid has also been studied. It is found that racemisation takes place readily in acid solution but not in neutral solution. From the results so far obtained the conclusion is drawn that the racemisa- tion is almost entirely restricted t o the non-ionised acid and is deter- mined by the presence of the bromine ion.The halogen in the I-bromo-acid is readily replaced by iodine by the action of potassium iodide in neutral solution ; the iodosuccinic acid thus formed is lzevorotatory but could not be isolated in a pure con- dition. The pure I-acid can however be obtained by the action of potassium iodide on a solution of sodium salt of d-propiolactonecarboxylic acid prepared in the manner described above. It has m. p. 150- 152' (decomp.) [a]=. - 74.1' in ethyl acetate solution. The interaction of sodium and potassium xanthate with the sodium potassium barium strontium and calcium salts of kbromosuccinic acid under various conditions has also been investigated and it is found that the sign of rotation of the resulting xanthosuccinic ucids CO,H*CH(S* CS*OEt)*CH,* CO,H depends not only on the particular salt of the bromo acid but also on the concentration of the solution and the amount of xanthate employed.The purest specimen of E-xanthosuccinic acid hitherto obtained has m. p. 131-132" [UlD -92.6' in etbyl acetate solution. I-Bromosuccinamic acid reacts with the potassium and sodium xanthates yielding d-xunthosuccinarrvic acid CO,H* CH( S* CS*OEt) *CH,* C0.N H which forms flat obliquely-cut colourless prisms m. p. 137-138' (decomp.),.[,llD + 64O in etbyl acetate and is hydrolysed to d-xantho- siiccinic acid. F. B. Crystallography of Symmetric Dibasic Aliphatic Acids. Malonic acid (D" 1,6305 ; triclinic a b c = 0.7440 1 0.4573 ; a = 102'42' /3 = 100"44' y=.63'48').JULIEN DRUGMAN (&?ilScA. Kryst. Lwh,. 1913 53 240-259).-ORGANIC CHEMISTRY. i. 141 Dimethylmalonic acid (D17* 1.357 ; tetragonal-trapezohedral cc c = Potassium hydrogen dimethylmalonate + 2H,O ( D1lZ 1.540 ; /3 = 10Ool4g' 1 14830). triclinic a b :c = 0,6299 1 1,2682 ; a = 89"14' y = 94'39'). Calcium dimethylmalonate (rhombic (6 b c = 0.6 17 1 0,937). Diethylmalonic acid (triclinic a b c = 0.6925 1 0.5334 ; a = 89'35' Potassium hydrogen diethylmalonate + H,O '1 (tetragonal pseudo- Glutaric acid (D14'5 1.429 ; monoclinic a b c = 2.0448 1 2,6734 ; P/3-Dimethylglutaric acid (T. 1911 99 434 ; monoclinic a 6 c = 0,4909 1 1.1171 ; p=91'55'). ay-Dihydroxy-ay-dimethylglutaric acid (triclinic a b c = 1.6589 1 0.9910; a=91'54' p=9s019fr' y=95'46').ay-Dihydroxg-ay-dimethylglutaric acid-monolactone (rhombic a b c = 0.6186 1 1.4939 Prendel 1891). n-Pimelic acid,a-modification (m.p.(?) 101-102c D1"'j 1.329 ; monoclinic a b c = 3.697 1 1.2058; /3 = 105"40' von Lzng 1893) ; P-modificit- tion (m. p. 101-102' DI5 1.282 ; monoclinic a b c = 2.15 1 :?; p = 136'). y-Methylpimelic acid (D" 1,641 ; monoclinic cc b c-1.696 1 C r y s t a l l o g r a p h y of the I s o m e r i c Citraconic and Mesaconic JULIEN DRUGMAN (Zeitsch. Kryst. Min. 1913 53 (triclinic a b c = 1.1525 1 0.7550 ; p = 93'37' y = 88'29'). cubic a c = 1 1 .OOO ; optically uniaxial and positive). p = 97"Y). 1.648 /3 = 103'22'). Acids (C,H6O4>. 260--262).-C!itraconic acid L.J. S. a = 98'22' p = 10S048&' r = 88'3 1'). Mesaconic acid (rhombic a b c = 0.8536 1 0*8421). Syntheses by means of Organometallic Derivatives of Zinc. Preparation of a-Ketonic Acids. E. E. BLAISE (Compt. rend. 1913 157 1440-1443. Compare A. 1912 i 236 410).- a-Ketonic acids can be prepared indirectly by aid of zinc alkyl iodide through the formation of the corresponding mixed cycloacetals. Ethyl chloroglyoxylate condenses with a-hydroxgisobutyric acid giving the acid OEt*CO*CO,*CMe,*CO,H m. p. 83' which on warming with thionyl chloride gives the chloride b. p. 120.5"/12 mm. and yields an anilide m. p. 95'. The acid chloride reacts with zinc propyl iodide L. J. S. $!Me2*0 co-0 t o give the cycloacetaZ >CPr*CO,Et b. p.123-124'/11 mm. which on heating on a water-bath with alcoholic hydrochloric acid yields ethyl butyrylformate b. p. 70-5'/11 mm. and ethyl hydroxyiso- butyrate. At the same time a small amount of the corresponding diethylacctal b. p. 96'/11 mm. is formed this compound being also obtained by the action of ethyl orthoformate on the a-ketonic ester in the presence of one drop of sulphuric acid. Ethyl butyrglformate is readily hydrolysed by boiling with 5% aqueous oxalic acid giving the corresponding acid b. p. 79'/12 mm. which furnishes a p-nitro- phenylhydraxone m. p. 205' and a semicarbaxone m. p. 220'. W. G.i. 142 ABSTRACTS OF CHEMICAL PAPERS. Action of Lime on Reducing Sugars and the Products formed thereby. A. SCHWEIZER (Chem. Zentr. 1913 ii 1791 ; from Arch.8uikerind. N e d . - l d e 27 reprint 12 pp.).-The action of alkali on dextrose solutions leads to the formation of products which are more or less deeply coloured according to the temperature of reaction etc. The dextrose is thereby decomposed with formation of salts of lactic and saccharic acids etc. Addition of acids renders the solutions colourless. The author is led to the conclusion that this phenomenon is t o be attributed to the alcoholic function of the decomposition products and that tho metallic atoms of these compounds are displaced by acids in accordance with the following scheme I HC(OH)*CH(OM)*CO,M -+ HC-CH*CO,H -+ bH,-CO*CO,H \/ 0 where M represents the atom of a univalent metal. This supposition receives support from the deep colorations imparted by the addition of ferric salts.From carbonation experiments made a t 2s' with an excess of lime the conclusion is drawn that the colourless salts of lactic acid and the coloured salts of saccharic glyceric acids etc. are simultaneously formed at all temperatures in contrast to the assumption that the former are alone produced by the action of alkali on dextrose below 55O whilst the latter are formed above this temperature. Por the investigation of the properties of the product of decom- position solutions of dextrose decomposition product (prepared by the action of lime on invert sugar) were treated with lime and then carbonated. The following results were obtained On boiling the colour of the solution deepens and an additional quantity of calcium salts is formed.When carbonated a portion of the coloured salt is removed (it is shown that the primary products of the action of alkali on dextrose are here involved) whilst the portion of the salts which remains undergoes further decomposition whereby fresh quantities of lime are dissolved. The removal of coloured products occurs not only in alkaline but also in neutral solution but whether in the latter case additive products are formed from calcium carbonate and the salts of organic acids has not been determined. The alteration in colour of the calcium salts of these compounds with increasing alkalinity or acidity has also been investigated. The colour is lightest in acid media and increases in intensity until the neutral point is reached; a sudden marked darkening then occurs which diminishes with increasing alkalinity.H. W. Action of Cyanides of the Alkali and of the Alkaline Earth Metals on Dextrose. E. XUPP and A. HOLZLE (Arch. Pharm. 1913,25 l,553-556).-Equal molecular quantities of dextrose and potassium cyanide in aqueous solution react according to the equation OH-CH,*[CH-UH],*CHO + KCN + 2H20 The quantity of ammonia evolved and of potassium carbonate obtained = OH*CH,*[CH*OH],*CO,K + NH,.ORGANIC CHEMISTRY. i. 143 by the incineration of the dried residue correspond very closely with the theoretical amounts. The acid has been isolated in the form of its anhydride which exhibits all the properties of a-glucoheptoic an- hydride. The reaction between dextrose and barium cyanide follows a similar course. c. s.Some Acyl Derivatives of Dextrose and Mannose. EMIL FISCHER and RUDOLF OETEER (Ber. 1913 46 4029-4040).-Follow- ing the discovery of the galloyldextroses and of pentabenzoyldextrose (A. 1912 i 888) the authors found that cinnamoyl chloride condensed even more readily than did benzoyl chloride when shaken with dextrose and quinoline in chloroform solution The study of this reaction has been extended to substituted cinnamoyl chlorides and to mannose and mannitol. The derivatives of mannose so obtained were all Zaevo- rotatory and consequently the configuration of the sugar may be retained in them. Hexacinnamoylmannitol C6H,06(C,H70) from very finely powdered dry mannitol and cinnamoyl chloride forms tufted prisms or needles from ethyl acetate m. p. 99-loo' [a] +12.96' [a] +13.15' (in chloroform).a- Pentacinnamoyldex t rose and /3-pentacinnamoyl dextrose have already been described (ibid.). Pentucinnamoylrnannose crystal- lises with 1 mol. benzene in mycelium-like masses m. p. 108-112' [a] - 91.3' - 91-66' (benzene) [a] calculated for the benzene-free compound - 99*9' - 100.3O. Pentubenzoylmannose c6H7o6Bz5 forms long radiating needles from alcohol m. p. 161-161*5' (corr.) [a] - 80*44' - 80.7' (chloroform). Penta-acetyhnannose C6H7O6AC5 was obtained by shaking together mannose pyridine and acetic a D - hydride at 0' ; it has m. p. 127.5' (corr.) [a] - 24*8O [a] - 24.9' (chloroform) and a very bitter taste. Similar derivatives were prepared from caffeic acid which was applied in the form of the dimethylcarbonato-derivative. Methyl chlorocarbonate was gradually added to a dilute solution of the sodium salt at - 5 O in a hydrogen atmosphere when the solution was acidified and the 3 4-dimethyZcarbonatocinnan.~ic acid C6H3(O*C02Me~*CH:CH* Co2H precipitated.It formed curved needles from aqueous acetone m. p. 145-146' (corr.). The chloride C13H,,07Cl was obtained by the action of phosphorus pentachloride in glistening needles m. p. 108.5-109ti' (corr.). From it the esters were prepared; the ethyl ester forms flat needles or prisms m. p. 98' (corr.) and the methyt ester crystallises in tufted spikes m. p. 95-96.5O (corr.). The chloride was condensed with a-dextrose forming penta-3 4-dimethylcarbon- atocinnamoyZ&extrose C,H706(C13H1107)5 as a colourless amorphous mass with indefinite constants.The easily hydrolysed carbonato-gronpe were removed by the action of dilute sodium hydroxide below ZOO in an atmosphere of hydrogen. On acidifying a resinous mass was formed which was fractionally precipitated by chloroform from a solution in ethyl acetate. The pale yellow amorphous mass so obtained was probably the expected penta-3 4-dihydroxycinnamoyl- dextrose but the constants and analytical data were inconclusive. It is very sparingly soluble in hot water and gives a deep greeni. 144 ABSTRACTS OF CHEMICAL PAPERS. coloration with alcoholic ferric chloride and a pale yellow precipitate with alcoholic potassium acetate. J. c. w. Influence of Alcoholic C o n t e n t on the Biochemical Synthesis of a-Methylglucoside by a-Glucosidase. A AUBRY ( J .Pharm. Chim. 1914 [vii] 9 19-23).-The biozhemical synthesis of a number of alkylglucosides has been effected by Bourquelot HPlrissey and Bride1 (A. 1913 i 323 428 747) by the action of a- glucosidase on solutions of dextrose in water containing the respective alcohols. I n every case excessive concentration of alcohol destroys the ferment. The present investigation was undertaken to determine the concentration of alcohol most favourable to the synthesis and also the point at which the ferment is immediately destroyed. Experiments were performed by adding a constant amount of a maceration of bottom yeast to solutions of dextrose in water made progressively richer in methyl alcohol. The course of the reaction was followed polarimetrically and finally the dextrose determined by the method of Mohr-Bertrand.Small amounts of toluene (which appears to have a slightly toxic effect on the ferment) were also added. The synthesising action of the ferment is very obvious even in the most dilute alcoholic solutions and increases until the solution contains 16 grams of methyl alcohol in 100 C.C. At greater concentrations of alcohol the toxic effect becomes more marked occurring immediately in solutions containing 34-36 grams of methyl alcohol in 100 C.C. a t the ordinary temperature. At higher temperatures the toxic action becomes more pronounced ; thus at 40° immediate destruction of the ferment takes place in a solution containing 16 grams of methyl alcohol in 100 C.C. H. W. Influence of the Strength of the Alcohol on the Biochemical Synthesis of a-E thylglucoside and a-Propylglucoside.lh. BOURQUELOT and A. AUBRY (Compt. T e n d 1914 158 70-72; J. Pharrn. Chirn. 1914 [vii] 9 62-66. Compare preceding ab- stract).-The optimum concentration of alcohol for the synthesis of aglucosides by a-glucosidase is for ethyl and prop91 alcohols respectively 20% and 16%. Above these concentrations the synthesis is masked by the more rapid decomposition of the glucoside by the same ferment. W. G. Optimum Experimental Conditions for the Preparation of P-Ethylglucoside. J. COIRRE (J. Piiarm. Chim. 1913 [vii] 8 653-559).-The conditions under which the maximum amount of /3-ethylglucoside is formed by the interaction of emulsin dextrose and alcohol are discussed theoretically and a process for the preparation and purification of this compound under these conditions is described.T. A. H. Characterisation of the Organ Pentose as &Ribose. J. VON BRAUN (Bey. 1913,46 3949-3951).-4 4'-Bismethylhydrazino- diphenylmethane (von Braun A. 1908 i 700 737; 1910 i 524) proves a very convenient reagent for distinguishing between theORGANIC CHEMISTRY i. 145 various pentoses. It is already known that whereas xylose fails to react with this subtance active arabinose readily gives an amorphous sparingly soluble hydrazone m. p. 180'. &-Ribose is now found to yield a microcrystalline dihydraxone (C,H,,O,:N*~~~e*C,H,),CH m. p. 141-1 42' whilst d-lyxose gives an analogous but much more sparingly soluble dihydrrmone m. p. 156'. The behaviour of a specimen of the pentose obtainable from inosic acid towards this reagent proved the identity of the pentose with &-ribose. D.F. T. Starch and its Hydrolytic Degradation Products. OSCAR VON FRIEDRICHS (Arkiv. Kenz. Mia. Geol. 1913 5 No. 2 1-40)- It has been shown already that starch can be converted completely into maltose. Since maltose is a dextrose-a-glucoside it follows that the amylase which converts starch into maltose but cannot hydrolyse it further t o dextrose is a @-enzyme and consequently every other linking between the glucoside-forming dextrose residues in starch corresponds with the P-configuration in P-dextrose. Starch may be represented therefore thus Dextrose-6-glucoside. Maltose. P P P . . . C,,H2~Og-O-C12H2009.. .O-C,~H,,O,O O P The dicarbonyl binding represented as -0- may occupy any other possible position t o that just given but both linkings must have the @configuration otherwise dextrose would be liberated during the hydrolysis of starch by diastase.That starch is not hydrolysed by emulsin is not remarkable for i t is known that gentianose which contains a P-glucoside linking is not hydrolysed by emulsin. If the amylase which hydrolyses starch is a @-enzyme i t might be expected to hydrolyse @-methylglucoside ; this however was not found to be the case; on the other hand neither does it hydrolgee a-methylglucoside. Assuming the above formula for starch to be correct then starch when hydrolysed by acids should yield dextrose maltose and a dextrose-P-glucoside. i t has been found possible to isolate a P-glucosidodextrose from the products of the hydrolysis of starch by acids which appears to be identical with Fischer's isomaltose but this point could not be established definitely.The disaccharide isolated had La]D +59*1' was readily hydrolysed by emulsin and yielded an osazone m. p. 146'. The products formed by heating starch with an aqueous solution of oxalic acid under pressure have been isolated as far as possible by means of repeated fractional extraction with aqueous alcohol. The properties of many oE these compounds are given below also the molecular weights determined by the diihsion method of Oholm (A. 1905 ii 147 ; 1910 ii 273). VOL. CVI. i. Ii. 146 ABSTRACTS OF CHEMICAL PAPERS. Amylodextrin probably a mixture [a] + 196' ; mol. wt. 13630 ; reducing power 0-6-0*9% of that maltose.Erythrodextrin I [a]:" + 196'; mol. wt. 3290; reducing power 3.6% of that of maltose. Erythrodextrin 11 [a] + 193.1'; mol. wt. 2080; reducing power 10%of that of maltose. Achroodextrin [a]? + 179' probably identical with the malto- dextrin a of Ling and Baker; mol. wt. 1060 ; reducing power 30% of t h a t of maltose. Achroodextrin [a] + 172*8' probably identical with the malto- dextrin p of Ling and Baker and the achroodextrin I11 of Prior; mol. wt. 1020; reducing power 42% of that of maltose. Achroodextrin [a] + 162.6"; mol. wt. 680 ; reducing power 58% of that of maltose. The molecular weight values obtained indicate that the last described achroodextrin is formed by the condensation of four dextrose mole- cules whilst the molecule of amylodextrin is built up of four molecules of erythrodextrin I which is probably formed by the condensation of twenty molecules of dextrose.An investigation of the rate of formation of fermentable sugar from erythrodextrin I and erythrodextrin I1 by the action of oxalic acid shows that at first very little if any is formed although a decided diminution in optical rotatory power takes place from the very com- mencement of the interaction of the reagents; fermentable sugar is formed in rapidly increasing quantity only after the lapse of a relatively long period which under the conditions of the experiment extended t o about 280 minutes in the case of erythrodextrin I and about 120 minutes in the case of erythrodextrin 11. The conclusion is drawn from this that maltose and dextrose are not formed in the early stages of the hydrolysis of starch or the higher dextrins by acids but only after these have been broken down into simpler compounds.W. H. G. Behaviour of Starch Dextrins towards Certain Yeasts. OSCAR VON FRIEDRICES (Arkir. Kern. Hin. GeoZ. 1913 5 No. 3 1-14).-The behaviour of the dextrins formed by the action of acids on starch (compare preceding abstract) towards certain yeasts has been studied and the rate a t which they are fermented by some of them measured. The achroodextrins [a] + 162.6' + 172%' and + 1 7 9 O and the erythrodextrins [a]D + 193.1' and 196' are not fermented by Saccharom yces frayilis 8. JIarxianus 8 ellipsoideus 11 8. exiguus or 8. Pastorianus I although the two last mentioned are possibly able t o ferment slowly the achroodextrins [a] + 162.6" and + 172.P.The three achroodextrins are slowly fermented by Saccharomyces thermantiton but the two erythrodextrins are not attacked by it. The yeast Sinner 11 appears to be unable to ferment the two erythrodextrins or the achroodextrin [a]. + 179O although the achroodextrins 172.8' and + 162.6' are destroyed by it the latter more readily than the former.ORGANIC CHEMISTRY. i. 147 ~chixosaccharornyces Pornbe attacks energetically all the dextrins investigated the erythrodextrin [.ID + 196" least readily and the achroodextrins most readily. The achroodextrins are also fermented very readily by Sacchsia suaveolens and Mucor Rouxii ; the erythrodcxtrins are also attacked with ease by the latter. Generally speaking the dextrins with the higher molecular weights are not so readily attacked as those with the lower molecular weights whilst Schizosacchnromyces Pombe alone is capable of fermenting the achroodextrins as rapidly as i t does dextrose The yeasts which are found to split up a-methylglucoside are capable of fermenting the dextrins only to a very limited extent whilst Sacchsia SuaveoZens which is known to be capable OF fermenting /3-methylgIucoside is found to ferment the ncht oodextrina very energetically.The results support the view that P-glucoside linkings are present in the starch and dextrin molecules. W. H. G. Synthetic isoMaltose. OSCAR YON FRIEDE~ICHS ( Arkiv. Kern. Min. Geol. 1913 5 No. 4 1-13).-The product obtained by the action of four parts of concentrated hydrochloric acid on one part of dextrose a t 10' for twenty-four hours is composed approximately of 68% dextrose 18% isomaltose 8% maltose and 6% unknown polysaccbarides.The assumption has been made that isomaltose is a /3-dexhrosegluco- side since it is hydrolysed by emulsin and not by maltase (compare E. F. Armstrong A. 1906 i 127); but several trials have shown definitely that the optical rotatory power of a solution of isomaltose which has been partly hydrolysed by emulsin is lowered on the addition of alkali a behaviour which it is difficult to explain except on the assumption that isomaltose is a n a-dextroseglucoside. It mas also observed that the optical rotatory power of the solution instead of decreasing as the isomaltose was hydrolysed into dextrose increased as the interaction of the isomaltose and emulsin proceeded the measure- ments being made in each case after the addition of alkali; i t has not been found possible to account for thie.isoMaltose is hydrolysed by a n extract of Aspeygillus niger but not by an extract of Kephir. It undergoes fermentation when treated with Aspergillus niger Sacchclromgces frap'lis 8. exiguus and 8acchsic6 suaveolens but is not affected by Xaccharcm pces ILp3r 8. fifarxianus S. ce~evisice Saaz or S. cerevisiae Frohberg. W. H. G. Theory of the Dry Distillation of Wood. PETER KLASON (Arkiv. lienz. Min. Geol. 1913 5 No. 7 1-42. Compare A . 1908 i 717 955).-The author has distilled dry beech ~ o o d under tho following conditions in a cathode-light vacuum under 5 mru. pressure and at ordinary pressure with various velocities in which the distillations between the temperatures 250° and 400' lasted respec- tively three eight and sixteen hours and four teen day,..The percent- ages of charcoal pitch acetic acid formic acid wood spirit mtthgl alcohol acetone and formaldehyde were determined in each case and 1 2i. 148 ABSTRACTS OF CHEMICAL PAPERS. also the percentage composition of the charcoal and pitch. The gases obtained were also analysed and their calorific values determined. The conclusion is arrived at that the dry distillation takes place in two stages. The first stage which is practically the only one when a cathode-light vacuum is used takes place essentially according t o the equation 2C,,H,,O,,( wood) = 3CIoH,O(primary charcoal) + 19H20 + 3c02 + 3CO + 2*5CH;CO,H + H*CO,H + CH,*OH + C,,H,,O,,(pitch) + C,H,O(primary t a r oils).The second stage which takes place cam- pletely when the heating is very slow since no pitch is then obtained is represented by the equation C,,H,,O,,( pitch) = C,oH200,(secondary charcoal) + 9H20 + 2C0 + C,H,,(secondary t a r oils). l'he slower the rise in temperature the more the yield of pitch diminishes and the yields of charcoal water carbon dioxiode and t a r oils increase. The yield of acetic acid is about 6.5% under ordinary pressures and is independent of the rate of heating ; under diminished pressure the yield is increased only about 0.5%. The yield of formic acid (2.4%) i s greatest under diminished pressure ; a t ordinary pressures it varies from 0.71 to 0.33% as the time of distillation is increased.Contrary to what has been stated previously by Norlin the yield (1.5%) of methyl alcohol is independent of the rate oi heating whilst the quantity of water and carbon dioxide formed increases with the time of distillation. Acetone is essentially a secondbry product produced from the acetic acid and consequently its yield decreases as the time of distillation iucrerses. The formaldehyde in the wood spirit forms about 1% of the dry wood taken. The heat of reaction calculated a t Oo during the dry distillation which is taken as the difference between the heats of combustion of the wood and its products of distillation is positive both for the primary and secondary reactions. The heat developed during the actual dry distillation between 2.50'- and 400' is negative for vacuum distillations and positive for distillations at ordinary pressure.The ratio between the acetic acid and formic acid percentages is a measure of the rate of carbonisation of the quantities of pitch and charcoal and of the character of the charcoal. The ratio is about 32 for vacuum distillations and 11 and 5 respectively for quick and slow distillations at ordinary pressures. If it sinks below 5 it denotes that the reaction products have been strongly overheated. T. S. P. Action of Chlorine on Pinewood. ENIL HEUSER and RUDOLF SIEBER (Zeitsch. angew. Chem. 1913 26 801-806).-The action of chlorine on pinewood is very energetic at first and quickly reaches a point when very litt.le change occurs; thus treatment of the wood for thirty minutes one hour and two hours leads to the production of hydrogen chloride to the extent of ZO% 27% and 32% respectively of the weight of dry wood taken and the treated wood loses about 20% 36% and 42% respectively of its original weight when extracted with an aqueous solution of sodium sulphite ; the interaction proceeds very slowly after two hours for only about 35% of hydrogen chloride is formed in twenty-two hours and only about 45% of the wood is removed by a solution of sodium sulphite.During the first two hours,ORGANIC CHEMISTRY. i. 149 that is so long as lignin is present the chlorine acts to only a very slight extent on the cellulose but when all the lignin has been converted into chlorinated derivatives the cellulose slowly undergoes oxidation being converted entirely into oxycellulose in twenty-two hours.As stated already about 32% of hydrogen chloride is formed in two hours but only about 9.5% of chlorine is found combined with the wood a t the end of this period ; similarly only about 7% of a chlori- nated lignin compound can be extracted from the treated wood by means of ethyl alcohol ; it is probable therefore t h a t the greater part of the hydrogen chloride formed during the reaction owes itas origin to the oxidation of the '' wood-lignin " by the chlorine. It was not found possible t o obtain a derivative of pyrogallol from the chlorinated " wood-lignin " compound and not a trace of furfuraldehyde was obtained by treating it with 12/ 0 h y drochloric acid. W.H. G. Ethylamine Compounds of Mercuric Chloride. RAGNAR WJDMAN ( A ~ k i v . Kern. Min. Geol. 1913 5 No. 1 1-36).-The author has investigated the various equilibria which exist between the com- ponents mercuric chloride ethylamine and hydrochloric acid in aqueous solutions at ordinary temperatures (compare Strom holm A 1906 i 935) and finds that the following compounds each of which is white in colour are capable of existing as solid phases HgCI,,NH,Et NHEt*Hg,Cl HgCl,,BN K,Et (NEt) Hg,Cl (NEt),.Hg5C16. The two first are obtained from solutions containing an excess of mercuric chloride and can be transformed one into the other according to the followin'g scheme 2HgCl,,NH,Et z NHEt*Hg,CI + NH,EtCI. The third and fourth compounds are prepared from solutions con- taining an excess of ethylamine and are connected by the equation 3(HgC1,,2NH2Et) (NEt),Hg,C12 + 4NH,EtCl.The compound (NEt),Hg,CI is obtained among other ways by shaking or boiling the compound NHEt*Hg,CI with a strong solution of mercuric chloride. The compound (N Et),Hg,Cl18 described by Stromholm does not exist. T S. P. Decomposition of Betaine by Alkali. FR. ALBERS (Chem. Zeit. 1913 37 1533-1534 1545-1547).-0n heating betaine with potassium hydroxide a t 200-220° about one-third of the nitrogen is eliminated as trimethylamine the only other volatile compound formed being carbon dioxide. A compound stable in alkaline solution at 220" is formed giving a hydrochloride C,H90,N,HCI m. p. 187-189O. The plcctinicldorzde forms a yellow matted crystalline mass m.p. 120- 1 2 lo. When the decomposition is effected at 500-540° rather less trimethylltniine is found as well as methylamine and ammonia the last being formed by secondary decomposition from the amines. About 15% less than the theoretical quantity of amines is formed. Methane and hydrogen are liberated as well as a little carbon monoxide and perhaps nitrogen ; no hydrogen cyanide is formed.i. 150 ABSTRACTS OF CHEMICAL PAPERS. The treatment thus fails t o liberate more than 85% at most of the betaine nitrogen as ammonia or amines. E. F. A. Preparation of Dimethylaminomethyl Alcohol. FARBEN- FABRIICEN VORM. FRIEDR. BAYER cb Go. (D.R.-P. 268012. Compare this vol. i 20).-Dimethylaminomethyl alcohol can be prepared by treating trimethylamine or its salts with a halogen (such as chlorine) or hypochlorous or hypobromous acid in the presence of water thus avoiding the preparation of the halogen additive compounds of trimethylamine as described in the chief patent (Zoc.cit.). J. C. C. Combinations of Carbamide with Acids. D. F. DU TOIT (Proc. K. Akad. Ketensch. Amstei*dam 1913 16 555-556).-The author has investigated the nature of the solid phases which occur in contact with solution in the system carbamide-acid-water for a number of different acids. I n the case of oxalic acid the compound 2CO(NH,),,H,C,04 was found at 20' and 30°. but no evidence of the compound CO(NH,),,H,C,O,,H,O mas obtained at these temperatures. With acetic acid a t 16*5O,-3Oo and 32G the compound CO( NH,) 2CH3* C0,H was obtained. It melts a t about 35" is very soluble in but not dissociated by water.In tho case of hydrochloric acid the compounds ZCO(NH,),,HCl and CO(NH,),,HCl were found at ZOO whilst with nitric acid CO(NH,),,HNO was the only salt formed at this temperature The solubility of the nitrate decreases a s the concentration of nitric acid in the solution increases attaining a minimum at about 70%. At ZOO sulphuric acid was found to give rise t o the compounds 2CO(NH,)2,dH2S0 and CO(NH,),,H,SO but no evidence was obtained of the existence of CO(NH2),,2H,SO which has been described by Hsntzscb. H. M. D. I n t e r n a l l y Complex Salts. X. Salt and Complex Salt Formation with Imido-compounds. H. LEY and I?. WERNER ( B e y . 1913 46 4040-4050).-The formation of complex salts of compounds in which the alkyl or aryl radicles and the oxygen atoms of the acid-imides have been successively replaced by imino- or amino- groups has already been studied in a number of cases (A 1907 i 301 730).The remaining possible imidocompounds namely the acid-imides acjlcarbamides biuret and the imino-acid-imides are now reviewed. 1. Acid-imides.-The copper and magnesium salts are very readily hydrolysed. The dialysis of the copper oxide sol obtained by hydrolysing a 1-2% solution of copper succinimide has been quantitatively followed succinimide being estimated by distilling with concentrated alkali and titrating the ammonia evolved. Even after twenty-one days the solution still contained about 1% of succinimide and was with difficulty prevented from coagulating. Magnesium succinimide was obtained in the form of an alkaline solution by the addition of magnesium filings to mercury succinimide or by the action of mag-ORGANIC CHEMISTRY.i. 151 nesium powder on aqueous succinimide. From such a solution silver nitrate deposited silver succinimide C,H,O,NAg,$H,O in slender columns. On evaporating the solution of msgnesium succinimide magnesium succinamflte Mg(C,R,O,N) 6 H,O crystallised in large hexagonal tablets m. p. 86-88'. The salt is extremely soluble and is considerably dissociatod in solution. Certain indications were obtained of the existence in concentrated solutions of complex salts of the type [(RN),Mg]Na interesting from their connexion with the grouping N,Mg*-* *N in chlorophyll. Ferric salts of succinimide could not be obtained.Compounds containing the above complex anion were obtained in the case of cyanuric acid. Copper acetate and the sodium salt in concentxated solution gave sodium CupricyanuratS as a hetivy violet crystalline precipitate. Claus and Putensen (A. 1889 30) assigned the formula Cu[NH,(C,HO,N,)] to this compound from which the conclusion might be drawn that copper dimethyl cyanurate would not combine with ammonia. A n ammoniacal solution of dimethyl hydrogen cyanurate gives with copper sulphate however a deep blue coloration followed by precipita- tion of the reddish-violet diammine Cu(C,H603N,),.2NH3 which becomes dark blue in a n atmosphere of ammonia probably forming a tetrammine. Claus and Putensen's comporind is therefore a diammine. I I and 111. Acplcarbamicles and Biwet.-No metallic derivatives of acylcarbamides (benzoylcarbnmide and benzoy lphenylcar bamide) could be obtained.Owing to the similarity in colour between the alkali-copper acid-imides of the type (CuS,)M and the alkali-copper biurets (compare Tschug,iev A 1907 i 595) attempts were made to prepare similarly constituted compounds of biuret. Only the known derivative K,CU(C,H~O,N,)~ and a basic salt KCu(C2H,02N3),,3H,0 well-defined reddish-violet column8 could be obtained. rhey are internally complex salt$ akin to those prepared from amino- and hydroxyacethydroxarnic acids ( A . 1913 i 346). IV. Imino-acid-imides. -Sodium dibenzamide and copper acetate gave the normal bluish-green easily hydrolysed coppel. dibenxamide. Iminodibenzamide however gave a lustrous pale greyish-brown copper salt CU(C,,H,,ON~)~.I t dissolves in pyridiue with deep blue colour. Similarly nickel forms a psle yellow very stable s d t . These abnormally-coloured salts are most probably represented by the [ cu (C3H203N3) 4 1 2H,0 Copper cyanurate combines with two molecules of ammonia. ,CP h L - N H formula N/ NCPh*O*i!I ' J. C. W. Some Double and Complex Cyanates. PAUL PASCAL (Bull. Soc. chim. 1914 [iv] 15 11-19).-When a fresh solution of potassium cyanate in 70% alcohol is added to a neutral solution of uranyl nitrate a voluminous yellow precipitate possessing a greenish fluorescence of potassium uranylcyanats [UO,( CNO),]K is produced. This compound is very soluble in water and owing to hydrolysis the solution gives all the tests for uranium.After a few minutes thei. 152 ABSTRACTS OF CHEMICAL PAPERS. aqueous solution deposits a yellowish-orange insoluble compound having the composition [(U02)2( CNO),]K. If t o a 25% solution of uranyl nitrate a tenth of its weight of potassium uranylcyanate is added and then sufficient alcohol to produce a turbidity urccnyl cyanate UO,(CNO) is obtained as a golden-yellow precipitate. On the other hand a solution of potassium uranylcyanate containing 30-50% of potassium cyanate deposits spontaneously the yellow compound [ UO,(CNO),]K. The cryoscopic behaviour of solutions of urnnyl cyanate containing various proportions of potassium cyanate indicates that the compound [UO,(CNO),]K is present in solutions containing a n excess of potassium cyanate. Solutions containing cobaltous cyanate and potassinm cyanate behave similarly indicating that potassium cobaltous cyanate is present ; moreover the molecular magnetic susceptibility is much less than that for ordinary cobaltous salts and in migration experiments the cobalt wanders t o the anode.T. 5. P. Polymerisation of Cyanamide to Dicyanodiamide in Aqueous Solution. G. GRUBE and J. KRUGER (Zeitsch. physikul. Chem. 1913 86 65- 1O5).-The polymerisation of cyanamide in aqueous solution to dicyanodiamide CN*NH2 -+ (CN-NH,) has been investigated by the usual kinetic method and by means of potential measurements I n the latter method the concentration of the hydrogen ion has been determined under different conditions. It is shown that the presence of alkali accelerates the reaction in a marked degree.Ammonia accelerates the velocity of polymerisation to a n increasing amount as its concentration increases; in the case of sodium hydroxide and calcium hydroxide a maximum velocity is reached at a definite concen- tration and at greater or smaller concentrations than this value the velocity becomes smaller The dissociation constant of cyanamide is of the order of magnitude 10-11 and that of dicyanodiamide From these figures it follows that a molecular solution of monosodium cyanamide is dissociated to the extent of 3% and one of mono- ammonium cyanamide to the extent of 79-89%. It is shown that the polymerisation occurs according to the echeme This is proved by the fact that the react.ion has a maximum velocity when the condition (CNNH‘) = (CNNH,) is fulfilled.The method of preparation of dicyanodiamide from calcium nitride is discussed and a method proposed for its preparation without the addition of any further alkali. J. F. S. CN*NH + CN*NH’ = C?N,N,H,’. Chloro- and Bromo-oximinoacetic Acids. J. HOUBEN and H. KAUFFMANN (Bey. 1913 46 4001-4010).-1t was hoped from a n examination of t,he behaviour of chloro- and bromo-oximinoacetic acids to decide whether the easy decomposition of oxalic acid bromide (and chloride) [bromo- and chloro-glyoxylic acids] occurs in the stages COBr*C02H -+ (CO),O + HBr -+ CO + CO + HBr (Staudinger and Anthes A. 1913 i 604) or COBr*CO,H - + HCOBr + CO -+ CO + HBr + CO,.ORGANIC CHEMISTRY. i. 153 The present results however fail to give a decisive answer t o this question.Chloro-oximinoacetic acid (compare Houben and Kauff mann A . 1913 i 1159) when neutralised with sodium hydroxide in aqueous solution gives a green precipitate with coprer acetate a deep red coloration with ferrous sulphate a yellow precipitate with silver nitrate and a yellow turbidity with lead acetate; ammonium salt colourless precipitate from ether. The molecular weight of the acid in acetic acid solution by cryoscopic measurement agrees with that of an acetyl derivative. When heated with acetyl chloride for half an hour the acid is converted into chloroacetoximinoacetic acid OAc*N:CCl*CO,H stellar aggregates of needles m. p. 73-74' (decornp.) which is con- verted by phosphorus pentachloride under light petroleum into chloro- acetoximinoacetyl chloride OAc*N:CCI*COCI a colourleas oil b.p. 93'/13 mm. Ethyl bromo-oximinoacetate (compare Jovitschitsch A. 1906 i 1161) is obtained conveniently by shaking a mixture of the nitrolic acid of ethyl acetate NO,*C( :NOH)*CO,Et with aqueous hydro- bromic acid and ether for two hours when the nitro-group becomes replaced by bromine; the product m. p. 93O was hydrolysed by heating under reflux condenser with ether and hydrobromic acid the resulting brorno-oximinoacetic acid OH*N:CBr*CO,H being found in the ethereal solution Bromo-oximinoacetic acid is a very hygroscopic crystalline substance decornp. a t 1 lo' which unlike the chloro-oximinoacetic acid is decomposed by water with great readiness the products of decomposition being iulminic acid hydrobromic acid and carbon dioxide.If the acid is heated carefully in a vacuum (15 mm.) decomposition occurs and pale yellow crystals form in the ice-cooled receiver but these could not be further examined as they decompose rapidly with formation of gaseous products. These crystals may have been of the formula yo>C:N*OH or CHBr:N*O€€ 0- which would be expected respectively if the decomposition had occurred analogously to either of the two suggested modes of decomposition of bromoglyoxylic acid. D. F. T. Organo-metallic Ester Compounds. 11. Iodo-zinc-ester Com- pounds. BRUNO EMMERT and WILHELM ELLER (Bey. 1913 46 1508-1511. Compare A. 1911 i 846).-Zinc reacts with ethyl iodoacetate in the presence of iodine to form the compound which when rapidly heated decomposes a t 133-140'.I n the presence of ethyl ether reaction takes place more readily and after removal of the solvent a syrupy mass remains which evolves the remainder of the ether when placed in a vacuum for a protracted period. The crystalline compound desxibed above is thereby obtained which is only partly dissolved on protracted contact with ether. When cautiously decomposed by water it yields ethyl acetoacetate which is recognised by its odour and by the ferric chloride reaction whilst with I,Zn,(CH,.CO,*Et),,i. 154 ABSTRACTS OF CHEMICAL PAPERS. dilute sulphuric acid i t gives ethyl scetoacetate and ethyl iodoacetate. On distillation i t yields a few drops of a n iodine-free organometallic liquid which commences to boil at about 180° thereby becoming black and exploding.With anhydrous ethyl alcohol it yields the crystalline additive product 1,Zn (C H,* CO,E t)3 2 E t OH needles. Compounds of zinc with ethyl P-iodopropionnte and ethyl o-iodo- benzoate were also obtained by heating the requisite components; on account of their extreme sensitiveness to moisture they were not further investigated. H. W. Hydration and Certain Other Transformations of 1 1 2- Trimethylcyclopropane. N. KISHNER and C. CHONIN (J. Russ. Phys. Chem. Xoc. 1913 45 1770-1779).-Attempts to nitrate 1 1 2-tri- methylcyclopropane by means of nitric acid (D 1*075) as suggested by Konovalov gave unsatisfactory results the hydrocarbon being either unattacked or at higher temperatures converted into oxidation products. The action of nitric acid in presence of glacial acetic acid causes rupture of the trimethylene ring and formation of products oE hydration of the trimethylcyclopropane.These products consist principally of dimethylisopropylcarbinol but the other possible alcohol methy1tert.-butylcarbinol could not be detected. The action of hydrobromic acid on 1 1 2-trimethyIcycZopropane has already been referred to briefly (compare Kishner A 1912 i 245) but has now been more thoroughly investigated. The bromo-pro- ducts obtained on distillation with aniline to convert them into the corresponding unsaturated hydrocarbons yield Py-dimethyl-AP-butene and py-dimethyl-ha-butene ; the parent bromo-compound of the former of these is P-bromo-Py-dimethylbutane whilst the latter may be derived also from ,8- bromo-py-dimethylbutane or from a- bromo- Py-dimethylbutane. The action of fuming hydrochloric acid on 1 1 2-trimethylcyclo- propane in a sealed tube at 100' gives a theoretical yield of P-chloro- fly-dimethylbutane CMe,Cl*CHMe,(?) b.p. 11 2-1 12*5'/759 mm. DF 0.8724 n 1.4178. T. H. P. Stability of Cyclic Hydrocarbons in Connexion with their Configuration. The Transformation of cycZoHexene in to Benzene and cyctoHexane. J. BOESEKEN and K. H. A. SILLEVIS (Proc. R. Akad. Wetensch. Amsterdam 1913 16 499-506).-When cyclohexoce vapour mixed with carbon dioxide is passed in a slow current over finely-divided nickel heated at lSO' it is converted into benzene and cyclohexane in accordance with the equation The quantity of benzene actually obtained amounted to about 40% the remainder consisting of cyclohexane and from 2-4% of unchanged cyclohexene.Since carbon monoxide was also found to have been yroduced it is probable that the excess of benzene is due to a part of the hydrogen which is formed as an intermediate product in accordance with C,Hl0 = C,H + ZH being used up in the reduction oE the admixed carbon dioxide. The experiments show that cyclohexene at 180' is metastable with 3CfiHio = C6H + 2CfiHIpORGANIC CHEMISTRY. i. 155 respect t o a mixture of benzene and cyclohexane and also with regard to a mixture of benzene and hydrogen. Observations of other workers relative to the stability of the cyclic hydrocarbons are referred t o in connexion with thew experiments. H. M. D. Thermal and Cryoscopic I n v e s t i g a t i o n of Mixtures of Benzene and Ethyl Alcohol.F. VIALA (BuU. SOC. chim. 1914 [iv] 15 5-ll).-The freezing point curve of mixtures of alcohol and benzene has a eutectic point at a molecular concentration of 97.5% of alcohol; no compound is formed. The freezing point of alcohol is found t o be - 113.9'. The specific heat of a mixture of benzene and alcohol is greater than corresponds with the law of mixtures. From the results of the specific heat measurements the author has calculated the heat of dilution of various solutions and then applied Baud's equation (A. 1913 ii 233) in order to determine the molecular weight of alcohol i n benzene solution. It was found that in dilute solutions t h e alcohol consist,s of simple molecules but association takes place with increasing concentration until in concentrated solutions (50% and over) the association into double molecules is complete.The association does not vary with the concentration in the latter solutions and consequently the conclusion is drawn that pure alcohol consists of double molecules at all events between the temperatures 231' and 275.5O abs. T. s. P. The Supposed Benzene-potassium of H. Abelj anz. W. SCHLENE and HEINRTCH MEYER (Ber. 1913 46 4060-4061).- Abeljanz (A. 1876 i 703) described a bluish-black crystalline mass which he obtained by heating benzene with potassium at 240-250' and assumed to be a mixture of the compounds C,H,K and C,H,K,. The authors find that the substance is merely potassium coated with a film of carbon. A considerable quantity of dipheiiyl was present in tho solvent.The evolution of hydrogen under the influence of moisture and the formation of diphenyl and diphenylbenzene which Abeljanz observed are thus accounted for. J. C. W. Vacuum Coal-tar. AMF PICTET and NAURICE BOUVXER (Compt. rend. 1913 157 1436-1439. Compare A. 1913 i 1315).-A study of the t a r obtained by distilling coal under reduced pressure (15-18 mm.) at 4504 The tar contains neither phenols nor aromatic hydrocarbons but yields both on decomposition at a red heat. The tar after washing with dilute sodium hydroxide and dilute sulphuric acid was fractionated under reduced pressure. The fractions were found to contain alcohols and unsaturated hydrocarbons which were not obtain- able in sufficient quantity for identification. Tliese fractions freed from the alcohols by treatment with sodium and from the unsaturated hydrocarbons by treatment with sulphuric acid were then furkher fractionated and two of the principal fractions studied.Fraction I b. p. 172-174' D23 0,7765 r'$ 1,4196 had by analysis and molecular weight determination the composition C,,H,,.i. 156 ABSTRACTS OF CHEMICAL PAPERS. Fraction 11 b. p. 189-191' Dz 0.7838 7'E 1.4234 had the com- position Cl,H2,. These two fractions had all the properties of naphthenes and were identical in physical properties with two hydrocarbons isolated by Mabery from Canadian petroleum (compare J. Amer. Chem. sbc. 1911 33 251). A chemical study of the hydrocarbon CloH20 shows it to be 1 2 4 5-tetramethylcyclohexane and from it the authors have prepared a dibromo-derivative m.p. 202O and a dinitro-derivative m. p. 205'. They suggest that the other hydrocarbon CllH2 is the analogue of the first being pentamethylcyclohexane. W. G. A Method of Synthesis of Benzyl Chloride and its Homo- logues. MARCEL SOMMELET (Compt. rend. 191 3 157 1443-1 445). -Methyl chloromethyl ether reacts readily with benzene and its homologues in carbon disulphide or carbon tetrachloride in the presence of stannic chloride to give benzyl chloride and its homologues The chloro-ether and the hydrocarbon in solution are cooled to - lo' and the stannic chloride run in drop by drop. By this method the author has prepared benzyl chloride p-tolpl chloride and the three dimethylbenzyl chlorides. 3 4-Bimethylbenxyl chloride is a liquid b. p. 116-117'/24 mm.which on heating with potassium acetate in acetic acid yields 3 4- dimethylbertzyl acetnte C6HsMe,*OAc b. p. 146-148'/28 mm. furnishing on hydrolysis 3 4-dimethylbenzyl ulcohol m. p. 62.5-63.5'. 2 4-Dirnethylbenzyl chloride b. p. l l O o gives the acetate '0. p. 157'/50 mm. and the cclcohol b. p. 151-152'/44 mm. yielding a phenyl- uretham m. p. 78-79". These two alcohols on oxidation give the corresponding dimethylbenzoic acids. 2 5-Dimethylbenzyl chloride b. p. 120-121'/28 mm. yields an acetate b. p. 138-141°/28 mm. and an ulcokol b. p. 142-143'1 37 mm. which gives aphenylurethccrze m. p. 86'. All these chlorides are readily converted into the corresponding aldehydes by warming in aqueous alcoholic solution with hexa- methylenetetramine (compare A. 1913 i 1395 j.Friedel and Craft's Reaction. XIII. Action of Chlorides of Ethylene on Benzene. J. B~ESEKEN and M. C. BASTET (Rec. trav. chiin. 1913 32 184-209. Compare A. 1911 i 522 and earlier abstracts),-It has been previously shown that the Friedel and Crafts' reaction takes place when three molecules are present the first of which is unsaturated the second of which can be activated to such an extent that i t is decomposed during the reaction into two parts which then unite with the first molecule and the third of which is a catalyst which can activate the two molecules (compare Boeseken and Prins A. 1911 i 173). In such con- densations in the presence of benzene it has been assumed that the molecule of the latter is always supersaturated but from observations of Sieger (Diss.) the authors are led to the conclusion that this is not invariably the case.I n the present paper they describe a series of condensations of benzene with various chloro-derivatives of ethylene in W. G.ORGANIC CHEMISTRY. i. 157 which in the first stage the molecule of benzene is disrupted and forms a compound with the unsaturated molecule; this latter molecule becomes in its turn disrupted and combines with a second or third molecule of benzene which now behaves as if it were unsaturated. Vinyl chloride b. p. - 1 8 O is obtained by the decomposition of ethylene dichloride a t 600'. A small quantity of carbon is simultaneously formed and in addition to hydrogen chloride the gaseous product contains carbon dioxide carbon monoxide oxygen and unsaturated hydrocarbons in small quantity.For purposes of experiment the vinyl chloride was not condensed but after being freed from hydrogen chloride and dried was passed directly into the reaction mixture. The latter is prepared by warming a mixture of mercuric chloride and aluminium powder with benzene. A vigorous reaction occurs with the formation of a complex product containing mercurous chloride aluminium chioride and benzene which remains for some time a t 0' in supersaturated solution. I n these circumstances vinyl chloride is readily and completely absorbed with the formation of aa-diphenylethane and small amounts of 9 10-dimethyldihydroanthracene m. p. 178-179". Benzophenone is obtained by oxidation of the former the absence of benzoic acid showing that the original product does not contain dibenzyl.A possible explanation of the course of the reaction consists in the assumption of an initial formation of styrene and subsequent combination of the latter with benzene. To test this point styrene (obtained by the rapid distillation of cinnamic acid with the help of a long fractionating column) has been condensed with benzene at 0' in the presence of aluminium-mercury couple. The product appears to be a polymeride of styrene having a mean molecular weight of 250 in benzene solution ; it does not contain aa-diphenyl- ethane. When agitated with aluminium chloride in carbon disulphide solution (without benzene) styrene yields a substance of indefinite b. p. and mean molecular weight 1'72 in benzene solution. The possibility of the intermediate formation of ethylidene chloride has also been examined.Under conditions similar to those used in experiments with vinyl chloride ethylidene chloride gives aa-diphenyl- ethane but the yields are considerably lower than in the original experiments and further augmentation of the concentration of hydrogen chloride diminishes the quantity. Finally the interpretation is adopted that the first stage of the reaction consists in a disruption of the benzene molecule and combination with vinyl chloride to form a-chlorophenylethane Ph*CHCl*CH which in its turn is disrupted and combines with a further molecule of benzene to yield aa-diphenylethane (compare Schramm A. 1893 i 563). The formation of 9 10-dimethyldihydro- anthracene is explained by the assumption of the condensation of two molecules of a-chlorophenylethane.aa-Diphenylethane when prepared by Priedel and Craft's reaction and freshly distilled shows a marked fluorescence. This appears to be due to an impurity formed during the condensation. The fluorescence gradually disappears when the substance is preserved but re-appears oni. 158 ABSTRACTS OF CHEMICAL PAPERS. repeated distillation especially in an oxidieing atmosphere. It can be removed by boiling under ordinary pressure or by treatment with sodium in alcoholic solution. The condensation of the two symmetrical acetylene dichlorides (compare Chavanne A 1912 i 330) with benzene in the presence of aluminium-mercury couple a t 20° has also been investigated. The products obtained in each case are identical consisting of dibenzyl triphenylethane and tetraphenylethane.At Oo reaction is extremely slow. A t 80° reaction is more complete than a t 20° but also more complicated a larger quantity of residue being formed whilst also the amounts of dibenzyl and tetraphenylethane (which are certainly the products of an abnormal reaction) are increased relatively to the amount of triphenylethane. Trichloroethylene CCI,:CHCI scarcely reacts with benzene in the presence of the aluminium-mercury couple a t the ordinary temperature. A t higher temperatures the main products are aa-dipheuylethane and tetraphenylethane and the coiirse of the reaction is represented by the equations CHC'l:CCI + C,H = C,H,*CKC1*CHC12 and It has been previously shown that tetrachloroethylene does not react to a perceptible extent with benzene in the presence of powdered aluminium chloride at 80° (A.1912 i 65). The authors now show that very little action occurs between the pure substances a t 80' in the presence of aluminium-mercury couple. The reaction observed with commercial tetrachloroethylene is attributed t o impurities. The authors are led to the conclusions that the intensity of the action diminishes with an increase in the number of atoms of chlorine and that reaction commences by an addition of benzene a t the double bond. The chlorine atoms do not become active even in tetrachloroethylene but are activated in the additive products. With increase in the number of chlorine atoms the second stage of the reaction becomes more complicated.H. W. C,H,*CHCi*CHCl + 3C,H6 = CH(C,H,),*CH(C,H,) + 3HCI. Quantitative Investigations on the Nitration of the Chlorotoluenes. J. P. WIBAUT (Rec. trav. chim. 1913 32 244-320).-The author has prepared the four nitro-o-chlorotoluenes in a state of purity and has studied the six curves of solidification of binary mixtures prepared from them. He has thus been enabled to investigate the products of nitration of o-chlorotoluene at Oo and has shown by chemical means that all four possible isomerides are formed whilst from thermal analyses the relative proportions of the isomerides are deduced. A similar series of experiments has been effected with rn-chlorotoluene. The results are in accord with the theoretical predictions of Holleman. o-Chlorotoluene has h. p. 159-5O/759.5 mm.(corr.) n69'4 1.4977. 2-Chloro-4-nitrotoluene is prepared by the nitration of o-toluidine dissolved in concentrated sulphuric acid and successive treatment of the nitrotoluidine with nitrous acid and cuprous chloride. It has v P 4 1.5470 m. p. 62*3* instead of 65' and 6s' recorded in the literature. Reduction with 'iron powder in the presence of a small quantity of sulphuric acid converts it into o-chloro-p-toluidine,ORGANIC CHEMISTRY. i. 159 m. p. 23*1°. The acetyl derivative m. p. 105' and the benxoyl derivative needles m. p. 122" have been prepared. 2-Chloro-6-nitrotoluene 7269.4 1.5377 m. p. 35.3" (Green and Lawson T. 1891 59 1017 give 37") is prepared by reductions of 2 6-dinitro~ toluene by hydrogen sulphide in ammoniacal solution and replacement of the amino-group by chlorine in the usual manner.6-Chloro-o- toluidine has m. p. 2%" and rapidly darkens on exposure to air. The acetyl and benzoyl derivatives have m. p. 156' and 170' respectively. For the preparation of 2-chloro-5-nitrotoluene finely powdered acet- o-toluide is added to a mixture of nitric acids (D 1-52 and 1.40 respectively) at 30'. The temperature must not rise above 35-37'. After remaining for twenty-four hours a t the ordinary temperature the product is poured on to ice. The mixture of acetyl compounds is hydrolysed with boiling hydrochloric acid and 3-nitro-o-toluidine removed by passing steam through the mixture accompanied by a smaller quantity of 5-nitro-o-toluidine. Crystallisation from alcohol enables the two isomerides to be obtained in the pure state m.p. 95' and 130' respectively. The yields are unsatisfactory but no improvement could be effected by nitrating in sulphuric acid or acetic acid solution. 2-Chloro-5-nitrotoluene has m. p. 42*9" n69-4 1.551 1. 6-Chloro-m- toluidine has m. p. 83" (acetyl derivative m. p. 92" ; benxoyl derivative needles m. p. 119.5'). 2-Chloro-3-nitrotoluene prepared from 3-nitro-o-toluidine described above has m. p. 22*1° T ' ~ ~ ' ~ 15327 ; the corresponding amino-com- pound (compare Wynne and Greeves T. 1895 67 1548) solidifies at 6.6' (acetyl derivative m. p. 133'; benzoyl derivative needles m. p. 125'). o-Nitrotoluene is nitrated by gradually adding to it four times its weight of nitric acid (D 1.52) a t - 1 to + 1". After treatment with ice and extraction with benzene the product is distilled under diminished pressure.Measurement of the index of refraction of the various fractions proves the absence of unchanged o-chlorotoluene or dinitro-derivatives. Attempts to separate the isomerides by distilla- tion under diminished pressure or by crystallisation at low temperatures were unsuccessful Better results were obtained by reduction and acetylation of the mixture. Crystallisation from benzene then yields aceto-6-chloro-o-toluidide whilst on concentrating the mother liquors aceto-2-chloro-m-toluidide is obtained. 6-Chloro-m-toluidine is isolated during the distillation of the primary reduction product with steam. Neither 2-chloro-4-nitrotoluene nor any of its derivatives could be isolated but the presence of the former is deduced from the fact that by precipitation of the acetylamino-derivatives (remaining after crystal- lisation of the greater bulk of the products) from benzene solution by addition of light petroleum fractions are obtained which show a rise in m.p. on admixture with aceto-2-chloro-p-toluidide. The solidification curves of the six binary mixtures of the o-chloro- nitrotoluenes have been determined. The curve has the ordinary form in the cases of the following pairs of isomerides (in which the methyl group and chlorine atom are in the positions 1 and 2 respectively) and the eutectic point is appended in brackets 1 2 5 and 1 2 6 (7.2') ; 1 2 ; 5 a n d 1 2 3 ( + 1 ° ) ; 1 2 6 and 1 2 4 (17.2"); 1 2 4 and 1 2 3 (8.2') ; in the case of the isomerides 1 2 5 aod 1 2 4 thei.160 ABSTRACTS OF CHEMICAL PAPERS. curve rises to a maximum indicating the existence of a compound formed by a molecule of each component whilst with isomerides 1 2 6 and 1 2 3 a maximum is also found corresponding with the formation of a compound from two molecules of the latter and one of the former The application of Valeton's method (Acccd. Xci. Amsterdam 1910 754) to synthetic mixtures of the four o-chloronitrotoluenes has shown that the proportions of the isomerides 1 2 4- 1 2 5- and 1 2 6- can be determined with sufficient accuracy; estimation of the 1 2 3-isomeride is not directly possible since the formation of the compound 1 2 3- and 1 2 6- causes too great deviations. The mixture of isomerides obtained by the action of nitric acid (D 1.52) on o-chlorotoluene at 0' during one and a-quarter hours is thus shown to contain 43.4% of 1 2 5- 17.0% of 1 2 4- 20.7% of 1 2 6- and (by difference) lS*S% of the 1 2 3-isomeride.3-Chloro-6-nitrotoluene is obtained by the following method which differs in several respects from t h a t described by Cohen and Hodsman (T 1907 91 974) ; aceto-m-toluidide is dissolved in cold concentrated sulphuric acid and nitrated a t - 5Oto - 3 O with a mixture of nitric acid (D 1.52) and Concentrated sulphuric acid. After elimination of the acetyl group 6-nitro-m-toluidine m. p. 135' (instead of 138' recorded in the literature) is obtained which is converted into 3-chloro-6-nitro- toluene in the usual manner. The latter has n68'6 1.5495 and appears t o exist in a stable modification m.p. 24*9O and a metastable form m. p. 24.2O. 3-Chloro-2-nitrotoluene is obtained by the mathod recommended by Brand and Zoller (A 1907 i 755). 1.5204 temperature of solidification 23.4O. Certain observations lead the author to the conclusion that it may also exist in a metastable state. For the preparation of 3-chEoro-4-nitrotoluene n68'5 1.5428 m. p. 24*2O acet-o-toluide has been converted into 5-chloro-4-nitro-o-toluidine m. p. 1 2 4 O according to the method of Claus and Stapelberg (A. 1893 i 580) who give 128O as m. p. Removal of the amino-group of this compound by the usual methods leads to the desired product the structure of which is confirmed by transforming it into aceto-3-chloro- m-toluidide.3-Chloro-5-nitrotoluene has n68'5 15404 m. p. 5S.4O whereas Hanig (A. 1887 1034) gives 55O. m-Chlorotoluene has been nitrated under the same conditions as the o-isomeride. Measurement of the index of refraction of the various fractions proves the absence of unchanged m-chlorotoluene or of its di- nitro-derivatives. The author has not attempted to isolate directly the various isomerides ; but since on theoretical grounds the formation of 3-chloro-5-nitrotoluene is considered improbable he has applied Valeton's method to the determination of the proportions in which the three other isomerides are formed when m-chlorotoluene is nitrated a t Oo ; he thus finds 58.9% 3-chloro-6-nitrotoluene 32.3% 3-chloro-4-nitro- toluene and 8e8yA 3-chloro-2-nitrotoluene. Investigation of the curves of solidification of binary mixtures of these three substances yields normal results in the cases of 3-chloro-4-nitrotoluene and 3-chloro- 2-nitrotoluene (eutectic temperature about - 4.5') and of 3-chloro- It hasORGANIC CHERI1STK.Y.i. 161 6-nitrotoluene and 3-chloro-2-nitrotoluene (eutectic temperature about - 5') ; in the case of 3-chloro-6-nitrotoluene and 3-chloro-i-nitrotoluene a compound appears to be formed from one molecule of each constituent which however is mainly decomposed in the liquid state. By somewhat modifying the theories of Holleman and Huisingiz a mathematical expression has been devised according to which the relative quantities of isomerides obtained by nitrating the chloro- toluenes can be su6ciently accurately calculated.Tri-arylmethyls. XI. Tetra-arylquinodimethanes [Tetra- aryldimetbylenecycZohexadienes]. W. SCHLENK and MAX BKAUNS (Rer. 1913 46 4061-4066).-1t was previously found that the introduction of diphenyl or naphthyl groups in the hexa- phenylethane molecule considerably enhanced the dissociation into free tri-arylmethyl radicles. The conclusion was therefore drawn that the above groups make larger demands on the affinity of the carbon atom than does the phenyl group. I t wag expected that the introduction of these groups into Thiele's tetraphenylquinodimethane [ 1 4-bisdiphenylmethylene-42 ' '-cyclohexadiene] (I) (A. 1904 i 49 1) would similarly loosen tbe fourth valency of the methane-carbon atom and that compounds of the type (11) would be obtained. H.W. (1.1 (11.) The diphenylbidiphenylyl- and bidiphenylyldi-a-naphthylquinodi- methanes (111 and IV) however proved t o be indifferent towards additive agents like Thiele's hydrocarbon. (111.) UV.1 The above conclusion was however justified since it was found that the tetra-aryl-p-xylylene hsloids which contained diphenyl or naphthyl groups dissociated into the quinonoid hydrocarbons and the free halogen erren more readily than did the tetraphenyl compound. Terephthaloyl chloride was condensed with diphenyl by means of aluminium chloride to form p-phmylene bidiphenylyl diketone CGH4[ 00 *C,H,Ph],. The not quite pure compound formed colourless leaflets m. p. 280-285'. I t was converted into diphenylbidiphcnylylxylylene glycol C,H,[CPh(OH)*CoH,Ph] which formed a microcrystalline powder m.p. 1 0 5 O by the action of magnesium phenyl bromide and into di-a- m~piithylbidipiLenyl?/l~~l~Zene glycol C,,H,,O by the action ol magnesium a-naphthyl bromide. Both cornpounds gave deep blue solutions in sulphuric acid. Hydrogen chloride converted them into the correspond- i ng xylylene dicldorides C,,H,,CI and C,,H,,CI,. The former gave white crystals m. p. 254' (decomp.) and the latter crystallised with 2C,H6 and they both gave coloured solutions on boiling in benzene or xylene owing to dissociation into the quinodimethanes. These compounds were prepared by boiling benzene solutions with copper powder in carbon dioxide atmospheres. Diphenylbidiphenylylquino- VOL. CVI. i. mi. 162 ABSTRACTS OF CHEMICAL PAPERS dimethane [ 1 4-bisphenyldiphenytyl~ethylene-h2 K-cyclohexadiene] (111) forms bright red slender needles decomp.about 200' and di-a- naphthylbidiphenytytquinodimethalne [ 1 4 - big - a - naphthyldiphenytyl- methylene-h2 5-cgclohexadiene] (IV) forms orange needles m. p. above 290'. Their solutions are strongly fluorescent but soon become colourless in the light. They do not absorb iodine and are scarcely affected in the air. J. C. W. Combinations of Aniline with Hydrochloric Acid. J. C. THONUS (Proc. K. Aknd. wet end^ Amsterdam 19 13 16 553-555)- The equilibrium conditions characteristic of the system anilice-hydro- chloric acid-water have been investigated. The following compounds occur as solid phases at 0' GNH,Ph,HCl ; 5NH,Pb,3HCl,H20 ; NH,Ph,HCl ; lONH,Ph,llKCl. Of the above four compounds the first and second cease to exist a t 25O whilst experiments a t 35Oshow that solid phases occur of the composition 4NH2Ph,5HCI ; lONH,Ph,liHCl ; NH,Ph,HCl; SNH,Ph,HCl ; 3NH2Ph,HC1.solid phases and solution a t 0'. A diagram is given showing the relationship between the various H. M. D. P r e p a r a t i o n of N-Monoalkyl Derivatives of Homopiper- onylamine. HEHMAN DECKER (D.R.-P. 267700). - N-Monoalkyl derivatives of homopiperonylamine are prepared by treating alkylidene derivatives of homopiperonylamine with alkylating agents in absence of water and decomposing the resulting quaternary ammouium compounds. Benzylidenehomopiperonylamine when treated with methyl iodide furnishes ultimately N-methylhomopiper- onylamine b p. 156-158'/24 mm. (corr.).This forms a hydrochloride m. p. 178-180° a nitrate m. p. 166-167' (corr,) a carbonate m. p. 72-75' and a hydviodide m. p. 135-1 36' (corr.). N-Ethythomopiper- onyZamine similarly prepared by means of ethyl iodide has m. p. 1 26 - 1 28'. J. C. 0. Preparation of 1 6-Dibromo-2-naphthylttmine. HARTWIG FRANZEN and ADOLF EIDIS (J. pr. Chem. 1913 [ii] 88 755-764). -The preparation of 1 6-dibromo-2-naphthylamine (compare Claus and Jack A 1898 j 324; also Claus and Philipson A 1891 461) is best accomplished by the bromination of benzylidene-/3-naphthyl- amine in the manner indicated below; the isolation of the inter- mediate products is however unnecessary. Benzylidene-P-naphthyl- amine combines with bromine in chloroform solution to form a dibromide CIoH,*NBr*CHPhBr which separates as a light yellow crystalline powder and is converted by boiling in alcoholic solution into 1- bromo-2-naphthylamine.This crystallises in colourless needles m. p. 63-64' and condenses with benzaldehyde in alcoholic solution yielding zt benxytidene derivative (slender yellow needles m. p. 94') which unites with bromine in chloroform solution to form a dibyornide CloH,Br*NBr*CHPhBr m. p. 220° with previous sintering and darkening at 210'. When boiled in alcoholic solution the dibromide yields 1 6-dibromo-2-naphthylamine.ORGANIC CHEMISTRY. i. 163 Bromination of aceto-/3-naphthylamide in glacial acetic acid gives rise to acsto - 1 - bromo-P-naphthg2arnk-h hydrobromide C,?H,,ONBr a colourless crystalline powder m p. 180-190' (compare Cosiner A 1881 605).On treatment with ammonia or when crystallised from alcohol the hydrobromide is converted into the free amide which is hydrolysed by alcoholic hydrogen chloride to l-brom0-2-naphthylamine identical with that obtained by the method described above but different from the compouud m. p. 76-79' described under the same name by Morawski and Gltiser (A. 1888 1096). F. €3. Acetylation of Organic Compounds. E. KNOEVENAGEL (Annalen 1913 402 lll-l48).-1t has long been known that the presence of sodium acetate sulphuric acid or zinc chloride greatly facilitates the acetylation of organic compounds by acetic anhydride but the manner in which the catalyst operates is still obscure. It does not act in virtue of its dehydrating power because not only is a very small amount of the catalyst employed but also other substances such as strong acids or metallic wlts of strong acids which are devoid of desiccating propertiee can also function as catalysts.Different catalysts produce different results and a t present generalisatione cannot be stated but this much is certain that the action of a catalyst is not dependent simply on the concentration of the hydrogen ions or on its dehydrating power Acetylatiou by means of acetic anhydride is not limited to organic compounds containing hydroxyl groups ; with a suitable catalyst oxidee especially aldehydes likewise certain unsaturated and ethereal compounds such as ethers unsaturated ketones open and cyclic anhy- drides of polyhydric alcohols amongst them poly saccharides dextrin stsrch and cellulose can unite with acetic anhydride in consequence of a more or less easy rupture of the linking between carbon and carbon cr carbon and oxygen.When the acetate formation is accompanied by a degradation of the organic molecule the phenomenon (which is quito analogous to ordinary hydrolysis) is termed acetolysis. The acetylation of hydraxylic compounds the acetate formation in the case of the compounds mentioned above and the occurrence or non- occurrence of acetoly sis are dependent apart from the temperature and the quantity of the catalyst 60 largely on the nature of the catalyst that it is possible under selected experimental conditions sim iiltarieously to acetylate hydroxyl groups to promote acetate forma- tion at a carbon-oxygen linking and with suitable Substances to degrade the molecule or sometimes to leave it undegraded.The preceding processes are being applied to elucidate the constitu- tions of the polysaccharides dextrins starch and cellulose ; the present paper however deals with their application to simpler classes of compounds. The catalysts employed are ferric chloride zinc chloride hydrated stannous chloride phosphorus trichloride sulphuric acid sulphoacetic acid hydrated ferrous sulpbate hydrated copper sul phate hydrated zinc sulphate ammonium sulphate and methylamine sulphate. The last two although active in the acetylation of hydroxyl groups are without effect in the conversion of aldehydes into diacetates. This m 2i. 164 ABSTRACTS OF CHEMICAL PAPERS. conversion is readily effected by all of the other catalysts the modus operandi being to mix the aldehyde (1 mol.) acetic anhydride (1.1 mol.) and cataljst (1-5%) a t the ordinary temperature external cooling being employed to keep the temperature below 70".Benzaldehyde gives an almost quantitative yield of benzylidene diacetate in the presence of copper sulphate or zinc chloride and also with sulphuric acid or ferric chloride when the reaction is commenced in a freezing mixture. Similar experiments have been performed with furfural- dehyde (at 0-loo) cinnamaldehyde (ferric chloride acts too vigorously but by dilution with glacial acetic acid a quantitative yield of cin- namylidene diacetate is obtained) vanillin (stannous chloride produces a nearly quantitative yield of the triacetate) anisaldehyde (successful results obtained only with stannous chloride phosphorus trichloride and copper sulphate ; anisylidene diacetate bas m.p. 67O) piperonal (quantita- tive or nearly quantitative yields with ferric chloride stannous chloride sulphoacetic acid ferrous sulphate and copper sulphate ; piperonyli- dene diacetate has m.p. SOo) and protocatechualdehyde (the tetra-acetate has m. p. 131'; no success is obtained with copper sulphate). Salicylal- dehyde yields the triacetate m. p. 1 0 3 O or disalicylaldehyde m. p. 1 2 9 O or a mixture of both; the triacetate is tho main product in the presence of ferric chloride zinc chloride or sulphuric acid whilst disalicylaldehyde is entirely or mainly produced when the catalyst is phorphorus trichloride copper sulphate or zinc sulphate ; the remain- ing catalysts produce an approximately equal molecular mixture of both substances.In all cases disalicylaldehyde is the primary reaction product and is subsequently converted into the triacetate in the presence of a suitable catalyst. The converse change OP the triacetate into disalicylaldehyde cannot be accomplished. Salicylaldehyde and acetic anhydride yield the triacetate in the presence of 2% of sulpho- acetic acid but disalicylaldehyde when about 50% of the catalyst is employed ; in the presence of acetylsulphuric acid only the triacetate is formed Paraformaldehyde and acetaldehyde are readily converted into the corresponding alkylidene diacetates by acetic anhydride and a little sulphuric acid or ferric chloride respectively. Ketones unlike aldehydes do not react additively with acetic anhydride to form diacetates even in the presence of the preceding catalysts.p-Benzoquinone and acetic anhydride however react in the presence of a little ferric chloride to give an almost quantitative yield of Thiele's hydroxyquinyl triacetate m. p. 9 6 O . [With JuNa and RUMscHI~.]-styryl methyl ketone and acetic an- hydride react in the presence of a little sublimed ferric chloride to form after three to four days 5-acetoxy-2-acetyl-3 ; 4diphenyZ-l-naethyl-A~-cyclo- pntene CMe<OH(oAc),CHPh m. p. 1 1 8 O by the hydrolysifi of which is obtained li-hydroxy- 2-acet yl-3 ; 4 -diphen yl- 1 -meth yl-A'- c yclopentene 020H2002 m. p. 95' (oxime m. p 103' [decomp.]; phenylhydraxone m. p. 9 4 O [decomp.] ; tribromo-derivative C20H,,0,Br3 m.p. 1 8 3 O [decomp.]) ; the preceding acetate forms a tribrorno-derivative C22H,10,Br m. p. 194' (decomp.). CAc-FHPhORG Ah7 C CHEMISTRY. i. 165 [With Runrsc~1~.]-Ethy1 ether is almost mattacked by acetic anhydride a t 100' in the presence of sulphriric acid potassium hydrogen sulphate pyridine hydrogen sulphate or ammonium per- sulphate. I n the presence of a little ferric chloride however acetolysis occurs t o a slight extent ethyl acetate being formed. Epichlorohydrin and acetic anhydride react at the ordinary temperature in the presence of ferric chloride (but not of copper sulphate or srilphuric acid) to give an almost quantitative yield of diacetin-a-chlorohydrin OAc*CH 2*CH( OAc) CH,Cl b. p. 116-118'/11 mm. Epichlorohydrin glacial acetic acid and a little ferric chloride react at the ordinary temperature t o form a-acetin-y-chlorohydrin OAc*CH,*CH(OH)*CH,Cl b.p. 120-1 21°/ 14 mm. in about 90% jield. [With JAKOB TRANSIER.]-cim?Ol and acetic anhydride react to form according to the temperature and the catalyst employed a terpineol acetate b. p. 104-106'/10 mm. and terpin diacetate b. p. 145'/' 14 mm. in varying amounts; the most effective catalysts for the rupture of the cineol ring are sulphuric acid and ferric chloride. The terpineol thus formed is appnren tly identical wit,h the compound syrithesised by Perkin (T. 1904 85 654) since i t has b. p. 102-103O/ 14 mm. D"," 0.9337 and lz; 1.4783 and forms a phenylurethane m. p. logo and nitrosochloride m. p. 117'. Cineole and glacial acetic acid yield dicinene by warming with a little concentrated sulphuric acid on the water-bath.The preceding experiments illastrate well the different results obtained by the action of acetic anhydride in the presence of various catalysts. The 6-ring in cineole is readily ruptured in the presence of many catalysts the 3-ring in epichlorobydrin by only a few catalysts at the ordinary temperature whilst the acetolgsis of ethyl ether is only slight even with the strongest catalyst at 100'. [With J u N a and RUjnisc~~h'.]-Ethyl furylidenemalonat,e and acetic anhydride in the presence of n little sublimed ferric chloride react ultimately on the water-bath to form a substance C,,H,,07 or C,,H,,O m. p. 70° from which an acid C15H2007 or C1H160fi m. p. 1444 is obtained by boiling with wntef or hydrochloric acid m d a n acid m.p. 192-195' (barium salt C,,H?,O6Ba,4H,0) by boiling with a n excess of aqueous barium hydroxide. The investi- Compounds of the Aminophenols with Zinc Chloride Bromide and Iodide. A. KOPPITZ (J. pr. Chem. 1913 [ii] 88 744-754).-The three isomeric aminophenols combine with zinc haloids in aqueous solution yielding additive compounds of the formula 2CGH,0N,ZnX,. On account of the tendency of the aminophenols to form basic zinc compounds the preparation of the additive compounds is best accomplished by dissolving the aminophenols in n hot concentrated solution of the zinc haloid. The compounds are decomposed by water but may be crystallised from strong solutions of the corresponding zinc haloid.The compounds of zinc chloride with 0- and p-aminophenols crystallise in reddish-violet needles m. p. 184" and 247' gstion of these substances is being continued. c. s.i. lG6 ABSTRACTS OF CHEMICAL PAPERS. resp~,ctively ; the corresponding cornpounds of zinc bromide in light brown or reddish-brown needles m. p. 170' and 234'. The compound of zinc iodide with p-aminophenol forms dark brown needles m. p. 208'. The compounds formed by m-aminopbenol with zinc chloride (lu.;trow white silky needles m. p. 235') zinc bromide (m. p. N S ' ) and zinc iodide (white needles m. p. 190') are also described. All the above compounds melt with decomposition. F. B. Nitration of Acyl DerivrttiverJ of m-Aminophenol and m-Anisidine. F R ~ D ~ R I C REVERDIN and KARL WIDMER ( B e y .1 9 13 46 4066-4076).-The knowledge of mono- and dinitro-derivntives of these bases is extended by the preparation of some new compounds and by a re-examination of several of those already known. I. A cyl Derivntires of m-Aminophenol. -m- Acet y laminophen y 1 acetate (Ikuta A 1893 i 265) was prepared by heating m-aminophenol with acetic anhydride and sodium acetate at 150-160'. It was accompanied by the unstable tyiacetyl derivative C,H,(OAc)*NAc which is less soluble in water than the diacetyl compoiind and h w m p. 75-7 7'. Toluene- p-sulphonyl-m-aminophenol 0 He C,H,*NH*S02* C6H M e (Reverdin and de Luc) has m. p. 158' and yields with acetic anhydride the acetory-derivative C,,H,,O,NS in white needles m. p. 166'. Tho di-toluene-p-sulphonyl-m-aminophenol C,oH,,0,NS2 forms white needles m.p. 110'. 11. Nitration o j the Diacyl Compounds.-By the action of nitric acid on m-acetylaminophenyl acetate Meldola obtained a mixture of 4- and 6-nitro-3-acetylaruinophenols (T 1906 89 925). This coiild not be confirmed. The addition of the compound- to fuming nitric acid below 4O resulted in the formation of 6-nitrodiacetyl-m-anainophenol [6-nitro- 3-acetylaminoplhenyl acetate] CloH1005N2 as white needles m. p. 11 3' which were hydrolysed by warm sodium carbonate to 6-nitro-3-acetyl- aminophenol (m. p. ZOO'; Meldola 221'). The latter was completely hydrolysed by means of 6% hydrochIoric acid t o 6-nitro-3-aminophenol (Meldola) the constitution of which was confirmed by conversion into 3-chloro-6-nitrophonol and 6-aitroresorciuol.Other mononitro- derivatives could not be obtained By dissolving the diacetyl compound in a mixture of fuming nitric acid and acetic anhydride 4 6-dinitro-3-acctylaminophenyl acetate mas obtained in almost colourless needles m. p. 157'. It was hydrolysed by sodium carbonate to the N-acetyl derivative and finally by con- centrated sulphuric acid to 4 6-dinitro-m-aminophenol (both described by Rleldola). Other acyl derivatives could likewise only be nitrated in the mme positions. Thus rn-benzoylaminophenyl benzoate (Ikuta loc. cit.) yielded 4 6-dinitrobeizzoyl-m-aminophenyl benzoate C,H,(NO,j,*CO~NH-C,H,*OBz as a white crystalline powder m. p. 70-72'. Similarly the above toluenesul phony1 derivative formed 4 6-dinitrototuei~e-p-sul~l3lonyl-m- ctxi&nophenyl toluene-p-sulphonate C,oH170,N,S2 in whito needles m. p.120-123'.ORGANIC CHEMISTRY. i. 167 111. Nitration of m-Acetanieididu.-By the addition of rn-acet- anisidide to nitric acid (D 1*4) 4-nitro- and 6-nitro-derivatives were obtained. The former waa extracted by light petroleum. Meldola (Zoc. cit.) obtained it by other means. It was diazotised and coupled with P-naphthol .giving a red azo-compound C17H,,0,N m. p. 2029 The insoluble 6-nztro-m-acetarcisidide crystallised from water in golden- yellow needles m. p. 165O which were further nitrated to the 4 6-dinitro-compound of proved constitution (Meldola). It W ~ E I hydrolysed to 6-nitro-rn-anis~dhedine OMe*C6.H3(NH,)*NO2 which formed dark yellow needlm m. p. 169'. By nitrating m-acetaniaidide in glacial acetic acid solution a 2-nitro-compound was also formed.It was the first to crystallise from a mixture with the 6-nitro-derivative dissolved in hot water. 2-Nitro-rn-acetanisidide is a brown powder m. p. 2 6 5 O and 2-nitro-m-anieidine forms lemon-yellow needles m. p. 143O. The only known dinitro-derivative was the 4 6-member (Meldola). Using fuming nitric acid in acetic acid solution 2 4-dinit.ro-m- acetaizisidide has also been obtained. It is less soluble in water than the 4 6-isomeride and forms pale yellow needles m. p. 202". It was hydrolysed to 2 4-dinitro-m-anisidine (Blanksma A 1909 i 150). Using acetic anhydride as the solvent 2 6-dinitro-m-acatanisidide was also obtained. It crystallises from hot water as a middle fraction between the 2 4- and 4 6-isomerides.It forms white needles m. p. 190° and is converted by nitric acid into the 4 6-compound 2 6-Dinitro-macnisidins forms dark yellow needles m. p. 146'. The constitution is assumed from the improbability of a substituent entering position 5 owing to the ortho-para orientating influence of the methoxy- and amino-groups. Other dinitro- and also trinitro-compounds could not be obtained by nitration. J. C. W. A New Synthesis of Higher Phenols. RIHO MAJIMA and IKUYA NAHAMURA (Ber. 1913 46 4089-4095).-The preparation of tetra- penta- and hexa-decylveratroles and some allied products is dexcribed. Myristyl chloride was condensed with veratrole by means of aluminium chloride giving a 25% yield of veratryl tridecyl &tom ( 3 4-dimethoxybensoyZtridecccne) C6H3(OMe)2'COoC13~,7 which formed long slender bulky needles m.p. 74-75' and was oxidised by nitric acid (D 1-12) to 3 4-dimethoxybenzoic acid. The oxime formed thick needles m. p. 54-55' whiuh were reduced by aluminium amalgam to a-veratryZtetradecyZamine the .hydroch~orids of which formed prisms m. p. 199O. The phosphate of the base was distilled under 0.8 mm. when tetradecsnylveratro~6 (a-veratryl-Aa-tatradecene) C6H,(OMe),*CH:CH0C1~HPL was obtained in thin plates m. p. 38-40°. This was reduced by platinum and hydrogen to tetradecylvemtrole (a-oeratryztetr~deca?~) C,H,(OMe),*C,,H, which formed long flat crystals m. p. 49-503 b. p. 185-190°/0*5 mm. Hubsequently the same compound was ob- tained by the direct reduction of the above ketone by means of zinc amalgam (Clemmensen A 1913 i 733).Pentadecyl chloride was also condensed with veratrole yieldingi. 168 BBSTRACTS OF CHEMICAL PAPERS. verat$ tetradecyl ketone C25H3803 b. p. 220°/0*3 mm. m. p. 64-65' which was reduced t o pentadecylveratroZe (a-veratrylpentadecane) CpH,(OMe),*Ci,H, b. p. 1 85-195"/0*5-0*8 mm. m. p. 50-51". Similarly palmit,yl chloride yielded veratryl pentadecyl ketone b. p. 230°/0*5 mm. m. p. 79-80" which was reduced to hexadecylueyatrole (cetylveratrole) C,H,(OMe),*C,,H, b. p. 1 90-200'/0*5 mm. m. p. 56-57". For the preparation of pentadecoic acid methyl myristate was re- duced by Bouveault's method t o tetradecyl alcohol which was converted into tetradecyl iodide b. p. 192-195"/17*5 mm. then into the nitrile b. p. 181-185'/23 mm. DT 0.8187 and this was hydrolysed. The method is alternative t o that devised by Le Sueur (T.1905 87 1898). J. C. W. Benzhydrol P r e p a r a t i o n of s-Tetraphenylethane. PAUL SABATIER and M. ~S~URAT (Compt rend. 1913 157 1496-1500).-A ritsum6 for the most part of the chemistry of benzhydrol. Attempts to prepare this compound by the action of water on the Grignard compound CHPh,*ONgBr gave only 3% of the desired alcohol a little benzophenone a large amount of diphenylmethane and s-tetraphenylethane the two hydrocarbons being separable by their solubilities in alcohol. Their formation is explained by the equattions 3CHPh,*OH = 2H,O + COPb + CHPb,*CHPb 2CHPh,*OH = H,O + COPh + CH,Ph and is comparable to the action of ethyl alcohol and benzhydrol (compare Schmidlin and Banus A 1913 i 34).JOSEPH SAMUEL HEPBURN (Chem. Zentr. 1913 ii 2052-2053; from J. Franklin Inst. 1913 176 405-452).-The brains of the sheep after dehydration with alcohol are extracted with three portions of ether at the ordinary temperature. Lipoids are removed from the concentrated ethereal solution by precipitation with acetone. The residue from the ether- acetone solution of each fraction is then saponified in two ways either by hot alcoholic potassium hydroxide or by sodium ethoxide a t the ordinary temperature. All six preparations of cholesterol so obtained melted between 148.4' and 149.1". Two specimens of cholesterol obtained from gall stones had m. p. 147.4" and mixtures of the different specimens had 113. p. 147.7-148". Determination of the iodine number according to the methods of Hiibl Havas or Wys gives uniformly too high values for cholesterol so that the usual iodine reagents cannot be employed for the volumetric determination of cholesterol in fat.The author has also examined the various gravimetric methods which have been recommended for the estimation of cholesterol. R i t t e i s process (A. 1902 ii l l l ) depending on the direct weighing of free cholesterol gives unsatisfactory results. Concordant analyses could not be obtained either by use of carbon dioxide or of hydro- chloric acid to neutralise the excess of sodium ethoxide employed for saponification; the yields obtained by use of hydrochloric acid were very bad. Excellent duplicates were obtained by Cappenberg's method (Chem. Zeit. 1909 33 985) but the yield was about 94%.The W. G. Biochemical S t u d i e s on Cholesterol.ORGANIC CHEMISTRY. i. 169 estimation of cholesterol as benzoyl derivative (Dorde and Gardner A. 1908 ii 515) is not quantitative giving as a n average 42*S6% of the cholesterol actually present. The best and most trustworthy method is that recommended by Windaus (A 1910 ii 462) which consists in precipitation and weighing as digitonin-cholesteride. The average yield is 97.3704. isoCholestero1 Coprosterol and the Classification of the Sterols. CHARLES DOR~E (Biochem. J 191 3 7 616-621).-A useful summary of the properties of the ctiief sterols of animal origin (zoosterols) and of plant origin (phytosterols) is given. Animal cholesterol is modified when excreted by the skin glands into isocholesterol or by the intestinal juices into coprosterol.Phyto- sterol is also converted into coprosterol in the intestine and by excretion as in rubber into isocholesterol. The term metasterols is suggested for the derived sterols coprosterol and isocholesterol. Spongosterol (Henze) is probably in the same class. The position of stigmasterol (Windaus and Hauth A. 1907 i 129) and of brassicasterol (Windaus and Welsch A 1909 i 229) is uncertain. Of the chemical relation- ships between cholesterol phytosterol and the metasterols little is known at present. W. D. H. The Oxidation of Coprosterol and Goprostanone. JOHN ADDY- MAN GARDKER and WILLIAM GODDEN (Biockem. J. 1913 7 SSS-595). -When coprosterol (C21rH,80) is oxidised with the theoretical amount of chromic acid the ketone coprostanone (Cz7H,,0) is produced but the yield is only 60% (Dorbe and Gardner T.19OS 93 1628). I n the present work a n excess of chromic acid was used and tha yield was 70%. The sodium hydroxide extracts on acidification also yielded an acid which was crystallisable (m. p. 24c0) and a n oily substance which was not further investigated. Analysis of the acid and of its salts showed i t had the composition C(27H4604. Direct oxidation of coprostanone with chromic acid also gave a small yield of the same acid. After oxidation with ammonium persulphate the products obtained were separated into three fractions all of which were obtained in crystalline form Some preliminary details are given of their properties and further work is in progress.Molecular Rearrangements in the Camphor Series. XII. Derivatives of i8oCamphoric Acid ; Decomposition Products of Aminoisodihydrocampholytic Acid. WILLIAM A. NOYES and LLOYD F. NICKELL (J. Amer. Chem. Soc. 1914 36 118-127).-Noyes and Potter (A. 1912 i 786) have studied the decomposition of aminodihydrocampholytic acid with nitrous acid. Similar work on aminoisodihydrocampholytic acid has been carried out by Noyes and Knight (A. 1911 i 11 l) but the products were not fully investigated. An improved method has now been devised for preparing the latter acid and a further study has been made of its decomposition with nitrous acid acid C02H*CH<c”e2 ?Me*NH2y m. p. 235-236’ [a] - 32.9’ furnishes a hydrochlwide m. p. 296-298’ H. W. IV. D. H. A mi noisodih y drocampholy t ic C H -CH1.170 ABSTRACTS OF CHEMICAL PAPERS. (decomp.) [a? - 45.8' which when heated with acetic anhydride and sodium acetate is converted into the anhydride of d-aminodihydro- campholytic acid. On decomposing aminoisodihydrocampholytic acid with nitrous acid the following products are obtained d-cam- pholytic acid 35.8% ; I-campholytolactone 4.2% ; Z-tvans-hydroxy- dihydrocampholytic acid 19.1% ; and a small quantity of isolaurolene. The Walden inversion occurs only to a slight extent in this decom- position. Z-Campholytolactone has m. p. 114-1 IS' [a] - 8.2" (in alcohol) and on hydrolysis is converted into I-cis-hydroxydihydrocampholytic acid m. p. 117-118' [aID - 53.1' (in alcohol). d-Campholytic acid has Dii 1.006 and [a] +66-35'. The formation of this acid in the decomposition furnishes direct evidence that it is the secondary asymmetric carbon atom of d-camphoric acid which rearranges to form I-isocam phoric acid.E. G. J. J. BLANKSMA (Chena. Weekblad 19 14 1 1 5 9-6 l).-Five halogen-nitro-derivatives of benzoic acid have been prepared. Bromination of 5-nitro-3-amino- benzoic acid yields 2 4 6-tribromo-5-nitro-3-atninobenzoic acid reddish- brown crystals m. p. 117'. The methyl ester of the former acid is converted by the diazo-method into methyl 3-b~omo-5 -nilrobenxoccte colourless crystals m. p. 70° converted by saponification into the corresponding acid. Acetylation of ethyl 5-nitro-3-aminobenzoate produces ethyl 5-nitro-3-acetylaminobenzoate colourless crystal$ m. p. 168'. Saponification of the former ester yields the corresponding 5-nitro-3-aminobenzoic acid orange-red crystals m.p. 208'. Bromina- tion transforms ethyl 5-nitro-3-aminobenzoate into ethyl 2 4 6-tri- 6~om1-1-5 -nitro-3-aminobenxoate light brown crystals m. p. 96' ; and the diazo-method converts it into ethyl 3-chloro-5-nitrobertxoate colourless crystals m p. 54' saponifiable to the corresponding acid Ethyl 3-bromo-5-nztrobenxoate is prepared analogously to the methyl ester and has m. p. 44'. Halogen-nitro-derivatives of Benzoic Acid. Saponification converts it into the corresponding acid. A. J. W. Investigation of Binary Systems Containing Beneoyl Chloride and Various Other Organic Compounds. B. N. MENSCHUTKIN (J. Russ. Phys. Chem. Soc. 1913 45 1701-1709). -The author has investigated the temperature-concentration diagrams of seven systems all of which gave perfectly similar diagrams no molecular compound being formed in any case.The different systems were composed of benzoyl chloride and (1) benzene this sbowed although not very clearly a eutectic arrest corresponding with a eutectic point at - 26.8' the composicion being COPhCI,1*03C6H,; (2) p-xylene the eutectic lies at - 18.5' and corresponds with COPhCl,O*6 5C6H,Me2 ; (3) rnesitylene the eutectic is situated at about - 70° the corre- sponding composition being COPhC1,4*7C6H,Me ; (4) chloro- benzene eutectic. point - 54-2O composition COPhCl,S*lPhCl ; (5) nitrobenzene - 20.5' and COPhCl,l.14Ph*NO2; (6) diphenyl - 8' and COPhCl,c).2C6H5Ph ; (7) diphenylmethane - 15' and COPhCI,0*42CH2Ph2.The detailed results of the measurements are given in tabular form. T. €1. P.ORGANIC CHEMISTRY. i. 171 p-Nitroso - N - phenylglycine and p-Nitroso - N - o - carboxy- phenylglycine. J. HOUBEN (Ber. 19 13 46 39S4-4000).- Previous attempts to cause phenylcurboxymethylnitroso imine NO*NPh*CH,*CO,H to undergo rearrangement into the corresponding p-r;itrosophenylgl ycine have proved unsiiccessfczl (Fischer and Hepp A 1887 1115; Fischer A. 1899 i 349) the isolation of a con- siderable quantity of p-hydroxylaminobenzenediazonium chloride OH*NH*C,H,*N,CI indicating that the greater portion of the starting substance must have lost the nitroso-group without undergoing re- arrangement. The autbor regards the rearrangement which generally occurs as the result of two reactions the first involving the scission of the nitrdso- radicle and the second its introduction into the nucleus and finds that by the action of sodium nitrite and fuming hydrochloric acid the above p-nitrosophenylglycine can be produced in excellent yield.I n a similar manner o-carboxyphenylcarboxymetbylnitrosoamine can be converted into the hydrochloride of p-nitroso-o-carboxyphenylglycine. Pbenylglycine was prepared by boiling 9.5 grams of aniline with 9.3 grams of chloroacetic acid in a solution of 4 grams of sodium hydroxide in 60 C.C. of water for a few minutes; the clear yellow solution obtained when cooled in ice deposited phenylglycine in approx. 85% yield. A solution of nitrosyl chloride was obtained by adding 50 grams of sodium nitrite to one litre of concentrated hydrochloric acid cooled in a freezing mixture keeping the closed flask cold until most of the nitrite was decomposed and a deep reddish- yellow solution was produced. To 650 C.C.of this ice-cold solution 50 grams of finely granular phenylglycine was introduced and the mixture shaken in the closed flask until the substance was entirely con- ver ted into a brownish-yellow powder which was pure p-nitrosophenyl- glycine hydrochloride the yield Frequently attaining 80%. The conversion of phenylglycine into this nitroso-derivative can also be effected by the direct addition of sodium nitrite to a mixture of phenylglycine with concentrated hydrochloric acid the yield being the same. The hydro- chloride readily loses its acid and when washed with water passes into the free p-nitroso~henyZgZyc~ne a sparingly soluble brown substance which decomposes explosively when warmed ; with concentrated ammonia solution i t gives a green colour due to the green amnzonium salt which can be separated by the addition of alcohol. It is interest- ing to note that the isomeric 5-nitroeo-N-methylanthraniiic acid is green and the suggestion is made that the brown colour of the sub- stance just described may be due to a quinonoid configuration N OH:C,H,:N*CH,*CO,H. Preliminary experiments with p-nitrosophenylglycine show that i t may be successfully used for the preparation of dyes condensation with a-naphthol a-naphthylamine m-tolylenediamine gallic acid ethyl gallate and p- naph t hylamine producing respectively reddis h-violet violet-blue blue reddish-violet red and reddish-brown substances.Under the influence of sodium methoxide solution condensation can be effected with p-nitrobenzyi cyanide to an azomethine compound deep red needles from toluene solution. LV-Phenylmethylglycine is conveniently obtained by heating togetheri. 172 ARSTRACTS OF CHEMICAL PAPERS. methylaniline and chloroacetic acid with sodium hydroxide solution for four hours; the resulting base is extracted with ether and precipitated as the hydrochloride; the yield is 74% of the theoretical; hydro- chloride m. p. 215-216' (compare Hinsberg and Rosenzweig A. 1895 i 144). Attempts to prepare a nitroso-derivative were unsuc- cessful this result indicating that the introduction of a carboxyl group into one of the methyl radicles of dimethylaniline checks the formation of a para-nitroso-derivative.This view is supported by the action of sodium nitrite and concentrated hydrochloric acid on methyl dimethylanthranilate which gave rise only to a very small quantity of methyl 5-nitrosomonomethylanthranilate. Treatment of o-carboxyphenylglycine with nitrosyl chloride or sodium nitrite as described above for phenylglycine effects almost quantitative conversion into the yellowish-brown hydpocldoride of p-nitroso-o-cnrboxyphenylglycine which decomposes above 1 00' without- melting The free base NO-C,H,(CO,H)*N H*CH,*CO,H obtained by the action of sodium carbonate or acetate on the hydro- chloride is a green solid which rapidly changes when moist to a brown colour possibly of a quinonoid form.It decompoFes when heated and condenses with benzyl cyanide in the presence of sodium methoxide giving a yellow a zomethine derivative malonitrile cnder similar conditions giving a blood-red azomethine compound ; the azomethine compound CO,H*CH,*NH C,H,( C0,H) N C( CN)*C,H,* NO obtained with p-nitrobenzaldehyde forms red needles m. p. 256-258'. When the above hydrochloride is warmed in acetic acid with a-naphthol P-napht hol gallic acid rn-tolylenediamine and naph t hy lethy lamine substances are produced with blue violet-red violet bluish-violet and greenish-blue colours respectively. [With TR ARENDT.] -Met hyl o-carbomet h ox yphen y I gl ycine pre- pared by the interaction of methyl anthranilate and methyl bromo- acetate when treated with sodium nitrite and concentrated hydrochloric acid gives methyl p-nitroso-o-carbomethozyphenylglycine NO*C,H,(C0,Me)*NH-CH2*C0,Me green needlee m. p.164-165'. Ethyl p-nitroso-o-carbethoxyphenylglycine prepared in an analogous manner has m. p. 131' (decomp.). By heating met'hyl anthranilate with ethyl bromoacetate ethyl o-carbomethoxyphenylglycine m. p. 48O was obtained ; this could be further converted in the usual manner with sodium nitrite into ethyl p-nitroso-o-carbomethoxyphenplglycine green needles m. p. 125' (decomp.). I n a similar manner ethyl p-nitroso-o-carboxyph8nylgl?/cine green needles m. p. 115-116' (decomp.) mas obtained ; this substance when treated in hydrochloric acid with oxidising agents gave with aniline and e t h j laniline bluish-black precipitates and with P-naphthyl- amine a reddish-brown substance ; with benzyl and nitrobenzyl cyanides in alcoholic solution containing sodium methoxide con- densation occurs to yellow azomethine compounds ; the action of sodium methoxide solution itself on the nitroso-ester causes the separation of a yellow substance possibly the sodium salt of ethyl nitrosoindoxylcarboxylate.Methyl o-carboxyphenylglycine is most conveniently prepared byORGANIC CHEMISTRY. i. 173 boiling together in aqueous solution for one hour potassiuni anthranilate and methyl chloroacetate ; the action of sodium nitrite and concentrated hydrochloric acid causes its conversion into methyl p - n ~ l r o s o - o - c a r b o x ~ p ~ 6 n y ~ g ~ y ~ ~ ~ ~ e a green solid m. p. 115 -1 16'. D. F. T. Proof of the Chemical Isomerism of allo- and isoCinnamic Acids.HANS STOBBE and CURT SCEONBURG (Annalen 1913 402 187-259).-Whether GcZEocinnamic acid m. p. 6S0 isocinnamic acid m. p. 58O and isocinnamic acid m. p. 42' are three chemically different isomeric compounds or three modifications of one chemical individual is a problem of very old standing. Since the results of numerous investigations of the physical properties of the three acids lead to the coiiclusion'that they are different in the solid state but alike i n the fluid (dissolved or fused) state Biilmann's theory that the three acids are three modifications of one trimorphous (cis-)cinnamic acid might be accepted were it not for a few observations of Liebermann and of Stobbe which cannot be brought into harmony with the theory.Stobbe in particular advances reasons for his belief that two chemi- cally different isomeric acids exist namely the monomorphous aZlo- cinnamic acid m. p. 6S0 and the dimorphous isocinnamic acid m. p. 58' and 42' (A. 1911 i 859). On the contrary Meyer (A. 1911 i 975) supports Biilmann's theory The objects of the present investigation are to find an explanation of the discordant experimental results obtained by Meyer and by Stobbe (Zsc. cit.) and evidence in favour of one or other of the two theories. h sufficient proof of the chemical isomerism of the three acids mill be obtained if i t can be shown that (i) the acids exhibit differences in the fused or dissolved state; (ii) unlike mixtures of two acids in the fused or dissolved state can be prepared and (iii) regularities obtain during the transformations of the acids.The precautions which must be observed during the manipulation of the acids are emphasised; also i t is essential that the 68O-acid be crystallised from petroleum b. p. 30-33' as well as from water. Evidence of (i) is obtained as follows Saturated aqueous solutions of the 68'-acid prepared at temperatures not exceeding 30° are heated for seven hours a t 3 5 O 55O and 70" in elongated closed glass tubes. The tubes are cooled and after crystals have been deposited each tube is inverted and the m. p. of the damp acid is observed; the tube is then opened in a desiccator and the m. p. of the dry acid determined in the usual manner. Similar experiments are performed with saturated solutions of the 68O-acid in petroleum b.p. 30-33". The results show that the 6So-acid is always obtained from the solutions which have been heated only at 35' but from solutions which have been heated at 56' or 70° generally the 6B0-acid occasionally the 42'-acid never the 58'-acid is obtained. Experiments on the 42O-acid under the same conditions show that the 42O-acid is always obtained from aqueous or petroleum solution. I n a second series of experiments solutions of the 68'-acid in petroleum (b. p. 30-33') of different concentrations are shaken fori. 174 ABSTRACTS OF CHEMICAL PAPERS. half an hour at 35' in a closed vessel (shaped like a three-limbed star- fish) to ensure solution of all crystal seeds. The solution is then collected in one limb and the solvent is distilled at 35' into a second limb.The m. p. of the residue which is crystalline a t once or becomes so after short cooling is determined by immersing the limb in water a t 45O 60° or 70'. The residue is thus found always t o consist of the 68O-acid. Similar experiments on the 42O-acid show that the 42O-acid is always obtained. The results of seventy experiments by the two preceding methods prove that the stable 68O-acid and the metastable 42O-acid in the absence of crystal-seeds can be crystallised unchanged the former however only with certainty when the temperature during the process of solution and during the subsequent heating of the solution does not attain to the rn. p. of the acid or to the m. p. of the acid depressed by the solvent (in other word@ when fusion of the 68O-acid is avoided ; if this occurs the 42O-acid may be produced) Consequentfly each acid retains its individuality in solution under definite conditions and the two therefore are chemical isomerides.Evidence of (ii) cannot be ohtained by an examination of mixtures of the fused 68'- and 42'-acid because the composition of the mixture is uncertain owing t o the ease with which the fused 68O-acid changes t o the 42O-acid. However when a solution of the 42O-acid in petroleum is mixed with increasing quantities of a petroleum solution of the 68'- acid in the t hree-limbed vessel with the necessary precautions against inoculation by crystal-seeds the residue obtained by the distillation of the solvent a t 3 5 O has always rn. p. 42" until the amount of 68O-acid in the mixed solutions has been increased to about 3.5%; then the residue has m.p. 68'. Consequently the relative quantities of the components in the solution determine the character of the solutes and of the residue obtained by evaporation. Once again it is thus shown that the 68O-acid and the 42O-acid are not identical in the fluid state and are therefore chemical isornerides. The fact that the residues obtained by the evaporation ef the mixed solutions always have m. p. 42' or 68' is explained as follows. The residues must be solid solutions of khe two acids because it is known that a heterogeneous mixture of the 42'- and 68O-acids is incapable of prolonged existence. When the solid solution contains about 3.5% or more of the 68'-acid i t is super- saturated with respect to this acid ; solid 68O-acid separates and converts the remaining saturated solid solution entirely into the 68O-acid.When the solid solution contains less than about 3.5% of the 68O-acid t h e mixed crystals are more stable and heterogeneity occurs only after some .possibly a long time when owing t o the spontaneous change 42O-acid -+ 68'-acid so much 68O-acid has been produced that the limit of miscibility is exceeded. Solid solutions of the two acids containing less than about 3.5% of the 68O-acid all have m. p. 42O because the small amount of the 68O-acid present produces no or only an inappreciable depression of the m. p. A crystal having m. p. 42O therefore may be either the pure 42O-acid or a solid solution containing not more than about 3.5% of the 68O-acid ; the more nearly this percentage of 68O-acid is present the more readily will the *' 42O-acid " change to the 68O-acid.I n thisORGANIC CHEMISTRY. i. 175 manner an explanation is found of the conflicting statements of Liebermann Biilmann Stobbe and others regarding the " life " of the '* 42O-acid " a t the ordinary tamperature. The same considerations also serve to account for Stobbe and Reuss's remarkable observation (A. 1911 i 859) that the velocity of transformation of the solid 42O-acid into the 68'-acid increases as the temperature falls ; since the solubility of the solid 68O-acid in the solid 42O-acid decreases as the temperature falls the mixed crystal must the more readily become heterogeneous the lower is the temperature.Evidence in support of (iii) above has also been obtained. A systematic investigation of the conversion of the fused 68'-acid into the 42O-acid has hitherto not been undertaken Biilmann attribntes the transformation to the mere process of fusion (A 1909 i 382) whilst Liebermann ascribes the frequent failure of the transforma- tion to a certain sluggishness of the 68O-acid. Now if the two acids are isomeric the transformation must depend on the time of fusion and on the temperature of superheating. To ascertain the effect of the time of fusion a large number of closed capillary tubes containing a little 68O-acid are heated at 70' for periods varying from 0.5 to sixty minutes. The result of 500 experiments shows that the longer the time of heating the greater is the number of cases in which the 42'-acid is produced. (The contents of a capillary tube after fusion do not form a coherent liquid but a number of short liquid columns separated by air spaces ; after the contents have solidified it is not uncommonly observed that in one and the same tube some of the columns have m.p. 42O and others m. p. 68O.) The effect of super- heating is exhibited in 625 experiments similar to the preceding in which the capillary tubes are heated at 70' loo' l l O o 130' or 150'. The percentage number of cases in which the 42O-acid is produced increases with the temperature and reaches 100% when the tubes are heated a t 130' for not less than two minutes. It is noteworthy that in no case has the 58'-acid been obtained. Since Meyer claims t o have obtained 42'-acid 58'-acid and 68'-acid by the solidfication of fused 42O-acid (A 1911 i 975; 1912 i 32) 175 experiments have been performed with the 42O-acid for different periods of heating and at temperatures from 45' to 130° but in no case has any acid other than the 42O-acid been obtained. The acids m.p. 42' obtained in the previous experiments are not all identical substances because some of them can be kept unchanged for a year,whilst others change to the 68O-acid a t the ordinary temperature after a few minutes or hours. They are in fact solid solutions of the 42'-acid and 68'-acid like those obtained by the evaporation of the mixed solutions in petroleum (see above). According to the results of those experiments the least stable '' 42O-acids " are those which contain the greatest amount (up to about 3.5%) of the 68O-acid.So also in the preceding experiments on the heating of fused 68'-acid i t is proved that the most stable ' L 42'-acids," that is the solid solutions containing the smallest amounts of the 68"-acid are those which have been prepared by heating the fused 68'-acid for the longest periods and at the highest temperatures. The proof is obtained by ascertaining the maximum amount of 68O-acid which can be added to the 42'-i 176 ABSTRACTS OF CHEMICAL PAPERS. acids" without changing the m. p. A second method of proving the same point is based on Stobbe and Reuss's observation that the change of the 42O-acid to the 68O-acid proceeds rapidly a t low tempera- tures (Zoc. cit.). The " 42O-acids " obtained from the fused 68'-acid in the previous experiments are kept a t - 14' for periods varying from 5 to 600 minutes and the m.p.'s are then determined. The results of 110 such experiments show once again that the 68O-acid is obtained most frequently and in the shortest times from those ''42'-acids" which have been obtained by heating the fused 68'-acid for short periods at the lower temperatures (70' and llOo) and which therefore are the solid sdutions containing relatively the greatest amounts of the 68O-acid. Experiments similar to the preceding at - 14O have been performed with "42'-acids" after recry stallisation from water. Such recrgstallised acids behave like the " 42O-acids " obtained from the longest and most highly superheated 68O-acid fusions that is they are solid aolutions contaiuing very little 68O-acid.Biilmann and also Liebermann have observed (Zoc. cit.) that the change liquid 68'-acid -+ 42'-acid depends also on the amount of substance employed. This observation has been confirmed by heating portions of 10 25 or 50 mg. of the 68O-acid a t 70" for varying times and determining the m. p.'s of the solidified products After short heating the 68' is recovered by longer heating " 42O-acids " of varying stability are obtained and the change proceeds more slowly the greater is the quantity of material employed. I n this investigation the formation of the 58O-acid was first observed i n the following series of experiments. Crystalline 42'-acid prepared from the fused 68'-acid is invariably converted into the 68O-acid by keeping at - 75" for two minutes; the same result is obtained with 42O-acid crystallised from aqueous solution.Amorphous '' 42'-acids,'' prepared by heating the 68O-acid for five minutes a t l l O o or for thirty minutes a t 130° solidifying re-fusing at 45' and finally cooling to - 75' yield sometimes the 68O-acid or the 58'-acid or the 42'-acid and occasionally in one and the same capillary tube mixtures of any two or even of all three acids. The results in general are similar to those obtained at - 14O with the very important difference how- ever that the 58O-acid makes its appearance. The presence of 58O-acid in the '' 42O-acids " is due to the spontaneous change of the 42'-acid to the 58O-acid (see below) and its separation from the solid solutions at -75' is due like that of the 68'-acid to the decreased solubility of the 58O-acid in the 42O-acid at low temperatures.The fact that the 58O-acid is produced by the strong supercooling of amorphous but not of crystalline "42'-acids" is in complete agreement with the observations of Stobbe and Renss (Zoc. cit.). The proof that the 58O-acid is a chemical individual different from but isomeric with the 68O-acid and the 42"-acid has been established by the same methods as those employed above in the case of the 68'- and the 42'-acids and t o avoid repetition only the results of the numerous experiments will he recorded. The 58O-acid retains its individuality in solution in water or petroleum and can be crystallised therefrom unchanged provided that the solution has not been heatedORGANIC CHEMISTRY.i. 177 to a temperature at which fusion of the 58O-acid occurs. Determina- tions of the m. p.’s of the residues obtained by the evaporation of mixed solutions of the 58’- and the 68O-acidg show that the residues having m. p. 58’ may be either the pure 58O-acid or solid solutions (of the 68O-acid in the 58O-acid) having m. p. 5S0 (denoted by “58O-acid”). In such solid solutions the maximum percentage of the 68O-acid is about 4 (certainly greater than the maximum solubility of the 68O-acid in the ‘‘ 42O-acids ”) ; when this maximum is exceeded heterogeneity occurs and 68O-acid separates and converts the residual caturated solid solution into the 68O-acid. Since therefore the 58O-acid forms with the 68O-acid fluid mixtures and solid solutions different from those produced by the 42*- and the 6S3-acids the 58O-acid must be isomeric with the 42O-acid and all three acids are isomeric with one another. This conclusion is supported by the facts that the “ 58O-acids ” change into the 68O-acid rapidly at low temperatures and the velocity of the change a t - 75’ is smaller than that of the “ 42O-acids.” It has long been known that the 58O-acid changes into the 42O-acid by fusion.This change has been examined with ‘ k 58O-acids ” crystallised from solution and is shown to depend on time and temperature. The higher the temperature and the longer the time during which the “ 58O-acid ” is kept fused the larger is the percentage number of cases (in 657 experiments) in which the “ 42O-acid ” is produced.The k‘42°-acids” thus obtained are not all alike; some can be kept unchanged for years others change to the 58O-acid at the ordinary temperature in a few minutes. The very important observations are made that a “42O-acid” obtained from liquid 58O-acid changes if it changes at all always to the (solid) 5S0-acid whilst a ‘‘ 42O-acid ” prepared from liquid 68”-acid changes if a t all always t o the (solld) 68O-acid. The ‘‘ 42O-acids” obtained from the two different sources are therefore not identical ; a “ 42O-acid ” prepared from the 68O-acid is a bolid d u t i o n of the 42’- and the 6So-acids only whilst a “ 42O-acid ” obtained from the 58O-acid contains 42’-acid 5S0-acid and a very little 68O-acid. In addition to the proof of the chemical isomerism of the 68O- 58O- and 42’-acids the authors draw the following conclusions from the preceding experiments.Since the 5 8 O - and the 42O-acids are meta- stable i t is probable that the two can never be obtained in a pure state; the relative amounts of the components in each are determined by the source and age of the specimens. The 6S0-acid which has the smallest solubility of the three acids can be obtained practically pure provided it is old enough. I n the solid solution representing any ‘‘ 42’-acid,” the changes 42O-acid -+ 68O-acid and 42O-acid -t 58*-acid are continuously although they may be slowly proceeding. In course of time the solid solution becomes supersaturated with one or the other of the 5 8 O - and 68O-acids ; such acid separates and immediately sets up “ internal inoculation ” of the residual saturated solid solution.The effects of such iiiternal inoculation of different types of “ 42O-acids ” are discussed at length. The phenomenon of “ internal inoculation ” is described. VOL. CVI. i. I Li. 178 ABSTRACTS OF CHEMICAL PAPERS. The paper closes with an explanation in the light of the results of the preceding experiments of the discordant observations of Stobbe and Meyer (Zoc. cit.). c. s. Anhydride Formation with Acylaminocarboxylic Acids. GUSTAV HELLER (Ber. 1913 46 3974-3983).-The author has already observed certain cases of anhydride formation with amino- acids (compare Heller and Tischner A. 1910 i 7 7 0 ; 1913 i 365) and now publishes further results in this direction. m-Nitromandelic acid prepared by the cyanohydrin synthesis from m-nitrobenzaldehyde was reduced by ferrous hydroxide to m-aminoman- delic acid,needles m. p.131-132' (decornp.); when treated with benzoyl chloride in pyridine solution this acid gave a benzoyl derivative granular crystals m. p. 178O unaccompanied by any anhydride. I n the action of benzoyl chloride on rn-aminocinnamic acid in sodium carbonate solution the resulting benxoyl derivative needles m. p. 229O is accompanied by an insoluble substance m. p. 148" which appears to be benxoyl -m-aminocinnamic benxoic anhydride NHBz*CGH,*CH:CH*CO~OBz. This reacts readily with phenyl hydrezine giving benzoyl-m-amino- cinnarnic phenylhydraoide crystalline aggregates m. p. 197-1 9 9 O and wit,h sodium hydroxide solution on warming passes into benzoyl-m- aminocinnamic acid.The formation of the mixed anhydride is attributed to the primary formation of benzoic anhydride which then entere into reaction with the second acid. Similarly to the last cam p-awinobenzoic acid with benzoyl chloride in sodium carbonate solution gave benxoyl-p-amilsobenzoic benxoic anhydride NBBz*C,H4*CO*OBz a granular substance which after melting at 128' resolidifies t o re-melt near 210O. When heated with dilute sodium hydroxide solution the subRtance passes slowly into benzoyl- aminobenzoic acid and when mixed with phenylhydrazine in ethereal solution gives a gradual deposition of p-benxoylaminobenxoic phenyl- hydraside leaflets m. p. 248'. In the light of the above results the substance obtained by Heller and Tischner (loc.cit.) by heating benzoyl-p-aminobenzoic acid with acetic anhydride and described as benzoyl-p-aminobenzoic acid cycloid with acetic anhydride of crystallisation is in all probability benxoyl-p- arninobenzoic acetic anhydride ; it does not react with phenylhpdrazine. The action of boiling acotic anhydride on benxoyl-p-aminocinnamic acid (needlea m. p. 274' with decomp.; obtained by benzoylation of aminocinnamic acid in aqueous alkaline solution) for one hour gives benzoyl-p-aminocinnamic acetic anhydride m. p. 149O analogous t o the last substance. It is slowly converted by hot dilute sodium hydroxide solution into the sodium salt of benzoyl-p-aminocinnamic acid and with phenylhydrazine gives no phenylhydrazide. Treatment with excess of benzoyl chloride in pyridine solution converts p-aminocinnamic acid into (polymeric 0) p-1 -benxoyL1C/-ca~bostyril m.p. 385O. When treated with benzoyl chloride and sodium carbonate solution o-aminocinnamic acid gave a n insoluble product m. p. near 2204 which slowly dissolved in hot dilute sodium hydroxide giving benzoyl-p-aminocinnamic acid and gave no phenylhydrazide withORGANIC GHEMISTRY. i. 179 phenyl hydrazine ; the substance was therefore probably benxoyl-o- aminocinnamic benxoic anhydride but was not pure. Benxoyl-m-amino- benxoic banxoic unhydride obtained in a similar manner from m-amino- benzoic acid and benzoyl chloride likewise could not be obtained pure. By heating benzoyl-o-aminocinnamic acid for half a n hour in boiling acetic anhydride it is converted into benxoyZ-o-iiminocin?zamic anhydride needles m.p. 194-195' which when boiled with ,z mixture of acetic and hydrochloric acids slowly gives car bostyril. Treatment of p-aminohydrocinnamic acid with benzoyl chloride in sodium carbonate solution gave rise to the benxoyl derivative leaflets m. p. 194-195' but the product from benzoylation in pyridine solution is a substance 2CI,H,,03N,C,H,N (compare Heller and Tischner Zoc. cit.) m. p. near 240'. D. P. T. The Stereoisomeric Camphanecarboxylic Acids. PH. BARBIER and V. GRIGNARD (BuZI. Soc. chim. 1914 15 26-37).-Having already investigated the liquid pinene hydrochloride t)y nicans of its organomagnesium derivative (compare A. 1910 i 40C) the authors have turned their attention to the solid hydrochloride but although oxidation of the corresponding organomagnesium compound gives satisfactory results (compare Zoc.cit.; also Hesse A. 1906 i 375) the results obtained by treatment of the same compound with carbon dioxide have proved less decisive (compare Houben A. 1906 i 21). The action of carbon dioxide on the organomagnesium derivative of solid pinene hydrochloride prepared by saturatiog an alcoholic solution of pinene at 75-80' with hydrogen chloride and collecting the crystals which separate from the fraction b. p. 80-82O/13 mm. on distillation gave an acid product b. p. 157-158'/16 mm. The original pinene had [aID - 3 5 * 1 7 O and the hydrochloride m. p. 126' [.ID - 21.66'; the resulting dihydropinenecarboxylic acid CloH17*C02H consists of two isomerides the more abundant forming needlep m.p. 76-78' and yielding a dextrorotatory solution in methyl alcohol whilst the other forms needles m. p. 78-80' and is probably identical with the racemic acid mentioned below. Solid pinene hydrochloride prepared by saturating the same pinene in the cold with hydrogen chloride and therefore comparable with the specimen used by Houben gave the lavorotatory acid m. p 73-74" described by Houben (Zoc. cit.) which is doubtless a complex of two stereoisomerideu. The solid hydrochloride obtained from dl-pinene by the former method when treated successively with magnesium and carbon dioxide gave a racemic acid crystallisiag in needles m. p. 78-80'. The two specimens of active acid obtained above give the same anilide needles m. p. 179O and p-toluidide needles m.p. 185'; also when heated alone with alcoholic potassium hydroxide aromatic amines or especially with mineral acids they undergo isomerisation into one and the same lavorotatory acid m. p. 88-89'; the acid m. p. 73-74' is certainly more resistant to this treatment. These results are interpreted as due to the formation of a more Etable geometrical isomeride which is designated the a- or I-camphane- carboxylic acid whilst the less stable form is the p- or d-isocamphane- n 2i. 180 ABSTRACTS OF CHEMICAL PAPERS. carboxylic acid. The acid m. p. 76-78' is considered to be composed mainly of the /I-acid associated with a small quantity of the a-isomeride whilst in the acid m. p. 73-74' the proportion of the a-isomeride is greater. The a- and /3-acids thus possess the property of forming homogeneous crystalline mixtures.Under the influence of isomerising agents the racemic acid m. p. 78-80" or dl-iso- camphanecarboxylic acid undergoes conversion into a stereoisomeric d-Z-cnmyhanecarboxylic acid m. p. 93-94O. From these results i t would appear that under the conditions of the two methods mentioned for the conversion of pinene into the solid hydrochloride a cettain amount of isomerisation similar to the above is effected but it is also demonstrated that such isomerisation can also occur in the organomagnesium compound as already suspected by Houben and Doescher (A 1911 i 61) the properties of the acid product beiug found to vary with differing conditions for the interaction of magnesinm with the hydrochloride.Preparation of Chlorides of Hydroxy-acids. EDUAKD KOPETSCHNI and LADISLAUS KARCZAG (Bey. 1914 47 235-237 ; D.R.-P. 262883 266351).-When the salts of hydroxycarboxylic acids are treated wit,h thionyl chloride (Be?.. and 1st patent) or carbonyl chloride (2nd patent) the acid chlorides are obtained. SaZicyloyl chloride forms white needles m. p. 17-5-18'. m- and p-Hyd~oxyben2oyl chlorides are oils having penetrating odours which do pot solidify a t - 15' to - 20'. GZycolEoyl chloride is a n oil of similar properties. These chlorides are very reactive giving for example with methyl alcohol the corresponding methyl esters of the acids. Preparation of Derivatives of Aromatic Hydroxycarboxylic Acids. RICHARD WOLFFENSTEIN (D.K.-P. 267980. Compare this vol. i 45).-/3/3/3-l'richloro-tert.-butyZ 4-i~ydroxy-m-toEuate prepared by the interaction of ,3/3/3-trichloro-tert.-butyl alcohol and 4-hydroxy-m- toluic acid has m.p. 97'. /3/3P-~richloro-tert.-butyE vanillate has m. p. 1 30° and PPP-tric?~loro-tert.-butyl 1-naphtho1-2-cccrboxyZ~te has m. p. 133'. These compounds have properties similar to those described in the chief patent (loc cit.). R. LESSER and R. WEISS (Ber. 2913 46 3937-3946).-When heated with formic acid tetrachloroanthranilic acid (compare Villiger and Blangley A. 1909 i 922) gives aformyl derivative CO,H* C,CI NH* COH colourless needles m. p. 304-306' soluble in dilute sodium carbonate solution; the product obtained on heating with acetic anhydride is a very pale yellow needles m. p. lactonic compound C6C1,< 198-199* which when heated with aqueous acetic acid becomes hydrated to the corresponding acid tetrachloro-o-acetyZccm~nobenxo~c acid CO,H*C,CI,*NH*COMe needles m.p. 240-241' which easily reverts in the atmosphere t o the original lactone (compare Mohr and Kohler A 1910 i 11 6). Tetrachloroanthranilic acid is only D. F. T. J. C. C. J. C. C. Halogen S u b s t i t u t e d P h t h a l i c and Anthranilic Acids. CO*? N=CMe'ORGANIC CHEMISTRY. i. 181 diiiicultly and iocornpletely diazotisablo (compare Orndorff and Nicholls A 1913 i 99); the solution of the diazo-compound was converted through the xanthate by treatment with chloroacetic acid into tetrachloro-o-carboxyphenylthiolacetic acid CU2H*C6CI,*S*OH2*co2H indistinct crystals m. p. 225' (decomp.); this substance of which the yield was poor gives ' I octacl~lorothioindigo " when warmed with fuming sulphuric acid.The action of bromine in acetic acid solution on isatoic acid gives rise to 3 5-dibromoanthranilic acid colourless needles m. p. 234-235' (compare Dorscb A. 1886 359) which is converted by acetic anhydride into an internal anhydride of the acetyl derivative (compare above) colourless needleg m. p. 174-175' and can be made to pass through the stages diazo-compound and xanthate to 3 5-dibromo- 2-carboxyphenylthiokucet~c acid C02H*C6H2Br2*S*CH,oC~2H colour- less prisms m. p. 186-187' (decomp.). I n the action of excess of bromine in hot acetic acid solution on isatoic acid there is obtained occrtsionally a tribrol72oanthranilic acid colourless needles m. p. 245-246' (decomp.) ; this acid when warmed with ammonia solution gives a red insoluble substance and also gives a crystalline barium salt.When treated with boiling acetic anhydride tribromo- anthranilic acid yields tribromoanthranil needles m. p. 145 -146'. The authors were unable to produce tetrabromoanthranilic acid by the action of bromine on isatoic acid (compare Dorsch Zoc. cit.) but were able to obtain i t by the action of potassium hypochlorite in alkaline solution on tetrabromophthalimide. Tetrabromoanthvanilic acid forms colourless needles m. p. 204-205'; barium Ralt crystal- line ; silver salt amorphous. When heated with acetic anhydride it gives the internal anhydride of the acetyl derivative (see above) needles m. p. 257-2589 It is already known that phthalic anhydride can be converted by the theoretical amoiint of bromine into 4 5-dibromophthalic acid m.p. 208-209'. This substance has now been converted through the imide m. p. 245-246' into 4 5-dibromoanthranilic acid colaur- less needles m. p. 228-229' (decomp.) ; barium salt needles ; calcium salt needles ; silver salt amorphous and insoluble; the internal anhydride of the acetyl derivative forms microscopic needles m. p. 184-185'. The diazotised solution of 4 5-dibromoanthraoilic acid slowly deposits colourless needles of the diazo-compound ; when boiled with alcohol and dilute sulphuric acid respectively the diazo-solution gives rise to 3 4-dibromobenzoic acid needles m. p. 234-235' and to 4 5-dibromosaZicylic acid m. p. 217-218' qrobably identical with the isomeric .acid of unknown constitution (Hubner A.1578 148). The diazo-compound was also converted through the xanthate by means of chloroacetic acid into 4 5-dibromo-2-carboxyphenylthiolacetic acid C02H*C,H2Br2*S-CH2-C02H needles m. p. 240-241' (decomp.). I n one experiment on the bromination of phthalic anhydride a n exceptional result was obtained in the formation of another dibromo- phthalic acid needles m. p. 194-195'; anhydyide needles m. p. 152-153' ; imide small rods m. p. 280-281'. 3 6-Dichloro-4 5-dibromophthitlic acid is already known ; itsi. 182 ABSTRACTS OF CHEMICAL PAPERS. anhydride m. p. 269-270° can be converted into the irnide yellow needles m. p. 362-364' which on treatment with alkaline sodium hypochlorite gives 3 6-dichloro-4 5-dibromoc~nt~ranilic acid colourless needles m.p. 193-194' (decomp.); barium salt small rods ; the anhydride of the acstyl derivative C9H302NC12Br2 forms needles m. p. 213-214". Isomeric Phenylphthalimides and Some Allied Compounds. 111. MITSURU KUHARA SHTGERU KOMATSU and ROEUHACHI NISHIYORI (Mem. Colt. Sci. Eng. ILy6t6 1913 5 343-363).-1n an earlier paper (A 1911 i 205) i t was shown that a mixture of a phthalamide with a colourless normal and a yellow unsymmetrical phthalimide results when phthalyl chloride reacts with an aromatic primary bass a t a low temperature. To account for this it was assumed that the chloride exists as a mixture of the two forms at the temperature of experiment. Pitwlewski (A. 1895 i 134 414) and Dobrev (A 1895 i 360) pre- pared the nitrophenylphthalimides but they obtained different substances.It is now shown that Pawlemski had isolated the white symmetrical compounds whereas Dobrev had obtained the coloured as-isomerides. Both compounds are formed in the same operation according to the above viems. The as-nitrophenyiphthalimides were also obtained by the action of acetyl chloride on the nitrophenyl- phthalamic acids They are more soluble in alcohol than their isomerides into which they are transformed by mineral acids. The three nitrophenylphthalamic acids give coloured soliitions in alkalis those obtained from the 0- and p-nitro-compounds being deep orange-red whilst the meta-derivative gives a yellow solution. The ortho- and para-salts are therefore represented by the quinonoid formula CO,K.C,H,*CO*N UGH4 NO-OK whilst the meta-salt is derived from the enolic form of the acid and is represented by C0,K*C,H,*C~OK):N*C,H4*N02. The behaviour of the phthalamic acids a8 pseudo-acids was investigated by the preparation of a number of salts. A t low temperatures disilver sa1t.s were obtained from which dimethyl esters were prepared. ALI ethereal solution of o-ni troaniline reacted with phthalyl chloride on warming and gave as-o-?titswophenylphthulinzide The acid was not diazotisable. D. F. T. v6H4-y :N* C,H,*NO co-0 canary-yellow needles m. p. 152-153' the s-isomeride white m. p. 1 98-200° and o-nitropheny?phthalamide pale yellow lustrous cryst.als m. p. 187-189' (probably identical with Pawlewski's o-nitrophthalanilide). as-p-Nitrophenylphthalimide m.p. 191 -1924 and the as-?n-derivative m. p. 234-235' were identified wit,h Dobrev's compounds and the symmetrical isomerides with Pawlewski's. Disilvey phthakc6mate CO,Ag*C,H,*C(OAg):N H was obtained by adding silver nitrate (2 mols.) to ammonium phthalamate at - 5' as a white precipitate. It reacted with methyl iodide and the oily ester gave ammonia on hydrolysis. Ammonium phenyl phthalamate was ? C,H,( CO*NH*C,H NO,) 2 .ORGANIC CHEMISTRY. i. 183 converted into the silver disilver barium and lead salts the last three being derived from the acid in its enolic form. Pinzethyl phenylphthalamate CO,Me*G,H,*~(OR/le) NPh was obtained in plates m. p. 90' which were hydrolysed to aniline and phthalic acid. Silver and disilver salts of m- and p-tolylphthalamic acids; silver and disilver salts of m-xylylphthalamic acid ; a silver and orange lustrous dipotassium salt of o-nitrophenylphthalamic acid ; a silver and yellow lustrous scaly dippotassium salt of m-nitrophenylphthalamic acid ; and a silver and lustrous orange-red dipotassium salt of p-nitro- phenylphthalamic acid are described.Most of these phthalamic acids were discovered by Tingle and Rolker (A. 1909 i 28). Isomeric Phenylphthalimides and Some Allied Compounds. IV. h!fITsuRu KUHARA and SHIGERU KOMATSU (Mern. toll. 8 c i . Eng. KyGt6 19 13 5 363-366).-Phthalyl chloride has been condensed with 4-nitro-m-toluidine and with 6-nitro-o-toluidine and three J. C. W. products isolated in each case (compare preceding abstract). as-4-Nitro-m-tolyZphthaZimide %H4'F):N* c6H'Me'No2 forms canary- co-0 yellow needles m.p. 156-158' ; the symmetrical isomeride crystal- lises in white needles m. p. 180-18 I ' and 4-nitro-m-tolylphthalamic acid gives alkaline solutions which are orange-yellow when cold and orange-red when hot. The eilver salt was annlysed. as-6-Nitro-o- tolylphthalimide forms yellow needles m. p. 183-184' 231-232' after solidification ; the symmetrical compound has m. p. 231-232' and 6-nitro-o-tolylphthcclamic acid forms yellow crystals and a silver salt. Condensation Products of Phthalic Anhydride with m- and p-Aminobenzaldehyde and their Derivatives. P. GELMO (J. pr. Chem. 191 3 [ii] 88 810-828).-m-Aldehydophenylphthalimide C,H,:C,O,:N*C,H,*CHO prepared by heating phthalic anhydride with anhydro-m-aminobenzaldehyde at 150° crystallises in lustrous white felted needles m.p. 177' (corr.j and forms a phenylhydraxone crystallising in small yellowish-white needles which become brown and decompose at about 224'; the oeime forms lustrous white leaflets m. p. 212O (decomp. corr.). When heated with aqueous alkali hydroxides it is hydrolysed to m-aminobenzaldehyde and phthalic acid ; wit'h aqueous sodium carbonate containing a little sodium hydroxide i t yields m-aldehydopheny!phthaZamic acid CO,H*C,H,*C@ * N H* C,H,*CHO. This crgstallises in flat yellowish-white needles m. p. 157' (decomp. cow.) and yields a phenylhydraxone as a light yellow crystalline powder m. p. 2 16-217' with previous darkening and decomposition at 207' ; the oxime cryst'allises in small yellowish-white leaflets which begin to decompose at 130° m.p. 177-178'; the salts with the alkali-metals together with the barium calcium zinc and silver salts are readily soluble in water. J. C. W.i. 184 ABSTRACTS OF CHEMICAL PAPERS. p-Aldehydophenylphthalimide prepared from phthalic anhydride and p-aminobenzaldehpde at 1 60° forms yellowish-white clusters of broad needles m. p. 202' (corr.) and resembles the meta-isomeride in being readily hydrolysed by strong alkalis to phthalic acid and the original arninoaldehyde thephernylhydraxone crystallises in long slender citron- yellow needles m. p. 235-236" with previous darkening and decomposition a t 225' ; the oxime forms yellowish-white leaflets m. p. 227' (decomp. corr.}. It is hydrolysed by aqueous sodium carbonate t o p-aldehydophenylphthcclamic acid This forms a citron- yellow crystalline powder m.p. 139-140O (decomp.) and yields a deep orange phenylhydrazone which begins t o decompose at 210° m. p. 231-233' ; the oxime crystallises in yellowish-white needles m. p. 176" with previous decomposition at 170". F. B. Preparation of Dia,nthraquinonylaminecarboxylic Acids. BADJSCHE ANILIN- & SODA - FABRIK (D.R.-P. 2682 19).-Dianthraquin- onylaminecarboxylic acids are prepared by heating halogen- or amino- anthraquinonecarboxylic acids with amino- or halogen-anthraquinones respectively in a solvent of high boiling point in the presence of a catalyst such as copper and an oxide or salt of the alkaline-earth metals Examples are given illustrating the preparation of a dianthraquinon ylaminecarboxylic acid from 1 -chloroanthraquinone-2- carboxylic acid and 1-aminoanthraquinone or alternately from 1-aminoanthraquinone-2-carboxylic acid and 1-chloroanthraquinone of 2 2'-dianthraquinonylamine-3-carboxylic acid from 2-chloroanthra- quinone-3-csrboxylic acid and 2-aminoanthraqninone and of 2 1'- dianthraquinonylamine-3-carboxylic acid from 2-aminoanthraquinone- 3-carboxylic acid and 1 -chloroanthraquinone.J. C. C. Constitution of Naringenin. Phloroglucinol Esters of Phenol- carboxylic Acids. ADOLF SONN (Ber. 191 3 46 4050-4059).- Will (A. 1885 i 906; 1887 i 715) supposed naringenin to be a n ester compounded of phloroglucinol and p-coumaric acid whereas Tutin (T. 1910 97 2054) from analogy t o eriodictyol and hesperitin assumed that i t has a ketonic structure. The ester from the above phenol and acid synthesised by Fischer's method is not identical with naringenin which indirectly supports the alternative constitution. p-Coumaric acid was prepared by Perkin's reaction at 175' in an open vessel pressure being unnecessary.It was dissolved in N-alkali treated with methyl chloroformate in a freezing mixture and then the solution was acidified when p-rnelhylcarbonatocinnamic acid C0,Me*O*C6H4*CH:CH*C0,H separated. It crystallised in thin prisms from acetone m. p. 198-199'. The chloride CllH904Cl formed white silky prisms or needles m. p. 337-138" from which the anilide was obt.ained in pearly leaflets m. p. 165-166' which yielded p-cournarundide thin lerrflets m. p. 202' when hydrolysed by dilute sodium hydroxide.Phloroglucinolcarboxylic acid was digested with N-sodium hydroxide (2 mols.) and then treated with the above p-methylcarbonatocinnamoyl chloride in acetone. The solution was acidified poured into water and the crude product treated with cold N-alkali (3-4 rnols.) when the carbonato-group was hydrolysed. OnORGANIC CHEMISTRY. i. 185 acidifying the deep yellow solution p-coumaroyZphZorogZucinolcarboxyZic [4(or 2)-p-coumaroyloxy-2 6(or 4 6)-dihydroxybenxoic] acid OH*C,H,*CH CH*CO*O*C,H,(OH),*CO,H was isolated. It crystallised with 1$H20 1n long thin needles m. p. 194' and gave fa deep violet coloration with ferric chloride. It was converted into p-coumaroyZphZorogZuc~noZ [ 3 5-dihyd~oxypAenyl p-coumarate] OH C,H,-CH C H* CO* 0 C,ET,( OH) by heating in vacuum at 200-220'.A yellow indefinite powder m. p. about 200° mas thus obtained almost insoluble in benzene whereas naringenin forms well-defined crystals m. p. 248' and is soluble i n benzene. Similar phloroglucinol esters of the p-hydroxy benzoic acid derivatives were also prepared. p-Methylcarbonatobenzoylphloroglucinolcarboxylic acid was obtained from p-methylcarbonatobenzoyl chloride (E. Fischer A. 1908 i 892) and hydrolysed by cold sodium hydroxide to p- h ydroxy henxoylp hlorog Zucino Zcar box y lic [ 4( or 2 ) - p- hy droxy benzo y Zoxy - 2 6(or 4 6)-dihydroxybenzoic] acid OH*C,H,*CO*O~C,H2(OH),*C0,H. The latter crystallised in thin tufted needles m. p. ZlS' and gave a deep violet-red coloration with ferric chloride. When maintained for a short time in vacuum above its melting point it yielded p-hydroxybenxoylph ZorogZucinoZ[3 ; 5 -dih ydrox?l;lhenyZ p- h y d ~ o x y benzoate] OH*C,H,*CO-O*C,H,(OH) which was obtained in white moss-like masses of needles m.p. 218'. p - Coumaric acid was also reduced t o @-p-h y d roxy ph enyl propionic acid and the crude ethereal extract of the latter was condensed as above with methyl chlorocnrbonate. /3 - p - illethylcarbonntophengz- propionic acid CO,Me* 0. C,H,*CH,* CH,*CO,H forms thin glistening tablets m. p. 86-87O. The crude chloride was condensed with phene- tidine in the cold. The phenetidide C19H2105K crystallised in prisms m. p. 142-1 43' and was hydrolysed to @-p-hydroxyphenyl~opiorto- phenetidide OH*C,H,*CH,*CH,*CO*NH*C,H,*OEt which formed thick prisms m. p. 175-176'.The above chloride was also condensed with glycine in the presence of the theoretical amount of N-alkali hydroxide. The colourless oil obtained on acidifying was extracted with ether and hydrolysed by cold alkali and finally @-p-hydroxy- pheny Zpropion yZgZ ycine OH*C,H,* CH,*CH,*CO*N fl CH CO H was obtained iu glistening prisms from hot water m. p. 179'. It may be a constituent of normal urine since P-p-hydroxyphenylpropionic acid is. J. C. W. Oxides and Isomerides of Trithiobenealdehyde. 0. HINSBERG (J. p r . Chem. 1913 [ii] 88 800-810).-Baumann and Fromm (A. 1890 25) have shown that trithiobenzaldehyde exists in two isomeric forms termed p- and y-trithiobenzaldehydes which are considered to be stereoisomerides of the cis-trans-ty pe. By the successive oxidation of the @-form with hydrogen peroxide and reduction with hydriodic acid the author has obtained a third isomeride which he terms 6-trithiobenzaldehyde.The new isomeride is converted into the @form by crystallisation from glacial acetic acid benzene or chloroform. The author suggests t h a t the p- and S-forms are sulphur isomerides of the same type as the a-.and P-trimethylene sulphides (compare A,i. 186 ABSTRACTS OF CHEMICAL PAPERS. 1913 i SlS) whilst the /3- and y-forms are to be considered as cis-trans-isomerides. The different behaviour of the P- and y-forms on oxidation is however difficult to reconcile with this view ; on oxidation with hydrogen peroxide P-trithiobenzaldehyde is converted into a tetroxide belonging t o the &series whilst the y-isomeride gives rise t o a pentoxide.Further both the 8-tetroxide and y-pentoxide on oxidation with potassium permanganate yield the same trisulphone. 6- Trithiobenxaldeh yde tetroxide ( F- tribenzylidenedisuZphoxid~sulphone) CHPh<SO~CHPh>~~2 prepared by oxidising P-trithiobenzaldehyde with hydrogen peroxide for several days at the ordinary temperature in glacial acetic acid solution cry stallises in slender colourless needles m. p. 256-257' (decomp.) but slowly decomposes on pro- longed heating at 130-140'. When kept in contact with hydriodic acid (D 1.96) for several days it is reduced to &trithiobenzaldehyde which forms a pale brown crystalline powder m. p. 180'. y- Trithiobenzaldehyde pent oxide ( y-tribenz ylidenes21lphoxidedisulphone) C H P h < ~ ~ ~ ~ ~ ~ ~ > S O obtained by oxidising y-trithiobenzaldehyde under the same conditions as given above for the oxidation of the P-isomeride crystallises from glacial acetic acid in small colourless needles (decomp 254") and is reduced by hydriodic acid to /3-trithiobenzaldeh yde. ~ibenxylidenetrisulp~one CHPh<so~.Caph>S02 SO *CHPh prepared by oxidising the S-tetroxide or y-pentoxide with potassium permanganate and sulphuric acid crystallises from ethyl acetate in small needles which are not fused at 300'. It differs from the 6-tetroxide and y-pentoxide in not being reduced by hydriodic acid and in forming a sodium salt which undergoes no change when boiled with aqueous sodium peroxide.Methylation of Ketones. J. D. RIEDEL AKT.-GES. (D.R.-P.266405).-Rlethyl derivatives of ketones aldehydes and esters are readily prepared by reducing the corresponding hydroxyrnethylene compounds with hydrogen by the aid of colloidal palladium as catalyst. Examples are given of the preparatim in this way of 1-methylcyclo- hexan-2-one methylcamphor and ethyl methylacetoacrtate [compare following abstract]. J. C. C. A New Method of M e t h y l a t i o n Methyl Compounds from Hydroxymethylene Compounds. A. KOTZ and E. SCHAEFFER (J. pr. Chem. 1913 [ii] 88 604-640).-The method is only applicable for the methylation of aliphatic and hydroaromatic ketones and esters of ketonic acids. It consists in converting the ketone into the hydroxymebhylene derivative (I) and reducing the latter by means of hydrogen in the presence of eolloidal palladium to the corresponding methyl derivative (IV) SO*CHPh F. B.-q:0 y:0 y o -+ q:0 + -+ -C:CH*OH CH *CH,*OH C:CH CH-CH; (1.) w.1 (In.) (IT. 1ORGANIC CHEMTSTRY. i 187 I t is probable that ketone-alcohols of the type (11) are f'ormed as intermediate products in the reduction and that these readily lose water yielding unsaturated compounds (111) which then undergo further reduction. Evidence in support of this view is furnished by the isolation of a ketone-alcohol of this type in the reduction of hydroxymethylenedihydrocarrone although attempts to reduce P-h;rdroxybutaldehyde which contains the grouping sh?wn in (11) were unsuccossful. On Rccoiiut of their marked acid character the hydroxymethylene compounds often precipitate the palladium from its colloidal solutions and in these cases the reduction cannot be carried out by the usual methods of Pita1 and Skita.The following method however was found to be very serviceable where precipitation of the palladium occurred a methyl-alcoholic solution of the hydroxymethylene com- pound is placed in the absorption vessel and an aqueous solution of palladous chloride (without any protective colloid) caref iilly intro- duced below this solution. On vigorously shaking a rapid absorption of hydrogen takes place and although the palladium is very soon pre- cipitated the reduction is complete provided that only small quantities of the hydroxymethylene compound are employed ; for large quantities successive treatment with palladous chloride in this manner is necessary.The following compounds have been prepared by reduction of hydroxymethylene compounds in this manner or according to Skita'B method. 1 3-I>imethylcycZohexan-2 -one from 3-hydroxymethylene-1 -methyl- cyclohexan-2-one ; methylcyclohexnn-2-one from hydroxymethylene- cyclohexnn-2-one ; 1 4-dimethylcyclohexan-%one from 4-hydroxy- met h j lene- 1 -methylcycZohexan-3-on e ; met hylmenthone 1 -methylcycZo- pentan-2-one and rnethy Icam pbor from the corresponding hydroxy- met hyleue compounds ; rnethy5sothujone ( 1 3 5 - t ~ . i m e t h y l - 2 - i s o ~ ~ o p ~ ~ - CO-y Me A1-cycloiue?ztcn-4-one) CMe< anoil b. p. 103-105°/11 mm. CMe CPrp ' and 229-330° under ordinary memire. The reduction of hydroxyieihy lenedi hydrocnrvone yields hydroxy- CO*CH(CH,*OH)>CH.CMe CH CH methyldihy cl r o c a r vo n e CH Me<CH - a - a which was isolated in the form of i t s benzoyl derirative'(1ustrous crystals m.p. 11 1 O) and methyldihgdroccwvone CHMe<Co'CHMe>CH*CMe:CH CH,-C H a liquid b. p. 226-227O h a v i n i an odour resembling t h a t of menthone (sernicarbnzone m. p. 168O). Hydroxymet hylene cornpounds of diketones and ketonic esters can be reduced by this method but not those derived from esters o€ dicarboxglic acids. OEt*CH:C( COMe)2! and ethyl hydroxymethyleneacetoacetate yield aa-diacetylethane and ethyl methylacetoacetate respectively whereas the hydroxymethylene derivatives of ethyl malonste and etbyl slwcinate do not undergo reduction. Thus ethoxymethyleneacety lacetone,i. 188 ABSTRACTS OF CHEMICAL PAPERS.O€ the ethers and esters of hydroxymethylene compounds only those which are readily hydrolysed by water can be reduced by this method ; the ethyl ethers of ethyl hydroxymethyleneacetoacetate and hydroxy- methyleneacetylacetone being readily hydrolysed by water are quanti- tatively reduced to the corresponding methyl derivatives whilst methoxymethylenecamphor and ethyl ethoxymethylenemalonate which are not readily hydrolysed cannot be reduced. Similar results were obtained in the case of the acetyl derivatives. The reduction of the iron and copper salts aud also the amide imide and anhydride of hydroxymethylenecamphor was investigated but with negative results. On the other hand the chloromethylene derivatives of camphor and ethyl succinate are readily reduced to methylcamphor and ethyl methylsuccinate respectively.The behaviour of acetplacetone acetylcamphor and 4-acetyl-1-methyl- cycZohexan-3-one which in the enolic form have a structure CO-C:CMe*OH similar to that of the hydroxymethylene compounds has also been investigated but no reduction was found to take place; a similar negative result was obtained with the enolic form of dibenzoylacetyl- methane F. B. Influence of the Substituent on the Interaction of Benzene and its Derivatives with Benzoyl Chloride . i n Presence of Antimony Trichloride. B. N. MENSCHUTKIN (J. Buss. Phys. Chem. Soc. 1913 45 1710-1738).-1n preceding papers (1911 and 1912) the author has shown for a number of subdituents the immense influence these exert on the capacity of aromatic compounds of combining with antimony trichloride and tribromide and on the properties of the products of such combination.In order to obtain a greater insight into this influence the in- vestigation has now been extended to a more complex reaction that of benzoyl chloride on benzene and its near derivatives in presence of antimony tri-haloids. This reaction proceeds with less ease than in presence of aluminium chloride and all the experiments were carried out a t 150-155' at which temperature evolution of hydrogen chloride proceeds with moderate rapidity . The tem perat ure -concen tration diagrams of binary systems composed of benzoyl chloride and a number oE aromatic hydrocarbons indicxte in no case the formation of a molecular compound (this vol. i 170). Preliminary experiments were made at 150-155' in absence of antimony tricbloride but only with mesitylene did the reaction hydrocarbon + benzoyl chloride = ketone + hydrogen chloride take place to an appreciable extent and even in this case the velocity was very small.I n the presence of antimony trichloride these reactions proceed readily and give good yields of ketone. The first phase in the reaction consists in the formation of a compound of antimony trichloride with the hydrocarbon 2SbC1,,C6H,R ; this is then acted on by the benzoyl chloride the result being a compound OF antimony chloride with the ketone SbCI,,C,H,*CO*C,H,R which decomposes into i t s constituents at the temperature of the experiment; theORGANIC CHEMISTRY. i. 189 antimony trichloride thus liberated may then react with fresh quantities of hydrocarbon and benzoyl chloride.The total reaction expressed by the equation ArH+ C,H,*COCl+ SbCI = Ar*CO*C6H + HCl + SbCI proceeds to an end and gives results in accord with the equation representing a bimolecular equation the hydrocarbon and the benzoyl chloride being taken always in molecular proportions. The velocity of the reaction varies directly as the square of the concentration of the antimony trichloride. With benzene and its monoalkyl derivatives the velocity con- stants of the reaction in presence of BSbCI and 1SbC1 are as follows 2SbC1,. lSbCI,. - - C6H6 .................. 0'000224 1 0*0000546 1 C,H,Me .............. 0.00272 12 0.00067 12 C6H5Et ............... 0'00466 21 0~00111 20 C6H,Pr ............... 0.0051 23 0,0012 22 - - C&,'C,H,,............ 0 *0052 23 These figures indicRte the great influence of the benzene sub- stituent on the velocity of the reaction The identity of the results for propyl- and isoamyl-benzenes seems to indicate the attainment of a limiting velocity of reaction but the explanation perhaps lies in the marked resinification accompanying the reaction in these two cases. With dialkylbenzenes the results are as follows 2SbC1,. 1 SbCl,. - - C6H6 .................. 0'000224 1 0*0000546 1 p-C:,H,Me ............. 0.00476 21 0 -001 12 21 o-C,H,Me ............ 0'00725 32 0.00176 32 m-C6H4Me,. ........... 0'0178 80 0.00446 81 p-C H,MePr ......... 0 '0089 40 0'0028 40 The influence of the position OF the second substituent is very marked (compare Menschutkin A.1898 i 186 ; 1900 j 335 341 ; de Bruyn and Steger A 1899 i 744) whilst the increasing magnitude of the influence as the size of the substituent increases is peen on comparing the results for p-dimethyl- and p-metbylisopropyl- benzenes. The effect of a third substituent is shown by the following figures 2SbC1,. 1 SbC1,. - - CeH6 .................. 0'000224 1 0.0000546 1 C&f,Me .............. 0.00272 12 0.00067 12 m-C6H4Me ............ 0'0178 80 0.00446 81 1 3 5-C6H,Me ... 0.107 478 0.0266 493 1 2 4-C6H&h?3 ... 0.0316 141 0.00760 139 The constants for 1 3 5- and 1 2 4-trimethylbenzene are in the ratio 3.4 with BSbCl 3.5 for lSbCl and 3.6 for 0.5SbC1,. The constant for mesitylene is lowered from 0.107 at 155' to 0.0049 at 84" when 2SbC1 is taken and from 0.0269 a t 155'to 0.0169 a t 125' and to 0.0059 a t 105' when 1SbC1 is used.i.190 ABSTRACTS OF CHEMICAL PAPERS. I n presence of 2SbC1 the following constants were obtained diphenylmethane 0.0 175 ; diphenyl 0*0035 ; triphenylmethane 0.0030 but in these cases marked resinification and blackening occur. For benzene cblorobenzene bromobenzene and nitrobenzene the constants are in the proportions 1 0.1 0.023 0102. The results of the series of measurements made with each compound are given in full. T. H. P. Synthesis of 2 3-Dihydro xyacetophenone. HEINRICH VON KRANNICHFELDT (Ber. 191 3 46 40 16-4025).-The synthesis of 2 3-di hydroxyacetophenone has been accomplished by the methods of Klages (A 1904 i 45) and Posner (A. 1912 i 453). Incidentally typical derivatives of 2 3-dimethoxybenzaldehyde have been prepared [with M.HAARSMA]. 2 3-Dimethoxy-1-a-hydroxyethylbenzene (Klages Zoc. cit.) mas added to ;t solution of potassium dichromate and sulphuric acid at 30' when the resulting yellow oil was immediately removed by steam. 2 3-Dimethoxyucetophcnone C10H1203 was thus obtained as a n almost colourless refractive mobile faintly smelling liquid b. p. 143-144'/14 mm. The semicarbazone formed white prisms m. p. 166-167' and the oxime crystallised in white glistening scales m. p. 96-97'. The methoxy-gronps were replaced by hydroxyl by heating with hydriodic acid or with powdered aluminium chloride in chlorobenzene. 2 3-Dihydroxyucetophenone (v-ucetocuteclhol) CsHsOq formed dark yellow prisms m.p. 97-98' which gave yellow solutions in alkalis and concentrated sulphuric acid. I t is best purified by the hydrolysis of the acetyl derivative C12H,,0 which crystallises in white leaflets m. p. 109'. The above oxime was also obtained by boiling 2 S-dimethoxycin- numic acid Cl,H120 with hydroxylamine (Posner's method). This acid was obtained from o-veratraldehyde by Perkin's method in white silky crystals m. p. 180-181° which sublime in beautiful needles. The dibrornide forms colourless prisms m. p. 152O and the ethyl ester crystallises in colourless glistening scales m. p. 44-45'. p-2 3- Dimet hoxyphenylpropionic acid C1?H,,O was obtained by reduction in colourless crystals m. p. 63'. l'he chloride is a pale yellow mobile oil b. p. 165-166O/15 mm. and the unilide forms white needles m.p. 106-107'. 2 3-Dimethoxybenzaldehyde was also converted into the bisulphite compound and this was filtered washed with alcohol and treated with a saturated solution of potassium cyanide. On pouring the product into water 2 3-dimethoxymundelonitrile solidified. It crystallised in white microscopic tablets and prisms m. p. 76' and was hydrolysed to 2 3-dimethoxymandelic acid C,H,(OMe)2*CH(OH)*C02H by solu- tion in concentrated hydrochloric acid. This acid crystallises in microscopic white prisms m. p. 93' and forms an acetyl derivative m. p. 114'. The nitrile was also heated with hydriodic acid but the 2 3-dihydroxyphenylacetic acid could not be purified and was there- fore methylated by methyl sulphate and the ester hydrolysed. 2 3-Dimethoxyphenylacetic acid CI0Hl2O4 was then obtained in white needles m.p. 82-43'.ORGANIC CHEMISTRY. i. 191 [With E. ROSSELET.1-Attempts were also made to obtain 2 3-dihydroxyacetophenone by the action of aluminium chloride on guaiacol chloroacetate (compare Fries and Finck A. 1909 i 42)) but rearrangement into the para-position resulted the product being o-chloro-3 4-dihydroxyacetophenone (Mannich and Hahn A. 1911 i 649). The above compound was prepared by heating guaiacol with chloroacetyl chloride and obtair?ed in white needles m. p. 60' (compare Einhorn A. 1903 i 90 and Dzierzgovsky A. 1894 i 74). Creosol chloroacetate (Einhorn loc. cit.) was pre- pared by the same method. When heated to 100" with aluminium chloride i t yields 3 4-dihydroxy-o-tolyl chloromethyl ketone C,H,03Cl which crystallises in almost colourless microscopic prisms m.p. 130° provokes to sneezing and gives dark green colorations with ferric chloride. 3 4-Dihydroxy-o-tolyl methyl ketone 0 H1003 was prepared from the compound by the action of zinc dust in acetic acid. It formed white needles m. p. 168-169' and gave a dark green coloration with ferric chloride. The chloroacetyl group was eliminated from the above chloroacetates and also from p-creosol chloroacetate (Fries and Finck Zoc. cit.) by the action of aniline in cold ethereal solution when w-chloroacetanilide was obtained. J . C. W. Dinaphthgl Ketones and Dinaphthyl Ketimines. A. E. TSCHITSCHIBABIN and S. I. KORJAGIN (J. Buss. Yhys. Chem. Xoc. 191 3 45 1823-1829).-The authors have prepared the three dinaphthyl ketimines by the method given by Moureu aud Mignonac (A.1913 i 873)) and have converted them by boiling with dilute hydrochloric acid into the corresponding ketones which are obtained in good yields. Di-/I-naphthyl ketimine C(C,0H7)2:NH crystallises in white plates m. p. 121*5-122*5O and is a moderately strong base; its hydyo- chloyide and picrate m. p. 230.5-232" (decomp.) mere prepared. a-Nc6phthyl P-nuphthyl ketimhte C(C,,H,),:NH crystallises in hemispherical masses of prismatic needles m. p. 103-104" ; the hydrochloride and picrate m. p. 223.5-225-5' (decomp.) were prepared. Di-a-naphthyl ketimine C(CloH7),:NH forms white prismatic needles m. p. 87-88'; its hydrochloride and picrate m. p. 191-192.5' (decomp.) were prepared.Di-a-naphthyl ketone forms a picmte crystallising in large prisms m. p. 121*5-122'. T. H. P. Benzyl Derivatives of Anthraquinone and 05 Indigotin. M. TSCHILIKIN [with E. PAULSEN] (J ~ u s s . Phys. Chem. soc.,''1913 45 1834-1845).-The author has investigated the interaction of antfira- quinone and phenyl benzyldimekhylammonium chloride in presence of sodium hydroxide and hyposulphite. According to the results of Hole (Fdde Zeitung 1910 244) and of Porai-Koschic (J. Buss. Phys. Chem. Soc. 1910 42 1079) this reaction would be expected to lead to ethers of anthraquinol (oxanthranol) the latter being formed by the reduction of the anthraquinme. The product obtained is however,i. 192 ABSTRACTS OF CHEMICAL PAPERS. analogous to that obtained by Liebermann (A 1882 855) and must he regarded not as an ether of oxanthranol but as an alkyl derivative namely benzyloxanthrone.I n its formation the anthraquinone is first converted into the disodium derivative of anthraquinol which is a red unstable compound and readily undergoes re-oxidation t o ant hraquinone. thus -+ This comDound From this disodium compound <he reaction proceeds ONa CH,Ph OH CH,Ph \/i .\/ /\A/\ /\/\/\ I I/ I I -+ I I/ I1 I \/\/\/ \/\//\/ /'. ..* I1 ONa C1 0 C C C C has the properties ascribed to it by Liebermann (Zoc. cit.),ievi (A. 1885 1140) and Bach (A 1890 1144) and on treatment with concentrated sulphuric acid the >C(CH,Ph)*OH group is transformed into >C:CHPh the compound thus formed having m. p. 117' and not 127' as stated by Levi (Zoc. cit.).I n addition t o beuzyloxanthrone the above reaction gives yellow needles o€ 9-hydroxy-9-benxyl-9 10-dihydroanthracene C(OH)( CH Ph) m. p. 135-136' which Bach (A. 1890,1425) described as 10-hydroxg- 9-benzpl-9 10-dihydroanthracene m. p. 130-140'. The above results throw a new light on the structure of the benzyl- derivatives of leucoindigotin and ethers of indigotin in general as well as on the whole reaction of benzylation which is of great technical interest. That two isomeric leucoindigotins exist may be regarded as indicated by the existence of two diacetyl derivatives to which the author attributes the structures C6H4<-CH 2 > C f 3 H 4 ? and only one tetra-acetyl derivative is known corresponding with the /?-form. Leucoindigotin is assumed to consist of an equilibrated mixture of the ketonic and enolic isomerides corresponding with the above diacetyl compounds the eiiolic modification always being formed in the larger quantity.Etherification by the action of benzyl chloride either alone or in presence of dimethylaniline or by the action of phenylbenzyldimethylammonium chloride (leucotrope) yields only one benzyl derivative for which the constitution is proposed. Evidence such as the identity of this compound with that obtained from the organo-magnesium compound is quoted in support of this structure. T. H. P.ORGANIC CHEMISTRY. i. 193 Preparation of P-Nitro-derivatives of Acyl-p-diaminosnthra- quinones. FARBENFABRIKEN VORM FRIEDR. BAYER & Co. (0.R.-P. 267445).-When 1 4-dibenzoyldiziminoauthr q u i n ~ r l e IS treated wich nitric acid in nitrobenzene suspension a t 90° it yields 2-nitro-1 4- dibenxoyldiaminoanthrapuinone orange needles which on hydrolysis gives 2 - mti-o - 1 4 - diaminoanthraquinone greenish-blue needles.Similarly 1 4-diamiuoanthraquinoneurethane gives 2-nztro-1 4-di- arniikoanthraquinoneurethune orange-red prisms which on h y drol J sis yields the above 2-nitro-1 4-diaminoanthraquinone. The urethane of 1 4 5 8-tetra-aminoanthraquinone yields a 2-nitro-derivative which on hydrolysis furnishes %nit&- 1 4 5- 8-tetra-aminoanthraquinoae. J. C. C. The Constituents of Oil of Calamus. H. THOMS and R. BECKSTROEN (Ber. 1913 46 3946-3948).-The divergence between the results of the authors (A 1901 i 396; 1902 i 809 810) and thobe recently published by Seumler and Spornitz (this vol.i 69) is attributed to the different origin of the samples investigated that of the latter investigators being a Russian oil whilst that of the authors was Japanese. D. F. T. The Constituents of Ethereal Oils. (The Sesquiterpene Fraction of Java Citronella Oil.) P. W. SEMNLER aud K. E. SPORNITZ (Bdr. 191 3 46 4025-4029).-A specimen of the sesquiter- pene fraction of Java citronella oil was freed from methyleugenol by washing with dilute alcohol. It then had the constauts b. p. 153-166'/ 15 mm. D 0,8659 n 1,50386 and the analysis suggested the . presence of some sesquiterpene alcohol. After boiling with sodium followed by several fractionations sespuicitronellene C H24 was obtained ; b. p. 138-140'/9 mm. D 0.8489 n 1.53252 a + 0'36'.The exaltation of the molecular refraction 7453 instead of 69.6 the reduction by sodium and alcohol to inactive dihydrosesquicitronellene C15H26 b. p. 131-133O/12 mm. D 0,8316 ~n 1.4800 and the reduction by hydrogen in presence of platinum to inactive octahydro- sesquicitronellene CI5H3 b. . p. 115-1 17O/Y mm. D 0.7789 n 1.43518 indicate that the oil is an aliphatic sesquiterpene with two conjugated double linkings homologous with the aliphatic terpene ocimene (Eoklaar A. 1906 i 377). cycloSespuicitronelZene C15H249 was obtained by heating the aliphatic oil with concentrated formic acid. It had b. p. 129-138"/15 mm. D2,,- 0.8892 n 1,5069 a,+56'. I t could no longer be reduced by sodium and alcohol but reduction with hydrogen and platinum did not conclusively prove whether the compound is moao- or di-cyclic.The mashed starting material was also ozonised and amonq the products of subsequent hydrolysis was found a parafin C20H38 b. p. 165-167°/15 mm. D 0,8387 n 1.46370. It 1s uncertain whether the substance is a normal constituent or due to sophistication of the citronella oil with petroleum. The above-mentioned sesquitsrpene alcohol C,,H,,O was isolated. It is tertiary contains conj ugitted double linkings and readily submits to ring formation. J. C. W. VOL CVI. i. 0i 194 ABSTRACTS OF CHEMICAL PAPERS Review of the Pioneer Work on the S y n t h e s i s of Caout- chouc. FRANCIS J. POND (J. Arner. Chem Xoc. 1914 36 166-199). -The literature relating to the early work on the synthesis of caoutchouc is reviewed in detail The author bas repeated Bouchardst's experiment but has failed to obtain any product which could be regarded as caoutchouc.E. G. T h e Oleo-resins of Jeffrey and Singleleaf Pines. A. W. of Pinus monophylla contains from 80 to 85% of d-a-pinene; 4 to 5% of I- or i-limonene; 4 to 6% of d-cadinene ; losses by polymerisation etc. 4.5%. The colcphony contains 7.22% of resen and resin acids isomeric with abietic acid. The volatile oil of Pinusjefreyi consists of about 95% of n-heptane and 5% of an aldehyde apparently citronellal. The colophony contains 12.5% of resen and resin acids isomeric with abietic acid. w. P. 8. SCHORGER (J. Ind. Eng. Chew. 1913 5 971-973).-The volatile Oil The Main Constituent of Japanese Lac. IV. Some Derivatives of Hydrouruehiol.RIKO MA JIMA and IKUYA NAKAMURA (Ber. 1913 46 4080-4088. Compare A 1912 i 883). -Further derivatives of hydrourushiol confirm the assumption that i t contains two ortho-hydroxyl groups and a straight hide-chain para t o one of the hydroxyl groups. The nature of this alkyl substituent is shown by oxidation with peruanganate in cold aqueous acetone t o palmitic acid The side-chain should therefore be C15H31 and not C14H20 as was originally 6uggeskd. I n another paper (this vol. i 167) the preparation of 1-tetradecyl- and 1-pentadecpl-3 4-di- methoxybenzenes is described. Unfortunately neither of these products is identical with dimethoxyhydrourushiol although they seem to be nearly related to it. The following derivatives of hydrourushiol are described lead salt ; dibenzoyl derivative colourless needles m.p. 59-60.5' ; di-m-dinitro- benzoyl derivative white spherical tufts m. . p. 93' ; 6romodiacetyZ- hydrourushiol colourless m. p. 35-43' dzbro~~ohydrourucshiol a brown powder m. p. 60-66'. Dirnethoxyhydrourushiol was nitrated and f u i ther derivatives were obtained from the nitro-compounds. Fuming nitric acid in acetic acid solution yielded nitrodinzethoxyhydl.c,~ydroui.ushioZ in long needles m. p. 72-73' which were dissolved in fuming nitric acid aud thus con- verted into a &nitro-derivative which formed almost colourless long flat crystals m. p. 53'. The mononitro-derivative was readily reduced by zinc dust and glacial acetic acid to aminodiinethozyhydrourushiol which yielded small purple granules m.p. 65-66.5'. The white hydyochloride had m. p. 152-153' ; the platinichloride formed slender yellow prisms m. p. 17S0 and the acetyl derivative had m. p. When warmed with a mixture of fuming nitric acid and sulphuric acid it yielded dilz~trornonocccetyEhyd~ourush~o2 which formed colourless needles m. p. 69-70*5' and gave a yellow potassium salt. It was hydrolysed to 66-67' Diacetylhpdrourushiol was very difficult to nitrate.ORGANIC CHEMISTRY. i. 195 dinikohydrourushiol pale yellow needles m. p. 122-1 22.5') and this was converted into the diacetyt derivative pale brown granules m. p. 72-5-73.5'. The analyses of all these derivatives give values which agree with either C,,H or C,,H for the side-chain. On heating hydrourushiol over a free flame or a t 350-400' in a sealed tube only catechol could be isolated from the decomposition products.J. C. W. Synthesis of Picein the Glucoside of the Pine (Pinus picea); New Artificial Glucoside. F. MAUTHNER (J. pr. Chm. 191 3 [ii] 88 764-770).-The gluco-p-hydroxyacetophenone obtained by the condensation of /?-acetobromoglucose with p-hydroxyaceto- phenone and hydrolysis of the resulting tetra-acetogluco-p-hydroxy- acetopheuone (A. 1912 i 574) is now found to be identical with picein the glucoside isolated by Tanret (A 1894 i 616) from the needles of the pine. The preparation of tetra-acetogluco-p-hydroxyacetophenone is best accomplished by t h e gradual addition of aqueous sodium hydroxide to a solution of p-hydroxyacetophenone and P-acetobromoglucose in acetone the temperature not being allowed to rise above 16'.Tetra - acetogluco - p - hydroxybenxophenone C27H28011 . prepared by shaking an ethereal solution of /3-acetobromoglucose with p-hydroxy- benzophenone dissolved in aqueous sodium hydroxide crystallises in colourless needles m. p. 167-168O and is hydrolysed by barium hydroxide at the ordinary temperature to gluco-p-hydroxybenzophenme which forms colourless needles m. p. 178-1779' [a] - 55.58' in alcoholic solution. Methyl tetra-acetogluco-m-hydroxybenxoate C22H26012 prepared from /?-acetobromoglucose and methyl rn-hydroxybenzoate iu acetone solution in the presence of sodium hydroxide has m. p. 114-115' and is hpdrolysed by aqueous barium hydroxide t o gluco-m-hydroxybenxoic mid C13H1608 crys tallising in colourless needles m.p. 143-1 44O [ax - 68.41' in aqueous solution. biCrystallised Rhein" of Commerce. 0. A. OESTERLE and E. R. HAUGSETH (Arch. Phnrm. 1913,25 1,550-552).-" Crystallised rhein " of commerce is insoluble in cold aqueous sodium carbonate and does not contain a methoxy-group and therefore does not contain rhein (1 8-dihydroxyanthraqiiinone-3-carboxylic acid) or emodin methyl ether. Its m. p. is 192' and after recrystallisation from benzene 196O ; its acetyl derivative has m. p. 208'. These constants are those of chrysophanic acid and its acetyl derivative respectively. '' Crystallised rhein," therefore is almost pure chrysophanic acid ; the analytical data correspond with the formula C,,H,&IeO,(OH),. F. B. c. s. Comparative Examination of the Constitution of Tannin from Turkish and from Chinese Gall-nuts.K. FEIST and H. HAUN (Arch. Phcwm. 19 13 25 1 468-526).-A comprehensive survey is given of the chemistry of tannin since its discovery by Scheele in 1787. 0 2i. 196 ABSTRACTS OF CHEMICAL PAPERS. Finely powdered Chinese gall-nuts are dried at 100' and then extracted successively with chloroform benzene and ether. (The last solvent removes a crystalline substance which proves to be gallic acid.) The tannin is then extracted from the galls by means of acetone. The tannin is obtained from the acetone extract as an amorphous powder and yields by hydrolysis with boiling dilute sulphuric acid 93.5% of gallic acid and about 5.5% of dextrose (identified by its reducing properties rotatory power fermentibility and in the form of its OFazone m.p. 205'). Hence tannin from Chinese gall-nuts like that from Turkish contains chemically bound dextrose ; the latter contains more dextrose than the former. Turkish tannin freed as completely as possible from glucogallic acid yields by hydrolysis gallic acid and about 9% of dextrose. Since tannin therefore is apparently a compound (or several com- pounds) of gallic acid and dextrose the most rational method of ascertaining its constitution is an examination of the '' simplest tannio," that is the crystalline substance glucogallic acid which is extracted by ether from Turkish galls after they have been extracted with chloroform and with benzene. Glucogallic acid has a molecular weight about 320 (by titration and by the ebullioscopic method in acetone) and yields about equal molecular quantities of gallic acid and dextrose by hydrolysis with boiling dilute sulphuric acid.By methyl- ation by an excess of ethereal diazomethane glucogallic acid yields a substance m. p. 7' sofltening at 60° yellow crystals which does not develop a coloration with ferric chloride does not reduce Fehling's Eolution even after boiling for a short time contains 49"L of methoxyl and is hydrolysed not by boiling dilute sulphuric acid but by methyl alcoholic potassium hydroxide yielding gallic acid trimethyl ether. Hence in glucogallic acid the dextrose cannot have condensed with the gallic acid at a phenolic hydroxyl group. Glucogallic acid there- fore is an ester of dextrose and gallic acid. The following considera- tions determine a t what point of the dextrose molecule ester formation has occurred.Glucogallic acid reduces Fehling's solution (this does not prove the presence of an aldehyde group because gallic acid con- trary to statements in the literature also reduces Fehling's solution) but does not form an osazone ; moreover methylated glucogallic acid does not reduce Fehling's solution. Hence glucogallic acid does not con- tain a free aldehyde group and therefore has the constitution 1--0- I C,H,(OH),*CO*O*CH*[CH*OH]2-CH*CH(OH)*CH2*OH. It is quite different in its behaviour from Fischer and Strauss's /3-glucosidogallic acid 1 C0,H*C,h',(OH),*O*CH~[CH*OH]2*CH*CH(OH)*CH2*OH. Attempts have been made to synthesise glucogallic acid by means of bromotetra-acetylglucose. I n the first place i t is shown t h a t bromo- tetra-acetplglucose in ether reacts with an excess of silver phosphate or arsenate in the sense of the equation C,H70Br(OAc)4+ AgA = AgBr + C,H70(0Ac),A (where A denotes an acid radicle).Silver triacetylgallate cannot be prepared but by shaking an ethereal solutionORGANIC CHEMISTRY. i. 197 of bromotetra-acetylglucose and triacetylgallic acid with silver car- bonate silver bromide and silver acetate are formed and an amorphous substance is produced which is probably incompletely acetylated gluco- gallic acid ; the evidence for this deduction however is by no means satisfactory. Attempts to acetylate glucogallic acid have been unsuccess- ful as also have been attempts to hydrolyse the preceding amorphous substance both decomposing during the respective operations.By treatment with an excess of ethereal diazomethane Chinese and Turkish tannins hare been converted into methylated derivatives which have been separated into fractions containing different per- centages of methoxyi. This result is regarded as yet another proof of the heterogeneity of tannin. The same conclusion is drawn from the results of an investigation of the rotatory powers in water and in 96% alcohol of various samples of commercial tannin. Although glucogallic acid cannot be extracted from Chinese gall-nuts and is not produced by the hydrolysis of Turkish tannio the authors regard it as highly probable that this acid is the basis of the Turkish and the Chinese tannin molecules. Both are esters of gallic acid and dextrose; in Chinese tannin the percentage of gallic acid is milch greater than that of dextrose.I n agreement with this the molecular weight of Turkish tannin in .acetone is very much smaller than that of Chinese tannin and all the fractions of methylated Turkish tannin contain a greater percentage of methoxyl than the corresponding fractions of methylated Chinese tannin. The fraction of methylated Chinese tannin which is insoluble in cold absolute alcohol is identical with Herzig's methylotannin; it is not an individual substance however its percentage of methoxyl correspond- ing with that required by a mixture of methylated undeca- and dodeca-galloyldextrose. The fraction of methylated Turkish tannin which is Eoluble in cold absolute alcohol is excluding glucogallic acid the only crystalline derivative cf tannin hitherto obtained ; i t again however is not an individual substance but is a mixture of methylated mono- di- and tri-galloyldextrose.c. 5. Combination of Caffeine with Phenols. A. BAUMANN (GIbem. Zentr. 1913 2 2036-2037; from Arb. Pharrn. Imt. U&v. Berlin 10 127-147).-Chlorocaffeine has been condensed with a number of phenols reaction being carried out in the presence of alkali hydroxide in aqueous solution under reflux sometimes at higher temperatures under pressure and sometimes in the presence of xplene. The phenol compound of caffeine CI4Hl4O3N forms needles m. p. 143' which are soluble in concentrated hydrochloric acid without decomposition and are stable towards 15% aqueous sodium hydroxide. The guaiacol compou.nd prepared by heating t'he requisite materials in aqueous solution a t 140° consists of colourless needles of faintly bitter taste m.p. 151-152'. The thymol compound C,8H2203N4 needles m. p. 130-132' is prepared in xylene solution at 155'. With the three cresols in aqueous solution chlorocaff eine yields the 0-cresol compound C,,H,,O,N needles m. p. 150-151" the m-cresol compound needles m. p. 144-145' and the p-cresol compound needles m. p. 138-139Oi. 198 ABSTRACTS OF CHEMICAL PAPERS. The eugenol cornpound C,,H,,O,N consists of needles m. p. 11 9-120° whilst the carvuwol compound needles has m. p. 145-146'. The cntechol-monocaffeine compound [o-hydroxyphenoxycafleine] C1,Hl,O,N crystallises in needles m. p. 215' which are soluble in dilute sodium hydroxide and yield an acztyl derivative CI6Hl6O5N4 needles m.p. 186-1 87". The corresponding di-caffeine compound has m. p. 280-281' and is insoluble in dilute sodium bydroxide. I n a similar manner resorcinol yields a monocaff eine compound needles m. p. 197-198' (acetate m. p. 123-124') and a dicaffeine compound m. p. 288-289'. Analogously quinol gives a monocaffeine com- pound m. p. 206-207' (acetate m. p. 210-211") and a dicaffeine compound m. p. 285". p-Hydroxybenzoic acid likewise condenses with chlorocnff eine to yield the substance Cl,fI,,O,N m. p. 213-244' needles of slightly bitter taste soluble in dilute sodium carbonate solution. o-Hydroxybenzoic acid and methyl salicylate could not be condensed with chlorozaffeine in the presence of alkali whilst hydroxy- caffeine could not be condensed with phenols. The phenol and thymol compounds of caffeine are stable towards boiling coricentrated hydrochloric acid and are not attacked a t 160' by a solution of hydrogen chloride in ether or xylene.They are however decomposed by concentrated aqueous hydrochloric acid a t 160" into pbenol or thymol and hydroxycaffeine. A similar decompo- sition is caused by heating with aqueous more rapidly with alcoholic sodium hydroxide. H. W. Fermentative Decomposition of Creatinine. 11. D. A CKER- MANN (Zeitsch. Biol. 1913 63 78-82. Compare A. 1913 i 1049).- N-Methylhydantoin could not be detected as a product of the decompo- sition of creatinine by means of macerated cat's liver in the presence of toluene. When creatinine is decomposed by putrefactive bacteria for a period of four weeks sarcosine is formed.It is considered that the sarcmine is derived from 117-methylhydantoin but other possibilities of its formation are suggested also X. I?. A. Preparation of Salts of Hgdrastinine and its Homologues. HERMAN DECKER (D.R.-P. 267699. Compare A 1911 i 906).-Salts of hydrastinine and its homologues of the annexed general fornula (R = hydrogen alkyl aryl or alkylaryl ; CH2 X = acidic group) are obtained by con- densing N-acylalkyl derivatives of homo- (). /\/'\CH CH2<O*t INX*Alkyl piperonylamine \/\/ CR CH, 0, c,B,*cH,*cH,*N<~~~ and converting the dibydroisoquinoline derivatives so obtained into their salts. N-Form ylmethylhomopiperonylamine when condensed by means of phosphoric oxide yields hydrastinine ; N-formy lethylhomopiperonyl- amine gives N-ethy lnorhydras tinine (platinichlorids brown prisms m p.1 95-1 97' decomp.) and beneoyl-N-methylhomopiperonyl- amine m. p. 80-81' furnishes 1 -p~~enylAydrastinine which formsORGANIC CHEMISTRY. i. 199 white needles m. p. 152-153' (decomp.). base forms silky needles m. p. 98-99' The picmte of the latter J. C. C. Strychnos Alkaloids. XIX. Some New Oxidation Pro- ducts of Bruoine. HERMANN LEUCHS and HUBERT RAUCH (Be?. 1913 46 3917-3922).-1n addition to brucinonic acid and dihydro- brucinonic acid (Leuchs and Brewster A. 1913 i 210) the oxidation of brucine by potassium permanganate in acetone solution gives rise to a mixture of nehtral substances which amounts to 10% of the brucine used. By a complex process of extraction and reaytallisation with various solvents the amorphous mixture could be made to yield three new crystalline substances.The chief of these appears to have the composition C23H2407N2 and the name trihydroxydehydrobrucine is suggested ; it crystallises in cubes or prisms which are very sparingly soluble in chloroform and benzene and has [u] +87.4' (in hydro- chloric acid D 1.19) and m. p. 336' (decomp.). I t is of interest that the solution in acetic acid exhibits no optical activity The second product which has the composition C,,H,,P,N of a trihydroxybrucine and so is possibly a dihydro-derivative of the previous compound crystallises from benzene solution in needles or prisms m. p. 130-135O (decomp.) which contain benzene of crystallisa- tion; the product recrystallised from water has m.p. 240' (decomp.). I n acetic acid solution the substance has [u] + 5 - 6 6 O . The third substance C,,H,,O,N crystallises from acetic acid in pale green quadratic pyramids m. p. 290' (decomp.) [ag + 72.8' (in acetic acid). All three substances give the well-known colour reaction x i t h nitric acid. D. F. T. Synthesis of Hygrine. 11. Synthesis of Racemic Hygrine. A New Oxidation Method. Further Remarks on the Catalytic Reduction of Pyrrole Derivatives. KURT HESS (Ber. 1913 46 4104-4115. Compare A. 1913 i 1378).-In the former paper an account was given of the preparation of two isomeric 1-methyl- pyrrolidylpropanols one of which should yield hygrine on oxidation to the ketone. Difficulty was then experienced in the methylation of the pyrrolidy 1 derivative.For this purpose formaldehyde has now been employed with the unexpected result that oxidation of the hydroxyl group also took place during the one operation so that almost quantitative yields of the desired ketones were obtained. A comparison of these compounds with hygrine establishes the alkaloid although the resolution of the synthetic substance a i d the rac>matioa of the natural product are yet to be accomplished. Willstatter's assumption (A 1900 i 405) is therefore justified. The oxidation of hydroxy-aminee to amino-ketones (according to the scheme :C*NHR.**CH(OH).** + CH,O = :C*NMeR***CO..* + H,O) seems to be of general application and is the subject of future worki. 200 ABSTRACTS OF CHEMICAL PAPERS.by the author. The preparation of diacetonmet hylamine from diacetonalkamine is now described. a-2-Pyrrolidylpropan-a-01 was acidified with hydrochloric acid and heated with 40% formaldehyde at 115-120' in a sealed tube The CH,*r hle product a-l-met?~ylpyrrolidyI-2-iuroiunne-a-one was dried over barium oxide and obtained as a colourless mobile hygroscopic oil b. p. 70-75"/12 mm. bath 90-95' 69-74'/14 mm. bath 85-90' 80-82'/21 mm. bath 95-100'. I t has a powerful basic and narcotic odoiir is very soluble and gives the pyrrole reaction. It reduces alkaline but not acid permanganate and also silver nitrate and neutral gold chloride but from an acid solution of the latter the auricldoyide was obtained in yellow microscopic needles m. p. 106' (corr.). The oxime C,H,,ON was obtained as a clear syrup b.p. 140'116 mm. which did not form a picrate. The picrate C1,H,,O8NJ4 of the ketone formed long yellow needles which sintered at 95' (corr.) and had m. p. 103' (corr.). Similarly a-2-pyrrolidylpropane-P-ol was converted by formaldehyde in to a- 1 -met?~yZpyr~oZidyl-2-propane-/3-one (formula above) which forms a colourless oil b. p. 79-83'/14 mm. bath 90-looo 89-92'/ 21-22 mm. bath 100-110'. It is not so mobile as the isomeride is not discoloured by light and its poppy-like odour is not so unpleasant. The picrate forms slender yellow needles which sinter at 162' (corr.) and have m. p. 176' (corr.). The picrate from a specimen of natural hygrine with b. p. 79-81'/11-12 mm. bath 90-95' [a];l*2' had m. p. 158' (corr.). The oxime had m.p. 125' (corr,) and the picrate of the oxime agreed exactly with that of the oxime of natural hygrine (Liebermann and Kiihling A. 1893 i 446). Attention is again called to the influence of traces of oxygen on the spongy platinum used in the catalytic reductions. Much better results are obtained when the preparation is not dried in vacuum but is simply wabhed with the solvent which is subsequently employed Admission of air t o the catalyst causes a rise of temperature and cohesion of the finely divided metal. Using spongy palladium as catalyst complete reduction of the pyrryl aloohols t o a-2-pyrrolidyl- propane [2-propylpyrroZidine] C7H15N was effected. This compound is very volatile in steam and could thus be fractionated from the less volatile partially-reduced products.It is a clear mobile narcotic oil b. p. 145-150'/765 mm. Diacetonamine prepared by Heintz's method (A. 1874 1080) was successfully distilled in a high vacuum; b. p. 25'/0*14 mm. I t was reduced by sodium and alcohol to diacetonalkamine (Kahan A. 1897 i 494) b. p. 70- 75'116 mm. and this was heated with 40% formalde- hyde at 115-1 20'. ~iacetonmelhylomine C7H,,0N was then obtained as a colourless mobile very soluble oil b. p. 50-53'/15 mm. It has a peculiar menthol-li ke overpowering odour. A New Method for the Preparation of 1-Substituted Isatine. R. STOLL~ (Ber. 1913 46 3915-3916).-A preliminary account of the formation of 1-substituted isatins by the intra- CH'<CH,*CH*COEt J. C. W.ORGANIC CHEMISTRY. i. 201 molecular condensation of oxalic amide chlorides [chloroglyoxylamides] of the type COCl*CO*NRPh which are obtainable by the interaction of oxalyl chloride and mono-substituted anilines under suitable conditions.C/~l~roglyolc:ylod~p~en~lamide COCl*CO*NPh needles m. p. 70" when treated with water forms diphen$oxamzc acid needles m. p. near 146" (decomp.) and with alcohol produces the corresponding ethyl ester platelets m. p. 87'. If a bimolecular proportion of diphenylamine i p taken with oxalyl chloride the product is OXCdO- dipi~en?/Zaniide plates m. p. 1 6 9 O 'which often accompanies the amide chloride as by-product. The intramolecular condensation of chloroglyoxylodiphenylamide gives 1-phenylisntin which when treated with alkalis is converted into the sodium salt of the corresponding isatic acid ; this regenerates 1 -phenylisatin on the addition of acids.When heated with phosphorus pentachloride phenylisat in gives a dichloro-derivative leaflets m. p 1 00'. Ethylaniline reacts in carbon disulphide solution with oxalyl chloride in the presence of aluminium chloride forming 1-ethylisatin m. p. 95". D. F. T. o-Aminopropiophenone its Acyl Derivatives and Their Condensation to 2- and 4-Hydroxyquinolines. E. WOHNLICH (Arch. Yharm. 1913 25 1 526-550).-o-Nitrop~opiop?~enone b. p. 175"/25 mm. a viscous yellow liquid is obtained i n 42-46% yield by treating a n ethereal solution of o-nitrobenzoyl chloride with a n ethereal suspension of ethyl sodiomethylacetoacetate and hydrolys- ing the resulting ethyl o-nitrobenzoylmethylacetoacetate by boiling dilute sulphuric acid.By reduction with tin and concentrated hydrochloric acid on the water-bath i t is converted into o-amino- pi*opiophenone m. p. 45-46' yellowish-white leaflets from which the following acyl derivatives bave been prepared by the action of the respective acid anhydrides acetyl derivative NHAc*C,H,*COEt m. p. 71" colourless plates; propionyl derivative m. p. 51° stout rhombohedra ; butyryl derivative m. p. 39-40' large rhom bohedral crystals and benzoyl derivative m. p. 130° colourless ueedles. In acordance with Camps' rule (A. 1900 i 115 310; 1902 i 178 336) the preceding o-acylaminopropiophenones except the last yield 2- and 4-hydroxyquinoline derivatives by condensation with the calculated quantity of sodium hydroxide in boiling aqueous alcohol. The 4-hydroxyquinoline derivatives exhibit distinctly basic and acidic properties and develop red colorations with ferric chloride whilst 2-hydroxyquinoline derivatives do not give a ferric chloride reaction and are feebly acidic and basic.Thus o-acetylarninopropiophenone yields IConrad and Limpach's 4-hydroxy-2 3-dimethylquinoline (A. 1892 78) and 2-hydi.oxy-4-ethytpuinoline XI. p. 197" m a l l prisms (hydrochloride long needles ; platinicJ&ride 2C,,H 10N,H,PtCI,,H,O decomp. 199-ZOO" pale yellow needles ; yicrate m p. 149-150° yellow need ies). o-Pro pion y laminopropio phenone yields 4-h ydroxy- 3-me1l~~l-2-ethylpuino2ine m. p. 297" (hydrochloride m. p. 180-1 85" ; NO,*C,H:,*COEt,i. 202 ABSTRACTS OF CHEMICAL PAPERS. picrate m p. 184' yellow needles ; ptatinichboride 2C,,H,,0N,H2PtCI,,2H20 decomp.21 8' [rapidly heated] reddish-yellow needles) and 2-hydroxy- 3-methyZ-4-ethyZquinoZine m. p. 1 88' colourless needles (picrate m. p. 183" ; hydrochloride m. p. 120-1 30'). o-Butyrylaminopropiophenone yields 2-hyd~oxy-3 4-dicsthplquinoline m. p. 174-175' (picrate m. p. 156-1 57' small yellow needles ; platinichloride 2C SH ,ON H,Pt Cl,,H20 m. p. 194-1 95' red needles) and 4-hydroxy-3-methyZ-2-propyZ- puinoline m. p. 275 (picrate m. p. 179'; pZatinic?2oride 2 C,,H,,ON H,PtCI 6 2H,O m. p. 201-202°). Only one quinoline derivative can be formed by the condensation of o-benzoylaminopropiophenone. 4-Hydroxy-2-phenyE-3-math~t~~inoZine m. p. 276O develops a coloration with ferric chloride but is only feebly basic. By treatment with phosphorus pentachloride the preceding hydroxy- quinolines are converted into the corresponding chloro-derivatives ; by reducing the latter by hydrogen iodide in glacial acetic acid or by dis- tillation with zinc dust the corresponding alkylated quinolines are obtained.It is found that chlorine in position 4 is more difficultly re- moved than chlorine in position 2 ; the difficulty increases with the number of carbon atoms in the alkyl groups so that the halogen can be eliminated from the higher 4-chloroalkylquinolines only by distillation with zinc dust. 4-Chtoro-2 :3-dimethylpuinoZine has m p. 78' (decomp.). 2-ChZoro-4-ethylquinoline m. p. 76-77' crystallises in colourless prisms. 4- ChZoro-3-meth yZ-2-ethyZquinoZine and the corresponding io do- compound have m. p.22-23' and 64-65' respectively. By distilla tion with zinc dust under diminished pressure 4- hydroxy-3-methyl- 2-propylquinoline yields two substances one of which is probably 3-methyl-2-propyZqeinoline m. p. 59' (platinichloride m. p. 228O) whilst the other m. p. 65-70' is possibly an indole derivative since i t responds to the pine-shaving test. 2-C'hloro-3-methyZ-4-ethyZquinoZine m. p. 7 2-7 3O is converted into 2-iodo-3-rnethyZ-4-ethyZquinoZine9 m. p. 103O by hydriodic acid potassium iodide and amorphous phosphorus but is reduced by hydrogen iodide in glacial acetic acid a t 275' to 3-methyZ-4-ethyZpuinoZ~ne ?. p. 172-1 73'127-28 mm. (picrate m. p. 196-197O ; platinichlorzde m. p. 230' reddish-yellow needles). In a similar manner 2-chioro-3 4-diethylquinoline b.p. 203-205°/24-25 mm. is reduced to 3 4-diethylquinoZine b. p. 177-178'/25 mm. (picrate m. p. 179" yellow needles ; pEatinichZoride m. p. 230' [decomp.] yellowish-red needles). Equal molecular quantities of o-aminopropiophenone and ethyl acetoacetate react a t 160-165O to form only Z-hydroxy-3-acetyk 4-ethyZpuirnoZine m. p. 198-199' colourless needles which is quite devoid of basic character whilst under similar conditions o-amino- propiophenone and ethyl benzoylacetate yield 2-hydroxy-3-benxogl- 4-ethylquinoline m. p. 213O about 8-10% of the intermediate sub- stance CH,Bz*CO*NH*C,H,*COEt m. p. 94-95O also being obtained ; the latter is converted into the former by aqueous alcoholic sodium hydroxide. c. s.ORGANIC CHEMISTRY. i 203 Preparation of Anthraquinoneacridinecarboxylic Acids.FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (J).R.-P. 262469 j.- 1-Anilinoanthraquinone-2-carboxylic acid when heated with sulphuric acid (60°B6) t o 90-looo yields a mixture of anthraquinone-l :2- acridone and l-acridineanth~*upuinone-2-carboxylic acid Similarly 1 -p-chloroanilinoant~1raquinone-2-carboxylic acid gives 1-p-chloro- ncridineanthraquinone-2-carboxylic acid and a corresponding acid is produced by the condensation of 1 -p-toluidinoanthraquinone-2-carboxylic acid. J. C. C. The Decomposition of Phenylbenzylideneisooxazolone by Phenylhydrazine. ANDRB MEYER (Bull. SOC. chim. 19 13 [iv] 13 1106-1107. Compare D i n s and Griffin A. 1913 i 1086).- l-Phenyl-4-benzylideneisooxazol-5-one is decomposed by boiling in alcoholic solution with phenylhydrazine giving phenylbenzylidene- hydrazone.Hydroxylamine and bases capable of combining with aldehydes and ketones can take the place of the phenylhydrazine. The reaction is general to such isooxazolones as the above. W. G. Preparation of Anthraquinone-N- 1 1 '-oxazines. FARBWERKE Antbraquinone-N 1 1'-oxazines are obtained by heating a mixture of 1 -halogen-anthraquinones having the 2-position free and 2-halogen-1 - aminoanthraquinones in nitrobenzene solution with sodium acetate (to fix mineral acid) and a catalyet. VORM. MEISTER LUCIUS & BRUNIXG (D.R.-P. 266945 266946).- Anthrapuinone-N-1 1'-oxaxine C,,H,02<-O->C,,H,02 NH is pre- pared from 1-chloroanthraquinone and 2-bromo-l-aminoanthraquinone using copper acetate as catalyst.It separates from quinoline as a brownish-violet crystalline powder. The compound is also obtained (second patent) by heating a mixture of 1-nitro-2-hydroxyanthra- quinone and 1-chloroanthraquinone in nitrobenzene solution with metallic copper. J. C. C. Preparation of Anthraquinonethiazoles. BADISCHE ANILTN- & SODA-FABRIK (D.R.-P. 267523. Compare this vol. i 87).-When 2-aminoanthraquinones containing a free ortho-position are heated with sulphur or sulphur-yielding substances and benzylidene chloride (instead of benzotrichloride as previously described Zoc. cit.) anthra- quinonethiazoles are produced. These are yellow crystalline powders which dye cotton in yellow shades from the hyposulphite vat. J. C. C. P r e p a r a t i o n of Phenazselenonium Colouring Matters.FARB- interaction of potassium selenocyanate and o-nitrodiazobenzene yields o-ni troselenocyanobenzene which with alkalis gives o-nitroselenophenol and this on reduction furnishes o-aminoselenophenol. The latter condenses with di- or tri-nitrohalogenbenzenes to nitroselenazines which on reduction and subse- quent oxidation give phenazselenonium colouring 1 3-ljinitro~~~nosel~ncczi.ne (annexed formula) prepared from picryl chloride and o-aminoseleno- WERKE VOHM. MEISTER LUCIUS dZ BRUNIM (D.R.-P. 261969).-The NH I I 1 'NO matters \/\/\/ Sei. 204 ABSTRACTS OF CHEMICAL PAPERS. phenol is a deep red powder m. p. 195'. It yields by the above treatment 1 3-diaminophenazseZenoniun chloyide dark olive needles. On nitration dinitrophenoselenazine gives 1 3 6-lrinitro33heno;eZenaxine a red powder m.p. 180° and the 1 3 G-triaminophencczseZeno~i~m chloride prepared from it forms needles with a metallic lustre. J. C. C. The Mechanism of the Rearrangement of Amiaobenzyl- a n i l i n e s i n t o Dipbenylmethane Bases. A Contribution to the Partition of Chemical Valency. J. VON ERAUN and 0. KRUBER (Bey. 1913 46 3952-3965).-p-Aminobenzylaniline and it.s deriv- atives when warmed with aromatic amines in acid solution become con- verted into pp'-diaminodiphenylmethane derivat.ives in the manner represented by the equation N~le,*C,H;CH,*NH*C,~,~e + C6H5NMt.2 = NRle2* C,H4*CH2*C,H,*NMe2 + C,H,Me*NH but I ittle i s known of the mechanism of the change A suggestion bas been made (von Eraun A. 1908 i 684) that the action occurs in two stages the first involving the fission of the molecule of tbep-amino- benzylaniline derivative by the action of water the second stage being the condensation of the p-aminobenzyl alcohol derivative formed with the aromatic amine producing the diaminodiphenylmethane com- pound; taking the above example the rquations would be NMe,*C',H,*CH,*NH*C,H,Me + H20 = and NMe,*C,B,*CH,-OH + C6H,*NMe - NMe,*CGH,*CH,~C,H,*NMe2 + H,O. This view of the change has proved n useful working hypothesis (com- pare von Braun and collaborators A.1912 i 968; 1913 i 1327 1330) but as aminobenzyl alcohol compounds with a tertiary nitrogen atom cannot be made to give the condensation assumed above the explanation must be sought in an entirely different direction.New facts have now been discovered concerning the rearrangement. The solutions used must not be too acidic otherwise the yield will be far from satisfactory; the amount of acid should he that required for dissolving the reagents. It is found that such a solution for example of the dihydrochloride of a p-aminobenzylaniline has characteristic properties and on warming or adding a little alkali a reddish-yellow colour appears which disappears when a large excess of acid is intro- duced. m- Aminobenzylaniline derivatives do not produce this colour change neither do they give the rearrangement with aromatic amines. The conclusion is therefore drawn that it is those molecules of the p-arninobenzylaniline derivative which are less rich in acid which enter into the action and that tbe lack of acid must exert a weakening affect on the linking C*N in the centre of the molecule.'I'he colour reaction mentioned above also indicates that the same influence cause8 a tendency t o alteration to some quinonoid configuration. The only explanation which appears to be compatible with the evidence is that represented by the scheme NMe,* C6H4* CH,*OH + C,H41\IXe*NH NMe,(HCI) C,H,*CH,*NH* C,H 4Me -+ or NMe,*C6H,-CH2*NH(HCI)*C6H4Me -+ NBle,C1~-C,H,~-CH,*~~NH~C,H4Rle 1 .... . .............. . H __...__.._.______.__..... ! NMe,-=C,H,==-CH2***NH2*C6H4Me. i-... ..... _.-__- ..-. a1 -.-_....._...__.....- IORGANIC CHEMISTRY. i. 205 The weakening thus produced a t the CON linking in the centre of the molecule renders possible the interaction with a n aromatic amine to produce a diaminodiphenylmethane derivative.It is considered that the balance of the evidence is decidedly in favour of the latter of the two possibilities for the first stage. It is possible that the conversion of diazoamino-compounds into aminoazo-compounds in the presence of the hydrochloride of an aromatic amine depends on a similar preliminary disturbance of the N*NH NPh:N*NHPh,HUl -3 NPhEN***NH,Ph The mole- linking thus I ,,_.__......._. CI--- cule then becomes able to react with the aniline hydrochloride NPh-N***NH,Ph + C6H5NH,,HCl + ! _______.._.. C1 ........ i NPh:N*C,H,*NH,,HCi + NH,Ph,HCl (compare Goldschmidt and Reinders A. 1896 ii 525 556). The following substances are described nz-Aminobenzylaniline hydro- chloride has m.p. 63" (compare Purgotti and Monti A. 1901 i 22). p-Dimethy laminobenzy 1-p-toluid ine di hydrochloride forms colour- less needles m. p. 186-187O and can be converted into a platini- chloride m. p. 189'; when heated in the crystalline conditi0.n or in solution the dihydrochloride assumes a reddish-yellow colour ; this is not due to a fission of the molecule into p-toluidine and a qriinonoid substance of the type NMe,Cl:C,H,:CH for no appreciable amount of p-toluidine is formed. By the action of P-naphthalenesulphonyl chloride on a n aqueous acetone solution of dirnethylaminobenzyltoluidine i n the presence of alkali at the ordinary temperature the ncbphthalenesulphonyl derivative NMe2=C,H,*CH,*N(S0,*C,,H7).C,H4~~e needles m. p. 137" is obtained ; its hydrochloride and sulphate are sparingly soluble in water.If finely divided dimethylaminobenzyltoluidine is shaken with a n equal quantity of powdered cymogen bromide dinretl~ykcniinobenxyl- cymo-p-lohidine NMe,*C,H,-CH,* N(CN)*C K,Me a colourlees crys- talline mass m. p. 1 3 5 O is obtained (hydrochlwids leaflets m. p. 165' ; platinichloride m. p. 1 16 -1 1 So) which is accompanied by some methgl- cyanoantino6enzylcyccno-p-to?uidine CN *NMe *CGH4*CH,*N( CN)*C,H,Me m. p. 140'; this is also obtainable by the action of cyanogen bromide on the monocyano-derivative. The monocyano-compound is easily hydrolysed by warm dilutja hydrochloric acid giving as-p-tolyl- d~meth~~urn~nobenxg~carbam~de NMe2*C,H,*CH,*N(CO*NH2)C~H4Me m. p. 178-1'79'; like the cyano-compound this is a mono-acid base ; platinichloride m.p. 169". p-Dimethylttminobenzyl-p-toluidine gives a p-nitrobenzoyl deriv- ative deep red needles m. p. 144O; hydrochloride m. p. 65-66" (decomp.) ; platinichloride m. p. 153-154O. The above acyl derivatives of p-dimethylaminobeuzyl-p-toluidine combine fairly readily with methyl iodide ; the monocyano-derivative gives a methiodide NMe,I*C,H,*CH,*N(CN)*C,H,Me m. p. 95-looo (decornp.) ; the corresponding methiodides of the nitrobenzoyl and of the benzoyl derivatives have m. p. 120-121" and 150-151O respect- ively. The methiodide colourless leaflets m. p. 16P of the acetyl derivative was converted by silver chloride into the correspondingi. 206 ABSTRACTS OF CHEMICAL PAPERS. methochloride m. p. 188'; platinichloride m. p. 210' (decomp.).On repeatedly evaporating its solution in concentrated hydrochloric acid to drynees this methochloride compound loses its acetyl group with production of p-dimethy~minobe~nxyl-p-toluidine methochloride hydro- chloride NNe3Cl*C,H,*CH2*NH( HCl)*C H Me a colourless powder m. p. 177O ; pZatinichZoride m. p. 1996 !Chis methochloride hydro- chloride as also the acyl derivatives of p-dimethylaminobenzyl-p- toluidine do not give a colour reaction when their aqueous solutions are warmed or treated with alkali and they do not undergo the condensation with aromatic amines thus confirming the authors' view as to the mechanism of this condensation. D. F. T. Aminohydrazines. 11. Benzylidene-p-aminophenylhydrazine ( Benzaldehyde-p-aminophenylhydrazone). HARTWIG FRANzEN'and B.VON FURST (Bey. 1913 46 3965-3974. Compare FrmzeD A 1 S07 i 321).-It has already been shown that benzaldehyde-o-nitro- phenylhydrazone can be reduced by sodium hy posulphi te in ammoniucal alcoholic solution to benzaldehyde-o-aminophenylhydrazone but this product could not be hydrolysed to the free hydrazine on account of its conversion under the influence of acid into 2-phenylbenziminazole. As the para-isomeride could not be capable of this condensation it has now been submitted to investigstion. When an aqueous solution of sodium hyposulphite is gradually introduced into a boiling alcoholic solution of benzaldehyde-p-nitro- phenylhydrazone to which one-fifth its bulk of a cold saturated alcoholic solution of ammonia has been added reduction is effected tbo benzalde~~yde-p-aminop~enylhydraxone yellow needles or leaflets m.p. 133-134' (decomp.) which rapidly darken. This substance when treated with benzaldehgde in boilkg alcoholic solution is converted into its benxylidene derivative CHPh:N*C,H,*NH*N:CHPh golden- yellow leaflets m. p. 163-164' which is also obtained occasionally as a product of the above reduction. I n a similar manner p-anisaldehyde and m-nitrobenzaldehyde condense with benzaldehyde-p-aminophenyl- hydrazone producing the p - anisylidene and m-nitrobenxylidene derivatives a yellowish-brown crystalline powder m. p. 14S0 and an intense yellow powder m. p. 15b0 respectively. With phenylthio- carbimide the benzaldehyde-p-aminophenylhydrazone yields a thio- carbanilide derivative NHPh*CS.NH*C,H,=NH*N :CHPh an almost colourless crystalline mass m.p. 157O. Unlike the ortho-isomeride (loc. cit.) benzaldehyde-p-aminophenpl- hydrazone when added in hot alcoholic solution to dilute hydrochloric acid at - 10' gives a violet-red .powdery hydrochloride m. p. 179-18lo which is unstable in a moist condition; on the addition of concentrated ammmia solution the hydrochloride regenerates the original benzaldehy de-p-aminophenyl hydrazone. The sdphate can be obtained in a similar manner and shows similar properties. The suggestion is made that them strongly coloured salts are possibly of an azo-structure for example NH,(HCI)*C,H;N:N*CH2Ph or a - - - quinonoid structure 3>4H4:N( HCI)*X CHPh. When benzaldehyde-p-aminophenylhydrazone is treated in boilingORGANIC CHEMlSTRY.i. 201 alcoholic solution with 2N-snlphuric acid a deep-coloured solution is obtained mbich after the addition of water and subsequent cooling gives a deposit of almost colourless leaflets of a sulphate ; the lack of colour is indicative of a normal structure and confirms the occurrence of a rearrangement in the formation of the coloured salts just described. Under the action of a hot alcoholic solution of hydrcigen chloride the behaviour of benzaldehyde-p-amioophenylhydrazone is quite different; instead of a hydrochloride or of the likely hydrolytic products benzaldehyde and p-aminophenylhydrazine there is obtained p-phenylenediamine together with benzaldehyde and ammonia. This result indicates a fission of the molecule a t the N-N linkiug instead of at the C:N linking as might be expected and throws light on the intramolccular condensation of the ortho-isomeride under the influence of acid I n the latter case the primary products are probably o-phenylenediamine benzaldehyde and chloroamine of which the two former condense t o a dihydrobenziminazole; this is then oxidised by the chloroamine t o benziminazole itself D.F. T. Crystallography of Some Aromatic Nitrogen Compounds. JUL~EN DRUGMAN (Zeitsch. Kryst. A4in. 191 3 53 266-270).-The following compounds prepared by F. D. Chattaway were measured. Bismethylphenylazimethylene (monoclinic a b c = 1.3335 1 1.2667 ; p = 103’44’). N-Dichlorobenzylidenediacetamide (T 1912 101 1207). N-Chlorophthalimide (rhombic-bisphenoidal a b c = 0*3000 1 0 9 7 5 ) . I!-Dichlorobenzenesulphonimide (monoclinic a b c = 0 72 I3 1 1 -2009 ; p = 100029’).1,. J. S. C o n s t i t u t i o n of Acetylacetonecarbamide 14 6-Dimethyl- dihydropyrimid-2-oneI. W~LLIAM J. HALE ( J . Amer. Chena. Xoc. 19 14 36 104-1 15).-Acetylacetonecarbamide exists in two modifica- tions one colourless the other yellow. It has been suggested by Haan (A. 1908 i 577) that the former is 4 6-dimethyl-2 3-dihydro- pyrimid-2-one CHGCMeeNH>CO and the latter 4 6-dimethyl- CMe=N 2 5-dihydropyrimid-2-one CH2<U;\le CMe:N>Co. 0 t h compounds crys- tallise with 2H,O and have m. p. 1 9 7 O . A potussiunz. salt can be prepared from a n aqueous solution of either of these compounds and is completely decomposed by the carbon dioxide of the atmosphere. On adding silver nitrate t o a solution of either modification a white silvei.salt is precipitated which reacts with methyl iodide with formation of a red crystalline methyl iodide additive compound of a trimethylpyrimidone. Mercuric chloride also yields a n insoluble salt with the dimethyldihydropyrimidone. When R solution of the yellow acetylacetonecarbamide in methyl alcohol is boiled with methyl iodide the additive cornpound C,H,ON,,MeI is produced in the form of colourless crystals which gradually become red when left in the air. If diazomethane vapour is passed into a cold solution of acetyl-i. 208 ABSTRACTS OF CHEMICAL PAPERS. acetonecarbamide in chloroform 3 4 6-trimsthyl-2 3-dihydropyrimid- a-one m. p. 63' is obtained which forms colourless crystals. The same compound can be prepared by the condensation of methylcarbamide with acetone ; its hydrochloride crystallises in colourless prisms.The conclusion is drawn that acetylacetonecarbamide does not contain a hydroxyl group and that the tautomeric forms must have the constitutions ascribed to them by Haan. E. G. Preparation of 5-Mono- and -di-allylbarbituric Acids. GESELLSCIEAFT FUR CHEMISCHE INDUSTRIE (D.R.-P. 268158). -The interaction of ally1 bromide and barbituric acid according to the quantities used leads to the production of 5-nllylbarbituric acid m. p. 1 6 2 O and 5-dic~llyZbarbituric acid. The latter forms colourless leaflets m. p. 169-170' and has a stronger hypnotic action than the corresponding diethyl derivative (veronal). J. C. C. Constitution of Benzoylhydrttzicarbonyl. R.STOLLE and K. 0. LEVERKUS (Ber. 1913 46 4076-4080. Compare A. 1913 i 898).-The authors have carried out the proposed condensations of nitrobenzoylhydrazicarbonyl with benzoyl chloride and benzoylhydrazi- carbonyl with nitrobenzoyl chloride and have obtained different products. This argues against the hydrazicdrbonyl structure for these derivatives. The formation of 2 5-diphenyl-1 3 4-oxadiazole by the action of heat on dibunzoylhydrazicarbonyl and the preparation of ethyl dibenzhydraziodoformate by the action of sodium ethoxide (A. 19 13 i 97) agree with the alternate oxadiazole formula. The tautomeric formulEe most nearly correspond with the behaviour of '' benzoylhydrazi- carbonyl " and its substitution products. On this basis the compound is re-named 2-keto-5-phenyl-2 3- dihydro-1 3 4-oxadiazole ; " dibenzoylhjdrazicarbonyl " is called 2-keto-3- benzoyl-5-phenyl-2 3-dihydro-1 3 4-oxadiazole ; and Sches- takov's methyl derivative of '' benzoylhydrazicarbonyl " (A.1913 i 97) which yields berizoylhydrazine on heating with water and therefore exists in the tautomeric form corresponding with (11) is re-named 2-methoxy-5-phenyl-1 3 4-oxadiazole. 2-Keto-3-p-nitrobenxoyl-5-phen$-2 3-dihpdro- 1 3 4-oxndiaxole CPh:? O<CO-N* coo C6H,.N0,' o<C*--NBz was obtained by heating '' benzoylhydrazicarbonyl " with p-nitro- benzoyl chloride in pyridine in leaflets m. p. 193'. 2-Keto-3-benxoyl- 5-p-nitrophenyl-2 ; 3-dihydi-o-l 3 4-oxadiccxoZe C( C6H;NO2):T formed glistening needles and leaflets m.p. 196O. A mixture of the isomerides me1 ted about 30" lower. Both compounds yielded benzogl- p-nit~obenxoylhydrazine C1,H,,O,N on warming with dilute sodiumORGANIC CHEMISTRY. i. 209 hydroxide and precipitating with acids. The compound was also prepared from p-nitrobenzoylhydrazine and benzoyl chloride. It is a white powder m. p. 236'. On heating alone they also gave the same phenyl-p-nitrophenyl-1 3 4-oxadiaxoZe C,,H,O,N the evolution of carbon dioxide being quantitative. This compound was also obtained by heating benzoyl-p-nitrobenzoylhydrazine with thionpl chloride. It forms glistening leaflets m. p. 209'. J. C. W. The Formation of Methenylbis[phenylmethylpyrazolone] from Phenylmethylpyrazoloneglyoxylic Acid. WILHELM WISLI- CENUS and OTTO BILFINGER (Ber.1913 46 3948-3949).-A correc- tion. The substance recently obtained by heating a n alcoholic solution of l-phenyl-3-methyl-5-pyrazolone-4-glyoxyl~c acid ( Wislicenus Elvert and Kurtz A. 1913 i 1387) and described as l-phenyl-3-methyl-4- methylene-5-pyrazolone is in reality methenylbis[phenylmethyl- pyrazolone] ~ p h * C o > ~ ~ ~ ~ ~ ~ < c N N=CMe (compare Betti and CO-rPh Mundici A. 1907 i 543). D. F. T. Preparation of 1 7-Dimethylguanine. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 262470).-2 4 5-Triamino-6-pyrimi- done is converted into the 5-formyl derivative by treatment with dilute formic acid at a moderate temperature the latter methylated and the 1-methyl derivative boiled with concentrated formic acid whereby 1 -methylguanine XFii:&:gZ$A3H crystallising in needles is produced.m. p. 337-339' is obtained. On mkhylhion 1 7-dimethylguunine needles J. C. C. Carbamides of the Rosaniline Series. GUIDO MAYER (J. pr. Chena. 1913 [ii] 88 699-730).-An account of the preparation and properties of carbamide derivatives of the following three types from pararosaniline rosaniline and tri-p-aminophenyldi-m-tolylcar binol the dye-base of new-magenta I. NH2*CO*NH*C,H,*C(C6H,~~H2)2~OH. 11. NHPh*CO*NH*C,H,*C(C,H,*NH,),*OH. C,H,-NH*CO*NH*C H III. OH~C/C,H~*NH*CO.NH*C~H:~C*OH. \C,H,*NH*CO*NH~C,H,/ The compounds of the first type are obtained in the form of their hydrochlorides (1) by the addition of potassium cyanate to aqueous solutions of the hydrochlorides of the dyes and (3) by fusing the dye- bases with carbamide and heating the product with hydrochloric acid The following compounds were prepared in this manner 4' ; 4"-Diumino-4-carbamidotripheny~carbinol hydrochloride ~H,C~:C6~~,:C(C6H4'NH2)*C6~,~NH'CO~~~ from pararosaniline ; 4' 4"-diamino-4-carbc~midodiphenyl-m-tolylcarbinol hydrochloride from rosaniline and 4' 4"-diamino-4-carbamidophenyL di-m-tolylcurbinol hychochloride from the dye base of new-magenta.VOL. CVI. i. Pi. 210 ABSTRACTS OF CHEMICAL PAPERS. The corresponding bases which probably have a quinonoid structure are obtained by heating the hydrochlorides withdilute aqueous potassium hydroxide for several days at 90-95'. The compounds described above decompose when heated with the evolution of ammonia and aniline give red colorations on treatment with strong mineral acids and yield diazonium compounds which couple with resorcinol and R-salt to form yellow azo-dyes. They are reduced to the corresponding leuco-compounds with zinc and hydrochloric acid and give characteristic colorations with potassium chlorate and hydrochloric acid and other oxidising agents ; the picrates and nzcrcurichlwides are mentioned.When the sulphate of the carbamide derived from pararosaniline is treated with acetic acid and solid sodium nitrite and the resulting solution diluted with water an unstable flesh-coloured diazonium oompound fi H,*CO*N( ~ O ) * C ~ 4 * C ( O H ) ( C H ~ " C I is precipitated. The diazonium compound rapidly loses nitric oxide yielding a product from which 4"-amino-4'-hydroxy-4-carbamidotri- phenylcarbinol hydrochloride NH,Cl C,H, C( C,H,* OH) *C,H,*NH* CO*NH is obtained by boiling with water and subsequent treatment with hydrochloric acid.When boiled the filtrate from the above unstable diazonium compound yields aurin and 4' 4"-dihydroxy-4-carbamido- t riphen ylcarbinol 0 C6H4 C( C,H4*OH)*C6H,*NH* CO-NH a black substance which gives intensely violet solutions in dilute aqueous potassium hydroxide. The phenylcarbamides of type I1 are obtained in the form of their hydrochlorides by fusing the dye bases with phenylcarbamide arid dissolving the product in hydrochloric acid. The hydrochlorides of 4' ; 4"-d~am~~zo-4-phe~ylcarba~nidot~~p~nylcarbino~ NH2C1:C,H,:C( C,H4jNH,)~U6H,~NH.C0.Nf-3;Ph from pararosaniline of 4' 4 -diamino-4'-phenylcarbamidod+henyl-m- tolylcarbinol from rosaniline and 4' 4"-diamino-4-phe.izylcaybamido- phenyldi-m-tohjlcarbinol from the dye base of new-magenta were pre- pared in this manner; the corresponding imino-bases are formed by heating the hydrochlorides with aqueons potassium hydroxides.The above phenylcarbamides form picrates and mercurichlorides can be diazotised and give characteristic colorations on treatment with strong mineral acids and oxidis- C,H,:NHCl*CO*NH*C,H ing agents. When heated they C//C,H4*NH-co*NH*C,~~~c decompose without melting. The tricarbamides of type 111 are obtained in the form of their hydrochlorides (annexed formula) by passing carbonyl chloride into a hydrochloric acid solution of the dyes ; the hydrochlorides are sparingly soluble in water and decompose when heated with evolution of aniline and ammonia.The free bases are also described. F. B. \C6H,*~Ho~O*NHCI:C6H4~ Some Thiocarbamides of the Rosaniline Series. SIEGFRIED HILLER (J. pr. Chem. 1913 [ii] 88 731-743. Compare preceding abstract).-When heated with carbon disnlphide in alcoholic solutionORGANIC CHEMISTRY. i. 211 in the presence of a little sulphur pararosaniline in converted into a trathiocarbccmide of the annexed con- /C6H4*NH*CS*NH*CGH4\ stitution ; similar compounds bGH4:N--GS-N :C6H C-C,H,*N H*CS*NH*C,H4zC C43H32N6S3 and C45H34N6S3 have also been pre- pared from rosaniline and 4 4' 4"- triaminophenyldi-rn-tolylcarbinol. The three compounds are brownish-red to blackish-red substance$ having a metallic lustre yield in acetic acid solution metallic precipi- tates with picric acid copper sulphate and mercuric chloride and are decomposed by hot acids with liberation of hydrogen sulphide.On treatment with sodium hydroxide their solutions in acetic acid yield the corresponding red carbinol bases. When heated with benzoic acid and aniline the trithiocarbamides from pararosaniline and rosaniline yield blue phenyl derivatives which yield reddish-brown solutions in strong acids. Attempts to prepare the trithiocarbamide derived from para- rosaniline by the addition of ammonium thiocyanate to a hot alcoholic solution of pararosaniline hydrochloride gave tri-p-aminotriphenyl- carbinol thiocyanate C2,H,8N4S as ft lustrous green metallic precipitate. 4 ; 4'-Diarnino-~''-phanylthiocnrbarnidotri~?~enylca~binol NH C6H4 C( C6H ;NH2) C H4*NH CS* NHPh 4 4'-diarni~ao-~''-phenyZbhiocn~bamidodiphenyl-m-tolylcarbinol NH:C,H,:C( C6H40NH2)*C H,Me*NH*CS*NHPh and 4 4'-diamino-4"-p?~enylthiocar bamidophen yldi-m -tol y Zcarbinol are obtained by heating phenylthiocarbimide with alcoholic solutions of pararosaniline rosaniline and tri-p-aminophenyldi-m-tolylcarbinol respectively.They are amorphous violet substances which give orange- red solutions in sulphuric acid and when heated with dilute acids or water are partly resolved into their components and partly converted into the corresponding cltrbamides with evolution of hydrogen sulphide. When heated with benzoic acid and aniline they yield bluephenyl derivatives. The hydrochlorides (BHCI) prepared by the direct union of phenylthiocarbimide and the hydrochlorides of the original dye bases form red aqueous or alcoholic solutions from which the corresponding carbinol bases are precipitated on the addition of sodium hydroxide.NH:C,H4:C(C,H,Me*NH2)*C6H~Me*NH*CS*NHPh F. B. The Kinetics of the Sandmeyer Reaction. P. WAENTIG and JOHANNA THOMAS (Ber. 1913 46 3923-3937. Compare Heller A. 1910 i 240; Heller and Tisehner A. 1911 i 243).-The cuprous hdoid employed in the Sandmeyer reaction is f airlg generally believed t o form an intermediate additive compound with the diazo-compound although various views are held as to the details of the mechanism of the change. Cryoscopic experiments with a solution of cuprous chloride in dilute hydrochloric acid give probability to the view that it is the double molecule Cu2C12 and not CuCl which is involved in the change.P 2i. 212 ABSTRACTS OF CHEMICAL PAPERS. By adding a concentrated solution of benzenediazonium chloride at - 17" gradually to a saturated solution of cuprous chloride in 25% hydrochloric acid at -60° the authors have obtained a n unstable bulky red precipitate of composition C,H,N2CI,Cu2C1 analogous to the cuprous bromide compound isolated by 'Hantzsch (A 1895 i 516). Measurements of the velocity of the decomposition of benzenedi- azonium and p-toluenediazonium chloride solutions at 0' in the presence of an approximately equimolecular quantity of cuprous chloride dissolved in hydrochloric acid by means of the volume of liberated nitrogen show that the p-tolueneaiazonium salt decomposes much more slowly than the benzencdiazonium salt.The constants calculated for a unimoleculsr change in any one experiment were satisfactory but the higher the initial concentration of diazonium Ralt and cuprous chloride the greater the constants obtained. This effect appears to be due to the cuprous chloride and the deduction may be drawn that of the two successive reactions that expressed by N,PhCl + Cu,Cl = N,P~CI,CU,CI is of measurable velocity and seems to be unimolecular on account of the constancy of the concentration of the cuprous chloride during an experiment whilst the change N,PhCl,Cu,Cl = PhCl + N + Cu,CI2 is very rapid. The simplicity of this view is somewhat discountenanced by the impossibility of obtaining satisfactory constants when the diazonium Ralt and cuprous chloride are present i n other than equimolecular proportions and by the authors' discovery that with equimolecular proportions of diazonium and cuprous salts the velocity of the reaction is very considerably depressed by increased concentration of the hydrochloric acid present.A rise OF loo in the temperature of the reaction increases the velocity to twice its original value This result indicates that in the preparation of a phenol from a diazonium salt (for which the tempera- ture-coefficient is above 3*5) a high temperature will be advisable whilst a lower temperature should prove more satisfactory for the formation of an aryl haloid. It is suggested that the decomposition of the diazonium haloids may to some extent follow the course Ar C1 Ar C1 Ar C1 NiN+ I -+ N-N -+ N I I I I c1 Ii HC1 I 61 H analogous to the well-known explanqtion of phenol formation for the investigation of which it will be necessary to investigate the velocity of decomposition with various concentrations of acid in the absence of the disturbing effect of cuprous chloride D.F. T. The Nature of the Free Amino-groups in Proteins. DONALD. VAN SLTKE and FREDERICK J. BIRCITARD (J. Biol. Chsm. 1914 16 639-547).-1n various native proteins (haemoglobin cweinogen gelatin edestin gliadin etc.) the amount of free amino- nitrogen is equal to one-half the lysine nitrogen ; in glisdin there is a difference of 0.7%. The period required for complete reaction of theORGANIC CHEMISTRY. i. 213 proteins with nitrous acids (thirty minutes) is longer than that required by a-amino-acid s (three to four minutes) but corresponds with that found for lysine with an a-amino-group free. The conclusion is drawn that the same group is free in the protein molecule; and this group practically represents the entire amount of free NH determin- able in native proteins by this method All the others are condensed into peptide linkings.With the primary proteoses the relations are different the free NH exceeding half the lysine nitrogen by 3 to 5%. W. D. H. The Colloidal State of the Mixed Protein and Gold Sols. FRIEDRICH JACOBS (Biochem. Zeitsch. 1913 58 343-351).-The effect of the addition of gold sols to protein solutions was investigated by measurement of the changes in the viscosity and osmotic pressure of the solutions. Under the conditions of the experiments this addition caused no appreciable change in the viscosity.It produced however a lowering of the osmotic pressure which mas 7.4% in the case of albumin and 3.9% in that of ha?moglobin. I n the case of globulin no change could be detected owing to the small absolute pressure. S. B. S. The “Gold Numbers” of the Proteins of the Blood. W. HEUBNER and FR. JACOBS (Biochein. Zeitsch. 1913 58 352-361). -The “ gold numbers ” of various fractions of albumin globulin and bzemoglobin were determined. The variations in different prepara- tions of the same substance were however somewhat large. The “gold numbers ” cannot be used therefore for the identification of auy given blood-protein. Some Protein Derivatives. KARL LANDSTEINER (Biochem.Zeitsch. 19 13 58 362-364).-The products obtained from proteins of horse-serum precipitated therefrom by alcohols by treatment with acetic anhydride with alcohol in the presence of hydrochloric and sulphuric acids and with diazomethane are described. The first and third of these products when tested by the complement-deviation method were found to have lost their species specificity. S. B. S. S. B. S. The Clotting of Caseinogen Solutions. SAMUEL BARNETT SCHRYVER (Biochem. J. 1913 7 568-575).- Casein prepared by the use of pepsin (or rennin) differs from metacaseinogen a product obtained by the action of water a t 3’7” on caseinogen in that it cannot be converted by solution in alkali hydroxide and reprecipitation into a more soluble product which dissolves in calcium hydroxide t o yield clottable solutions.Psrncreatin clots caseinogen only in the presence of soluble calcium salts; the casein produced has only half the aolubility in half-saturated lime water of the casein prepared by pepsin. Caseins are regarded as combinations of the protein and enzyme. The action of the enzymes is not an ordinary proteoclnetic one; the same view has also been expressed by van Slyke and Bosworth. “ Natural caseinogen ” is probably not a calcium salt. W. D. H,i. 214 ABSTRACTS OF CHEMICAL PAPERS. The Hexone Bases of Caseinogen. DONALD. VAN SLYKE (J. Biol. Cham. 1914 16 531-538).-The following figures were obtained by Kossel’s and by the author’s methods Kossel’s Nitrogen distribu- method. tion method. Histidine ..................... 4 -1-4 *5 6-2 Arginine ........................75-79 7‘4 Lysine. ......................... 8.7-9 -3 10.3 The loss of histidine in Kossel’s method is ascribed to adsorption by barium phosphotungstate. The results with arginine are practically the same in both methods. The Kossel-Patton method as modified by Osborne Leavenworth and Brautlecht gives more consistent results for histidine. W D. H. Ovo-ruucoid and Metallic Hydroxides. J. NEUMANN (Zeitsch. physiol. Chem. 191 4 89 149-150).-0vo-mucoid can be completely precipitated by zinc hydroxide in the presence of potassium hydroxide or sodium carbonate. This is attributed to the formation of a hydrate; other metallic hydroxides act in the same way and there is in the quantity used an inverse proportion between it and the moleculnr weight of tho metallic hydroxide.Primary proteins and proteoses act in the same way but not peptone. Enzyme Action Facts and Theory. HENDRIK PIETER BARENDRECHT (Riochem. J. 191 3 7 549-561).-A criticism of some of the recent researches on the kinetics of enzyme action. The radiation theory of enzyme action (Barendrecht A. 1904 ii 551) is extended. Enzyme action spreads like radiation from a centre. The radiation may be absorbed by the substrate by the products of action or by any other foreign substance. The enzyme particle extends its catalytic action in a sphere as regards both hydrolysis and synthesis A new isomeride of dextrose enzyme made is postulated the transformation of which to stable dextrose is a balanced action. W. D. H. E. F. A. The Auto-catalysis of Trypsinogen.H. M. VERNON (J. Physiol. 1913 47 325-338).-When once trypsinogen is activated that is converted into trypsin by enterokinase the view is taken that further activation is mainly due to trypsin itself (auto-catalysis) or rather to a variety of trypsin called ‘‘ unstable try psin.” Behaviour of Diastase in the Presence of a Specjflc Precipitate. AGNES ELLEN PORTER (Biochem. J. 1914 7 599-603). -The action of diastase is accelerated by the presence of serum. In the presence oE antigen (dilute egg-white solutions) the enzyme’ is more active with normal rabbit serum than when rabbit serum immunised against egg-white is used hence the immune serum exercises the greater absorption. A similar difference is observed when horse- serum is used as the antigen. Taka-diastase displayed no tendency to become absorbed by a specific precipitate. Serum from which the globulins had been precipitated by saturation with carbon dioxide and removed after centrifuging retained most of the original enzyme activity.E. F. A. W. D. H.ORGANIC CHEMISTRY. i. 215 Hydrolysis of Glycogen by Diastatic Enzymes. 11. Influence of Salts on the Rate of Hydrolysis. ROLAND VICTOR NORRIS (Biochern. J. 1913 7 622-629. Compare A. 1913 i 308)-A dialysed extract of pig's pancreas has practically no hydrolysing action when added to a dialysed glycogen solution. The addition of small quantities of neutral salts restores the activity of the enzyme. The most effective salts are those of the halogen acids the activity diminishing in the order chloride bromide iodide.PotasRium sodium and also calcium barium and magnesium chlorides produce quantitatively the same acceleration. Nitrates have a slight acceler- ating action but sulphates are almost without action in restoring activity to the dialysed enzyme. They have no depressing action neither do they hinder the acceleration produced by sodium chloride. The concentration of salt required to produce a maximum degree of hydrolysis rises with increasing enzyme concentration but appears to be independent of the glycogen concentration. The anion is much more concerned in the reaction than the cation and the action of the salts is chiefly confined to the enzyme. The Preparation of Protein-free Emulsin. KOHSHI OHTA (Biochem. Zeitsch. 1913 58 329-338).-1f the commercial prepara- tion of emulsin is digested with one-tenth part of its weight of pancreatin in 100 times its weight of water rendered slightly alkaline with ammonia a considerable amount of protein passes into solution.If the digest is dialysed concentrated and precipitated with alcohol a product is produced which is somewhat more active than the original emulsin and which is quite free from proteins. The substance thus obtained contains calcium magnesium and phosphorus and yields a reducing substance on hydrolysis with acids. Whilst the protein-free emulsin hydrolyses amygdalin and salicin it is free from other ferments which are present in the crude product. S. B. S. The Optimum Temperature of Salicin Hydrolysis by Enzyme Action is Independent of the Concentration of Substrate and Enzyme.ARTHUR COMPTON (Proc. Roy. Soc. 1913 B 87 245-254).-The temperature of the greatest activity of sweet- almond emulsin acting on salicin is determined under different conditions according as the concentration of the substrate and that of the enzyme are varied separately or together. The optimum is shown t o be constant at about 34'. The Reduction Ferments. V. The Go-ferment of Per- hydridase. Formation of Aldehydes from Amino-acids. A. BACH (Biochem. Zeitsch. 1913 5 8 205-212).-1t has been shown t h a t erepton (a commercial digestion product of protein) acts as a co-ferment to perhydridase. It is now found that this preparation yields aldehyde when its solution is submitted t o distillation. The aldehyde appears entirely in the first third of the distillate.If the regdue is kept for twenty-four hours and again distilled a quantity cjf aldehyde equal to that given in the first distillation is obtained. If the distillation is now continued in a current of air aldehyde is again produced each fraction of the distillate containing approximately E. F. A. E. F. A.i. 216 ABSTRACTS OF CHEMICAL PAPERS. the same amount of aldehyde. Strecker’s reaction will explain the formation of aldehyde from erepton which can be imitated very nearly when aniline is distilled with p-benzoquinone. The oxidation of the amino-acid is effected by the water and the hydrogen thus set free reduces the “acceptor.” I n a curreut of air the latter is again oxidised. The action of erepton as a co-ferment to perhydridase can therefore be explained by the fact that under certain conditions it can give rise to a simple aldehyde which is the true co-ferment. Perhydri- dase is a true aldehydase. S. B. S. The Conditions of Action of Rennin. L. MICHAELIS and A. MENDELSSOHN (Biochem. Zeitsch. 19 13 58 315-328).-The optimal precipitation point of caseinogen by acid from either pure solution or milk lies at [H’]=2*5 x 10-5. I n presence of lime it is shifted in the acid direction and is then less distinct a t about [H’] = 3 x 10-4. The optimal coagulation point by rennin in the presence of lime lies between [H’] = 4 x 10-7 and 1 x but cannot be determined with greater accuracy. and [H’) = 1 x 10-7 are certainly outside the region of optimal activity. Between the optimal point of acid precipitation and of rennin action there exists a zone which lies outside the optimal conditions for both these actions This indicates that the rennin action and the acid precipitation are distinct actions conclusion which is confirmed by the fact that the caIcium ion action in rennin clotting cannot be replaced by increased hydrogen-ion concentration. Preparation of Organic Arsenic Compounds. HEINRICH BART (D. R. -P. 2 6 7082).-3 - ~arbethoxyam~no-4-hyclroxyp~eny~ar8in6 (annexed formula) prepared by the electro- lytic reduction of the corresponding arsinic acid is a colourless crystalline powder m. p. \-/ 155-160O ; on treatment with sulphurous ASH acid and subsequent hydrolysis it furnishes a base which is useful for the preparation of therapeutically active compounds HEINRICH BART (D.R.-P. 268 1 72).-3-Carbethoxyamino-4-hydroxyphenylarsinic acid is prepared by adding a solution of diazotised 5-amino-2-hydroxyphenyl- urethane (m. p. 1 3 0 O ) to a solution of sodium arsenite and sodium hydroxide to which copper paste has been added. Sodium p-hydroxy- phenylarsinate is similarly obtained from p-aminoyhenol. Preparation of Aromatic Stibino-compounds Aromatic Stibine Oxides and their Derivatives. CHEMISCHE FABRIK VON HEYDEN AKT.-GES. (D.R.-P. 268451).-Aromatic stibino-compounds and stibine oxides are prepared by reducing the corresponding mono- arylstibinic acids. Stibinobenzene C,H,*Sb:Sb*C,H is obtained by reducing pheaylstibinic acid Kith sodium hyposulphite in sodium hydroxide solution ; m-aminophenylstibine oxide NH2*C6H,*Sb0 by reducing m-nitrophenylstibinic acid with stannous chloride (the intermediate compound m-aminophenylstibine chloride hydvochlorids The points [H’] = 3 x S. B. S. OH C02Et.NH/-\ J. C. C. Preparation of Organic Arsenio Compounds. J. C. C.PHYSIOLOGICAL CHEMISTRY. i. 217 HCI,NH,*C,H,*SbCI has m. p. 215") ; di-m-aminostibinobenzene from the intermediate compound just mentioned and sodium hyposulphite or hypophosphite and mm'-diamino - pp' - dihydroxystibinobenxene from m-nitro-p-hydroxyphenylstibinic acid and sodium hyposulphite. J. C. C. Preparation of Secondary Aromatic Stibine Oxides and their Derivatives. CHEM ISCHE FABRIK VON HEYDEN AKT.-GES. (D.R.-P. 269206).-Secondary aromatic stibine oxides are prepared by reducing the chlorides of the corresponding stibinic acids with suIphur dioxide in methyl-alcoholic solution. m-Aminodiphenylstibine oxide NH2*C,H,*SbPh*O*SbPh*C6H4*NH2 is a faintly-coloured powder which sinters a t 70". J. C. C. Preparation of Aromatic Nitrohydroxystibinic Acids. CHEMISCHE FABRIK VON F. HEYDEN AKT.-~ES. (D.R.-P. 262236. Compare A. 1913 i 1122).-Nitrohalogenarylstibinic acids are treated with a1 kali hydroxides and furnish nitrohydroxystibinic acids. p Chlorophenylstibinic acid prepared from diazotised p-chloroaniline and antimony oxide yields on nitration 4-chloro-3-nitrophenyZstibinic acid the aqueous solution of which with hydrochloric acid gives the chloride N02*C,H,Cl*SbOC1,. OR warming the acid with potassium hydroxide solution potassium 3-nilro-4-hydroayphenyZ-l-atibinate is produced as a scarlet crystalline powder from which the yellow 3-nitro- 4-hydroxyphenyl-l-stibinic acid is obtained on acidification (compare loc. cit.). J. C . C. CHEMISCHE FABRIK VON HEYDEN AKT.-GES. (D.R.-P. 269205. Compare A. 1913 i 41 6).-Secondary and tertiary stibinic acids are prepared by treating an aromatic diazonium salt with a mono- or di-aryl substituted antimony oxide in the presence of alkali hydroxide. The interaction of benzenediazonium chloride and rrt-aminophenylstibine oxide fur - nishes m-aminodiphenylstibiizic mid a faintly-coloured powder. Chloro-m-pheny2enestibinic acid a brown powder is obtained by de- composing diazotised p-chloro-m-aminophenylstibine chloride with cold sodium hydroxide and by a similar method phenyl-m-phenylenestibinic acid C,H,:SbPh(OH)2 a &own powder is prepared from nz-amino- diphenylstibine oxide. J. C. C. Preparation of Aromatic Stibinic Acids.

ISSN:0368-1769    

DOI:10.1039/CA9140600129

出版商:RSC    

年代:1914

数据来源: RSC