摘要:

ii. 136 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Decomposition of Hauerite in t h e Air and its Action on Silver and Copper. A. RECJTELL (Centr. Mirt. 1913 758-767).- Striiver in 1901 noticed that crystals of hauerite (MnS,) in contact with silver or copper p.roduced a dark stain on the metal. The same action takes place without contact (up to a distance of 1 cm.); it is ascribed to the oxidation of the mineral and the liberation of free sulphur. When the mineral is heated a t 50-60° in a Tacuum the free sulphur is distilled off and only after re- maining again in the air for twenty-four hours is the activity regained. L. J. S. OTTO WESTPHAL (DiSs. Leipzig 1913 1-41 ).-Etch-figures on brucite from Texas Lancaster Co. Penn- sylvania prove the mineral t o be ditrigonal-scalenohedral in sym- metry.2.38 H Zi. The axial ratio a c varies from 1 1.5208 a t ZOO to 1:1*5301 a t 200O. The refractive indices for light of different wave-lengths were determined for the same range of tem- perature; a t 20° for sodium-light o = 1.5662 E = 1.5853. When heated the mineral does not give off its water a t a definite tem- perature but there is a gradual loss of the bulk of the water between 380° and 480O; a t 550° about 1% is still held. The sub- stance thus behaves as an adsorption compound rather than as a crystalline hydrate. The completely dehydrated material (" meta- brucite ") still retains its crystalline structure being optically uniaxial but now negative (w,,=1*644 ~ ~ ~ = 1 ' 6 3 4 ) . D 3.666 which is increased t o 3.683 by intense ignition.Metabrucite re- Brucite and Metabrucite.NINERALOGICAL CHEMISTRY. ii. 137 absorbs water from a moist atmosphere but to a smaller degree than does amorphous magnesium oxide. Less water is reabsorbed after the material has been intensely ignited. L. J. S. Optical Constants of Calcite etc. ERWIN MARBACH (Dim. Laipzig 1913 1-47).-Tbe refractive indices of fluorite halite sylvite calcite aragonite and boracite were determined for light of different coloum over considerable ranges of temperature (up t o 670O). The values for calcite from Egremont. Cumberland vary slightly from those obtained by other authors for Iceland-spar this difference being attributed to a slight difference in chemical composition. Analyses by Dreibrodt gave I for calcite from Egremont 11 from Iceland CaO.3 r 0 . UgO. UO,. Total. I. 56.33 trace 0.13 44'33 100.79 11. 56'41 - trace 44.25 100.66 Aragonite is transformed into calcite at 425O and boracit e becomes optically isotropic a t 290°. L. J. S. Pickeringite from the Schuroveki Glacier. V. A. ZILBERMINC (Bull. Acnd. Sci. St. PStersbourg 1913 997-1000).-Tbe sample of pickeringite described was obtained from the Schurovski glacier on the northern slopes of the Turkestan Mountains and consists of thin crusts and stalacites containing many mechanical admixtures. Its composition is A1,0,. FeO. MnO. MgO. CaO. NiO. COO. K 2 0 . SO,. C1. H20. Total. 11'91 0'74 trace 3'12 0.37 1'21 0.10 0'16 37-76 trace 44'74 100.11 These results are in good agreement with the formula MgA1,(SO,)* + 22H,O in which part of the MgO is replaced by other oxides of the forin RO and by K20.T. H. P. Pisanite from Tennessee. FRANK ROBERTSON VAN HORN (Anzer. J. Sci. 1914 [iv]. 37 40-47).-Pisanite is found in Considerable amount as encrusting botryoidal and stalactitic masses on surfaces of pyrite pyrrhotite and chalcopyrite in the abandoned open work- ings a t Isabella in the Ducktown district. The material is trans- parent and blue or green in colour. Analyses by 1,. R. Veazey gave I for the blue and I1 for the green variety SO,. FeO. CnO. MgO. H,O. Total. I. 27-87 17-18 5'50 0.47 46'45 100'49 11. 28'72 21'45 8.83 0.39 45.58 99-97 Both conforin to the general formula RS04,7H,0 being inter- mediate between boothite (CuS04,7H,0) and melanterite (FeS0,,7H20). Analysis I corresponds with 2Fe0,Cu0,3S0,,21H20 and T I with 6Fe0,Cu0,7S0,,49H20.A crystallographic descriptioii is given of the blue pisanite and also of arsenopyrite crystah and large crystals of staurolite from the Ducktown district. L. J. S.ii. 138 ABSTRACTS OF CHEMICAL PAPERS. Dimorphism of the Apatite Group. WILLY EISSNER (Diss. Leipzig 1913 1-54).-Detailed measurements were made of the crystal angles of apatite vanadinite pyromorphite and mimetite and of the optical constants of apatite over considerable ranges of tempera- ture (-160° to +650°). The curves plotting these results show in the case of pyromorphite and mimetite a considerable break indicating that these substances are dimorphous. Artificially pre- pared vanadinite (3Pb,V,08,PbC1,) pyromorphite (3Pb,P,08,PbCl,) and mimetite (3Pb,As,08,PbC1,) fuse a t 976O 1103O and 1079O respectively and show a transformation point at 710° 670° and 395O r espectivelg.L. J. S. New Occurrence of Cuprodescloizite. ROGER C. WELLS (Arne?.. J. Sci. 1913 [iv] 36 636--638).-The mineral is fouud in the Shattuck Arizona mine at Bisbee Arizona in the form of stalactites and reniform masses. On fractured surfaces i t shows a radiating structure and a dark brown colour ; the ,streak is ‘( dark olive-buff.” The mineral is soluble in dilute nitric acid and on analysis gave PbO. CuO. ZnO. V,O,. As,O,. P,O,. CrO,. H,O. Insol. Total. 55.64 17-05 0.31 21-21 1.33 0.24 0.50 3.57 0.17 100’02 These results agree approximately with the descloizite formula with the zinc replaced by copper namely 2Pb0,2Cu0,V20,,H20.The percentage of copper which is higher than in any cupro- descloizite yet recorded suggests psittacinite but this mineral is possibly only an altered form of descloizite. L. J. S. Silicic Acid Gels Obtained by the Decomposition of Silicates. MARTIN THEILE (Diss. Leipxig 191 3,1-39).-Heulnndite and scolecite from Berufjord Iceland stilbite from the Faeroe Islands and natro- lite from the Puy de Marman Auvergne were examined by Tschermak’s method (A. 1906 ii 771; A. 1908 ii 490) for the determination of the composition of the silicic acid separated by the action of acid. It was found that the break in the drying curves varies in its position according to the temperature a t which the drying takes place and also with the nature of the drying agent.When the water of the gel is replaced by alcohol chloroform or carbon tetrachloride the amounts that are taken up vary with the densities of these liquids. Artificially prepared ortho- and meta- silicates of lead and of lithium in all cases yielded a silicic acid of the same composition (with a break in the drying curve a t about 26% H,O and therefore all corresponding according t o Tschermak with metasilicates). Fayalite (Fe2Si0,) from a slag and artificial forsterite (Mg,SiO,) on the other hand gave widely differing results (38.31 and 22.47% H20 respectively) although here with iso- morphous substances the results should be the same if the method is to really indicate the constitution of the silicate. L. J. S. The Chemical Formula of Tourmaline. V. I.VERNADSKI (Zeitsch. Kmyst. Jfin. 1913 53 273-288).-Pen6eld and Foot& general formula as modified by Schaller namely H2,B,Si,02 (A. 1913,MINERALOGICAL CHEMISTRY. ii. 139 ii 68) is discussed in connexion with the author's theory of the alumosilicates (A. 1901 ii 249). Since tourmaline is sometimes formed by the alteration of felspar and on weathering yields kaolin or alkali-mica it may be regarded as possessing a constitution analogous to these and thus be an additive derivative of the kaolin ring Ml2Al2Si2O O*Al(OJI)*O ):si<o. 1 (oM).o>s':o. Further since boron is a.n essential constituent it is necessary to assume a similar ring with boron in place of aluminium; and by joining the two rings the formula becomes M~,A1,B2Si,Ol6. By the addition of various groups to this double ring three fundamental molecules are arrived at namely A = M',A1,B,Si,Ozl B = M114A12B2Si4021 arid C = l!t/2A16B2Si4021 each conforming to Schaller's formula ; structural formulz are written. The composition of all tourmalines is expressed by the mixing -of these three components which are referred to as kalbnite b elbaite and elbaite respectively. Schaller's analysis of pale red tourmaline from Elba corresponds approxi- mately with the molecule G and tourmaline from De Kalb New York contains 97% of molecule A with 3% of molecule B.L. J. S. [Zeolites from near Leitmeritz Bohemia.] J. E. HIBSCH and F. SEEMANN (Tsch. Min. Mitt. 1913 32 1-128).-Explxnntion of the geological map of the Bohemian Mittelgebirge sheet ix Leitmeritz and Triebsch.Several analyses are given of the volcanic rocks. A brief account is given of the mineral species principally zeolites that are found in this district. Analyses are given of the follow- ing all from the basaltic rock at Eulenberg (=Katzenburg) near Schiittenitz. Phillipsite I colourless I1 rose-red crystals. Sanidine (III-V) occurring a6 small colourless crystals and drusy coatings on the phillipsite and on calcite; D 2.568. Thomsonite (VI and VII) D 2.388. SiO,. I. 48.73 11. 51-31 111. 63'64 1V. 65-11 V. 61.46 VI. 38-44 VII. 36-90 A1,0,. 19 -89 18'31 19.46 18.72 18.58 31.48 31 .a3 Fe,O,. CaO. MgO. 5.45 - 4'94 - 0.16 - - - - I 0.38 0.31 1.48 0.60 0.25 13'60 - 13.66 - - - K20. Na,O. 7.36 2.31 6-96 2.37 15.00 1.84 12.87 1-26 15.73 1.93 - 3-53 0.72 4'01 H,O. 16-26 16'12 0.45 0.50 0-75 12.93 13.36 Total.100~00 100*01 10055 99'15 100.78 99'98 100'48 L. J. S. Colour of Zircons and its Radioactive Origin. Hon. R. J. STRUTT (Proc. Roy. Soc. 1914 [ A ] 89 405-407).-0F the two brown varieties of zircon the opaque Find occurs in plutonic rocks whilst the transparent zircon iXfound only in basalts and other lavas. The transparent zircons are thermoluminescent but colour and thermoluminescence are both destroyed by heating to about 300O. In view of this the question arises as to how the basaltic mineral has regained its colour and its capacity to glow. Since zircon con-ii. 140 ABSTRACTS OF CHEMICAL PAPERS. tains hundreds of times as much radioactive matter as ordinary rock masses i t is suggested that the zircons found in l a v a have had their colour and thermoluminescence restored by the slow action of the radium which they themselves contain.The opaque brown zircons are not thermoluminescent nor can they be made so by exposure t o radium. They are not decolourised by moderate heating. I n the belief that the transparent are formed from the opaque zircons by the action of molten basalt an attempt has been made to imitate this experimentally. After twenty-four hours' immersion in molten basalt it was found that the opaque brown zircon had become white although not trans- parent. On exposure to radium the zircons assumed the deeper red colour of hyacinths and became like them thermoluminescent. H. M. D. Chemical Investigation of Certain Minerals from Ceylon Gravel. IV. G. P. TSCHERNIK (Bull. Acad.Sci. St. Pbtersbo?irg 1913 1029-1041. Compare A 1913 ii 970).-The mineral here described is obtained from the Southern Province of Ceylon and occurs as small pebbles which give Kransparent thin sections con- taining very small crystals of calcium fluoride and more rarely tetragonal prisms of titanite. Sections taken from near the surfaces of the pebbles include earthy brownish-red opaque particles the number of which increases as the periphery is approached. The fluorspar crystals are distributed uniformly throughout the main bulk of the pebble but. beginning with the zone containing the earthy particles increase considerably in number towards the surface. I n one direction the pebbles form thin cleavage plates exhibiting an intense vitreous lustre and the fracture is imperfectly conchoidal the streak whit'e and the brittleness slight; the specific gravity is 3-49 and the hardness almost identical with that of orthoclase. SiO,.TiO,. Cb,O,+T+O,. ZrO,. FeO. MnO. CaO. 31.97 2'48 4-03 30.63 4-50 4-43 9.57 Chemical analysis gives the results MgO. K,O. Na,O. H,O. F. Total less OG2F. 0.04 0.32 7.50 2'24 2.36 99.08 These results give the formula 34Si0,,2TiO2,Cb,0,,1 6Zr0,,4Fe0,4Mn0,11Ca0,8N~O,8H,0,8F which may be expressed thus 4N+O(Zr02)2 4Na20(Si0,) + CaO(ZrO,) + (CaO),Cb,OB + CaO(TiO,) + CaO(SiO,) + 4CaF2 + 4FeO(SiO,) + 4Mn0(Si02),+ 4Zr?,(SiO,) + 8&0. The properties of the mineral indicate its close resemblance t o IAvenite. T. H. P. General Principles Underlying Metamorphic Processes. JOHN JOHNSTON and PAUL NIUULI (J. Geol. 1913 21 461-516 588-624).-The authors give an account of the more important general principles which may be usefully apptied in the study of rock metamorphism. The influence of temperature pressure stressANALYTICAL C H EMISTRP. ii. 141 (non-uniform pressure) and gross coinpositiou of the system when metamorphism occurs are considered in detail with reference t.o certain special cases of changes iii condensed systems. H. X. D.

ISSN:0368-1769    

DOI:10.1039/CA9140605136

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ANALYTICAL C H EMISTRP. Analytical Chemistry. ii. 141 A Modifled Hempel Gas Pipette. STANLEY R. BENEDICT (Bio- cham BUZZ. 1913 3 I).-The pipette is designed to avo;d shaking. the gas being made to bubble through the apparatus. W. D. H. Filter from which a Precipitate may be Removed Quantita- tively. E. THUTZER (Chem. Zeit. 1914 38 55).-A tube slightly widened out at its lower end fits over the upper end of a second tube which is connected with a pump. A perforated plate carrying a layer of filtering material (asbestos) is placed in the upper tube and rests on the edge of the lower tube. After the precipitate has been collected and washed the lower tube and the perforated plate are removed and the filtering material and precipitate are rinsed Properties of Soma Chlorohydrocarbons and their Uses in Chemical Analysis.L. GOWING-SCOPES (Analyst. 191 4 39. 4-20). -After recording the physical constants of the chloroethanes and chloroethylenes the author describes the action of these substances on various metals and other inorganic substances. The solubility of 248 organic substances in the chlorohydrocarbons was deter- mined and the results a;re given in tabular form; these organic substances included hydrocarbons ethers alcohols phenols alde- hydes ketones and quinones acid anhydrides acids and esters carbo- hydrates glucosides halogen derivatives amides nitro-compounds purine derivatives azo-compounds gums and resins colouring substances (aniline dyes) etc. The different solubilities of the colouring substances in the chlorohydrocarbons suggests a method of separating these substances and a table is given indicating the kind of separations possible but much further work is required in this direction.Trichloroethylene is suitable as a solvent for fat extractions (compare A. 1910 ii 647) and the chloroethanes and dichloroethylene may be found useful in the analysis of caoutchouc. Various reactions of the chlorohydrocarbons are described. into any suitable vessel. w. P. s. w. P. s. Winkler's Method for the Estimation of Oxygen in Water ; the Effect of Nitrite and its Prevention. FRANK E. HALE and THOMAS W. MELIA ( J . Ind. Eng. Chem. 1913 5 976-980) -The results obtained by this method are trustworthy and are not affected by the presence of nitrites in quantity less than 0*2 part per million.ii.142 ABSTRACTS OF CHEMICAL PAPERS. With larger amounts of nitrites the results are too high owing to the reaction between the nitrous acid and hydriodic acid; the reaction is catalytic the nitric oxide formed absorbing oxygen from the air and yielding nitrous acid which in turn decomposes a further quantity of hydriodic acid. This effect may be prevented by carrying out the method in the usual way and introducing 2 C.C. of potassium acetate solution (1000 grams per litre) when the precipitate has dissolved in the added hydrochloric acid. The acetate solution should be added by means of a pipette reaching to the bottom of the bottle. w. P. s. Estimation of Oxygen in Organic Compounds. 11. MAITLAND 0. BOSWELL (J. Amev. Chem. Soc. 1914 36 187-132).-The method described in an earlier paper (A 1913 ii 334) gives satisfactory results with highly oxygenated compounds but if the oxygen is less than 30-40% the results are too high.A method has now been devised which can be applied to any organic compound irrespective of its oxygen content,. It consists in heating a weighed quantity of the substance in a quartz combustion tube in a current of nitrogen causing the vapours to pass over a small quantity of heated copper oxide of known oxidising value distributed over a long layer of asbestos weighing the water and carbon dioxide formed and deter- mining the oxidising value of the copper oxide which has not been reduced. The weight of oxygen x in the weighed quantity of substance is calculated by means of the equation x = b + c + d - a where a is the weight of the total oxygen available from the copper oxide in the tube b the weight of oxygen available from the copper oxide remaining after the combustion c the amount of oxygen in the water produced and d the amount of oxygen in the carbon dioxide formed.The hydrogen content of the substance may be calculated from the weight of water produced. This method gives results differing by 0.3% from the calculated values in the case of hydrogen and by 0*3-1*0% in the case of oxygen. E. G. Rapid Estimation of Sulphur in its Different S t a t e s in Biological Liquids and in Particular in Urine. R. GAUVIN and V. SKARZYNSKI (Bull. Soc. chim. 1913 [iv] 13 1121-1127).-The authors have estimated the total sulphur sulphur as sulphates and sulphur as ethereal sulphates in urine as follows.For total sulphur the oxidation was performed by boiling with dilute hydrochloric acid and potassium ch1orat.e for twenty minutes the excess of oxidising agent being destroyed by addition of 1 C.C. of a 10% sugar solution. The solution was just neutralised 2 C.C. of hydrochloric acid added and the sulphates present precipitated by addition of a dilute solution of benzidine hydrochloride in excess according t o Raschig's method. The sulphates and ethereal sulphates were pre- cipitated together by the same reagent after hydrolysing the esters by boiling with dilute hydrochloric acid. Finally the sulphates in the urine were estimated by direct precipitation with benzidine hydrochloride solution. I n each case the benzidine sulphate pre-ANALYTICAL CHEMISTRY. ii.143 cipitate was collected well washed and finally suspended in water and titrated a t boiling point with N / 10-sodium hydroxide using phenolphthalein as indicator. W. G. Decomposition of Large Quantities of Organic Substance in Kjeldahl’s Method. EMILE CARPIAUX (Bull. SOC. chim. BaZg. 29 13 27 333-334).-In order to avoid troublesome frothing when large quantities of organic substance are digested with sulphuric acid the following procedure is recommended. Thirty grams of the sub- stance (for instance straw or hay) are placed in a 500 C.C. flask and about 30 C.C. of sulphuric acid are added the mixture is shaken and set aside for about one hour. The spongy mass is then treated with a further quantity of sulphuric acid and heated until a clear colourless solution is obtained.The greater part of the excess of sulphuric acid may be removed by adding small quantities of sugar STANLEY R. BENEDICT and EMIL OSTERBERG (Uiochem. Bull. 191 3 3 41-44).- Steel recommends that in urines containing ammonio-magnesium phosphates sodium hydroxide and sodium chloride should be employed t o replace the sodium carbonate employed in Folin’s method t o liberate ammonia. I n the present research it is shown that all urines yield more ammonia when Steel’s method is followed. The reason is that the addition of sodium carbonate to urine always causes the formation of ammonio-magnesium phosphate crystals and this substance does not yield its ammonia quantitatively when decomposed by sodium carbonate.Folin’s latest micro-chemical method of urea estimation is also criticised for as Folin and Macallum themselves state a trace of something which colours Nessler’s reagent continues to come off long after all the ammonia is removed. This unknown factor may lead to results 12% too high. Aeration Methods for the Estimation of Ammonium Nitrogen. 111. The Ammonium Nitrogen in Beef. JACOB SHULANSKY and WILLIAM J. GIES (Biochem. Bull. 191 3 3 45-53).- Steel’s method gives better results than Folin’s for the reason stated in the preceding abstract. The error may be specially great in the case of meat subjected to cold storage if the original Folin method is used. W. D. H. to the boiling solution. w. P. s. Estimation of Ammonia in Urine. W. D. H. Estimation of Nitrogen by the Nitrometer.C. M. JOYCE and HARRY LA TOURETTE (J. Ind. Eng. Clmn 1913 5 1017-1018).- The nitrometer used by the authors consists of a gas generating bulb fitted a t the top with a two-way tap leading to a dissolving cup and an exit tube; the bottom of the bulb is connected with a levelling tube. The gas measuring apparatus consists of a graduated tube connected with a levelling tube through a T-piece leading to an equilibrium tube. Three drops of sulphuric acid are introduced int’o the latter a t the time the volume of air in i t is adjusted. The apparatus gives trustworthy results in the case of nitrateii. 144 AESTRACTS OF CHEMTCAL PAPERS. uitrogen but is not available for the estimation of nitrogen in celluloid or other substances containing carbon ring compounds.In the case of nitrocellulose abnormally high results were obtained when the estimations were made a t a temperature above 28O. This was due to the diminished solubility of nitric oxide in sulphuric acid and to the partial decomposition of cellulose into carbon mon- oxide and carbon dioxide. The algebraic sum of these two correc- tions for temperatures from 20° to 35O is as follows 20° to 27*5O +0+90 c.c.; 2 8 O +0*74 c.c.; 29O +0*34 c.c.; 29*5O +0.10 c.c.; 30° -0.14 c.c.; 30*5O - 0.70 C.C. ; 31° to 35O -0.94 C.C. w. P. s. Comparative Investigation of Certain Reactions for the Detection of Nitrites in Potable Water. M. BORNAND (Chem. Zentr. 191 3 2 1823-1824 ; from Mitt. Letens I4ittelunters. HYIJ.. 1913,4,285-289).-The following processes have been investigated (1) the von Ilosva-Lunge met-hod in which on the one hand sulph- anilic acid (0.5 gram) is dissolved in dilute acetic acid (150 c.c.) whilst on the other hand solid naphthylamine (0.2 gram) is boiled with water (20 c.c.) the colourless solution filtered from the bluish- violet residue treated with dilute acetic acid (150 c.c.) and the two solutions mixed.The reagent (2 c.c.) is mixed with 50 C.C. of the water under investigation; after five to ten minutes the presence of the slightest trace of nitrous acid is indicated by the red colora- tion of the liquid. (2) Rochaix’s method (Semaine Mtd. 1909 6 72) in which 20 C.C. of a 0’2 per cent. solution of neutral-red are treated with 10 C.C. of the water and then with 1 to 3 C.C. of 20% sulphuric acid; the presence of nitrites (even 0.00005 gram N,O in 1 litre) yields a violet to blue colour.(3) Barbet and Jandrier’s method (A. 1897 ii 234) according to which resorcinol (0.1 gram) is dissolved in the water (2 c.c.) and concentrated sulphuric acid (1 c.c.) added; the presence of nitrite (0.1 mg. per litre) causes a rose coloration a t the junction of the liquids. (4) The method of DenigGs (A. 1911 ii 655) and (5) that of Chwilewsky (Ohem. Zentr. 1913 i 1218). According to the author’s experience all the above methods are well adapted f o r the detection of nitrous acid in potable waters with the exception of that of DenigBs which is unsuited for practical use in the laboratory on account of the unstability of the reagent. The first-described process is however preferred as i t can be readily used not only in the laboratory but also a t the place of collection of the sample.H. W. Gravimetrio Estimation of Nitrites. N.!BUSVOLD (Chem. Zeit. 1914 38 28).-1*4-1*5 Grams of silver bromate are dissolved in 100 C.C. of water 110 C.C. of 2N-acetic acid are added and the whole heated to 80°; 200 C.C. of the sodium nitrite solution (about 1 gram per litre) are added from a dropping funnel and then 30 C.C. of dilute sulphuric acid (1 4) a t 85O. The precipitate consisting of silver bromide is washed with boiling water collected in a Gooch crucible and dried at 130O. From the weight should be deductedANALYTICAL CHEMISTRY ii. 145 any silver chloride determined previously; 1 mol. of silver bromide = 3 mols. of nitrous acid. L.DE K. Phenoldisulphonic Acid Method for Estimating Nitrates in Soils. C. B. LIPMAN and L. T. SHARP (Bied. Zentv. 1913 42 72 1-726 ; from Univ. California Publ. Agric. Sci. 1912 1 2 1-37). -In presence of sodium sulphate considerable losses of nitrogen take place when the phenoldisulphonic acid method is employed; the losses are however less Lhan when chlorides are present. Low results are also obtained with soil extracts which have been clarified by means of alum or animal charcoal; and small iosses occur when a clay filter is employed. Calcium hydroxide (2% of the weight of soil) may be employed. The presence of sodium carbonate in soil extracts seems to be without appreciable effect. N. H. J. M. The Pemberton-Kilgore Method for the Estimation of Phosphoric Acid.P. L. HIBBARU (J. Ind. Eng. Cham. 1913 5 998-1009).-This method which consists in precipitating the phosphoric acid with molybdic acid and titrating the yellow p r e cipitate formed has been submitted to a critical examination by the author mainly with the object of eliminating certain sources of error in the process. The phosphate solution should contain about 0.02 gram of P20 per 100 c.c. and this quantity requires 15 grams of ammonium nitrate and 30 C.C. of 5% molybdic acid solution con- taining 7% of free nitric acid for precipitation. Chlorides in general cause low results whilst the presence of sulphates causes the results to be too high. When the yellow precipitate is contaminated from any cause it may be purified by reprecipitation. Ignition with magnesium oxide is recommended for the removal of organic substances from a phosphate previous to the estimation of the phosphoric acid and the use of silver phosphate is suggested for standardising the sodium hydroxide employed for the titration of the yellow precipitate. w.P. s. Preparation of Neutral Ammonium Citrate Solution. PAUL RUDNICK and W. L. LATSHAW ( J . Ind. Eng. Chem. 1913 5 998).-Two separate ammonium citrate solutions when examined according to the method described by Patten and Marti (A. 1913 ii 790) showed ratios of ammonia to citric acid of 1 :3*786 and 1 3.748 respectively. Comparative analyses of a sample of acid phosphate with these two solutions yielded identical figures indi- cating that the variation of these solutions from the ratio given by Patten and Marti (1 :3-765) was not sufficient to affect the results obtained.w. P. s. Rapid Method for the Estimation of Arsenic in Sulphuric and Hydrochloric Acids. €3. KOELSCH (Cham. Zeit. 1914 38 5-6).-Twenty-five C.C. of sulphuric or 100 C.C. of hydrochloric acid are diluted in an Erlenmeyer flask with 200 C.C. of water 5 C.C. of potmsium iodide (50 grams per litre) are added and the whole is VOL. CVI. ii. 10ii. 14G ABSTRACTS OF CHEMICAL PAPERS. boiled until the liquid becomes yellow. Five C.C. of sodium sulphite solution (25 grams of crystals per litre) are added and the boiliiig is continued for another five minutes. After neutralising the acid with alkali hydroxide solution (the total volume should then be 700 c.c.) a little sodium hydrogen carbonate is added and the arsenious acid formed titrated as usual with standard iodine.Minute traces of nitric acid do not interfere with the process L. DE I(. Estimation of Arsenic and Antimony in Alloys and of Arsenic in Copper. G. BRESSANIN (Ann. Chim anal. 1913 18 465-468).-The process is based on the fact that tin in the higher state of oxidation and dissolved in sulphuric acid of D 1-53 (a little tartaric acid may be added t o facilitate solution) is precipitated as stannic iodide on adding potassium iodide whilst arsenic and antimony in the quinquevalent state liberate iodine and are pre- cipitated as the lower iodides which may then be readily estimated iodometrically . Arsenic in commercial copper is estimated by dissolving 0.8 gram in 5 C.C. of aqua Tegia the solution is evaporated to dryness and the residue dissolved in 250 C.C.of sulphuric acid (U 1.53). When cold 25 C.C. of 30% potassium iodide are added; this precipitates both copper and arsenic as the lower iodides which are collected on an asbestos filter and washed with 30-40 C.C. of the above acid to which have been added 5% potassium iodide solution. The arsenic tri-iodide is now dissolved off the filter by means of 100 C.C. of dilute sulphurous acid and to the clear filtrate is added starch solution and sufficient iodine to impart a very faint blue colour. Excess of sodium hydrogen carbonate is then added and the arsenic titrated with weak standard iodine. L. DE K. Method for Estimating Extremely Small Quantities of Boron in Organic Substances. GABEXEL BERTRAED and H.AQULHON (compt. rend. 1913 157 1433-1436).-A colorimetric method of estimating minute quantities of boron in dry matter of animal or vegetable origin. The method is based on the reaction of boric acid with turmeric under conditions already dhcribed (com- pare A. 1910 ii 241 345). The dry matter is rendered alkaline by the addition of a few drops of sodium hydroxide and calcined a t a red heat.. The ash is triturated with phosphoric acid transferred to a flask and distilled with methyl alcohol the distillate being collected in a capsule containing five drops of N-sodium hydroxide solution. This is then evaporated to dryness four drops of N/10-hydrochloric acid added and the whole transferred to a test- tube by means of distilled water the volume being made up to 1.5 C.C.A strip of turmeric paper 45 mm. long and 3 mm. wide is inserted allowing 15 mm. to project and the amount of boron present is determined by the length of the coloration produced a t the end of the paper after two hours a t 35O as compared with standard control solutions. W. G.ANALYTICAL CHEMISTRY ii. 147 A Dennstedt Combustion Furnace with Internal Electric HeatiDg. C. MILCHSACK and W. A. ROTR (Zeitsch. ccngew. Chem. 1914 27 5-7).-The disadvantage of the ordinary Dennstedt furnace with electric heating is that the contents of the tube cannot be observed during the combustion. The authors describe an arrangement by means of which the tube can be electrically heated internally and the process of combustion observed continuously. Good results were obtained with such substances as naphthalene benzoic acid toluene and cinchonine.T. S. P. Volumetric Estimation of Small Amounts of Potassium. LEOPOLD ZALESKI (Lnndw. T%rsucAs. -Stat. 1 9 1 3 83 22 1-25q.- Direct precipitation with de Koninck’s reagent is considered more certain as well as simpler than Mitscherlich’s method especially when the following modifications are adopted. The reagent which is added in drops or a thin stream and stirred in is employed in considerable excess (0-5 to 1 C.C. of reagent per mg. of K,O). Filtration follows after twelve to twenty-four hours and the potassium factor is simultaneously tested under the same conditions as the esbimation. N. H. J. Rf. Eetimation of Lead in the Defecated Liquids of Molasses. H. PELLET (Ann. Chim.anal. 1913 18 475-476).-The 1e.d (in absence of interfering substances,) is precipitated as sulphite by passing a. current of sulphur dioxide. The precipitate is collected on a counterpoised filter and dried. Multiplied by 0,721 the amount of lead is obtained. Sometimes the sulphite is somewhat coloured but this does not appreciably affect the weight. L. DE K. Method for the Assay of Native Copper Sulphidee Pyrites Copper Mattes etc. 1,. BERTIAUX (Ann. Chirn. anal. 1913 18 468-478).-A process f o r the estimation of copper silver gold arsenic antimony nickel and cobalt iron bismuth lead sulphur and silica in the above materials and practically the same as that published by Holland and Bertiaux (Analyse des Metaux 2nd Ed.). L. DE K. Separation of Iron and Aluminium. HERMANN BORCK (Chem.Zeit. 1914 38 7).-The old process of separating the two oxides by igniting in a mixed current of air and hydrogen chIoride (when the alumina is left) is but rarely applied as it is not very accurate. The author however finds that by using a boat made of quartz instead of one made of platinum or porcelain the results are quite trustworthy. An illustration of a convenient apparatus is given. L. DE K. The Estimation of Chromium by Oxidation in Alkaline Solution. F. BOURION and A. SBRBCHAL (Conapt. rend. 1913 157 1528-1531).-The estimation of chromium by oxidation in alkaline solution in the cold with hydrogen peroxide removal of the excess of hydrogen peroxide by boiling reduction of the 10-2ii. 148 ABSTRACTS OF CHEMICAL PAPERS.chromic aeid with a known quantity of ferrous sulphate in the presence of sulphuric acid and titration of the excess of ferrous sulphate with potassium permanganate gives exact results in the presence of iron but is vitiated by the presence of nickel cobalt and manganese Sodium sulphate greatly facilitates the destruc- tion of the large excess of hydrogen peroxide which is necessary and this action is also catalysed by ferric oxide. Electro-analytical Studies. [Arsenic. Bismuth.] BURT P. RICHARDSON (Zeztsch. anorg. Chem. 19 13 84 277-3 17).-The experi- ments have been inada with a gauze cathode and a rotating anode using a cylindrical glass vessel with tap and outflow tube. Arsenic is reduced during electrolysis from the quinquevalent to the tervalent condition.The deposition of copper free from arsenic is only possible when the arsenic is originally present in the quinquevalent form. To deposit 0.27 gram of copper from a solution containing 0.1 gram of arsenic the total volume should be 70 C.C. and the temperature 50° 0.6 C.C. of concentrated nitric acid being present. Using 2 amperes deposition of pure copper is complete in twenty minutes. Bismuth is best deposited a t 50° from a solution containing tartaric acid (15 grams for 0.16 gram of bismuth) the voltage being reduced in stages from 1.9 t o 1.5 and the total time thirty- five minutes. This is necessary in order to lessen the evolution of hydrogen. The deposited metal must be washed a voltage of 1.7 being maintained with 1% sodium hydroxide solution; other- wise there is a loss of bismuth by re-solution.It is not practicable to separate bismuth electrolytically from antimony. Arsenic should be present in the quinquevalent form a t a temperature of 60°. Bismuth is separated from cadmium in a solution containing lactic acid at the ordinary temperature. The voltage is gradually lowered during the deposition. Some anoma- lies in the process are still unexplained. Bismuth deposited in the ordinary way is separated quantitatively from lead. Measurements of the cathode potential during the deposition of several metals have also been made and the results brought into relation with the formation of spongy deposits under certain conditions. The best cathode potential having been once deter- mined i t is sufficient in practical determinations to meaaure the difference of potential between the electrodes.Bismuth does not form complex ions with tartaric acid to any considerable extent. C. H. D. Determination of the Oxidisability of Mineral Waters. N. NIKITIN (J. Russ. Phys. Chem. Soc. 1913 45 1697-1700).-The determination of the oxidisability (oxygen absorbed) of natural waters containing chlorides by means of permanganate in presence of sulphuric acid results in interaction of the hydrochloric acid set free and the permanganate with liberation of chlorine. It is therefore necessary to diminish the total amount of permanganate used up by that destroyed by thO chlorine. The addition of manganese sulphate which retards the action of permanganate W. G.ANALYTICAL CHEMISTRY. ii. 149 does not mem t o ensure satisfactory results there being no guararrtee that the organic matter is completely oxidised or that the chlorides are not oxidised to some extent..A better method consists in absorbing the chlorine in potassium iodide solution. The iodine liberated may then be titrated with sodium thio- sulphate or the potassium iodide and iodine solution may be added to the excess of p2rmanganate in the oxidation flask and the whole of the iodine titrated with sodium thiosulphate. Diminution of the original volume of permanganate by that corresponding with the iodine liberated gives the amount employed in oxidising the water. I n determining the oxygen absorbed by a saline water contain- ing 0.5855 gram of sodium chloride and 0.0565 gram of potassium chloride per litre the author prepared a control solution free from organic matter but otherwise of the same composition as the saline water.To each of two flasks containing 100 C.C. of the water and the control solution were added in equal amounts sulphuric acid and a large excess of permangahate solution. The flasks were immersed in a bath of saturated salt solution which was heated in twelve minutes to boiling this heing maintained for exactly ten minutes; at the end of this time the flasks were removed from the bath left in the air for fifteen minutes and then cooled under the tap. After addition of a known amount in excess of standard sodium oxalate solution the contents of each flask were titrated with the permanganate solution. The difference between the amounh of the latter used up in the two flasks represents the organic matter of the water.The uncorrected value for the saline water is four to nine times as great as the value obtained after correction for the control solution. T. H. P. Estimation of the Acidity or Alkalinity of Waters. A Study in Indicators. JAMES MOIR (J. CAem. Met. Mining SOC. S. Africa 1913 14 114-118. Compare A. 1907 ii 389).-Attention is directed to the misleading conclusions which may be drawn m to the acidity of a mine water o r the alkalinity of a town water if the titrations are made with the wrong class of indicator. The true neutral point is difficult to fix and no hard and fast rule can be laid down as to the indicator to be used especially in the case of mine waters; for instance methyl-orange indicates the point a t which free acid has been neutralised lacmoid that at which the free acid and iron and aluminium salts have been neutralised and so on.A “ neutral ” solution prepared by mixing recently-boiled M / lO-solutions of disodium hydrogen phosphate and sodium dihydrogen phosphate in the proportion of 1 volume of the former ts 3 volumes of the latter may be used for determining tha neutral colour of any indicator. The author tabulates some fifty-four colour substances in the approximate order of their Formation of Sediment in Bottled Mineral Waters. Esti- mation of Silica Iron and Aluminium in Natural Mineral Waters. L. DEDE (Chem. Zeit. 1914 38 53-55).-The liability (‘ strength ” as indicators. w. P. s.ii. 150 ABSTRACTS OF CHEMICAL PAPERS.of mineral waters to yield a quantity of sediment after being stored for some length of time in bottles appears to depend on the amounts of alumina and silica contained in the waters; the formation of the sediment is not due to the presence of iron salts since many highly ferruginous waters do not give a deposit. Generally the sediment consists chiefly of hydrated ferric oxide alumina silica and calcium carbonate. It is probable that ferrous carbonate is first of all oxidised and the resulting hydrated ferric oxide causes the precipitation of alumina silica (also finely-divided clay held in suspension) and calcium carbonate. For the estimation of silica etc. it is recommended that the water be neutralised with hydro- chloric acid evaporated to a small volume in a silver basin then transformed to a platinum basin and evaporated with an excess of hydrochloric acid to dryness.The residue should be heated to l l O o for thirty minutes before the silica is collected. W. P. 8. Estimation of the Lime Requirement of Soils. J. A. BIZZELL and T. L. LYON (J. Ind. Eng. Chem. 1913 5 1011-1U12).- Albert (Zeitsch. angew. Chem. 1888 1 533) has proposed a method in which the solution is distilled with barium hydroxide solution and ammonium chloride the amount of ammonia found in the distillate being taken as a measure of the free barium hydroxide not required to saturate the soil (barium hydroxide is preferable to calcium hydroxide since the compounds of the latter with the soil tend to decompose and react with the ammonium chloride). The absorp- tion of the barium hydroxide by the soil is not however imme- diate and certain soils when boiled with ammonium chloride yield coneiderable quantities of ammonia,.The author in order to avoid these sources of error carries out the method as follows Twenty- five grams of the air-dried soil are heated on a boiling water-bath for one hour with 50 C.C. of boiled water and 50 C.C. of N/lO-barium hydroxide solution. One hundred and fifty C.C. of water and 5 grams of ammonium chloride' are then added and the mixture is distilled the ammonia being titrated in the distillate. A further quantity of 25 grams of the soil is then distilled with 5 grams of ammonium chloride omitting the barium hydroxide. The results obtained by the modified method agree with those found by the Vietch process.w. P. s. Identification of Ethyl Alcohol and Methyl Alcohol. J. J. BLANESMA (Chern. Veekblad 1914 11 26-29).-Ethyl alcohol and methyl alcohol can be identified by the action of their sodium derivatives on 1-chloro-2 4-dinitrobenzqne the identity of the 2 4-dinitrophenetole or 2 $-dinitroanisole formed respectively being given by the melting point. R. J. MANNING and M. NIERENSTEIN (Bey. 1913 46 3983-3954).-The author8 find that the addition of acetic anhydride as sometimes recommended for the Zeisel determination introduces a source of error for in the absence of any third substance the mixture of acetic anhydride A. J. W. Determination of the Methoxyl Group.ANALYTICAL CHEMISTRY. ii. 151 and hydriodic acid may give rise to the formation of appreciable quantities of silver iodide.The application of phenol is also untrustworthy for a similar reason. D. F. T. New Method fur the Eatimation of Glycerol in Wine. S. ROTHENFUSSER (Zeitsch. Ndw. Gcnussm. 1913 26 535-544).-The method depends on tGhe oxidation of the glycerol to oxalic acid by means of permanganate after other oxidisable substances (sugars) have been removed by treatment with ammoniacal lead acetate solution. I n the case of wine containing not more than 1% of sugars 50 C.C. of the sample are mixed with 30 C.C. of a 20% sodium carbonate solution 5 grams of crystallised stannous chloride are added the mixture is diluted to 250 c.c. and filtered; 200 C.C. of the filtrate are then treated with ammoniacal basic lead acetate solution (40 C.C.of basic lead acetate solution mixed with 20 C.C. of 10% ammonia) diluted with 10% ammonia to 300 c.c. filtered and 200 C.C. of the filtrate are evaporated t o 50 c.c. after the addition of 5 C.C. of 10% sodium phosphate solution and 6 grams of anhydrous sodium carbonate. The solution without filtration is now transferred to a flask diluted to 100 c.c.,cooled to 25O and 10 grams of potassium carbonate and 2 grams of potassium perman- ganate are added. After forty-five minutes the excess of perman- ganate is destroyed by the addition of hydrogen peroxide the mixture is diluted to 250 c.c. filtered and the oxalic acid is pre- cipitated from 230 C.C. of the filtrate as calcium oxalate the solution being first acidified with acetic acid. The calcium oxalate is then collected and titrated with standardised permanganate solution.With wines containing up to 6% of sugars 50 C.C. of the sample are mixed with 15 C.C. of sodium carbonate solution and 2.5 grams of sttannous chloride diluted to 250 c.c. filtered and 220 C.C. of the filtrate are diluted with 5% ammonia to 250 C.C. h mixture consisting of equal volumes of basic lead acetate solution and 10% ammonia is then added until a small portion of the solution after filtration gives a black precipitate with ammonium sulphide and no longer reduces Fehling's solution; 20 C.C. of 10% ammonium carbonat'e solution are now added the whole'is diluted with 10% ammonia to 500 c.c. and filtered. To 250 C.C. of the filtrate are added 5 C.C. of 10% sodium phosphate solution and 6 grams of anhydrous sodium carbonate and the process is proceeded with as described.The method may aIso be applied to sweet wines. w. P. s. [Estimation of Cholesterol.] JOSEPH SAMUEL HEPBURN (Cham Zentr. 1913 ii 2052-2053; from J. Pranktin Inst. 1913 176 405-452).-See this VO~. i 168. Rotatory Power of Laevulose and of Invert Sugar. J. LABORDE (Ann. Falsif. 1913 6 650-660).-Laevulose was found to have [u] -93.60° and invert sugar [u]; -20*30° (compare A. 1913 ii 447); the method of preparing the lamdose or invert sugarii 152 ABSTRACTS OF CHEMICAL PAPERS. (heating with hydrochloric acid or by enzymic action) do- not affect these constants. If however a solution containing lavulose has been heated with an acid then cooled and neutralised the polari- metric reading must not be taken until after the solution has been kept at 20° for about one hour; when the reading is taken imme- diately after the solution has been cooled and neutralised the result will differ by several degrees from the true value.This is due to the muta-rotation of the lav~~lose; this source of error may also be eliminated by taking the reading on the acid solution or after the addition of a slight excess of ammonia. Dextrose exhibits muta- rotation to a much less extent than does laevulose. The rotation of laevulose is also affected by temperature since it increases as the temperature is lowered; for readings between 9 O and 2 5 O the correc- tion is 0’32O (polarimetric) for each degree of temperature when the latter differs from 20°. Since lzvulose is more readily destroyed than dextrose by caramelisation and by the action of yeasts the presence of added dextrose (“glucose”) in sweets etc.is not indicated with certainty unless the excess of dextrose over the l~vulosexceeds 9% (calculated on the quantity of the two sugars). w. P. s. Estimation of Carbohydrates especially in Plant Extracts. WILLTAM A. DAVIS and ARTHUR JOHN DAISH (J. dgric. Sci. 1913 5 437-468).-The plant extract is evaporated under 700-740 mm. pressure and made up to definite volume (500 c.c.) of which two portions of 20 C.C. are used for estimating dry matter whilst the rest is precipitated with basic lead acetate filtered washed and diluted to two litres. A portion of this (300 c.c.) is precipitated with solid sodium carbonate and diluted to 500 C.C.This solution is employed (1) for direct reduction and polarisation and (2) for sucrose; 50 C.C. are inverted by invertase after being made faintly acid to methyl-orange by a few drops of sulphuric acid. Autolysed yeast (1-2 c.c.) and two or three drops of toluene are added to the solution which is kept for twenty-four hours at 38-40°; it is then treated with 5-10 C.C. of alumina cream filtered washed and diluted to 100 C.C. It is then polarised and the reducing power estimated in 50 C.C. Another portion is inverted by 10% citric acid by adding 10% of the crystallised acid to the solution slightly acidifying with sulphuric acid and boiling for ten minutes. It is then cooled neutralised to phenolphthalein with sodium hydroxide and diluted to 100 C.C.This is polarised and the reducing power estimated. The values obtained by the two methods should agree closely. Maltose is estimated in another 300 C.C. of the original solution which is precipitated with hydrogen sulphide filtered and washed until the filtrate is about 450 C.C. Air is then drawn through for ono and a-half hours and a little ferric hydroxide added to remove the last traces of hydrogen snlphide. The filtered solution is made up to 500 c.c. and portions of 50 C.C. fermented with S.murxian~1~ S. nnomalus and S. exigums respectively and two others with ordinary yeast The difference between the average reducing powerANALYTICAL CHEMISTRY. ii 153 of the first three and that of the last two eolutions givee the reduction due t o maltose. When the reduction in the first solution (precipitated with sodium carbonate) due to pentose and maltose has been allowed for the remaining direct reduction is due t o dextrose and laevulose the actual amounts of which are calculated from the reducing power combined with the corrected specific rotation.As regards the gravimetric method the purification of the asbestos by boiling with 20% sodium hydroxide should be continued for not less than half an hour. The volumetric method of Ling is preferable to that of Bertrand which is only roughly approximate. The employment of basic lead acetate does not give rise to losses of sugar the supposed loss being probably due t o incomplete inver- sion in presence of sodium acetate. Maltose cannot be completely hydrolysed by dilute hydrochloric acid either a t 70° or looo without destroying large amounts of la3vulose or dextrose.The only available method consists in employ- ing special maltose-free yeasts such as the three referred to a correction being introduced for pentoses etc. by a special fer- mentation with bakers' or brewers' yeast. Fatty Acids and Detection of Araohidic Acid. S. FACHINI and G. DORTA (Chcm. Zeit. 1914 38 18).-'l'he authors have noticed that the potassium salts of the liquid (oleic) acids are readily soluble in solution of acetone whilst those of the solid acids are insoluble therein. In order to detect arachidic acid in the acids isolated its usual from 10 grams of olive oil these are dissolved in 90 C.C. of pure acetone a t boiling heat and 10 C.C. of N-potassium hydroxide are added.When quite cold the crystals are collected on a filter using a suction apparatus and washed with small portions of acetone. The fatty acids liberated by means of dilute acid are if necessary purified by means of light petroleum and then tested as to their melting point and molecular weight. Arachidic acid may be iqolated and further identified by re- crystallisation from 90% alcohol. If to the acetone solution is added an insufficient amount of potassium hydroxide the precipi- tate will consist mainly of the arachidic compound and the identi- Applied Michrochemistry of Plants. VIII. Identification of Lichesteric Acid. 0. TUNMANN (Chem. Zentr. 1913 ii 2060-2061 ; from Apoth. Zeit. 1913 28 892-893).-The identifica- tion of lichesteric acid in Iceland moss can be accomplished by sublimation of the finely-divided thallus whereby rhombic crystals and granular aggregates are obtained which are unchanged by ferric chloride insoluble in water soluble in alkalis alcohol and ether slowly soluble in acetic acid.The microchemical preparation of the ammonium and sodium salts is particularly adapted to the detection of lichesteric acid. The latter appears to be previously formed in Iceland moss and to be localised in the under layer of the lichen. H. W. N. H. J. M. fication will then be easier. L. DE K.ii. 154 ABSTRACTS OF CHEMICAL PAPERS. A Colour Reaction of Glycine when Boiled with Chloral Hydrate. EDWIN D. WATKINS (Biochem. Bull. 1913 3 26-27).- Glycine even in very dilute solutions gives a red colour when boiled with chloral hydrate.Phenol glycerol resorcinol acetone ethyl alcohol glyoxylic acid orthophosphoric acid and chloral when boiled with glycine yield no colour. Acetone boiled with barium hydroxide solution and then with glycine solution yields a green colour which changes to red in thirty minutes. W. D. H. Detection and Estimation of Benzoic Acid in Milk and Cream E. RINKS (Analyst 1913 38 555-557).-The presence of 0.01% or mom of benzoic acid in milk or cream may be detected with certainty by means of the following method 25 C.C. of the milk or from 10 t o 20 grams of the cream are heated with an equal volume of concentrated hydrochloric acid until the curd has dissolved completely. The mixture is cooled shaken with 25 C.C. of a mixture consisting of 2 volumes of light petroleum and 1 volume of ether the ethereal solution is separated and shaken after the addition of 1 drop of ammonia and 5 C.C.of water. The aqueous layer is now separated heated on a water-bath for a few minutes to expel the excess of ammonia and then tested with ferric chloride solution. On the addition of the ammonia a precipitation of ammonium benzoate takes place and this reaction although less characteristic is more sensitive than the ferric chloride test. The quantity of benzoic acid present may be estimated by heating 25 C.C. of the milk with hydrochloric acid under a reflux apparatus extracting the cooled solution three times with 20 C.C. of the mixture of light petroleum and ether and shaking the separated ethereal portions with 10 C.C.of water and 1 drop of ammonia; this extraction is twice repeated. The mixed aqueous portions are then a c i a e d with hydrochloric acid extracted three times with the ethereal solvent the extracts are evaporated at the ordinary temperature and the residue is dried in a desiccator to constant weight. The benzoic acid is then volatilised at looo the The Identiflcation of Carbamide and its Precipitation from Extremely Dilute Solutions. R. FOSSE (Compt. rend. 19 1 3 15 7 948-951).-By means of its xanthhydrol derivative it is possible to separate carbamide and identify i t by analysis a t a dilution of 5 parts in 100,000. It can be identified microscopically a t a dilution of 1 in 100,000 and precipitated a t a dilution of 1 in 1,000,000. A t the first dilution the precipitation is best carried out by adding to 2 parts of the solution 7 parts of acetic acid and 1 part of a 10% alcoholic solution of xanthhydrol.I n the second and t h i d cases acetic acid should be added until the final solution contains 10% of this acid. The precipitate recrystallised from alcohol forms radiating microscopic filaments. Volumetric Estimation of Carbamide. ADOLF JOLLES (Biochem. Zeds&. 1913 57 414-419).-Tt is found that by the addition of loss in weight giving the amount of the acid. w. P. s. W. G.AXALYTICAL CHEMISTKY. ii. 155 potassium ferricyanide to the hypobromite solution results nearer to those required by theory are obtained than when the former substance is omitted; 2.5 C.C. of the carbamide solution (diluted so as to contain 2.3% urea) are treated with 5 C.C.of 20% potassium ferricyanide solution and then 20 C.C. of a solution produced by dissolving 150 grams of sodium hydroxide and 25 grams of bromine in 250 C.C. of water are added. The nitrogen evolved is collected in a nitrometer a convenient form of which is described and figured in the text. Estimation of Caffeine in Kola Preparations particularly in Granulated Kola. MAURICE FRARQOIS (Ann. FuZsvY. 1913 6 596-608).-The whole of the caffeine present in kola preparations such as the extract fluid extract and granulated products may be extracted by means of chloroform provided that the prepara- tion is mixed with magnesia dried thoroughly and then ground up with sand before the extraction is commenced. The caffeine thus obtained is free from ash and does not contain more than 1% of impurities which are insoluble in hydrochloric acid.I n the case of kola nuts themselvee the method yields low results owing to the fact that the magnesia does not penetrate the particles suffi- ciently to liberate the whole of the caffeine; in this respect the New Test for the Cinchona Alkaloids. G . N. WATSON (dntsr. J . Pliarm. 1913 85 502)-X vellow precipitate is foimed w1ic.n n sulphuric acid solution of quinine cinchonine or cinchonidine is treated with a few drops of a saturated alcoholic solution of a-naphthol to which a small quantity of sulphuric acid has been added; the precipitate is soluble in excess of the reagent yielding a yellow solution. Other white alkaloids do not give the yellow coloration.The test will detect the preseiice of the cinchona alkaloids in mixtures of the same with atropine morphine cocaine S. B. S. method requires further investigation. w. P. s. strychnine caffeine brucine and codeine. w. P. s. A Colorimetric Method for the Estimation of Histidine. MORIZ WEISS arid NIKOLAUS SOBOLEV (Biochem. Zeitsch. 1913 58 119-129).--The Pauli diazo-reaction for histidine waa employed. The reagents used were a solution of sulphanilic acid in hydro- chloric acid and a solution of sodium nitrite. A mixture of these was added to the solution under investigation and then 10% sodium carbonate was added. The total volume of the mixture was kept constant and the colour obtained wit^ then compared with that got under similar conditions with a 1 / 10,000 histidine solution.The solution under investigation was then diluted and the test repeated until a dilution equivalent to a histidine content of 1 / 10,000 was obtained. For accurate estimations the control and test solutions could then be compared in a Duboscq colorimeter. Certain inhibitory substances are sometimes present which appear to combine with the diazonium compound. In these cases larger quantities of the reagents must be employed and a scheme isii. 156 ABSTRACTS OF CHEMICAL PAPERS. Pruggested by means of which the influence of the inhibitory aubstancw can be removed by carrying out the reaction systemati- cally in the presence of varying amounts of the reagents. S. B. S. The Non-interference of ‘‘ Ptomaines ” with Certain Tests for Morphine. JACOB ROSENBLOOM and S.ROY MILLS (J. Bid. Chem. 1913 16 327-330).-Bacterial products formed during amobic and anaerobic putrefaction of human organs did not in any way give reactions simulating those due to the presence of morphine and in no way interfered with the detection of morphine when this alkaloid was added. Each of the many reactions for morphine are dealt with. W. D. H. The Reaction of Some Purine Pyrimidine and Hydantoin Derivatives with the UriclAcid and Phenol Reagents of Folin and Denie. HOWARD B. LEWIS and BEN H. NICOLET (J. BioZ. Chem. 1913 16 369-374).-Many derivatives of the groups mentioned give the reactions referred to; long lists of these are given in reference to these reactions. With the exception of thiocarbamide no substance was observed to react typically with the phenol reagent which does not contain a phenol group or react with the uric acid reagent. With the exception of the thiopurines none of the purines react positively. Funk and Macallum’s suggestion that in the purines the substitution of the hydrogen atoms of the ring lessens or destroys the power to react with the uric acid reagent does not hold for the hydantoin group. W. D. H. Estimation of Gliadin in Flour and Gluten. GEO. A. OLSON (J. Ind. Ey. Chem. 1913 5 917-932).-The &implest method for the estimation of gliadin in flour consists in estimating the nitrogen in the uncoagulable portion of the alcohol extract and deducting the result from the total alcohol-soluble nitrogen. Alcohol solutions extract two groups of nitrogenous substances from flour; when the alcoholic solution is evaporated and water is added gliadin separates whilst the other group of substances remains in solution. A 1% sodium chloride solution extracts a part of the gliadin contained in wheat flour. Solutions containing from 50% to 65% by vol. of alcohol extract equivalent amounts of gliadin from flour; when the alcoholic strength is above 65% the amount of coagulable nitrogen diminishes. For the estimation of gliadin the use of 50% alcohol is therefore recommended. About 68% of the total alcohol-soluble nitrogen is coagulable whilst the soluble portion may be precipi- tated completely by means of phosphotungstic acid. W. P. S.

ISSN:0368-1769    

DOI:10.1039/CA9140605141

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii. 157 General and Physical Chemistry. Index of Refraction of Binary Mixtures. AXRIGO MAZZUC- CHELLI (Atti R. Accad. Lincei 1913 [v] 22 ii 691-696).-The author replies to the criticisms of Schwers (A. 1913 ii 453 537). T. H. P. Ultra-violet Emission Bands of the Mono- Di- and Tri- atomic Oxygen Molecule. J. STARK (Ann. Physik 1914 [iy] 43 319-336).-Experiments are described the object of which was to ascertain the ultra-violet spectra emitted by oxygen mole- cules containing one two and three atoms. The observations were made with a special form of end-on discharge tube having a quartz plate at right angIes t o the capillary. It h a been previously shown (Goldstein A. 1903 ii 723) that ozone is formed in the discharge through oxygen a t low pressures and i t is to be expected that the emission spectra of both 0 and 0 will be observable in these circumstances.By reference t o the absorption spectra of oxygen and ozone it is possible to assign certain bands in the emission spectrum to' 0 and others to 0,. I n this way it has been found that the triatomic molecule gives rise t o a large number of bands which stretch from the green of the visible spectra up to A 210 ,up. These bands are shaded off towards the long-waved end of the spectrum and can be resolved into lines. The diatomic oxygen molecule emits bands which extend from A 200 to beyond A 185,up. These bands correspond exactly with the fluorescence bands of oxygen. The so-called '' ultra-violet water vapour bands " in the region h 340 to h 230 ,up have been shown by Steubing (A. 1910 ii 913) to be due to oxygen and evidence is now brought forward in support of the view that these are emitted by monatomic oxygen.These bands make their appearance in pure oxygen when the energy of the electrical discharge is sufficiently high. They appear in greater intensity if oxygen compounds are present which on dissociation give rise t o oxygen atoms and other molecules which are stable a t low temperatures. Such compounds are water and carbon dioxide which on dissociation yield atomic oxygen and the stable molecules H and CO respectively. H. M. D. Line Spectrum of Nitrogen in a Geissler Tube. C . POR- LEZZA (Gctxzetta 1913 43 ii 699-708).-This paper gives the results of measurements of the wave-lengths of the lines of this spectrum many of which have hitherto been ascertained only approximately.A table is given showing also the wave-lengths determined by others both in a Geissler tube and at atmospheric pressure. R. V. S. VOL. CVI. ii. 11ii. 155 ABSTRACTS OF CHEMICAL PAPERS. Precise Study of the Second Group of Bands of Nitrogen in the Magnetic Field. Recognition of the Nature of the Displacements. H. DESLANDRES and L. D’ AZAMBUJA (Compt. rend. 1914 158 153-159).-A study of the second group of bands in the spectrum of nitrogen produced in a field of 35,000 gauss the observation being photographic. The results show that the law that the rays of an even arithmetic series are all displaced in the same sense or are all divided in the same manner with dissymmetries of the same type the displacements variations and ratios of the brightness of the components being variable only from one ray t o another holds good for this group and is probably general.They also verify Deslandres’ previous views on displacements in band spectra. I n this group the displacements occur with division and polarisation and result in slightly modified ordinary Zeeman divisions. Further these divisions show only a feeble difference between components which can correspond with mobile electric charges positive or negative and of a mass greater than that of the electron. W. G. Wave-length Normals of the Third Order from the Arc Spectrum of Iron between A4282 and X4903. 1;. JANICKI (.i?eilsch. wiss. Photochern. 19 14 13 173-1 85).-Accurnte measure ments of wave-lengths of lines in the arc spectrum of iron have been made with the aid of a large concave grating.A table is given in which the lines suitable for use as standards of the third order ar0 grouped together. It has been found that more accurate measurements can be obtained by using the middle portion of a long arc than by observations on a relatively short arc. Lines which are comparatively indistinct in the short arc become quite sharp when a long arc is utilised as the source of light. It is prob- able that the observed differences are due to differences in the density of the vapour. I n the neighbourhood of the cathode the temperature is much higher than in the mor0 remote regions and the density of the vapour is consequently much larger. With a short arc the cathode influence extends more o r less over the whole region occupied by the arc.H. M. D. Absorption Spectra of Some Salts of Uranium. ARRIGO MAZZUCCHELLI and Ucto PERRET (Atti R. Accad. Lincei 1913 [v]. 22 ii 445-451. Compare Mazzucchelli and Greco d’Alceo A. 1913 ii 167).-Further experiments show that although as formerly stated the addition of carbamide to dilute solutions of uranyl nitrate does not alter the absorption spectrum yet in concentrated solutions (30% of carbamide t o 40% solution of uranyl nitrate) a change is produced which is not due merely to the basic properties of carbamide because ammonia although more basic produces less alteration. When potassium hydroxide ammonia pyridine or aniline is added to a solution ( M / 1 0 ) of uraiiyl malate the absorption spec- trum ie altered but the new spectrum is almost the same in all four cases so that potassium hydroxide and the amines appearii. 159 GENERAL AND PHYSICAL CHEMISTRY.to a c t only in virtue of their basic properties and not in the direction of forming specific complexes. The addition of free acid to a solution of uranyl malate does not render the absorption bands sharper but on the contrary more diffuse. The spectra of the following compounds both before and after tho addition of a base are described uranyl tartrate citrate lactate and quinate. The reaction between uranyl sulphate and potassium malate or tartrate can be followed spectroscopically to some extent but the method does not lend itself to accurate determinations. The spectra are described of a number of organic salts of quadri- valent uranium including the malate tartrate quinate citrate lactate glycollate and oxalate as well as potassium uranotetr- oxalate and potassium uranomalonate.R. V. S. The Phototropy of Inorganic Systems. JosB RODRIGUEZ MOUHELO (Comipt. rend. 10 1 4 158 1 22-1 25).-Severd samples of calcium sulphite examined were phototropic as well as phoephor- escent whilst others exhibited only one of the two phenomena. The effective rays are the violet rays for both phosphorescence and phototropism. There is a limit temperature above which both these properties disappear. I n all cases where the calcium sulphide or other similar sulphides were phototropic i t was found that they contained traces of manganese to the presence of which t,he author considers that this phenomenon is due.W. G. Polymerisahion of p - Methylanthracene (Correction). FRITZ WEIGERT and OTTO KRUGER (Zeitsch. physikal. Chem. 3.9 14 86 383. Compare this vol. ii 11).-It is shown that the specific photochemical action 4 t h =1*22 x 10-5 mols. per cal. is one-half the value given in the previous paper (loc. c i t . ) . Dependence o P the Relative Ionisation in Various Gases by /3-Rays on their Velocity and its Bearing on the Ioniss- tion Produced by 7-Rays. R. D. KLEEMAN (Proc. Camb. Phil. SOC. 1914 17 314-320. Compare A. 1910 ii 474).-Further experi- ments on the relative ionisations produced in hydrogen air and methyl iodide by &rays indicate that the relative ionisation is independent of the velocity of the P-ray. The &rays from radium were admitted into an ionisation chamber through an aluminium window 0.16 mm.in thickness. By means of a magnetic field the beam of rays could b6 hardened to any desired extent by deflecting the more slowly moving rays. The application of the field was found to have practically no influence on the relative ionisation values for the three gases under examination. According to previous experiments on the ionisation produced by y-rays of varying hardness (A. 1909 ii 636) i t appears that the ionisation in methyl iodide relative to that in air increases greatly with the softness of the rays. Since this cannot be due to differences in the nature of the P-rays which are given off by the walls of the vessel i t is probable that the observed change in relative J.F. S. 11-2ii. 160 ABSTRACTS OF CHEMICAL PAPERS. ionisation is due to the secondary y-rays given off by the walls. One part of the ionisation due to these rays varies as the square of the pressure of the gas and the other part directly as the pres- sure. The latter ionisation effect increases with increase in the softness of the rays. D. C . H. FLO~~ANCE (Phil. Mag. 1914 [vi] 27 225-244).-The origin of the scattered y-rays which emerge at all angles when a beam of primary y-radiation is passed through matter is discussed and the conclusion is arrived at that they are primary y-rays which have lost energy and have become altered in type. They are not in any way characteristic of the material by which they ate produced. Their penetrating power is less the greater the angle they make with the direction of the original primary beam and Lhey are completely heterogeneous.With heavy elements as radiators there is a small amount of a scft radiation returned from the incidence side of the radiator which may possibly be a characteristic radiation. The quality and distribution of the scattered y-radiation under a variety of con- ditions have been examined. H. RICHARDSON (Phil. Mag. 1314 [vi] 27 252-256). -The y-radiation from uranium-X separated from 3 kilos. of uranyl nitrate has been examined. The absorption curve in aluminium showed the presence of a radiation amounting to about 40% of the total completely absorbed by 2 mm. of aluminium for which p was 24 (cm.)-l. The determination for greater thicknesses was difficult owing to the smallness of the effects but the results confirmed those of Soddy and Russell with the uranium-X from 50 kilos.of uranyl nitrate in showing in addition to the very penetrating y-rays for which p is Om140(cm.)-l an intermediate type for which p is 0-70 (cm.)-1. It is assumed as most probable that the most pene- trating type of y-rays arises from uranium-X2 and the two less penetrating types from uranium-X,. The softest radiation for which p is 24 is probably a characteristic radiation of the L-series and this absorption coefficient for an element of atomic weight 234 in relation to those of the other radiations of the same type given by the other radio-elements supports the view that actinium is a branch product of uranium-X and has an atomic weight 230.H. M. D. Secondary 7-Radiation. F. S. Analysis of the ?-Rays from the Uranium Products. F. S. The Number of Ions Produced by the y-Rays of Radium. A. S. EVE (PhiZ. Mag 1914 [vi] 27 394-396).-A recent redeter- mination of K the constant of the equation q = KQ/+erV where q ions are produced per C.C. of air at N.T.P. by Q grams of radium at distance rcm. and p is the absorption coefficient of the y-rays in air gave the value 4 x 109 in good agreement with earlier results. The total number of ions N produced per gram of radium by the y-rays calculated from N=47rKQ/pu is 8.4 x 1014. This is con- siderably less than a value for N 13 x 1014 obtained by Moseley and Robinson but the discrepancy may be due t o the latter value including the softer y-rays of radium-B not included in the formerGENERAL AND PHYSICAL CHEMISTRY.ii. 161 result. For the purpose of calculation of the atmospheric ionisa- tion du0 to radium and its equilibrium products in the earth the former value should be used. Whereas for calculations of the heating effecb of the y-rays of radium it is necessary to include also the effects of the softer rays and the calculation becomes a difficult one. F. S. Positive Ions from Hot Metals. 0. W. RJCRARDSON (Proc Roy. Soc. 1914 A 89 507-524. Compare A. 1913 ii 903 and previous papers).-The apparatus employed in previous experiments has been improved in a number of details and a new series of ob- servations has been carried out with platinum iron manganin and potassium sulphate. I n the case of all three metallic substances the values obtained f o r the electric atomic weight are in general very close to 40 which is the value found f o r the ions emitted by potassium sulphate.The wide distribution of potassium and its highly-developed capacity for ionising lead the author to the conclusion that the above value for the electric atomic weight is really due to the emission of potassium ions resulting from adventitious impurities in the heated metals. The experimental data are entirely opp,osed to the view that the positive ions consist of charged atoms or molecules of one or more of the common gases such as carbon monoxide carbon dioxide hydrogen oxygen or nitrogen. Argon is the only common gas for which the electric atomic weight is in close agreement with the experimental value but in view of the strong evidence in favour of potassium it is difficult to suppose that any appreciable part of the emission effect is due to argon.It might also be supposed that the carriers are calcium atoms with a single positive charge but the ionising tendency of calcium is too small to account for the observed facts. From experiments with platinum in which the metal was heated for a long period of time it would seem possible to exhaust the metal of the impurities which give rise to the potassium ion. After such prolonged thermal treatment the electric atomic weight was found to fall from 40 to about 23 (sodium ion) afterwards rising quickly to about 60. This is supposed to correspond with the emission of singly-charged iron atoms. Tables of Exponential Functions Relating to the Radium Emanation.L ~ O N KOLOWRAT (Le Radium 191 r2 10 389-392).- This coneists of a reprint of the tables relating to the disappear- ance and accumulation of radium emanation with the value for the disintegration constant h = 0-00751 (hour)-1. The first table gives the fraction of radium emanation remaining at hourly in- tervals from 0 to 52 hour8 a t two-hour intervals from 54 to 72 hours a t three-hour intervals for the fourth and fifth day and so on for thirty days. The second table gives the amount of ernana- tion accumulating in a radium solution for the same intervals in terms of the hourly rate of production as the unit or of the equilibrium amount 1 / A as 133.156. H. M. D. F. S.ii. 1.62 A RSTRACTS OF CHEMICAL PAPERS.Dependence of the Photoelectricity of Metals on the [Surrounding] Gas with Special Reference to the Cause of the Strong Photoelectricity of Potassium. G. WIEDMANN and W. HALLWACHS (Bey. h u t . physikal Ges. 1914 16 107-120).- The question as t o whether the photoelectric behaviour of metals is dependent on the presence of gas in the surface layer has been examined with reference to the observation that electrons are emittjed during chemical reactions (compare Haber and Just A. 1909 ii 853). As a result of the recent work of Ullmann and of Paech (this vcl. ii 89) there can be little doubt that' the photo- electric emission of metals is to a large extent dependent on the nature of the surrounding gaseous medium. On the assumption that the gas might prove to be essential for the development of the photoelectric effect experiments have been made with potass- ium cells.By means of a special form of apparatus in which the potassium could be subjected to a succession of distillations during which the highest possible degree of exhaustion was maintained it has been found that potassium is ultimately obtained in a con- dition in which it is photoelectrically inactive. This result in- dicates conclusively that the presence of gas in the surface layer of the metal is necessary for the development of its photoelectric properties. H. M. D. Influence of Temperature and of the Occlusion of Gases on the Photoelectric Behaviour of Metsls Metallic Oxides and Metallic Sulphides. ADOLF HALLERMANN (Zeitsch. wiss. Photo- chew,. 19 14 13 186-207).-From experiments on the photoelectric properties of platinum gpld palladium and of the oxides of copper calcium barium zinc cerium thorium and uranium at various temperatures up to about 600° it has been found that the photoelectric activity is in all cases independent of the tempera- ture.Fatigue effects are not observed at higher temperatures and this fact is considered to be in favour of the view that such effects are connected with the adsorption of gases by the electrodes. The current potential curves which are obtained by plotting the photoelectric current against the potential applied to the electrodes are found to be of exactly the same form for the oxides as for the metals and the nature of these curves is the same at high as at low temperatures.Rise of temperature reduces how- ever the sparking potential. From experiments made with cupric and silver sulphide which exhibit transition points at 1 0 5 O and 170° respectively i t has been found that the polymorphic change is without influence on the p!istoelectric activity of the sulphides. When a metal has been employed as anocie in the glow discharge its photoelectric sensitideness is found t o be diminished whilst the opposite effect is observed when the metal has been used as cathode. The influence of the electrical treatment diminishes with rise of temperature and it is no longer observable a t temperatures above 400O. The nature of the gas in the discharge tube does not appear to have any influence on the change in the photoelectricGENERAL AND PHYSICAL CHEMISTRY.ii. 163 behaviaur of the metal. According to Skinner (A. 1905 ii 797) gases are evolved when the metal functions as cathode and ab- sorbed when i t acts as anode; this would seem to show that the occlusion of gases diminishes the photoelectric activity. H. M. D. Dielectric Constant of Hydrogen at High Pressures. A. OCCHIALINI (Atti R. Accad. Lincei 1913 [v] 22 ii 482-484. Com- pare following abstract) .-Measurements of the dielectric constant of hydrogen at pressures between 94 and 196 atmospheres lead to the formula ( K - 1)/ ( K + 2)d= 90154(10-9). Extrapolation gives the value 1*0002705 for the dielectric constant of hydrogen a t ordinary pressure. R. V. S. Dielectric Constant of Nitrogen at High Pressures. E. BODAREU ( A t t i R. Awad. Lincei 19 13 [v] 22 ii 480-482).-Deter- minations of the density (d) and dielectric constant (R) of nitrogen a t pressures ranging from 87 to 226 atmospheres lead to the formula ( K - 1) .l O 7 / ( R + 2)d= 1954. By extrapolation the value 1*000587 is obtained for the dielectric (.onstant of nitrogen a t the ordinary pressure. R. V. S. Experiments with Liquid Helium. The Electrical Re- sistance eto. VIII. The Sudden Disappearance of the Ordinary Resistance of Tin and the Super-conductive State of Lead. H. KAMERLINUH ONNES (PYOC. K. Akad. Wetensch. Amsterdam 1913 16 673-688. Compare A. 1913 ii 748 822).-The elec- trical resistance of tin and lead wires has been investigated at. helium temperatures. I n the pase of tin the resistance practically disappears when the temperature is lowered to 3*8Oli the ratio of the resistance a t this temperature t o that at 273O K being less than 10-7.I n addition to the sudden disappearance of the resis- tance it has been found as in the case of mercury (Zoc. cit.) that for each temperature below the vanishing point there is a " thres- hold value" of the current density below which the current passes without any perceptible fall of potential. For current densities higher than this the passage of the current is accompanied by potential phenomena which increase rapidly as the excess of the current above the " threshold value " increases. Pure lead also passes into the super-conducting state at helium temperatures. The temperature at which the resistance disappears haa not yet been determined but from observations made at helium and hydrogen temperatures i t lies between 4.3O K and 14O R.Further observations have reference to the potential phenomena in the super-conducting condition and from these conclusions are drawn relative to the maximum value of the residual resistance in the super-conducting state. For tin the ratio of the resistance at 1.8O K to that a t 273O K is less than 6 x 10-10 whilst the corre- sponding ratio for lead is less than 0.5 x 10-10. For mercury at 2 . 4 5 O R this ratio was found to be less than 2 x 10-lo. H. M. D.ii. 1G4 ABSTRACTS OF CHEMLCAL PAPERS. Couples with Flames Charged with Chlorine. G. MOREAU (Conzpt. rend. 1914 158 260-262).-The E.M.F. of the couple Pt 1 flame I flame 1 Pt coated with an alkaline earth oxide (compare this vol. ii 22) and of the similar couple where on0 flame is charged with the vapour of some salt (compare this vol.ii 22) is increased by 0.55 volt on the introduction o i chlorine or bromine into the flame in contact with the pure platinum. The same results are obtained by the introduction of chloroform or carbon tetrachloride. This is explained by the fact that the radiation from the platinum electrode is annulled by thO active substance and the E.M.F. is increased by an amount equal to the E.2II.P. of a couple Pt coldlpure flamelPt hot. The resultcs give a value of 4.4 x l o 7 cm./sec. for the mean velocity of emission of corpuscles from the platinum (compare Zoc. cit.). W. G. Study of the Hydrogen Electrode of the Calomel Elec- trode and of Contact Potential.C. N. MYERS and s. F. ACREE (Amw. Chem. J. 1913 50 396-411).-1n earlier papers (Loomis and Acree A. 1912 ii 124 125; Desha and Acree A. 1912 ii 125) an account has been given of a study of the hydrogen electrode and its application t o the determination of hydrogen ion concentrations in organic reactions. I n continuation of this investigation efforts have been made t o render the hydrogen electrode more accurate for the purpose and to make the calomel cell more nearly standard. The present paper gives a preliminary account of the work. A record is given of a O*1NKCl-HgC1-Hg battery showing the changes taking place from the time that the battery was first pre- pared. The cells required thirty-six to forty-eight hours to settle down and then their relation remained approximately constant for over a year.The total change in a battery amounted to 0*000085 volt in a year bui the individual cells did not vary to so great an extent. A comparison of two f reshly-prepared calomel batteries shows that they were in good agreement after a year. The relation between a freshly-prepared battery and one of a year’s standing is also given; in the first three months the difference of potential between them was about 0.000045 volt. Hydrogen electrodes after standing dry throughout the summer showed considerable disagree- ment and some difficulty was experienced before they gave satis- factory agreement. A typical comparison is given of the hydrogen electrode O*lNW@l~ Pt--H and a fresh calomel electrode and t,lie methods of applying the correction are ‘shown.The corrected average value agrees closely with those obtained with two fresh calomel batteries. The results are recorded of experiments in which Bjerrum’s ‘‘ sandfiillung ” was used between the calomel and hydrogen electrodes and also of a typical contact potential ex- periment with one Hg-HgCl-O*12C’HCl battery against a fresh calomel battery. The results of the work show a constancy in the values of theGENERAL AND PRYSICAL CHEMISTRY. ii. 165 vacrious systems mentioned which is explained by their having been completely saturated with hydrogen before being joined. E. G. Application of the Theory of Allotropy to Electromotive Equilibria. A. SMITS (Proc. K. Akad. Wetensch. Amsterdum 1913 16 699-710).-The author’s theory of allotropy (A.1910 ii 195 400) is applied to the electrolytic dissolution and deposition of metals which consist of mixtures of allotropic modifications. The theory indicates that electrolytic deposition will in many cases give the metastable form. If the reversible changes take plaoe with very small velocity it is shown further that the surface of the metal will become more noble during the process of electro- lytic dissolution. The periodic oscillations in the potential differ- ence a t the surface of contact between a metal and solution can be accosunted f o r from the same point of view. The fact that the contact of a metal with the solution of one of its salts exerts an accelerating influence on the setting up of the equilibrium between the allotropic forms is also consistenb with the theory.The remarkable chemical reactivity of metals obtained by re- duction a t low temperatures is supposed to be due to the wide divergence between the actual condition and the equilibrium con- dition. Pyrophoric forms may possibly be explained in this way the metals in this condition containing an abnormally large pro- portion of simple molecules. Nickel-plating on Aluminium. J. CANAC and E. TASSILLY (Compt. Tend. 1914 158 119-121).-Aluminium is readily plated with a durable coating of nickel by the following procedure. The metal to be plated is first plunged in a bath of boiling potassium hydroxide solution and then scrubbed with milk of lime. This is followed by steeping in a 0.2% solution of potassium cyanide for several minutes after which i t is transferred to a bath made up of 500 grams of hydrochloric acid and 1 gram of iron in 500 C.C.of water. Between each bath it is well washed with water and after the last washing it is plated electrolytically in a solution of nickel chloride. The deposit so obtained is very adhesive and durable as the metal can be folded or hammered without it cracking. The metal can be heated to the melting point of alu- minium without the nickel separating and is not attacked by dilute alkali glacial acetic acid or concentrated sodium chloride solution cold or hot. From the point of view of the conduction of electrical energy the coefficient of dilatation of the metal is lowered by plating. The Kelvin effect is nil. The success of the plating apparently depends on the use of the ferruginous bath.Measurements in the Electromagnetic Spectrum of Water with Feebly Damped Vibrations of 65 to 20 cm. Wave- length. A. R. COLLEY (Ann. Phyaik 1914 [ivJ 43 309-.318).-A reply to Rukop’s criticism (compare A. 1913 ii 1018) of the author’s measurements. Further observations relating to the nature of the electromagnetic spectrum confirm the results obtained in the previous experiments. H. M. D. W. G. H. M. D.ii. 166 ABSTRACTS OF CHEMICAL PAPERS. Uses of the Concentrated Filament Tungsten Lamp in the Laboratory. F. ALEX. MCDERMOTT (J. Amcr. Chem. Soc. 1914 36 454-455).-A stereopticon type of tungsten lamp rated a t 100 watts for 110 volts and giving about 60 c.P. is recommended for use in microscopic work and for the polarimetry of highly coloured or turbid liquids.No bright-line images of portions of the filament are formed in the field of the instrument and the intensity is very much greater than that obtainable with the frosted-bulb lamp. T. S. P. Temperature of Non-homogeneous Flames. HEDWICI KOHN (Physikal. Zeitsch. 1914 15 98-105).-1f a Nernst filament is placed in close proximity to a flame containing the vapour of a metallic salt so that the rays emitted by the filament pass thrcugh the heated salt vapour on their way t o the slit of a spectrometer i t is found that the lines emitted by the vapour appear bright or dark according to the intensity of the continuous spectrum which is emitted by t.he filament. The temperature a t which transition occurs from one condition to the other has been termed the inversion temperature and measurements of this temperature have been made by Kurlbaum and Schulze (A.1906 ii 726) for a number of metallic salts. Similar experiments have been carried out by the author who finds that the inversion temperature for a Bunsen flame containing the chlorides of lithium sodium potassium thallium and rubidium depends on the nature of the salt introduced into the flame. I n the case of the lithium line h=670pp it was found that the inversion temperature increases when sodium potassium or rubidium chloride is simultaneously introduced with the lithium chloride into the flame. These results are in general agreement with the observations made by Kurlbaum and Schulze. The theoretical discussion of the observed changes in the inversion temperature indicates that these can be satisfactorily explained on the assumption of pure temperature radiation if the inhomogeneity of the flame is taken into consideration.H. M. D. The Critical Condition. PAUL HEIN (Zeitsch. physikal. Chem. 1914 86 385-426).-The phenomena occurring a t the critical temperature have been examined in the case of carbon tetrachloride sulphur dioxide and carbon dioxide. I n the case of the two last- named substances experiments have been carried out in which air has not been entirely removed and in which the gas was n o t con- taminated by more than 1 part of air in 40,000 of the gas. The substances under examination were placed in narrow cylindrical tubes together with a number of “ density pellets,” and sealed up.The temperature was then slowly changed from a few degrees below the critical temperature t o a few degrees above and observa- tions made on the density and the formation of fog in the tube. It is shown that the presence of impurities in the substances examined affect the phenomena occurring near the critical teiiipera- ture in a marked degree. Density differences are observable with pure substances above the critical temperature but these vanishedGENERAL AND PHYSICAL CHEMISTRY. ii. 167 in the case of carbon dioxide a t a temperature 0'46O above the temperature a t which the meniscus disappeared and they were only of the smallest chsracter. On the other hand with carbon dioxide containing air density differences amounting to 13% were observable a t a temperature 3'2O above the temperature at which the meniscus disappeared.The author is of the opinion that his results are in accord with the two-phase theory a t the critical temperature rather than with the onephase theory. Determination of the Transformation Points of Sodium and Potassium Sulphates Molybdates and Tungstates. B. S. VAN KLOOSTER (Zeitsch avrory. Chem. 1914 85 49-64).-Tn place of cooling curves heating curves have been adopted. The trans- formation point may be overstepped in this way but by cooling until reconversion is complete and again heating the true point may be found and recognised by the fact that i t is independent of the rate of heating. The temperature is reproducible within +lo. The following transformation and melting points have been deter- mined with this degree of accuracy J.F. S. Triins- Trans- formation I. formation 11. - Nn,SO ......... 241" N+MoO ...... 445 592" Na,WO ......... 58'7 - K,SO ......... - 582 K,MoO ......... 327 454 K2 W 0 ......... 388 - Trttns- formation 111. M. p. - 884" 640" 687 694 - 106'7 479 919 - 92 1 - C. H. D. Matter in the Superfused State. R. NASINI and U. BRESCIANI (Hem. R. Accad. Lincei 1913 [v] 9 735-750).-The authors have repeated and extended their investigations on sulphur (compare A. 1913 ii 555) solidifying a t 1 1 4 O and have confirmed the con- clusions previously deduced. Study of the superfusion phenomena of triphenylmetliane m. p. 90*4O solidifying point 87*B0 and of trimethylcarbinol solidifying point 23.4O reveals no appreciable abnormality in either the ordinary or the differential cooling curves so that these substances do not exhibit the " Moreschini effect." Experiments on sodium thiosulphate indicate unexplained dis- cordance between Bruner's data for the specific heat (A.1895 ii 482) and those afforded by the cooling curves. Superfused thymol contains no nucleus capable of inducing crystallisation. Ultramicroscopic observations on acetic acid and anethole reveal no change occurring when the superfused liquids pass through the melting point. Even in the superfused state these liquids must therefore be regarded as optically empty and if crystalline nuclei are formed these must be of less than ultra- microscopic magnitude. T. H. P. The Temperature of Solid Carbon Dioxide Cooling Baths. 9. THIEL and E.CASPAR (Zeitsch. phgsikal. Chem. 1914,86 257-293). -The temperatures of mixtures of carbon dioxide snow wit11 ether,ii. 168 ABSTRACTS OF CHEMICAL PAPERS. alcohol and acetone have been determined by means of a vapour- pressure thermometer. The method of measurement consisted in immersing a bulb containing pure carbon dioxide snow in the freezing mixture and measuring the vapour pressure of carbon dioxide in the bulb by means of a manometer and from the known temperature-coefficient of the vapour pressure (57.0 mm. E g per degree) calculating the amount by which the temperatures of the various baths dirTered from that of pure solid carbon dioxide. Theoretically the temperatures ought in all cases to be the same a s that of carbon dioxide snow itself but experimentally they were found all to be a little higher; in the case of the ether mixture the temperature was about.0'09O higher. It is shown that the lower temperatures found for acetone mixtures are t o be explained by the heat of solution of carbon dioxide and that they do not repre- sent the true equilibrium temperature. The vapour pressure of the ether in the ether mixture is so small that it cannot influence the temperature to a measurable amount. The reason f o r the slightly higher temperature is found in the fact that in addition to the atmospheric pressure the hydrostatic pressure of the liquid column has t o be overcome. Calculations made show that the pressure of this column of liquid corresponds exactly with the experimentally found temperature differences.The phase-rule diagram (Oc) is worked out and described for the binary system carbon dioxide- ether and the three-phase points characterised. 3. F. S. Freezing Points of Organic Substances. JEAN TIMMERMANS (Bull. Xoc. Chim. Bdy. 1913,27,334-342. Compare A 1911 ii,854). -The reduced melting point is defined as the ratio of the melting- point temperature to the critical temperature both being expressed on the absolute scale. These reduced melting points have been compared for a large number of substances but the results afford no evidence' of the existence of general relations connecting the reduced temperature with the composition and constitution. The values range from 0.20 for helium and 0.235 for propane to 3.714 for carbon dioxide and 0.929 for phosphoniuni chloride.H. M. I?. Properties of Iodine as a Cryoscopic Solvent. I. F. OLIVARI ( A t t i R. Accad. Lincei 1913 [v] 22 ii 697-702).-The marked solvent power of iodine towards many organic solvents and various salts has been noted in the author's previous investigations (A. 1909 ii 37 39 128 226). Determinations of the velocity of crystallisa.tion of iodine give results which are of considerable magnitude near the melting point and increase rapidly with the degree of superfusion. The crystal- lisation of iodine hence responds to the requirements of good thermometric readings and this is confirmed by direct cryoscopic measurements. Dilute solutions of stannic antimony arsenic and mercuric iodides give the mean value 213 for the molecular de- pression of the freezing point.Beckinann (A. 1909 ii 642) gave 204 and Timmermans (A. 1906 ii 429) 253.5.GENERAL AND PHYSICAL CHEMISTRY. ii. 169 The uncertainty of the value 11.7 Cal. obtained by Favre and Silbermann for the latent heat of fusion of iodine renders i t impossible to calculate the cryoscopic constant by means of van’t Hoff’s formula. From Dewar’s indirect data (P. 1899 15 241) Beckmann calculated the value 14.87 Cal. which gives 201.4 for the cryoscopic constant. Cryoscopic investigation of so’lutions of iodof orm pdibromo- benzene azobenzene naphthalene diphenyl pdinitrobenzene benzoic anhydride phenanthraquinone and 8-iodopropionic and benzoic acids in fused iodine confirm the earlier indications that (1) the molecular weights are normal in very dilute solution but increase more or less rapidly with the concentration even with compounds which exhibit no appreciable tendency to polymerise and (2) this increase becomes more marked in passing from hydro- carbons to hydroxyl derivatives. For solvents of high specific gravity such as iodine the weight- concentrations commonly adopted in osmotic calculations are much smaller than the volume-concentrations which according to van’t Hoff’s theory should be used.Assuming as a rough approxima- tion that solutions in iodine have D about 4 weight-concentrations of I 2 3 etc. would correspond with volume-concentrations of 4 8 12 etc. For hydrocarbons and halogenated derivatives the abnormalities disappear if volume-concentrations are used in the calculations but for /3-iodopropionic and benzoic acids they persist in diminished degree ; intermediate behaviour is shown by benzoic anhydride and phenanthraquinone which theref ore exhibit a slight tendency to polymerise.T. H. P. Cyanamide as a Cryoscopic Solvent. U. PRATOLONGO (Atti R. Accad. Lincei 1913 [v] 22 ii 716-720).-The latent heat of fusion of cyanamide m. p. 42’9O is 49*8+0*7 cals. and the value of hhe cryoscopic constant calculated by means of van’t HOB’S relation 39.8. Direct determination of the cryoscopic constant with the following solutes gives the numbers water 28.4-26-1 ; ethyl alcohol 28*1-26*6 ; formamide 30*‘?-30~2 ; carbamide 29.7-29.1; dicyanamide 32-1-32.8. Thus as in the case with solvents of analogous constitution the calculated and experimental values of the cryoscopic constant for cyanamide differ appreciably.Further this solvent shows marked associating properties which are most clearly manifested with hydroxylip solutes. Description of the (‘ Cryoecope,” and Several Freezing- point Determinations of a Single Sample of Fresh Milk with Varying Degrees of Supercooling. M. C. DEKHUYZEN (Chem. Weekbkcd 1914 11 126-131).-A m9di6ed form of Beck- mann apparatus designed t o facilitate accurate measurement and rapid working. The cooling bath is large and consists of two con- centric glass cylinders the inner one 17 x 27 em. and the outer 23 x30.5 cm. The copper cover is replaced by a thick plate of ebonite. The freezing tube is round a t the closed end and is surrounded by a two-wzlled Dewar vacuum tube. The part projectr T.H. P.ii. 170 ABSTRACTS OF CHEMICAL PAPERS. ing above the ebonite cover is protected by a wooden air chamber to prevent change of temperature. Rapid cooling is promoted by immersing in the co,oler a wide test-tube containing mercury cooled to a suitable temperature. The results of a series of experiments on a sample of milk are given. A. J. W. New Formula for Determining the Latent Heat of Evapor- ation of Different Compounds. (Mlle.) ALEXANDRA RODZEVXTSCZZ ( J . Russ. Ph,ys. Chem Soc. 1913 39 Phys. Part 355-361).-All the ordinary empirical formulx for calculating the latent heat of evaporation are inapplicable f o r high temperatures and especially for temperatures approaching the critical point. This is also the case with the thermodynamical formula p = AT(u-s).dp/dT where p is the latent heat of evaporation A = 1 /425 u is the specific volume of the saturated vapour s the specific volume of the liquid and p the vapour pressure a t the absolute temperature T ; little is known of the values of cr and s a t high temperatures.The author shows that the above formula may be converted into the form p = iVT2(r-p) / m r p . d p / d T N representing a coefficient P the critical pressure and m the molecular weight. The coefficient AT is derived as follows. The value of (c-s) depends on r/ and T the simplest assumption being that CT-s = kT(n-p) / p from which follows k = (u-s)p/ T(P-p) ; with water and carbon disulphide k is found t o be independent of the temperature. It is further shown that for a number of compounds of different chemical characters the value of the product k .A . m . a is practically constant and equal t o 1-95 x 103 (1.90-2*03 x lO3) and this product represents the coefficient AT of the author’s equation. The latter gives values for the latent heat of evaporation of water a t various temperatures from Oo t o 200° in good agreement with the experimental numbers obtained by different investigators. ERNST BECKMANN and OTTO LIESCHE (Zeitsch. physikal. Chern. 1914 86 337-348).-A simple deduction of the following five formulze for calculation of the ebullioscopic constant is given (1) k =ill/ 100 . p . (dt / d p ) ; (2) k = mGA/ 1OOg ; (3) k=RT2/w; (4) k=0*0096MT; and (5) k=0~0011089T2/u2 in which k represents the constant. m the molecular weight of the dissolved substance 17-1 that of the solvent g the weight of the dissolved substance and G that of the solvent p the vapour pressure of the solvent d p the lowering of the vapour pressure dt the boil- ing-point elevation due to dp A the elevation of the boiling point when 1 gram molecule of a substance is dissolved in 100 grams of solvent u’ the heat of vaporisation per gram of the solvent and a2 the specific cohesion of the solvent a t the boiling point.The second expression is also worked out for the case where the dissolved sub- stance is volatile and then has the form rn = 100kg/AG(1 - a) where a is the ratio of the concentrations of the solvent and dissolved substance in the vapour and liquid phases (that is n‘N/nN’). The trustworthiness of the five formulae is discussed and the un- certainty in the case of (4) and (5) has led t o the deduction of the T.H. P. Ebullioscopic Constants.GENERAL AND PHYSICAL CHEMISTRY. ii. 171 formula (6) k =0*004343MT(l-T/O)/log ~ / p . This is based on work of Cederbergs (A. 1911 ii 854) and is not limited like (4) and (5) which are based respectively on Trouton’s rule and Walden’s formula. This last formula is tested by means of data taken from the literature and found t o be trustworthy. J. F. S. The Experimental Handling of Small Quantities of Volatile Substances. ALFRED STOCK (Bar. 1914 47 154-156).-The author describes the advantages of the apparatus he has used extensively in his investigations of the boron hydrides and carbon sulphidotelluride and sulphidoselenide. The apparatus is so designed that fractional distillations can be carried out a t low temperatures during which it is completely closed so that no sub- stance is lost; a high vacuum is maintained in the apparatus during the operations.The fractionation is carried out by using different freezing mixtures by which temperatures varying from - Z O O to - 190° are obtained f o r cooling the various tubes in which condensation is to take place. The purity of each fraction is ascertained by deter- mining its vapour tension a t some particular temperature a mano- meter forming part of the apparatus for this reason. T. S. P. Heats of Combustion of Octanes. Errata. T. W. RICHARDS and R. H. JESSE (J. Amer. Chem. Soc. 1914 36 248).-A list of corrections t o the authors’ previous paper (A.1910 ii 269). T. S. P. Higher Valencies in Oxygenated Organic Compounds. 111. Basic Properties of Oxygen in Alcohols of the Aro- matic Series. V. V. ‘FSCHELTNCEV (J. Buss. Phys. Chcnr. SOC. 1913 45 1904-1911).-The author has measured the heat effects accom- panying the formation of complexes of the three types Pr*OMgI,R*OH PrONgI,ZR-OH and PrOMgI,3R*OH for phenyl- carbinol diphenylcarbinol triphenylcarbinol phenylmethylcarbinol y-phenylpropyl alcohol and cinnamyl alcohol (compare A. 1913 ii 924 925). The results show that the aromatic nucleus has a very marked influence on the manifestation of higher valency by hydroxylic oxygen. Thus the amounts of heat developed in the formation of the complex Pr*OMgI,3R*OH are 23.42 Cal. 17-94 Cal. and 0 for phenyl- diphenyl- and triphenyl-carbinol respectively ; for methyl- dimethyl- and trimethyl-carbinol the corresponding numbers are 29.63 22.50 and 13.58.The effect of replacement of methyl groups by phenyl is shown by the values 22.50 18.68 and 17.94 Cal. for dimethyl- phenyl- methyl- and diphenyl-carbinol respectively. The influence of the distance of the phenyl group from the hydroxylic oxygen on the higher atomicity of the latter is illustrated by the values 14.18 23.42 and 27.07 Cal. for phenol phenyl- carbinol and y-phenylpropyl alcohol respectively. That unsaturation of the carbon chain is almost without influenceii. 172 ABSTRACTS OF CHEMICAL PAPERS. is seen from the practical identity of the values obtained for y-phenylpropyl (27.87 Cal.) and cinGamyl alcohols (27.87 Cal.).T. H. P. Higher Valencies in Oxygenated Organic Compounds. IV. Basic Properties of Oxygen in Alcohols of the Terpene Series. V. V. TSCHELINCEV (J. Russ. Phys. Chem. Soc. 1913 45 191 2-191 7) .-Measurements similar to those already described (see preceding abstract and A. 1913 ii 924 925) have been made with menthol terpineol d-borneol and isoborneol. Each of these alcohols forms complexes of the types PrOMg1,R-OH and PrOMgI,2R*OH but in no case is a tri-alcoholic complex formed owing either to weakening of the higher valency in these alcohols or to steric influences. The number of Calories developed by the addition of the first and second molecules of the alcohol t o PrOMgI are 7.44 and 2.30 for menthol; 5.76 and 2-14 for terpineol; 7.78 and 4.29 for d-borneol; 7.46 and 4.17 for isoborneol.The approximation of the values for menthol borneol and isoborneol is in correspondence with the characters of these alcohols which are all secondary and all possess substituents in the 2- and 5-positions to the hydroxyl. The lower values for terpineol are in accord with its tertiary structure which in the aliphatic series is generally accompanied by a lower heat effect and with the presence of the hydroxyl in the side-chain. T. H. P. Higher Valencies in Oxygenated Organio Compounds. V. Relation between Principal and Supplementary Valencies in Alcohols. V. V. TSCHELINCEV (J. Russ. Phys. Chew. Soc. 1913 45 1917-1925).-The author has measured f o r a considerable number of aliphatic alcohols phenols aromatic alcohols and alcohols of the terpene series the heat effect of the reaction R*OH + MgPrI = ROMgP + C,H (I) in benzene solution.The numbers thus obtained which correspond with the functioning of the principal valencies of the oxygen are then compared with those given in the preceding papers f o r the reaction PrOMgI + 3R-OH (11) in which the supplementary valencies of the oxygen function. In general i t is found that if a change from one alcohol to another is accompanied by increase of the heat effect OF reaction (I) the heat effect of reaction (11) exhibits a decrease. Acoustic Method for the Measurement of the Density of Gases and Liquids. A. KALBIINE (Ber. Dew!. physikal. Ges. 1914 16 81-92).-The frequency of an acoustic vibrator varies to some extent with the density of the surrounding medium and this variation is made the basis of a method of determining the density of gases or liquids.I n order t o obtain effects sufficiently large for this purpose i t is essential that the mass of the vibrating system should be small and the surface relatively large. The apparatus designed and employed by the author for density T. H. P.GENERAL AND PHYSICAL CHEMISTRY. ii. 173 measurements consists of a seamless aluminium tube which is clamped a t the nodal pointxi and is made to vibrafe transversely by striking it with a small hammer. The change in frequency when the tube is made t o vibrate in air and afterwards in the gas under investigation can be ascertained by counting the beats which are produced when a suitable tuning-fork is made to vibrate simul- taneously. This change is found to be proportional to the differ- ence in the densities but is otherwise unaffected by the nature of the gas.The acoustic pyknometer is recommended for the measurement of the densities of compressed gases and modified types of the instru- ment are described which have been designed f o r technical purposes. H. M. D. Density of Some Metals in the Liquid State. PAUL PASCAL and A. JOUNIAUX (Compt. rend. 1914 158 414-416).-The authors have determined the density in the liquid state of some six metals a t their melting points and a t various temperatures up to 1300° by weighing a flask of quartz suspended in the molten metal. Formula= are given for each metal by means of which it is possible to calculate their specific volumes a t any temperature inside a given range.I n the case of tin the curve of specific volumes possesses a point of inflexion a t 620° corresponding with a very rapid increase of dilatation a t high temperatures and suggests a possibility of dynamic allotropy. W. G. Theory of Molecular Volumes. GERVAISE LE BAS (Phil. Hug. 1914 [vi] 27 344-356).-An examination of the relations between the molecular volumes of substances a t their boiling points has shown the necessity of changing many of the values previously assigned to the elements as representing their atomic volumes. The values deduced by the author are as follows carbon 14.8; hydrogen 3.7 ; oxygen-hydroxyl ester and phenolic 7.4 ethereal 11.0 in combination with sulphur nitrogen or phosphorus 8-3 ; sulphur bivalent 22.1 and 25.6 quadrivalent and sexavalent 25.6 ; phosphorus tervalent and quinquevalent 27.1 ; nitrogen tervalent and quinquevalent 15.6 in primary amines 8.6 in secondary and tertiary amines 10.0-11*5.It is said that double and triple link- ings have very little influence on the volume of carbon compounds a t their boiling points but that benzene ring formation is acconi- panied by a contraction represented by -14.3. When a comparison is made between the volumes of phosphorus trichloride and pentachloride and of phosphorus tribromide and pentabromide it is found that the combination of the two halogen atoms is accompanied by a contraction of about 8 units and it is suggested that this may be due to ring formation. The existence of periodic relations between the atomic volumes of the elements is discussed in reference to the available data.If the volumes are plotted against the atomic weights four curves are obtained which pass through the points corresponding with elements VOL. CVI. ii. 12ii. 174 ABSTRACTS OF CEIEMICAL PAPEkd. of the same fundamental valency. the lowest and the quadrivalent elements on the highest curve. H. M. TI. The univalent elements fall 011 Contraction on Mixing Abnormal Liquids. E. V. I~IHON arid (Mlle.) 0. M. MORGULEVA ( J . Ziuss. P h y ~ Chew. Soc.. 1513 45 1985-2002).-Tlie object of the work described in this and the following papers was t o explain the form of the curves showing the contraction occurring on mixing on the one hand associating liquids and on the other liquids which enter into chemical com- bination one with the other.The liquids here considered are aniline and nitrobenzene ; the latter is usually regarded as lion-associating but the magnitude of its dielectric constant and other properties tend to indicate that i t is not quite normal. Besides mixtures of aniiine and nitrobenzene mixtures of each with a typical normal liquid benzene were investigated. The following symbols are used x is the molecular content of the component named first S the specific gravity of the mixture Y its actual molecular volume and 8V that calculated from the law of mixtures D the contraction accompanying mixing = 8 V-V and fJll &I2 the molecular weights of the liquids. For aniline and nitrobenzene a few mixtures were examined by Dutoit (Thesis “ Effets theriniques produits par les mhlanges des liquides organiques,” 18971 but his results are insufficient to show whether the variable character found for the coefficient li’ of the relation holding for normal liquids namely D = Xx(1- x) (I) is accidental or characteristic of these liquids.More complete measurements by the authors show that for 30-70 mol. % of aniline the contraction is expressed approximately by the above formula ; the other mixtures show abnormal contraction. This behavioar the author regards as due t o dissociation of the associated aniline (or nitrobenzene) molecules by dilution with the other con- stituent of the mixture ; association being slight in amount the aniline (or nitrobenzene) soon reaches’ concentrations such that its condition is that of a normal liquid that is composed of simple molecules.A similar explanation has been advanced by Schroeder to account for the variation of the specific heat of alcohol dissolved in normal liquids. If such explanation is correct a solution of aniline o r nitrobenzene in a normal liquid should give contraction curves which obey the law for normal liquids in the region where the molecules of the abnormal liquid are completely dissociated and which depazt from the simple law when the aniline or nitrobenzene is in considerable excess. With aniline and benzene the simple law is obeyed by solutions containing about 30-65 mol. % of aniline the maximum contrac- tion corresponding with 50 mol. %. With benzene and nitrobenzene the maximum Contraction is shown by the solution containing about 65 mol.% of benzene so that formula (I) cannot hold. Solutions containing excess of benzene obey the law 1) =Px2(1- x) (11) but for those contain- ing excess of nitrobenzene the curve assumes a complex course.GENERAL AND PHYSICAL CHEMISTRY. ii. 175 Mixtures of aniline and o-toluidine obey the law for normal liquids. Doroschevski’s data (A. 1911 ii 468) have been employed for calculating the contractions for various binary mixtures of mono- hydric alcohols. W’itli methyl and ethyl alcohols all mixtures exhibit expansions but these are so small as to lie almost within tlie limits of error; the same is the case with ethyl and propyl alcohols. TrJith inethyl and propyl and with ethyl and isobutyl alcohols appreciable expansions occur and these obey the law for normal liquids.With methyl and isobutyl alcohols however the curve follows a course completely analogous to the benzene-nitro- benzene curve. It will be seen from these results that mixtures of typical associating liquids such as alcohols may represent solutions of different degrees of complexity some forming isofluidic mixtures others obeying and others again not obeying the law of contrac- tion for mixtures of normal liquids. The one cr the other degree of complexity is conditioned by the positions of the components in the homologous series. T. H. P. Contraction on Mixing Liquids which Unite to Form Chemical Oompounds. E. V. BIRON N. T. NIKITIN and S. G. JAKOBSON (J. &us& phy8. Ohern. soc. 1913 45 2002-2013.Compare preceding abstract) .-At 35O aniline and phenol which form the stable crystalline compound NH,Ph,PhOH undergo considerable contraction on mixing the maximum contraction corresponding with 50 mol. % of aniline and ths coefficient K of the expression D = Ks( 1 - x) (I) (see preceding abstract) gradually diminishing as the concentration of the aniline increases. This diminution in the value of K occurs also with mixtures of other liquids with aniline and is evidently a secondary phenomenon probably con- nected with change in the degree of association of the relatively strongly associated component. Indeed for all the liquids used in the present investigation the temperature-coefficient of the surface energy is less-than the normal value 2.12 Aniline and nz-cresol and aniliiie and pcresol a t 20° exhibit beliaviour exactly aiialogous to that of aniline and phenol.With o-toluidine and phenol a t 3 5 O K is practically constant for the range 30-60 mul. 76 of the amine but has lower values outside these limits. Each of the above four pairs of liquids forms one compound R-O€I,R’NH and each shows very marked contraction varying from 0’35% to 0-’7% of the volume for the 50 mol. % mixture. It may be assumed that the contraction depends on two factors one determined by a physico-mechanical and the other by a chemical modificstioii of the molecules. If such factors are characterised by the constants K and K then D = K,x( 1 - x) + Kzz(l - x) = ( K l + K,)z(l - z) so that Ii = + K and tlie mixtures should obey the law for normal liquids.Phenol and acetone form the compound CH3*COMe,2PhOH containing 66.67 mol. % of phenol. From tlie law of mass actioii 12-2ii. 176 ABSTRACTS OF CHEMICAL PAPERS. i t follows that the contraction formula takes the form If the contraction is conditioned almost exclusively by the chemical factor this equation will become D = Klx2(1 - x) and the maximal contraction will correspond with 66.67 mol. % of phenol. But if the physico-mechanical factor plays the chief part the equation takes the form D = B,x(l - x). If neither factor is negligible the curve will exhibit an intermediate form and in this case A- will not be constant but wiil vary linearly with x that is K= K,x + K,. At 3 5 O the maximal contraction of 1.8% corresponds more nearly with 50 than with 66.67 mol.% of phenol so that the physico-mechanical factor exerts a predominating influence. The values K =. - 1.77 and K2= + 6*44 give calculated values in close agreement with the observed contractions. A series of measurements on mixtures of phenol and acetone was also made a t 15'6O. It is not possible t o supercool phenol t o this temperature so that the molecular volumes of phenol and mixtures containing it in excess could not be ascertained. The character and magnitude of the contraction may however be determined in the following manner D = V,x + V2(1 - x) - 17 where Y is the volume of a gram-mol. of the solution and Vl and 8 the molecular volumes of the components If the contraction obeys equation (I) so that D = Kx(1- x) substitution gives or if [V-IT2(l-x)]/x be termed linear function of x but if D =I!lx;2(1 - x) then which represents a curve of the second order with respect t o x and gives a maxinium or minimum for x ~ 0 .5 . Calculation from the results obtained a t 1 5 * 6 O shows that the values of @ increase gradually with x the method of least squares applied t o the ex- pression @ = Ti' K(1- x) giving Vl = 87.577 and E = 5.44. The values of 4 obtained with the help of these constants do not agree well with tlie experimental values the greatest divergence corre- sponding with a 50 mol. % solution. The use of the more complex expression = Yl - K,lr(l- x) - K,(l - x) gives slightly improved agreement but the experimental data are evidently of insufficient accuracy for such complicated calculations.The results obtained show however that both a t 35O and a t 1 5 . 6 O the contraction of mixtures of phenol and acetone is conditioned principally by the physico-mechanical factor. T. H. 9. Minimum Temperatures for Annealing. HANRIOT and LAHURE (Compt. rend. 1914 158 262-264) -The liardness of a metal after annealing varies with the temperature and duration of the annealing and in tlie case of silver and zinc the two metals studied the annealing; effect was found t o be marked a t compara- D = Ki~'(1- X) + KZx(1- x). Tr = V1z + V Z ( 1 - Z) - Kx( 1 - x) @=Vi-K(l-x) which is a @ = vi - K,x(l - x) tively low temperatuGs providing sufficient time was allowed. A W. G. Ascending and Descending Hammer Hardening. HANXIOT and LAHURE (Cornpi. rend. 1914 158 404-406).-8 comparison ofGENERAL AND PHYSICAL CHEMISTRY. ii.177 the physical properties of plates of the same metal having the same hardness but prepared on the one hand by annealing the plates from maximum hardness and on the other by hardening the metal from complete annealing. The results obtained for physical measurements dlffer considerably in the two series those for the plates obtained by annealing varying the more regularly with vary- ing hardness. These pIates have greater breaking strains elongate further and harden more readily under the same effort than the corresponding plates obtained by hardening. The former also anneal more rapidly a t the same temperature than the latter. W. G. Viscosity of Undercooled WaterA as Measured in a NQW Viscometer. GEORGE F.WHITE and RALPH H. TWINING (Amcr. Chem. J. 1913 50 380-389).-A method is dcscribed for deter- mining the viscosity of liquids which obviates many of the known sources of error and is applicable t o the exceptionally viscous undercooled liquids. The accuracy of the method has been tested by measurements of the viscosity of undercooled water and the results obtained agree closely with those recorded by previous observers. F o r detaiIs of the method and a description of the apparatus which is a modified form of that devised by Bingham and White (A. 1912 ii 1144) the original should be consulted. E. G. Viscosity of Liquids under High Pressures. 0. FAUST (Zeitsch. physikol. Chem. 1914 86,479-495).-A method of measure- ment of viscosity a t high pressures is described and employed for the measurement of the viscosity of ether a t Oo ZOO and 34O; ethyl alcohol a t Oo 20° 40° and 54O; and carbon disulphide a t 0 20° and 40°.The determinations were carried out a t pressures up to 3000 kilograms per sq. cm. It is shown that in the region of small volumes in which according to Tammann (A 1912 ii 538) the molecular attraction is constant the viscosity is approximately a linear function of the volume. All three liquids exhibit a viscosity which increases with the pressure in a manner which is almost linear up t o a pressure of 1500 kilograms per sq. cm. Alcove this pressure all three substances have viscosities which increase more rapidly with pressure that of ethyl alcohol increasing the most and that of carbon disulphide the least.Relationship between the Viscosity Density and Tem- perature of Salt Solutions. m7. J. WALKER (Phil. Hag. 1914 [vi] 27 288-297) .-Measurements have been made of the viscosity and density of aquebus solutions of sodium and calcium chloride a t temperatures between Oo and looo. F o r sodium chloride solutions a t 17O the connexion between the viscosity (p) and the density (p) is given by the equation p =Om042265 + O.O4428(p - 1) + 0*03228(p - 1)2. J. F. S. If !og ( p - 1) is plotted against log (1 - p ' / p ) where p' is the viscosity of pure water a t the same temperature it is found thatii. 175 ABSTRACTS OF CHEMICAT PAPERS. straight lines are obtained for both the sodium and calcium chloride solutions. The relation between viscosity and density may there- fore be expressed by the equation ( ~ - l ) ~ = A ( l -,u'/p) whera 71.and -4 depend on the nature of the dissolved salt and also on the temperature. In the case of sodium chloride 71. is given by the equation 72 = 1.4 - 0*004T and for calcium chloride by the equation 1~ =0.95 - 0*002T where T is the temperature on the Centigrade scale. The corresponding variations of A with temperature are given by log A = - 0.6790 + 0.003747' for sodium chloride and log = - 0.3580 + 0-0005T for calcium chloride. H. M. D. The Sorption of Hydrogen by Wood Charcoal at the Temperature of Liquid Air. JAMES B. FIRTH (ZeilRch. physiknl. Cham.. 191 4 86 294-308).-The author has examined the sorption of hydrogen by cocoanut charcoal by means of pressure determina- tions effected a t measured times after the introduction of the gas t o the charcoal.The charcoal prepared from the shell of the cocoanut absorbs more hydrogen than that made from the nut itself when equal volumes of the two charcoals are compared but if equal weights are compared the amount of gas absorbed is similar in both cases. The sorption of hydrogen by charcoal is made up of two processes (1) an adsorption t~hat is a condensation of gas on the surface which is complete in a very few minutes and (2) an absorption that is the formation of a solid solution which takes place slowly and only reaches an equilibrium after several hours. One gram of charcoal dissolves 15 C.C. of hydrogen after the gas has stood in contact with the charcoal for twelve hours at atmospheric pressure and a t the temperature of liquid air.This volume although constant fcr a given specimen of charcoal varies when other specimens are employed. It is shown that all fornis of wood charcoal contain both a crystalline and an amorphous variety of carbon the former of which has little absorptive power; the absorptive power of a given specimen of charcoal depends mainly therefore on the percentage content of amorphous carbon. J. F. 8. Sorption of Hydrogen by Palladium. FRANZ HALLA (Zeitsch. physikal. Chem. 1914 86 496-505. Compare Holt Edgar and Firth A. 1913 ii 330; Andrew and Holt A. 1913 ii 839).-The work of the above-mentioned authors is discussed. It is shown that the palladium characterised by Graham as inactive is not in reality inactive but apparently so owing to a film of occluded oxygen on its surface.It is also shown that the occlusion of hydrogen by active palladium is not affected by the contact of inactive palladium with the active variety. The author's absorption curves are shown t o be in agreenient with those of the above-mentioned authors. J. F. S. Theory of Dyeing. WILDER D. RANCROFT ( J . PI~yvs'L'caZ Chew. 1914 18 1-25).-The nature of the process involved in the dyeing of wool silk and cotton fibres is discussed in reference t o theGENERAL AND PHYSICAL CHEMISTRY. ii. 179 experimental data recorded in the literature. The author arrives a t the conclusion that dyeing is generally due to adsorption although definite compounds may be formed in certain special cases. On the assumption that all the constituents of the ciye-bath are adsorbed t o a greater or less extent i t has been found possible t o give a satisfactory interpretation t o many facts recorded by previous observers.Since the hydrogen and hydroxyl ions are readily adsorbed i t follows that the acid or alkaline nature of the dye-bath will have an important influence on the adsorption of the dye. The adsorp- tion of hydrogen as ion will tend t o increase the adsorption of an acid radicle whilst the adsorption of hydroxyl as ion will tend t o increase the adsorption of a basic radicle. I n accordance with this it is found that an acid dye is taken up most readily in an acid solution that a readily adsorbed anion decreases the adsorption of an acid dye and that a readily adsorbed cation increases the amount of an acid dye taken up from solution.Since the sulphate icn is adsorbed more readily than the chloride ion i t follows that the addition of sulphates to the dye-bath will have a greater effect in diminishing the adsorption of an acid dye than the addition of chlorides. This is quite in accordance with practical experience. H. M. D. [Tension of Metal Ammonias.] FRITZ EPHRAIM (Zeitsch. physikal. Chem. 1914 86 506-507).-Polemical. An answer to Biltz (this vol. ii 34; compare also Ephraim A 1913 ii 677; Biltz ibid. ii 404.) J. F. S. The Thickness and Structure of the Capillary Layer. G . BAHKER (Zeitsch. physikal. Ch,~w. 1914 86 129-176).-A theoretical psper in which the capillary layer of liquids is studied with respect to its thickness energy relationships and tension.The general results arrived a t are investigated by means of experi- mental data in the case of a large number of substances. It is shown that the cohesion of a liquid cannot be explained by either the Boltzmann or the van der Waals forces. The author adopts the Laplace force ads that acting between the molecules and finds that the radius of the sphere of influence of this force is between six and seven times the molecular diameter. According to van der Wads the dimension of the radius of the sphere of influence is given by 2H/;ri where H is the surface tension and li the mole- cular pressure. Kelvin gave the thickness of the capillary layer as H I K this being the lower limit; the author deduces as the thickness of the capillary layer <=14H/II and calculates the value of 5 for water as 1-2 millimicrons. The expression is also found for water in which represents the density of the liquid and +2 that of the vapour.a s far as the determination of the values of IZ and +2 have been made i t is shown that for water the value of 3 is independent of the temperature and between Oo and 140° has a value G f 1.6 millimicrons and by extrapolation g=4.o66 1 0 - 9 ~ - 1 . ~ 1 5 ( 1 - ~ / ~ ' ~ ) ~ ( 4 ~ - +2)2ii. 180 ABSTRACTS OF CHEMICAL PAPERS. it is shown t o have the same value at; 200O. I n the case of ether the value of 3 is shown by two different methods to be 2.6 and 2.1 millimicrons respectively. If the ratio of the energy change from liquid to capillary layer and from capillary layer t o vapour is represented by p then ~ = ( E ~ - E ) / ( E - E ~ ) and a general ex- pression for the thickness of the capillary layer is obtained which has the form in which ri is the internal heat of vaporisation.A t lower tempera- tures where & the density of the vapour can be neglected q = ( 7 ( 1 + T / T K ) / ( 1 - T I H . d H / d t ) } -1. This formula gives a value for water a t 46O of p=5*2 and for mercury a t Oo q=5*3. If the temperature-coefficient of the surf ace tension is represented by y and the coefficient of expansion of the liquid by k then y/k=3*6-3*7 for all liquids except water and amyl alcohol. If a is the coefficient of the Laplace expression for the molecular pressure then (= 14H/a(& - &)2 and if a is given the value where v is a coGstant then y=2E+ v/TA- and it is shown that for many substances this formula evaluated has the form (=(1+q)/($y-q+2) x q z - T .d H / d t ) / T i a = c o n s t n ~ i t x ~ V ( ~ - Y / T K ) y = 2k + 1-15 / TK. J. F. S. Osmotic Pressure and Moist Air. WILDER D. BANCROFT (J. Physical Chem. 1914 18 67-69).-An extract is given from a paper (Ferguson this Journ. ,1854 6 122) describing the absorp- tion of water vapour by molasses contained in wooden casks which had been stored for a considerable period in a damp cellar. H. M. D. The Molecular Condition of Some Substances in Solution. NILRATAN DHAR (Zeitsch. anorg. Chem. 1913 85 206-213).-The molecular condition of some substances dissolved in water is calcu- lated by van’t Hoff’s formula from the known solubilities at different temperatures.The results obtained with carbon dioxide sulphur dioxide hydrogen sulphide chlorine bromine ammonia mercuric cyanide cadmium iodide thallium chloride arsenious oxide boric acetic and oxalic acids and barium and calcium hydroxides are in qualitative agreement with those obtained by other methods. The heat of solution thus calculated for mercuric chloride is too low. C. H. D. Crystallisation and Solution in Aqueous Solution. 11. MAX LE BLANC (Zeitsch. p2;ysikaZ. Chem. 1914 86 334-336. Com- pare ibid. 1911 77 614).-The author has repeated a series of experiments on the velocity of crystallisation and solution of crystals of potassium dichromate in a saturated solution of the same salt. The method adopted differs from that in the earlier experiments (Zoc.c i t . ) in the fact that instead of exposing the whole crystal t o the solution only one face was exposed; this was carriedGENERAL AND PHYSICAL CHEMISTRY. ii. 181 out by embedding the crystal in paraffin wax and leaving the brachypinacoid only free to the solution. Using the formula dx/dt=KO(C-c) in which 0 is the uncovered surface values of K are obtained which show that the process of solution is a pure diffusion phenomenon whilst that of the growth of the crystal is not. These results are in accord with the earlier work but they emphasise more clearly the difference in the nature of the two processes. J. F. S. Analysis of Crystals by the X-Ray Spectrometer. W. LAWRENCE BRAGU (Proc. Roy. ~ o c . 1914 A 89 468-489. Compare ibid. 1913 A 88 428).-The structure of a number of crystalline substances has been determined from observations on the reflection of X-rays with the aid of the X-ray spectrometer.I f monochromatic radiation such as is emitted by an X-ray bulb with an anti-cathode of palladium falls on a series of equally spaced planes each of which can reflect only a small fraction of that radiation reflection is practically inappreciable except when the relation n ~ = 2 d sin 8 holds good. I n this equation A is the wavelength of the incident radiation 6 the glancing angle of reflexion d the distance between the successive planes and n a whole number. Reflection of the incident radiation is therefore observed a t a series of angles e 02 e etc. the sines of which are in arithmetical progression. I n order to obtain the requisite data for the deduction of the structure of a particular crystal the faces (loo) (110) and (111) are examined in detail one by one.From the known value of ~ = 0 * 5 7 6 x 10-8 cm. and the observed angles of reflection e 8 etc. d may be obtained from the above equation. The ‘‘ normal ” spectra reflected from a simple series of identical planes have intensities which diminish according t o the series 1 0.2 0.07 0.03 0.01. I f one of these spectra is missing or is abnormally strong ths. reason is t o be found in the existence of reflecting planes which occur in groups each group containing several planes of different nature. By combining together the results obtained from the examination of the different faces a number of equations are obtained from which i t is possible to obtain a solution of the structure of any crystal.I n this way the author has obtained the structure of zinc blende fluorspar calcite and iron pyrites. As was anticipated from its close structural relationship with calcite sodium nitrate gives spectra in every way analogous to calcite. Rhodochrosite (MnCO,) chalybite (FeCO,) and dolomite have also been examined and on the basis of their X-ray spectra found to be structurally identical. It has been previously found from observations on potassium chloride that atoms of approximately the same weight have the same diffracting power. A similar relation holds good when the diffracting power of a single atom (Ca=40) is compared with that of two atoms of half the atomic weight (F=19). According to these relations the diffracting power of an atom is proportional to its atomic weigh€.This general relationship has been found to beii. 182 ABSTRACTS OF CHEMICAL PAPERS. of coiisiderablc assistance in the deduction of the structural relations. H. M. D. A Sudden Change in the Form of Liquid Crystals Caused by a Molecular Transformation 0. LEHMANN (Compt. rend. 1914 158 389-393).-An account of the changes observed under a microscope in li9uid crystals of ammonium oleate and of protagon a t their transformation temperatures. The different forms of the crystals are described and the way in which they change into one another. 1%'. G. The Results of Colloid Investigation. THE. SVEDBERO (Rvr 1914 47 12-38).-A lecture before the German Chemical Society giving a review of the present knowledge of colloids.D. F. T. Colloidal Solutions. 111. Influence of Colloids on the Dissociation of Electrolytes. E. PAT ERN^ and b1. C m G o L m r (Gaxzetta 1914 44 i 36-50; KOlloid-Z~it8ch. 1914 14 74-81. Compare Paternb and Salimei A. 1913 ii 849).-From numerous series of experiments (chiefly cryoscopic but in some cases by d-eter- mination of the electrical conductivity) the authors find that solu- tions of electrolytes (potassium chloride sulphate and phosphate) do not alter in m. p. on addition of considerable quantities of colloids (gum arabic dextrin) so that the latter do not appear t o exert any influence on the electrolytic dissociation of salts. Experi- ments of the same kind with some other substances exhibit slight anomalies for which specific explanations can be found.R. V. S. Influence of Capillary Active Substances on Suspensoid Hydrosols. H. K. KRUYT and C. F. VAN D~JIN (Koll. Chem. B<iIwftlp 1914 5 269-298).-The coagulation of arsenious sulphide hydrosol by electrolytes has been found t o be influenced by the addition of organic substances and experiments have been made to determine the change in the limiting concentration of the electxolyte which is attributable t o the added non-electrolyte. The organic substances examined were ethyl propyl isobutyl and iso- amyl alcohols and phenol and from the observations made with them i t appears that the limiting concentration o l the electrolyte is diminished in the case of uni- and ter-valent incrganic cations and increased f o r bi- and quadri-valent cations.From the experiments with barium chloride i t is found that the increase in the coagulating concentration runs parallel with the absorbability cf the organic substsnces by charcoal. I n the case of univalent cations the effect of phenol on the coagulating con- centration is greater than that of isoamyl alcohol whilst the reverse holds true for tsrvalent cations. The effect of the two substances is the same towards quadrivalent cations. The added non-electrolytes have no appreciable effect on the ultramicroscopic appearance of the colloidal particles on the viscosity of the suspension CT on the movemerit c€ the particles in an electrical field,GENERAL ASD PHYSICAL CHEMISTRY. ii. 183 Some observations on the influence of phenol and isoamyl alcohol on the coagulation of a ferric hydroxide sol show that the lirnit- ing concentration of the electrolyte is diminished both in the case of uni- and bi-valent anions.From experiments with colloidal gold it was found that the concentration of the electrolyte which produces a change in the colour of the gold solution is increased by ethyl ether and isoamyl alcohol in the case of uni- and ter-valent cations and diminished when the coagulating ions are bivalent. I n connexion with the above experiments some measurements have been made on the adsorption of phenol froin solutions of potassium chloride. It is found that adsorbed phenol is not sensibly displaced by the electrolyte. On the other hand both potassium and chlorine ions are displaced t o a considerable extent by phenol.The results are discussed from the point of view of the adsorption theory of Freundlicli a d also in reference t o the view that the dielectric constant of the dispersiva niedium is an essential factor in the determination of the stability of the colloidal particles. I n neither case is i t possible t o cbtain an entirely satisfactory explana- tion of the observed results. H. M. D. The Precipitation of Colloids by Salts. I<. SPIRO {BiocLw/. Zeitsch. 1914 59 337-338).-A reply to 8 criticism of Pechsteiii (this vol. ii 38). S. B. S. Swelling of Gelatin in Aqueous Solutions. RUDOLF EHREN- BERG (Biocheni. Zeitsch. 191 3 53 356-390).-Experiments have been made on the swelling of gelatin jellies containing 10 or 20% of gelatin in aqueous solutions of acids bases and salts.The influence of salts on the swelling action of acids has also been in- vestigated and comparative observations made on the behaviour of pure aqueous jellies and jellies containing various salts o r dextrose. It has not been found possible t o give any satisfactory explanation-of the results obtained but i t seems quite certain that the facts are inconsistent with any simple osmotic interpretat'ion. From the results obtained with approximately isosmotic solu- tions (freezing point 0.5O) it appears that a t these concentrations the order in which the salts arrange themselves is not the same as that in which they are arranged according t o the swelling powers of more concentrated solutiom. The reduction in the swelling power of acids on the addition of small quaiitities of salts leads however to the same series ar,d in this case the order of the salts remains unchanged when the concentration is increased.H. M. R. Experiments on Emulsions. F. R. NEWMAN (.I Physical Chefm.. 1914 18 34-54).-The author has investigated the nzture of the emulsions which are formed by benzene and water and has determined the conditions under which different types of emulsions can be obtained. When benzene and water are emulsified by shaking in presence cf small quaiitities of sodium oleate water always forms the external phase. Emulsions can be obtained containing up t oii. 184 ABSTRACTS OF CHEMICAL PAPERS. 0.5% of benzene by volume and also from about 80 to 90% of benzene. I n the preparation of the latter series it was found necessary to add the benzene gradually.When the quantity of sodium oleate per C.C. of water is decreased from 0.05 to 0.02 gram the maximum volume percentage of benzene in the emulsions decreases from 99 t o 98. When magnesium oleate is used as emulsifying agent emulsions are obtained in which benzene is the external phase. These emulsions are much more stable if a little sodium oleate is also present. By varying the proportions of magnesium oIeate and sodium oleate it is possible to prepare emulsions of water in benzene or of benzene in water. Emulsions of the former type which were obtained with the author’s shaking apparatus con- tained from 75 to 96% of water but i t is considered that these limits are of no particular significance and would be changed by more perfect emulsification.Whether one liquid is emulsified in a second or the second in the first depends on the nature of the emulsifying agent. A hydrophile conoid will tend to cause water t o become the external phase whilst a hydrophobe colloid will have the opposite effect. An active emulsifier must be capable of forming a coherent film round the external phase. For determining which of two liquids is the external phase in an emulsion the so-called drop method is recommended. A small drop of the emulsion is placed on a glass plate and a drop of water placed on the drop of emulsion and the two stirred together by means of a glass rod. I f the emulsified globules spread in the water water is the external phase whereas if no spreading is observed water is present in the emulsion as internal phase.Some observations are also recorded with respect t o the emulsioiis formed by carbon disulphide olive oil and linseed oil with water. In mixed paints water is the internal and oil the external phase and it has been found that rosin acts as the emulsifying agent. H. M. D. Equation of Condition Equilibrium Diagram and Asso- ciation Hypothesis. L ~ O N SCHAMES (Ber. Dzut. physikal. Ges. 1914 16 121-122).-A correction of certain statements made in a previous paper (A. 1913 ii 1036). Equilibria in Ternary Systems. XI. F. A. H. Scfmmm- MAEERS (Proc. K. Aka&. Wetonsch. Amstordam 1913 16 597- 609. Compare this vol. ii 41 113).-A discussion of the nature of the equilibria in ternary systems f o r the case that a binary compound occurs as one of the solid phases.H. M. D. H. M. D. Chemical Equilibria in Gaseous Systems. 11. UGO GRASSI (Nuovo Cim. 1913 [vi] 6 ii 164-172. Compare A . 1913 ii 395). -The author deduces f ormulz which permit of the confirmation of Nernst’s formulze regarding the chemical equilibria in gaseous systems by experiments similar to those described in the earlierGENERAL AND PHYSICAL CHEMISTRY. ii 185 paper (Zoc. cit.) and his results with acetone methyl ethyl ketone diethyl ketone and dipropyl ketone confirm these formuls in the interval of temperature in which the reactions were studied (1 37-182'). R. V. S. The Equilibrium between Lead Chloride and Potaasium Chloride in Aqueous Solution. (Mme.) DEMASSIEUX ( C m p t . rend.1914 158 183-184. Compare Lorenz and Ruckstuhl A. 1906 ii 853).-A study of the equilibrium between lead chloride and potassium chloride in aqueous solution a t 14O 50° and 100'. The curves obtained with the results a t each temperature are similar in character and show three transition points namely PbC1 to 2PbC12,KC1 ; 2PbC12,KC1 t o PbCl,,KCl,&H,O ; and PbCh,KCl,&H,O to KC1. W. G. Theory of Binary Mixtures and Concentrated Solutions. The Mixture Benzene-Carbon Tetrachloride. ALFRED SCHULZE (Zeitsch. physikul. Chem. 19 14 86 309-333. Compare Dolezalek and Schulze A 1913 ii 482).-The vapour pressures of mixtures of benzene and carbon tetrachloride have been determined at temperatures from loo to 65O. Measurements are also given of the specific heats of the various mixtures and of the refractive power for light of long wave-length.The object of the work is to examine the Dolezalek vapour-pressure hypothesis in the case of a binary mixture which contains an associated component. The hypothesis has previously (Zoc. cit.) been applied t o the case of a mixture (ether-chloroform) the components of which combine to some extent. A theory is put forward on the basis of the law of mass action and the Dolezalek hypothesis which enables the mole- cular constitution <jf a binary mixture to be deduced from the vapour-pressure measurements. It is shown that on mixing un- saturated benzene vapour with unsaturated carbon tetrachloride vapour a dilation occurs which points to the association of one of the constituents in the vapour phase; this is shown t o be the carbon tetrachloride which a t 90° and under a pressure of one atmosphere is associated to form double molecules to the extent of 0.3% in the vapour phase.The vapour-pressure curves of the benzene-carbon tetrachloride mixtures are concave to the composi- tion axis and they can all be obtained by calculations based on the Dolezalek hypothesis. The divergence of the curves from the straight-line curve which would be obtained if the simple mixture law held decreases as the temperature rises a fact which is in accordance with the hypothesis. The specific heats of the mixtures are smaller than those calculated by the mixture law but if the degree of association is taken account of in the calculations the experimental values agree well with the calculated values.The same relationships are found for the refractive power for light of long wave-lengths and quite generally it is shown that the whole physico-chemical behaviour of the mixture can be characterised from a single determination of the mass-action constant obtained from the vapour pressure of a single mixture. J. F. S.11. 186 ABSTRACTS OF CHEhiICAI PAPGRS. Binary Mixtures. The Mixtures Benzene-Ethylene Di- chloride and Benzene-Stannic Chloride. ALFRED SCHULZE and HEINHICII HOCK (Zeitsch. physikul. Clrem. 191 4 86 445-457 Compare Dolezalek and Scliulze A. 1913 ii 482; Schulze p r e ceding abstract) .-The vapour pressure of mixtures of benzene and ethylene dichloride have been dete~mined a t 8"75O 2 5 O 8 5 O and 95' and from the results i t is shown that the vapour-pressure curve is a straight line wliich is in accord with the Dolezalek theory (Zoc.cit.) since both substances are non-associated. I n the same way the molecular heat a t SOo and 3 5 O of mixtures also lies on a straight-line curve but a t ZOO a slight divergence from the straight line is observed €or mixtures containing a large amount of ethylene dichloride. This indicates that a t lower temperatures ethylene dichloricle is somewhat associated. The mixture benzene- stannic chloride was also iiivestigated. The vapour-pressure curve is concave to the composition axis. On mixing the two liquids there is with decreasing temperature a considerable dilation and a iiegative heat change. It is shown that a t looo staniiic chloride consists of double molecules Lo the exterit of SO% and that a t 30° i t is completely associated and contains in addition t o double molecules also more complex molecules.Knowing that stannic chloride is an associated liquid its behaviour when mixed with benzene is strictly in accord with the Dolezalek theory of binary mixtures. J. F. S. Deflagrrttions in a Steady State in Conducting Media. L. CRUSSARD (Compt. rpnd. 1914 158 125-1 28. Compare Jouguet ibid. 1913 156 872).-The author shows that i t is possible t o write directly a first integral of the equation of conductivity the consideration of which notably simplifies all r.esearches on combustion. W. G. Influence of Temperature on the Velocities of Transform- ation of Physico-chemical Systems. H. ~ J A ~ ~ C E L I N ( C O ~ I Z ~ ~ .vntl.. 1914 158 407-409. Compare this vol. ii 115).-A mathematical discussion of a method for evaluating by the application of the Boltzmann-Gibbs law of distribution the critical energy E neces- sary t o transform a molecule from the niean state into the active state this being a measure of the energy necessary t o convert a system into an unstable state such that i t will react to give a new system. A formula is given showing the variation with respect t o temperature and the author has shown that his results are in agreement with the experimental data f o r evaporation and sublimation in a vacuuni the former in the case of nitrobenzene and the latter in the case of naphthalene and iodine. Expression of the Velocities of Transformation of Physico- chemical Systems as a Function of the Afbity.R. MARCELIN (Compt. rend. 1914 158 116-118. Compare t h i s vol. ii 115).- A deduction from the Boltzmann-Gibbs rule of the formula already given expressing the relationship between the velocity of trans- formation of physico-chemical systems and their affinities. W. G . W. G .GENERAL AND PHYSICAL CHEMlSTRY. ii. 181 Limits of Inflammability and Specific Retardation of Ignition. L. CRUSSARD (Compt. r e n d . 1914 158 340-343).-A theoretical discussion of the conditions governing the specific retardation of ignition and retardation of the temperature of ignition of gaseous mixtures. A Case of Decrease in Reaction Velocity with Rise in Temperature. A. SKHABAL arid 8. R. WEBERITSCA (Bsr. 191it 47 117-119).-Skrabal (Chem.Zeit. 1913 37 1169) has shown that the temperature quotient kttl,Jkt of a reaction must undergo a change if the substances taking part in the time reaction are transformed into complexes. The relation between the tempera- ture quotietit 7 of the original reaction and tlie quotient 7’ of that between the complexes is given by the relation where the Q’sreprescnt the heat effects of the reactions foriniiig tlie complexes and the sum ( n + p + T -t- . . .) represents the order of the reaction. From this equation i t follows that a decrease in reaction velccity with rise in temperature may be realised if one starts with a reaction of high order and possessing a small temperature quotient and causes a t least one of tlie reacting substances t o be trans- formed into a complex with absorption of heat.The form of the above equation shows that such cases will be rare. The authors have realised such a case with the reaction between iodate and iodide which Dushman (A. 1904 ii 718) has shown t o proceed according to the equation and to have the small temperature quotient 1.3. If sodiuiii sulphate is added in sufficient quantity to a solution made acid with sulphuric acid the hydrions are transformed into the complex HS0,’-ions according t o the reaction H’ + SO,// = HSO,’ which takes place with the absorption of 5000 cal. The velocity of reaction is then represented by the equation - d[IO,’]/dt = k’[I’]2[I03’]~HS0,’]2/[S0,’’]2 and the calculated temperature quotient is 0.73 which indicates that the reaction velocity should decrease with rise in tempera- ture.0*0025-lllKI + 0~0005-~111~10,-/- 0*0O15-MH,SO4 $- 1.0-JlNa,S04 showed that the reaction proceeded more slowly at SOo than a t Measurement of Velocity of Reaction by means of Colloidal Precipitation. H. F~~EUNDLICEI and H. PAPE (Zeitsch physiknl. Chrm. 191 4. 86 458-478).-The coagulation of arsenic sulphide sols containing about 3 grams per litre is investigated for the following binary mixtures of electrolytes potassium nitrate and sodium nitrate ; potassium nitrate and strychnine nitrate ; potassium nitrate and barium nitrate ; potassiuin nitrate and cerous nitrate; and barium nitrate and cerous nitrate. Tlie precipitation value was determined for a large uurnber of different mixtures for each pair of electrolytes W.G. ,-‘/,- = e1(J(JL&14-PQ~fl‘&af.. . .. .)/kr( l’+ It)) -d[I03‘]/dt =Ji[H’]2[I‘]2[I03‘] Experiments with a solution of the composition 17*5O and that the temperature quotient was 0.83. T. s. P.ii. 188 ABSTR.ACTS OF CHEMICAL PAPERS and the values obtained exhibited regularities which are strictly in accord with the absorption theory of colloid precipitation. The presence of even a small quantity of a cation of high valency or of one which is easily absorbed in a solution of a cation of lower valency o r one which is not easily absorbed causes the concentra- tion required for complete precipitation of the colloid to be very much reduced. With the help of the data collected in the fore- going experiments the velocity of two reactions in which there is a change in the valency of the cation was determined.The reactions studied were (1 j the change of chloropurpureo- chromium chloride into roseochromium chloride [Cr(NH,),Cl]Cl + HzO = [Cr(NH,),,H20]C1,; (2) the change of cisdichlorodiethylenediaminechromium chloride into cisdibisacruadiethvlenediaminechromium chloride unimolecular reactions. I n ihe first case thve reaction velocity was measured a t 25O 30*3O and 3 5 O and the temperature coefficient is found to be 3.3 per loo between 2 5 O and 35* and the reaction is in accord with the formula of Arrhenius The second reaction was investigated a t Oo and 2 5 O and the temperature-coefficient calculated to 3.1 per loo between 2 5 O and 3 5 O . J. F. S. log&= - A / T + B . Completely Unstable Forms [of Substances].A. H. RICHARE MULLER (Zeitsch. physikd. Chem. 1914 86 177-242).-Totally unstable substances are characterised by the fact that their thermodynamic potential (that is the 3 surface) lies above the corresponding surface of the stable form a t all temperatures and pressures. The author has measured the velocity of crystallisation and the velocity of transformation the volume changes surface tension heat of crystallisation and heat of transformation of both the stable and unstable forms of 4-bromo-l 2-dinitrobenzene phthalide acetamide monochloroacetic acid sodium thiosulphate a/3-dibromopropionic acid ethyl /3-aminocrotonate erythritol glycollic acid nitro-p-acetotoluide m-chloronitrobenzene m-bromo- nitrobenzene m-dinitrobenzene 4-chloro-1 2-dinitrobenzene pnitrotoluene pbromotoluene piodotoluene acetanilide benz- amide etliylcarbamide and thymol.It is shown that the volume change (Av) on melting and the heat of fusion rp can be the same in the case of both the stable and unstable forms or widely different. I f T and T' are the melting points of the stable and unstable varieties the relationships T)T' rp>rpl and Av)Av' hold and consequently it is extremely unlikely the two forms can be in equilibrium a t any point and the unstable forms are there- fore t o be regarded as totally unstable forms. That these sub- stances never can be in equilibrium with the stable forms is con- firmed from the direction of the curves which are calculated from the expression dT/dp= TAvlr,. From the molecular surface tension temperature-coefficient it is shown that with the exceptionGENERAL AND PHYSICAL CHEMISTRY.ii. 189 of ethyl aminocrotonate and benzophenone the whole of these sub- stances are strongly associated. It is shown that in many of the cases examined the velocity of crystallisation is abnormally dependent on the amount of supercooling in the sense that in regions where the velocity of crystallisation should be independent of temperature it increases with further supercooling. This abnormality is found only in those substances which are shown from the temperature-coefficient of the molecular surf ace tension to be associated. The maximum velocity of crystallisation of the stable form is shown to be greater than that of the unstable form in nine cases and smaller in eighteen cases.A comparison of the maximum velocity of transformation of a substance with the maxi- mum velocities of crystallisation of the stable and unstable forms shows that the velocity of transformation is not always the greatest as might have been expected. It is shown that in many cases the velocity of transformation is nearer the velocity of crystallisation of the stable form than that of the unstable form. J. F. S. Action of Hydrochloric Acid on Alcohol. SULO KILPX (Zeitsch. physikal. Ciaem. 1914 86 427-444).-Equations have been deduced for calculating the velocity of the reaction between alcohol and hydrochloric acid in the presence of water. Three cases are treated in the equations (1) that undissociated hydrogen chloride molecdles alone take part in the change; (2) that chlorine ions only take part in the reaction; and (3) that both hydrogen chloride molecules and chlorine ions react.The action of hydrogen chloride on a 46.2% alcohol-water mixture has been observed a t 97O 102O and l l O o . The concentration of the hydrogen chloride was 0*25N 0*5N and 1-0N in the various cases. A further series of experi- ments were carried out in which the influence of ammonium chloride on the reaction was investigated. I n the calculations made from the experimental data it is assumed that any action of the chlorine ions can be neglected. It is shown that the influence of temperature on the reaction between alcohol and hydrogen chloride is greater than that in the case of the reverse reaction ethyl chloride and water.The relationship between the tempera- ture and the velocity of reaction is in accord with the Arrhenius equation. J. F. S. Velocity of Reaction between Merouric Acetate and Aniline. G. ROSSI (Gazwtta 1913 43 ii 665-669).-The author's measurements verify the law of chemical equilibria for this reaction ths value of the reaction constant being 0-000841 a t 2 5 O . R. V. S. Velocity of Reaction in Catalytic Hydrogenations in the Preeence of Platinum Black. G. VAVON (Compt. rend. 1914 158 4 0 9 4 1 2 . Compare A. 1911 i 657; 1912 i 628).-From a study of the rate of hydrogenation of limonene first into carvo- menthene and finally into menthane by deans of platinum black VOL. cvi. ii. 13ii. 190 ABSTRACT8 OF CHEMICAL PAPERS. the amount of the catalyst employed being varied the author shows that the curve of the velocities of hydrogenation of sub- stances capable of taking on several molecules of hydrogen pre- sents varied forms according t o the quantity and quality of the catalyst’.By prior heating of the catalyst t o temperatures between 300° and 500° the second stage in the hydrogenation was hardly apparent although on the introduction of more limonene this was still reduced t o carvomenthene. By heating platinum black t o suitable temperatures i t is possible to diminish its activity and thus render it incapable of effecting difficulti hydrogenations although i t is still capable of catalysing easy hydrogenations. W. G . The Combustion of Oxalic Acid in Contact with Blood Charcoal and the Retardation of thie Reaction by Indifferent NarcoticB.OTTO WARBURG (P’iiger’s Archiv 1914 155,547-560). -The author shows that a t 38O oxalic acid is oxidised t o carbon dioxide and water a t the surface of blood charcoal; the tempera- ture quotient of the reaction for loo is 2.1. Investigation of the action of the indifferent substances methyl- ethyl- propyl- and phenyl-urethane sliows that they diminish the velocity of oxidation the order of their effect being the same as that already observed by the author in his experiments with red blood corpuscles (A. 1911 ii 49). The influence of increase in concentration of the narcotic is however not so great as in the case of the blood corpuscles. T. S. P. Application of Spectroscopy to the Study of Chemical Equilibria. The Sytitems Formed by Oxalic Acid and Urangl Salts.VICTOR HENR~ at~d MARC LANDAU (Curtrpt. rend. 1914 158 181-183).-The quantitative measurement of the absorptioil spectra in the ultra-violet can be used to study chemical equilibria and velocities of reaction in the case of substances which possess absorption spectra different from those of the initial substances. This method has been applied t o mixtures of oxalic acid and uranyl salts in aqueous solution. The mixture oxalic acid + uranyl salt produces a greater absorption of the ultra-violet rays than the sum of the absorption of the two constituents this being a further proof of the general law ’that chemical lability causes an increase in absorptive power for ultra-violet rays. The increase of absorp- tion produced by oxalic acid is greatest with uranyl sulphate and nitrate and least for the chloride and acetate.Uranyl acetate and cjxalate absorb ultra-violet rays much more strongly than the chloride nitrate and sulphate. There is a direct relation between the photocatalytic power of uranyl salts and the increase in absorption produced by these salts on oxalic acid. W .G. Study of Diazotisation by the Spectroscopic Method. E. TASSILLY (Compt. rend. 1914 158 335-338).-The author bas applied the spectroscopic method for studying the progress ofGENERAL AND PHYSICAL CHEMISTRY. ii. 191 diazotisation of aniline (compare this vol. ii 42) t o the diazotisa- tion of a number of other bases and has found in each case the time necessary for complete diazotisation. W. G. Velocity of Reaction in Phototropic Transformations. RJ .PADOA arid TERESA flrlVasNT1 ( d t l i k. Accrd. hints? 19 13 [v] 22 ii 500-505. Compare Padoa and Tabellini A. 1912 ii 879).-The preparation of solutions of the two forms of the phototropic sub- stance salicylidene-P-naphthylamine (Senier Shepheard and Clarke T. 1912 101 1950) has enabled the authors to pre- pare mixtures containing known proportions of the two modifica- tions in this case. By matching the colours of these mixtures with suitable dyes standard tints are obtained by means of which the phototropic change can be followed quantitatively. The value for the reaction constant obtained (which is the product of the true reaction constant and the intensity of the light) is constant on the assumption that the reaction is unimolecular.The tempera- ture-coefficient is 1.47. Similar experiments on the decolorisation of the substance indicate that this reaction is bimolecular and the temperature-coefficient has the value 2.0. From these results it appe'ars that phototropic change in the solid state is due to a poly- merisatioii. The observations made in the case of benzaldehydephenyl- hydra,zone are similar. The colouring reaction is unimolecular and its temperature-coefficient is 1*065-1*068. The decolorising action ,Is bimolecular and in this case the temperature-coefficient is 1.7. R. V. S. Temperature-coefficients of Phototropic Transformatione. 11. 14. PADOA and B. FORESTI ( A t t i R. Accad. Lincei 1913 [v] 22 ii 576-579. Compare preceding abstract) .-From the results of their previqus work on this subject the authors deduce the law that the ratio of the intensities of light required to maintain in a pboiotropic substance the same coloration a t two temperatures differing by loo is equal t o the ratio between the temperature- coefficient of the colouring reaction and that of the inverse reaction.Experiments with salicylidene-P-naphthylamiiie and benzaldehyde- phenylhydrazone yield results in accordance with this law. R. V. S. Heterogeneous Catalysis in Rigid Systems. .EOBERT MARC (Zeitsch. nnoyg. Chem. 1914 85 65-74).-The view that the lowering of the velocity of crystallisation by the presence of impurities is due to adsorption (Freundlich A. 1910 ii 1045) is preferable to the view that the effect is merely one of lowering of melting point (Tammann A.1912 ii 1147) as the latter would require an abnormally high temperature-coefficient of the velocity. The idea of adsorption must also be applicable to the crystallisation of glasses and t o the polymorphic transformation of solids. The acceleration of the change Se,+ S e by the presence of silver selenide (A. 1906 ii 742) is probably a case of heterogeneous 13-2ii. 192 ABSTRACTS OF CHEMICAL PAPERS. catalysis in a rigid system. The two modifications of selenium probably form a compound Se (A. 1906 ii ZSO) which would be adsorbed by metallic selenides (compare this vol. ii 196). C. H. D. Experiments on Abel’s Theory that Incombustible Dusts Act Catalytically in Igniting Weak Mixtures of Methane and Air. HAROLD B. Drxo~ and H. M. LOWE (Mem.Xanchester Phil. Soc. 1913 57 No. 15 1-10).-A critical discussion of the available evidence is first given and then new experiments are described. Two series of experiments were made (1) the direct combustion of weak mixtures of coal-gas and air with and without non-combustible dust (calcined magnesia) in order to see whether any difference in the propagation of the flame could be noticed; (2) the heating of a length of platinum wire in weak mixtures by an electric current t o show that by this means a non-explosive mixture could not be made to explode as Abel supposed but rather that an explosive mixture thus treated would become non- explosive owing to the combustion on platinum wire. Great care was taken in mixing thoroughly the gases this being the weak point of Abel’s experiments.It was found that the presence of a non-combustible substance does not cause the ignition of a weak gas mixture which is not ignited by a flame or spark and that if any local combustion takes place on the dust causing self-heating such an action causes the remainder of the gas t o be less and not more explosive. T. S. P. The Structure of the Atom. W. PEDDIE (Phil. Mug. 1914 [vi] 27 257-268).-A theoretical paper in which the question of atomic structure is discussed in reference to recent work on radiation. Although the phenomena of radiation have led t o the postulation of a unit of energy which is regarded as an actual physical entity it may be doubted whether the emission or absorp- tion of energy in multiples of definite quantities is not really due t o structural peculiarities of the emitting or absorbing mechanism.Bohr’s deduction of formulze for line spectra (A. 1913 ii 689 943) is referred to in particular and it is shown that atomic structures are possible for which it does not appear t o be necessary to throw over the ordinary dynamical laws in order t o explain the proper- ties of the atom. H. M .D. Constitution and Structure of the Elements. HAWKSWORTH COLLINS (Ckem. ATew8 1914 109 26-28. Compare A. 1913 ii 1045).-If the nearest whole numbers to the atomic weights of the elements in the second horizontal row of the Periodic Table are taken they may be written as 23 23 + 1 23 + 1 + 3 23 + 1 + 3 + 1 23 + 1 + 3 + 1 + 3 etc. The number of parts into which the atomic weight (nearest whole number) is thus divided corresponds with the maximum valency of the element.Assuming that one valency emanates from a mass of 23(Na) one from a mass of 1(H) and two from a mass of 4( = 1 + 3 =He) the author deduces that sodiumGENERAL AND PHYSICAL CHEMISTRY. ii. 193 is the basis of all the& elements the expulsion of helium from any element giving the element with next but one lower atomic weight. Other elements of higher atomic weight are then considered in pairs consisting of elements which are especially associated in chemistry o r mineralogy or both. The differences between the atomic weights of the pairs are found to be approximate multiples of 23 ; for example 112.40(Cd) - 65*37(Zn) = 2 + 23.515 and hence i t is deduced that Cd=NapZn. Eight pairs of elements have a difference of 90 which corresponds with the atomic weight of zirconium; this element is assumed to contain three atoms of sodium in its constitution. From such results the author states the principle sodium takes a prominent part in the formation of all elements of greater atomic weight than itself.” T.S. P. The Electron Conception of Valence. V. Polar and Non- polar Valence. K. GEORGE FALK and J. M. NELSON (J. Amer. Chcm. Soc. 1914 36 200-214).-Polemical against the views of Bray and Branch (A. 1913 ii 945) the authors maintaining that valence is of a polar nature in all cases. T. S. P. Stratified Systems. RAPHAEL ED. LIESEQANQ (Kolloid. Zeitsch. 1914 14 31-34).-The formation of stratified systems may be modified not only by external rhythmic disturbances but also by internal disturbances of a similar rhythmic type.The question as to whether i t is possible t o distinguish between the effects pro- duced by external and internal rhythm is discussed and the author arrives a t the conclusion that this is not possible in the case of natural objects or even of laboratory preparations which have not been under observation during the period of their evolution. H. M. D. Some Exercises in Physical Chemistry. ANTONIO BACCARINI (Nuovo Cim. 1913 [vi] 6 ii 286-290).-A scheme of work based on the reaction studied by Fraenkel (A. 1907 ii 746). R. S. V. Contributions to the History of Science (Period of Priestley-Lavoiaier-Dalton) Based on Autograph Docu- m ents. KURT LOEWENFELD (Mem. Munchester Phi,?. SOC. 19 1 3 57 No.19 1-50).-Historica1 dealing (1) with Dalt,on and his contemporaries William Henry William Charles Henry and letters by Berzelius Schonbein and Volta ; (2) with Priestley and Lavoisier. T. S. P. A New Steam Generator. J. ALAN MURRAY (Chem. New4 1914 109 29-30).-The apparatus consists of a copper cylinder 5 inches high by 4 inches in diameter and fitted with an air- tight lid; the bottom is externally concave. A copper tube half an inch in diameter which passes through the bottom and projects t.o within about 1+ inches from the top is coiled in two folds in the hollow outside the bottom. A space of about one-eighth of anii. 194 ABSTRACTS OF CHEMICAL PAPERS. inch is left between the two folds of the coil and also between the upper fold and the bottom of the cylinder t o allow the proper spread of the flame used for heating. Water is maintained a t a constant. level by the usual arrangement. Steam is generated very quickly and is superheated in the coil. T. S. P. An Apparatus for Extraction with Hot Solvents. H. TTTAR (Blochem. Zeitsch. 19 14 58 503-505).-The apparatus is OH the principle of that of Soxhlet. The condenser has a wide pro- longation which is ground at the lower end t o fit the flask ill which the solvent is heated. I n this is suspended the cylinder with the syphon which contains the material t o be extracted. The apparatus is figured in the text. S. B. S. A New Gas Generator for the Permanent Generation of Large Quantities of Gases. BRODTMANN and RODEWALD (Chcn?. Zsit. 1914 38 187).-The rrpparatus consists ewentially of an enter vessel containing the acid and an inner bell-jar fitted with a twc- holed rubber bung. Through the cne hole passes an outlet tube fitted with a stop-cock and through the other central licle a glass rod supporting a special cage open at both ends containing the material to be acted on by the acid which can be raised and lowered a t will. The outer vessel is constricted at the bottom thus supporting the inner bell-jar and then expands t o form a foot into which is fitted a stoppered tube f o r running off the waste acid. T. S. P. A Modifled Kipp Apparatue. LAU (Chenz. Zeit. 1914 38. 147).-The middle globe is not fused t o the lower half-globe but drawn out funnel-shaped and then ground into the neck cf the lowest portion. The prolongation of the upper globe opens towards the bottom of the funnel the lower end of the prolongation being drawn out and turned upwards. The side tube of the lowest globe is placed on the upper part and fitted with a two-holed bung through wliicli pass a syphon tube and a T-tube. The manipula- tion of the apparatus is described many advantages being claimed for it. T. S. P. Arrangement for Emptying Kipp’s Apparatus. GEORG LOCREMANN (Chcm. Zeit. 1914 38 222).-The side-tube of the middle bulb is fitted with a two-holed rubber bung; through one hole passes the usual gas tap and through the other another tube fitted with a stop-cock. Connected with the latter tube by means of a piece of indiarubber tubing is a glass tube which passes down into the bottom part of the kipp. By opening the stop-cock the pressure of the gas in the apparatus forces the acid out through the tube. T. 8. P.

ISSN:0368-1769    

DOI:10.1039/CA9140605157

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

INORCh!STC CHEMISTRY Inorganic Chemistry. ii. 195 Plumboxan Process for the Separation of Air into Oxygen and Nitrogen. GEOHQ KASSNER (Arch. PAUTWL 1913 251 596-609) .-The author describes his plumboxan process for the separation of the oxygen from the nitrogen in air. Plumboxan NazPb03,NazMn04 is an emerald-green compound or solid solu- tion of sodium metaplunibate and sodium manganate. This is con- tained in a combustion tube which is placed in a slightly sloping position in a furnace and heated a t 430-450O. The ends of the tube are bent a t obtuse angles and are connected a t the one end to supplies of steam and air (freed from carbon dioxide) and a t the other end to the gasometers water-pump and a vacuous vessel. By passing steam over the plumboxan oxygen is obtained; subsequently air is passed through the tube whereby the plumboxan is regenerated the issuing gas being practically pure nitrogen during the first stages of the regeneration.The oxygen obtained by the action of the steam on the plumboxan is also practically pure provided the combustion tube has been put after the passage of the air and before the passage of the steam into communication with the vacuous vessel in order to remove the last traces of nitrogen from the pores of the plumboxan. The plumboxan process has an advantage over the barium oxide process in that the absorption of the oxygen by the plumboxan and its regeneration by steam are two distinct and a t temperatures above 400° irreversible reactions. According t o the author’s ex- planation the liberation of the oxygen is not due t o a mere thermal dissociation but is a catalytic process in which the water in com- bination with the sodium metaplumbate in the plumboxan acts as the catalyst.Several experimentally ascertained facts taken in con junction with the results of the author’s previous researches on the behaviour of calcium ortho- and meta-plumbates serve to indicate the course of the whole reaction. I n the first place free sodium hydroxide is not produced by the action of steam on plumboxan (as is the case in the Tessi6 du Motay process). Secondly sodium plumbite is present not in plumboxan itself but only after it has been treated with steam. The following equations indicate the reactions which are supposed to occur (1) 2Na2Mn0 + 2H,O =O + 2Mn0 + 4NaOH ; (2) 2NaOH + Na,PbO = H,O + Na,PbO ; (3) Na,PbO + H,O = Pb(0Na),(OH)2 ; (4) 2Pb(ONa)2(OH) + 2NazMn0 = 2H,O + 2PbO,(ONa) + ZNa,MnO ; (5) PbO,(ONa),= 0 + Na2Pb02 ; (6) Na2Pb0 + Na,MnO = Na,PbO + Na,MnO,.c. s. Ebullioscopy of Sulphur ERNST BECKMANN and OTTO LIESCRE ( Z e i t d . ~ Y Z O T ~ . Chcm. 1914 85 31-43) -The boiling vessel is of Eorosilicate glass with electrical heating (A. 1908 ii 663) theii. 196 ABSTRACTS OF CHEMTCAL PAPERS. jacket being also of borosilicate glass containing sulphur vapour heated by a tin bath. The temperature is measured by means of a platinum resistance thermometer. The ebullioscopic constant of sulphur is calculated t o be 157.6 from determinations of the boiling point under different pressures. This is on the assumption that liquid sulphur a t the boiling point contains 33% of S molecules an assumption which is justified by recent determinations (Smith and Holmes A.1906 ii 157; Kruyt A 1913 ii 132). The heat of evaporation per gram is 64.8 cal. The following numbers of atoms in the molecule are found by ebullioscopic measurements a t atmospheric pressure Se 2.42; Te 1.32; As 1.0; Sb 1'17. C . H. D. Preparation of Sulphuric Acid Free from Oxygen Com- pounds of Nitrogen. ACH. GR~GOIRE (Bull. Soc. chim. Belg. 1914 28 32-33).-The acid to be purified is diluted with its own volume of distilled water and then boiled vigorously in a Kjeldahl flask until concentrated once more. If oxygen compounds of nitrogen still remain the process is repeated. T. S. P. The Nature of the Catalysis of the Transformation of Selenium by Silver Selenide.EDWIN BERGER (Zeitsch. anorg. Chem. 1913 85 75-11'?. Compare Marc this vol. ii 191).- The true melting point of selenium is not readily determined owing to the viscosity and the low velocity of crystallisation. Heating curves indicate that selenium rich in Se has a higher melting point than that rich in Se,. but that equilibrium is reached during melting. Silver selenide does not appreciably lower the melting point of selenium. The sudden change of the electrical conductivity on melting allows of a more accurate determination the result being 220.2O k 0.5O. Silver selenide in quantities of 0.1% is recognisable under the microscope in amorphous selenium. It is also insoluble in crystal- line selenium and the devitrification is not directly proportional to the silver content.The electrical conductivity of selenium pastilles containing the maximum quantity of Se increases slowly with time a t 25O. I n presence of silver selenide the increase is more rapid the effect being approximately proportional to the silver content up t o 4% Ag,Se. The catalysis thus occurs in a heterogeneous rigid system. A comparison of the electrical conductivity of selenium quenched from different temperatures favours the hypothesis of a compound Se, which forms solid solutions with both components. The electrolytic potential of selenium in a solution of sodium selenide (0.3%) is -0.05 volt and is independent of the previous treatment of the selenium. C. H. D. Active Nitrogen. 111. ERICH TIEDE and EMIL DOMCKE (Bey.1914 47 420-425).-In continuation of their previous work (this vol. ii l22) the authors have devised an apparatus by meansINORGANIC CHEMISTRY. ii. 197 of which oxygen may be removed completely from nitrogen by heating with copper. With such nitrogen the Strutt phenomena are not observed; i t is necessary however in removing the oxygen by this method not to heat the copper to a temperature above the dissociation temperature of copper oxide otherwise the glow is always formed. Using the pure nitrogen thus obtained the authors have repeated Strutt’s experiments with iodine sulphur sodium and thallium chloride and in no case obtained the phenomena he describes; the addition of the least trace of oxygen gives rise to the various phenomena.T. S. P. The Nitrites. MARCEL OSWALD (Ann. Chirn. 1914 lix] 1 32-112).-The only practical method for the preparation of pure nitrites of the alkali and alkaline-earth metals is by double decom- position of silver nitrite with the chlorides of these metals (compare A. 1913 ii 135).. Two new nitrites have been isolated namely calcium nitrite Ca(N0,),,4H20 and lithium nitrite LiNO,,H,O. I n the action of heat on sodium nitrite in addition to the ordinary reactions the following take place NaN0 + NO,+ NaN03 + NO ; 2NaN0 + NO + 2NaN03 + N (compare the action of heat on silver nitrite A. 1911 ii 281). The dis- covery of these reactions has enabled the author t o explain the actions occurring in the action of nitrogen peroxide on lime and on the alkali and alkaline-earth carbonates and in the decomposi- tion of the complex nitrites of cobalt nickel and silver.When nitrogen peroxide acts on calcium oxide there is always a loss of free nitrogen no matter what the conditions of temperature in accordance with the equation 2Ca0 + 5N0 + 2Ca(N03) + 0.5 N2 a fact which is of industrial importance. The hydrated nitrites can be dehydrated in a vacuum over phos- phoric oxide without undergoing decomposition ; in concentrated aqueous solutions lithium nitrite and the alkaline-earth nitrites undergo hydrolysis a t looo. The solid nitrites or their saturated solutions are not oxidised by oxygen at atmospheric pressure neither are the dry salts acted on by nitric oxide so long as decomposition of the salt itself does not occur. Oxidation of solutions of the nitrites only occurs in the presence of acids and is then due t o oxidation of the decom- position products (nitric oxide) of nitrous acid.The solubility curves of the various nitrites have been determined (compare A. 1913 ii 701 for that of sodium nitrite) and also the mutual solubilities of silver nitrite and the nitrites of potassium sodium lithium barium strontium and calcium. The following double salts were the only ones formed Na,Ag,rNO,),,H,O K,Ag,(NO,),H20 and- BaAg,(NO,),,H,O. The physical properties of the variou,s salts and solutions and the action bf heat on the various salts were also studied in detail. The nitrites readily give supersaturated solutions and barium and strontium nitrites Ba(Sr) (N02)2,H20 were shown to be isomorphous by the method of inoculation.T. S. P.ii. 198 ABSTRACTS OF CHEMICAL Pill’E11S. The Melting Point of Arsenic. R. GOUBAU (Compt. rend. 1914 158 121-122).-A determination of the melting point of arsenic the metal being heated in a quartz flask immersed in sand and the temperature measured by an electric thermometer. Arsenic melts a t 817O and if the heating is continued there is a violent explosion at 900°. The vapour pressure of arsenic is very high long before the melting point is reached. W. G. Melting Point of Arsenic. PIERRE JOLIBOIS (Compt. rend 1914 158 184-185. Compare A. 1911 ii 720)-A claim for priority over Goubau (preceding abstract). Colloidal Carbon Obttrined by a Chemical Method. L. SABBATANI (Kolloid. Zeitsch. 191 4 14 29-31).-A method for the preparation of a colloidal solution of carbon is described in which 2 grams of finely-powdered sucrose are slowly added to 20 C.C.of well-stirred siilphuric acid. After the dark-coloured solution has been kept for twenty-four hours at room temperature i t is poured slowly into 80 C.C. of distilled water the mixture being shaken con- tinuously during the process. The liquid is then filtered and di- alysed until free from sulphuric acid. The solution prepared in this way is very stabre and the ultramicroscopic particles which it contains are found to be negatively charged both in acid and alkaline solution. The solu- tion prepared by dissolving 2 grams of sucrose in 20 C.C. of sulphuric acid is kept a t room temperature for three or four days and then poured into a shallow dish which together with a vessel contsining water is placed under a glass globe.Water vapour is absorbed by the sulphuric acid solution and at the end of about a week it is found that the solution has been transformed into a gelatinous mass. This is transferred to a vessel containing distilled water which is renewed from time to time until the sulphuric acid has been completely removed. During this process the gelatinous mass retains its original form but when removed from the water and dried in the air it contracts very considerably. The dry powder swells to a slight extent’ in contact with water and with alkalis traces of carbon dissolve forming a colloidal solution. The Electrolytic Reduction of Carbon Dioxide and Carbon Monoxide in Solution under Pressure. FRANZ FISCHER and O ~ K A R PRZIZA (Bv.1914 47. 256-260).-lVith the same nppsrfltne as that used in the electrolytic reduction of dissolved oxygen (A. 1913 ii 285) the authors find that with the very high current densities of 10-15 amperes per sq. dcm. carbon dioxide may be reduced quantitatively t o formic acid (compare Coehn and Jahn A. 1904 ii 614; Ehrenfeld A. 1906 ii 83). High concentrations cannot be obtained owing t o the migration of the anion of formic acid in the anolyt’e. Carboii monoxide under similar conditions except that low current densities must be used gives a poor yield of methyl alcohol. A form of gelatinous carbon hw also been obtained. H. M. D.INORGANIC CHEMISTRY. ii. 199 For the above experiments galvanised and afterwards amal- gamated copper foil was used as cathode.Lead purified according to Tafel's method was also used? it being necessary then to use a lead anode and not one of platinum. The-electrolyte used was an almost saturated solutioii of potassium sulphate ; solutions of sodium and lithium sulphates gave similar results. T. S. P. Carbon Sulphidotelluride CSTe. ALFHED STOCK and PAUL PRAETORIUS (Bw. 1914 47 131-1 44\.-JVhen a n arc is maintained under carbon disulpliide between a graphite cathode and an anode of graphite and tellurium containing 10 parts or more of graphite to 100 parts of tellurium the anode is disintegrated and reddish- brown solutions are. obtained in which black particles of tellurium and graphite are suspended. The solution contains non-volatile decomposition products of carbon disulphide and the compounds C,S (compare A.1913 ii 46) and CSTe which are volatile with carbon disulpliide vapours. The separation of these two compounds is a very difficult matter owing to the extreme ease with which the carbon sulphidotelluride decomposes ; it was accomplisned by the authors by a combination of the following two methods (1) The repeated fractional extraction of the solution with carbon di- sulphide vapours in a special apparatus the distillate becoming poorer and poorer in carbon subsulphide C,S,. (2) Transforma- tion of the carbon subsulphide into a non-volatile compound and subsequent distillation of the solution ; the non-volatile compound was thionialononaphthpl3mide produced by interaction of the sub- sxlpliide and j3-naphthylamine (compare A.1913 ii 46). The dilute solution of carbon sulphidotelluride thus obtained after drying with phosphoric oxide was concentrated on the water- bath to a strength of 5-10% using a Hahn fractionating column (A. 1910 ii 583). The isolation of the pure product could then only be carried out in a weak light and when the temperature was maintained below - 30° continuously. This was accomplished by means of a special apparatus (this vol. ii 171) when ca~boic suZphidoteZZuride CSTe was obtained as yellowish-red crystals nielt- ing a t - 5 4 O t o a brilliant red liquid of high refractive power which becomes blcod-red a t room temperature then black and decomposes completely after a short time. The substance has a slightly penetrating garlic odour; if i t is smelled for a short time the breath retains a strong odour of garlic for a considerable time. Cryoscopic and ebullioscopic measurements in benzene and carbon disulphide respectively gave molecular weights varying from 176 t o 181 theory 172.D-5"" 2.9 and vapour pressure a t loo about 2 mm. Carbon sulphidotelluride either pure or in solution decomposes very rapidly on attaining room temperature; i t is very sensitive towards light decomposition taking place even at -5OO. The solution in carbon disulphide gives a precipitate of tellurium tetra- bromide with bromine ; mercury extracts all the compound from solutions. By the refined methotis used in this investigation no evidenceii. 200 ABSTRACTS OF CHEMICAL PAPERS. could be obtained of the existence of a carbon telluride CTe,; the phenomena observed in a previous communication (Stock and Blumenthal A.1911 ii 722) were due t o the decomposition of carbon sulphidotelluride. T. S. P. Carbon Sulphidoselenide. ALFRED STOCK and ERNST W ILLFROTH (Ber I 9 14 47 144-154).-Capbon sulphidoselenide CSSe was obtained in carbon disulphide solution by a method similar t o that used in the preparation of carbon sulphidotelluride (compare previous abstract) the anode containing 17.5 parts of graphite to 100 parts of selenium. It was much more readily isolated from solution than the sulphidotelluride owing to ib greater stability. At room temperatures carbon sulphidoselenide forms an intense yellow liquid stable in the air and possessing a pungent odour of onions.It does not take fire when brought in contact with a flame although the vapours of the boiling liquid burn with a beautiful blue flame. It has m. p. -85O b. p. 84O ,uko 1.7349 vapour pres- sure a t loo 45 mm. D20 1.979. It is decomposed by light by heating and on long keeping a t room temperature but is very much more stable than carbon sulphidotelluride. The decom- position produch do not contain any substance corresponding with a compound of the formula CSe nor has it been possible to pre- pare such a compound. That carbon sulphidoselenide is analogous t o carbon disulphide was shown by the fact that with an alcoholic solution of sodium ethoxide sodium monoselenomnthate SeC(SNa)(OEt) is produced A solution of this very deliquescent yellow crystalline substance gives characteristic precipitates with solutions of the salts of the heavy metals behaving very similarly to sodium xanthate.Selenium vapours when passed over charcoal heated at 1000° in a vacuum do not give rise to the formation of any compound of carbon and selenium. Under similar conditions sulphur gives carbon disulphide. T. S. P. Action of Hydrogen Peroxide on the Silicic Acid Gel. A. KOMAROVSKY (Ch~m. Zed 1914 38 121-122).-The evaporation on the water-bath of a silicic acid gel with a slight excess of 30% hydrogen peroxide gives a vitreous amorphous residue which can be triturated to a white powder. It liberates chlorine from hydro- chloric acid iodine from potassium iodide decolorises permanganate and liberates ozone with concentrated sulphuric acid.It gradually and continuously evolves ozonised oxygen ; analysis of the freshly- prepared substance gives a formula corresponding with either H,SiO,,l *5H20 or H,Si0,,H,0,,0~5H20 that is either a persilicic acid or a perhydrogel of silicic acid. A similar compound is obtained when hydrogen peroxide is added to the hydrosol of silicic acid. It is not possible yet t o say whether it is a peracid or a perhydrogel. T. S. P. Persilicates. EDUARD JORDIS (Chem. Zeit. 191 4 38 22 1-22.2). The author confirms many of the results of KomarovskyIKORGANIC CHEMISTRY. ii. 201 (preceding abstract) with respect t o the possibility of the existence of persilicates. He has also found that when sufficiently concen- trated solutions of sodium silicate are left exposed t o the air for several months and then hydrochloric acid added chlorine is evolved. T.S. P. Attempts to Observe the Production of Neon or Helium by Electric Discharge. HON. R. J. STRUTT (Proc. Roy. Xoc. 1914 A 89 499-506).-The experiments described were begun in the hope of confirming the work of Collie and Patterson (T. 1913 103 419; P. 1913 29 217) according to which helium and neon are to be found in tubes containing hydrogen which have been sub- jected to the action of an electrical discharge. The author’s results are negative. Special attention was devoted to the possibility of atmospheric contamination for i t has been found that the neon in less than ljl00 C.C. of air can be readily detected by the spectroscopic test. The capillary discharge tube employed in the detection of the neon was made from the finest thermometer tubing and the discharge from an induction coil was passed through the tube by means of wires twisted round the outside of the tube.From a series of experiments in which varying small quantities of air were admitted into the apparatus and in which after the oxygen had been ab- sorbed by cooled charcoal the residual gas was transferred to the capillary discharge tube it would seem that the neon in 1/1000 C.C. of air is nearer the true limit of sensitiveness of the spectro- scopic test. I n order to avoid the possibility of air contamination of this order of magnitude a method was adopted by which the hydrogen could be removed in the discharge tube itself and the test for neon applied without pumping the gas out of the apparatus or manipulating it over a pneumatic trough in any way.This result was attained by the attphment of a small tube to the apparatus which contained a small quantity of potassium permanganake. When the current had been passed through the hydrogen in the discharge tube for a sufficient length of time a little oxygen was admitted and the discharge passed intermittently for a few seconds at a time. The water vapour formed was rapidly condensed in a cooled tube in close proximity to the discharge tube. The re- sidual gas was then subjected to the action of well-cooled charcoal and then transferred by means of freshly-distilled mercury into the capillary detection tube. The conditions of the discharge through the hydrogen were suitably varied in different experiments but in no case in which air contaminakion could be said to be rigidly excluded was any evidence of either neon or helium ob- tained.The author is confident that the negative results are not due to any defect of the technique in looking for neon. I n two of the experiments which are described potassium chloride and iodide respectively were introduced intlo the discharge tube and subjected to bombardment by the catho,de rays. Although evidence of helium would have been expected in these circumstancesii. 202 ABSTRACTS OF CHEMICAL PAPERS. according to Thomson's results (A. 1913 ii 820) its absence may possibly be due to deficient sensitiveness of the spectroscopic as compared with the positive ray method of analysis. H. &I. D. Metastability of the Metals in Oonsequence of Allotropy and itrJ Significance for Chemiatry Physics and Technics. ERAST COHEN ( P ~ o c .l<. Akad. Wdensch. Amstesdam 1913 16 632-634. Compare A. 1913 ii 779; this vol. ii 52).-In view of the fact that a number of metals have been shown to consist of mixtures of two allotropic modifications and the probability that many others will be found to be similarly constituted it is pointed out that the physical constants of metals have in general no definite significance since these constants refer to mixtures of undefined composition. It will be necessary to redetermine all the physical constants and study the physico-chemical properties by rnakirig use of the pure allotropic forms. H. M. D. New Crystalline Silicates of Potassium and Sodium Their Preparation and General Properties.GEORQE W. MOREY (J. Amer. Chena. Soc. 1914 36 215-230. Compare Niggli A. 1913 ii 1036) .-Known quantities of wat'er and finely-pglverised glasses were heated to high temperatures up to 500° in a gold crucible contained in a specially constructed bomb and the products ob- tained were investigated. The glasses were made by fusing mixtures of quartz and alkali carbonate in different proportions; the same components were also introduced into the bomb in other forms the alkali as chloride carbonate hydroxide and as silicate glass; the silica as quartz and as an amorphous precipitate; these varia- tions however had no influence on the resultant product. Four new crystalline alkali silicates have Feen prepared namely K,Si,O E(HSi2O5 Na,Si,O and N+SiO,. The first three are derivatives of disilicic acid and form ortho-rhombic crystals which differ markedly in their behaviour towards water.K,Si,O is quickly attacked by water Na,Si,O less readily whilst KHSi,O may be left in contact with water even for some hours at looo without appreciable decomposition. The fourth compound is an- hydrous sodium metasilicate which has hitherto been known only as a somewhat indefinite hydrate; i t is readily attacked by water. I n addition to the crystalline products a lseries of hydrated glasses was obtained consisting of supercooled liquids each of which represents the composition of a solution unsaturated under the conditions of experiment. They are perfectly hard even though they contain up to 25% of water; when heated in the air water is lost and they swell up in the process t o a sponge-like structure often with extremely thin vesicular walls.Preparation of Potassium Manganifluoride. I. BELLUCCI (Atti It. Accad. Lincei. 1913 [v] 22 ii 579-582).-Thir salt may be readily prepared in quantity by adding ether drop by drop with constant stirring to a solution of 2 grams of potassium perman- ganate in 30 C.C. of 40% hydrofluoric acid the reaction being T. S. P.INORGANIC CHEMISTRY. ii. 203 carried out in a platinum dish. until the solution has almost lost its purple tint. szttles in the form of a yellow microcrystalline precipita.te. The addition of ether is continued The product R. V. S. The Preparation of Sodium. BERNHARD NEUMANN and SIGURD GIERSTEN (Xeitsch.angew. Chcm. 1914 27 65-7t~).-The authors have constructed a large experimental apparatus on the principle of the Castner apparatus for the preparation of sodium by the electrolysis of fused sodium hydroxide using however a special arrangement by which the water formed a t the anode is evaporated largely by the heat of the fusion and is prevented from coming into contact with the sodium a t the cathode. The best conditions of current and temperature were investigated and are discussed in detail as also the various phenomena which occur during electrolysis. The most important factor for succees- ful electrolyses is the temperature which in the catholyte must be maintained very close to that of the melting point of the sodium hydroxide. Pure sodium hydroxide does not give such good results as the commercial substance owing to its high melting point.C’urrent yields of 53% were obtained whereas the average yield in the manufacturing process is 30-40%. The details of the authors’ experiments and considerations can oiily he appreciated by reference to the origiiial paper. T. S. P. The System Sodium Sulphate-Water. J. +P. WUITE (Zeitsch. phzpiknl. Chcm. 1914 86 349- 382).-A rchomd of the fusion curves of the system sodium sulphate-water is given as far as this is known from previous work. The present paper gives an account of the determination of the missing details of these curves. The non-agreement of Tilden and Shenstone (A. 1884 254) and Atard on the solubility a t high temperatures is explained by the fact that some of the values of both are iiicorrectly deter- mined. The transition point of the rhombic anhydrous salt into the monoclinic anhydrous salt is determined as 235O from solubility determinations on both sides of it.The PT curves for the different three-phase equilibria are drawn from the experi- mental data and the two transition points a t 24’4O and 32.4O accurately determined. The diff ereiice in the vapour pressure of pure water and that of the three-phase system a t the equilibrium point 235O is experimentally shown. Doub!e Salts of Haloids with Silver Nitrate. G. SCARPA ( A t t i 12. Accad. Liszcei 1913 [v] 22 ii 453-459) -The paper deals with the thermal analysis of the systems AgN0,-AgCl &NO,-AgBr and AgN0,AgI. Silver nitrats and silver chloride do not form any compound.There is an eutectic corresponding with 160° and about 75 mol. % of silver nitrate. Mixed crystals are formed between certain limits. J. F. S.ii. 204 ABSTRACTS OF CHEMICAL PAPERS. Silver nitrate and silver bromide form a compound AgNO,,AgBr m. p. 188O (decomp.). There is an eutectic corre- sponding with 155O and 75 mol. % of silver nitrate. Mixed crystals are formed in mixtures rich in silver nitrate. Silver nitrate and silver iodide form a compound 3AgN03,2AgI m. p. about 105O which does not decompose on melting. There is an eutectic corresponding with about 80° and 45 mol. % of silver nitrate. Mixed crystals of each of the forms of silver iodide with the compound 3AgN03,2AgI are formed. R. V. S. Tendency of Alkali Haloids to Combine with Silver Haloids.C. SANDONNINI and G. SCARPA (Atti R. Accud. Lincei 1913 [v] 22 ii 517-524. Compare Sandonnini A. 1912 ii 941).-This paper deals with the thermal analysis of the systems LiBr-AgBr NaBr-AgBr LiI-AgI and NaI-AgI. Lithium bromide arid silver bromide form solid solutions which crystallise a t temperatures intermediate between the melting points of the components. 11. Sodium bromide and silver bromide behave similarly. Lithium iodide and silver iodide form solid solutions within very wide limits. The diagram of the system belongs to the fifth type of transformation of mixed crystals described by Roozeboom. Sodium iodide and silver iodide are insoluble in the solid state the eutectic mixture corresponding with 394O and about 60 mol. % of silver iodide. The Binary Systems of Calcium Chloride with Barium Chloride and Strontium Ghloride.WALTER SCHAEFER (Jalrrb. Mi%. 1914 i 15-23).-CaIcium and barium chlorides form the double salt C'aCl,,*BaCl (m. p. 631°) but no mixed crystals. Calcium and strontium chlorides form a continuous series of mixed crystals with a minimum melting point a t 658O with 66 mol. % CaC1,. L. J. S. Carbonate Fusions under Carbon Dioxide Pressure. H. E. BOEKE (Jnhrb. Mh. 1914 i RP$ 9-10; from dlztt. Nuturf Ges. Balk 191 3 3).-Barium carbonate undergoes two reversible trans- formations a t 811O passing from the y form (witherite ortho- rhombic and pseudo-hexagonal) to the /3 form (hexagonal) and a t 982O to the a form (cubic); m. p. about 1740O. The systeni barium carbonatecalcium carbonate (represented by the minerals alstonite and barytocalcite) gives isodimorphous mixed crystals with an eutectic a t 1139O and 524 mol.% CaCO,. Up to 30 mol. % CaCO the orthorhombic alstonite is the stable form but with more calcium carbonate this is replaced by trigonal barytocalcite. Monc- clinic barytocalcite is not present in the fusions. Strontium carbonate shows an inversion a t about 929O and melts a t 1497O. R. V. S. L. J. S. Magnesium Chloride as a Mineral Former; and Specfro- chemistry of the Rare Earths I(. A. HOFMANN and KURT HOSCHELE (Ber. 1914 47 238-247).-The authors have found thatINORGANIC CHEMISTRY. ii. 205 fused anhydrous magnesium chloride is an excellent solvent and crystallising inedium for many inorganic oxides. I n some cases interaction takes pace with the oxides or especially with the sulphates if they are used giving the volatile chlorides for ex- ample of glucinum zinc iron and tin; in other cases spinelle- like compounds are formed owing to the decomposition of the magnesium chloride by water vapour from the flame or by oxygen from the air for example magnesium ferrite Mg(FeO,) and its transition products (Mg,Fe) (FeO,) towards magnetic iron oxide Fe,O,.Magnesium orthoborate SMgO,B,O and magnesium uranate Mg,U,O were obtained by using boric and uranic acids respec- tively. Cerium and zirconium sulphates give the corresponding dioxides the latter readily dissolving other rare earths giving coloured crystals. Erbium neodymium praseodymium and samarium sulphates gave the corresponding oxychlorides the spectra of which in reflected light were examined and compared with the spectra of other salts.T. S. P. Equilibrium of the Double Salts of Cadmium-Sodium Chloride and Gadmium-Pot assiurn Chloride with their Aqueous Solutions. KATHE SUDHAUS (Jcchb. Min. i914 BeiLBd. 37 1-50) .-Crystallisation experiments and solubility determina- tions made for the ternary systems CdCl,-NaCl-H,O and CdC1,- KCl-H,O between 19O and 5 5 O show that the following crystalline phases occur the simple chlorides of sodium and potassium; two hydrates of cadmium chloride CdC1,,24H2O and CdCl,,H,O ; and the three double salts CdC12,4KC1 CdCl,,KCl,H,O and CdC1,,2NaC1,3R2O. L. J. S. Anhydrous Sulphates. VII. Cadmium Sulphate with Lithium Sodium and Potassium Sulphates. G.CALCAGNI and D. MAROTTA (Atti R. Accad. Lincei 1913 [v] 22 ii 442-445. Compare this vol. ii 52).-Continuing this paper the authors now give the results obtained in the thermal analysis of the system CclS0,-K,SO,. 2CdSO,,K,SO (at 7 6 3 O ) and 3CdSO,,K,SO (at 813O). Two compounds are formed namely R. V. S. Crystallographic and Thermal Investigation of the Binary Systems of Thallous Chloride and Chlorides of Bivalent Metals. E. KORRENB (Jahrb. Mirt. 1914 Be&?.-Bd. 37 51-124).- The binary systems investigated were cuprous chloride with chlorides of the alkali metals lithium sodium and potassium and thallous chloride with chlorides of the bivalent metals magnesium calcium strontium barium zinc cadmium tin and lead. Mixed crystals were formed only with the systems CuC1-LiC1 and TlC1- ZnC1,; in all other cases (except CuCl-NaC1 and TlCl-BaCl,) double salts were obtained.Allotropy of Copper. I. ERNST COHEN and W. D. HELDERMAN (Proc. K. Akad. Wstensch. Amsterdam 1913 16 628-632).-From VOL. CVI. ii. 14 L. J. S.ii. 206 ABSTRACTS OF CHEMICAL PAPERS. dilatometric observations it has been found that there are two allotropic modifications of copper with a transition point at 71.7'. The experiments were made with electrolytic copper which was melted in an electric furnace and poured out into cylinders of asbestos paper. As soon as the metal had solidified the cylinders were chilled in water and turned into thin shavings on a lathe. If the copper is in a finely divided state the reversible change takes place with considerable velocity but the rate of change is very much smaller in the case of the solid metal.The experi- ments show that ordinary copper must be considered as a meta- stable mixture of a- and 8-copper which is continually changing into the stable modification (a-copper) a t temperatures below 71.7'. That the allotropic transformation has not been previously observed is due t o the extreme slowness of the change in the case of the compact metal. It is pointed out however that several observa- tions recorded in the literature afford evidence of some change in copper a t the ordinary temperature. Special reference is made to the experiments of Matthiessen and Bose (Ann. Phtys. Chem. 1862 115 353) who found changes in the electric conductivity (at 0') of pure copper wires after these had been heated for several days a t looo. H.M. D. Approximate Melting Points of Some Commercial Copper Alloys A. B. NORTON and H. W. GILLETT (J. Physical Chem. 1914 18 70-77).-The authors have determined the melting points of a number of ternary and quaternary alloys containing copper zinc tin and lead. The following values are recorded the numbers in brackets giving the percentage amounts of copper zinc tin and lead respectively in the alloys gun-metal (88 2 10 -) 995O; leaded gun-metal (85.5 2 9.5 3) 980°; red brass (85 5 5 5) 970O; low-grade red brass (82 10 3 5) 980O; leaded bronze (80 - 10 lo) 945O; bronze with zinc (85 5 10 -) 980O; cast yellow brass (67 31 - 2) 895O; half yellow half red (75 20 2 3) 920O; naval brass (61.5 37 1-5 -) 855O; manganese bronze (Cu 56 Zn 41 Fe 1.5 tin 0.9 A1 0.45 Mn 0*15) 870O. The r+ corded temperatures are _those a t which freezing begins and measurements in duplicate were found to agree within &I0.H. M. D. Influence of Shaking on the Solution of Copper in Nitric Acid. MAURICE DRAPKER (Compt. rend 1914 158 338-340).-For a given strength of nitric acid the amount of copper dissolved in a given time is very considerably reduced by shaking or rotating the copper and if the velocity of rotation is increased sufficiently may be reduced practically to zero. This is not due t o the destruc- tion of local heating effects since the flow of cold water through a copper tube has no effect on its rate of solution in nitric acid. The author considers that the effect is due to the distribution of the nitrous acid primarily produced a t the surface of the metal and to the consequent inhibition of its catalysing effect on the solution.The addition of increasing quantities of sodium nitrite to the nitric acid gradually nullifies the shaking effect. W. GINORGANIC CEEMISTRY. ii. 207 Cupric Oxide Jellies. L. S. FINCH (J. Physical Chm. 1914 18 26-33).-Cuprk oxide jellies have been prepared by the addition of a suitable quantity of ammonia to a saturated solution of copper acetate. The jelIies are not permanent; cupric hydroxide separating out sooner or later. The stability of the jelly is increased if a small quantity of manganous sulphate potassium sulphate or sulphuric acid is added to the copper acetate solution previous t o the addition of the ammonia.The best conditions are obtained by mixing together 50 C.C. of saturated copper acetate solution 4 drops of concentrated sulphuric acid and 3 - 4 C.C. of diluted ammonia (1 1). I f such a jelly is allowed to dry up it can be regenerated by shaking the dried mass with water. H. M. D. Modiflcation of Lothar Meyer’s Apparatus for the Purifl- cation of Mercury FRITZ FRIEDRICHS (Zeitsch. mqcw. Chem. 1914 27 24).-In this apparatus the mercury is allowed to fall through dilute nitric acid contained in a vertical tube about 1 metre in length the lower end of the tube being connected with a capillary which is bent upwards for a short distance and then outwards. The modification described consists in making a number of indentations at opposite sides of the vertical tube so that the drops of mercury are deflected from side to side and caused to take a longer passage through the nitric acid.The mercury is admitted to the top of the tube through a funnel the stem of which is drawn out to a fine jet; the mercury may be filtered previously through muslin w. P. s. Mercuric Polyhaloids in Solution. W. HERZ and W. PAUL (Zktech. anorg. Chern. 1914 85 214-216).-The solubility of iodine and mercuric chloride and of bromine and mercuric bromide in water indicates the formation of readily soluble polyhaloids. Partition experiments using carbon tetrachloride indicate the existence of HgBr212 HgBf4 and HgCl,I and probably of other polyhaloids. C. H. D. Basic Compounds of Mercury and Copper. B. Fmzr (Gazzctta 1913 43 ii 708-712.Compare A 1912 ii 168).- When yellow mercuric oxide is dissolved in a hot almost saturated solution of copper nitrate the compound Cu(N03),,Hg0,3&0 is precipitated (in small quantity) in the form of tufts of pale blue needles. R. V. S. The Preparation of Cerium and its Alloys. MAX MOLDEN- EAUEB (Chum. Zeit. 1914 38 147).-Cerium oxide is not reduced to cerium by the Goldschmidt method using either aluminium mag- nesium or calcium. Cerium fluoride is however readily reduced by excess of calcium giving an alloy containing 12% Ca and about 86% Ce; it is necessary to cover the crucible with a layer of calcium fluoride during the reaction in order to prevent oxidation. If the cerium fluoride is mixed with iron oxide reduction with calcium 14-2ii. 208 ABSTRACTS OF CHEMICAL PAPERS. gives an alloy of cerium and iron containing 40% Ce.If the calcium is replaced by aluminium an aluminium (10*2%)-cerium (25*3%)-iron (62.5%) alloy is produced. All the above alloys show the properties of the ordinary iron- cerium alloy. T. 5. P. Physical Nature of Colloidal Hydrous Aluminium Sili- cates. H. STREMME (Centr. Hin. 1914 80-85).-A reply to R. Gans (this vol. ii 55). L- J. S. The Transformation Points and the Structure of Nickel Chrome Steels. L ~ O N GUILLET (Compt. rend. 1914 158 412-414. Compare A. 1913 ii 603).-The action of chromium on the trans- formation points of nickel steels by cooling is not proportional t o the amount present. I n a steel containing between 3 and 5% nickel the influence of chromium is very slight. Chromium in small amounts acts far less on nickel steels with low nickel content than on those with high nickel content.Chrome nickel steels can be divided into three classes (1) those in which the transformation point on cooling is but little different from that on heating; (2) those in which this difference increases proportionally with the chromium content up to a value of 5 0 0 O ; (3) those which still show this difference but in which the influence of the chromium is only slight. This classification is in fairly close agreement with the structures of the alloys. Class (1) corresponds with perlitic stsucture ; (2) corresponds with steels Containing martensite ; (3) corresponds with steels containing carbide and in which in consequence all the chromium is not in solution.The martensite structure commences when the transformation point on cooling is about 350O. W. G. Ternary Alloys of Nickel Copper and Gold. P. DE CESARIS (Gazzettcc 1914 44 i 27-35. Compare A 1913 ii 1061 ; 1914 ii 57).-A description of the space diagram of this system based on the diagrams of the constituent binary systems (Zoc. cit. and Kurnakov and Shemtschuschny A. 1907 ii 525) and on further experimental results here recorded. R. V. S. Peroxides. S. TANATAR (Be?..,.. 1914 47 S7-89).-A reply to Tubandt and Riedel (A. 1911 11 987). The author has carried out repeated experiments which show that a solution of nickel peroxide in sulphuric acid contains not only persulphuric acid but also hydrogen peroxide. The greatest amount of hydrogen peroxide is produced when the nickel peroxide is dissolved in a solution of hydrogen cyanide containing potassium cyanide ; this cannot be due t o the autoxidising action of the nickel-cyanogen complex produced since neit'her nickel hydroxide nor nickel salts when free from cobalt give rise to hydrogen peroxide under the same conditions.The different results obtained by Tubandt and Riedel were probably due to t'he fact that the nickel peroxide used by them contained cobalt it being well known that hydrogenINORGANIC CHEMISTRY. ii. 209 peroxide is produced during the oxidation of potassium cobalto- cyanide (compare Manchot and Herzog A 1900 ii 546). T. S. P. The Apparent Exploaibility of Uranyl Nitrate. WALTER EICHHORN (Chem Zed. 1914 38 139).-A 3-4 year old cpecimen of uranyl nitrate showed triboluminescence but no explosions could be heard on shaking it in a flask (compare Ivanov A.1912 ii 455). Uranyl nitrate obtained by the extraction of a concentrated aqueous solution with ether contains less water of crystallisation than the ordinary nitrate. No explosions could be obtained with such a product (compare Andrews A. 1913 ii 60). Isolation and Separation of Thorium from Other Rare Earths. DEUTSCHE GASGLUHLIC~T AKT.-GES. (AUERGESELLSCHAFT) (D.R.-P. 268866).-Solutions containing thorium and other rare earths such as are obtained in the working up of monazite sand and containing an excess of hydrochloric acid are treated with hypophosphoric acid or its sodiuq salt whereby thorium hypo- phosphate separates in a pure state. MARCEL DELPPINE (Compl.rend. 19 14 158 264-267.* Compare A. 1911 ii 806).-The author has submitted the yellow powder obtained by the action of sulphuric acid on irido- chlorides to the action of dry hydrogen chloride a t ZOOo 300° 400° 450° and 500O. The colour remains practically the same but there are progressive variations in Composition which approaches nearer and nearer to that of IrC13 there being probably traces of hydrogen chloride and water still retained. The chlorides so obtained are distinguished from the anhydrous chloride by being hygroscopic and soluble in water. On evaporating the aqueous solution re- dissolving the residue and again evaporating the solution there is obtained a black feebly hygroscopic mass having the composition IrCl3,1&H,O after desiccation a t looo. It is soluble in water and alcohol t o a greenish-yellow solution giving with silver nitrate a precipitate having the composition IrCl,,AgOH a t 1 loo. Anhydrous iridous chloride is rapidly transformed by concentrated alkalis on a water-bath into the blue oxide of iridium. T. S. P. J. C. C. Iridium Chlorides. W. G. Is there a New Element in the Platiniferous Minerals of the Urals? ANGEL DEL CAMPO Y CERDAN and SANTIAGO P I ~ A DE RI.JBIES(A~C~Z. Fi8. Quim. 1913 11,562-599).-Holtz (A.,1913 ii 143) suspected the existence of a new metal in the copper-palladium fraction of the platinif erous Ural minerals. The aut'hors have made a spectrographic analysis not of the fraction examined by Holtz but of a small specimen of metal " black " arising from the same mineral. Two spectrographs gave 360 and 600 lines respectively but no new lines were observed. Tin lead chromium and magnesium were found to be present in addition t o the metals observed by Ho1t.z. G. D. L. * and Bzcll. SOC. chi^. 1914 [iv] 15 231-241. .- ___ -. -

ISSN:0368-1769    

DOI:10.1039/CA9140605195

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii. 210 ABSTRACTS OF CHEMICAL PAPERS Miner alogic a1 Chemistry. Tables for Crgstrtllochemical Analysis. E. YON FEDOBOV (Zeitsch. Kryst. Min. 1914 53 337-388. Compare A 1913 ii 393). -Further remarks and conclusions based on the author's tables. Not suitable for abstraction. L. J. S. Temiskamite a New Nickel Arsenide from Ontario. T. L. WALKER (Amer. J. Sci. 1914 [iv] 37 170-172).-This mineral occurs with niccolite bismuth and silver in calcite veins in the Moose Horn Mine *Elk Lake Ontario. It is silver-white with a tinge of red and a metallic lustre; on exposure it tarnishes quickly to madder-grey; streak brownish-black. H 53 D 7.901. It forms radiating fibrous masses with a botryoidal or arborescent surf ace. It is s1owly attacked by liydrocliloi-ic acid but readily by nitric acid and is easily fusible.Analysis gives the formula Ni,As3 which is near to that of maucherite (A. 1913 ii 516). Ni. Co. Fe. As. S. Sb. Bi. Total. 49.07 1-73 trace 46-34 1'03 n.d. 0-55 93-72 L. J. S. Syngenite from Sonderahausen. HENRWO SCHREIBER (JuArb. Min. 1914 Beit?.-Bd. 37 247-284).-A detailed review of the literature is given Crystals from Sondershausen Germany are tabular parallel t o the ortho-pinacoid with a b c = 1.352 1 0.871 ; B = '75O55' a t the ordinary temperature (20°) and a Z c =1*359 1 0.894; /3=76*3/ a t 200O. Analysis agrees wit11 the usual formula CaS04,K2S04,H,0. CJaO. K20. SO,. II,O. Total. Sp. gr. 17.20 28.80 48'40 5.41 99'81 2.579 The crystals commence t o become cloudy owing t o loss of water a t 220-250° minute crystals (probably of anhydrous calcium potassium sulphate) being formed.Detailed determinations were made of the optical constants a t various temperatures up to 230O. With rise in temperature the optic axial plane changes from being perpendicular to parallel to the plane of symmetry. L. J. S. Carphosiderite and Hydrozincite from Mexico. ERNESTO WITTICH (Jahrb. Min. 1914 i Ref. 28-29; from Bol. Soc. Geol. Mexicans 191 3. 8 47-51).-Carpho~iderite occiirs in fair amount at several localities in the State of Chihuahua forming straw-yellow to dark yellow crystalline masses with silky lustre and consisting of minute six-sided plates with basal cleavage optically uniaxial character and strong negative birefringence. The mineral has been deposited from solutions formed by the decomposition ofMINERALOGICAL CHEMISTRY.ii. 211 sulphides in mineral veins. 3Fq0,,4 8 0,l OH,O . Analyses approximate to the formula SO,. Fe,O,. MnO. AI,O,. H,O. Total. 28-73 51.68 0'12 - 19'42 99-95 56.18 53.59 - 0.17 20.01 99'95 32-83 47.07 - 0.10 19-90 99-90. Hydrozincite occurs as fibrous silky aggregates and as white crusts on calamine and other zinc minerals. ZnO. CO,. H,O. 13-50 69.17 17-10 15.01 68-09 16.80 Analysis gave Aurichalcite is also recorded from Chihuahua. L. J. S. Ghemical Investigation of Certain Minerals from Ceylon Gravel. V. G. P. TSCHERNIK (Bull. Bead. Sci. St. PBtsrsbouvg 1914 41-50).-Gravel from the Uva Province contains variegated pebbles showing a large number of shining inclusiom some of which are well-developed cubical crystals.These crystals are steel-black and those in the interior of the pebbles have a metallic diamond- like lustre whilst those near the surface are duller. I n mass the crystals are opaque but the edges of thin sections transmit a faint brownish-red light. The mineral exhibits marked cleavage and readily scratches apatite; D =4*13. CdO. Ce,O,. Fe,O,. FeO. MnO. NbO,. (+Ta,O,). TiO SiO,. N+O. MgO. Total. 21.69 8-80 4-76 1.81 0.17 22'32 (trace) 39.90 trace trace true 99-05 These results are represented by the formula Its chemical composition is (Ce,Y)203,14Ca0,Fq03,(Fe,Mn)0,3Nbz0,,l 8Ti0 or 14(CaO,TiO2) + Fe203(Ti20& + (Fe,Mf)OlTi02 + (Ce,Y),0,,(Nb2~S),. The physical and chemical properties indicate the mineral to be a modification of dysanalyte. The methods of analysis are described in detail.Optical Study of the Amphiboles. T. H. P. W. E. FORD (8me-r. J. Sci. 1914 [iv] 37 179-193).-The materials analysed by Penfield and Stanley (A. 1907 ii 102) were examined optically. The mean index of refraction ranges from 1-61 ta 1-71 increasing in a more or less regular manner with the percentages of iron and aluminium and decreasing with increased amounts of silica and magnesia. I n the tremoliteactinolite series (with SiO 51-58%) the angle of optical extinction on the plane of symmetry ranges from 8 O t o 20° and in the hornblende series (SiO 3 6 4 4 % ) it is 9-33O; in both series the value of the extinction-angle increases with the per- centage of iron present. Decomposition and Isomorphism of the Felepars. J. SPWCHAL .(.Tdrb.Min. 1914 i Ref. 12-15; from Abh. bohm. Akad. 1913 No. XII l-ZO).-Orthoclase from Kragero (D 2.549 analyses 1-111) and anorthite from Miyake Island Japan (D 2.69 anal. IV and V) were treated a t the ordinary bmperature for several L. J. S.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. weeks with various acids (concentrated sulphuric dilute hydro- chloric formic and carbonic acids) and the amounts of the several oxides dissolved were determined The mineral acids and formic acid extract silica and alumina in amounts comparable with the lime and alkalis; but with carbonic acid the amounts of the latter are much greater indicating that the reaction here tends t o the formation of kaolin. The action of sodium hydroxide solution chloric perchloric and acetic acids was also determined.The character of the gelatinous silica obtained from anorthite varies greatly with the nature and the concentration of the acid employed. Loss on SiO? AlZO9. Fc,O,. CaO. MgO. KZO. Na,O. ignition Total. I. 65.48 18.07 0.93 0.58 1.03 11-91 2.14 0.20 100.34 11. 65'32 18.13 0.62 0.78 0.94 10'83 3'47 0.15 100.24 111. 65.75 17.84 1-08 0.53 0.99 11'68 2.35 0.25 100'47 1V. 44'17 34.53 1-47 19.50 0.44 trace 0.60 0.35 lOl*Ol[?] V. 44.90 34.90 1.39 18.32 0.72 trace 0.50 2.25 lOO.93[?] VI. 68.87 20.30 0.62 1.32 1.07 - 7'06 0.25 99-49 VII. 63.30 23-44 0.73 4'83 0'25 1-30 6-74 0-55 101.14 Experiments were also made with a view to determine whether the solubility of mixed crystals of plagioclase is an additive character of the solubilities of albite and anorthite.Albite (" tschermakite") from Bamle (D 2.585 anal. VI) and oligoclase from Arendal (D 2.627 anal. VII) were used. It was found that hydrochloric acid extracts only 6.21% of the lime from oligo- clase whilst from anorthite the whole of the lime is extracted. The conclusion is therefore drawn that plagioclase does not repre- sent mechanical mixtures of albite and anorthite. I;. J. S. Montmorillonite in the Granulites of Gala Francese (Island of Maddalena). DOMENICO LOVISATO ( A tti R. Accad. Lincei 191 3 [v] 22 ii 670-675).-The author describes a sample of mont- morillonite of a peach-red to almost white colour occurring in a small pocket in a mass of granulites. It is greasy t o the touch can be scratched with she nail and its lustre is faintly resinous or in its more compact portions almost vitreous; D14 2.027. Its composition is SiO,.A1,0,. Fe,O,. CaO. MgO. Nn,O. K20. a t 130". Total. 42-12 21.98 5.90 0.84 1.88 2-77 0.42 22.37 98-28 T. H. P. LOCS Allophane-like C l a p . B. AARNIO (Centr. Mind. 191 4 69-75).- A greenish-grey talcose clay from Transylvania which becomes soapy in water gave analysis I. A yellowish-brown greasy clay from Galicia gave 11. A white t o yellowish gelatinous substance ( ' I rock-butter ") formed in the mine levels traversing pyritiferous chlorite-schist a t Canezza in southern Tyrol gave 111. SiO2. TiOz. AIzOa. Fe~03. CaO. MgO. K20. NazO. P205. SOS. at 1 0 5 O . ign. Total. I. 57.58 trace 14.01 2.65 2-60 2.95 1.69 0.96 0.12 - 14.60 3'29 100.45 11. 50.17 trace 15.58 2.18 2-51 3.95 0.96 0.16 0.16 - 19-13 4.75 99-55 111.7.48 - 10.86 1.96 0.20 0.48 0.11 0.35 trace 0'44 71.93 5'94 99-75 H2O LossonANALYTICAL CHEMISTRY. ii. 213 In analysis I A1,0 SiO = 1 7 ; and in I11 the ratio is 1-17 1.0 corresponding with allopliane. Hydrochloric acid (D 1.19) dis- solved from these three clays 21.95 27.81 and 92.89% respectively. L. J. S. Meteoric Iron from Durango Mexico. JUAN S. AGRAZ (Zeitsch. K y s t . Jlin. 1914 53 405; from 302. A'oc. Geol. Jfexicccna 1909 6 9-91).-Analysis of this octahedral iron gave Fe. Xi. c'o. c'. w s i . sII. glv. 96.60 0.99 2 -39 0.1 3 100*11 i *7S2 L. J. S. Meteoric Iron from Muonionalusta North Sweden. A. G. HOGBOM (Zeitsch. Kqst. Min. 1914 53 408; ftom Bull. Geol. Zmt. Univ. Upsala 1910 9 229-238).-This iron found in 1906 weighs 7-53 kilos.and has D 7.9. It consists of kamacite tzenite and plessite together with grains of troilite the latter with a nucleus of daubreelite. The structure is octahedral with fine lamellz. The nickel-iron which forms more t'han 99% of the mass gave on analysis by R. Mauzelius Fe . Ni. co. cu. Or. P. Total. 91.20 8 -02 0 '69 0.01 0.01 0.05 99.88 L. 5. S. Composition of the Water of Lake Huacachiaa (Peru). M. EMM. POZZI-ESCOT (BUZZ. SOC. chim. 1914 [iv]. 15 96-100).-The author has analysed the water of Lake Huacachina and in addition has invwtigated the mud from the bottom of the lake the more or less crystalline efflorescence from the shors and t'he subsoil at a distance of 25 metres from the shore. The waters are rich in sodium and potassium salts chiefly the chlorides sulphates and carbonates; thiosulphates are present in sensible amount together with traces of phmphates bromides and iodides; iron nitrites or nitrates are not present. The formation of the lake appears to be due to the infiltration of water from the subsoil of the region which accumulates in a depression without outlet and becomes progressively charged with saline matter from the neighbourhood. Production of hydrogen sulphide and of thiosulphates is due t o the reduction of the sulphates by the living matter which pollutes the water. H. W.

ISSN:0368-1769    

DOI:10.1039/CA9140605210

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. 213 An Improved Absorption Tube for Spectral Analysis. ULRICH M~LLER (Chem. Zeit. 1914 38 116).-Near the one end of the tube a narrow side-tube is fused in; on the opposite side a t the other end a bulb tube with stopcock is fused. The ends ofii. 214 ABSTRACTS OF CHEMICAL PAPERS the main tube are covered with glass plates as usual. By dipping the narrow side-tube in the solution to be invmtigated and applying suction at the bulb tube the main tube can be filled without loss of liquid and is of course equally readily emptied. T. S. P. Modified Hempel’s Gas Pipette. R. P. ANDERSON (Zeitsch. angew. Chew&. 1914 27 23-24).-1n order to prevent drops of the absorption solution which may collect in the capillary from passing over into the burette a small bulb 3 mm.in diameter is blown on the capillary. When using fuming sulphuric acid in the pipette the ends of the latter may be closed with glass caps during the time the pipette is not in actual use. w. P. s. Determination of Weight by Titration. HUGO DUBOVITZ (Chew. Zeit. 1914 38 222).-It was necessary to determine the weight of a quantity of oil which was to be refined. The acid number of the oil was determined and then a known quantity of sodium hydroxide insufficient for complete neutralisation added and the acid number again determined. From the resulb the weight of the oil was readily calculated. T. S. P. Filtration and Extraction Tubes. R. PETERS (Zeitsch. angew. Chrrm,. 1914 27 64).-The tube described by the author is very similar to the tube ordinarily used for collecting cuprous oxide in quantitative sugar estimations except that a lipped funnel is fused on to the top so that liquid in the tube can be poured out readily.Cotton wool is used as the filter medium. The tube is recommended for filtration of solutions in benzene ether light petroleum etc. since the evaporation of the solvent and also creeping are prevented. The Detection of Hydrochloric Acid in Medicine. 0. KRUMMACHER (Zeitsch. Biol. 1914 63 275-304).-This is an experimental investigation of the value of Gunzberg’s reagent (phloroglucinol-vanillin ; A. 1888 61 7) as a test for hydrochloric acid in the stomach contents and a discussion of the meaning of the reaction. The conclusions drawn are that the reagent in question is a delicate indicator for hydrogen ions and that its range of delicacy corresponds with a concentration of 2 x gram ions of hydrogen per litre.T. S. P. to 3 x W. D. H. Detection of Bromides in Presence of Thiocyanates and of Farrocyanides. Action of Chromic Acid on Oyanogen Bromide. VI. ICILTO GUARESCHI (dtti 12. Accad. Sci. Torino 1914 49 15-21. Compare A. 1913 ii 333).-The detection of bromine in presence of thiocyanates by the ordinary analytical methods is difficult and the author formerly experienced difficulties with his method also in these circumstances. He now finds however that if the substance t o be tested is in solid form or in concentrated solution and if an excess of chromic acid is added to destroy the thiocyanate it is possible by his method to detect very small quan-ANALYTICAL CHEMISTRY.ii. 215 tities of bromide in the presence of much thiocyanate. The same modification of experimental conditions is effective also in the case of bromide in the presence of ferrocyanide or ferricyanide. The use of potassium permanganate instead of chromic acid for the liberation of bromide in these cases is undesirable as it leads to the evolution of ammonia which reacts with the test paper used. Cyanogen bromide is decomposed by chromic acid with formation of bromine chromium sesquioxide carbon dioxide and ammonia. R. V. S. Estimation of Total Sulphur in Commercial Benzene. KONRAD SCHENK (Che~n. Zeit. 1914 38 S3-84).-The niithor recommends the combustion of benzene from a specially constructed apparatus absorption of the sulphur dioxide in 1% hydrogen per- oxide solution and estimation of sulphuric acid by titration with A7/ 10-alkali using methyl-orange as indicator.The acidity of the hydrogen peroxide is separately determined. To volatilise the benzene the author uses a flask with a broad base. It is provided with two tubulures which can be closed by stopcocks; through one tubulure a tube passes to the bottom of the flask whilst the other carries a glass tube drawn out to a fine point. To increase the surface of the benzene the flask is loosely filled with cotton wool. To carry out the experiment the flwk is weighed and a suitable quantity of the sample introduced. A regulated stream of air is passed through it and the mixture of benzene vapour and air ignited at the fine jet.The size of the flame should be about 0.5-4*7 cm. and the rate of air supply can easily be so controlled that deposition of soot does not take place. The products of combustion are drawn through three washbottles each con- taining 30 C.C. of 1% hydrogen peroxide solution the arrangement of the apparatus being similar to that used in determining sulphur in coal gas. To aid the volatilisation of the sample the flask is immersed in a water-bath the temperature of which. is raised during the course of the experiment from 30° to 75O. Even a t the latter temperature commercial benzene is not completely vaporised but this is of no conseguence since the sulphur compounds are completely removed with the more volatile portions. I n practice therefore the temperature is not raised above 75O and the ex- periment is discontinued as soon as combustible produck are no longer obtained.Explosion; owing to striking back of the flame are not to be feared. The accuracy of the method is indicated by a series of experi- ments on the combustion of pure benzene to which thiophen and carbon disulphide have been added. About 2-1-5 grams of benzene per hour can thus be burnt. H. W. - New Method of Analysis by Reduction of Nitrates Ohlorates and Peroxides. C. Russo and G. SENST (Gctzzetta 191 4 44 i 9-15).-The estimations depend on the mDde of titra- tion of ferric salts described in a preceding paper (this vol. ii 222).ii. 216 ABSTRACTS OF CHEMICAL PAPERS. Nitrates are estimated in the following way two flasks are con- nected together by corks and tubes so that a current of carbon dioxide can be passed through both in series.I n the first flask is placed the weighed quantity of nitrate an excess (3 grams) of Mohr’s salt (ferrous ammonium sulphate) and when all the air has been expelled 10 C.C. of concentrated hydrochloric acid. I n the second flask are placed 120 C.C. of water and a solution of two drops of methylene-blue (1%) which has been decolorised by boiling with one drop of iV/5 stannous chloride. The contents of the first flask are now boiled carbon dioxide passing meanwhile until all nitrogen peroxide has been driven off. The water in the second flask is brought to the boiling point by the time this has been effected. Both flames being now extinguished the aqueous solution of indicator in the second flask siphons back into the first into which the tubes are also washed.The ferric salt in the first flask is then titrated with stannous chloride. For the estimation of chlorates i t is not necessary t o work in the absence of air. The chlorate solution is boiled with an excess of Mohr’s salt a.nd hydrochloric acid and the ferric salt formed is titrated with stannous chloride. Manganese dioxide and lead peroxide can be analysed in the same way. R. V. S. Volumetric Estimation of Nitro- and Nitroso-compounds by means of Titanium Trichloride. HEINRTCH SALVATERHA (Chem. Zeit. 1914 38 90-91). -1Cnmht’s process of determining nitro- and nitrosp-compounds by reduction with titanium trichloride a t the boiling point and subsequent estimation of the excess of reagent with ferric alum solution a t the ordinary temperature suffers from the defects that the end point is not sharp and that the solutions must be allowed to cool before the experiment can be finished. The author proposes the following modification the solution of the nitro- or nitroso-compound is treated at its boiling point with a measured excess of titanium trichloride solution; after a short time a known volume of methylene-blue solution (previously standardised against the titanium chloride d u t i o n ) is introduced and the process finished by gradual addition of titanium chloride solution.The end point from green to pale yellowish-brown or yellow is very distinct and‘the accuracy of the process is established by experiments with known quantities of picric acid.A slight modification of thO apparatus is recommended in which the lip of the burette is connected with a tube bent twice at right angles. This tube is first somewhat constricted then allowed to retain its normal diameter for a length of 1 cm. and finally drawn out to a point. I n this manner the burette is not placed directly over the boiling liquid whilst a.180 the addition of the reagent can be accurately controlled. Solubility of Calcium Phosphates in Ammonium Citrate 1-6) .-Since mono- di- and tri-basic calcium phosphates are soluble H. W. Solution. T. WARYNSRI and J. LANGEL (Ann. C h h . ctnd. 1914 19,ANALYTICAL CHEMISTRY ii. 417 in both water and ammonium citrate solution to an appreciable extent the method of separating these salts which depends on the insolubility of tribasic calcium phosphate in ammonium citrate solution and on the inso1ubilit.y of dibasic and tribasic calcium phosphates in water yields only approximately trustworthy results. The solubility of the salts in ammonium citrate solution reaches an equilibrium in about one hour a t 30° but this does not apply in the case of manures where the phosphates may be coated with other substances.The best separation is attained by treating the phosphates f o r one hour with a cold saturated ammonium citrate solution. It may be noted that the solubility of the monobasic and tribasic phosphates variea with the concentration of the citrate solution and reaches a maximum with a concentration of from lo?& to 15%. w. P. s.Rapid Estimation of Boric Acid Normal or Introduced in Foodstuffs. GABRIEL BERTRAND and H. AGULHON (Compt. rend. 1914 158 201-204).-The authors have applied their colorimetric method for the rapid estimation of minute quantities of boric acid (compare this vol. ii 146) to the analysis of a number of fruits vegetables meats and other common articles of food. It is neces- sary in such cases to distil off the methyl borate in order satisfac- torily to apply the test. W. G. The Estimation of Boric Acid in Substances Alimentary or Otherwise. JAY (Compt. rend. 1914 158 357-358. Compare A. 1896 ii 76).-A claim f o r priority over Bertrand and Agulhon (compare this vol. ii 146) for the estimation of boric acid in Vegetables fruits and other foodstuffs and in animal secretions.W. G . The Estimation of Carbon by the Wet Method. Simul- taneous Estimation of the Halogens. F. H. TI-IIES (Chem. Zeit. 1914 38 115-116).-The author has improved his method (com- pare A. 1912 ii 1001) in such a way that halogens can be estimated simultaneously with carbon. The products of oxidation with the dichromate mixture are passed through a heated lime tube to absorb the halogen and part of the carbon dioxide and then through a weighed soda-lime tube to absorb the remaining carbon dioxide. The halogens and the carbon dioxide are then estimated in the lime tube. If iodine is present silver nitrate is added to the oxidation flask in order t o retain the iodine as silver iodide; bromine and chlorine are not thus retained. The results given are satisfactory.T. S. P. Combustions with Tellurium Dioxide. R. GLAUSER (Chem. Zeit. 1914 38 187).-The author recommends the use of tellurium dioxide for combustions in dealing with substances such as alum- inium nitride calcium cyanamide ferrochrome certain hard steels,ii. 218 ABSTRACTS OF CHEMICAL PAPERS. etc. The tellurium dioxide melts to a mobile heavy liquid in which the substances mentioned readily dissolve. Carbon Dioxide Apparatus. 111. Another Special Ap- yaratus for the Estimation of Very Minute Quantities of Carbon Dioxide. SHIRO TASHIHO (J. Biol. Chern. 1914 16 485-494. Compare A. 1913 i 313; ii 725).-The author has modified his previous apparatus (Zoc. cit.) to make it suitable for a complete determination of the carbon dioxide production from a single tissue the metabolic rate of which is constantly changing and the available amount of which is not great. There is a device by which the air can be withdrawn into a tube from the respiratory chamber and can be analysed subsequently.By this means it is possible not only to make a complete analysis with one sample of the tissue but also to make several complete estimations with it. A sketch of the apparatus is given and full details for using it. T. S. P. W. G. Titration of Small Quantities of Carbon Dioxide. ALFRED J ~ O R N E H . (Zeitsch. physiol. Chem.. 191 3 88 425-429. Compare Warburg A. 1909 ii 830).-In this method the heating of the barium hydroxide previously recommended has been given up because it leads in glass vessels to appreciable changes of titre of the barium hydroxide.I n the modified process here described good results are obtained by absorbing the carbon dioxide with cold iV/ 100 barium hydroxide using an apparatus (which is figured) which permits of a prolonged contact between the gas and the absorbing solution. R. V. S. Method of Correcting Silica for Included Ealts. S. B. KUZIRIAN (Amer. J. Sci. 1914 37 61-64).-The silica is ignited treated with a few drops of sulphuric acid again ignited over a Bunsen flame and weighed. After the silica has been removed by treatment with hydrofluoric acid the residue is treated with sulphuric acid ignited a t the same temperature and for the same duration of time as was the silica and weighed. The weight of this residue is deducted from the weight of the silica found in the first instance.w. P. s. Estimation of Free Alkali Hydroxide in Soaps. E. BOSSHARD and W. HUWENBERG (Zeitsch. angew. Chem. 1914 27 11-'20).- Five grams of the soap are dissolved in 100 C.C. of 50% alcohol the mixture being heated gently under a reflux apparatus to ac- celerate the solution of the soap; after cooling the solution is treated with from 15 t o 20 C.C. of 10% barium chloride solution and the mixture is titrated with N /40-alcoholic stearic acid solution using a-naphtholphthalein as indicator. This titration gives the quantity of free alkali present as hydroxide. When free alkali carbonate is also present a further quantity of 5 grams of the soap is dissolved in 100 C.C. of 50% alcohol and the cold solution is titrated with N/40-stearic acid solution the indicator being phenol-ANALYTICAL CHEMISTRY.ii. 219 phthalein or a-naphtholphthalein ; the difference between the two titrations gives the quantity of alkali carbonate. w. P. s. Estimation of Alkalis in the Blood. MAX FEDERER (Zeitsch. physiol. Chena. 1914 89 232-335).-Certain details of procedure in the estimation of the blood-ash of the alkalis present are given which have for their object the increase of accuracy in the results. W. D. H. Estimation of Calcium in Solid Substances and Fluids Derived irom the Animal Organism. S. GUTMANN (Biochem. Zeitsch. 19 14 58 470-47 l).-In Aron’s method of estimating calcium (A. 1907 ii 652) in which the calcium salts are precipi- tated by alcohol after destruction of the organic matter by a mixture of nitric and sulphuric acids there is it source of error due t o the adherence of calcium sulphate to the flask.This is obviated if alcohol is added (after eliminating the excess of nitric acid by boiling the contenta of the incinerating flask with water) and the precipitate formed is filtered off after remaining for a day. The precipitate is then returned to the flask and dissolved in 10% sodium carbonate solution with which it is heated for half-an-hour. The sulphate adhering to the flask as well as the precipitate is thereby converted into carbonate which can then be dissolved in acetic acid. From the neutralised solution the calcium can be precipitated as oxalate. S. B. S. Separation of Calcium from Magnesium. FRANZ HALLA (Chem. Zeit. 1914 38 100).-The following method is recommended for the separation of very small quantities of calcium in the pre- sence of large amounts of magnesium the neutral solution con- taining the chlorides of the two metals is heated to boiling and solid ammonium oxalate is added until the magnesium oxalate a t first precipitated redissolves ; the calcium oxalate remains insoluble.After a few hours the calcium oxalate is collected on a filter washed with hot water then with cold water ignited sulphated and weighed as calcium sulphate. The magnesium oxalate may be precipitated from the filtrate by the addition of acetic acid. w. P. s. Method for Determining the Amount of Zinc Chlo ide in Treated Wood. ERNEST BATEMAN (J. Ind. E97g. Chem. 1914 6 16-18).-Five grams of the ground wood or sawdust are treated in a 500 C.C.flask with 50 C.C. of concentrated nitric acid saturated previously with potassium chlorate ; when the reaction has subsided 10 C.C. of sulphuric acid are added the solution is boiled a further quantity of nitric acid containing chlorate is added and the boiling is continued until the solution is clear and practically colourlms when all the nitric acid has been expelled. Either of two volu- metric methods may now be employed for the estimation of the zinc in this solution. (1) The solution is boiled for five minutesii. 220 ABSTRACTS OF CHEMICAL PAPERS after the addition of 0.5 gram of sodium sulphite cooled diluted with 100 C.C. of water and the ferrous iron in solution is oxidised by the addition of 25 C.C. of bromine water. The excess of bromine is expelled by boiling the ferric salts are precipitated with ammonia and the filtered solution is neutralised with hydrochloric acid. Five C.C.of concentrated hydrochloric acid are now added the mixture is diluted to 175 c.c. heated to 80° and titrated with standardised potassium ferrocyanide solution using uranium acetate as an outside indicator. It is advisable t o add 25 C.C. of hydrogen sulphide solution immediately before the titration in order to ensure that the titration is carried out in a reducing solution. (2) The acid digestion solution is diluted with 100 C.C. of water 10 C.C. of 2% ferric chloride solution and 1 gram of citric acid are added the mixture is rendered slightly alkaline with ammonia diluted to 200 c.c. and titrated at 80° with potassium ferrocyanide solution The end of the titration is reached when a drop of the mixture yields a blue coloration with a drop of a solution con- sisting of equal volumes of glycerol and glacial acetic acid.Con- trol estimations using untreated sawdust o r filter-paper should be made a t the same time. w. P. s. Application of a New Reaction of Copper Cobalt and Nickel. GIUSEPPE MALATESTA and ETTORE DI NOLA (BoZZ. Chim. farm. 1913 52 819-823).-Uhlenhuth’s reaction for copper (A. 1910 ii 898) is given also by cobalt and nickel. All three reactions are modified but in different ways by the addition of electrolytes such as ammonium chloride of ammonia or of sodium hydroxide. Details are given of the alterations in the nature and sensibility of the reaction so obtainable and in this way it is possible to differentiate between tho three metals. The reaction can be ap- plied t o solutions in test-tubes to drops of suspected liquids on filter-paper or even to metal objects direct.The following modi- fied reagent is recommended 1 2-diaminoanthraquinone-S-sulph- onic acid (0.5 gram) concentrated ammonia solution (100 c.c.) water (360 c.c.) sodium hydroxide 40OBe. (40 c.c.). With this reagent a blue coloration is obtained with all three metals. I f it is due to nickel it turns reddish-violet on adding concentrated ammonia solution if due to copper i t becomes red on adding ammonium chloride whilst a coloration due to cobalt is not changed by either of these substances. R. V. S. I;. BERTIAUX (Ann. Chint. CcnuZ. 1914 19 6-14.Compare A 1913 ii 731 1078).-The following is an outline of the method proposed for the estimation of copper lead tin iron nickel cobalt manganese aluminium zinc arsenic and antimony in these alloys. Five grams of the sample are dissolved in a mixture of sulphuric and nitric acids and the copper is deposited electrolytically from the solution ; after the nitric acid has been removed by evaporation the tin is precipitated from the solution as sulphide the filtrate from this precipitate is oxidised with hydrogen peroxide and the iron alum- Analysis of Bronze German Silver and Brass.ii. 221 ANALYTICAL CHEMISTRY. inium and manganese are precipitated as hydroxides. The iron is then estimated by titration with permanganate the manganeae colorimetrically and the aluminium is taken by difference.Nickel and cobalt and subsequently zinc are deposited electrolytically from the residual solution. Lead is estimated by dissolving 5 grams of the alloy in copper nitrate solution adding nitric acid and depositing the metal as peroxide; when antimony is present the lead must first be separated as sulphate. For the estimation of tin the alloy is dissolved in nitric acid and the insoluble meta- stannic acid is collected and weighed. Arsenic and antimony are New Method of Quantitative Estimation of Mercury in the Solid State. C. DIXCINI (Gaxzettn. 191 3 43 ii 693-699).-The method depends on the separation of metallic mercury when solu- tions containing it are treated with a hydrazine salt in presence of alkali. Instead of measuring the volume of nitrogen produced (Rimini A.1904 ii ZO.i) the author weighs the mercury on a tared filter-paper. The results are accurate (0.10% error using about 0.25 gram of substance). It is of general application and is not affected either by the presence of free acid in solution or by the concentration of the solution. estimated by the distillation method. 'cv. P. s. R. v. s. Detection of Traces of Aluminium. G. H. PETIT (J. Phurm. Chim 1!114 [viil 9 66-69).-The test depends on the solubility of barium aluminate and is capable of detecting a quantity of 0.005 gram of aluminium in the presence of 5 grams of iron. The pre- cipitate of ferric chromium and aluminium hydroxides obtained in the usual way is washed until quite free from ammonium salts then rinsed into a beaker with water 2 grams of barium hydroxide are added and the mixture is boiled.After filtration a slight excess of sulphuric acid is added to the filtrate which is then evaporated to about 30 c.c. the barium sulphate is separated and the solution is rendered faintly ammoniacal. On boiling alum- HARI PADA BHATTACHARYYA (Chem. NBWS 1914 109 38).-Silicon is estimated by dissolving the metal in nitric acid and evaporating with hydrochloric acid; copper is precipitated its sulphide from the filtrate from the silica and the aluminium is precipitated as phosphate in the presence of sodium thiosulphate. The zinc present is precipitated as sulphide in the filtrate from the aluminium phosphate. Iron is estimated by dis- solving the metal in sodium hydroxide solution collecting the ferric hydroxide on a filter dissolving it in hydrochloric acid and re- precipitating it by the addition of ammonia.Sodium is estimated in the usual way and carbon by the sodium copper chloride method. w. P. s. G. FENDLER (ZeitscA. phv&ol. Chem. 191 4 89 279-288. Compare Neumann A. 1902 ii 176 583).-The author's experiments show that this inium hydroxide is precipitated. w. P. s. Analysis of Aluminium. The Estimation of Iron According to Neumann. VOL. cvr. ii. 15ii. 222 ABSTRACTS OF CHEMICAL PAPERS method fails when applied to products rich in the phosphates of the alkali earths and even in other cases is not very exact. The modification of Edelstein and v. Csonka (A. 1912 ii 184) gives more tsustworthy results. R. V. S. New Method of Titration of Ferric Salts by Reduction.C. Russo (Gazxsstn 1914 44 i 1-8).-The method depends on the use of a standard solution (N/5) of stannous chloride to reduce the ferric salt present. The end-point is recognised with the aid of a 1% solution of methylene-blue; two drops of this are added to the solution and when most of the ferric salt is reduced the liquid is boiled and the addition of stannous chloride is continued drop by drop until the blue coloration shows signs of disappearing. After boiling for two o r three minutes another drop of stannous chloride is added and so on until decolorisation occurs. The solution must not contain more than a certain amount of acid so that if neces- sary the liquid must previously be made just alkaline with ammonia and then re-acidified with hydrochloric acid.R. V. S. Volumetric Estimation of Titanium. B. NEUMANN (Zeitsch. angew. Chem. 1914 27 56).-A reply to Knecht (this vol. ii 73). w. P. s. Loss of Noble Metals during Cupellation. J. LOEVY (Chem. Zeit. 1914 38 82-83).-Los~ of metals during cupellation is attributed to evaporation and absorption by the cupel. The former cause is operative only in the case of silver since the highest tem- perature reached in the muffle is insufficient to volatilise gold to an appreciable extent. Loss of the latter is therefore solely due to absorption by the cupel. The author has examined the capacity of absorbing gold of a large number of cupels obtained from different firms and finds t h e loss of gold t o vary from 0.197 t o 0*370% whilst the loss in silver varies between 1.190 and 1.710% and even with the most careful work is partly due to volatilisation.Contrary to the opinion of the Commission of the Chem. and Metal. SOC. of South Africa (1899) he finds that French cupels possess no superiority over those of German manufacture. I n agreement with F. K. Rose (ibid. 1905) he finds that the quality of any batch of cupels obtained from any particular firm is very uneven and that the absorptive capacity of any one kind can only be accurately estimated by repeated determinations after definite intervals of time. The Use of Pyridine as a Solvent in the Estimation of Hydroxyl Groups by means of Magnesium Alkyl Haloids. ARTHUR P. TANBERU (J. Amer. Chem. Xoc. 1914 36 335-337).- It is stated that the use of pyridine as recommended by Zerevitinov (A.1907 ii 509; 1908 i 593; 1911 i 101; 1912 i 841) as a solvent for the estimation of hydroxyl groups by magnesium methyl iodide is not generally satisfactory ; with a-naphthol for example more than twice the theoretical volume of methane is produced. H. W.ARALYTICAL CHEMISTRY. ii. 223 The excess is a t least in part due to the pyridine for this substance in blank experiments at room temperature immediately gave rise to a considerable amount of gas. This result is the more surprising as the pyridine employed was of a higher degree of purity than that used by Zerevitinov. GUIDO GoLDsCHMrEDT (Be?*. 1914 47 389-392).-The addition of acetic anhydride or of phenol in the estimation of methoxyl by Zeisel’s method con- demned by Manning and Nierenstein (this vol.ii l50) is strongly recommended by the author. I n blank experiments in Mmeyer’s apparatus the amount of silver iodide produced after five to twelve hours’ boiling is only a few mg. a quantity which is quite negligible in compasison with the experimental error of the method. A Microanalytical Method for Estimation of the Sugar in the Blood. L. MICHAELIS (Riochen?. Zeitsch. 1914. 59 166-172).- For the method about 1.5 C.C. of blood suffice. It depends on two processes. (1) Separation of the proteins by a combination of heat coagulation with iron hydroxide precipitation (according to the method of Michaelis and Rona). (2) Estimation of the sugar in the filtrate by Bertrand’s method. For the latter purpose the cuprous oxide precipitated is separated by centrifugalisation dis- solved in Bertrand’s ferric sulphate solution which is then titrated from a small 3 C.C.burette with N/100-permanganate solution. The method is described in detail and yield results which are accurate to within 3 or 4%. D. F. T. [Estimation of Msthoxyl Groups.] C. S. S. B. S. The Picrate Colorimetric Method for the Estimation of Carbohydrates. WILLIAM M. DEHN and FRANK A. HARTMAN (J. Anzw. Chena. Suc. 191 4,36,403-109).-The reddish-brown colour which develops on warming solutions of sugars with picric acid and alkali and was first noticed by Braun (Zeits.ch. anal. Chem. 1865 4 185) can be adapted to the colorimetric estimation of the sugars provided that sodium carbonate is used in place of sodium hydroxide.The stan- dard for comparison is prepared from a known weight of a pure sugar preferably sucrose the colour being fairly permanent if the solution is kept in the dark. Hydrogen Ion Concentration in Beer and in its Preparation. FRITZ EMSLANDER (Kolloid. Zeitscl~ 1914 14,44-48).-A method for the estimation of the acidity of beer is described which consisb in the electrometric measurement of the hydrogen ion concentration in the original beer and of the concentration after the addition of 10 C.C. of 0.lN-alkali to 100 c.c.aof beer. I f on a diagram in which log [H’] is plotted aa ordinate against volume of added alkali zs abscissa a straight line is drawn through the two experimental points the point a t which this intersects the horizontal line drawn through the ordinate log [H’]= - 7.0 gives a measure of the acidity.Details as to the solutions and procedure are given. D. F. T. 15-2ii. 224 ABSTRACTS OF CHEMICAL PAPERS. The relation between the albumin content of the beer and its acidity is discussed and i t is shown that the inclination of the titration line towards the abscissa diminishes as the relative amount of albumin increases. The slope of this line affords therefore some indication of the albumin content of the beer. keeping power ” of a beer is related to the slope of the titration line the “ keeplng power ” increasing with the inclination of this line to the abscissa. It is also shown that the H. M. D. Estimation of Lactic Acid in Fluids containing Proteins. MAX OPPENHEIMER (Zeitech. phpiol. Chem. 1914 89 39-44).- The method suggested b Mondschein for the liberation of the lactic acid from the proteins gy means of boiling 10% sodium hydroxide solution is open to serious objection and the author recommends the precipitation of the proteins with hydrochloric acid and mer- curic chloride as proposed by Schenk.I n comparative experiments with blood muscle and yeast-juice it was found possible to deter- mine by the latter method upwards of 96% of the lactic acid added to the original fluids. Precipitation by means of colloidal iron failed to give satisfactory results about 30% of the lactic acid being retained by the proteins. Estimation of Pyruvic Acid. IDA SMEDLEY MACLEAN (Bio- c b m . J. 1913 7 61 1-61.5) -Pvruvic acid cannot he quantitatively estimated by precipitation as a hydrazone owing to the solubility of the latter.I n dilute solutions of the acid a method involving fiuch a process is useless. If a solution containing the acid is kept for half-an-hour with phenylhydrazine the excess of the latter used can be estimated by treatment with Fehling’s solution in the cold. It undergoes oxidation according to the equation 2C6H5*NH*NH2 + 3 0 = C6H6 + C6H5:OH + 2N2 + H20. It is not convenient to measure the nitrogen evolved but the amount of phenylhydrazine in the solution can be determined by filtering off the precipitated cuprous oxide dissolving this in Bertrand’s ferric sulphate solution and titrating the ferrous salt thus formed with permanganate. By the difference in the titration numbers of the phenylhydrazine solution in the presence and absence of pyruvic acid the amount of the latter can be calculated.The method is also available in the presence of dextrose which does not reduce the Fehling solution in the cold. H. B. H. S. B. S. A Reaction of Succinic and Malic Acids. W. CECRSNER DE CONINCR (Bull. SOC. chim. 1914 [iv) 15. 93-94).-When a con- centrated aqueous solution of succinic acid is added t o a suspen- sion of several grams of calcium salicylate in a little cold water and the mixture gently warmed a pale pink coloration is quickly developed which persists for several days even on exposure to direct sunlight. I n similar circumstances malic acid develops a fugitive delicate pink coloration which gradually disappears on gently boiling the mixture and is completely destroyed after several hours the liquid becoming yellowish-brown.H. W.ANALYTICAL CHEMISTRY. ii. 225 Triketohydrindene Hydrate. A Method for the Quantitative Estimation of the -NH2*C02H Group. E. HERZFELD (Biochem. Zeitsch. 1914 59 249-259).-1f ninbydrin (triketohydrindeae hydrate) solution is evaporated on a water-bath to dryness a coloured residue is obtained which gives an almost colourless solution in water o r alcohol. If however an amino-acid is present in the solution the residue dissolves in alcohol with practically no diminution of t,he colour intensity although the colour diminishes perceptibly when i t is dissolved in boiling water. When the solu- tion in alcohol has a reddish shade the latter can be converted into the violet shade by addition of traces of ammonia.The evaporation to dryness of the ninhydrin solution with the sub- stance under investigat’ion and the solution of the residue in hot alcohol is now suggested as a technique for the use of the ninhydrin reaction. Several substances have been investigated in this way. Ammonium oxalate gives a violet solution and ammonium thio- cyanate a red one. I n most of the other substances investigated a negative result was obtaiped. The reaction is however very sensitive to amino-acids and a metihod is described for the applica- tion to quantitative estimation of these substances (or -NH,*C?O,H groups) by measuring the extinction coefficient of the solution pro- duced when 0.5 C.C. of a 1% ninhydrin solution is evaporated to dryness with the solut.ion under investigation on a water-bath and the residue is dissolved in alcohol.For this purpose a spectro- photometer is employed. It was found that the percentage of -NH,-CO,H groups was ~/0.046 where E. is the extinction co- efficient under the described conditions of the experiment. The method has been applied by the author with satisfactory results to Abderhalden’s pregnancy reaction. The sera of pregnant in- dividuals alone was found to give dialysates with higher ninhydrin values than normal sera. S. B. S. The Solidifying and Melting Points of Mutton Tallow and Its Fattv Acids. ROBERT MELDRUM (Chem. News 1914 109 49-51 ).-Results of determinations of the solidifying and melting points of various samples of tallow and of the fatty acids obtained from the same are recorded.The difference bet.ween the lowest temperature to which a tallow falls du+g solidification and ifxi melting point varies frpm 1 2 O to 1 3 O ; in the case of the fatty acids this difference amounts to from Z0 to 4O. w. P. s. Estimation of the Reichert-Meissl and Polenske Numbers (of Fats). A. GOSKE (Zeitsci4. N a b . Gonrrmm. 1913 26 651-652). -The following method is recommended for the saponification of the f a t Five grams of the sample are placed in a flask together with 6 C.C. of glycerol-potassium hydroxide solution (1 2) two small fragments of pipe-clay are added and the flask is then heated on an air-bath so that its contents attain a temperature of 200° within about ten minutes; the burner is now removed from beneath the air-bath whilst the flask is allomed t o remain until the temperature of the contents rises to 2 1 5 O .Saponification willii. 226 ABSTRACTS OF CHEMICAL PAPERS. then be complete and the method is proceeded with in the usual way. A thermometer having a small bulb bent a t a right-angle to the stem so that the bulb may be immersed completely in the liquid is employed; an ordinary thermometer will indicate the temperature of the mixture t o be about 20° lower than the points mentioned w. P. s. Quantitative Analyses of Artiflcially-prepared Mixtures of Ethereal Oils. CAMILL HOFFMEISTER (Chern. Zsiztr. 19 13 ii 2062 ; from Arb. Pharrn. Inst. Unity. Rcr2in.. 1913 10 147-1 54).-Renz- aldehyde may be quantitatively estimated in the presence of alcohol by converting it into the osazone by means of a solution of phenylhydrazine in acetic acid.The osazone can be estimated gravimetrically (Dumer Z e i t . anal. Chem. 1889 29 228) or volumetrically (A. von Mayer Monntsh. 1891 12 525). Eugenol is determined under similar circumstances by transformation into benzoyleugenol. Benzaldehyde in the presence of oil of turpentine is estimated by conversion into its bisulphite compound. The latter is purified by repeated extraction with ether ; benzaldehyde is liberated by succes- sive addition of sodium hydroxide and acetic acid and converted into its osazone. Eugenol is separated from oil of turpentine by repeated extraction with sodium hydroxide and estimated by the method of Thoms (A. 1904 ii 93). I n a mixture of benzaldehyde eugenol and oil of turpentine the former is removed in the form of its bisulphibe compound and the eugenol is then extracted with sodium hydroxide the two substances being then estimated as above described.I n the estimation of linalool and linalyl acetate in oil of lavender the total linalool content is determined by acetylation and the linalyl acetate originally present (determined by saponification) is deducted. I n this manner 41.861% of the latter and 7.505% of the former were found in oil of lavender. Benzaldehyde eugenol linalool linalyl acetate alcohol and palmitic acid are determined as follows in the presence of oil of turpentine The specimen is shaken three times with sodium hydr- ogen sulphite and the bisulphite compound freed from the other substances by repeated treatment with ether. The benzaldehyde is estimated as previously described.Palmitic acid is then removed by cold 10% potassium carbonate solution the solution is acidified and the palmitic acid quantitatively extracted with ether. The ethereal solution of the remaining components is agitated with six portions each of 5 C.C. of cold 15% sodium hydroxide and allowed to remain for an hour after each agitation. Eugenol is determined in the alkaline solution according t o Thoms. The residue is made up to a definite volume with ether and the linalool and linalyl acetate determined in aliquot portions. The content in oil of turpentine is estimated by difference. The estimation of alcohol in the mixture is not described in the original paper. The accuracy of the processes is shown by a series of tables H.W,ANALYTICAL CHEMISI’R Y. ii. 227 Analysis of Fertilisers Containing Cyanamide. H. W. HILL and W. S. LANDIS (J. I n d . Ewq. Chem. 1914 6 20-22).-Tbe authors discuss the reactions which take place between calcium cyanamide and ‘( acid phosphates,” and show that in the case of a fertiliser containing these two substances the American Official Method of Analysis in no way gives results indicative of the character of the sample as taken when free calcium hydroxide or cyanamide are Lours BAUMANN ( J . Biol. Clkm. 1914 17 15-17).-Hashed muscle is boiled with 5N- sulphuric acid for three hours in a flask with reflux condenser. The product is filtered and a measured amount of the filtrate after dilution is mixed with 10% sodium hydroxide and the creatine+ creatinine estimated by Folin’s method.The results are accurate and the whole process is rapidly performed. present in the mixture. w. P. s. EBtirnation of Creatine in Muscle. W. D. H. Detection of ‘‘ Saccharin ” in Foods with a Modiflcation of Schmidt’s Methods. HALSEY DURAND (J. Ind. h g . Chew. 1913 5 987-989).-The following modification of Schmidt’s method in which the (( saccharin ” is converted into salicylic acid by heating with sodium hydroxide was found to be trustworthy. An aqueous extract of the sample to be tested is acidified with phosphoric acid and extracted with ether. The ethereal solution is filtered evaporated to dryness in a nickel basin and a portion of the residue is tested for salicylic acid; if this acid is present the residue is dissolved in hydrochloric acid an excess of bromine is added and the mixture filtered; the salicylic acid is thus removed completely as a bromine derivative.The filtrate is then rendered strongly alkaline with sodium hydroxide evaporated and the residue treated as described below. I n the absence of salicylic acid the residue obtained on evaporating the ethereal solution is moistened with 1 C.C. of saturated sodium hydroxide solution the basin is placed on a piece of asbestos board and heated for ten minutes over a Bunsen flame. After cooling the mass is dissolved in dilute hydrochloric acid the solution extracted with ether and the ethereal solution is shaken in a test- tube with dilute ferric chloride solution. A violet coloration is obt-ained in the aqueous layer.w. P. s. Microchemical Reaction for Caffeine Theobrornine Theo- phylline and Their Derivatives with Mercuric Chloride. Rf . WAUENAAR (Phorm. Wwkblad 1914 5 1 23-24).-Mercuric chloride is a delicate microchemical reagent for the detection and identi- fication of purine derivatives containing one or more methyl groups. It yields characteristic crystals with caffeine theobromine theophylline and their derivatives. Estimation of Creatinine and Creatine in Muscle. VICTOR C. MYERS and MORRIS 5. FINE (J. Biol. Chem. 1914 17 65-69),- See this vol. i 3,51. A. J. W.ii. 228 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Tannin in Cider. C. W. SPIERS (J. Agric. Sci. 1914 6 76-83).-A modification of Korner and Nierenstein’s method (detannising the solution with casein) in which the tannin removed is estimated by the difference in the permanganate titrations.The cider (5 c.c.) is added to 750 C.C. of water in a shallow porcelain dish with 20 C.C. of indigo solution (5 grams of indigo- carmine per litre). The permanganate solution (1 gram per litre) is run in slowly and well stirred for five to ten seconds after each C.C. Afterwards it is added more slowly until the liquid becomes a clear golden-yellow with a tinge of pink round the edge of the dish. For detannising Kahlbaum’s pure casein is employed. It is first extracted with ether for thirty-six hours and is added in two portions of 1 gram the liquid being filtered after each addition the second time through a barium sulphate filter. The permanganate is standardised with Scliering’s tannin leviss. puriss. It was found that the commercial pure tannins are not homo- geneous different samples of the same tannin giving somewhat different figures. Taking the average value of the tannins i t was found that 1 gram of ammonium oxalate = 0.4648 gram tannin. N. H. J. M. A t least three titrations should be made. Detection of Albumin in Urine. ADOLF JOLLES (Zeitsch. nngezo. Chem. 1914 27 20-22).-With regard to a test described recently by 0. Mayer (this vol. ii SO) the author refers to similar test.s proposed previously by himself (A. 1896 ii 344; 1900 ii 516); a modification of the test has been given recently (A 1913 ii 83). Mayer’s test is trustworthy only in the case of urines containing small quantities of albumin. w. P. s. A Modiflcation of Teichmann’s Test for Blood. CLAUDE TREVINE SYMONS (Biochem. J. 1913 7 596-598).-The use of n mixture of sodium iodide and lactic acid is recommended in place of sodium chloride and acetic acid for the preparation of Teich- mann’s hzmin crystals. The benzidine test for blood is not charac- ter istic. W. D. H. The American Method of Standardising Tetanue Anti- toxin. ALFRED MACCOSKEY (J. Hygienp 1014 13 467-493).- This investigation confirms the statement that the American method is simple accurate and trustworthy. The deterioration in samples examined over two years is absent or almost negligible. Tetanus antitoxin can be heated a t 57O for one hour on each of three successive days without loss of power provided no antiseptic is added. I n the presence of preservative there is a loss of 12% and this occurs during the first hour. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9140605213

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 217 The Removal of Diffusible Substances from the Circulating Blood by Dialysis. JOHN J. ABEL LEONARD G . ROWNTREE and B. B. TURNER (.L Pltarmacol. expt. T/Lw. 1914 5 275-316).-The artery of an animal (previously treated with hirudin) is connected to an apparatus consisting of tubes made of cellodin outside of whichi. 218 ABSTRACTS OF CHEMICAL PAPERS. is Ringer’s solution; the blood thus subjected to dialysis is returned to a vein of the animal. The blood is thus in part freed from diffusible substances and the operation does no harm to the animal. Quantitative results with salicylic acid show that the rate of removal of this from the blood compares not unfavourably with the kidney. The method is regarded as one of great promise even from the therapeutic point of view.W. D. H. “Sucre Virtue1 ” and Blood Glycolysis. R. L~PINE (J. Biol. Chem. 1914 16 559-561).-Polemical against Macleod (A 1913 i 1258) who is stated to have insufficiently or incorrectly quoted the author’s writings. The main point is that after the blood is removed an increase of sugar in i t may occur at 5 8 O before glyco- lysis sets in. W. D. H. The Sugar of the Blood Plasma. H. BIERRY and (MlIB.) LUCIE FANDARD (Compt. rend 1924,168,61-64).-The authors have deter- mined the amounts of free and combined sugar in the plasmas from venous and arterial blood drawn simultaneously from horses and dogs and from arterial blood from chicken. Except in two cases the animals were bled without an anasthetic and it was found that the venous plasma was richer in combined sugar than the corresponding arterial plasma.An examination of the nature of the reducing sugar obtained by hydrolysis of the serum points to it being dextrose. Possibly a little glucosamine is present. W. G. A New Vaso-constrictor Substance in the Blood and Adrenal Cortex. CARL VOECITLIN and DAVID I. MACHT (J. Ante+. Med. ABSOC. 1913 6 1 2136-2138). -From the blood of nieii and other animals a crystalline substance was isolated which had a powerful and lasting vaso-constrictor effect. The blood or serum was dried and extracted with chloroform; on evaporating the extract the residue was extracted with methyl alcohol; on evapor- ating off the alcohol the substance in question was obtained. It is probably related to cholesterol. The same material was also obtained from the adrenal cortex.It has a digitalis-like action on the heart. W. D. H. Fibrinogen. I. Its Origin and Destruction in the Body. G. H. WHIPPLE (Amev. J. Phqsiol. 1914 33 50-69).-The amount of fibrinogen in dog’s blood varies greatly but is not influenced by feeding or fasting; the variations in human blood are smaller. The amount of fibrinogen rises in pneumonia and septicaemia and it falls even to zero in acute liver injury; it is usually low in most (but not all) cachetic conditions. It has no relationship to activity or disease of the bone marrow. If the circulation of the blood is confined to head and thorax by tying the aorta the fibrinogen rapidly disappears as it is used by the tissues and the source of supply is cut off.If the liver is removed from the circulation the fibrinogen does not fall appreciably some other organ (thePHYSIOLOGICAL CHEMISTRY. i. 219 intestine) continuing the supply. I n chloroform poisoning of the liver the fibrinogen d r o p rapidly ; probably the injured liver cells effect a drain on the blood fibrinogen. No enzyme able to destroy fibrinogen could be isolated from them. Fibrinogen. 11. Association of Liver and Intestine in Regeneration of Fibrinogen. E. W. GOODPASTURE (Arner. J . Physiol. 1914,33,70-85) -In young dog. regeneration of fibrinogen after the blood has been defibrinated is rapid occurring in about half-an-hour. Ligature of the hepatic artery and spleen pedicle causes a slight delay and of the intestines a marked delay in regeneration. I f the intestines are entirely removed fibrinogen returns to the normal within eight hours.Chloroform anathe& also causes great delay. The conclusion is drawn that the produc- tion of fibrinogen is the result of the combined activity of the liver and intestine. W. D. H. W. D. H. The Influence of Phosphrttides on Blood Coagulation. C. A. PERELHARING (Zeitsch. physiol. Chem. 191 4 89 22-38).-Some recent workers have stated that phosphatidee hasten blood-clotting and have suggested that thrombokinase is a phosphatide. The present experiments with lecithin and blood-plasma or solutions of fibrinogen show that this phosphatide does not hasten the process or in cases where the clotting time is shortened the result can be explained in other ways.Distribution Inhi bition and Acceleration in Hzemolysis. SVANTE ARRKENIUS aod FR \N BUBANOVIB (Medd. K. Vet. NobeLinetitut. 1913 2 No. 32 1-22).-Observations have been made with refer- ence to the influence of various salts on the hzmolytic action of different substances on red blood corpuscles. From a comparison of the hzmolytic effects produced by the alkaline earth-metal chlorides i t is found that the activity increases with increasing atomic weight. The hzmolytic action of benzene is increased by calcium chloride whilst that of chloroform is diminished when hypotonic solutions are employed in the comparison. Potaesium oxalate reduces the activity of chloroform and ammonium chloride in hypotonic solution but has no appreciable influence on the activity of saponin and of acetone in isotonic solution.Sodium fluoride is also without effect on the action of saponin in isotonic solution. Other observations refer to the haemolytic action of various organic substances and from these i t appears that the hzmolysis is inhibited by weak hzmolysts if the action takes place in hypotonic solution. The distribution of the hzemolytic substances methyl ethyl and isoamyl alcohol ethyl ether and acetone between the blood corpuscles and the surrounding solution has been examined and the results show that the ratio of distribution is about 3 for methyl alcohol and acetone 3.3 for ethyl alcohol and ethyl ether and 5.5 for isoamyl alcohol. The absorption capacity of the blood corpuscles for these weak hzemolysts is therefore very much smaller W.D. H.i. 2‘20 ABSTRACTS OF CHEMICAL PAPERS. than for the strong hzemolysts for which the distribution ratio is of the order 100-1000. H. M. D. The Hemolytic Action of Mixtures of Cyclamin and Cholesterol. HERMANN LUMMERZHEJM (Metlo?. K. Vet. Nobelimtitut. 1913 2 No. 28 1-21).-From observations on the hzemolytic action of mixtures of cyclamin and cholesterol it would appear that these substances combine to form a dissociating complex compound. For a given quantity of cyclamin the hzemolytic effect decreases as the amount of cholesterol present increases. Consistent values can only be obtained when the observations are made with one and the same solution of blood corpuscles. The divergences are attributed to the presence of serum which reduces the hzmolytic effect of the cyclamin.H. M. D. The Secretion of Gastric Juice in the Cat. A. J. CARLSON J. S. ORR and W. F. BRINKMAN (Amer. J. Phpiol. 1914 33 86-94). -The experiments on cats with a Pavlov stomach pouch showed that the appetite secretion ” is practically identical with that in the dog. The drinking of water if the animals are thirsty causes secretion of gastric juice; this secretion is only partly “ psychic.” W. D. H. The Ferments of the Pancreas. 111. The Properties of Trypsin Trypsinogen and Enterokinase. JOHN MELLANBY and V. J. WOOLLEY (J. Physiol. 1913 47 339-360).-Tbe cffects of destructive agents on trypsin trypsinogen and enterokinase show great variations. The only effective agents for preserving trypsin at 38O are salts of the alkaline earths especially calcium.I n alkaline solutions (NO-1 6-sodium carbonate) trypsin is destroyed within forty-five minutes a t 50° and within five minutes at 60°. I n acid solution (NO-025-hydrochloric acid) destruction is much slower and some remains undestroyed even after boiling for five minutes. Trypsinogen keeps indefinitely in NO-1 6-sodium carbonate a t room temperature but is destroyed in five minutes at 6 5 O . Hydrochloric acid (NO-25) has no effect on it a t 40° and even at looo for five minutm 30% of it is undestroyed. I n the presence of neutral salts the tempe‘rature of destruction varies. The most marked property of enterokinase is its immediate destruction in the presence of free acid (NO.01-hydrochloric acid) at 1 6 O . I n water or NO.5-sodium chloride solution five minutes’ heating a t 6 5 O destroys i t ; the same strength of calcium chloride raises this temperature to 75O.Albumin peptone and amino-acids protect trypsin from heat destruction at 50° in varying degrees. The effect of amino-acids is small. The duration of protection is related to the length of time taken by the trypsin to digest the added protein. Serum contains anti-trypsin and anti-enterokinase but no anti- trypsinogen. The trypsin-antitrypsin compound cannot be broken up so as t o liberate the trypsin. Enterokinase occurs in the greatest quantity in the mucous membrane of the first 2 / 7 of the smallPHYSIOI~OGLCAL CHEMISTRY. i. 221 intestine and especially in the superficial layers. There is evidence that it. is not formed by Brunner’s glands.It is found in small amounts in almost every tissue of the body. The general view taken of the action of the various enzymes on one another is the following Enterokinase and trypsin are destroyed by the hydrochloric acid of the gastric juice but tryp- sinogen is not acted on. Trypsinogen however is destroyed by pepsin and hydrochloric acid. Trypsin has no effect on entero- kinase or trypsinogen. Enterokinase has no effect on trypsin but activates trypsinogen. Pepsin is destroyed by the alkali of pancreatic juice. W. D. H. The Adaptation of Entero-amylase to Chemical Stimulation. L. J. TE GROEN (Zeitsch. phyeiol. Chent. 1914 89 91-100).-Intes- tinal juice collected from a Vella’s fistula is smylolytic even when the secretion is excited by a non-specific substance such as sodium cliolate.I n the omega double fistula of Lombroso there is more such action in the oral than in the aboral half. On regular diets the amount of amylase is constant but stimulation of the intestinal mucous membrane with starch solution increases the amount of amylase formed. W. D. H. Fasting Studies. XII. Ammonia Phosphate Chloride and Acid Excretion of a Fasting Man. D. W. WILSON and P. B. HAWK (J. Amer. Chem. Soc. 1914 36 137-146).-An experiment is described which was undertaken with the object of ascertaining the relation between the ammonia phosphate chloride and acid ex- creted in the urine during a seven-day fast and during a subsequent low-feeding period of four days and a high-feeding period of five days. During a preliminary period of four days the subject was given a uniform diet containing 21.86 grams of nitrogen per day.The daily routine work of the subject (a laboratory instructor) was continued during the fast. In the course of the fast the ammonia excreted rose rapidly reaching a maximum on the sixth day; the acidity increased t o a maximum on the third day and then gradually diminished; the phoephate increased until the third day and then decreased the relative decrease being closely parallel to that of the acidity; the amount of chloride excreted decreased rapidly for three days and afterwards more slowly. During the low-feeding period the subject received a diet con- taining 5-23 grams of nitrogen per day. The ammonia nitrogen was higher during the first day of this period than on the last day of the fast but subsequently decreased although the minimum value was somewhat higher than any value observed in the pre- liminary period.The acidity fell immediately to a value lower than any noted in the preliminary period and continued to decrease until the fourth day. The phosphate diminished slightly on the first day and considerably on the second and subsequently in- creased to about half the value found in the preliminary period. The chloride decreased greatly on the first day reached a minimumi. 222 ABSTRACTS OF CHEMICAL PAPERS. on the second day and remained a t this value for the remainder of the period. I n the final period the amount of food given was increased to that of the preliminary period. The ammonia continued to de- crease for the first two days increased greatly on the third and decreased on the fourth and fifth days to a value rather above that of the preliminary period.The acidity increased on the first day to a value somewhat below the normal and did not vary greatly subsequently. The amount of phosphate increased rapidly was above the normal on the second and third days but for the re- mainder of the period was a little below the average of the pre- liminary period. The chloride increased during the first three days and all the values were higher t,,han those of the preliminary period. These results are discussed in their relation to the metabolic processes. E. G . Fasting Studies. XIII. Output of FEecal Bacteria a s Influenced by Fasting and by Low and High Protein Intake.N. R. BLATHERWICK and P. B. HAWK ( J . Amer. Cherm. SOC. 1914 36 147-152).-1n the preceding paper Wilson and Hawk have given an account of the study of the ammonia phosphate chloride and acid excretion of a subject undergoing a seven-day fast. During the course of the same experiment observations were made of the amount of k c a l bacteria excreted. It was found that the daily excretion of bacterial nitrogen was reduced from 1.571 grams to 0*101 gram whilst the actual weight of the excreted bacterial sub- stance fell from 14.336 grams to 0.920 gram per day. The propor- tion of the faecal nitrogen present as bacterial nitrogen was dimin- ished from 55.82% to 32'29% as a result of the fast. The percentage of dry bacteria in the fEces was slightly increased.During the period of the low protein diet the amounts of bac- terial nitrogen and of bacterial substance excreted were approxi- mately the same as during the fast but on the resumption of a high protein diet the amounts immediately underwent a consider- able increase. The proportion of the faecal nitrogen consisting of bacterial nitrogen was about the same in both the high and low protein feeding periods. No definite relation could be traced between the excretion of fecal bacteria and that of urinary indican. The ingestion of 5-23 grams of nitrogen after the fast was followed by an excretion of fzcal bacteria which was only one- fourteenth as great as that produced before the fast when four times as much nitrogen was ingested. E. G. The Influence of Drinking on Digestion.FRANZ GROBBELS (Zeitsch. physiol. Chem. 1914 89 2-21).-The observations recorded relate to the rate of outflow of the contents of the stomach in dogs. This increases the more flukd is administered; pure water leaves the stomach most easily. Alcoholic drinks and coffee slow the output in comparison. Thirst and the taking of fluid to allay it delays the digestion of a meal. W. D. H.PHYSIOLOGICAL CHEMISTRY i. 223 Water Drinking. XV. The Output of Faecal Bacteria as Influenced by the Drinking of Distilled Water at Meal Times. N. R. BLATHERWICK and P. B. HAWK (Biochem. Bull. 1913 3,28-40). -Two subjects were fed for a month on a uniform diet; in the facal nitrogen the bacterial nitrogen constituted 57.5% ; the pro- portion of dry bacteria in dry faxes was 30% and the weight of dry bacteria 6.2 grams a day.When 500 C.C. of distilled water were added to the usual water ingestion (100 c.c.) a t each meal there was a decrease in bacterial nitrogen; when the amount was in- creased to 850 C.C. per meal this decrease was more pronounced. The addition of water leads to better utilisation of proteins and better digestion and absorption ; this beneficial result continued during the periods after the water ingestion. Copious water drinking lessens the urinary indican. Studies in Water Drinking. XVI. Influence of Distilled Water Drinking with Meals on Fat and Carbohydrate Utilisa- tion. N. R. BLATHEBWICK and P. B. HAWK (J. Amer. Chem. Soc. 1914 36 15!2-157).-Mattill and Hawk (A. 1912 ii 64) ob- served a slight improvement in the utilisation of fat when large volumes of freshly-prepared aoftened water were taken with meals.I n an experiment now described two young men were given a uniform diet and the effect of the copious ingestion of distilled water was studied. It was found that the utilisation of fat and carbohydrate was not appreciably affected. Studies in Water Drinking. XVII. Ammonia Output as an Index of the Stimulation of Gastric Secretion following Water Ingestion. F. WILLS and P. B. HAWK (J. Amer. Chem. Soc. 1914,36 158-165).-8 study of the effect on two men of drinking water with meals showed that an increase took place in the amount of ammonia excreted which was directly proportional to the extra volume of water ingested. Evidence is adduced which indicates that this increase was directly due to the stimulation of gastric secretion by the water.It is suggested that the uniform relation between the water ingested and the ammonia excreted may be regarded as indicating an attempt on the part of the gastric cells to maintain a uniform acid concentration. The increased amount of ammonia excreted per 100 C.C. of water ingested was a little higher when moderate quantities of water were drunk than when very large voJumes were taken. The increase in the output of ammonia by one subject was 100% greater than in the case of the other in spite of the fact that the ingestion of water was increased by the same amount in each instance. During the period of the ingestion of large volumes of water reduced indican values were observed which indicates that the increase in the ammonia ex- cretion did not arise from intestinal putrefaction.Intermediary Purine Metabolism. I. The Purine Store in the Liver and its Relationship to Uric Acid Excretion. HANS ROSENBERG (Chem. Zentr. 1913 ii 1691-1692 ; from Zeitsch. expt. Path. Ther. 1913 14 245-254).-Certain purine derivatives can be W. D. H. E. G. E. G.i 224 ABSTRACTS OF CHEMICAL PAPERS. removed from the surviving liver of a dog by perfusion even when the animal has been kept on a purine-free diet. The amount can be altered (a) before the perfusion (with blood) by the alteration of the diet the amount being diminished by a purine-free diet and increased by a purinerich diet; ( b ) during the perfusion by drugs. Atophan and adrenaline increase the amount.The author draws the conclusion that the liver can store puSine substances in the same manner as it does glycogen and fats. When the amount reaches a certain limit the organ becomes saturated and the purine sub- stances enter the circulation. This fact will explain the variations in the uric acid excretion with purinefree and purine-rich diets. I n gouty subjects the saturation point is raised owing to the slow action of enzymes. Atophan can influence these pathological (and also the physiological) conditions by making the flow of purine substances from the liver continuous. S. B. S. Intermediary Purine Metabolism. 11. Uric Acid Piqure. EDGAR MTCHAELIS (Chern. Zentr. 1913 ii 1692; from Zeitsch. exp. Path. They. 1913 14 255-261).-The Claude Bernard piqzZre pro- duces in rabbits a transient but very marked increase in the allantoin excretion and a change in that of the other nitrogenous substances.The author believes that the sugar centre also controls the purine metabolism of the liver and has a marked influence on the general metabolism. The Influence of Diet on the Formation of Indole in the Organism. D. M. BEBTRAND (Ann. lnst. Pasteur 1913,27,76-82). -It was found that rabbits when fed with carrots excreted no indole derivatives in the urine whereas those fed on potatoes con- tained these substances. Detailed examination of the bacterial flora of the intestine failed t o reveal any marked difference between the animals fed on different diets. It is known that B. coli in the presence of a medium from which indole can be produced do not give rise to this substance when sugar is added.They attack by preference the latter producing acidity and do not degrade the proteins to indoles. The difference of indole production when the animals are fed on carrots and potatoes may be due therefore to the differences in the degradation of the carbohydrates and the presence or absence of acids in the intestine. S. B. S. S. B. S. Retention of Nitrogen after Feeding on Ammonium Salts and Urea. E. GRAFE (Zeitsch. physiol. Chem. 1913,88 389-424).- A discussion of the way in which the nitrogen is retained in the body after feeding on ammonium salts and urea. Further experi- ments on pigs are described which lead to the conclusion that the form in which the nitrogen is retained must be in combination as protein or protein-like substances.W. D. H. Fat Absorption. 111. Changes in Fat During Absorption. W. R. BLOOR (J. Biol. Chem. 1914 16 51'7-529).-During absorp- tion the lowering of melting point of fats of high melting pointPHYSIOLOGICAL CHEMISTRY. i. 225 points to an addition of an unsaturated (probably oleic) acid. An elevation of the melting point and lowering of iodine value in fats of low melting point points to an addition of saturated fatty acids. I n cocoanut oil which consists mainly of glycerides of saturated fatty acids there is addition of oleic acid without change in the melting point. I n cod liver oil which contains a large percentage of glycerides of highly unsaturated fatty acids lowering of the iodine value occurs. The intestine shows a tendency in producing these changes t o bring about a chyle fat of uniform nature presum- ably the characteristic body fat of the animal.W. D. H. The Rate of Absorption of Cholesterol from the Digestive Tract of Rabbits. EDWIN P. LEHMAN (J. BioZ. Chem. 1914 16 495-503).-1t is possible by giving rabbits small doses of chole- sterol by the mouth to demonstrate in the majority of experiments an increase of this substaace in the blood in the course of a few hours. W. D. H. Fatty Acids of Hen’s Eggs. V. H. MOTTRAM (Proc. physiol. Soc. 1913; J. Phpiol. 47 xviii-xix).-The iodine values of the fatty acids from hen’s eggs show that in the eggs from any one hen there is great constancy yet the value differs widely in different hens even of the same stock.In the first week of incubation whether the eggs are fertile or infertile the iodine value rises. Here there is a case in which the desaturation of fatty acids occurs independently of the action of the liver. W. D. H. The Galactosides of the Brain. I. OTTO ROSENIIEIM (Biochem. J. 1913 7 604-610).-A new method for the preparation of the two galactosides of the brain by means of pyridine is described and evidence is adduced that they exist in the brain in the preformed sta t-e. W. D. H. The 8ugar Consumption in the Surviving Normal and Diabetic Heart. E. W. H. CRUICKSHANK and S . W. PATTERSON (J. Physiol. 1913 47 381-388).-There are wide variations in the amount of dextrose disappearing from the fluid perfusing normal hearts and in diabetic hearts the glycogen content is inversely proportional to the disappearance of sugar.I n one case of a diabetic heart no sugar disappeared and a t the end of the experi- ment the heart still contained 0.4% of glycogen. I n another case no sugar consumption occurred until the second hour; this is ascribed to a failure in the glycogen store thus throwing the heart on to the sugar in the circulating fluid. Both in normal and diabetic hearts the heart uses up ita local store of glycogen in preference to drawing on the sugar circulating through it. As the local store varies so variations in the utilisation of the circulating fluid occur. I n diabetic hearts there is no abolition of the power t o utilise sugar but there may be a diminution in this power. W. D. H. VOL. CVI. i. Qi. 226 ABSTRACTS OF CHEMICAL PAPERS.The Influence of Carbon Dioxide on the Heart in Varying Degrees of Anaesthesia. E. P. CATHCART and G. H. CLARK ( J . Physiol. 1913 47 393-406).-When aazesthesia is deep and carbon dioxide has no effect on the amplitude of the heart beat there is no rise of blood-pressure although according to Starling and von Anrep the gas should provoke the secretion of adrenaline. With light anaesthesia when the amplitude of the heart is increased the rise of blood-pressure occurs. Further work is in progress before generalisations are possible. W. D. H. Glycogen and Sugar Formation in the Isolated Livers of Warm-blooded Animals. HERMANN K. BARRENSCHEEN (Biochem. Zeitsch. 1913 58 277-314).-1t is possible under suitable experi- mental conditions (with the use of the Mendel-Friese perfusion apparatus) tu produce glycogen in the surviving livers of rabbik and dogs.This happens when dextrose and Imulose are added to the perfusing blood. Under these conditions glycogen is not produced when lactic acid glyceric acid glycerol and glycol- aldehyde are substituted for the above-mentioned sugars. They give rise however to sugar when perfused through the livers of dogs which have been rendered glycogen-free by phloridzin treat- ment. Pyruvic acid alanine and serine do not give rise to sugar in the isolated liver. Livers removed from animals five to thirty- two days after removal of the pancreas are no longer capable of forming glycogen from dextrose or laevulose when added t o the perfusion blood (taken from normal animals) even after addition of extract of pancreas t o the perfusion fluid.If the pancreas is only partly removed the glycogen-forming function remains intact. The destruction of the liver function is not due t o the effects of operation and neither laparotomy nor adrenaline poisoning destroys the glycogenic functions. On the other hand phloridzin poisoning does prevent the liver from forming glycogen although the sugar-f orming function (from lactic acid glycerol etc.) remains intact. The destruction of the glycogenic function by phloridzin is not due therefore to the fatty infiltration into the liver. S. B. S. The Change of Lzevulose into Dextrose in the Artificially Perfused Liver. S. 'ISAAC (Zeitsch. physid. Chem. 1914 89 78-90). -In liver perfusion laevulose is changed into dextrose with great rapidity.Lzevulose may therefore quite well be an intermediate substance in dextrose formation as Embden and others have suggested. 111 laevulosuria i t is possible that the conversion does not occur. W. D. H. Negative Experiments on the Influence of %he Pancrem on Acetoacetic Acid Formation in the Liver. H. D. DAEIN and H. W. DUDLEY (J. Bid. Chem. 1914 16,515-516).-The addition of pancreas extract to blood perfused through dogs' livers had no marked effect on acetoacetic acid formation from butyric acid hornogentisic acid or tyrosine. The experiments were undertakenPHYSIOLOGICAL CHEMISTRY. i. 227 in the hope of clearing up the relationship between acetoacetic acid excretion and extirpation of the pancreas. Glyoxalase. IV.H. D. DAKIN m d H W. DUDLEY ( J . B ~ o l . Chem. 1914 16 505-513).-Glyoxalase is present and antiglyoxalase absent in all the glands of the body examined except the pancreas and the abdominal lymphatic glands; the anti-action of the latter is however trifling compared with the pancreas. The antiglyoxa- lase of the pancreas is a specific function of that organ and acts mainly by way of an internal secretion. Contrary to Neuberg’s statement it was found that glyoxal may be converted into glycollic acid by enzyme action. Glyoxalase is not the same as aldehydemutase (Neuberg) for the latter is unaffected by extracts of the pancreas. The Iodine Content of the Thyroid and of Some Branchial Cleft Organs. A. T. CAMERON (J. Biol. Chern. 1914 16 465-473). -Further support is given to the view that iodine is an invariable constituent of thyroid tissue; it is found in the thyroids of pigeon alligator frog and dogfish.Iodine is absent in the ventral branchial body of the frog. In the parathyroids of the dog the iodine is probably due to contamination with thyroid tissue. There is doubtless a differentiation of function between the two organs. W. D. H. W. D. H. W. D. H. The Action of Leucocytea and of Kidney Tiesue on Amino- acids. P. A. LEVENE and G. M. MEYER (J. Biol. Ch-m. 1914 16 555-557).-The authors previously found that leucocytes and kidney tissue produce no deamidation of alanine. The same negative result was found with other amino-acids (glycine aspartic acid asparagine leucine). Lactic Acid Formation Survival Respiration and Rigor Mortis in Mammalian Muscle.W. M. FLETCHER (J. Pfiysaol 1913 47 361-380).-b excision rabbit’s muscle contains but little lactic acid (estimated by tlie zinc gravimetric method) and this is accounted for by contractions just before or after death and by the manipulative treatment. A maximum yield is reached after the third hour from excision. The acid production is slower than in pale muscle. The survival output of carbon dioxide a t body temperature increases for a short time after excision and then declines to zero if uninterrupted by evolut,ion of the gas due t o bacteria. A t room temperature or in red muscles at body temperature there is no preliminary increase. The yield of carbon dioxide is due t o lactic acid displacing the preformed gas from loose combination. There is apparently no independent new formation of carbon dioxide.The post-mortem shortenings of white and red muscles were recorded but the time relations of the two kinds given by Bierfreund were not confirmed. The Origin and Destiny of CholerJterol in the Animal Organism. XI. The Cholesterol Content of Growing Chickens under Different Diets. J. A. GARDNER and P. E. LANDER (PTOC. Roy Soc. 1914 [ B ] 87 229-236).-Batches of chickens were fed on W. D. H. W. D. H. VOL. CVI. i. 7-i. 228 ABSTRACTS OF CHEMICAL PAPERS. normal diet diet freed from cholesterol and diet with cholesterol added. They were subsequently killed and analysed. The results for the first two weeks of growth show that the cholesterol content depends only on the cholesterol content of the diet and there is no indication\.that in the growing animal there is any power to synthesise cholesterol. It has previously been shown that in the egg there is no cholesterol synthesis. Cholesterol Contents of the Tissues of Cats under Various Dietetic Conditions and During Inanition. JOHN ADDYMAN GARDNER and PERCY EDWARD LANDER (Biochem J. 19 13,7,576-587). -The results agree with those obtained by Ellis and Gardner in the rabbit namely that cholesterol is a constant constituent of cells and when these break down it is utilised in the formation of new cells. The liver breaks down old cells and their cholesterol passes into the bile; this is reabsorbed probably as esters and then utilised in cell construction. Waste is made up from the cholesterol of the food.W. D. H. W. D. H. A Fat from the Butterfly H. THOMS (Chem. Zenti’. 1913 ii 2052 ; from Arb. Pharm. Inst. Univ. Berlin 10 180-181 ).-The fat was derived from Myelobia smerintha Huh. from which it was obtained in a 22% yield. It is yellowish-white of similar consistency to butter and optically inactive. The specimen examined was slightly rancid and had m. p. 29O; solidifying point 24O ; acid number 51.8 ; saponification number 192.7 ; iodine number 53.7 ; Reichert-Meissl number 0.74 ; Polenski number 0-84; Hehner number 96.5. The separated fatty acids had m. p. 46O; solidifying point 4Z0 ; saponification number 194.5 and yielded 56.8% liquid and 33.6% solid acids. The presence of stearic acid and of a liquid acid which yields elaidic acid m. p. 4 4 4 6 O was established.H. W. Influence of Cold Storage on the Composition and Nutritive Value of Fish CLAYTON S. SMITH (Biochent. Bull. 1923,3 54-68). -No change in the chemical composition or nutritive value of fish is noticeable during or after nine months’ coId storage. W. D. H. Influence of Prolonged Periods of Cold Storage on the Com- position and Nutritive Value of Fisb. WILLIAM A. PERLZWEIG and WILLIAM J. GIES (Biochem. Bull. 1913 3 69-71).-After two years’ cold storage the fish undergo no change in chemical composition o r nutritive value. This applies to fish which are fresh when placed in storage. The Alleged Excretion of Creatine in Carbohydrate Starva- tion. GEORGE GRAHAM and E. P. POULTON (Fvoc. Roy. Soc 1914 B 87 205-220).-In the present experiments on men a diet free from carbohydrates caused no excretion of creatine.The statement of others that i t does so is due to the fact that under this condition acetoacetic acid is excreted and this invalidates the analysis by the W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 229 Folin method. The error increases with the amount of acetoacetic acid and in amounh less than those which may occur in the urine may rise to more than 50%. The estimation of creatinine is there- fore too low when acetoacetic acid is present. In the processes involved in the conversion of creatine into creatinine the acetoacetic acid is removed and so the estimation of creatine + creatinine is correct. As the creatinine figure is too low and the creatine+ creatinine figure correct the conclusion is erroneously drawn that creatine has been excreted. It is therefore necessary to remove acetoacetic acid before creatinine is estimated and a method for this purpose is described.duce no error. Acetone and B-hydroxybutyric acid pro- w. D. H. Presence of Tyrosine Crystals in a Urinary Sediment. Y. J U ~ E (J. Pham. chim. 1913 [vii] 8 559-561).-Two specimens of urine from the same patient one taken immediately after his arrival from Vichy and the other ten days later were examined. The first was of dark yellow colour and of normal composition although there was a slight deficiency of urea and traces of protein and reducing sugars were present. The slight sediment consisted of uric acid calcium oxalate epithelial cells and very occasional leucocytes and granular hyaline cylinders.The second specimen showed an increase of all soluble constituents with the exception of urea which remained constant. The reducing sugar amounted to 1-81 grams per litre (1.99 grams in twenty-four hours) but protein was only present in traces. The sediment was abundant and heavy and consisted of crystals of tyrosine (yellow silky needles separate or partly or wholly united into spherical aggregates) calcium oxalate epithelial cells and very occasional leucocytes. Tyrosine is rarely found in urine and when it does occur is usually accompanied by leucine. Its occurrence is as- sociated with liver diseases among many other varieties of patho- logical conditions. T. A. H. Intermediate Reduction Processes in Physiological Break- down. F. KNOOP and RICHARD OESER (Zeitech.physiol. Chem. 19 14 88,141-148).-Unsaturated acids can be converted into saturated acids in the animal body; *CO and *CH(OH)* groups can be reduced to methylene groups. The presence of carbonyl groups or double unions in the removed part of an acid molecule remote from the carboxyl has no influence; but there appear to be reduction processes which are more easily brought about in the neighbourhood of the carboxyl groups. Theory of Diabetes. 11. GClycide and Acetol in the Normal and Phloridzinised Animal. J. R. GREER E. J. WITZEMANN and R. T. WOODYATT (J. Biol. Chem. 1914 16 455-464).-Glyc:de ~Hz>CH*CH,*OH was prepared in pure form and given to dogs; 0- i t is very toxic doses of 0.3 to 0.4 gram per kilo. of body weight causing narcosis and twitchings; larger doses kill.The ring is no doubt opened in the body with difficulty. W. D. H. r 2i. 230 ABSTRACTS OF CHEMICAL PAPERS. Acetol OH*CH,*CO*CH is relatively non-toxic ; doses of 2 grams per kilo. do not kill but even moderate doses cause hzmab uria and hzmoglobinuria. I n phloridzinised dogs given by the mouth or under the skin it causes no output of extra sugar and some unchanged acetol may appear in the urine. There is an apparent rise also of acetone substances. The conclusion is drawn that in the body i t dissociates into acetaldehyde and hydroxy- methylene but it is not an intermediate between substances of the formula c6H&6 and those of the formula C,H,O,. \IT. D. H. The Lactic Acid of the Muscles in Diabetes Mellitus and the Glycolytic Power of Muscles.J. FORSCHBACH (Biochem. Zeitsch. 19 13 58 339-342).-1n dogs with severe diabetes twenty days after the extirpation of the pancreas there was found in the muscles a diminution both of lactic acid and of lactacidogen the substance from which the lactic acid is formed. For the investiga- tion of the latter Embden's method was employed. S. B. S. The Mechanism of Certain Forms of Hyperglycaemie Produced Experimentally in Rabbits. IVAR BANG (Biochem. Zeitsck. 1913 58 236-256).-In view of the fact demonstrated by the author and others that psychic excitation of the animal pro- duces hyperglymmia it is necessary to repeat various experiments in which excess of sugar in the blood is produced under conditions which exclude this excitation. The influence of various narcotics on hyperglyczmia was therefore investigated with the object of finding a product which whilst sufficiently active t o exclude psychic excitation by itself produces no hyperglyczmia.It was found that by a combination of urethane with ether complete narcosis could be produced in which hyperglywmia was only produced after a long period; this differs therefore from the psychic hyper- glyczemia of which the onset is rapid. Under ether-urethane narcosis neither the operative procedure of exposing the carotid artery nor the removal of blood produced hyperglyczmia. Vene- section by itself does not appear therefore to cause hyperglymmia; the results of previous authors who ascribe hyperglyczmia to this effect are due to psychic excitation. PiqGre produced in animals narcotised with urethane and ether only a slight hyperglyczmia and in two out of three experiments no glycosuria.I n the ab- sence of ether (urethane narcosis only) the glycosuric effect was marked in both experiments performed. Narcosis also suppresses diuretin hyperglycaemia and glycosuria which may also theref ore be ascribed to psychic effect of the pain produced by the injection. The ether-urethane narcosis is a light one. Deep narcosis on the other hand appears to intensify various effects. The author gives in outline a general theory as to the methods by means of which hyperglyczmia can be produced. S. B. S. The Sugar of Pentosuria.. ERNST ZERNER and RUDOLFINE WALTUCH (Biochem. Zeitech. 1913 58 410-414).-The authors review the recent literature on this question and recapitulate somePHYSIOLOGICAL CHEMISTRY.i. 231 of their own results. They draw the conclusion that there are two kinds of pentosuria namely those due to the presence of dZ-arab- inose and those due to a sugar of the d-xylose group Disturbances of Garbohydrate Metabolism in Experimental Diphtneria. FELIX ROSENTEAL (Arch. expt. Palh. Phurm. 19 14 75 99-1 2 2) .-After diphtheria poisoning in animals carbohydrate metabolism a t first is unaltered; this is followed by a stage of dis- appearance of the liepatic glycogen without hyperglycaemia then by a stage of diminished glycogen fixation and finally by paralysis of carbohydrate formation with rapid disappearance of the blood sugar. The liver changes appear to be secondary to those in the suprarenal bodies. W.D. H. Pellagra. I. The Influence of the Milling of Maize on the Chemical Composition and the Nutritive Value of Maize Meal. CASJMTR FUNK (J. Phpsiol. 1913 47 389-392).-Tn maize a8 in rice the vitamines are chiefly in the outer layers. I n different countries the mode of preparation of maize meal varies and the manifesta- tions of pellagra vary from mild to severe forms. Milling also deprives the grains of much salt protein fat and lipoids. The present mode of milling should be abandoned and the whole grain used. W. D. H. The Secretion of Gastric Juice during Parathyroid Tetany. ROBERT W. KEETON (dmer. J. Physiol. 1914 33 25-49).-Aftt.r parathyroidectomy in cats the quantity acidity and digestive power of the gastric juice are reduced.During active tetany no relation between the secretion and the symptoms has been traced. When tetany is replaced by depression the secretion improves; improvement also occum when calcium salts are injected. S. B. S. W. D. H. The Influence of Parathyroid Tetany on the Liver and Pancreas. 0. 0. STOLAND (Amer. J. Physiob. 1914 33 283-299).- During parathyroid tetany in dogs no change in sugar tolerance is observed the blood fibrin is increased the amino-acids and ammonia of the urine are unchanged and the secretion of bile and pancreatic juice is lessened; the last condition appears to be secondary to the condition of the digestive tract. There is no other hepatic deficiency. W. D. H. The [Physiological] Action of Nitrous Oxide at High Pressures. JOHANNES BOCK ( A ~ c h .expt. Path. Z'harm. 19 13 75 43-52).-The lowest fatal pressure of nitrous oxide for rats is that of 3 atmospheres. The time it takes to kill varies from eight to twenty-two minutes. The cause of death is paralysis of the respiratory centre. W. D. H. The Effects of Nitrogen Peroxide on the Constituents of Flour in Relation to the Commercial Practise of Bleaching Flour with that Reagent. BENJAMIN MOOHE and J. T. WILSON (J. Hygiene 1914 13 438-466).-Bleaching by nitrogen peroxido isi. 232 ABSTRACTS OF CHEMICAL PAPERS. not a more rapid achie.vement of a slowly occurring natural procss; the natural whitening of flour is due to oxidation of the pigment carrotene; bleaching by nitrogen peroxide is due to a formation of additive compounds with the pigment.Nitrogen peroxide alters both fats and proteins by nitrating them; although the changes in the commercial process are small it cannot bs assumed that their continued ingestion over years is immaterial to health. The process of bleaching is condemned on ethical and economic grounds also. W. D. H. Astringent Action of Aluminium Salts. CARLO BARINETTI (Ch,em,. Zentr.. 1913 ii 1934-1935 ; from Arch. Fwm. 8perirn. 1913 16 210-240).-Aluminium salts give precipitates with organic colloids (blood serum white of egg muscle extract gelatin tissue) and precipitation attains a maximum when colloid and aluminium salt are present in a definite proportion. With excess of either reagent coagulation is a reversible process. If the coagulum remains for several hours in contact with an excess of the aluminium salt the reaction is no longer reversible.Amounts of aluminium salts which axe insufficient to cause coagulation bring about pro- found changes in the physical condition which can be followed by determination of viscosity and densitv; these changes are also those which subsequently lead to preiipitation of the colloid. Precipitation is probably not due to the Al-ion but to hydrolyti- cally formed aluminium hydroxide. The therapeutic action of aluminium salts is generally attributable to the precipitation of colloids and the usual medicinal solution containing 2 4 % of potassium aluminium sulphate represents exactly the concentration which is found necessary to yield a precipitate with blood aerum. The same relationships are observed with aluminium sulphate and aluminium chloride but reaction occurs in a smaller interval of time.Addition of potassium sulphate to potassium aluminium sulphate weakens the reaction of the latter by diminishing the ionisation. Experiments with blood in vitro show that aluminium salts greatly prevent coagulation ; a t greater concentration coagula- tion of blood occurs which corresponds with the coagulation in the experiments with serum. A t extreme concentration of aluminium salts the coagulum is again dissolved. The increase in the resist- ance of the red corpuscles and the lowering of the extensibility of the tissues which takes place in contact with aluminium salts are due to the fixation of the latter by the gelatinous cell proteins. The astringent action of aluminium salts is the result of physic* chemical modifications of the intracellular colloids and of the colloids of the histological elements whereby the resistance of the tissues is increased and the velocity of resorption of toxic products diminished.Intravenous injection of sodium aluminium sulphate causes non- coagubility of the blood; a direct action on the heart causes paralysis of the latter. The toxicity increases with increasing concentration of the injected solution. H. W,PHYSIOLOGICAL CHEMISTRY. i. 233 The Influence of Caffeine on the Excretion of Creatine and Creatinine. WILLIAM SALANT and J. B. RIEUER (Amer. J. Physiol. 1914 33 186-203. Compare A. 1913 i 547).-The effect of caffeine in rabbits and dogs on the excretion of creatine and creaticine is variable and depends largely on the diet; the differ- ence is attributed to differences in the amount and rate of trans- formation of glycogen. Stimulation of the nervous system or muscles per se does not affect creatine-creatinine metabolism nor the excretion of nitrogen.The effect of a substance on protein metabolism is not a safe guide for drawing inferences regarding its toxicity. W. D. H. The Influence of Dextrose and of Sodium Potassium Calcium and Magnesium Ions on the Excitability Con- tractility and Fatigue of Motor Nerves and Skeletal Muscle. ROBEHT BENDA (Zeitsch. BioZ. 1913 63 11-77).-.The influence of dextrose and aucrme diminishes the fatiguability of the muscle- nerve complex (frog) especially if the muscle is poorly nourished. If however thO fatigue is intense as when the sodium ions are diminished sugar has little or no effect; although treatment with a fluid containing less sodium ions than normal leads to small contractions of the muscle its excitability rises ; the two functions are therefore different.Other salts were investigated direct and indirect stimulation of the muscle being employed ; potassium ions as a rule depre+ss excitability and contractility but numerous exceptions are noted. Experimenh with calcium and magnesium ions bring out the difference between muscle and nerve fatigue. W. D. H. Influence of Phytin on the Separation of Nitrogen Corn- poundB in Normal Individuals. FRANCESCO VENTURI and VLADIMIRO MASSELLA (Chem. Zentr. 1913 ii 1935; from Arch. Farm. sperina. 1913 16 97 -1 18).-Dsily administration of 1'5-2 grams of phytin diminishes the output of carbamide. Uric acid and ammonia elimination remain practically unchanged whilst extractive nitrogen (creatinine hippuric acid xanthine bases) are greatly diminished. A t the same time loss of nitrogen in the faxes is lessened 50 that the nitrogen balance in the phytin periods is four to five times as great as in the normal periods.H. W. Pyrobromon a New Organic Bromo-compound. GIULIO NARDELLI (Chem. Zentr. 1913 ii 1935 ; from Arch. Farm. sperim. 1913 16 169-177).-Pyrobromon C,,H,,ON,Br white needles m. p. 190° is a bromo-compound of pyrazolone. It has a faintly acid taste. Determinations of rubazonic acid C20H1702N6 and of bromine in urine show that the elimination of pyrobromon speedily commences (five minutes after intravenous twenty minutes after subcutaneous and thirty-five minutes after oral administration) and is comparatively rapidly complete (after twenty-four hours).The toxic doses are 0*12-0*15 gram by intravenous 0*50-0*60 gram by subcutaneous and 1.10-1.20 gram by oral administra-i. 234 ABSTRACTS OF CHEMICAL PAPERS. tion whilst the lethal doses are 0.20 0.80 and 1.40 gram respec- tively. Doses up to 1.0 gram are readily tolerated by man whilst larger quantities occasion intestinal disturbance ; 0.5 gram (sub- cut,aneously) led to a slight reduction in the blood pressure in a rabbit but a similar effect could not be observed in man whilst action on the kidneys and respiratory system was not evident. The nervous system of healthy persons is not affected but a thera- peutic action is noticed with epileptic subjects.The temperature is lowered in fever. H. W. Lipoproteins. The Action of Lipoproteins in vivo. G. IZAR and C. PATANB (Biochem. Zeitsch. 1913 58 195-201).- Emulsions of compounds of various proteins with palmitic stearic and other fatty acids when injected into sparrows and rabbits in sufficient doses cause the death of the animals. The symptoms are similar to those produced by the injection of aqueous emulsions heated for one hour at 50° of methyl-alcoholic extracts of testes pancreas and thyroid. Exophthalmos is not however produced The symptoms produced by sub-toxic doses (paresis convulsions etc.) are only very transient. Injection of small doses of the lipo- proteins causes a diminution of the complement of the blood.Sub-lethal doses of the lipoproteins do not render the animals resistant to immediate subsequent lethal doses and in this respect they differ from certain organic extracts. The toxicity of the latter is increased on heating the aqueous emulsions to 50° for one hour. This phenomenon is observed only to a very small extent with tlhe lipoprotein emulsions. The Action of Strophanthin on the Oxygen Consumption of the Frog’s Heart. GERTRUD GOTTSCHALK ( A ~ c h . expt. Path. Pitarm. 1913 75 33-42).-The principal action of strophanthin on the oxygen consumption of the frog'^ heart is never stimulating; the lowering action is probably indirectly the result of inhibition of the mechanical function. W. D. H. S. B. S. Copper Balance on Seven Experimental Subjects to Deter- mine the Effect of Eating Coppered Vegetables.CARL L. A. SCHMIDT (J. Arner. Chern. Soc. 1914 36 132 -136).-An account is given of an experiment in which seven men were put on a constant diet which included vegetables coloured with copper. The amount of copper excreted was estimated in each case. After making the necessary allowance for copper normally ingested in foods the results’ indicated clearly that part of the copper had been retained in the system. It is probable that copper so retained would be but slowly eliminated. E. G. The Action of Poisons which Affect Body-temperature on Animals which have no Heat Regulation. I. Sodium Salicglate Antipyrin. Quinine Morphine. R. ISENSCHMID (Arch. rxpt. Path. Pharm. 1913 75 10-32).-1n rabbits in which central heat regulation was excluded sodium salicylate in smallVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 235 doses causes a rise of temperature which is independent of motor stimulation. Antipyrine in the paralysed animals causes no alter- ation in the utilisation of energy; and in those not paralysed a small increase in heat development is due to motor unrest. Quinine in moderate doses produces a fall of heat production; in large doses this effect may be masked by the result of motor stimulation. Morphine in the smallest doses depresses heat development ; in paralysed animals this is not so marked and is produced by the result of depression of mobility. W. D. H. Synergism of Poisons. 111. The Antagonistic ‘Influence of Solubility of Narcotics. HERMANN FUHNER ( A ~ c h . exp. Path. Pharm. 1913,75,53-74).-Numerous narcotics throw others out of aqueous solutions; in strong solutions in the case of those which are slightly soluble separation in the form of drops may occur; in dilute solu- tions the smaller amount in solution may be detected by the capillarimeter or stalagmometer. I n organic solvents many pairs of narcotics may undergo increase of solubility which can be ex- plained as a shifting of the partition coefficients. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9140600217

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ii. 229 General and Physical Chemistry. The Refractive Indices and Dispersion of Liquid Hydrogen. H. W. W. AUGUSTIN (Chum. Zentr. 1914 i 609; from Bey. K. Suchs. Ges. Wtss. 1913 65 229-336).-The following values for the refrac- tive index of liquid hydrogen were obtained by Liveing and Dewar's method and are correct t o two units in the last place A ......... 656'3 579.0 546.1 435.9 404-7 n-1 ... 0.10924 0.10974 0'10003 0.11179 0.11262 The value for the density was D = 0.07086. Selective Reflexion of Solutions of Nitrides. a. I(. ANG~TROM (Zeitsch. physikal. Chem. 19 14 86 525-528).-The infra-red reflexion of saturated solutions of the nitrides of sodium potassium ammonium calcium and barium has been investigated by means of a spectroscope and a Nichol's radiometer. It is shown that in the region 1-lop there is only one selective reflexion position f o r the nitrides of sodium potassium and ammonium and this lies approximately a t 4 .9 ~ . It is shown from the reflexion curves that these nitrides have a strong absorption band between 4.6 p and 4 . 8 ~ which can be regarded as characteristic of the N group. This band is not exhibited by the saturated solutions of calcium and barium nitride but its absence is attributed to the small concentration of the salts in saturated solution. These nitrides show the characteristic reflexion a t 4.9 p. Determination of Tertiary Normal8 in the Region h 2987 to A4118 in the Arc Spectrum of Iron. HEINKICH ViaFaaus (Zeatsch. wiss. Photochem. 1914 13 209-234 245-264).-Receot work on the arc spectrum of iron which has been carried out by different observers with the object of determining the wave-lengths of lines which may be used as tertiary normals in spectroscopic investigations indicates that the conditions of the arc discharge have not been sufficiently sharply defined in the recommendations of the International Union.The requirement that the strength of the current should be from 5 to 10 amperes is quite insufficient and a more complete specification of the conditions of the dis- charge is found to be essential to the attainment of agreement between the results of different observers. The author's own measurements were made with an arc between cylindrical iron rods of about 1 cm. diameter the strength of the current being 7 amperes. Each line on the photographic plates was measured eight times under stipulated conditions and from these data the wave-lengths and the probable error of the measurements are deduced. Those lines f o r which the mean error does not exceed 0-003 A.are recom- mended for use as tertiary normals. The whole of the lines are grouped in a series of tables according to the magnitude of the mean error. J. C. W. J. F. S. VOL. CVI. ii. 16ii. 230 ABSTRACTS OF CHEMICAL PAPERS. A comparison of the results with those obtained by Burns (A. 1913 ii 541 and following abstract) shows that the agreement between the wave-length values of lines which have been measured by both observers is not nearly so good as would be expected from the magnitude of the errors which are assigned to the measurements by the individual observers.Arc Spectrum of Iron. H. BURNS ( Z d s c h . wiss. Photochem. 1914 13 235-244. Compare A. 1913 ii 541).-Further measure- ments of wave-lengths have been made by the method described previously. The recorded data have reference to lines between A5434 and ~ 8 8 2 4 . From observations made with an arc between two nickel eleo trodes and also with an arc between a nickel and an iron electrode it has been found that the nickel lines obtained under the latter conditions are too diffuse for use as normal lines. From the measurements of barium lines in the iron arc it is found that the wave-lengths are shorter than those recorded for the same lines in a carbon arc. Similarly it is found that the manganese lines measured by the author in the iron arc spectrum have wave-lengths greater than those recorded by Kilby (Astrophys.J. 1909 30 243) in the case of 75% of the lines examined. In some few cases however the author’s values indicate that the lines are displaced towards the violet end. H. M. D. The Optical Effect of the Different Alkali and Alkaline Earth Metals in Salt Formation in the Ultra-violet. A. HANTZSCH (Eeitsch. physikal. Chem. 19 14 86 624-632. Compare Hantzsch Garrett and Gajevski A. 1913 ii 893).-The absorp- tion spectra of the acetates and trichloroacetates of the metals of the alkalis and alkaline earths have been determined in various solvents a t a series of concentrations in the neighbourhood of ~ 4 0 0 0 . It is shown that ionisatiou even in the extreme ultra- violet is an optically indifferent process and that sometimes but not always the solvate formation preceding ionisations as well as the salt formation of carboxylic acids bring about small optical and chemical changes.Normal salt formation is also an optically indifferent process and the hypsochromatic and bathochromatic effects sometimes produced are due to a difference in constitution between the acid and its alkali salt. All alkali and alkaline earth salts of the same acid possess an identical absorption. From the last fact the conclusion is drawn that every noticeable difference in the absorption of alkali and alkaline earth salts of the same acid even in the presence of two polychromatic forms of the same salt is a direct proof that the salts in question can exist in two chemically different chromatic isomerides. Influence of the Ethenoid Linking and the Carbonyl and Carbvxgl Groups on the Absorption of Ultra-violet Rays.JEAN BIELECKI and VICTOR HENRI (Compt. rend. 1914 158,567-570. Compare this vol. ii 7).-In continuation of the study of the H. M. D. J. F. S.ii. 231 GENERAL AND PHYSICAL CHEMISTRP. influence of constitution on the absorption of the ultra-violet rays the authors have now obtained the following results. The band characteristic of the carbonyl group is displaced towards the red by a carboxyl group in a conjugated position whilst if it is in the y-position there is no displacement of the band but an increase in the absorption. Similar results are obtained by an ethenoid linking in.a conjugated and a y-position and a t thk same time in the first position a new band appears in the extreme ultra-violet towards ~ = 2 3 5 0 .If the molecule contains a carbonyl group and two ethenoid linkings which latter occur either one or both in conjugated positions in the first case the band characteristic of the carbonyl group is displaced slightly towards the red whilst in the second case this displacement is twice as great. I n both cases the band due to the ethenoid linking is present but in the second case it also is displaced towards the red. When a molecule contains two chromophores they influence one another mutually. If they are not too close to one another in the molecule there is simply an increase in the absorption or a hyper- chrome effect whilst if they are in conjugated positions there is a displacement of the characteristic bands of each chromophore towards the red or a hypsochrome effect.W. G. Absorption Spectra and Constitution of Benzene Deriv- atives IV. Binuclear Compounds Diphenylamine Diphenyl Ether and Diphenylmethane. N. A. VALIASCHKO and G. M. DRUSHININ (J. Buss. Phys. Chern. Xoc. 1913 45 ~014-2063).-1n- vestigations similar to those previously published (A. 1913 ii 367) have been made on aniline methylaniline diphenylamine p-aminodiphenylamine p-phenylenediamine acetanilide methyl- acetanilide diacetanilide acetyldiphenylamine anisole diphenyl ether toluene and diphenylmethane. The results obtained show that aniline methylaniline dimethyl- aniline and p-phenylenediamine are completely analogous to the alkali derivatives of phenols their molecules existing in a strongly developed phenolic form in dynamic equilibrium with a feeble a-modification.Acetanilide met.hylacetanilide and diacetanilide possess molecules oscillating between very weak phenolic and a-f orms. Toluene exhibits an absorption band intermediate t o that of benzene on the one hand and those of anisole and phenol on the other and must be regarded as feebly phenolic. With binuclear benzene derivatives two similar forms a and 4 exist. The presence of the two rings favours increased develop- ment of the two forms each ring inclining alternately to one or the other; a t one and the same time the two rings are in different forms + Z al + &. When the two rings are united by way of an imino-group or an oxygen atom the conditions exist for the development of a strongly phenolic form ; the absorption spectra of diphenylamine and acetyldiphenylamine are perfectly analogous to those of aniline and acetanilide and the spectrum of diphenyl ether to that of anisole.Connexion of the two benzene rings through a methylene group 16-2ii. 232 ABSTRACTS OF CHEMICAL PAPERS. creates conditions f avouring the development of the a-modification determined by the so-called quinonoid character of the compound ; introduction of a third benzene ring intensifies this modification. The above results have an intimate bearing on the various hypo- theses which have been advanced concerning the origin of the triphenylmethane colouring matters. They do not for example confirm von Baeyer’s hypothesis (A.1907 i 7571 since they indicate that even mononuclear non-colouring benzene compounds give rhythmic motion and possess characteristic absorption spectra the presence of two nuclei united by carbon atoms only resulting in* conditions especially favourable for the development of such motion. The authors’ results also lead further than the conclusions of Meyer and Fischer (A. 1913 ii 167) who compared the absorp- tion spectra of fuchsone and benzaurin and those of fuchson- imonium chloride and Dobner’s violet and found that no funda- mental difference exists between simple quinones and quinones containing an auxochrome group. The observations described above show that the absorption spectra of triphenylmethane colour- ing matters exhibit no essential difference from that of diphenyl- methane.The introduction of a third benzene ring or of an amino- or hydroxyl group or the conversion into ca_rbinol and the removal of water from the latter with the formation of a quinonoid struc- ture-if this really occurs-exerts an intensifying influence on the motion already in existence in the molecule and a t the same time retards it and consequently displaces the absorption spectrum towards the red. The spectrum of diphenylmethane is indeed the forerunner or original type of the spectra of the triphenylmethane colouring matters differing from these especially in the pronounced development of its a,-band and in the marked displacement of the whole spectrum towards the red. The chromogen must be regarded as a simpler compound than triphenylmethane namely either diphenylmethane o’r to go further back the benzene ring itself.These considerations are advanced in opposition to Hantzsch’s fundamental theorem stating that the typical chromophore of colouring matters arises only on conjugation of a quinonoid chromo- phore by means of supplementary valencies with a second unsatu- rated aniline o r phenol residue in which the benzene rings play a quite subordinate part (Zeitsch. Elektrochem. 1912 18 478). The suggestion cannot be excluded that compounds containing no benzene ring may under certain conditions give absorption spectra similar to those of benzene derivatives. Indeed Hantzsch has pointed out the similarity between the absorption spectra of nitrobarbituric acid and pnitrophenol.Under the influence of substituent groups the benzene nucleus may so change that its properties approximate t o those of unsaturated aliphatic com- pounds. Kaufrnann’s hypothesis of the constitution of triphenylmethane dyes (A. 1912 i 397) regards all the three nuclei as of the sameGENERAL AND PHYSICAL CHEMISTRY. ii. 233 kind and denies their conversion into the quinonoid form; this too is not in accord with the authors' observations. Baly and Tuck (T. 1908 93 1902) have shown that the absorp- tion spectrum of diphenylmethane is quite similar to that of anthracene so that diphenylmethane is also the chromogen of anthraquinone compounds. The relation between the latter and triphenylmethane dyes is thus established and the similarity between their absorption spectra explained.T. H. P. Production of a Very Intense Sodium Flame. R. W. WOOD (Phil. Mag. 1914 [vi] 27 530-531).-1f a small fragment of a Welsbach mantle is laid upon the grill of a Meker burner and two or three pieces of fused sodium chloride are placed on this a sodium flame of great brilliancy is obtained. The intensity is com- parable with that of the oxy-hydrogen sodium flame. The effect is due t o the spreading of the material over a large surface of very small heat capacity. Photometric Study of the Fluorescence of Iodine Vapour. R. FV. WOOD and W. P. SPEAS (Phil. Mag. 1914 [vi] 27 531-538.* Compare A. 1911 ii 82 169 950).-Further experiments on the fluorescence of iodine vapour have been made with the object of determining t o what extent the lumino'sity due to a molecule of iodine is diminished by the proximity of other iodine molecules.From observations of the intensity of the fluorescence a t different pressures i t is found that this increases rapidly with the pressure attains a maximum a t a pressure of 0.2 to 0.3 mm. and then decreases gradually. A t the lowest pressures the intensity is directly proportional to the number of iodine molecules but a t higher pressures the int'ensity is diminished in consequence of the interaction of the separate molecules. This intermolecular effect has already been observed when other gases are present in the tube containing the iodine vapour and on comparing the action of iodine with that of other gases and vapours i t is found that the intensity of the fluorescence is reduced to the same extent by hydrogen a t 24 mm.air a t 11 mm. carbon dioxide a t 7 mm. ether vapour a t 3 mm. iodine chloride a t 1.8 mm. and by iodine at a pressure of only 0.4 mm. The high activity of iodine vapour is t o be attributed t o its strongly electronegative character. The colour of the fluorescent light changes from yellow to red as the density of the iodine vapour increases and this is probably due t o absorption f o r i t has been found that the fluorescent light is more strongly absorbed by iodine vapour than light of the same colour which was obtained by filtering the light from a Welsbach burner through suitable colour-filters. The effect of absorption is however small in comparison with that which results from the mutual action between the molecules.H. M. D. G. PELLINI and A. COPPOLA ( A t t i €2. Accad. Lincoi 1914 [v] 23 i 144-150) -The data hitherto available do not suffice to show the nature of inactive alanine. By * and Phpikal. Zeitsch. 1914 15 317-321. H. M. D. Solubility and [Optical] Activity.ii. 234 ABSTRACTS OF CHEMICAL PAPERS. simultaneous measurements of solubility and rotatory power in various mixtures of d-alanine and I-alanine in water a t Oo 17O and 30° the authors obtain material for the construction of diagrams which indicate that inactive alanine is a true racemic compound and in a discussion of the curves obtained the authors show that they afford a t least a partial confirmation of Meyerhoffer’s rules regarding the solubility of optically active substances. The specific rotatory power of alanine hydrochloride in aqueous solution is independent of the concentration.Discovery of the Sensitiveness of Silver Salts to Light. FELTX FRITZ (Chem. Zeit. 19 14 38 246-247).-Historical. Schulze is generally believed to have been the first t o discover in 1727 the action of light on silver salts. The author points out however that W. Homberg in 1694 showed that when bones were immersed in a solution of silver nitrate they blackened on exposure to sun- light. The reference is found in “ Regiae Scientiarum Academiae Historia,” by Joanne-Baptista du Hamel. Chemical Action of Light. XXIX. Autoxidations VII. G. CIAMICIAN and P. STLBER (dtti R. Accad. Lincei 1914 [v] 23 i 113-119 ; Ber. 1914. 47 640-646. Compare A 1913 ii 545).- Acetic acid undergoes slow autoxidation when exposed to light formic acid being formed.Glycollic acid in the light in the presence of oxygen is almost completely oxidised to carbon dioxide and formaldehyde. Oxalic acid in similar circumstances yields carbon dioxide. Malonic acid yields carbon dioxide formaldehyde and acetic Succinic acid yields carbon dioxide acetaldehyde acetic acid Pyrotartaric acid is but little affected by oxygen and light. Glyceric acid yields carbon dioxide formaldehyde and glyoxal. Saccharic acid is oxidised t o a considerable extent with formation of carbon dioxide and formic acid. Coumarin yields principally the polymeride Dyson’s dihydrc- coumarin which is formed in the absence of oxygen in smaller quantity salicylic acid and a substance of m. p. 163O.Oleic acid yields formic acid nonoic acid azelaic acid dihydroxystearic acid a substance of m. p. 56O and some of the lower members of the fatty acid series. R. V. S. T. S. P. acid. possibly propionic acid and glyoxal. R. V. S. Syntheses in Organic Chemistry by means of Light. VIII. Various Experiments. E. PAT ERN^ [with G. CHTEFFI and G. PERRET] (Gazzetta 1914 44 i 151-164. Compare A . 1909 i 393; 1910 i 41).-In the experiments here described the reagents were subjected to the action of light for periods varying from a few months t o two or three years. Acetaldehyde and alcohol seem t o give butane-By-diol (see Eltekov A. 1883 566) which was however not isolated in a pure state. Benzaldehyde and acetophenone give a polymeride of benz-GENERAL AND PHYSICAL CHEMISTRY ii.235 aldehyde and benzaldehyde and benzophenone apparently yield the trimeric benzaldehyde described by Mascarelli (A. 1906 i 962). Salicylaldehyde and amylene do not react. pTolualdehyde and decane (diisoamyl) give toluln’nacone which forms colourless needles m. p. 155-157O. p-Tolualdehyde and amylene yield hydrotoluylide CI6Hl8O2 and an’ additive compound C,3H180 b. p. 250-252O Do 0.9714 D9-2 0.9646 D38.6 0-9424 D*OO.24 0.8955 1.5081 which has the normal molecular weight in freezing benzene. Acetone with either amylene or acetic or butyric acid gives no products which could be readily isolated. Acetophenone and benzyl alcohol give a/3-diphenylpropanediol. Tiffeneau and Dorlencourt (Ann. Chim. Phys. 1909 [viii] 16 252) prepared a compound m. p. 192O which they described as the carbazone of this glycol but the action of semicarbazide hydro- chloride on the glycol obtained by the author yields acetophenone semicarbazone m.p. ZOOo the glycol thus undergoing resolution into its components. Anisaldehyde and toluene give only a little hydroanisoin benzylphenol and benzophenone only benzopinacone and oxalic acid and amylene traces of polymerides of amylene. Benzil reacts with decane but no product could be isolated; with amylene benzil gives a pasty resin of liquid crystals having the composition of a compound of the two components. Saligenin gives (1) with benzophenone only benzopinacone ; (2) with acetophenone salireton (compare Giacosa A. 1880 716) ; (3) with amylene no additive product the phenolic hydroxyl like that of salicylaldehyde hindering the reaction.Deoxybenzoin and alcohol yield the a- and /3-pinacones of deoxybenzoin described respectively by Limpricht and Schwanert (Annalen 1870 155 60) and by Wislicenus and Blank (A. 1889 261). Deoxybenzoin and toluene give benzoic acid and the a-pinacone of deoxybenzoin which is also obtained together with another crystalline compound and a resin from deoxybenzoin and ethylbenzene. Deoxybenzoin and phenylacetic acid seem to form a complex acid which could not be purified. I n presence of chloroform xanthone and amylene give a corn- pound C,,H,,O ( ?) crystallising in dark orange-red needles m. p. 190-192O. With toluene or acetophenone piperonaldehyde yields a corn- pound (C 58.85% H 4.39%) forming colourless crystals m.p. 226-228O. I n presence of amylene dimethylpyrone is converted into a dimeride m. p. 1 8 3 O . This polymerisation of dimethylpyrone occurs also under the influence of the sun’s rays alone but does not take place in alcoholic solution whilst in aqueous solution it proceeds to a slight extent. I n aqueous solution pyrone undergoes no sensible alteration but alone or in presence of amylene i t is converted into a rust-red amorphous polymeride which is virtually insoluble in water or organic solvents. This polymeride resembles some of the pentosansrii. 236 ABSTRACTS OF CHEMICAL PAPERS. and like pyrone itself gives some of their reactions although it yields no f urfuraldehyde. Phloroglucinol gives with arabinose a red coloration which is also obtained less intensely with pyrone and still less intensely with the polymeride.With orcinol arabinose gives a violecgreen coloration whilst pyrone and its polymeride yield orange-red colorations changing t o greenish. With 1 3-dihydroxynaphthalene arabinose gives a violet-blue coloration and a precipitate whilst pyrone and the polymeride form intense blue colorations and also precipitates. From their composition pyronel and its polymeric modification may be regarded as dehydration products of pentosans. T. H. P. Fitful Point Discharges and t h e Electric Method of Count- ing a- and @-Particles. L. MYSSOVSKI and K. NESTURCH ( A m . Phgsik 1914 [iv] 43 461-472).-The '' natural dist4urbnnces " in counting a-particles by the electric method which Rutherford and Geiger ascribed t o the natural radioactivity of the walls of the cylindrical condensers were found to depend on the unevennesses of the electrode-surf aces.Such natural disturbances often exceed in magnitude those produced by a-rays and because of them no electrical method of counting a-particles can be used as a control of the optical or scintillation method. F. S. Fresh Verifications of the Laws of Transparency of Matter to X-rays in the Special Case of Inorganic Complexes. LOUIS BENOIST and HIPPOLYTE COPAUX (Compt. rand. 1914 158 559-561. Compare A. 1901 ii 215).-The authors have examined three inorganic complexes namely potassium f erricyanide purpureo- cobalt chloride and potassium silicomolybdate and find a close agreement between the values calculated and found for E the equivalent of transparency.The calculation is made from the equivalents of transparency of the elements in the complexes according to the formula d.i/E=Sm/e. H. RUBENS and H. VON WARTENBERQ (Sitzungsber. h'. Akad. Wiss. Bedin 1914 7 169-190. Compare ibid. 1913 530 ; A. 1910 ii 172).-Seven new groups of residual rays with wavelength in the neighbourhood of 50 p from ammonium chloride and bromide thallium chloride bromide and iodide silver cyanide and mercuric chloride have been examined and their mean wavelength determined and compared with the frequency formula of Madelung and of Lindemann. The plates are prepared between steel dies in a hydraulic press under 3000 at. pressure and are turned in the lathe. An unpolished surface is advantageous as after three or four reflections all shorter waves are scattered and eliminated.Measurements are made with the quartz interferometer through a total thickness of 2 mm. of quartz in a desiccator when necessary to avoid absorp- tion of the rays by water vapour a common Auer burner being the source of light. F o r ammonium chloride the mean wave-length W. G. Long- waved Residual Rays (Reststrahlen).GENERAL AND PHYSICAL CHEMISTRY. ii. 237 is 51.5 p which is almost exactly that of rock salt. For the other substances the wavelengths found were ammonium bromide 59.3 ; thallium chloride 91.6 ; silver cyanide 93 ; mercuric chloride 95; thallium bromide 117; and thallium iodide 151.8. A com- parison of the results with theoretical formula showed general agreement but the data are insufficient t o decide between them.F. S. Extraction of Radium from the Olary Ores. S. RADCLIFF (J. SOC. Chenz. Ind. 1914 33 229-232).-An annlysis of the Olary ore has already been published by Crook and Blake (A. 1910 ii 308); even when concentrated itl contains only 8 mg. of radium calculated as bromide per ton. After dry-crushing and sieving the ore is concentrated magnetic- ally. The concentrates amounting to about 30% of the ore crushed give the following analysis CaO. PbO. Fe203. FeO. MnO. ThOz Ce203 (La,Di,Y)203. Cr.03. U:+Os. VzOj. TiOs. SiOz. 055 016 17'4 169 trace 327 0'85 1'6 086 45'85 1270 After fusion with sodium hydrogen sulpliate the fused product is crushed and then agitated in a continuous current of water in such a way that the coarse material which separates is almost free from radium and uranium. The turbid liquid carries in suspension the radium lead and barium as sulphates together with a con- siderable amount of finely divided silica; in solution are the uranium rare earths and part of the iron and acid earths contained in the ore.The ((slimes" from the turbid liquid when dry form about 10% of the weight of the concentrates and are treated for the recovery of radium; the clear liquid from the slimes is treated for uranium. To recover the uranium the clear liquid is treated with an excess of a mixture of sodium carbonate and hydrogen carbonate whereby the iron and most of the other bases are precipitated. After collecting the precipitate the filtrate is made acid with sulphuric acid the carbon dioxide expelled with a current of air and the uranium precipitated with ammonia.After collecting the pre- cipitate drying crushing and washing i t to remove sodium salts a residue is obtained which when dry contains about 75% of U,O,. They are treated with sulphuric acid to form the insoluble sulphates of barium lead and radium. After washing free from sulphuric acid the sulphates are converted into the carbonates by boiling with a solution of sodium carbonate a large amount of the silica being thereby dissolved. The washed carbonates are then con- verted into chlorides by treatment with hydrochloric acid and the sulphates again precipitated from the solution. The crude sulphates thus obtained are fused with sodium carbonate in graphite pots and the product digested with hot water.The in- soluble residue after picking out the metallic lead is heated with hydrochloric acid the solution evaporated t o dryness to dehydrab the silica the residue treated with acid and hot water and the The radium is recovered from the slimes as follows.ii. 238 ABSTRACTS OF CHEMICAL PAPERS. silica collected. The chloride solution is then saturated with hydrogen chloride whereby barium and radium chlorides are pre- cipitated nearly free from the other elements (Soddy's method). The chlorides are then converted through the carbonates into the bromides for the purpose of fractionation. About 1500 grams of dry chloride which when freed from radio- active substances other than radium have an equilibrium activity of 40 t o 50 are obtained weekly.T. S. P. Uranium-Y. OTTO HAHN and LISE MEITNER (Physikal. Zeitsch. 1914 15 236-240. Compare this vol. ii 89).-The existence of uranium-P has been put beyond doubt. It gives low-velocity P-rays and its half-period is given as 25.5 (k0.5) hours. I n chemical properties i t is the same as uranium-X or thorium and i t results either from uranium-l together with uranium-X or from uranium-11 together with ionium. I n several experiments on the decay of uranium-X + uranium-P preparations the value for the half-period varied between twenty- one and twenty-six hours. The recovery curve of uranium purified with great care from uranium-X+uranium-P showed the effect of uranium-P and the period calculated from this curve agreed with that found for the decay curves. Uranium-P was shown to be non- separable from uranium-X by adding thorium to the mixture and precipitating it by characteristic reactions which failed to alter the ratio between uranium-X and uranium-P.F. S. The Action of the Electric Discharge in Helium on t h e Radium Emanation. L. BRUNER and E. BEKIEH. (Physikal. Zeitsch. 1914 15 240-241).-With the idea of ascertaining whether the rate of disintegration of the radium emanation would be affected by increase of the concentration of one of the reaction products namely charged helium atoms the rate of decay of the y-rays from a tube containing radium emanation and helium through which a discharge was kept passing was measured. The result was negative and no alteration of the disintegration constant of the emanation under these conditions was observed.F. S. Decomposition of Ammonia Gas under the Action of Radium Emanation and Influence of t h e Temperature on the Chemical Effects Produced by the Radiations from Radioactive Substances. EUGENE WOURTZEL (Compt. Tend. 191 4 158 571-573).-The results obtained with hydrogen sulphide as to the influence of temperature and pressure on the decomposition produced by radium emanation (compare this vol. ii 18) being inconclusive owing to the possibility of re-combination of the hydrogen and sulphur under the experimental conditions the author has repeated the work with ammonia and obtained more conclusive results. Ammonia is decomposed by the emanation into nitrogen and hydrogen without any other reaction taking place. The quantity of gas decomposed for destruction of unit radiation increases withGENERAL AND PHYSICAL CHEMISTRY. ii.239 the pressure but approaches a limit the pressure effect being solely one of improving the absorption of the radiation of the gas. The amount of ammonia decomposed by 1 curie of emanation a t the ordinary temperature is 219.2 C.C. (compare Usher T. 1910 97 389 1193). Rise in temperature favours the destruction of the ammonia being twice this amount a t 108O and more than three times it a t 220O. W. G. Helium of Goal Mine Gases and Radioactivity of Goals. CHARLES MOUREU and ADOLPHE LEPAPE (Compt. rend 1914 158 598-603. Compare A. 1911 ii 1087).-In view of the fact that the various samples of coal mine gases examined (Zoc. c i t . ) were found t o contain appreciable quantities of helium the authors have examined samples of coal from the same sources as the natural gases for the presence of thorium and radium.Minute quantities of these two elements were invariably present but these were far too small to account for the amount of helium evolved. The source of the helium in the coal is not a t present solved. W. G. Radioactivity and Atoms. GIUSEPPE ODDO (Gazzettcc 19 1 4j 44 i 200-218).-Historical acco3unt of radioactivity since Rontgen's discovery in 1895. T. H. P. Molecular Structure of Radioaotive Atoms. GIUSEPP E ODDO (Gazzetta 1914 44 i 219-235).-1n order to explain the loss of helium atoms during the disintegration of radioactive elements the author suggests that these atoms are arranged in the form of one or of two contiguous hexagons in the same way as the carbon atoms of the benzene o r naphthalene molecule.The uranium atom would thus contain eight helium atoms in two hexagons which must differ in some way one from the &her loss of four helium atoms occurring and radium emanation He Actinium emanation. in two "modes to Urariinin. The loss of He from the a'-position term which undergoes transformation yield actinium emanation He He/\/\ 1 1 - IHe -3 He( He!,, He .' Radium emanation. would Five an unknown into @I) representing uranium-2 whilst fuither loss of He would yield uranium-P (IV) uranium-X (V) and ionium (VI) three and only three such isomerides being known He He He He He He He He He/\/\ He /\/\ HJ 1 /He HJ I 1 \/A/ He He \/\/' He He Heii. 240 ABSTRACTS OF CHEMICAL PAPERS.Elimination of He from (VI) gives only one product radium (VII) which in its turn gives only radium emanation or niton (VIII) He He He He (VII.) (VIII.) Continuing the elimination and indicating the positions by the numbers 1 2 3 4 we get 1 2 3 ( 2 ) ; 1 2 4 radium-A; 1 2 radium-B; 1 3 radium-C; 1 4 radium-Cz; 1 radium-D ; 2 radium-E ; 3 radium-3’ =polonium. Complete elimination would render the material residue of the new atom ( 1 lead) non-radio- active. Thus of the sixteen elements which should exist according to the author’s hypothesis fourteen are known t,he positions of the heliums in the two as yet unknown being 1 2 3 4 5 6 7 and 1 2 3. The analogies between these two structures suggest that there is no tendency t o form such elements so that in nuclei con- taining four atoms of helium the elimination commences a t the p- rather than a t the a-position; it may be however that such elements are formed but that they give no rays and are of short duration.For the other two1 series of radioactive elements we have similarly Actinium series uranium-1 ; 1 2 3 5 6 7 8 1 ; 1 2 4 5 6 7 8 homouranium-2 ( 1 ) ; 1 2 5 6 7 8 homouranium-y ( 2 ) ; 1 3 5 6 7 8 actinium ( 2) ; 1 4 5 6 7 8 radioactinium ; 1 5 6 7 8 actinium-z ; 5 6 7 8 actinigm emanation; 6 7 8 ? ; 5 7 8 actinium-A ; 7 8 actinium-B ; 6 8 actinium-C; 5 8 actinium-C ; 8 actinium-D ; complete elimination lead ( 1). Here too all the known terms are foreseen by the hypothesis there being four gaps.anthorium-( 1 ) ; 1 2 3 4 6 7 8 1 ; 1 2 3 4 5 7 8 thorium; 1 2 3 4 7 8 mesothorium-1 ; 1 2 3 4 6 8 mesothorium-2 ; 1 2 3 4 5 8 radiothorium; 1 2 3 4 8 thorium-z; 1 2 3 4 thorium emanation; 1 2 3 ? ; 1 2 4 thorium-A ; 1 2 thorium-23; 1 3 thorium-C; 1 4 thorium-C,; 1 thorium-D. A table is given showing in parallel columns for the corre- sponding members of each of the three series the atomic weight the nature of the rays emitted and the time in which onehalf of the element undergoes transformation. Taking the table given by F. W. Clarke t o show the percentages of the twenty elements occurring in the largest proportions in the earth’s crust the author calculates in each case by how much the atomic weight differs from a multiple of 4.Thus the first few elements are oxygen 49*78% 16 = 4 x 4 + 0 ; silicon 26.08% 28.3 =4 x 7 + 0.3 ; aluminium 7.34% 27.1 =4 x 7 -0.9 ; and so on. These twenty elements together make up 99.54% of the earth’s 1 2 3 4 5 6 7 8 Thorium series 1 2 3 4 5 6 7 8,GENERAL AND PHYSICAL CHEMlSTRY. ii. 241 crust and with only five of them namely sodium barium manganese nitrogen and fluorine which give a total of 2-54% is this atomic-weight difference equal to or greater than 1; with three namely aluminium potassium and phosphorus the total percentage content is 9.73 and the difference equals or exceeds 0.9; then follow chlorine (0*21%) 0.54; strontium (0*03%) 0.37 ; and magnesium (2*24%) 0.32. So that with the elements constituting 86.5% of the earth’s crust the differences of the atomic weights from multiples of 4 are not greater than 0.3.This may be mere coincidence or it may be that non-radioactive atoms or a t least certain of them are to be regarded as stable condensation terms of helium atoms (compare Collins A 1913 ii 313). T. H. P. The Amount of Radioactive Products in the Atmosphere. SHINZG SAT^ (Sci. Reports T8hoku Imp. Cniv. 1913 2 171-174).- Details are given of experiments a t the T6hoku University on the amount of active deposit obtained from the atmosphere upon a negatively charged wire. The mean ratio of the effect due to radium to that due to thorium was 9.7 which corresponds with the ratdo of 5000 t o 1 for the relative concentrations of the two emana- tions in the atmosphere. Expressed in terms of curies per cubic metre the mean value for the radium emanation wits 83 x 10-l2 which agrees with results obtained in Montreal Chicago and Cam- bridge but is greater than that found in Tokio.F. s. Acceleration of Electrical Conductors RICHARD C. TOLMAN EAHL W. OSGERBY and ‘1’. DALE STEWAHT (J. Amer. Chem. Soc. 19 14 36 466-485).-1n an earlier paper (A 1911 ii 248) attention was directed to the fact that there is a difference of electrical potential between the two ends of a vertical tube of a salt solu- tion which is due to the effect of gravitation and experiments were described on the measurement of the E.M.P. produced by centrifugal force. It is now pointed out that a tube of a salt solution when sub- jected to acceleration should show a difference of potential between the two ends and a theory is developed leading to an expression f o r calculating the value of this potential difference.Experiments are described in which an apparatus was employed which consisted essentially of a glass tube provided with electrodes and bent to fit into the rim of an ordinary bicycle wheel. The tube was filled with the electrolyte the wheel given a sudden acceleration and the current noted wliich flowed through a galvanometer placed in the external circuit which connected the two electrodes. The electrolytes used were solutions of potassium sodium and lithium iodides containing 1 mol. of the salt and 1/100 mol. of iodine per kilogram of water. The results afford conclusive proof that poten- tial differences are developed a t the ends of a column of accelerated electrolyte and they agree fairly well with the requirements of the theory.Experiments have also been made with metallic conductors.ii. 242 ABSTRACTS OF CHEMICAL PAPERS. Insulated copper was wound in a groove cut in the edge of a disk of an aluminium alloy the ends of the wire being connected with insulated binding posts a t the centre of the disk. The disk was caused t o rotate very rapidly and was then suddenly stopped and observations were made of the pulse of electricity through the galvanometer which was connected directly in series with the rotating coil. The results show that the mass of the mobile carrier of electricity in metals is probably less than l / 2 0 0 of that of the hydrogen atom. It is considered that it would be possible to increase the sensitiveness of this method to a point a t which the electron if i t really is the carrier of electricity in metals with a mass of 1/1800 of that of the hydrogen atom should produce an appreciable effect. E.G . The Specific Inductive Power of Liquids. C. GUTTON (Compt. Tend. 1914 158 621-623).-The specific inductive power of liquids such as toluene in which the value is low shows no varia- tion with increase in intensity of the electric field. F o r liquids of higher specific inductive power such as a-bromonaphthalene there is a feeble decrease with increase in the magnetic field. For the specific inductive powers a t 1 5 O the following values were obtained toluene 2.36 ; carbon disulphide 2.61 ; - a-bromo- naphthalene 4 .7 2 4 - 6 9 varying with the intensity of the field. W. G. Passivity of Metals. WILHELM RATHERT (Zeitsch. physikccl. Chern. 1914 86 567-623).-The author has examined the metals iron nickel and chromium in solutions of sulphuric acid and several sulphates during anodic polarisation. It is shown that the potential a t which the passive metal becomes active is not the same as that a t which the active metal becomes passive and that the point of sudden change of potential observed by Flade (A. 1912 ii 558) does not represent the boundary potential below which the metal is active and above which i t is passive. It is shown that a metal may be active o r passive on both sides of this point depending on its previous treatment. The potential a t which iron becomes passive is dependent in a marked degree on the concentra- tion of the electrolyte in which the anodic polarisation is effected whilst the potential a t which passive iron becomes active is not.The appearance of the passivity potential and the activity potential during anodic polarisation is dependent on the current density and consequently on the oxygen concentration on the electrode. These various facts are not t o be explained on the oxide theory of passivity but they find an easy explanation on the hydrogen theory. The passage of the one form into the other under stated conditions takes place a t definite potentials in the case of iron and chromium but there is no such definite potential in the case of nickel the passage of the one form into the other taking place gradually.Polished chromium is not active in hydrogen as is demanded by the oxide theory; this fact is however in accord wit.h the hydrogen theory. Nickel is also not active after polishing in hydrogen andGENERAL AND PHYSICAL CHEMISTRY. ii. 243 then dipping into a liquid which has the property of rendering metals passive. Passive chromium becomes active when it is charged electrolytically with hydrogen ; the potential of nickel is also very much reduced by charging with hydrogen and in a solu- tion which ought to render it passive in these circumstances i t becomes active. Molecular hydrogen has hardly any action on the potential of a passive chromium electrode. It is also shown that passive iron which does not pass into solution electrolytically on the absorption of hydrogen ions by diffusion becomes active and then dissolves strictly in accordance with Faraday’s law. The same fact is also observed in the case of chromium which is further evidence in favour of the hydrogen theory.A Scheme for the Dissociation of Ternary Electrolytes. CARL DRUCKER (Zeitsch. Elektrochem. 191 4 20 83-84).-Polemical; an answer to Wegscheider’s (this vol. ii 95) criticism of the author’s previous paper (A 1913 ii 1015). Influence of a Magnetic Fmld on the Electromotive Force of Elements and on Chemical Processes. W. RATHERT (Zeitsch. Elektrochem. 1914 20 145-15l).-The effect of a magnetic field on the element Fe I FeSO I CuSO I Cb is investigated; it is shown that there is no difference in the E.M.F. set up whether a mag- netic field is applied or not.The experiments of Remsen (La Lumibre EEectripe 1882 4 126) show that when a solution of copper sulphate is placed on an iron plate lying across the poles of a magnet the copper is deposited in different thicknesses on the plats thinner just above the poles and thicker further away. The author is able to confirm these results and offers the following explination. The copper is a t first uniformly deposited with the formation of ferrous sulphate; this substance being more magnetic than copper sulphate is held t o the surface of the iron over the poles and so fresh copper sulphate cannot diffuse t o the plate and so react whereas in the regions remote from the mag- netic poles the iron sulphate is free to diffuse and in consequence the layer of copper in these places can become thicker.Similar results are observed with other metals and this appears to be a complete proof that the phenomena observed by Remsen are not due t o a change in the solubility of iron under the influence of a magnetic field. It is shown that if the susceptibility of the salt produced in reactions similar t o that described above is greater than that of the original salt then the deposit of metal will be thinner in positions of great magnetic intensity and thicker in positions of weaker magnetic intensity and if on the other hand the susceptibility of the original salt is the greater then the metal will be deposited in greatest thickness in the regions of greatest magnetic intensity. This explanation also makes it clear why an E.2CI.P.is set up in cells of the type Fe (magnetised) H,SO Fe (non-magnetised). I n the case of the magnetised iron the ferrous sulphate produced is held t o the metal whereas in the case of the non-magnetised iron the ferrous sulphate diffuses so that the element resolves itself into a concentration cell. It is also J. F. S. J. F. S.ii. 244 ABSTRACTS OF CHEMICAL PAPERS. shown that a magnetic field is unable to bring about a separation of a liquid mixture even when the salts in solu- tion have very different susceptibility. A magnet which is protected from chemical action (that is by covering with varnish) when placed in a magnetic solution is also unable to effect a change in the concentration of the solution. This is only possible when the magnetic substance is being produced by chemical action on the magnet itself. Transition Temperatures of the Hydratea of Sodium Carbonate as Fixed Points in Thermometry.THEODORE W. RICHARDS and AUGUSTUS H. FISKE (J. Arner. Chem. Xoc. 1914 36 485-490).-1n earlier papers (A. 1898 ii 555; 1899 ii 354; 1903 ii 411; 1906 ii 727; 1908 ii 16; 1911 ii 695) it has been shown by Richards and his co-workers that the transition tempera- tures of certain hydrated crystalline salts form convenient fixed points for standardising thermometers. Attention has now been directed t o the use of sodium carbonate for this purpose. The work of previous observers especially that of Wells and McAdam (A. 1907 ii 542) has been confirmed which shows that the stable hydrates of this salt are between - 2 * l 0 and 32'0° the decahydrate; between 32'0° and 35*4O the heptahydrate ; and above 35*4O the monohydrate.The transition temperature between the decahydrate and the heptahydrate has been carefully determined and found t o be 32'017O on the hydrogen scale as compared with the value 32*00° obtained by Wells and McAdam (Zoc. cit.). When the hydrates are left a t the ordinary temperature in air dried by sulphuric acid they all easily lose water and become converted into the anhedrous salt. Specific Heat cp of Air between 1 and 200 Atmospheres. L. HOLBORN and M. JAKOB (S'ttzungsber. K. Akarf. Viss. Bedzn 1914 213-219).-Measurements of the specific heat of air have been made a t pressures of 1 25 50 100 150 and 200 atmospheres by the continuous-flow method described by Callendar.Observations a t each of these pressures were taken with three and in some cases four different rates of flow of air. Over this range of pressure the specific heat (at 59O) increases from 0.2415 t o 0.2925. The experimental values are satisfactorily represented by the equation 104.c = 2413 + 2.8613 + 0 * 0 0 0 5 ~ - O.OOOOlp3. The increase in the specific heat with increase of pressure is much smaller than that indicated by Lussana's measurements. The authors' results are however in good agreement with those calcu- lated from the Thonison-Joule effect on the basis of Linde's theory. Specific Heat of Solids. 111. H. VON JUPTNER (Zeitsch. Elektro- chem. 1914 20 105-109. Compare A 1913 ii 921 ; t h i s vol. ii 99).-A mathematical paper in which formulz are deduced giving the atomic and molecular heat of solid substances.The author deduces the equations from the idea of an energy value under J. F. S. E. G. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 245 which the atoms just fail to vibrate and from this it is shown that the mean vibrational energy E of a solid substance is of the same dimensions as the mean kinetic energy E of a gas the ratio between the original energy value €1 and the mean energy E is given by d/Eo=/3v/T whereby PV has a value twice as large as the value /3v’ of the previous publications (Zoc. c i t . ) . Also /3v (Juptner) =4/5Pv (Nernst and Lindemann) = S / 15pv (Einstein). On the above expression N,e-p’T gives the number of atoms in vibration. J. F. S. Variation with Temperature of the Specific Heat of Sodium in the Solid and t h e Liquid State; also a Determination of its Latent Heat of Fuaion.EZER GRIFFITHS (Proc. Roy. Xoc. 1914 A 89 561-574).-The mebhod described in a previous paper (A. 1913 ii 753) has been employed in the determination of the specific heat of sodium in the solid state between Oo and 94O and in the liquid state between looo and 140O. About 350 gram3 of sodium were employed in the measurements the solid being enclosed in a copper envelope which was filled while the sodium was ih the molten condition. The specific heat of solid sodium increases with temperature but its absolute value a t a given temperature has been found to depend on the previous thermal treatment of the metal. At temperatures below about 60° the specific heat is greater in the “quenched” condition than in the “ annealed ” condition and from measure ments of the density by a differential method it has been found that the density of annealed sodium is greater than that of the quenched metal to the extent of 1 part in 7000.The specific heat of liquid sodium varies with the temperature according to a linear equation the temperature-coefficient being equal to - 0*00034 per lo. By a slight variation in procedure the method has been applied to the determination of the latent heat of sodium giving a mean value of 27-52 cal. The melting point of the metal was found to be 97.61O. H. M. D. The Heat of Fusion of Hydrated Salts and of Hydrates in General. CH. LEENHARDT and A. BOUTARIC (Compt. rend. 19 14,158 474-477) .-A theoretical paper in which the authors show that as a first approximation in the majority of cases the heat of fusion of a hydrate is equal to the heat of fusion of the water it contains. If a greater precision is desired the authors do not think that it is a t present possible to affirm that the heat of fusion of the hydrate is the sum of the heats of fusion of the anhydrous sub- stance and the water a t the temperature of fusion of the hydrate.The chemical affinity between the anhydrous substance and the water does not appear to be necessarily the same in the solid and liquid states. W. G. Properties of Iodine as a Cryoscopic Solvent. F. OLIVARI (Atti tz. Accad. Lincei 1914 [v] 23 i 41-45. Compare this vol. ii l68).-The results obtained in the case of sulphur confirm those VOL.CVL ii. 17li. 246 ABSTRACTS OF CHEMICAL PAPERS. previously published (A. 1909 ii 37). The numbers obtained for the molecular weight of selenium dissolved in iodine are inter- mediate between those required by Se and Sez except in very concentrated solutions where the values approximate to Se,. Tellurium dissolves in iodine with development of heat. It yields depressions corresponding very nearly with those calculated for monatomic molecules. The alkali iodides KI RbI NH,I and the organic ammonium iodides NH2Ph,HI NMe,I NMe,PhI C,H,Me*NNe,I show a characteristic anomalous bebaviour in fused iodine. In very dilute solutions the molecular weights are almost normal. They increase rapidly with the concentration up t o a certain point then decrease again until in some cases a t very high concentrations values below the theoretical are found.R. V. S. An Efficient Boiling Rod. GREGORY TOROSSIAN (J Amer. Chem. SOC. 1914 36 513-514).-A piece of an alundurn crucible or porous porcelain plate is crushed to fragments about 0-5 mm. in diameter and heated t o redness. The end of a glass rod 10-12 cm. long is softened by heat and dipped into the coarse powder so that some of the particles adhere t o it. This is re- peated until a suitable quantity has been collected on the end of the rod. The rod is then heated to make the fragments adhere and when it has cooled all the loose particles are rubbed off. Another form of rod can be prepared by fusing one end of a narrow rectangular or triangular piece of alundum or porous porce- lain into the end of a glass rod and bending the latter so that the piece of alundum or porcelain will lie on the bottom of the beaker o r flask.The boiling rod should not be placed in the liquid until it reaches the boiling point. E. G. The Binary Systems Cyanamide-Water Cyanamide-Garb- amide and Cyanamide-Dicyanodiamide. M. PRATOLOPGO (Atti R. Accad. Lincoi 1914 1.3 23 i 46-52).-The thermal analysis of these systems shows that in all three cases simple eutectics exist corresponding with 37.8% of cyanamide and -16*6O 63.9% of cyanamide and 17*4O and 85.0% of cyanamide and 3 5 . 6 O respectively. R. V. S. Thermodynamical Calculation of Chemical Affinities. W. NEHNST (Bey. 1914 47 608-635).-8 lh'cture delivered before the German Chemical Society.D. F. T. Thermodynamics of Calcium Hydride Formation. J. N. BRONSTED (geilsch. Emkbvochem. 19 14 20 81-83) -The autlior has determined the dissociation pressure curve of calcium hydride between the temperatures 641O and 747O and has shown that the values of logep calculated from the expression logep= - Qo/RT + { (Cp - CH) /B}log,T + i agree well with the observed values. C is the molecular specific heat of gaseous hydrogen a t constant pressure and C the specific heat of solid hydrogen to which theGENERAL AND PBYSICAL CHEMISTRY. ii. 247' value 2.3 is attributed. Q0 and i are determined from the curves and have values 42710 and 6-21. The equation therefore becomes log,p= - 42710/RT + 4.2 log,T/B + 6.21 and from this the heat of formation of calcium hydride at 1 8 O is found to be 43930 cal.The heat of formation is determined experimentally from calori- metric experiments on the heat of solution of calcium and calcium hydride in hydrochloric acid A t 1 8 O these values are found t o be per gram 3280 cal. and 2110 cal. respectively or 135,400 cal and 90,300 cal. per molecule respectively. The heat of formation of calcium liydride is therefore 45,100 cal. a t 1 8 O (compare Guntz and Bassett A. 1905 ii 300). Moldenhauer and Roll-Hansen (A. 1913 ii 705) have shown the probability of the existence of a lower hydride of calcium and in conlzexion with this the author shows that the heat of combination of each hydrogen atom is about the same Ca+H -3 CaH+23,100 cal. and CaH+H + CaH,+ 22,000 cal. J. F. S. The Heat of Formation of Manganese Sulpbide.S. WOLOGDINE and B. PENKIEVITSCH (Compt. rend. 19 14 158,498-499). -A determination by two methods of the heat of formation of manganese sulphide MnS. The first which did not give con- cordant results consisted in oxidation of the sulphide in a calori- meter filled with oxygen. The mean value for the molecular heat of formation in this case was 70.535 caI. The second method consisted in measuring the heat evolved by the direct combination of finely powdered manganese and sulphur in an atmosphere of nitrogen in a Mahler bomb. The two sub- stances were compressed into a pastille and lit by a known quantity of a mixture of aluminium and potassium chlorate with a fuse of fulminating cotton. The values obtained in this way were with one exception concordant and gave for the molecular heat of formation the mean value 62.901 cal.W. G. Heats of Combustion of Phototropic Substances. M. PADOA and E. FORESTI ( A t t i R. Accad. Lkncei 191 4 [v]. 23 i 95-98). -The two forms of salicylidene-P-naphthylamine are found to have the same heats of combustion within the limits of experimental error as also have the two forms of benzaldehydephenylhydrazone. R. V. S. Apparatus for the Determination of the Density of Gases. M. HOFSASS (Zeitsch. angew. Chem,. 1914 27 136) -The apparatus makes use of the principle of the Bunsen diffusiometer. It consists essentially of a U-tube the limbs of which are in connexion with a straight tube through which the main current of gas flows. By means of appropriate stop-cocks in the U-tube and the straight tube the current of gas for example in a lighting system can be deflected through the U-tube which is thereby filled with gas under the pressure in the system.The U-tube is fitted with a mano- meter and also with a Bunsen diffusion plate the latter being cut off from the U-tube by means of a stop-cock. When this cock is 1'7-2ii. 248 ABSTRACTS OF CHEMICAL PAPERS. opened the gas passes through the plate and the time necessary for a given fall in the manometer reading to take place is noted. The apparatus having been previously calibrated with air the density of the gas can thus be found. T. S. P. Molecular Attraction. X. J. E. MILLS (J. PhysicaZ Chem. 1914 18 101-117).-A reply to Mathews’ criticism (A. 1913 ii 674) of the author’s views on molecular attraction.It is pointed out that the equation h = k ( 7 2 - vp) where A is the internal heat of vaporisation d the density of the liquid and D that of the saturated vapour is not empirical in the ordinary sense of the word but was derived by the author as the final result of a definite theoretical argument. It is not t o be expected that the above equation will agree with van der Waals’ equation of condition for this is known t o be contradictory to observed facts. I f the masses of the attracting molecules are supposed to be const-ant the law of gravitational attraction leads directly t o the equation h = k(V2 - vp). The assumption that the molecular attraction is not determined by the product of the masses of the molecules was not made as alleged by Mathews because of the disagreement of the author’s equation with experimental data.H. M. D. Viscosity of Some Protein Solutions. HARRIETTE CHICK and EVA LUBRZYNSKA (Biochem. J. 1914 8 59-69. Compare A 1912 ii 1042).-The authors have investigated the influence of concen- tration and of temperature on the viscosity of solutions of crystal- lised egg-albumin and (horse) serum-albumin. The data for egg-albumin indicate that for solutions which con- tain less than about 9% of protein the relation between viscosity and concentration can be approximately represented by a linear equation. A t higher concentrations the slope of the viscosity- concentration graph increases rapidly until a t a concentration of 28% the viscosity reached the value 10 (H,O = 1).Between Oo and 40° the relative viscosity of solutions which contain less than 20% of egg-albumin falls t o a slight extent only but there is a much greater decrease in the case of a 28% solution. Measurements made with solutions prepared from dialysed and undialysed material show that the ammonium sulphate associated with the undialysed substance has no influence on the nature of t.he solution. The data for (horse) serum-albumin show that the relative viscosity of its solutions is much greater than that of corresponding solutions of egg-albumin and that the influence of temperature on a 20% solution is also much larger in the case of the serum- albumin. Similar relations are exhibited by solutions of whole serum (horse). The relative position of the viscosity-concentration curve shows that proteins of higher viscosity than egg- o r serum-albumin are present in the whole serum. Viscosity of Binary Mixtures.EUGENE C. BINGHAY (J. PhysicuZ Chem. 1914 18 157-165).-A criticism of Kendall’s view that the H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 249 logarithmic viscosity (or fluidity) is the property of a binary mixture which shows additive relations (this vol. ii 109). The fact that the average percentage deviation between the calculated and observed viscosity according t o Kendall's formula is smaller than that shown by any of the formula which have been previously put forward is said to be due t o the circumstance that contraction and heat development are characteristic of the majority of the mixtures which were submitted to examination.The fact that the specific volume of a liquid has been shown recently to be a linear function of its fluidity (Batschinski A. 1913 ii 26) is distinctly in favour of the view that the additive property is the fluidity. H. M. D. Viscosity of Liquid Mixtures. I. A. SACHANOV and N. RJACHOVSKI (Zeitsch. physikal. Chom. 1914 86 529-537).-1t is shown that the viscosity and fluidity of binary liquid mixtures is not a linear function of the composition and consequently the viscosity and fluidity of mixtures cannot be represented by an equation of the form ~ = ~ l ( l O O - p ) / l O O + q ~ / l O O . The author deduces the following expression to represent the viscosity of mixtures. In this expression p is the molecular percentage of one constituent ql q2 and 7 the viscosities of the two c0nstituent.s and the mixture respectively and n is a constant varying between -1.43 and 2.08.This equation is applied to mixtures benzene-chlorof orm chloroform-bromobenzene chloro- form-phenetole chloroform-diphenyl ether and ethyl iodide- phenetole which have been determined by the author. By suib able choice of the value of n an agreement is obtained which is always within 3%. Similar agreement is also found with the measurements of Linebarger (A. 1897 ii 247) Dunstan (T. 1905 85 222) and Faust (A. 1912 ii 333). Some mixtures do not agree with the above expression but the divergence is only found in those cases where one of the liquids has an abnormallv hiPh 'I = r] (1 00 - p)2/( loop + 7)&/ 100)2 + n J'Ilrl,c( 1 00 - p ) p / ( 1 OOY] viscosity and an abnormally high vi&osity temperature-coefficienc.J. F. S. The Absorption of Gases by Cod. F. LEPRINCE-RINGUET (Compt. rend. 1914 158 573-576).-A study of the absorption of gases such as methane carbon dioxide air or oxygen by different kinds of coal under different conditions of temperature and pressure. There is a state of equilibrium for each temperature and pressure the absorption decreasing rapidly with rise in tempera- ture and increasing a t first rapidly and then more slowly with increase in pressure. The absorpbion is slow. The evolution of the gases absorbed occurs in puffs like small explosions even whes the phenomenon is made extremely slow. Relationship between Surface Tension and Adsorption WALTER A. PATRICK (Zeitsch.physikal. Chern. 1914 86 545-563).- The surface tension of mercury in solutions of various concentr?- W. G.ii. 250 ABSTRACTS OF CHEMICAL PAPERS. tions of mercurous sulphate salicylic acid picric acid new magenta morphine hydrochloride and caffeine has been determined by allowing mercury t o fall in small drops into the various solu- tions. In each case 60 drops were collected and weighed and from the weight the surface tension was calculated. The value of the surface tension in each case diminishes with increasing con- centration. The reduction of the surface tension is greatest in the case of mercurous sulphats and least in the case of caffeine the other substances effecting it in the order given above. The adsorp- tion of the above-mentioned substances on the surface of mercury was also determined by allowing a finely divided stream of mercury to fall through a solution of the substance in question which was flowing in the opposite direction The concentration of the solu- tion was determined before and after the adsorption.It is shown t'hat mercurous sulphate is most strongly adsorbed and the other substances are adsorbed in the order of their influence on the surface tension. Curves are given for the influence of concentra- tion on the surface tension and on the adsorption. It is clear from these that the adsorption is similar to that obtained with solid adsorbents-a large increase in the adsorbed amount from weak solutions and a saturation value from concentrated solutions. No satisfactory quantitative relationship could be found between the adsorption and the surface tension. J.F. S. Adsorption of Colloidal Ferric Hydroxide. PAUL ROHLAND (Zeitsch. physikn'l. Chrzm. 1914 86 633-634).-Cnrli (A. 1913 ii 1029) has shown that kaolin does not adsorb ferric hydroxide; the author points out that there is a non-plastic form of kaolin which contains no col_loidal substance and consequently cannot exhibit any adsorptive properties. This variety only forms colloids on long keeping in moist air and then i t possesses strong adsorptive proper- ties and reacts with hydroxyl ions. J. F. s. Theory of Dyeing. 11. WILDER D. BANCROFT (J. Phjylsica'l Chem. 1914 18 118-151. Compare this vol. ii. 178).-Further observa- tions recorded in the literature have been examined and further conclusions are drawn relative to the behaviour of dyes towards cotton wool and silk fibres.Basic dyes are taken up most readily from an alkaline solution although dyeing may occur in both neutral and acid solution. Readily adsorbed anions increase the quantity of basic dyes which are taken up by the fibre whilst readily adsorbed cations have the opposite effect. F o r this reason basic dyes are taken up by wood to a greater extent on the addition of sodium sulphate to the dye- bath and the effect produced by sulphuric acid is found t o be much greater than that produced by an equivalent quantity of hydro- chloric acid. H. M. D. Compounds of Dissolved Substance and Solvent in Solution. NTLRATAN DHAR (Zeitsch. E'lektrochem. 1914 20 57-79).-The author gives a survey of the evidence on which the explanationGENERAL AND PHYSICAL CHEMISTRY.ii. 251 that the discontinuity in the physical properties of a series of solu- tions of a given substance in a given solvent is due t o the forma- tion of one or more compounds between molecules of the solvent and the dissolved substance. A very complete critical account is given of the work in this connexion with respect to the following physical properties of solutions (1) abnormal electrical con- ductivity ; (2) Kohlrausch’s hypothesis on viscosity and electrical conductivity ; (3) transport numbers; (4) osmotic pressure ; (5) influence of other substances on solubility; (6) boiling point; (7) vapour pressure; (8) freezing point; (9) refractivity and mole cular sefraction ; (10) absorption spectra ; (11) density and volume relationships; (12) viscosity ; (13) surface tension ; (14) magnetic rotation ; (15) anomalous electric absorption ; and (16) specific heat.J. F. S. Compounds of Dissolved Substance and Solvent in Solution. C. DRUCKER (Zeitsch. Elektroehem 19 14 20 79-81. Corn pare preceding abstract) .-The author adds several points as an adden- dum to Dhar’s paper which tend t o show the presence of com- pounds of the dissolved substance with the solvent in solution. J. F. S. Ideal Concentrated Solutions. J. N. RRONSTED (Zeitsch. Elektrochena. 19 14 20 151 -153).-Polemical. The author criticises statements of Nernst (“Theoretische Chemie,” 1913) on his work in connexion with ideal concentrated solutions (A. 1910 ii 112). It is maintained that Nernst’s criticism is unjustified and that the condition f o r an ideal concentrated solution dU /dx =dA / d x as given by Nernst must be replaced by (dZi’/,dx)z:= (dA/dx)z;. Ideal solutions are those which conform to the equations A = - RT log,z .4 = - RT log,(l - x ) where the symbols have their usual meanings.It is also held that Nernst’s proof of his heat theory for sulphuric acid solutions is imperfect because he applies the Thomsen formula outside the range in which it is strictly true and because he has only made use of older data taking no account of the newer data. Further the calculation of the temperature relationship of the heat change is also open to criticism. J. F. S. [Ideal Concentrated Solutions.] W. NERNST (Zeitsch. EZPktro- chem 1914 20 153-156.Comvare preceding ;cbstract,).-Polemical; an answer 60 Bronsted’s criticism. It is shown that Brijnsted’s condition for an ideal concentrated solution is identical with that of Nernst but is written in an unusual way. Determinations of t h e Degree of Hydration of Salts in Concentrated Solutions. E. H. RTESENFELD and C. MILCHSACK (Zeitsch. anorg. Chem. 1914 85 401-429).-When t h e niiinbrr. of mols. of water per mol. of anhydrous salt in a saturated solution is plotted against the temperature all salts acids and bases which contain water of crystallisation give similar curves with maxima J. F. S.ii. 252 ABSTRACTS OF CHEMICAL PAPERS. a t the number of mols. of water which enter into the crystalline hydrate. Dissociation in solution is indicated by a flattening of the niaximum.Away from the maximum the curves are nearly straight lines so that the theoretical melting point of the un- dissociated compound may be found by extrapolation and the dis- sociation of the hydrate at its melting point may then be com- puted. The degree of dissociation of a number of hexahydrates of metallic nitrates has been calculated in this way. Cobalt nitrate hexahydrate is much more dissociated than the nickel salt although they both have the same melting point. Copper gives curves deviating widely from a straight line probably owing to complex formation. The heat of fusion of a number of nitrates and chlosides has been determined in a calorimeter composed of two concentric vacuum vessels the salt being melted in a small silver shell by means of a vapour-bath.Toluene is the most suitable calorimetric liquid. The latent heat of fusion is then compared wit.h the “total heat of fusion” computed from the solubility curves the latter being always greater. The difference between the two values may be accounted for by assuming a higher molecular weight for water in the solutions. Walden’s rule is confirmed that the molecular heat of fusion divided by the absolute melting point is a constant. Good agreement is also found when the specific heat of the solid salt is calculated by Nernst’s method from the specific heat of the liquid the latent heat of fusion and the temperature of fusion. C. H. D. Surface Tension and Hydration in Solution. M. PADOA and G. TABELLINI ( A t t i R. Accad. Lincei 1914 [v] 23 i 88-94).-The paper records the results of measurements of the surface tension of solutions by ‘the method of Morgan and Higgins (A.1908 ii 668) with a view to the detection of association or hydration. The solutions dealt with included aqueous solutions of ammonium chloride (N and 3N) cobaltous chloride ( N ) sodium bromide ( N ) magnesium chloride ( N ) and hydrogen chloride ( N ZN and 3 N ) . The results are most striking in the case of the solutions of hydrogen chloride which give values indicating a very high degree of association. R. V. S. Decline of the Hypothesis of Ionic Dissociation. F. P. WORLEY (Phil. Mag. 1914 [vi] 27 459-467).-A criticism of the ionic theory with special reference to the connexion between the chemical activity of electrolytes and their presumed degree of ionisation.The assumption that the hydrolytic activity of acids is partly due t o the action of the non-ionised molecules is supposed t o remove one of the strongest arguments in support of the theory. If applied to the interpretation of the author’s observations on the rate of inversion of sucrose in presence of hydrochloric acid it is found that the activity of the non-ionised acid is about twelve times as great as that of the hydrogen ion. In the author’s opinion the known. facts relating t o the chemicalGENERAL AND PHYSICAL CHEMISTRY. ii. 253 activity of electrqlytes are not in favour of the ionic theory and merely serve to show the existence of a close connexion between chemical and electrolytic activity. Crystallisation Phenomena in Binary Systems of the Ohlorides of the Univalent and Bivalent Metals.TR. LIEBISCH and E. KORRENG (Sitzungsber. K. Akad. Wist?. Berlin 1914 192-212).-The authors give a summary of the results which have been obtained in the investigation of the crystallisation of forty- two pairs of chlorides by thermal and microscopic methods. The chlorides of the following metals were used lithium sodium potassium rubidium copper silver thallium magnesium calcium strontium barium zinc cadmium tin and lead. The various binary systems are grouped according to the behaviour which is found on solidification and in these tables are recorded the data characteristic of the various systems such as crystallisation tempera- tures eutectic temperatures and composition transition tempera- tures and formulz of compounds.The following pairs of chlorides form neither compounds nor mixed crystals LiCl with KC1 SnCl PbC1,; NaCl with CuC1 CaCl SrCl BaCl SnCl PbCl ; TlCl-BaCl AgC1-PbCl,. Binary systems cliaracterised by the formation of compounds which melt without decomposition are indicated by the formulz of these compounds KCl,MgCl (487O) KC1,CaCl2 (740°) 2KC1,BaC12 (663O) TlCl,CaCl (683O) 2TlCl,ZnCl (352O) T1C1,2ZnCl2 (226O) T1C1,CdC12 (436O) 3TlCl,SnCl (310°) TlCl,SnCl (244O) 3T1C1,PbC12 (407O) TlCl,ZPbCl (435O) 2KC1,SrC12 (597O) EC1,2SrC12 (638O) KC1,3SnC12 (208O) ECl,SnCl (224O). The numbers in brackets represent the melting points of the respective compounds. Other pairs of chlorides also form compounds but these are decomposed below the melting point.The formuh of the com- pounds and the transition temperatures characterist.ic of these are indicated in the following list 2NaC1,CdCl2 (425O) 2KC1,CuCl (244O) TlC1,ZMgCl (499O) TlCl,SrCl (569O) CaCl,,BaCl (631O). I n three cases it has been found that compounds belonging to both the above classes are formed; the compounds with melting points are KCl,CdCl (431°) KC1,2PbC12 (440°) RbC1,2PbC12 (423O) RbCl,PbC12 (440O) ; those which exhibit transition points are 4KCl,CdCl (461°) 2KCl,PbCl (490°) 2RbC1,PbC12 (448O). The compound RbCl,PbCl changes from a rhombic into a regular modification a t about 3 1 0 O . From an examination of the compounds which the chlorides of the bivalent metals form with those of the alkali metals it is found that the calcium and barium compounds contain only 1 molecule of the alkaline earth metal chloride whilst the corresponding double chlorides of magnesium strontium zinc cadmium and lead may contain one or more molecules of the bivalent metal chloride. The alkali metal chlorides do not form compounds with one another and except irr the case of the pair CaCI,-BaCle this is true f u r the chlorides of the alkaline earth metals H.M. D.ii. 254 ABSTRACTS OF CREMICAL PAPERS. Pairs of chlorides which form complete series of mixed crystals are LiC1-NaCl NaCl-KC1 NaC1-AgC1 CaCl,-SrCl SrC1,- BaC1,. I n consequence of the dimorphism of barium chloride the series of singly refracting mixed crystals which are formed when mixtures of this with strontium chloride are allowed t o crystallise is transformed into a series of doubly refracting mixed crystals as the temperature falls.The fact that complete series of mixed crystals are formed in the system CaC1,-SrC1 is worthy of note in view of the circumstance that calcium chloride is monoclinic whilst strontium chloride is regular. The mixed crystals separate into the components when the temperature is lowered. Tables are given in which the degree of miscibility of the com- ponents in the various binary systems is indicated. These show that there is a marked difference in the behaviour of sodium chloride and potassium chloride towards other chlorides. H. M. D. Preparations of Colloidal Solutions by Mechanical Sub- division. GUSTAV WEGELIN (Kolloid. Zeitsch. 1914 14 65-69).- Colloidal solutions of silicon antimony tungstic acid titanic acid molybdic acid vanadium trioxide and vanadium pentoxide have been prepared by riducing the substances to a finely divided con- dition in an agate mortar.The time required for this varies with the substance; in some cases the process is accelerated by the addi- tion of a little water. The results were quite negative in the case of a large number of other substances which were subjected to this mechanical treatment. The colloidal solutions of the above- mentioned substances show great differences in stability. I n all cases the p@icles are negatively charged and coagulation occurs on the addition of sodium chloride. I f the colloidal solution of vanadium pentoxide is coagulated by adding a small quantity of sodium chloride the precipitate shows little change of colour on keeping but if a larger amount of sodium chloride is used in the coagulation the resulting precipitate changes its colour in the course of a few days from yellow to reddish- brown.Further observations have shown that this is probably connected with the existence of two modifications of the vanadium pentoxide. The black solution of vanadium trioxide is very stable in the absence of air. On standing in the air oxidation occurs and the solution becomes green a green precipitate being thrown down later which probably consists of V,O,. H. M. D. [The Condition Diagram of Water.] P. B. BRIDGMAN (Zeitd. physikal. Chem. 1914 86 513-524. Compare Tammann A. 1913 ii 935; Brideman Proc. Amer. Acad. 1912 47 441-558).- Polemical.The author doubts the existence of a second form of ice 11 and attributes the results on which Tammann (Zoc. c i t . ) bases his assumption that such a form exists to insufficiently accurate measurements. J. F. S,GENERAL AND PHYSICAL CHEMISTRY. ii. 255 The Laws of Displacement of Chemical Equilibrium. A. ARII~S (Compt. rend. 1914 158 492-494. Compare JitRVeiiU ibid. 1909 148 767).-A theoretical paper in which the author deduces a law which combines into one the two laws of Le Chatelier and van’t Hoff’s two laws. He enunciates it as follows In a traDsformation where the temperature the entropy the pressure or the volume remain invariable all the reactions are produced in the sense which exalts the change of volume or entropy foreseen by the laws of displacement of thermo-elastic equilibrium. W.G. Theory of Heterogeneous Chemical Equilibria. A. THIEL (Chem. Zentr. 1914 i 21 1-212 ; from Sitzungsber. Ges. Bef. Naturw. Marburg 1913 reprint 16 pp.)._The apparent discrepaiicy in the results obtained by the application of the mass law and the phase rule on the one hand and the molecular theory on the other to the equilibrium in systems with two solid phases and a gas phase such as that represented by CaCO t CaO+COD is due t o the assumption of a relation between the masses of the reacting sub- stances and the free surfaces. The apparent contradiction which a racemic compound offers to the requirements of the phase rule is shown to disappear if the system is regarded as a special case of one in which the d- and I-forms are separate components.The discrepancy met with in the case of sodium chlorate which exists in a rhombic and in two enantiomorphic rhomboidric-tetartroedric forms disappears in like manner if the enantiomorphic forms are counted as a single phase. H. M. D. Equilibria in Ternary Systems. XII. F. A. H. SCHBEINEMAKEBS (Proc. K. Akad. Wetnnsch. Amsterdam 1914 16 739-754. Compare this vol. ii 113 184).-A further discussion of possible types of equilibrium in ternary systems. H. M. D. Physical Chemistry of Magmas. P. NIGGLI (Zeitsch. Elcktro- chew. 1914 20 156-159) - A theoretical paper in which the constitution of magmas of silicates in the presence of volatile sub- stances such as carbon dioxide hydrogen chloride hydrogen fluoride and other gases is considered from the point of view of the phase rule.The object of the paper is mainly geological and is concerned with the conditions of formation of rocks from the molten magma. J. F. S. Photochemical Decomposition of Hydrogen Peroxide. I. J. HOWARD MATHEWS and HARRY A. CURTIS (J. PhysicaZ’Chm. 1914 18 166-178).-The rate of decomposition of aqueous solutions of hydrogen peroxide has been investigated when the solutions con- tained in a quartz tube provided with a quartz stirrer are sub- jected to the influence of the light emitted by a “uviol” lamp of constant intensity which is set up in close proximity and parallel to the tube containing the hydrogen peroxide solution. Afterii. 256 ABSTRACTS OF CHEMICAL PAPERS. measured time int'ervals a sample is removed and titrated with standardised potassium permanganate.The decomposition follows the course of a unimolecular reaction and ceases abruptly when the light is cut off. Between ZOO and 45O the ve1ocit.y of decom- position increases in the ratio 1 1.5 f o r a rise of temperature of loo. On addition of small quantities of sulphuric acid sodium chloride acetanilide sodium calcium and barium hydroxides the velocity of decomposition is retarded and these substances may consequently be regarded as negative catalysts in respect of the photolytic reaction. H. M. D. Velocity of Diazotisation of Some Amines. E. TASSILLY (Compt. rend. 1914 158 489-491. Compare this vol. ii 42).- In the case of the various amines previously examined the author now shows that their diazotisation is sensibly regulated as in the case of aniline by the formula d x / d t = k(100 - x)2 the variations between calculated and found values for x coming within the range of experimental error.W. G. Pseudo-Ternary Systems of Acid Anhydrides and Water. I. Phthalic Anhydride. H. R. KRUYT (Proc. K. Akad. Wetensch. Amsterdam 1914 16 712-'718).-1f the solution obtained by shaking water in contact with phthalic anhydride is titrated with standard alkali hydroxide after measured time intervals it is found that the acid titre increases t o a maximum and then falls t o a constant value. Further experiments in which the water was shaken with both phthalic anhydride and phthalic acid and in which the elec- trical conductivity of the solution was measured from time t o time show that the above variation in the acid titre of the solution is due t o the dissolution of the anhydride which subsequently undergoes rapid hydration with the formation of a supersaturated solution of the acid.The fall in the titre indicates the gradual attain- ment of an equilibrium condition in which the solution is in equilibrium with both acid and anhydride. The solubility of the acid is increased somewhat in the presence of the anhydride.- H. M. D. Mechanism of the Acid Formation of Aliphatic Acid Anhydrides in an Excess of Water. J BOESEKEN and P. E. VERKADE (Proc. K. A h d . Wetcnsch. Amsterdam 19 14 1 6,718-726).- The velocity of hydration of a number of acid anhydrides has been measured a t Oo and a t 25O by the conductivity method. The following represent the unimolecular velocity-coefficients which have been obtained for the several anhydrides the non-bracketed figures giving the value of 0.43431% for Oo and the figures in brackets the value for 25O acetic anhydride (0.0713) ; propionic anhydride 0.00700 (0.0372) ; m-butyric anhydride 0*00471 (0.0243) ; iso- butyric anhydride 0*00454 (0'0227) ; acetic propionic anhydride (0.0522). Since previous observations have shown that the velocity of hydration is determined by the magnitude of the ionisation coefficient of the acid the authors seek to eliminate this influenceGENERAL AND PHYSICAL CHEMISTRY.ii. 25’7 by dividing the hydration-coefficients by the corresponding ionisa- tion-coefficients. The numbers obtained in this way are found to diminish as the aliphatic series is ascended whilst the equality of the numbers f o r IZ- and iso-butyric acids shows that the branching of the carbon chain has no measurable influence on the rate of hydration.I n the case of isovaleric anhydride the rate of hydration does not fit in with the unimolecular formula. The actual behaviour can be explained if i t is assumed that the reaction occurs in two stages in the first of which a hydrate is formed by addition of water this hydrate being split up into two molecules of acid in the second stage. Whereas the first stage is relatively very rapid in the case of the lower anhydrides this does not hold f o r isovaleric anhydride and the valueas obtained for the unimolecular velocity- coefficient decrease as the hydration proceeds.H. M. D. Union of Hydrogen with Acetylenic 7-Glycols in Presence of Palladium or Platinum. Y. S. ZALKIND (J. Rum. Phys. Cherri. Soc. 191 3 45 1875-1895).-Previous investigations on the partial hydrogenation of compounds with an acetylenic linking have usually been limited to interruption of the reaction when the amount of hydrogen absorbed has reached that calculated for the conversion of the triple into a double linking. Arrest of the re- action a t this stage is however only possible if the conditions are such that the velocity of combination of hydrogen a t the triple bond is considerably greater than a t the double bond. If the reverse is the case a mixture of saturated and acetylenic com- pounds is obtained whilst if the two velocities are more or less of equal magnitude a mixture of saturated ethylenic and acetylenic compounds is naturally formed.It is hence of interest to study the velocities of such reactions under different conditions for instance in presence of different catalysts and this the author has done for y-glycols of the acetylene series making use of platinum black prepared according to Willstiitter and Hatt’s method (A. 1912 i 545) and of colloidal palladium made in the manner indicated by Paal and Amberger (A. 1905 ii 397). With the latter of these catalysts hydrogenation of Be-dimethyl- hv- hexinene-Pediol (compare Iocitsch this vol. i 405) proceeds with extreme slowness after two atoms of hydrogen have been com- bined. When platinum black is used however the hydrogenation not only proceeds as far as the conversion of the triple linking into a simple one but also leads to reduction of the hydroxyl groups. F o r each of these cases calculations have been made of the velocity constants of the conversion of the triple into the double linking k and of those of complete hydrogenation X.With palladium k remains virtually constant whereas K rapidly diminishes so that almost all of the hydrogen first reacts with the acetylenic glycol the ethylenic glycol thus formed subsequently undergoing but slow reduction. With platinum k exhibits a marked increase whilst K remains constant .until near the end of the experiment,ii. 258 ABSTRACTS OF CHEMICAL PAPERS. where it shows a slight increase which is probably caused by the reduction of the hydroxyl groups ; here then the hydrogenation of triple and double linkings proceeds with approximately the same velocity.These results show that if a saturated glycol is desired hydro- genation should be effected in presence of platinum black whereas when an ethylenic glycol is required colloidal palladium should be employed. I n either case i t is necessary t o measure the quantity of hydrogen absorbed and t o stop the reaction at the proper time but there is no necessity t o hasten the removal of the hydrogen from the vessel in which the reaction is taking place. I n the above case the individuality of the Pedimethylhexane- &-diol and the &-dirnethyldu -hexene-fie-diol obtained was established. Preliminary experiments have also been similarly made on the hydrogenation of Ar-hexinene-be-diol (compare Iocitsch this vol. i 375).The results obtained are analogous to those given by the dimethyl glycol the hydrogenation as shown by the values of ki and X varying markedly according as platinum black or colloidal palladium is present. With the former catalyst reduction of the hydroxyl groups proceeds more energetically than with bedimethyl- Ar-hexinene-B 6-diol . Further investigations are in progress. Union of Hydrogen with a&Diphenyl-hr-butinene-a8-diol. Y. S. ZALKIND and E. D. ISAKOVITSCH ( J . Rum Phys. Chem. Soc. 1913 45 1896-1 903).-Experiments similar to those previously described (see preceding abstract) have been made with as-diphenyl-A B- butinene-a&diol OH*CHPh*CiC*CHPh*OH (compare Iocitsch this vol. i 404). The curves representing the course of the hydro- genation in presence of platinum black or colloidal palladium and also the values of k and K are closely analogous t o those obtained with PE-dimethyl-A r-hexinene-Pediol. a&-DiphenyZbzctane-a&diol OH*CHPh*CH,*CH,*CHPh*OH the product obtained when platinum black is used forms crystals rn.p. 113-113'5°. Like its diacetyl derivative C?0H2204 m. p. 99-99*5O i t has the normal molecular weight in boiling ether. OH-CHP h- CH CH-CHP h*OH obtained when colloidal palladium is used forms acicular crystals m. p. 150-152° and decolorises bromine water and dilute per- manganate solution ; i t exhibits normal ebullioscopic behaviour in acetone. T. H. P. T. H. P. ab-Diyh e nyl-AD-b ut e ne-as-diol Demonstration of the Velocity of Chemical Reaction by means of the Galvanometer.M. CENTNERSZWER (CI~enr. Zentr. 1914 i 330 ; from Zeitcrch. physikal.-chem Unterr. 1913 26 344-349).- The velocity of the reaction between methyl sulphate and methyl alcohol (compare Kremann A. 1907 ii 157) has been calculated on the assumption that the conductivity of the mixture is approxi- mately proportional to the concentration of the methyl hydrogen sulphate. The mean values for the constant obtained in twoGENERAL AND PHYSICAL CHEMISTRY. ii. 259 experiments a t 2 5 O were 0.00154 and 0*00141. I n the original i t is described how the reaction may be used to demonstrate the laws of the velocity of reactions. I n one experiment i t map be shown by galvanometer deflections that the velocity decreases with time and in a parallel experiment that it is proportional to initial con- centration and that a rise of ZOO increases the speed about five times. The influence of catalysts cannot be demonstrated for the reaction is indifferent towards water acids alkalis or platinum.J. C. W. Determination of the Velocity of Reactions in Solution from the Change in Density. ERNEST ANDERSON and J. L. HOLDEN (J. Physical Chem. 1914 18 152-156).-1t is bhnwn t h a t tlre inversion of sucrose can be followed by measuring the density of the solution after measured intervals of time. Data are given for experiments in which hydrochloric sulphuric and oxalic acids were employed as catalysts. The values obtained for the velocity coefficient are in good agreement. H. M. D. Chemical Kinetics. I.The Influence of Synchronous Changes in Concentration on the Course of a Unimolecular Reaction. JULIUS HIRNIAK (Chem. Zen&. 1914 i 3-5; from Ukraiiz. SevEenko-Ges. Wzss. Lemberg 19 1 1 1-1 0 1 ) .-Formule have been deduced which represent the course of unimolecular reactions in which the concentration of the reacting substance increases as a function of the time. The equations for concurrent and con- secutive reactions of the first and second order are also discussed and reference made t o periodic chemical changes (compare A. 1911 ii 196). I n the experimental portion of the paper the author gives the results of measurements of the velocity of reaction. of ethyl iodide with heterocyclic bases and of the temperature-coefficients of these reaction velocities. The temperature-coefficient of the reaction between dimethyl- aniline and ethyl iodide in dimethylaniline solution is less than in methyl alcohol solution. Since the reaction proceeds according to the unimolecular formula in the former case and according to the bimolecular formula in the latter i t is suggested that this is an exception t o Halban’s rule according to which unimolecular reactions have a higher temperature-coefficient than reactions of the second and third order.From experiments with ptoluidine pyridine a-picoline quino- line collidine and a-naphthaquinoline i t is found that the tempera- ture-coefficient increases as the reaction velocity diminishes. The data obtained for isoquinoline @-naphthaquinoline and 2-methyl- quinoline indicate that the speed of the reaction falls as the nitrogen becomes more enclosed by other groups of atoms.A t the same time the temperature-coefficient increases as is shown by the data obtained for the members of the three following groups (1) dimethyl-p-toluidine dimethyl-o-toluidine ; (2) pyridine a-picoline collidine ; (3) isoquinoline quinoline a-naphthaquino-ii. 260 ABSTRACTS OF CHEMICAL PAPERS. line 2-methylyuinoline. I n the case of the two pairs of bases (1) pyridine and isoquinoline (2) quinoline and P-naphthaquino- line where the nitrogen is subjected to the same steric influence the temperature-coefficients are equal. An explanation of the steric influence is put forward. H. M. D. Reactions with Halogen Substituted Acids. Action of Aqueous Sodium Hydroxide on Bromomalonic Acid and on Alkylbromomalonic Acids.E. H&T MADSEN (Zeitsch. physikal. Chem. 1914 86 538-544).-Velocity reactions have been carried out with sodium hydroxide solution and solutions of bromomalonic acid bromobenzylmalonic acid bromoethylmalonic acid and bromoisopropylmalonic acid. In every case the reaction is unimolecular which indicates that the hydrolysis is brought about by undissociated water molecules and that the sodium hydroxide only serves to combine with the liberated hydrogen bromide. The relative velocities of hydrolysis of the four acids are bromoisopropyl- malonic acid 4165 ; ethyl bromomalonic acid 555 ; bromobenzyl- malonic acid 307; and bromomalonic acid 1. The influence of the substituting alkyl group on the velocity is of the same nature as that found by Senter for the action of silver nitrate on bromine- substituted fatty acids (T.1910 97 346). J. F. S. Catalytic Influence of Kaolin on the. Gombination of Hy- drogen and Oxygen. JACQUES JOANNIS (Cow@. rend. 1914 158 501-504).-Kaolin has a marked catalytic influence on the com- bination of hydrogen and oxygen a t temperatures when there is no combination under the influence of the glass vessel alone. The effect was noticeable a t 230° and up to 280° was proportional to the time of contact of the gases with the kaolin. The temperature to which the kaolin had been previously heated had a decided influence on its activity this diminishing as the temperature of preliminary heating increased. This effect was also noticeable after a short time in the results obtained in the cases where the kaolin was kept a t 300° or over without the preliminary heating the rate of combination slowly diminishing as the experiment progressed. W. G. Catalysis of the Addition of Halogens. L. BRUNER and J. FISCHLER (Zcitsch. Elektrochem. 191 4 20 84-88).-The author has investigated the catalytic action of halogen carriers on the addition of chlorine and bromine to unsaturated compounds. The experi- ments are carried out with acetylene dichloride and ethyl cinnamate in carbon tetrachloride and nitrobenzene solutions. It is shown that acetylene dichloride does not combine with bromine in either carbon tetrachloride o r nitrobenzene solutions when the halogen is present in 1/20 molecular quantity and that the catalysts iodine stannic bromide and ferric bromide are inactive when in carbon tetrachloride solution but antimony tribromide is markedly active. On the other hand antimony tribromide has no action in nitro- benzene solution. There is no addition of chlorine either whenINORGANIC CHEMISTRY. ii. 261 alone or in the presence of iodine chloride in these solutions. The catalysis is not strictly proportional to the concentration of the catalyst. The addition of chlorine and bromine to ethyl cinnamate is strongly catalysed by the addition of iodine and here also the velocity of the reaction is not strictly proportional t o the concen- tration of the catalyst. Ant'imony tribromide is a good catalyst for the addition of bromine t o ethyl cinnamate in carbon tetra- chloride solution and the reaction is shown to be apparently simpler than a firsborder reaction. MAX BRAUN (C'hem. Zeit. 1914 38 320).-An apparatus of the Dobereiner-Mohr type is Lecture Experiment on the Chlorination of Iron. 0. OHMANN (Chem. Zentr. 19 L4 i 331 ; from Zeitsch. phys.-chem. Unterr. 1913 26 365-366).-A tuft of steel wool will ignite in chlorine if sprinkled with powdered antimony. J. F. S. A New Gas-Generating Apparatus. described and figured. L. DE I(. J. C. W.

ISSN:0368-1769    

DOI:10.1039/CA9140605229

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 235 Chemistry of Vegetable Physiology and Agriculture. The Degradation of o?-Glucosamine by Bacteria. KURT MEYER (Biochem. Zeitsch. 19 13 58 415-416).-The author has already shown (this vol. i 117) that d-glucosamine is degraded by certain bacteria. Investigations have now been extended to the acetyl derivative to ascertain whether an intact amino-group is necessary for this action. It was found that acetylglucosamine is acted on by the following bacilli B. paratyphus R. coli and Fried- lander’s bacillus but is left intact by B. typhus B. p m t y p h w A . and Flexner’s dysentery organism. S. B. S. Chemical Composition of the Cells of Aaotobacter chroo- coccum. W. L. OMELIANSEY and N. 0. SIEBER (Zeitsch. physiol. Chew. 191 3 88 445-459).-Cultivations were made on agar containing the usual mineral salts with 2% dextrin.After about six days’ incubation a t 30° a characteristic dark brown growth was obtained and this after being scraped off and dried rapidly a t 30° was used for the investigation. The air-dried material was found to contain 6.63% water 4.16% ash and 12.92% protein. The nature of the nitrogen-free substance was not determined but i t would appe,zr to belong to the polysaccharides. Among the pro- ducts of hydrolysis lysine is present in greater proportion than arginine and only minute traces of histidine are formed. H. B. H.i. 236 ABSTRACTS OF CHEMlCAL PAPERS. Influence of Certain Colloids on Microbiological Processes. N. L. SOHNOEN (Chem. Weekblad 1914 11 42-59).-Nitrification processes are accelerated by the presence of colloidal ferric alum- inium and silicon oxides and humus.The presence of the two former hinders the amylum fermentation by B. ochyaceus that of the two latter promotes it. Negative colloids accelerate the de- composition of urea but positive colloids have little influence. Animal charcoal and peat facilitate the oxidation of alcohol by acetic bacteria. The alcoholic fermentation is hindered by alkali liumates promoted by biocolloids such as peat filter-paper animal charcoal and vegetable mould but unaffected by ferric aluminium and silicon oxides and humic acid. Colloids have little influence on denitrification processes. The oxidation of petroleum by bac- teria is facilitated by the presence of animal charcoal colloidal ferric oxide and silica.A. J. W. Effect of Carbon Disulphide and Toluene on Nitrification. P. L. GAINEY (Centr. Bakt. Pcw. 191 4 ii 39 584-595).-Nitritication is not affected by 0.1 C.C. of toluene in 100 grams of soil. A large amount of toluene generaliy has an inhibitory effect for a short time. When however the period of incubation is extended the injurious effect ceases when amounts of toluene up to 1 C.C. per 100 grams are employed. Carbon disulphide a t the rate of less than about 1 C.C. to 100 grams of soil has no appreciable effect. More than 1 C.C. generally retards nitrification for a time; with even as much as 5 c.c. the retarding effect is soon overcome. Soils treated with chemical substances in such amounts as inhibit nitrification for twenty weeks may recover without re-inoculation.The conclusion is drawn that toluene or carbon disulphide applied to fields will not materially affect nitrification if applied a t the rate of 0.1 C.C. per 100 grams of soil. N. H. J. M. Some Factors Influencing Ammoniflcation and Nitriflcation in Soils. J. E. GREAVES (Centr. Bakt. Pa?*. 1913 ii 39 542-560). -Arsenic is sometimes found in virgin soils whilst many cultivated soils contain considerable amolznts; i t has also been found in sub- soils down to three feet. The arsenic of “insoluble” insecticides is not completely insoluble; the greatest amount is soluble when Paris green has been used and the least with lead arsenate. The trisulphide seems t o become more soluble after remaining in soils. Ammopification and nitrification are not decreased by the presence of 100 per million of sodium arsenate in soils rich in calcium and iron ; smaller amounts may have a considerable stimulating action. Zinc arsenite lead arsenate and arsenic trisulphide stimulate am- rnonification and are only toxic when comparatively large amounts are present.The first two salts only reduce ammonification and nitrification one-half when the soil contains 1-12 grams of arsenic per kilogram. All the arsenic compounds and especially lead arsenate stimu- late nitrification which is however checked by large amounts ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 237 Paris green and arsenic trisulphide. The only substance which is likely to be injurious to soil bacteria in practice is Paris green and the quantity added would have to be large.The beneficial action of arsenic on ammonification and especially nitrification is attributed,. partly to stimulation and partly to its influence on injurious species. N. H. J. M. The Influence of Arsenic on the Biological Transformation of Nitrogen in Soils. J. E. (GREAVES (Bzochem. Bull. 1913 3 2-16).-One part per 100,000 of sodium arsenate applied to a soil rich in calcium and iron does not materially decrease the ammoni- fying or nitrifying powers of that soil; smaller amounts may stimu- late them. Similar details are given in respect to other arsenic compounds; Paris green is the most toxic; the toxicity of lead arsenate is least and this is the safest insecticide. W. D. H. Enzymatic Formation of Polysaccharides by Yeast Prepara- tions.ARTHUR HARDEN and WILLIAM JOHN YOUNG (Biochem. J. 1913 7 630-636) .-Dextrorotatory polysaccharides of the nature of glycogen are shown to be produced during the alcoholic fermenta- tion of dextrose and lzevulose by Lebedev’s maceration extract of dried yeast. The difference recorded by Euler and Johannson (A. 1912 ii 377) between the sugar removed and that equivalent to the carbon dioxide evolved is attributed t o the formation of these compounds; it does not mean as supposed by Euler that the hexose requires to undergo some change which renders i t directly fermentable and that the difference represents the amount which is in this intermediate condition. It is well known that living yeast forms glycogen when brought into excess of sugar solution (Pavy and Bywaters A.1908 ii 56). E. F. A. A. FERNBACH and M. SCHOKN (Compt. rend. 1013,157.1478-1480).-By fermenta- tion of sugar in the presence of calcium carbonate followed by concentration of the liquid in a vacuum and precipitation with alcohol a white powder is obtained which on decomposition in concentrated solution with sulphuric acid and extraction with ether finally yields a syrup after removal of the ether from which suc- cinic acid crystallises. The residual concentrated solution of acids furnishes all the reactions of a ketonic acid having the character- istics of pyruvic acid and yields a pnitrophenylhydrazone identical with that of pymvic acid. On distilling the syrup a t 70-90°/ 20 mm. an oily liquid having the properties of pyruvic acid passes over.W. G. Pyruvic Acid a Product of the Life of Yeast. Chemical Composition and Formation of Enzymes. IX. Formation of Invertase. HANS EULER and HARALD CRAMBR (Zeitsch. phyeiot. C1&m. 1913 88 430-444).-The amount of inver- tase in yeast is increased by previous treatment either with sucrose or with the products of its hydrolysis. Treatment of the yeast with mannitol or with sodium formate or lactate has no such effect.i. 238 ABSTRACTS OF CHEMICAL PAPERS. Mannose has the same favourable effect as sucrose and it is appar- ently the process of fermentation as such and not the substrate o r the products of the reaction which influences the formation of new invertase. Enzyme formation is closely correlated with the form- ation of fresh protoplasm.E. F. A. The Volatile Bases Produced in the Autolysis of Yeast. NICOLAUS IVANOV (Biochem. Zeitsch. 1913 58 217-224).-Evidence is brought forward which tends to show that trimethylamine is a product of the autolysis of yeast. Invertion of Sucrose by Water in the Presence of Moulds. L. VAUVEL (Ann. Pulsif. 1913 6 661-662).-‘1’0 ascertain the extent to which sucrose is inverted by the action of moulds two solutions containing 630 grams of sucrose per litre were kept for about four months in corked flasks one flask remaining in the laboratory wliilst the other was placed in a cellar. Moulds were introduced into the solutions and after the lapse of the time mentioned the first flask was found to contain sucrose 399.8 invert sugar 167.0 and dextrose (excess) 2.5 grams per litre whilst the solution kept in the cellar contained sucrose 326.7 invert sugar 258.1 and dextrose (excess) 5.4 grams per litre.A portion of the sugar in each case was destroyed by the moulds or their secretions laevulose being attacked to a gzeater extent than the dextrose. The solutions became acid in reaction. S. B. S. w. P. s. Cleavage of Benzoylalanine and Acetylglycine by Mo Jld Enzymes. ARTHUR W. Dox and W. EUGENE RUTH (Riochem. BUZZ 1913 3 23-25).-Benzoylalanine and to a greater extent acetyl- glycine are hydrolysed by an enzyme present in lower fungi. The enzymic cleavage of substituted amino-acids is not limited t o com- pounds analogous to hippuric acid. W. D. EL Autolysis of Mould Cultures. 11. Influence of Exhaustion of t h e Medium on the Rate of Autolysis of Aspergillus N ger.ARTHUR W. Dox (J. BioZ. Cham. 1914 16 479-484). -Autoly-is of cultures of AspergiEEus niger is due chiefly to exhaustion of carbo- hydrates from the culture medium. The rate of autolysis is in- creased by removing the autolytic products and replacing by dis- tilled water. Replacement of the medium a t regular intervals by a solution of sucrose reduces the rate of autolysis t o less than half that of the undisturbed culture and to less than onethird in cultures where replacement by water is carried out. Autolysis is attended by a loss in weight of the mycelium amounting t o about 50% in thirteen weeks. W. D. H. Zinc and “Sterigmatocystis Nigra” [Aspergillus niger]. H ENRI COUPIN (Compt. ~&crtd. 1913 157 1475-1476. Compare A .1903 ii 446).-A reply to Javillier (compare A. 1908 ii 124 317; 1909 ii 173) and an expression of agreement with the results of Lepierre (compare A. 1913 i 1423). W. G.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 239 Zinc and Aspergillus. The Experiments of Goupin and Jevillier. CHARLES LEPIERXE (Compt. rend. 1914 158 67-70. Compare A. 1913 i 1423).-A reply to Javillier (compare A. 1908 ii 124 317) in which the author confirms Coupin’s results (com- pare A. 1903 ii 44G) and the conclusions he drew as to the use- lessness of zinc for the culture of Aspergillus niger. W. G. Action of Anodic and Cathodic Solutions on Germination. HENRI MICHEELS (Bull. Acad. roy. Belg. 1913 831-887. Compare A. 1910 ii 883).-Further experiments have been made on the germination of wheat grains in the anodic and cathodic compart- ments of an electrolytic cell containing sodium or potassium chloride in 0.001 or 0.01 molar concentration.In order to ascer- tain the influence of the electrical treatment a comparison was made of the percentage number of germinations of the mean length of the first leaf of the mean length of the roots and of the mean increase in weight. Tables are given showing the ratios of these quantities for grains which have been submitted to cathodic and anodic treatment respectively. I n both series of solutions the maximum difference is exhibited in the case of root growth and this is most marked in the case of the experiments with solutions of sodium chloride. The conclusion is drawn that the effect on the germination in a given solution is approximately proportional to the quantity of electricity which has been passed through the solution in which the germinating seeds are immersed and it is claimed that the differ- ence between the cathodic and anodic effects cannot be accounted for on the basis of the alkali and acid which are formed as a result of the secondary decomposition.In particular it may be noted t h i t the relatively feeble development of the roob in the anodic liquor is attributed to the coagulation of the colloidal solution which they contain under the influence of the cations which can readily pass through the membrane of the root cells. H. M. D. Synthesis of Amides at the Expense of Ammonia Absorbed by the Roots. D. PRIANISCHNIKOV (Rev. Gbn Bot. 1913 25 5-13).-Barley maize and Cucurbita Pepo which are not injured by dilute solutions of ammonium salts absorb ammonia readily gnd produce asparagine (or glutamine) without special precautions being taken. With other plants such as peas and vetches the presence of ammonium salts retards the decomposition of proteins and the accumulation of asparagine whilst the absorption of ammonia proceeds with difficulty if a t all. I n presence of calcium carbonate these plants absorb ammonia vigorously and produce asparagine in considerable amounts. A third group of plants which includes lupines shows funda- mental disturbances in presence of ammonium salts which cannot be remedied by the presence of calcium carbonate. N. H. J. M.i. 240 ABSTRACTS OF CHEMICAL PAPERS. Passage of an Anthocyanin Pigment Extracted from the Red Autumnal Leaves into the Yellow Pigment Contained in the Green Leaves of the same Plant.RAOUL COMRES (Compt. rend. 1913 157 1454-1457. Compare this vol. i 121).-The led anthocyaniri pigment extracted from red vine leaves can be oxidised in alcoholic solution by hydrogen peroxide to a yellow pigment identical in every respect with that extracted from the green leaves of the same plant. The Passage of Dyes into the Plant Cell. XAPHAEL ED. LIESEUANG (Biochem. Zeitsch. 1913 58 213-216).-A criticism of Ruhland's hypothesis of permeability (A. 1913 ii 848). The author considers the process is one of diffusion rather than of ultra-filtration. S. B. S. W. G. The Anthocyanins. Artiflcial Anthocyanin. M. CVET ( rswwr) (Biochsm.Zeitscb. 1913 58 225-235).-In apples arid other pro- ducts alcohol-soluble substances exist probably related to the tannins which in the presence of mineral acids and formaldehyde or acetaldehyde are converted into a pigment similar to antho- cyanin. The artificial pigment is similar to the natural one both in its spectral and chemical properties. It undergoes the same colour changes with acids and alkalis and is decolorised by sodium hydrogen sulphite and phenylhydrazine. These results are not entirely in accord with the recent work of Willstatter (A. 1913 i 1371). S. B. S. Formation of Chlorophyll in Plants. 111. N. A. MONTEVERDE and V. N. LUBIMENKO (Bull. Acad. Sci. St. PSlersbourg 1913 1007-1028. Compare A. 1912 ii 8@0).-The authors have devised an improved apparatus for carrying out the spectrecolori- metric estimation of chlorophyll xanthophyll and carrotene previ- ously described (compare Lubimenko Trans.St. Petersburg SOC. Naturalists 1910 4 1). With this apparatus which is described in detail o'nly a very small volume of liquid is required. By means of alcoholic solutions containing respectively 1 gram and 0.2 gram of xanthophyll per 1000 litres i t is found that the mean of a number of separate estimations is 1.2% too high the maximum and minimum results showing errors of 5% and 3%. Measurements with a chlorophyll solution exhibit a similar degree of accuracy. The amounts of the three pigments per kilo. of fresh leaves have bee; determined with Thuja orientalis Viburnum Tinus (young leaves) Luffa giganten Albizziu Julibrissin Ruta graveotens d itamthus glanddosa Clematis Vitalba Hyssopus officinal& Rubus caesius and Amcndinaria japonica.The amount of chlorophyll increases in the above order from 0.8114 gram to 2.9 grams; the order is slightly changed in the case of xanthophyll and carrotene the amounts of which are 0*1317-0*4065 gram and 0.0208-0.1081 gram respectively ; thus the green colour of leaves is conditioned not merely by the greater colouring power of the chlorophyll but also by its predominating proportion the yellow pigments in theVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 241 chloroplasts being masked. From the separate experimental numbers the values have been calculated for leaves of each of the above plants of the ratios (1) chlorophyll both yellow pigments; in one case this is about 4 and in another about 7 the remaining values lying between 5 and 6; (2) chlorophyll xanthophyll which varies from 5 to 8; (3) chlorophyll carrotene for which most of the values are between 25 and 30 the extremes being 20 and 40; (4) xanthophyll carrotene which is mostly about 4 the limits being 3 and 6.Duplicate estimations of the amount of chlorophyll per kilo. of green and of brown leaves from the same specimen of Thuja gave the results 0.9434 and 0.9708 (green) and 0.5746 and 0-5714 (brown). As previous experiments show there is no intimate chemical coniexion between the chlorophyll and the yellow pigments each of which after its formation acts indepen- dently and may consequently undergo quantitative change apart from the others.It is therefore quite possible that under the influence of external or internal conditions the quantity of yellow pigments may change and so cause alteration of the above ratios. Further investigations have been made on the influence of various constituents of the ash of plants on the extent to which the leaves turn green this being measured by the proportion of chlorophyll formed. Two series of experiments were made the first wit6 etiolated Luffa seedlings which were freed as far as possible from adherent mineral matter by thorough washing in tap-water and then in distilled water; the effects of different salts were then compared with the result of control tests in which distilled water was employed. All the potassium salts used- dihydrogen phosphate nitrate chloride and permanganate-cause marked increases in the amoilnt of chlorophyll formed whilst magnesium sulphate produces a slight increase and calcium or magnesium nitrate a considerable decrease; sodium nitrate gives a small decrease and mdium dihydrogen phosphate a large increase.The second series of experiments carried out with etiolated wheat seedlings gave totally different results. In this case magnesium sulphate o r potassium permanganate or dihydrogen phosphate had virtually no effect on the amount of chlorophyll formed and potassium nitrate had but a slight positive influence. T. H. P. Willow Bark. 111. G. POYARNIR K. KRASIN and I. POYARNIN (J. Rusu. P h p Chem. Soc. 1913 45,1799-1810. Compare A. 1913 i 576).-Examination of two specimens of willow bark extract shows that both the products of their decomposition and also their non-tannide constituents contain gallic acid and catechol the non-tannides containing also phenol and an ethereal oil which readily undergoes bromination and is changed by the action of hydrochloric acid.One of the extracts includes a substance which gives the characteristic reaction for alicyclic compounds but was not identified. The tanning substance of willow extract is probably a mixture of tannide calcium tannate and a derivative of some nitrogen ring. The tannide gives acetic butyric and several non- identified aliphatic and other acids on decomposition whilsti. 242 ABSTRACTS OF CHEMICAL PAPERS. aldehydes are formed when it is distilled in a current of carbon dioxide. I n order to determine the nucleus of the tannides without subjecting them to hydrogenation reduction by means of aluminium in an atmof;phere of light petroleum may bO employed although this procedure d o a not exclude the possibility of secondary coupling reactions taking place.Platinised asbestos and hydrogen produce marked hydrogenation but the reaction proceeds a t a low tempera- ture. T. H. P. Willow Bark. IV. G. POVARNIN and V. TOLKUNOV (J. Buss. Fhys. Chem. SOC. 1913 45 181 1-1822).-Further investigations have been made with the bark of different varieties of willow with a view to their classification. A scheme has been evolved which is based on the colour of the supernatant liquid above the precipitate formed with ammoniacal copper sulphate solution (compare A.1913 i 576) and on the dyeing properties of the extract. The latter was determined with the standard yellow (y) red (T) and blue ( b ) glasses of the Lovibond tintometer the ratio (y - b ) / (T - b ) being used in the classification. These properties and the propor- tions of tannides and non-tannides present in extracts prepared under definite conditions have been determined for twenty-two varieties of willow. Action of Antiseptics in Increasing the Growth of Grope in Soil. EDWARD .JOHN KUSSELL and WALTER BUDDIN ( J . Soc. Chem. Ind. 1913 32 1136-1142).-m7hilst the general effects of different anti- septics is the same resulting in increased numbers of bacteria and increased production of ammonia the amounts of the various anti- septics required to produce these results vary considerably.As regards volatile antiseptics the amounts required were found to be as follows toluene and carbon disulphide 0.097& benzene less than 0.16% cyclohexane 0*17% chloroform 0.23% ethyl ether 0*74% hexane 0*86% methyl alcohol 3*2% and ethyl alcohol 4.6% of soil. In the case of cresol for instance although the initial effect is the same as that produced by toluene etc. the later effects are different in several ways; the number of bacteria increase enormously (in one case to 106 millions per gram) and the flora is very simple as com- pared with that obtained with volatile antiseptics. The high numbers are not maintained but fall rapidly. The increase in ammonia is much less than with toluene. Phenol gives similar and quinol somewhat similar results (with only 0.05%).The latter substance as well as cresol seems t o be utilised by the surviving bacteria as food. pBenzoquinone behaves similarly but is less potent. Formaldehyde is normal in its initial behaviour killing the pro- tozoa and reducing the number of bacteria; this is followed by a marked rise in ammonia but no increase in bacterial numbers. Pyridine has t o be applied a t the rate of O.S% smaller amounts being readily assimilated by the bacteria. The results obtained with various antiseptics on tomatoes grown T. H. P. The action of non-volatile antiseptics is more complex.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 243 in soils containing disease organisms showed that formaldehyde and pyridine are the most effective; next cresol phenol calcium sulphide carEon disulphide toluene benzene and petroleum ; whilst the least effective of the substances tried were the higher homo- logues of benzene and naphthalene and some of its derivatives.None of these antiseptics is however as effective as steam. Owing t o the different conditions in the laboratory and the culture experiments the order of effectiveness of the different anti- septics is not quite the same. I n the laboratory the possibility of re-infection was excluded and an organism once killed could not reappear ; in the vegetation experiments such rigid exclusion was of course impracticable. The Catalytic Action of Iron in the Development of Barley. J. WOLFF (Compt. rend. 1913 157 1476-1478. Compare this vol. i 125).-1ron in quantities so small as to make it impossible to detect and estimate tlie amount with certitude exerts a markedly favourable catalytic influence on the growth of barley.N. H. J. M. W. G. Action of Manganese and Aluminium on the Growth of Plants. TH. PFEIFFER and E. BLANCK (Lcmdw. Versuchs-Stat. 191 3 83 257-281. Compare A. 1912 ii 476).-Sand culture experi- ments in. which oats grown in pots holding 17 kilos. of sand received different amounts of manganese carbonate and sulphate and aluminium sulphate in addition to the usual salts supplying potassium calcium phosphoric acid and nitrogen. It was found that manganese salts slightly increased the yield of dry matter; to obtain the best results very considerable amounts of manganese are necessary especially when applied in a sparingly soluble form so that it is very doubtful whether the employment of manganese in practice could be remunerative. Very small amounts of aluminium sulphate in con junction with small amounts of manganese sulphate seem to have a slightly stimulating action ; the results however varied a good deal.When larger amounts of aluminium salt are employed the yield is more quickly reduced than by corresponding amounts of manganese salt. When the produce is increased by applications of manganese salts the plants give off less water which is possibly connected with the deposition of manganese in the leaves. It is suggested that the favourable effect of manganese may be connected with the retention of water. N. H. J. M. Plzmmas after Sugar Dialysie. M PIETTBE and A.VILA (Cmpt. rend. 1913 157 1542-1545. Compare A. 1913 i. 661).-An examination of the proteins contained in the plasma solution after removal of t'he fibrinogen by dialysis against a sugar solution and then against water. The liquid resulting from the dialysis is treated with 2-3 volumes of acetone. The proteins are precipi- tated filtered and washed with 50% acetone and finally with ether. The proteins so obtained can be separated by suitable treatment with water into two groups one of which is soluble in water andi. 244 ABSTRACTS OF CHEMICAL PAPERS. the other not. This insoluble fraction can be further sub-divided into two fractions one consisting of true globulins soluble in 7% sodium chloride solution and the other insoluble. The group soluble in water is obt,ained as a white hygroscopic powder on precipitation with acetone and its aqueous solution does not give the biuret action and is precipitated neither by acids nor alkalis but is entirely coagulated by heat.The Effects of Enzymes and Other Substances on the Growth of Burley Tobacco. J. Du P. OosrHurzm and 0. M. SHEDD (J. Biol. Chern. 1914 16 439-453).-1n two months t h e addition of varioiis enzymes improves the growth of some of the tobacco plants used. Pepsin and emulsin and also caseinogen caused the best results. The effsd is not proportional to the nitrogen added. Pepsin however in combination with caseinogen and trypsin failed to produce any increase of growth. A large number of other substances were tried ; most gave negative results some produced bad effects.Iron and manganese peptonates potassium cyanide hydrocyanic acid and iron and manganese lactate gave positive results and in the order named. W. D. H. W. G. Influence of Soils and the Amount of Water on the Ghanges in the Forms of Nitrogen. F. MUNTER and W P. ROBSON (Cerztr. Bakt. Par. 1913 ii 39 419-440).-With lorn percentages of water the decomposition of horn meal is much more rapid in sandy soil than in loam and clay soils whilst when considerable amounts of water are present there is no great difference. The ammonia produced from horn meal disappears rapidly in presence of high amounts of water; when however the percentage of water is low the ammonia remains a considerable time the maximum being reached earlier the lighter the soil. I n sandy soil (water 6%) the maximum was 36.7% in three weeks; in loam water (8%) 41.3% in six weeks; and in clay (water S%) 13.4% in twelve weeks. With the highest amount of water (18-24%) the sandy and loam soils contained- no ammonia in the sixth week and in the clay soil none in the third week. The nitrification of ammonium sulphate in soils deficient in water is greatest in sandy soils whilst in presence of sufficient water nitrification is more vigorous in heavy soils. Nitrification of horn meal was most satisfactory in sandy soil; in loam and clay soils the best results were obtained with medium amounts of water. Liberation of free nitrogen only occurred to any extent in presence of the largest amounts of water; with ammonium sulphate the greatest loss (19.8%) was in loamy soil and with horn meal 32.7% in clay soil. Additions of sucrose caused a more rapid dis- appearance of ammonium sulphate without a corresponding pro- duction of nitrates. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9140600235

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

245 Organic Chemistry. Origin of Ozokerite. MARCUSSON and H. SCHLUTER (Chsnt. Zeit. 1914 38 73-74).-The simultaneous occurrence of ozokerite and petroleum is pointed out and the rival theories that the former is produced from the latter and that formation occurs in the reverse order are critically discussed. According to the authors neither explanation is satisfactory and the theory is advanced that both products are simultaneously formed from the decayed complex organic constituents of plant and animal remains (compare Engler A. 1912 i 525). Fats and waxes contain a mixture of solid and liquid fatty acids the former OF which readily yield solid paraffins by loss of water and carbon dioxide whilst liquid oleic acid only gives liquid paraffins under the most varied experimental conditions.The oil containing solid paraffins is forced by earth- or gas-pressure through the overlying strata and thus undergoes a filtration and partial separation into its components the more liquid portions passing more readily through the strata and leaving thus a solid residue. The theory is supported by observations of the different samples of ozokerite obtained from various classes of rock and from actual experience during boring and is in accord with the experiments of Koss (A. 1911 i 761) on the distribution of optically active substances in ozokerite. The occurrence of amorphous ozokerite is explained in the following manner the crude oil contains both crystalline and amorphous paraffins. The former have a lower molecular weight and m. p. than the latter.When an oil rich in paraffios undergoes filtration in the earth the crystalline paraffins become more or less completely liquid and are therefore carried forward by the oil more rapidly than the less soluble amorphous paraffins which therefore alone have an opportunity to separate. The dark impurities in ozokerite are to be regarded as oxidation and polymerisation pi oducts of the hydrocarbons which are partly acquired from the oil partly formed subsequently. I n support of this theory the authors have observed the formation of dark waxy products (pipe wax) in the pipes which are used in Boryslav for conveyance of the crude oil. I n m. p. index of refraction density molecular weight and precipitation value this substance shows a close analogy to ceresin and can only be distinguished from ozokerite by its greater oil content.H. W. Preparation of Ally1 Haloids. CHENISCHE FABRIK AUF ACTIEN (VORM. E. SCHERING) (D.R.-P. 268340).-Ally1 haloids (chloride bromide or iodide) are obtained from ally1 esters (formate acetate etc.) by mixing the latter with the corresponding concentrated halogen acid saturating the mixture with the hydrogen haloid and heating in an autoclave or in an open vessel with the addition of a catalyst (for example zinc haloids). J. C. C. VOL. CVI. i. Si. 246 ABSTRACTS OF CHEMICAL PAPERS. A General Method for the Conversion of Fatty Acids into their Low31 Homologues. P. A. LEVENE and C. J. WEST ( J . Biol. Chem. 1914 16 4'75-478. Compare A. 1912 i 936; 1913 i 587). -The fatty acids are readily converted in to their a-hy droxy-derivatives by passage through their a-bromo-derivatives (compare Le Sueur T.1904 85 827 ; 1905 87 1888). These can then be readily oxidised in acetone solution by a warm solution of potassium permanganate in the same solvent giving the potassium salt of the fatty acid with one carbon atom less. The potassium salt is precipitated along with the manganese dioxide and can be extracted from this with alcohol The yield is 80-85% and avoids the preparation of the aldehyde (compare Le Sueur Eoc. cit.). The authors have applied this method to the preparation of lignoceric margaric and pentadecoic acids. W. G. History of the Discovery of Formic Acid. F. D. CHATTAWAY (Chern. NBWB 1914 109 61-63).-Historical. Action of Persulphates on Acetates.M.- A. GORDON (J. PhysicaZ Chem. 1914 18 55-66).-1f a solution containing sodium persulphate and acetic acid or sodium acetate is heated R mixture of gases is given off consisting of carbon dioxide and one or more hydro- carbons (methane ethane olefines). The amount of carbon dioxide and the composition of the hydrocarbon mixture varies with the conditions of the experiment. Simultaneously with the oxidation of the acetic acid this appear8 t o be catalytically decomposed by the persulphate in accordance with the equation CH,*CO,H = CH + CO,. The catalysed reaction is favoured by high concentration of the acetic acid low acidity and low concentration of persulphate. Those conditions which are favourable to the decomposition of persulphate give rise t o increased oxidation.Such factors are high coucentration of persulphate high temperature moderate acidity and the addition of manganous sulphate or platinum foil to the solution. H. &I. D. New Method of P r e p a r i n g t h e Diacetate of Glycerol a-Mono- chlorohydrin. JEAN NIV~ERE (Bull. Xoc. chim. 19 14 [iv] 1 5 82-83. Compare A 1913 i 697 ; also Aceiia A. 1905 i 7).-The diacetate of glycerol a-monochlorohydrin b. p. 113-1 14'/9 mm. is obtained in 75% yield when a mixture of a-monochlorohydrin and acetic anhydride is boiled for three hours under reflux. Acetic anhydride and acetic acid are removed by distillation under diminished pressure ; the residue is warmed with water to destroy any remaining acetic anhydride and to dissolve any unchanged a-monochlorohydrin and the product obtained is distilled under diminished pressure.The yield may be further improved by a second treatment with acetic anhydride after distillation of the acetic acid formed in the first operation whereby also the addition of water is rendered unnecessary. H. W. Some New Esters of Oleic Acid. N. SULZBERGER (Zeitsch. angew. Chem. 1914 27 40).-Menthyl oleate C,,H,,O b. p. about 24OC/ 4 mm. pltenyl oleute L. p. about 230°/7 mu. and m-tolyl obate b. p. about 240°/5 mm. are obtained as colourless oily liquids which can beORGANIC CHEMISTRY. i. 247 distilled without decomposition in a vacuum by the action of a slight excess of the respective alcohol or phenol on the chloride of oleic acid. The latter b. p. about 2OO0/l 1 mm. 190°/9 mm. is prepared by Krsfft and Tritschler’s method (A 1901 i 116) or by heating oleic acid 011 the water-bath with thionyl chloride in slight excess H.W. Organic Thio-acids. V. Action of Potassium Xanthate on Bromomalonic Acids. ErNAR BIILMANN and E. HOST MAUSEN (AwmZen 1914 402 331-342. Compare A. 1906 i 625 626)- In neutral or faintly alkaline aqueous solution the reaction between potassium xanthate and potassium bromamalonate bromoethyl- malona t e bromoisopropylmalona t e or bromo benzylmalona t e proceeds more or less rapidly according to the equation OEt*CS*SK + CBrR(C02K)2 = OEt*CS*S*CR(CO,K) + KBr so that 78-99% of the theoretical yield is obtained in twenty-four hours ; in acid solution however the reaction proceeds quantitatively and almost in- stantaneously in the sense of the equation BOEt*CS*SK + CBrR(C0,€€)2 + H Cl= S,(CS*OEt) + CHR(CO,H) + KC1 + KBr.The xanthomalonic acids obtained by the first reaction are very unstabIe readily losing carbon dioxids and forming xantho-fatty acid3 at temperatures very little above the ordinary. Aqueous sodium bromobenzylmalonate is reduced t o sodium benzyl- malonate by sodium hydrosulphide in slight excess. a-Xantho-P-phenyZp?.op~o~ic acid CH Ph CH( S * CS OE t) CO,H m. p. 89-90’ colourless crystals obtained by the decomposition of xanthobenzylmalonic acid is converted into a-thiol-6-phenylpropionic acid CH,Ph*CH(SH)*CO,H m. p. 46O b. p. 184-187°/11-12 mm. colourless crystals by alcohol and concentrated aqueous ammonia at the ordinary temperature; the latter acid in acid solution is oxidise3 by iodine to a- disulphido-di-6-phenylpropionic acid S,[ CH(CO,H)*CH,Ph] m.p. 105-107°. A convenient method is described for the preparation of bromo- malonic acid by the hydrolysis of ethyl bromomalonate by aqueous sodium hydroxide a t 5-10°. c. s. Transformations of Ethyl a-Cyano-a-isopropylbutyrate and Ethylisopropylmalonamic Acid. Ehm Fr SCHER ALICE ROHDE and FRITZ BRAUNS (Annulen 1914,402 364-382).-Recent researches on Walden’s inversion have shown that change OF configuration or racernisation may occur during ordinary substitution of a group attached to t h e asymmetric carbon atom. Two of the fundamental consequences of the theory of the asymmetric carbon atom therefore have been re-examined under conditions in which a group attached t o the asymmetric carbon atom is changed without being actually detached from the carbon atom.The first consequence that optical activity must disappear when two of the unlike groups attached to the asymmetric carbon atom are made like is tested by treating d-ethyl- isopropylmalonamic acid in aqueous ether with nitrous fumes whereby ethylisopropylmalonic acid is produced which proves to be quite s 2i. 248 ABSTRACTS OF CHEMICAL PAPERS. inactive optically. The second consequence that reversal of the rotation must occur when two of the groups attached to the asgnimetric carbon atom exchange places is tested as follows. An active ethyl- isopropylmalcnamic acid is converted successively into its methyl ester and methyl hydrogen ethylisopropylmalonic acid ; theoretically the latter should be converted by ammonia into the optical antipode of the original ethylisopropylmalonamic acid ; actually however the reaction follows a quite different course.The following new compounds are described dl-a-Cyano-a-isopropyl- butyric acid CN*CEtPrP*CO,H has m. p. 83-84'. I t s ethyl ester is converted by concentrated sulphuric acid on the water-bath into dl - ethy1isopropyZmalonunaic mid NH;CO*CEtPrP*CO,H m. p. 116-118' (decomp. corr.) and its ethyl ester m. p. 88' (corr.) colour- less prisms; the methyl ester obtained by means of diazomethane has m. p. 74'. An aqueous solution of dl-ethylisopropylmalonamic acid is converted by nitrous fumes a t 40' into ethylisopropylmalonic acid of which the ethyl hydyogen ester has b. p. 152' (corr.)/l9 mm. and DY 1.0349 and the methyl hydrogen ester llas m.p. 43'. a-isoPropyl- butyramide is obtained by heating dl-ethylisopropylmalonamic acid at 11 8" and finally at 130'. The resolution of dl-ethylisopropylmalonamic acid is effected by quinine in aqueous alcohol i u which the quinine salt of the d-acid is the less soluble; the 1-acid is purified by means of its morphine salt. d-E'lhy2isoywopylrnalolzcLmic acid crystallises in stout needles has m. p. or decomp. 11 6' and [a] + 14.59' in 3 0.06% alcoholic solution and yields with diazornethane the methyl ester m. p. 51-52' and [a] - 1.97' in 9.866% alcoholic solution (these constants are certainly too low because the d-acid used for esterification contained about 5% of the I-acid). l-Ethylisop~op&nalonamic acid [a] - 14.62' in 10.002% alcoholic solution forms a methyl ester m.p. 54' [u] 2.09' i n 9447% alcoholic solution. Methyl hgdrogen d-ethylisopropylmalonate m. p. 26' has [u]! 1.84' in 9 961% alcoholic solution and [a]? - 3.41' in N-potassium hydroxide (1.08 mols.) whilst the methyl hydrogen ester of the 2-acid has [a]= - 1.$8' in 11.47% alcoholic solution and [a]? 3.72' in N-potassium hydroxide. 1-Ethylisopropylmalonamic acid has been heated a t 120°/15-20 mm. and the carbon dioxide rapidly removed in the hope of obtaining an active acetamide ; the product however is found t o be dl-a-isopropyl- butyramide c. s. The Stereoisomeric Forms of Xanthosuccinic Acid. BROR HOLNBEHG (Ber. 1914 47 167-176. Compare this vol. i l40).-A few years ago the author treated sodium I-bromosuccinat.e with potassium xanthate but obtained an almost inactive xanthosuccinic acid. Recent experience on the inHuence of different cations on such r e d i o n s has led t80 the isolatiou of the active acids in a pure state (compare A 1913 ii 942).A dilute kolution of potassium I-bromosucciuate mas treated with the equivalent quantity of potassium xanthate and a day later with cjtrontium bromide when R strontium salt crgstallised which yielded a mixture of 3% d- aud 9iyo Gxanthosuccinic acid. From a coucen-ORGANIC CHEMISTRY. i. 249 trated solution of strontium I-bromowccinate with excess of potassium xnnthate and some sbrontium bromide however a mixture of 84,% d- and 1 6 O L Z-acid was obtained. Some preliminary experiments showed t h a t the racemic acid is less soluble than the active forms in water or in a mixture of ethyl acetate and benzene and that of tho acid salts with the active phenylethyl- amines those of the acid and base of opposite rotation are the less soluble.These differences were therefore employed in the final purification of the above acidp. c3-Phen~ZPlkyLa?rLine hydrogen 1-xantho- succinate C HMePh*NH,,CO,H*CH( S-CS*OEt) *CH,*CO €3 formed wbite crystals m. p. 1 17 - 1 18' and I-xanthosuccinic acid (Zoc. c i t . ) was finally obtained i n very pale yellow aggregates of small crystals [.I - 10 1.6" in ethyl acetate. d-Xanthosuccinic acid h w [a]" + 10 1 *7O in ethyl acetate + 82.8' in absolute alcohol. I n aqueous solution [a]:' is about +,72' whereas the acid potassium salt has about half chat rotation and the normal salt only &3'.The active acids have m. p. 130-131'; the racemic 14S-149' and the saturated aqueous solutions at 25O contain 24.1 and 8.2 grams per litre respectively. The racemisation of the acids and their acid and normal salts was studied. When heated alone a t loo' or warmed i n aqueous solution the active acids quickly become inactive but at the ordinary temperature the change is negligible. Complete neutralisation or the addition of a strong acid hinders racemisation at 35' but the half-neutrdised acids soon become inactive. It may be that the gradual formation of decomposition products in solution influences rmemisation but the kinetics of the change are being studied. Action of Magnesium Methyl Iodide on Ethyl Sebacate.(Mile.) E. KrsLovsKAJa (J Kuss. Pliys. Chern. so$. 1913 45 19 75-1 979 >.-PA- Dimethpldodecane-PA- d i d OH OMe,*[ C H,],*C Me,*OH obtained by treatment of ethyl sebacate with magnesium methyl iodide and subsequent decomposition by means of water forms long asbes toa- like crystals m. p. 57-5-58' PA- Dime thy Z-ApK- dodecadien e C Me CH [ CH,],* CH CRle obtai oed by heating the above glycol with nutiydrous oxalic acid a t 140-150° is a colourless mgbile liquid with an unpleasant odour b. p. 239-5-240.5" (cow.) DY 0.7932 ng 1.4535 and bas the normal molecular weight in freezing benzene. It combines readily with bromine forming an unstable oily tetrabromide which soon loses hydrogen bromide and it unites with nitrogen tetroxide giving a dark green product.With mercuric acetate solution it forms a white curdy precipitate which gives the hydrocarbon again on distillation with hydrochloric acid. I n the air the hydrocarbon thickens and on distillation after three months yielded a n aldehyde the semicarbazone of which m. p. 203' was prepared. Oxidation of the hydrocarbon by means of permanganate gives mainly sebacic acid and acetone small quantities of formic and acetic acid obtained being probably due t o further oxidation of the acetone. Production of Formaldehyde and Acetaldehyde by Oxida- tion. L. ROSENTHALER (Arch. Pharm 1913 25 1 587-595).-The J. C. W. T. H. P.i. 250 ABSTRACTS OF CHEMICAT PAPERS. detection of minute amounts of formaldehyde in the leaves of the hornbesm (Curtius and Frmzen A. 1912 ii 797) cannot be accepted as evidence of Bneyer’s theory of the assimilation of carbou dioxide by plants until it has been proved that the aldehyde cannot have been produced by any other process.The author shows that many substances which occur in placts yield formaldehyde by oxidation. The substance dissolved or suspended in dilute sul- phuric acid is treated with potassium permanganate in slight excess the excess is destroyed by oxalic acid the liquid is distilled and the distillate is tested for formaldehyde by the colour reactions of Denigb Marquis Hehner-Leonard Hehner arid Schryver (Lewin’s nitroprusside test for acetaldehyde has also been applied). The substances examined are alcohols aldehydes ketones acids carbo- bydrates phenolic ethers glucosides and alkaloids The results shorn that fcrmaldehyde is produced by the oxidation of substances con- taining methoxy- methylenedioxy- or methylimino-groups of most carbohydrates and of tri- avd pol y-hydric aliphatic alcohols. Acet- tl ldehyde is obtained by the oxidation of substances containing an ethoxy- or ethylimino-group and also of rhamnose (the last reaction may serve to distinguish rhamnose and possibly other methylpentoses from pentosee).In the case of glycerol dextrose sucrose and rham- nose suficient formaldehyde or acetaldehyde is obtained for the identification of the aldehyde in the form of its p-nitrophenpl- hydrazone or in the case of formaldehyde by Curtius and Franzen’s method. c. s. Preparation of Aldehydes and Ketones. FABRIQUES DE PRODUITS CHIMIE ORGANIQUE DE LAJXE (D.R.-P.268786).-Aldehydes or ketones are obtained when hexaruettiylenetetramine (or a mixture of 6 paits of formaldehyde and 4 parts of ammonia) is boiled in ;rlcoholic solution with a monobalogen compound. The reaction takes place with the intermediate formation of an additive compound and the conversion of the halogen compounds is represented thus R*CH,X -+ R-CHO; CR,HX -+ CE,O (where X= halogen). I n this manner ethyl iodide yields acetaldehyde benzyl chloride gives benzaldehyde a-chloroethylbenzene yields acetophenone and mention is made of a large number of aldehydes that may be prepared by this general met hod. Reduction of Aldehydes to a-Glycols. R. CIUSA and A . MILANI ( A t t i R. Accad. Lincei 1913 [v] 22 ii 681-685).-When treated with magnesium amalgam aldehydes undergo change mainly in the three directions ( 3 ) reduction to primary alcohols (2) reduction to dkecondary a-glycols 2CH3*CH0 + H = OH*CHBle*CHMe*OH ; (3) condensation to aldols and subsequent reduction of the latter t o /3-glycols,0H*CHMe*CH2*CH0 + H = OH*CHMe*CH,*CH,*OH.These three reactions proceed with different velocities which determine the relative proportions of the various products.Aliphatic aldehydes undergo aldol condensation with the greatest ease in either acid or alkaline solution and hence yield principally /3-glycols. J. C. C. CH ,*CHO + H = CH,*CH,*OH ;ORGANIC CHEMISTRY. i. 251 Thus acetaldehyde yields a large proportion of Pa-bu tylene glycol together with smaller amounts of ethyl alcohol aldol and Py-butylene glycol (4%) (compare Moureu Compt.rend. 1902 134 472). Propaldehyde gives mainly 8-methyl-ye-amylene glycol and also y8-hexylene glycol CH,*CH,*CH(OH)*CH(OH)*CH2*CH8 (5-6%) which is acolourless oily liquid b. p 233-334' and is converted into dipropionyl by the action of bromine water and sunlight and into diethylglyoxime by hydroxylamine. Benzaldehyde yields hydrobenzoin and isohydrobonzoin. Comparative Value of Catalysts in the Preparation of Ketones. J. B. SENDERENS (BuTE. Xoc. chim. 1914 [iv] 15 84-89).-34ainly polemical. The author points out the superiority of t h e oxides of thorium zirconium and uranium in the catalytic pre- paration of ketones from acids and claims priority in their use (compare Senderens A. 1909 i 226 627; 1910 i 11 179 318 489 ; 1912 i 496 537; 1913 i 342; Mailhe A 1909 i 452 692; 1910 i SO7 ; 1913 i 828 954 Stbatier and Mailhe A.1913 i 700). T. H. P. H. W. Syntheses with isoButyrone. MURAT and AMOUROUX (J. Z'hnrm. Ghim. 1914 [vii] 9 11 4-1 1 €!*).-The authors have obtained n series of tertiary alcohols by the action of Grignard's reagents on isobutyrone. The yields are generally not so good as in the case of butyrone (A 1912 i 527) and the alcohols are readily dehydrated so that phenylurethanes could not be obtained. Di-isopropyl ketone has b. p. 124-125' D! 0.8413 D:' 0*8250 n 1.417. Di-isopropylisobutylcarbinol C,H,*CPr,p*OH b. p. 102-1 05'1 40 mm. DY 0.8737 n 1.448 is obtained in poor yield by condensing di-isopropyl ketone with magnesium isobutyl chloride. Di-isopropylisoamylcarbi~zol b.p. 1 37-140°/65 mm. D1,6 0.8607 T) 0.8718 n 1.455 is obtained in 60% yield as a colourless syrup. Dehydration over oxide of thorium a t about 350' converts it into an olefine which appears to cousist of the two isomerides P[-dimethyl-y- isopropyl-AY-heptene C,Hl,:CPr,@ and pg-dimethyl-y-iso~op?/l-A@- heptene C,H,,PrP*C:CMe b. p. 188-190°/772 mm. Di6 0.7775 nD 1 *444 which when hydrogenated over nickel a t 200-250' yields PG-dimethyl-y-isopropylheptane b. p. 186-1 S8°/ortlinary pressure DY 0.7655 n 1.432. Phenyldiisopropylcnrbi?zol a viscous liquid of pale yellow colour b. p. 155-15S0/60 mm. Di2 0.9603 D 0.9755 n 2.531 is obtained in good yield by the acid of magnesium phenyl bromide. Catalytic dehydration by oxide of thorium converts it into y-phenyZ-P6-dirnethyL A s pentane CPh-PrKCMe b.p. 225-228'/760 mm. DY 0.9094 nD 1.532 which on catalytic reduction over nickel a t 250-300' yields y-phenyl-PG-dimethylpentane b. p. 220-225' DT 0.8822 fiD 2-51 2. The yield of benzyldiisopro~?/lcai.binoE a brown viscous liquid b. p. 161-164O/35 mm. DY 0.981 nD 1.538 from isobutyrone and magnesium beozyl chloride is considerably limited by the formation of *and Bull. Soc. chirn. 1914 [iv] 15 159-162.i. 252 ABSTRACTS OF CHEMICAL PAPERS. dibenzyl. On catalytic! dehydration by oxide of t,horium i t yields an olejne b. p. 252-255'/ordinary pressure DY 0.91 10 w 1,542. Magesium cyclohexyl chloride reacts readily with isobutyrone but on decomposition with water the complex is partly decomposed with formation of cyclohexene. cyc~o~ezy~daisopropy~cccrbinol b.p. 1 253/ 12 mm. 138'/25 mm. Ds 0.9153 n 1.474 i s therefore obtained in poor yield. On dehydration i t yields a n o h j n e b. p. 225-228'1 760 mm D1,2 0.8782 n 1.482 which probably consists of a mixture of the isomerides C,El,*CPrKCMe2 and C,H,,:CPr2P. Glucal and Hydro- glucal. EMJL FISCHER (Ber. 1914 47 196-210. Compare A. 1913 i 445).-A more romplete account and an extension of the work described in the earlier communication. Glucal absorbs two atoms of hydrogen in presence of platinum yielding a crystalline compound C,H,,O,. The same subqtance is obtained by reducing triacetylglucal (acetoglucal) and hydrolysing the product. Prom a study of these compounds the formula CBHl0O4 as against C6H803 is assigned t o glucal. On reduction glucal loses its aldehydic and unsaturated characters.It seeme possible therefore t h a t glucal contains a n oxymethylene group and the pine-splinter reaction further suggests a furan ring. The provisional formula is now considerably modified and the present suggestion is H. W. New Reduction Products of Dextrose. C( :CH*OH)-C;H*OH o<CH(CH,.0U)-CH2 ' I n whatever way the results are interpreted tbe reduction of aceto- bromoglucose to triacetylglucal is most remarkable. Triacetylglucal crystallises best from a mixture of alcohol with a little light petroleum but the process has t o be repeated many times before a n optically pure product is obtained. It has m. p. 55O [a]' - 15.76'; it may be distilled reduces Fehling's solution and absorbs two atoms of bromine When boiled with water it is partly hydrolysed one molecule of acetic acid being set free.The product ? diacetylgluccd C,,H,,O was distilled and obtained as a bitter amorphous substance which quickly restores the colour to Schiff's reagent and gives a deep violet coloration with cold fuming hydrochloric acid. It conld not be obtained optically pure and may be a mixture. Complete hydrolysis to glucal was effected by leaving a solution with a little more than the t,henretical quantity of baryta water in a n incub:itor. ~~iacetyZhl/drogZucaZ C6H9O48c3 was prepared by catalytic reduction quickly distilled under 0.5 mm. bath 160-165" and obtained as a vitieous mass with indefinite constants [a]:' about + 24-35'. It is indifferent towards Fehling's solution acids a1 kalis and bromine.Hydroglucal mas prepared by direct reduction but the best results were obtained by hydrolysing triacetylhydroglucal by means of baryta. HgdrogZucaZ forms colourless hexagonal prisms or plates m. p. 86-87' [u]z +16*31' and distils under 1 mm. bath 195-205'. It is very hygroscopic has a slight sweet taste and does not combine with water even when heated with concentrated hydrochloric acid. When heated with hydriodic acid and phospbonium iodide it is reduced to a,ORGANIC CHEMISTRY. i. 253 colourless oil b. p. 90-95' (bath)/O.4 mm. 128-131°/12 mm. 160' (corr.)/33 mm. The product has the ccnstitution and properties of R di-iodohexane but has not been identified. Glucal and hydroglucal were both directly acetylated to their parent triacetyl derivatives.Acetobromolactose was reduced to ncetolactal C,,H,,OI a colourless amorphous mass of leaflets and probably a hexa-acet,yl compound. J. C. W. H. HJ~RISSEP and A. AUBRY (Cornpt. rend. 1914 158 204-206*).-The authors have synthesised a-methylgalactoside by the action of air-dried bottom yeast macerated with water on a solution of galactose in dilute methyl alcohol. The action was slow owing to the small amount of the necessary enzyme in the yeast. The product was obtained in the form of colourless crystals having physical properties i n close agree- ment with those given by Fiscber (compare A 1895 i 437) for the substance prepared by purely chemical methods. The Inversion of Sucrose. EDXUND 0. VON LIPPMANN (Chem. Zeit. 1914 38 145-146).-A paper calling attention to the import- ance of the recent work of Snethlaga.(A. 1913 ii 1044) in which the catalytic effect of the undissociated acid molecule on the inversion of sucrose is discussed. I. Reactions among Certain Classes of Compounds Containing Nitrogen. 11. The Beckmann Rearrangement. LAUDER WILLIAM JONES (Amer. Chem. J. 1913 50,414-443).-The processes of oxidation and reduction may be regarded as an exchange of electrons between atoms a loss of negative electrons corresponding with oxidation and a gain of negative electrons with reduction. As Fry (A. 1912 ii 546) has pointed out a quadrivalent carbon atom would thus shorn five stages in the series of oxidation and reduction according as t o whether its valencies are all positive all negative or some positive and others negative.Similarly a tervalent nitrogen atom presents four stages corresponding with its statos of oxidation in ammonia hydroxylamine hyponitrous acid and nitrous acid whilst a quinquevalent nitrogen atom presents six stages. A consideration of the transformations characteristic of primary amines R*CH,*NH aldimides R*CH:XH nitriles R*CiN nitrile oxides R*CiN:O and related compounds suggested that the electronic hypothesis might be used to elucidate the relations between these compound8 and to indicate a mechanism i n terms of which their transformations might be represented more precisely than by the ordinary structural formulae. A discussion is therefore given on these lines of the relations (1) between primary amines and their products of hydrolysis ; (2) between aldimidee /3-alkylhydroxylamiries and aldehyde ammonias ; (3) between nitriles aldoximes and amides ; (4) between nitrile oxides isonitroparaffiins and hydroxamic acids and (5) between hydroxamic acids carbimidea and estrbarnic acids.It is stated that the various reactions generally regarded as examples of the Beckmann rearrangement consist in every case of processes of *and J. Plmrm. Chim. 1914 [vii] 9 226-230 Biochemical Synthesis of a-Methylgalactoside. MT. G. T. S. P. Applications of the Electronic Conception of Valence.i. 254 ABSTRACTS OF CHEMICAL PAPERS. intramolecular oxidation and reduction; and the bearing of this on the mechanism of the rearrangement is discussed in the light Gf the electronic hypothesis. E. G. The Preparation of Hydramine Ethers and Hydramines and a New Way to the Choline Group.J. HOUBEN and K. F~ERER (Ber. 191 4 4'7 75-82).-The interaction of ap-dichloroethyl ether and organomagnesium compounds to produce substances of the type OEt*CHR*CH,CI as already described by the authors (A.? 1908 i 73) can serve as R first step to the synthesis of several important groups of compounds because the remaining chlorine atom can be replaced in various mannew. A1 kali hydroxides remove the chlorine with formation of an unsaturated ether. The action of ammonia and primary amines is complicated by the usual formation of secondary and tertiary bases respectively by the further action of t h e halogen compound or the primary product. With dialkylaouines the chemical change proceeds smoothly with formation of substances of the general formula OEt*CHR*CH,*NR in which the ethoxg-group can be converted into hydroxgl by the action of concentrated hydrobromic acid. When butylene up-chlorohydrin ethyl ether OEt*CHE t*CH,CI was heated with a bimolecular proportion of diethylamine for twenty-four hours a t 135' followed by two hours at 160° the major poi*tion was converted into diethyl-0-ethoxy-n-butyzamine OEt*CHEt*CH,.NEt a mobile liquid b.p. 179-181' of strong basic odour; hydrochloride hygroscopic. If isohexylene-u~-chlorohydrin ethyl ether CHAle,*CH,*CH( OEt) *CH,Cl is heated with diethylamine first a t lOO'and then at 130° the product is diethyEP-ethoxy-6-methyZ-n-amylamine CHMe,*CH,*CH(O Et) *CH,.NEt a colourless basic liquid b. p. 86-89O/9 mm. 196-206"/ord.pressure of c herac t eris tic odour. isoKeptylene chlorohydrin ethyl ether reacted very incompletely with diethy larnine at 135O producing n small quantity of diethyl-,L3-ethoxy- E-metJj yl-n-hexylaazine b. p. 108'/9 mm. The interaction of phenylethylene chlorohydrin ethyl &her and diethylamine a t 128' gave rise to diet~yl-P-etrlloxy-P-phenylethylamine OEt*CHPh*CH,*NEt a liquid b. p. 124-125O/lO mm. of basic odour accompanied by a little acetophenone. From the reaction product of phenylethylene chlorohydrin ethyl ether and animonia obtained by prolonged heating of the mixture in alcoholic solution at 90° and 120° there could be separated by distilla- tion P-ethoxyphenylethykamine OEt*CHPhmCH,*NH a strong base b. p. 228-2SO0/ord. pressure 125'/20 mm. of characteristic odour and di-P-ethoqphenylethylamine NH(CH,*CHPh*OEt) a base of feeble odour b.p. 210-213'/10 mm. In a similar manner the interaction of phenylpropylene chlorohydrin ethyl ether and diethylamine in alcoholic solution at 120' produced P-ethoxy-y-phenpl- a-propylarnine CH,Ph* CH (OEt) CH,*NH b. p. 139*5-140*5O/14 mm. of basic odour together with di-P-etAoxy-y-phenyl-ORGANIC CHEMISTRY. i. 255 n-propylumins NH[CH,*CH( OEt) *CH2PhI2 b. p. 235-236"/13 mm. the latter substance preponderating. When diethyl-P-ethoxybutylamine is heated with hydrobromic acid (D 1-49) under such conditions that the ethyl bromide produced can pass away over 80% of the theoretical quantity of ethyl bromide can be collected in the course of five hours and the reaction flask contains diethyZ-P-l~ydroxy-n-but~lamine OH.CHEt*CH,*NEt a colourless liquid b.p. 63-64"/13 mm. of strong odour. It can be acetylated and its salts are easily soluble in water ; hydrochloride hygroscopic. The quaternary ammonium hydroxides derivable from this base will be homologues of choline. D. F. T. Physic0 - chemical Researches on Urotropine [Hexa- methglenetetramine] regarding the Constitution of the Baae. C. Russo (Gaszetta 1914 44 i 16-26).-Conductivity measurements in solutions of hexamethylenetetramine and hydrochloric sulphuric and nitric acids show the formation of monoacid saits and their hydro- lytic decomposition but afford no indication of the formation of diacid salts. The reaction which occurs is probably represented by the formula Conductivity measurements and also measurements of the change of rotatory power of dextrose show that hexamethylenetetramine is a little more strongly basic than aniline and this agrees with the cyclic formulEe which have been proposed rather than with the formula of Liisekann.C,H,,N,' + HI' + H,O = C5H14N4' + CH,O. R. V. S. Cobaltous T e t r a b o r a t e and Hexamethylenetetramine. G. ROSSI (Gazxetta 1913 43 ii 669-671)-Cobaltous tetraborate although i t exists in solution cannot be prepared in the solid state. When however a solution of cobaltous acetate and hexamethylene- tetramine is treated with a solution of sodium tetraborate a red amorphous substance (COB,O~)~,C,K,,N~,~H,O is obtained. R. V. S. Some Palladionitrites of Bivalent Metals Fixed by means of G. SCAGLIARINI and G.B. ROSSI (Atti R. Accclcl. Organic Bases. Lincei 1913 [v] 22 ii 506-508).-The compound is a straw-yellow crystalline substance which is obtained by the gradual addition of a cold solution of palladium chloride and sodium nitrite slightly acidified with hydrochloric acid to a cold saturated solution of magnesium nitrite and hexamethylenetetramine obtained by adding the requisite quantity of sodium nitrite and hexamethyl- enetetramine to a solution of magnesium acetate. The compound MnPd(N02),,8H20,2C,H:,,N forms yellow crystals. The compound NiPd(N0,)4,8H,0,2C,H,2N4 forms emerald-green crystals. The compound CoPd(N0,),,8H20 2C,H,,N forms pink crystals which rapidly alter in air SO that the preparation is best carried out in an. atmosphere of hydrogen.The substance is isomorphous with the corresponding magnesium and manganese compounds and forms solid solutions with them. MgPd(N02)4,~H20,2CgH12N4 R. V. S.i. 256 ABSTRACTS OF CHEMICAL PAPERS. Study of Some New Alkylhydroxylamines. CHARLES H. HECKER (Amer. Chem. J. 1013 50 444-466).-This work was undertaken with the object of discovering methods for readily obtain- ing good yields of a1 kylhydroxg lamio es. up-Dial ky Iliyd roxylamines have been prepared by Jones' method (A 1907 i 897) which consists in the hydrolysis of a hydroxyalkylurethane ether (carbetboxy-ap- dialkyl hydroxy lamine). By the action of ethyl iodide on carbethoxy-a-ethylbydroxylamine (hydroxyurethane ethyl ether) (JoneP A 1898 i 174) in presence of odium ethoxide carbethoxy-up-diethylhydroxylnmirie (bydroxy- ethylurethane ethyl ether) CO,Et*NEt*OEt b.p. 72 -74"/12 mm. is obtained which when heated with potassium hydroxide solution in a sealed tube at 1 OO" is converted into up-diethylhydroxylamine. Cadethoxy-a-ethyt-p-prop ylhydroxy lamine CO,E t O N Pra*OE t has b. p. 189"/740 mm. ; on hydrolysis i t yields a-ethyl-P-pro~ylhydrox?/lamine NHPra*OEt b. p. 83-8-84" DZ 0.8033 ng 1.39426 which is a colourless liquid with a n ammoniacal odour and a sweet pungent taste ; the hydyochlovide has m. p. 72-5-73' Carbethoxy-a-et?iyl-/3-isopropylh~ydroxylamine has h. p. 182"/748 mm. x n d 84 -8 7"/ 1 5 m m a-Ethyl-P - isopropylh y dy oxy lamine b . p. 7 so DZ 0.S132 has a n odour like that of ethplamine; its pkatinicldoride forms small lemon-yellow crystals.By the action of propyl iodide on the potassium salt of hydroxy- uret hane there are produced carbethox?l-a-propylhydroxylamine CO,Et* NH*OYra b. p. 109-1 11'115 wm. and carbethoxy-up-clipropyt- hydroxylamine C02Et*NPra*OPra b. p. 107*5-108°/20 mm. a-Propyl- hydroxylamine NH,*OPra b. p. 86*6-87' Dg 0,8687 obtained by the hydrolysis of carbethoxy-a-propylhydroxylamine i s R colourless liquid with a sweet amtxoniacal odour ; its ?&rochloridR M. p. 140-141° and platinichlorida are described. up-Bipropylhydrox3lamine b. p. 86-86" Di2 0.8141 obtained by the hydrolysis of carbethoxy-ap- dipropylhydroxylamin~ yields a hydrochloride m. p. 146*6" and a p latinichloride. ha s b. p. 191"/750 mm. aud 92.6O/20 mm. and on hydrolysis furnishes p-ethyZ-a-iM.o~jylhydroxylamine which gives a hydrochloride m.p. 96.2" and a platinichloride. Carbetl,oxy-a-isopropylhydi*ozylarnin~ b. p. 102-103°/1 2 mm. is almost od ourless ; carbethoxy-ap-rliisopro~~~~~y~roxy2umilz~ has b. p. 101- 101*5O/15 mm. a-isoP?.opylhycE1.oxylnmine b. p. 72.2' (uncorr.) Dii 0.8459 has a puDgent disagreeable odour ; its hydq*ochloride has m. p. 84.8O. ap-Diisop?.opylhy~roxyEamilze b. p. 76-6-77' DE 0.8525 yields ft hydrochloride m. p. 74.89 Curbethoxy-P-f!thyl-a-isopro~~Zl~ycll.ol ylamine has b. p. 18 1-1 83" and on hydrolysis f rirni+hes /~-elhyf-a-isopro~y~hydroxylc/lnine b. p. 8%" 0.8730 ; the Irydvochloricle and ykatinichloride of the latter are descri bed. The carbet hoxy-alkyl- and -dialkyl-hydroxylnmines are colourless oils with characteristic odours and do not reduce silver nitrate or Fehling's solution.The a-alkylhydroxylamines and the ap-dialkyl- hydroxylamines containing two identical groups are readily soluble in Car bethoxy-P-et h yl -a-prop/lhydrox y2 amnine CO,E t NE t OPr a,ORGANIC CHEMISTRY. i. 257 water whilst the mixed ap-dialkylhydroxylamines are not very soluble. Aqueous solutions of the 'a-alkylhydroxylamines exert an energetic reducing action but the ap-dialkylhydroxylamines are much less active in this respect. li:. G . Glycocyamidine. ERNST SCHMIDT (Arch. Phnrm. 19 1 3 2 5 1 557-562).-The conversion of glycocyamine into glycocyamidine by hydrochloric acid is much more difficult than that of creatine into creatinine (Korndorfer A. 1905 i 29). A nearly quantitative conversion can be eeected by heating glycocyamine just covered with concentrated sulphuric acid in a steam-bath for twenty-four hours ; the solution is diluted with water freed from sulphuric acid by aqueous barium hydroxide and finally barium carbmate and evaporated to dryness the residue of glycocyamidine is dissolved in boiling alcoho; and a little water and crystallised therefrom by spontaneous evapor- ation.The azcrichloride O,H,ON,,HAuCI m. p. 158O has been prepared. c. s. Synthesis of +-Leucine. F. KNOOP and GEORG LANDNANN (Zeitsch. phyttiol. Chem. 1014 89 157-159).-This substance q-butylaminoacetic acid has been syn thesised from trimethylpyruvic acid which yields an oxime C6HI1O3N,H20 m. p. 85-86' (anhydrous 121O decomp.). When the oxime is reduced by boiling with zinc dust and 50% acetic acid or with aluminium amalgam in 50% alcohol $-leucine C,H,,O,N is obtained ; it forms hard laminar crystals which begin to sublime a t 250'.The naphtiiccEenesulphony1 derivative C,,H,,O,NS form long acicular prisms m. p. 200-203°. The p-tolutvtesulphonyl derivative Cl,H19.U4NS crysiallises in short rect- angular prisms m. p. 226'. The mztrate forms needles m. p. about 151". R. V. S. The Action of Chlorine on Ethyl Carbamate. The Isolation of Ethyl Chlorocarbamate and its Behaviour towardst Amines and Acid Amides. RASIK LAL DATTA and SATYARANJAN DAS GUPTA (J. Amber. Chern. Soc. 1914 36 386-39O).-Although Schmidt (J. p Chem. 1881 [ii] 24 120) failed to obtain ethyl chloro- carbamate by the action of chlorine on ethyl carbamate a t 90-100° this substance can be obtained I € the reagents are brought together in well-cooled aqueous solution.A current of chlorine is passed into a dilute aqueous solution of ethyl carbamate when a yellow oil separates which from its behaviour towards potassium iodide must be ethyl chloyocarbamate NHCl*CO,Et. It is a pale yellow rather viscous oil do 1.44235 b. p. near 99' (decornp.). When kept either alone or uuder water it grddunlly decomposes. It has a pungent odour resembling the chlorocarbamides and painfully affects the skin causing a violet-black coloration or even a scar. Ethyl chlorocarbamate is an energetic chlorinating agent but less vigorous than dichlorocarbamide. With benzylaluine i t produces bensyl-chloroamine or -dichloroamine according to the relative amounti.258 ABSTRACTS OF CHEMICAL PAPERS. of the reagents whilst with benzamide the product is benzoyl- chloroamide. An alternative structure is suggested for the substance 4NBr,*UO,Et,NaBr described by Hantzsch (A. 1894 i 363). D. F. T. The Hydrolysis of Salts. NILRATAN DHAR (Zeitsch. c m o y . Chein. 1914 85 19S-205).-The elect.rica1 conductivity of solutions of carbamide nitrate and oxalate has been determined a t 30". Both salts are hydrolysed to a considerable extent even in the presence of an excess of the corresponding acid. C. H. D. Action of Bromine and Alkali Hydroxide on Garbamide and Guanidine Derivatives. 11. V. VON CORDIER (Monutsh. 1914 35 9-45. Compare A. 1912 i 684).-The author has extended his work and obtained results which for the main part confirm those previously described.Decomposition has generally been effected with sodium hypobromite occasionally with potassium hypo- bromite. Reaction generally takes place a t the ordinary temperature but in certain cases slight cooling is necessary to moderate the violence. I n many cases reaction occurs with extreme slowness. The most important new results may be summarised as follows I n the case of derivatives of thiocarbamide either no nitrogen or only one atom is evolved. The first behaviour is shown by all derivatives containing univalent radicles as substituents which have been hitherto assumed to be constituted according to the symmetrical formula. As previously observed the influence of the sulphur atom is restricted to the portion of the molecule in which it is contained The second mode of reaction (elimination of 1 atom of nitrogen) which had been previously observed only in the case of methylenethiocarbamide occurs when bivalent radicles are contained as substituents in the thiocarbamide molecule.As an alternative to the hypothesis of a restrictive action of the sulphur atom it is possible that the constitution of the thiocarbamide molecule may be the deciding factor and that derivatives of i t are not produced from the symmetrical form ; those compounds which do not yield nitrogen are con- NH:C<xH3 N H ' C < ~ ~ stituted according to the formula (I) of Werner (T. 1912 101 2180) whilst those giving 1 atom of nitrogen are derived from the iso-form of thiocarbamide (11) (compare Storch A 1891 548). Selenocarbamide evolves a certain amount of nitrogen which however does not attain the quantity oalculated for one atom A regularity in the evolution of nitrogen from alkyl derivatives of carbamide or guanidine could not be observed.This influence of alkyl groups is also apparent in the case of substances which contain in addition other substituents (acetylmethylcarbanuide nitrosomethyl- carbamide creatine) and is probably exercised i n additive compounds when the added component contains an alkyl (methyl) group; thus guanidinesarcosine hydrochloride in contrast to glycine guanidine NH m. (11.)ORGANIC CHEMISTRY. i. 259 carbonate reacts with hypobromite solution as ari ordinary additive compound that is it immediately gives the normal amount of nitrogen and no more which is probably due t o the methyl group of the sarcosi ne.Contrary to the opinion expressed in the previous publication no general conclusions can be drawn from the results which have been obtained up to the present with halogen derivatives (bromo- and chloro-guanidine). As far as can be judged the nitroso-group (nitrosoguanidine nitroso- methylcarbamide) appears to behave in the same manner as the nitro-group that is i t does not appear to hinder the evolution of nitrogen and itself yields free nitrogen; on the other hand the oximino-group (violuric acid) has apparently no influence on the evolution of nitrogen. In the compounds of carbamide with metallic oxides (carbarnide mercuric oxide CO(NH,),,SHgO) the latter substances do not inhibit the evolution of nitrogen.Nitrogen is only very slomly evolved by the action of hypobromite solutions on melamine and the amount corresponds but poorly with that calculated for one atom. The author is therefore led to the conclusion that melamine does not contain a free amino-group and thus regards the formula N H C < ~ ~ $ $ ~ { > N H as the most probable. H. W. Ethyl Diazoacetate and Thiocyanic Acid. BHOR HOLMBEHG (Be?.. 1914 47 165-166).-The speed of the reaction between the thiocyanate ion and ethyl diazoacetate has been measured by the method employed in the study of the influence of the sulphate and nitrate ions (A 1908 i 387). The thiocyanate ion is approximately as active as the iodine ion. On a preparative scale 20 grams of ethyl thiocyanoacetate were obtained by gradually acidifying a mixture of 150 grams of potassium thiocyanate in 200 C.C.of water and 34 grams of ethyl diszoacetate the decomposition of the latter almost exclusively following the course N,CH*CO,Et + I3 + SCN = NC*S*CH,*CO,Et + N,. J. C. W. Physico-chemical Investigations of Some Complex Cuprous Salts. NILRATAN DHAR (Zsitsch. ccnorg. Chem. 1914 85 44-48).-Cuprous thiocyanate dissolves in solutions of alkali thio- cyanates but is re-precipitated on dilution. The conductivity of solutions of ammonium or potassium thiocyauate is lessened by the addition of cuprous thiocyanate indicating the formation of a complex ion Cu(CNS),. C. H. D. Reactions in Non-Aqueous Solutions. VI. In Acetonitrile. Compare A. 1910 ii 21 1).-Qualitative and quantitative measure- ments of the solubilities in anhydrous acetobitrile of a large number of different salts and also of the halogens have been made.The ALEX. NAUMANN [With ADAM SCHIER] (Bey. 1914 47 247-256.i. 260 ABSTRACTS OF CHEMICAL PAPERS. following efflorescent compounds with acetonitrile of crystallisation were obtained CuC1,,2MeCN CuCI,,MeCN CuBr,,MeCN Cu12,2MeCN CaCl,,MeCN Ca(NO,)?,MeCN ZnCI2,2MeCN CoC1,,3MeCK. The reactions of the haloid salts of copper cobalt iron (ferric) bismuth zinc and tin (stannous) with various reagents in acetonitrile solution were also studied qualitatively and a number of abnormal reactions observed. T. 8. P. Univalent Compounds of Nickel. 111. I. BELLUCCI and R. CORELLI (Atti R. Accad. Lincei 1913 [v] 22 ii 485-489. Compare A. 1913 ii 604; i 839).-By effecting the reduction of R solution of nickelocganide (yellow) with potassium amalgam in a n atmosphere of hydrogen and adding to the red solution an excess OF alcohol the atmosphere of hydrogen being maintained the authors have isolated the red cyano-salt and find i t has the formula K,Ni(CN) so that i t contains univalent nickel.When ite solution is acidified an orange-yellow precipitate is formed which is nicke2 monocyanids NiCN. It is very readily oxidieed forming nickelic cyanide Ni (CN )2. R. V. S. Tungsten Cg anides. ABTHUH. ROSENHEIM and EITEL DEHN (Bey. 1914 47 392-400).-Several years ago Rosenheim described a molybdenum cyanide K4D~o(CN),,3H,O in which the molybdenum acted towards oxidising agents as a quinquevalent metal although according t o the formula it should be quadrivalont (compare A 1910 i 101,232).The authors have now prepared corresponding compounds of tungsten which show a similar behitviour. A solution of Marignac's compound H,[Si( w,o,),],28 H,O in con- centrated hydrochloric acid is reduced electrolyticdlg in the apparatus described by Roeenheim and Loebel (A.? 1908 ii 294) until the solution becomes greenish-yellow in colour. The excess of acid is then quickly neutralised with strong alkali hydroxide a large excess of potassium cyanide added and the solution concentrated on the water-bath. A similar solution may be obtained by treating the compound K,W,CI described by Olsson (A. 1913 ii 328) directly with potaseium cyanide. When this solution is treated with a concentrated solution of cadmium sulphate and digested on the water-bath a n impure cadmium salt separates ; this is dissolved in concentrated ammonia solution and the solution saturated with ammonia whilst cooled in a freezing mixture.Long golden-yellow needles of the cacdmiumtriarnmine tungsten cyanide [ Cd(NH3),],[W(CN),],2H,O separate in which the tungsten acts as a quinquevalent dement towards oxidation with potassium permanganate although according t o the formula it should be quadrivalent. On exposure to the air or on washing with water one molecule of ammonia is lost giving the corresponding diammine salt [Cd(NH,),],[W(CN),],2H20. On treatment with 1-2% sulphuric acid microscopic yellow prisms of cadmium tungsten cyanide are obtained from which the potasszum b a l t K,[W(CN)8],2H,0 is obtained as light yellow microscopic prisms by double decomposition Cd,[W(CN)*198H,O,ORGANIC CHEMISTRY.i. 261 with potadsium carbonnte. triammine salt towards potassium permanganate. All these salts act in the same way as the A tentative explanation of the anomalous behaviour is given. tr. s. P. Mercury Derivatives of a€-Dibromopentane and Multi- membered Ring Systems Derived from Them. SrEaFRr ED HILPERT and GERHARD GR~TTNER (Bey. 19 14 47 177-185).-Tiie discovery of t.he magnesium compounds of the cuw’-dihaIogenopardfXns has opened up the way of preparing simple mercury derivatives of the higher aliphatic hydrocarbons. When a n ethereal solution of the magnesium compound of a€-dibromopentane (von Braun and Sobecki A.! 1911 i 701) for example is treated with powdered mercuric bromide it is converted quantitatively into pentamethplene-ac-di- mercuri-dibromide. The mercury atoms are very firmly attached but the halogen atoms are reactive ; thus the compound can be converted into the iodide nitrate or hydroxide.Hydrogen sulphide and acetylene form ring compounds the simplest formulac for which would be although the substances may be polgmerides. The replacement of the bromine atoms by a dibasic acid radicle gives rise t o ring systems containing oxygen ; thus azelaic acid forms a compound with eighteen members in the ring. The bromide also reacts with magnesium phenyl bromide,. yielding the remarkable compound pentamethylene-a€-di- mercuridiphengl Ph*Hg=[CH,],*Hg*Ph a repre$entative of mixed mercury dialkyls of which other members will soon be described.The results obtained by Grigaard (A. 1907 i 687) and by von Braun (Zoc. c i t . ) in the action of magnesium on mc-dibromopentane do not coincide. The latter was able t o show in his experiment t h a t only about 50% of the normal organomagnesium salt had been formed whereas the former obtained products which corresponded with a high yield of that salt. The reaction with mercuric bromide affords ti clue t o the actual amount of normal magnesiurri derivative preseut. If t h e reaction is accelerated by using very dry ether and activated magnesium a 50% yield is obtained whereas with imperfectly dry ether the reaction is slow but the yield is 90%. Pentamthjtene-a€-dirnercuri-dibromide C,H,,Hg,Br forms white doubly refractive needles from toluene m.p. 150’. It is very solublo in pyridine but when not quite pure is blackened by that base. When boiled with alcoholic potassium iodide i t yields the di-iodide in slender white ueedles m. p. 117” whilst hydrogen sulphide precipitates the sutphide (I) from a cold pyridine solution quantitatively as a snow- white odourless insoluble powder. The hydroxide was obtsiued by boiling the bromide with silver oxide in SO% alcohol. It forms very slender white needles. Sulphuric acid gradually precipitated the sulphute C,H,,Hg,S04 from a 50% alcoholic solution of the hydroxide in microscopic white needles which suddenly blacken above 150‘. The nitmtz was obtained by treatiug the bromide with d v e r nitrate. Its solution in alcohol was used to prepare the chloride white needles VOL. CVI.i. ti. 262 ABSTRACTS OF CHEMICAL PAPERS. m. p. 184" the oxalate succinate and Jewocyanide white precipitateF the axdate C,,H,,Hg,O white scales and the acetylide (11) a white precipitate which takes fire on heating. Pentanietl~ylene-ac-diinercuridl:1Jhen~Z was obtained as a colourless viscous oil with repulsive smell. It only bogins to decompose in vacuum at 180'. It quickly decolorises iodine in benzene at 35' forming the above di-iodide and on prolonged boiling with the solution decomposes into mercuric iodide ac-di-iodopentane and iodobenzene J. C. W. Heterocyclic Systems Containing Metals. I. cycZoMercuri- pentamethylene. SIEGFRIED HILPERT and GERHARD GRUTTNER (Bey. 1914 47 186-196).-Attempts have been made to prepare simple mercury-carbon ring compounds by $he action of sodium amalgam on ww'-dihalogenoparaffins.Ethylene and trimethylene bromides did not react but aa-dibromopentane gave a mixture of a small quantity of a well-defined crystalline solid m. p. 120' a larger amount of a substance m. p. 41° but chiefly an oil. They have the same empirical formula C,H,,Hg and are identical in their reactions. Of these the most characteristic is the behaviour towards bromine or iodine. These agents cause the formation of the pentamethylene-arc- dimercury haloids (preceding abstract) and the dihalogenopentanes. Mercuric haloids also produce the same mercury compounds. The results can be interpreted on the basis of either of the annexed formulae The estimation of the molecular weights of mercury compounds in general by ebullioscopic methods gives unsatisfactory results but the product m.p. 120° corresponded roughly with the simple ring M.W. 270; the substance m. p. 41° has four times this molecular weight and the oil six times. Certainly the latter are polymerides the cycZomercuripentamethylene corresponding with the polymethylene- oxygen and -sulphur ring compound8 in its readiness to undergo polymerisation. Thirty grams of aedibromopentane 100 grams of benzene 3 grams of ethyl acetate and 900 grams of 1% sodium amalgam were shaken for twenty hours at 75" in a pressure flask when the solveut layer was washed evaporated and the residue extracted with absolute alcohol. The insoluble wax-li ke product (23 grams) was extracted with light petroleum and ether leaving the compound m.p. 41" (6.5 grams). The extract was allowed to evaporate when the substance m. p. 120' (2.5 grams) crystallised and was filtered from the oil. cycloMercuripentamethylene forms hard white rhombic doubly refractive crystals m. p. 120° from a mixture of benzene and light petroleum. The solid polymevide was purified by crystallisation froui much ether and obtained as a white powder m. p. 41". The behaviour of them and of the polymeric oil towards bromine iodine and mercuric haloids is described. The reaction with iodine at about 35' was followed quantitatively and theoretical yields of pentamethylenc- dimercuri-iodide and di-iodopentane were obtained. J. C. W.ORGANIC CHEMISTRY. i. 263 Interpretatione of Some Stereochemical Problem8 in Terms of the Electronio Conception of Positive and Negative Valences.I. Anomalous Behaviour of Certain Derivatives of Benzene. HARRY SHIPLEY FRY ( J . Ainer. Chem. Soc. 1914 36 248-262).-The theory given in previous papers (A. 1911 i 431 ; 1912 ii 713) is applied to explain (1) the formation of the different disubstituted benzene derivatives when chlorobenzene and nitro- benzene are respectively nitrated and chlorinated ; (2) the exchange of halogen for hydroxyl when 0- and p-bromonitrobenzene are treated with potassium hydroxide whereas the meta-compound is not affected; (3) the action of the halogens on silver benzoate ; (4) the elimination of only one molecule of carbon dioxide from the dihydrophthalic acids when oxidised ; (6) the elimination of carbon dioxide from o- and p-hydroxy- benzoic acids but not from the meta-isomeride when heated with water or aniline; (6) the elimination of carbon dioxide from ethyl chloroformate by heating with pyridine.In the latter case experi- mental evidence is given in support of the author’a theory which predicts the formation of an unstable intermediate compound. According to the author theory and various chemical reactions show tbat ethyl chlorocarbonate is the only correct name for the compound CI*CO,Et and not ethyl chloroformate as i t is often called. Positive and Negative Hydrogen the Electronic Formula of Benzene and the Nascent State. HARRY SHIPLEY FEY (J. Amer. Chem. Soc. 1914 36 262-272).-Applying the principles given in his previous papers (see preceding abstract) the author considers the evidence for the existence of positive and negative hydrogen and for the electronic formula of benzene in which the hydrogen atoms are alternatively positive and negative.The nascent state of a n element is defined to be “ a n unstable condition of a substance which manifwts an adaptability and a tendency to lose or gain electrons and thereby revert to a more stable conditioa. If the substance (ion atom o r compound) lose negative electrons it acts as a reducing agent. I f it combines with negative electrons it acts as an oxidising agent.” As a matter of fact practically all actions classed as “nascent” are of an oxidation or reduction type. FRED. WALLERANT (Compt. rend. 19 14 158 385-386).-Dichlorobenzene is trimorphous under atmospheric pressure and the three states can co-exist a t the ordinary temperature side by side in the same mass.The reversible transformations occur at -25’ and 2 9 O the three forms being biaxial monoclinic aud having the plane of the optical axes coinciding with the plane of symmetry. The author gives an account of these forms and the changes they undergo. Dinitro - derivatives of Meta - dihalogenated Benzenes. W. KORNER and CONTARDI (Adti R. Accad. Lincei 1913 [v] 22 ii 625-634).-With the dibromodinitrobenzene described below tbo whole of the eleven possible icomerides have been prepared. The crystallographic examinatiom were made by E. Artini. T. S. P. T. S. P. The Crystallographic Properties of Dichlorobenzene. W. G. t 2i. 264 ABSTRACTS OF CHEMICAL PAPERS. 3 5-Dibromo-1 2-dinitrobenzeneY C6H?Br2(NOa),,.prepared by the action of nitric and sulphuric acids on 3 5-dibromo-l-nitrobenzene forms almost colourless crystalp m. p. 84.8' and is trimorphow. The a-modification belongs to the prismatic class of the monoclinic system a b c=1*4301 1 1.1901 /3=81"39' D 2.317 ; the P-modification to the rhombic system a b c = 1,7917 1 0.5667 D 2.2'79 ; and the y-modification to the prismatic class of the monoclinic system u b c = 1.7040 1 0.5280 P= 86"27' D 2.274. It reacts with alcoholic amwouis even in the cold giving 4 6-dibromo-2-nitroaniline C,H,O,N,Br m. p. 127". 3 5-Dichloro-1 2-dinitrobenzene CGI€2C12(N02)2 obtained similarly t o the preceding compound forms tetragonnl crystals a c = 1 1.9767 m.p. 95O D 1.773 and is hence neither isolnorphous nor isosymmetrical with the corresponding dibroruo-derivative. 2 4-Dibromo-1 3-dinitrobenzene C,H,Br2(N02)2 obtained by nitrating 2 6-dibromo-l-nitrobenzene forms well-developed greenisli- yellow triclinic prisms m. p. 82.8' and on further nitration iu presence of sulphuric acid gives 2 4-dibromo-1 3 5-trinitro- benzene C6H13r,( NO,) in gretwish-yellow prisms m. p. 135". With alcoholic ammonia tho latter compound forms 2 4 6-trinitro m- phenylenediamine as a yellow powder m. p above 200" (decomp.) and this is converted by potassium hydroxide into potassium styphnate. 4 6-Dibromo-2 5-dinitroaniliue CGHBr2(N0,)2;NH obtained by the action of bromine 011 a suspension of 2 5-dinitroandine in bydro- bromic acid forms orange-yellow needles in.p. 143". 3 5-Bib?.orno-l 4-dinitrobemene C,H,Br,(NO,) obtained by the spontaneous decompositiou in presence of ice of the nitrite of the diazo-compound of 2 6-dibromo-4-uitro;tniline forms yellow striated monoclinic prisms m. p. 130". 3 5-Dichloro-1 4-dircitrobenzene7 C,H,CI,(NO,) obtained similarly to the preceding compound from 2 6-dichloi o-4-uitroanilioe forms chining colourless prisms m. p. 114'. 3 5-Bi-iodo-1 4-dinit~obeneene C,H2T2(N0,) prepared similarly to the two preceding compounds forms monoclinic prisms I ~ I . p. 155'. 3-Chloro-5-bromo-2 4-dinit~obenzene C6H2CIBr( NO,) prepared similarly from 2-chloro-6-bromo-4-nit roaniline forms driiost colourlees needles or prisms m. p. 114.59 3-Chloro-5-iodo-1 4-dinitrobenzeneY C,H,CII( NO,) similarly pt e- pared forms slender white needles or prisms m p.100". 3-Bromo-5-iodo-1 4-dinitrobenzene C6 11 BrI(N O,) similarly pre- pared foims monoclinic crystals m. p. 140". Etch of these dihalogenated dinitrobenzenes is converted by alcoholic ammonia into the dihalogenated nitroaniline from which it was prepared. T. H. P. Researches on Amines. IV. The Alkylation and Hydrolysis of Aliphatic Sulphonamides. A New Synthesis of Sarcosine. TREAT B. JOHNSON and JOSEPH A. AMBLER ( J . Amer. Chem. Soc. 1914 36 372-385).-~Toluene-o-sulphonamide is especially well adapted to the synthesis of amines by Hinsberg's method (A. 1892 64) asORGANIC CHEMISTRY. i. 265 the toluene-w-sulphonic acid produced on hydrolysis with hydrochloric acid undergoes complete decomposition into eul phur dioxide and benzyl chloride thus obviating the necessity oE the precipitation oE the synthesised base before its hydrochloride can be separated.Toluene-o-sul phonamide CH,Ph*SO,*NH possesses acidic properties and gives a sodium and a potassium salt the latter forming micaceous flakes. Both these salts react with a warm alcoholic solution of methyl iodide producing tolue?ze-w-sulphonmethylamide CH,Ph*SO,*NHMe colourless needles m. p. 109-1 I Oo tegether with toluene-o-sulphon- dimethylamide CH,Ph*SO,*NMe thin plates m. p. 102-103° which are readily separable by potassium hydroxide solution in which the latter is insoluble. I n a similar manner the potassium salt when digested with an alcoholic solution of ethyl bromoacetate undergoes condensation to form ethyl toluene-o-sulphonpZa??iinoacetate CH,Ph-SO,*NH*CH,*CO,E t a viscous oil which on hydrolysis with the requisite amount of potassium hydroxide is converted into the corresponding potassium salt a colour- less powder.Condensation of toluene-o-sulphonamide with chlor o- acetamide in an analogous manner gives rise to the formation of tol~ne-o-sulphonylarninoacetamide,CH2Ph *S0,*NH*CH,*CO*NH2,smnl I granular crystals m. p. 157O which on digestion with sodium hydroxide solution gives toluene-w-sulphonylaminoacttic mid CH,Ph*SO,*N H*CH,*CO,H plates m. p. 149-150°; this can also be obtained but in poor yield by the interaction of toluene-w-sulphonyl chloride and glycine in t h e presence of alkali This acid when heated with ammonium thiocyannte in acetic anhydride containing a little acetic acid yields 3-toluene- F.' 'CH2>N*S0,* UH,P h yellow prisms NH-US o-sdphonyl-2-thiohydantoin m.p. 204' (decornp.). Toluene- o-sulph on ylmet h ylaminoncet amide CH,Ph SO,*NMe*CH,*CO N H colourless crystals m. p. 206O can be obtained by the action of methyl iodide on toluene-w-sulphonylaminoacetamide as also of chloroacetamide on toluene-o-sulphonrnethylamide. It is hydrolysed qriantitntively by barium hydroxide giving toluene-w-sulphonylsarcosine CH2Ph*S0,*NMe*CH,*C0,H colourless prisms m. p. 1 3 6 O which is slowly hydrolysed further by hydrochloric acid with formation of stircosine NHMe-CH,*CO,H the accompanying benzyl chloride being easily evaporated away over a steam-bath. Toluene-w-sulpiwnbenzyZamide CH,Ph*SO,*NH*CH,Ph was prepared analogously to the methyl and ethyl derivatives above by interaction of benzyl chloride and the potassium derivative of toluene-w-sulphon- amide; it forms colourless needles m.p. 145-146O and for its hydrolysis needs to be heated with hydrochloric acid a t 130° when benzylamine is produced. A New Synthesis of Some Indene Derivatives. ALEX. ORECUOFF (Bey. 1914 47 S9-'35).-1n the course of an investigation D. F. T.i. 266 ABSTRACTS OF CHEMICAL PAPERS. on the pinacolin rearrangement the author has submitted deoxy benzoin pinacone CH,Ph*CPh(OH)*CPh(OH)*CH,Ph to the action of acetyl chloride with the result that a@yrS-tetraphenyl-Aay-butadiene was found amongst the products. The dibromide of this hydrocarbon when boiled with acetic acid yields 2 3-diphenyl-l-benzylideneindene and examination indicates that this is but one case of a general method for the formation of an indene ring.The changes are represented by the general formulae C,H,* CRR* OPh CHPh- C6H CRR'*CPhBr*CHPhBr+ C,H4<Cph->CPh. CRR' [In part with (MISS) R. GR1NBERa.I-w hen deoxybenzoin pinacone is heated with boiling ace tyl chloride apy8-tetraphenyl-AaY- butadiene CHPh:CPh*CPh:CHPh begins to crystallise after one and a-half hours but the heating should be extended to four to five hours The hydro- carbon colourless needles m. p. 183-184' on oxidation with chromic acid in acetic acid solution gives a mixture in which benzaldehyde benz6ic acid and benzylidenedeoxybenzoin CBzPh:CHPh can be detected thus giving evidence in support of the assumed structure ; a small quantityof a colourless substance m.p.236-237',was also obtained. If a chloroform solution of bromine is gradually introduced into a suspension of the tetraphenylbutadiene in chloroform the bromine colour persists after the addition of a unimoleculor proportion and evaporation of the solution yields a dibromide CHPh:CPh*CPhBr*CHPhBr colourless prisms m. p. 175-176' (decomp.). When this is heated under reflux with acetic acid a vigorous evolution of hydrogen bromide ensues but is ended after half an hour and the solution on cooling deposits golden-yellow needles m. p. 184-185' of 2 t 3-diphenyl-l- benxylideneindene c 6 H ~ ~ H ~ ~ . > c P h the constitution of which is indicated by its oxidation with chromic acid in acetic acid solution to benzoic acid and diphenylindone C,H4<Cph>CPh co- which is already known (Hey1 and Meyer A.1896 i 146). apy-Triphenylpropan-P-ol was prepared from ethyl benzoate and magnesium benzgl cbloride by a slight modification of Klages' method (A. 1904 i 488) in a yield 60-65% of the theoretical. It very easily parts with the elements of water for example when shaken a t the ordinary temperature with sulphuric acid forming apy-triphenylpropene CHPh:CPh*CH,Ph large colourless needles m. p. 62-63'. The dibrornide was obtained as a yellow viscous oil by evaporating the chloroform from the solution in which it had formed and on boiling for half an hour with acetic acid rapidly loses hydrogen bromide with production of 2 3-dip?~n$indene C6H,<g@CPh colourless needles m.p. 117-178'; this substance readily unites with bromine and slowly gives a deep green solution in eulphuric acid. A solution i n warm alcohol containing a little benzaldehyde on the addition of a few drops of potassium hydroxide solution gives a gradual deposition of the 2 3-diphenyl-1-benzylideneinderie described above. D. F. '1'.ORGANIC CHEMISTRY i. 267 Dinitrotolane and Some Tolane Derivatives. A. WINTHER (Be?. 1924 47 310-31 l).-The author claims co-operation in Reinhardt’s results (this vol. i 3 1). T. H. P. Aromatic Substances Containing Multivalent Iodine. VIII. L. MASCARELLI and G. BRUSA (Atti R. Accad. Lincei 2913 [v] 22 ii 494-498. Compare Mascarelli and Toschi A 1912 i 322 ; Mascarelli A.1913 i 171).-2 2’-Di-iodo-a a’-dinaphthyl C2,,H,,12 can be prepared by diazotising a suspension of the corre- sponding diamiriodinaphthyl and pouring the product into a solution of potassium iodide ; after purification the substance forms pale yellow acicular crystals m. p. 224-225’. If i t is treated in chloro- form solution a t 0’ with chlorine a dichloro-derivative C2013L2C1212 m. p. 118-120’ (decomp.) is obtained. It. v. s. Aromatic Substances Containing Multivalent Iodine. IX. L. MASCARELLI and M. NEGRI ( A t t i R. Accad. Lincei 1913 [v] 22 ii 498-500. Compare preceding abstract).-The paper records unsuc- cessful attempts to obtain 1 l’-diamioo-P P’-dinaphthyl by reduction of the corresponding dinitro-compound with stannous chloride colloidal platinum and other reducing agents.The Metaquinonoid Question. IV. 0. STARK and L.. KLEBAHN (Bey. 1914 47 125-130. Compare A 1913 i 361 849 1165).- The authors have very frequently failed to obtain the deep yellow quinonoid tetraphenyl-m-xylplene and indeed have not been able t o discover a method by which its preparation may be assured. I n unsuccessful attempts yellow benzene solutions were obtained which gave an absorption band rather more towards the violet than in the successful experiments and deposited a white powder decomp. 397-303’. This is most probably a polymeride of tetraphenyl-m- xylylene and the case is therefore analogous to Thiele’s tetraphenyl-p- xylylene and xylylenes in general which polymerise readily. The less than unimolecular values obtained in bromoform are probably due to addition of the solvent after depolymerisation.Halogen acids in the cold simply polymerise the hydrocarbon and the additive compound with hydrogen chloride (Zoc. clt. 849) is now cancelled. The action oE hydrogen chloride in the boiling original benzene solution leads to other products which will be studied. Tetraphenyl-m-xylylene glycol wds treated with potassium thio- cyanltte in glacial acetic acid yielding tetraphenyl-m-xglylene dithio- cyanccte C,,H,,N2S2 in white crystals m. p. 120-121’. A quantitative yield of tetraphanyl-m-xylene C32H26 was obtained by reducing the xylylene dichloride by zinc dust and acetic acid. The hydrocarbon forms stout colourless crystals m. p. 110-1 11’. R. V. S. J. C. W. Preparation of Pure Dimethyl-o-toluidine.J. VON BRAUN and E. AUST (Ber. 1914 47 260-262).-The authors’ previous investigations (A. 1912 i 968; 1913 i 1327 1330) have shown that excess of formaldehyde readily attacks methyl-o-toluidias and thei. 268 ABSTRACTS OF CEEMICAL PAPERS dimethyl derivatives of aniline and of m-and p-toluidines which all occur a s impurities in the product obtained on methylating imperfectly purified o-toluidine. The latter gives even by prolonged treatment with the aldehyde only a very small proportion of the corresponding dimethyl- aminomethylbenzyl alcohol and practically no diphenylmethane derivative. A yield of 88% of pure dimethyl-o-toluidioe was obtained from a mixture of the amine with the four above bases by treatment with formaldehyde distillation of the resultant product under a pressure of 10 mm.and redistillation at ordinary pressure of the fraction boiling below 100'. The pure ortho-amine was also readily obtained from commercial samples. The constants of pure dimethyl-o-toluidine are Dio'G 0.9252-0.926 1 and nz 15153-1-5155 (compare Briihl A. 1895 ii 194; Kshlbaum A 1898 ii 556) and those of the purest dimethyl-p-tolnidine prepared from p-tolyltrimethylammonium iodide by way of tho ammonium base are b. p. 211-211*5° nz 1.53664 Dio'6 0.9379 (compare BIuhl Zoc. cit. ; Kahlbaum Zoc. cit.). The preparation of pure 4-di1nethy1amino-5-methylbenayl alcohol requires the employment of dimethyl-o-t oluidine previously purified by treatment with formaldehyde since in presence of only 3% of the para- base nearly 20% of the isomeric 2-dimethylamino-5-methylbenzyl alcohol would be obtained. T.H. P. The Molecular Rearrangement of Triarylmethylhydroxyl- amines and the 4 1 Beckmann " Rearrangement of Ketoximes. JULIUS STIEGLZTZ and PAUL NICHOLAS LEECH (J. Amer. Chem. Xoc. 1914 36 272-301).-A preliminary account of some of the results embodied in this work has already been published (A 1913 i 852). The possible courses of the Beckmann rearrangement are discussed from the point of view of the electron conception of valency (Falk and Nelson A 1911 ii 104 ; Falk i6id. 711) combined with the general explanation of Stieglitz that the intermediate formation of the grouping :NPh plays an important part in such changes in nitrogen compounds (compare A. 1903 i 235 ; 1913 ii 398; etc.). Triphenylmet hylhydroxy lamine CPb,*NH*O€€ m.p. 130-135' was obtained by the interaction of triphenylrnethyl chloride and hydroxylamine in benzene alcoholic solution. When heated for approximately a half hour with phosphorus pentachloride in ethereal solution an almost quantitative conversion into benzopbenonesnil hydrochloride CPb,:NPh,HCI m. p. 187-189" was effected. With other agents which are employed t o induce the rearrangement of oximes the change proceeded in a different manner with formation of triphenylcarbinoi and hydroxylamine. Phosphoric oxide however wben warmed with triphenylmethylhydroxylarnine hydrochloride caused rearrangement into benzophenoneanil as in the former case possibly due to a primary dehydration of CPb,*NH-OH,HCl itlto :N*CPh,,HCI which would be exceedingly unstable and pass readily into CPb,:NPh,nCI.The benaoyl derivative (structure undetermined) m. p. 155O of triphenylrnethylhydroxylarnine when heated with soda-lime a t 160-1 65O also yielded benzophenoneanil.ORGANIC CHEMISTRY. i. 269 These results suggest the possibility of an analogous course for the Beckmmn rearrangement for example /H \Cl CRR’:N*OH -+ CRR’:N-OH -+ CRR’:NCI -+ CRCKNR‘ the last t.ypo of substance undergoing subsequent hydrolysis in the commonly accepted manner with the formation of a n amide. The wain distinction of this explanation from that of Hantzsch (A. 1892 338) lies in the assumption of the free valencies at the nitrogen atom; these render the case comparable with that of the univalent nitrogen already assumed by Stieglitz in other rearrangements (see above).These views are to a certain extent contirmed by the behavioiir of triphenylmeth ylmethylhydroxylamine CPh,* N Me 0 H (colou rless crystals m. p. 113’ obtained by the interaction of triphenylmethyl cbloride and methylhydroxylamine bydrochloride in the premnce of sodium methoxide),with phosphorus pentachloride; these give very little alteration under the conditions which are effective with the mono- substituted hydroxylamine above but under prolonged treatment a product is obtained consisting mainly of triphenjlmethyl chloride and methylhydrosylamine accompanied by a little acetomethyl- anilide. p-Chlorolriphen y Znteth y l h ~ d ~ o x y Zamine C,H,C 1 C P h ,* NH 0 H col our- less crystals rn. p. 11 To obtained from y-chlorotriphenylmethyl chloride aud hydrosylamine hydrochloride in methyl-alcoholic solution con- taining sodium methoxide undergoes rearrangement when treated with phosphorus pent>achIoride as easilyas does triphenylmethylhydroxyl- amine itself yielding p-chlorobenzophmoneanil and benzophenone-p- cliloroanil in an approximate proportion of 2 1.The condensation product of tripbenylmethylhydroxylamine and n benzaldehyde namely CPh,= N<Y m. p. 114O. forms colourless crystals CHPh’ D. F. T. Preparation of a Substituted Diaminodiphenylcarbamide. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 268658).- When a slow stream of carbonyl chloride is led through R solution of 2 6-dichloro-p-phenglenediamine below 20° in the presence of sodium acetate teti-achlorocliaminodiphenylcarbamide is produced J.C. C. Peat Tar. I. The Phenols of Peat Coke Tar. E. BORNSTEIN and FEHDINAND BERNSTBIN (Zeitsch. angew. Chem. 2914 27,71-72).- The author has ieolnted the following phenols in the fractionation of peat coke tar Phenol 0- p- and m-cresols 1 2 3- and 1 2 4-xylenol~ catechol resulting from guaiacol homocatechol resulting from creogol and pyrogallol. T. S. P. Acyl Derivatives of o-Aminopbenol. J. H. RANSOM and R. E. NELSON (J. Ameo.. Chem. Xoc. 1914 36 390-393).-.An extension of a n earlier investigation (Ransom A. 1900 i 218) in which i t was found that when two groups -CO,R and -CO,R are introduced intoi. 270 ABSTRACTS OF CHEMICAL PAPERS. o-aminophenol the lighter group is found finally to be attached to nitrogen whatever the order in which the groups are introduced.The rearrangement which occurs here is also found to occur when two ncyl groups are intxoduced whilst if one of the groups is of the type -CO,R whilst the other is an ncyl radicle the former will be fonnd attached to the nitrogen atom. When o-aminophenol is treated i n ethereal suspension with a bi- molecular quantity of isoamyl chloroformate isoamyl o-hydroxyphenyt- carbanzate colourless needles m. p. 68 5-69*5' is obtained ; the same substance was also obtained by the reduction of o-nitrophenyl igoamyl carbonate in which case rearrangement must have occurred. If how- ever the reaction mixture from the reduction of the carbonate is immediately thrown into a concentrated solution of potassium hydroxide a different substance giving a hydrochloride m.p. 134O can be obtained; this is stable when dry but ou warming with water is convetted into isoamyl o-hydroxyphenylcarbsmate and as a con- sequence must be regarded as of the isomeric o-aminophenyl isoamyt carbonats. The action of benzoyl chloride on an alkaline solution of isoamyl hy d roxyphenylcar bamate gave isoam y 1 beo zoy 1 oxyp henylcsr bama t e colourless needles m. p. 65*5' the same substance also being produced by the act ion of isoamyl chloroformate on benzoyl-o-aminophenol the chemical change in this case being accompanied by intramolecular rearrangement. In a similar mauner the interaction of ethyl hydroxyphenylcarbamate and isoamyl chloroformate as also of ethyl chloroformate and isoamyl hydroxyphenylcarbamate gave a substance b.p. 1 85-200'/15 mm. m. p. 65-66' namely ethyl o-cnrbisoamyloxyphenylcarbamate C,Hll C02*O*C6H,*NH-C02Et which is formed in the case of the latter pair of reagents by the re- arrangement of the primarily produced C02Et*O* C6H4*NH* CO,*C Hll. D. P. T. Trinitro-m-anisidine 3 5-Dichloro-4-bromonitrobenzene and Chlorination of p-Nitroaniline. BERNHARD FLURSCHEIM (Ber. 19 14 47 426).-A claim for priority ovor Reverdin and Widmer (this vol. i 166) and Korner and Contardi (A. 1913 i 963) in the preparatiou of trinitro-m-anisidine (Zeitsch. ges. Schiess- & Sprengstoflwesen I9 13 8 185) and of 3 5-dichloro-4-bromonitrobenzene (A. 1905 i 614) and the chlorination of p-nitroaniline in hot dilute hydrochloric acid (T. 1908 93 1773).c. s. Action of Grignard's Reagent on Alkyloxyl Groups. H. SIMONIS and P. REhXhIERT (Bey. 1914 47 269-271).-Although in general alkyloxyl groups are indifforent to Grignard's reagent yet the iodoanisoles for instaoce are capable of forming normal organo- magnesium compounds without appreciable secondary reactions occurr- ing. Further in the Griguard reaction anisole is of ten advantageously employed RS a solvent when i t is necessary to work a t a higher temperature than is allowed by ether or benzene. The view that in this case the anisole acts merely as an indifferent solvent is accurateORGANIC CHEMISTRY. i. 2'71 only when the temperature does not greatly exceed that of boiling water When however the boiling point of anisole is attained this solvent reacts as follows Ph*OMe + MgMeI = Ph*OMgI + C,H con- siderable quantities of phenol being formed according to the equation Ph*OMgI + H,O = Ph*OH + MgI*OH.A similar result follows when phenetole is used in place of anisole. When dimethoxybenzenes are employed ethane is vigorously evolved but as the formation of the solid C,H4(0MgI) proceeds a-tendency to decomposition appears. T. H. P. A General Method for the Reduction of the Carbonyl Group in Aldehydes and Ketones to the Methylene Group. 11. ERIK CLENMENSEN (Ber. 1914 47 51-63. Compare A 1913 i 733).-The method already applied by the author to the reduction of ketones and aldehydes is shown to be generally useful except for such substances as are decomposed by hydrochloric acid. It promises to be of especial value for the preparation of homologues of the various phenols from hydroxy-ketones and although its value for the reduction of hydroxj-aldehydes is diminished by the sensitiveness of many of these towards hydrochloric acid t h e methyl substituted phenols obtainable are of a high degree of purity.In the reduction of the ketones mentioned below the general pro- cedure was to take 100 grams of amalgamated zinc (produced by placing ordinary granulated zinc i n a 5% solution of mercuric chloride for R few hourb) with 35 grams of the ketone and to add 300-500 C.C. of hydrochloric acid obtained by mixing concentrated acid with an equal or double volume of water. A vigorous evolution of hydrogen was maintained for several hours by warming on a water- bath with the occasional addition of small quantities of more concen- trated acid.The reduction was then complete and the yield generally excellent. I n this mnnnerp-hydroxyacetophenone gave rise top-ethylphenol b. p. 217-217.5'/750 mm. m. p. 45-46'; acetate b. p. 286-227'/760 mm. has an odour like anise. The free phenol gives a blue coloration with ferric chloride. p-Hydroxypropiophenone in a similar manner undergoes reduction t o p-propylphenol a colowless crystalline solid m. p. 21-22' b. p. 228'/748 mm.; acetate with a feeble odour resembling anise b. p. 245-246'/745 mm. wAcety1-o-cresol on reduction yields Z-mstAyl-4-ethy~heno2 a strongly refractive liquid b. p. 224.5'/740 mm. with a feeble phenolic odour; it gives the general reactions of the phenols. o-Acetylresorcinol gives 4-etliyhesorcinoZ colourless leaflets (by sublimation) or stout prisms (by recrystallisation from chloroform) m.p. 97' ; this substance ebows the fluorescein rekction with phthalic anhydride and gives a deep red colour on warmicg with chloroform and a little sodium hydroxide ; the coloratiori with ferric chloride is deep blue changing slowly to a green. Acetylquinol is reduced to ethylquinol C,H,Et(OH) which crystal- lises in rosettes or sublimes giving needles m. p. 1 1 2' (compare Bayrac A. 1895 i 412). This is easily oxidisable to ethyl p-benzoquinone.i. 272 ABSTRACTS OF CHEMICAL PAPERS. The reduction of m-acetylcatechol gives rise to m-etbylcatechol ns a crystalline mass m. p. 37-39'; this gives a transient green color- ation with ferric chloride the subsequent addition of sodium carbonate causing a red colour.o-Acetylpyrogallol becomes reduced to 0-ethyZpyrogaZloZ silvery plates from chloroform m. p. 106'. The ferric chloride coloration is an evanescent deep blue and the subsequent addition of sodium carbonate solrition produces a violet colour. An alkaline solution of the substance does not darken so rapidly as one of pyrogallol. 4-Acety2-6-et~~lpyrogdloZ obtained by the action of acetyl chloride on the last product forms colourless prisms or fine needles m. p. 141'. It is reducible t o 4 6-diethylpyrogaEEo2 silky needles m. p. SO' of which the aqueous solution reduces silver nitrate. The reddish-violet coloration with ferric chloride soon disappears and the addition of a little sodium carbonate solution then gives a permanent violet colour which changes to reddish-brown with more carbonate.The structures assumed for the substances used above are those commonly accepted but in some cases these possibly require further confirmation. Of the hydroxyaldehydes investigated snlicylaldehyde rn-hydroxy- benzaldehyde and p-hydroxybenzaldebyde are reducible t o mxeeol b. p. 189*3'/750 mm. m-cresol b. p. 201.5°/750 mm. and p-cresol b. p. 201'/750 mm. respectively. The various descriptions of these substances are to be attributed to lack of purity in the specimens examined. o-Cresol has a pleasant carbolic odour and gives with one drop of ferric chloride solution a deep violet-blue colour which within a minute changes through green to a dirty yellow ; the colour reitction is not obtained with excess of ferric chloride.m-Cresol has a faint odour resembling that of leather and the reddish-violet coloration with ferric chloride fades more slowly and is still perceptible after a week. p-Cresol has as a n odour very like that of p-ethylphenol and the pure blue coloration obtctined with ferric chloride disappears in lees The ortho-and para-ieomerides remain un- /-\ coloured in the air even after six months but in this time he-gH m-cresol becomes yellow. The reduction of resorcylaldehyde gives rise t o cresorcinol (4-methylresorcinol annexed formula) m. p. 83-44'. The discrepancy between this m. p. and the 102-104* recorded in the literature may be due t o error i n the latter or t o the commonly accepted structure of resorcylic acid being incorrect.p-thymot aldehyde on rcduction gives prnethylthymol rhombohedra m. 1). 70° b. p. 250-250.5°/745 mm. with a pleasant odour quite distinct from that of thymol. OH than one day. D. F. T. Influence of Acetylation of Phenolic Uroups on the Velocity of Nitration and Measurement of the Latter in the Case of Ethereal Solutions of Phenols. ALFOXS KLEMENC (Monalsh. 1914 35 S5-117. Compare A. 1912 i 695).-The author shows in a number of cases that acetylation of the phenolic group destroys its powerful directive action on the position taken up by fresh sub- stituents and that a n advanbageous process is thus frequently providedORGANIC CHEMISTRY. i. 273 for preparing isomeric substitution products from phenols and phenol- carboxylic acids. Attempts to measure the velocity of nitration of phenols dissolved in ether or glacial acetic acid are also recorded.Acct?/lquinol momethyl ether b. p. 134-135'/18 mm. 147-148'1 33 mm. 243'/751 mm. is obtained by the action of acetic Anhydride and a little concentrated sulphuric acid on quinol monomethyl ether. When dissolved in acetic acid and treated with nitric acid (U 1-52) it gives 3-niti-oacetylqzlinol monomethyl sther colourless needles m. p. 106q from which on cautious saponification with potassium hydroxide 3-ne'troquinol monomethyl ether pale yellow needles m. p. 97-99' is obtained ; this acts as a delicate indicator. Direct nitration of quinol monomethjl ether yields 2-nitroquinol monomethyl ether (Weselsky and Benedikt A. 1881 1139). Vanillic acid can be nitrated by 8% nitric acid at 48' during twenty- four hours a mixture of 5-nitrovanillic acid m.p. 215" and 3 5- dinitroguaiacol being produced. When acetylvanillic acid is nitrated by fuming nitric acid ( D 1.52) at 0' and the product subsequently saponified by potassium hydroxide and then acidified 2-nitrovanillic avid decomposing at 246O is obtained (compare Tiemann and Matsmoto A 1876 ii 524; Pschorr and Sumuleanu A. 1900 i 178). The composition of the acid is proved by converting it by means of diazo- methane into methyl 2-nitroveratrate m. p. 126' which on saponifica- tion yields 2-nitrovoratric acid m. p. 201-203°. ieoVanillic acid is readily nitrated by 8% aqueous nitric acid at 4S0 giving 2 6-dinitroisovanillic acid (compare Matthiessen and Foster Juhi-eeber. 1867 520 ; Wegscheider and Klemenc A.1910 i 671). Acetylisovanillic acid yields with nitric acid (D 1.52) a substance which on successive treatment with potassium hydroxide and acid gives 5-nitroiaovanillic acid needles m. p. 174' (compare Matsmoto A. 1878 502). This compound has apparently without ground been described in the literature aR 6-nitroieovanih acid ; its constitution follows from its conversion by diazomethane into methyl 5-nitrovera- trate. In this instance of nitration only one nitro-derivative is formed. Guaiacolcarboxylic (2-hydroxy-3-methoxybenzoic) acid m. p. 15 lo is somewhat volatile a t looo SO that the water of crystallisation cannot be easily estimated directly. It cannot be accurately titr.rted with phenolphthalein as indicator. It is readily esterified by methyl alcohol and hydrogen chloride; it is not completely methylrrted by diazo- methane nor acetylated by acetic anhydride or acetyl chlorid+.When nitrated with 8% aqueous nitric acid a t 4 8 O or by nitric acid (D 1.53) in glacial acetic acid euspension it yields 5-nitrogusiacol- carboxylic acid needles m. p. 227' (decomp.) the orange-colonred ptccssium and sparingly soluble ammonium salt of which are also described. When boiled with aniline the acid yields 4-ni tr og:naixc*ol m. p. 99-100'. Methyl acetylguaiacolcarboxylat~ m p. 63-63° b. p. 193'/34 mm. is somewhat resistant to nitration but IS wuverted by protracted contact with fuming nitric acid (D 1-52) at first a t - 10' to -20° subsequently a t O' into a product from which at1 ctcid leaflets m.p. 195' (decomp.) is obtained iu tho usual uiauner. The constitution of this acid has not baan definitely aecertaincd but in all probability it is 4 6-dinitroguaiacolcarboxylic acid.i. 274 ABSTRACTS OF CHEMICAL PAPERS. The nitration of methyl 2-hydroxy-5-methoxy benzoate has previously been described (Klemenc A. 1913 i 49). The proof that the nitro- group enters in the position 3 is now given by conversion of the product by boiling with aniline into 2-nitroquinol monomethyl ether m. p. 80'. Methyl 2 acetoxy-5-methoxybenzoate b. p. 180-181°/1 14 mm. is nitrated by fuming nitric acid (D 1*52) and after treatment in the usual manner yields a mixture of 4-nitro-2 I~y(dror~-5-?nethoz~benxoic acid m. p. 191-1 92O and 6-nitro-2-hydroxy-5-methox~benzoic acid m.p. 221O (decomp.). The acids are very incompletely esterified by methyl alcohol and hydrogen chloride. Since the material was insuffi- cient for a direct determination of the velocity of esterification the author has relied on the heatrnent of the two acids under identical conditions with methyl alcohol and hydrogen chloride and the deter- mination of the percentage of -OCH in the crude products and has in this manner been able to assign probable formuls. By extraction of the above crude products with ammonia methyl 6-nitro-2-hydroxy-5- nzethoxybenxoate m. p. I 25-1 26" and methyl 4-?zitro-2-r'2.ydroxy-5- methoxybenxoute yellow leaflets m. p. 103' hare been obtained. Methyl 6-nitro-2 5-dimethoxybenaoate a yellow microcrystalline substance m. p. 117-118' is obtained by the action of diazomethane on 6-nitro-2- hydroxy-5-methoxybenzoic acid ; when saponified with potassium hydroxide i t yields an impure 6-nitro-2 5-dimethoxybenzoic acid partial elimination of a methoxy-group appearing to occur.Measurements of the velocity of nitration of phenol and guaiacol have been made in ethereal solution at 25". The course of the reaction is followed by estimation of the unused nitric acid either by addition of aliquot portions of the liquid after definite intervals to a solution of potassium iodide and potassium iodate to which sodium thiosulphate in known excess has been previously added and subsequent titration of the residual thiosulphate with iodine or by adding aliquot portions of solution to an excess of potassium hydroxide and estimation of unchanged nitrate by reduction with Devarda's alloy.The latter method however can only be used in certain cases since ammonia is sometimes obtained in appreciable quantity by the action of the alloy on the nitro-compound. In the presence of a small excess of nitric acid phenol and guaiacol are either not nitrated or only acted on extremely slowly. With excess of phenol on the other hand nitration occurs readily and follows approximately the law for a bimolecular reaction. Anisole and acetylphenol are only slowly nitrated in ethereal solu- tion even at considerable concentlation. In glacial acetic acid soluticjn the former is readily iiitrated whereas the latter is but little affected. The reactioD however does not take a simple course. During the nitration of acetylphenol the solution after some time becomes distinctly green and contains nitrous acid.With anisole the acetic-nitric acid solution becomes deep violet and efkrvescence occurs (evolution of nitric oxide). Nitration only occurs in the coloured solution ; after some time the colour disappears whereou nitration ceases. Probably the colour is due to an additive compound of anisole and nitric or nitrous acid which is decomposed by water. H. W.ORGANIC CBEMISTEY. i. 275 Bromoquinolsulphonic Acids and Their Conversion into Bromo-p-benzoquinonesulphonic Acids. A. SEYEWETZ and J. PARIS (Bull. SOC. chim. 1914 [ivl 15 121-125. Compare A. 1911 i 360; 1912 i 492 723).-~romoquinol on sulphonation with fuming sulphuric acid (containing 15% sulphur trioxide) a t a tempera- ture not exceeding 50° and subsequent treatment of the reaction product with a concentrated solution of sodium sulphate yields sodium brotnoqzLinoZauZpTLonale C,H,Br( OH) S03Na white needles which reduces cold silver nitrate solution and acts as a photographic developer in the presence of alkalis.Oxidation with sodium dichromate and sulphuric acid at a temperature not exceeding 20' converts it into sodium bromo-p-benxoquinonesuiphonate yellow needles. The aqueous solution has oxidising properties and decomposes slowly at the ordinary temperature rapidly when heated. Sodium p-benzoquinone-2-sulphonate is converted by a saturated aqueous Folution of hydrobromic acid at temperatures below 30' into sodium 6-b~omoquinol-2-sulphonate C,H,Br(OH),*SO,Na white needles.The aqueous solution has reducing power which seems t o be slightly less than that of the isomeride described above. A t a temperature exceeding 30° 2 6-dibromoquinol is produced. On oxidation under the conditions adopted for the isomeride sodium 6-bromoyuinol- 2-sulphonate is transformed into sodium byonzo-p-benxoquinonesulphonccte C6H,Br02*S0,Na golden-yellow needles soluble in water giving solu- tions which decompose rapidly when heated slowly in the cold and liberate iodine from potassium iodide in the presence of acids. H. W. Double Salts of Mercuric Chloride with Aromatic Tellurides. KARL LEDERER (Bey. 1914 47 277-279).-Aliphatic sulphides form well crystallised double salts with mercuric chloride biit analogous compounds of aliphatic selenides or tellurides are unknown. Aromatic sulphides or selenides do not appear to give double Ealts with mercuric platinic or auric chloride but aromatic tellurides form well crystallised stable double salts with mercuric chloride and also yield precipitates which mere not investigated with platinic chloride.Phenyl telluride and auric chloride give a double salt which rapidly blackens even when protected from the action of light and air. The following double salts were obtained by shaking ethereal solu- tions of the tellurides with aqueous mercuric chloride. Mercuric chloride and phenyl telluride give TePh2,HgC1 which forms needles sintering a t 155O m. p. 158' (rapidly from alcohol) or m. p. 160-161O (from acetic acid). The crystals formed slowly from alcoholic solution contain 5Et*OH sinter at 1 1 5 O and resinify at 130'.Mercuric chloride and o-tolyl telluride give Te(C,H,Me),,HgCI sintering at 209O m. p. 212'. Mercuric chloride and p-tolpl telluride give Te(C,H,Me),,HgCI which forms crystals containing GEt-OH m. p. 135-1 SCiO or sintering at 128' m. p. 132-133". 3CH3*C0,H,i. 2’76 ABSTRACTS OF CHEMICAL PAPERS. The chlorine present in them double compounds was estimated by the lime method that of Carius failing completely. T. €3. P. The Displacement of the Ethoxy-group by Radicles. A Synthesis of Ethers and of Hydrocarbons. A. E. TSCHITSCHIBABIN and S. A . JELGASIN (Bsr. 1914 47 48-50).- In the preparation of a-naphthaldehyde from ethyl orthoformate and magnesium a-naphthyl bromide by the well-known process (Tschitschibabin A.1904 i 221) indications have been obtained of a further st age in the reaction with formation of di-a-naphthylcarbinol. This has led to an extension of t h e investigation of the reaction between ethyl orthoformate and organomagnesium compounds and t h e results of preliminary experiments point to the possibility of the successive replacement of all the three ethoxy-groups with the formation of aldehyde-acetals ethers and hydrocarbons respectively according to the equations H*C(OEt) + R*Mg*Hal= CHR(0Et ) n + MgHal*OEt. CHR(OEt) + RMgHal = CHR,*OEt + MgHal-OEt and CHR,*OrEt + R*Mg*Hal= CHR + MgHd*OEt. Thus magnesium phenyl bromide acts fairly readily on a boiliug etheroal solution of benzaldehyde-acetal but the reaction develops much less heat than does the formation of the acetal from ethyl orthoformate.To induce the interaction of benzhydryl ethyl ether with magnesium phenyl bromide a higher temperature is necesFary and t.riphenglmethane can be obtained as the chief product by distilling off the ether during which process the third ethoxj- group becomes replaced by phenyl. Syntheses in the Fatty Aromatic Series. XII. J. VON BRAUN and G. KIRSCHBAUM (Bey. 1914 47 262-269. Compare A. 1913 i 772).-1t has been shown previously (von Braun Grabowski and Kirschbaum A 1913 i €112) that substitution by a methyl group a t the carbon atom adjacent either to the csrbinol group of phenylpropyl alcohol or to the aldehyde group of phenyl- propaldehyde is of greater influence on the odour than substitution a t the carbon atom next to the phenyl group.I n order to ascertain if this is a general rule and especially whether the P-positiou of the methyl to hydroxyl or its /?-position t o the benzene nucleus is the determining factor the investigations have been extended t o the two next higher homologous alcohols and aldehydes. With c-phenyl-P-methylamy1 and e-phenyl-PS-dimethylnmyl alcohols it is found t h a t $he complex *CHNe*CH,.OH is as readily converted by t h e “ ~ i t r o ” method into *CHMe*C‘HO as is the unbranched grouping *CH,*CH,*OH. The odours of these new alcohols and aldehydes differ somewhat from those of the non-methylated com- pounds but they are so weakened that accurate catnparison is scarcely possible. Further study in this direction should bence be confined to compounds with the alcoholic or aldehydic group i n the P- or y-position since with such compounds any regularities in odour are more clearly expressed.Ethyl C H 1’11 - C H a C b l e ( COJ4 t)2 prepared from methyl iodide and ethyl y-phsuyleth~lriialonate (com- D. F. T. p-pheny I ell y 1 me thy h a l o t late,ORGANIC CHEMISTRY. i. 27'7 pare Fischer and Schmitz A. 1906 i 484) is a colourless liquid b. p. 192'/20 mm. and the corresponding acid C1,HI4O4 m. p. 1603 is slowly converted on heating at 165' into y-phenyl-a-methylbutyric acid CH,Ph*CH,*CHMe*CO,H b. p. lSO'/19 mm. the ethyl ester of which b. p. 143-1 44'11 7 mm. yields 6-phenyl-P-methylbutyl ulcohol C,,H,,O b. p. 145-148'/18 mm. Dto 0.9719 on reduction. Ethyl y-phenylpropylmethylmalonate CH,Ph*CH,*CH,*CMe(CO,Et) b.p. 194'/15 mtn prepared by methylation of the corresponding phenplpropylmalonate (von Braun and Kruber A 1912 i 265) is converted on hydrolysis with aqueous-alcoholic potassium hydroxide (2 mols.) principally into the oily othyl hydrogen y-phenylpropgl- rnethylmulonate CH,Ph*CH,*CH,*CRIe(C02H)*C02Et which is con- verted on distillation into ethyl 6-phenyl-a-methyZvaZerate CH,Ph* CH2*CH2*CH ble*CO,Et b. p. 158'117 mm. ; 6-phenyl-a-rnethylvaleric acid C,,H,,O is a n oil b. p. 190°/19 mm. Although partial hydrolysis of a malonic ester is in general very difficult the above ethyl hydrogen malonate exhibits marked stability and is only with ditliculty attacked further by the hydrolysing agent. Where the malonic aster transformation is to lead to the formation of a n alcohol this partial hydrolysis allows of the diminution of the number of operations by two the distilled product of hydrolysis being directly reduced and the preparation of the di- and mono-carboxylic acids omitted. B- Phenyl-P-methylamyz alcohol CH,Ph* CH,*C H,* CHMe-CH,*OH prepared in this way has b.p. 159-160°/20 mm. Dfo 0,9642. a-C/doro-r-phenyl-/3-mathylpentane CH2Po* C H,*CH,* CHMe- CH2Ci has b. p. 140-142O/18 mm. The corresponding iodo-compound C,,H17T b. p. 160-166"/20 mm. reacts readily with silver nitrite giving in about equimolecular proportions (1) the nitrite b. p. 130"/18 mm. which is readily hydrolysed to the alcohol and (2) a-nitro-epheny2- P-methplpentane CH,Ph*CH,*CH,*CHMe*CH,*NO a yellow liquid b. p. 17% 180'. When this nitro-derivative is reduced with stannous chloride and the oily oxime boiled with 15% sulphuric acid solution OQ passing water vapour through the liquid 6-phen yl-a-inethylvaleraldehyde C,,H,,O distils as a colourless liquid b.p. 148-152"/21 mm. giving only oily derivatives with the usual reagents. C t1,Ph-CHMe*C H,* C H( CO E t) prepared from y-phenylisobutyl bromide (A. 1913 i 6 12) has b. p. 189"/ll mm. and on methylation yields ethyl y-phenyZisobutyL methyhalonate CH,Ph*CHMe*CH,*CMe(CO,Et) b. p. 192-194'/ 13 mm. which undergoes semi-hydrolysis less readily thau the lower homologues. The corresponding acid and also 6-phenyl-ay-dimethyl- valeric acid CH,Ph.CHMe*CH,*CHMe*UO,H b. p. 282-284O d not crystallise and the ethyl ester of the latter C15f&02 b. p.154O/ 23 mm. can be reduced t o B-pheiayl-PG-dimethylamyl alcohol b. p. 156-158'/17 mm. DY 0.9549. Ethyl y-phenylisobutyl nialonate CH,Ph*CHMe*CH,*CHIlle*CH,*OH a-Chloro-a-phenyl-PG-dimethy Zpentane CH,Ph*CHMe*CH,* CHRIe*CH,CI b. p. 146-1 4S0/20 mm. ; the corresponding iodo-compound C,,€F1,I VOL. CVI. i. PQi. 278 ABSTHACTS OF CHEMICAL PAPERS. b. p. 163-166O/20 mm. ; the nitro-compound C,,H,,O,N b. p. 1 76-1 8 1'120 mm . and 6 phon yl-ay-dime th y!vabraldehj yda CH,Ph*CHMe*CH,*CHMe*CHO b. p. 151-156O/20 mm. which forms only oily derivatives with t h e ordinary reagents for aldehydes were also prepared. T. H. P. The Splitting of Benzhydrols by the Action of Bromine. GUSTAVUS J. ESSELEN jun. and LATHAM CLARKE (J. Amer. Chern. ~Soc. 1914 36 308-324).-1n following up an observation that benzalde- hyde was produced in the action of bromine on p-aminobenzhydrol and 3 5-dibromo-4-aminobenzhydrol in chloroform solution (A.191 1 i 725) the authors have found that this action of bromine on p-aminobenzhydrol derivatives is a general one the molecule of the latter undergoing fission with formation of a n aldehyde and a bromo- substituted aniline. The following series of changes is suggested as representing the course of the action OH*CHPh*C,E,*NR -+ OH*CHPh*C,H,*NR,Br -+ OH*CHPh*NR,Br*C,H,Br -+ CHPhO + C,H,Br*NR,,HBr. 4-Amino-3-methyEbenxl~ydl.ol prepared by the reduction of 4-amino-3- methylbenzophenone by sodium amalgam in alcoholic solution forms colourless needles m. p. 110'; when boiled with acetic acid i t yields a greenish-yellow substance possibly an anhydride decomp.near 2 1 Oo. When treated in chloroform solution with a bimolecular proportion of bromine it readily 1 eacted giving benzaldehyde and 3 5-dibrorr;o-o- toluidine. p-Nitro-p'-methylaminobenzhydrol under similar conditions with a unimolecular proportion OF bromine yielded p-nitrobenzaldehyde and dibromomethylaniline m. p. 47' (compare Fries A. 1304 i 571). With p-dimethylaminobenzhydrol aud a bimolecular proportion of bromine benzaldehyde and p bromodimethylaniline were obtained but at - SOo a n amine dibromide mas first obtainable as an unstable yellow oil; the formation of this is a confirmation of the stages suggested above. 3-Bromo-4-dimet~ylarrzinobe~zxophenone colourless rhombic plates m. p. 80° obtained by direct bromination of p-dimethylaminobenzo- phenone can bb reduced by aluminium amalgam and alcohol to 3-bromo-4-dimetl~ylantinobenzhydrol a s t raw-coloured viscous oil b.p. near 275'/55-60 mm. (decomp.). This is converted by bromine into benzaldehyde and 2 4-dibromodimethylaniline. A t - 80° 3-bromo- 4-dimethylaminobenzhydrol behaved towards bromine in a manner similar t o p-dimethylaminobenzhydrol producing a very unstable red solid substance. p-Nitro-p'-dimethylaminoberizhydrol and pp'-tetramethyldiamino- benzhydrol were converted by bromine into p-bromodimethylamine mixed with p-uitrobenzaldehyde and p-dimethylaminolcenzaldehyde respectively. p-Nitro-p'-diethylaminobenzhydrol was similarly affected. 2-Amino-5-methylbeizxhydrol colourless feathery crystals or rhombo- hedra m.p. 107" which w:;s obtained by the reduction of 6-amino-3- methylbenzophe~one (Chattaway and Lewis T'. 1904 85 594) with sodium am:clgarn and alcohol was converted by bromine into 3 5- di bromop-toluid ine and benzaldehy de.ORGANIC CHENISTRY. i. 279 m-Aminobenzophenone was redaced t o m -arninobmxhydroZ colourlew rhombohedra m. p. 78" by sodium amalgam and alcohol. This benzhydrol compound as well as unsubstituted benzhydrol itself does not suffer fission under the action of bromine although in the former case a yellow oil of uncertain nature was obtained. Chlorine and iodine appear to affect p-dimethylaminobenallydrol in the same way as bromine but the change produced is less satisfactory being complicated by the formation of additional product?.'L'he use of chloroform as solvent is not essential as alcohol or ether is equally successful the latter indeed possessing the advantage of immediately separating the prodiicts the aldehyde remaining in solution whilst the hydrobromide of the aromatic smiue derivative is deposited. D. F. T. Reduction of Triphenylcarbinol. A. GARC~A B A N ~ ~ S (Anal. Fis. &uim. 1913 11 599-601).-Triphenylcarbinol ( I gram) ia dissolved in 10 C.C. of boiling glacial acetic acid with 0.3 gram of trioxymethyl- ene and 2.5 C.C. of concentrated sulphuric acid added at 45-50 C.C. I n a few minutes 1 gram of triphenylmethane of m. p. 89-90' or on recrys tallisation 9 0-9 2O separates. Boiling for four hours with acetic acid and ti-ioxymethylene without sulphuric acid also gives a good yield but the action is accelerated by the addition of three or four drops of sulphuric acid.Preparation of Optically Active a-2 6-Dihydroxyphenylpro- panolamines. FARBENFABRIK VORN. FRIEDR. BAYER & Co. (I).R.-P. 2 6 9 3 2 7).-A mino-a-2 6 - di h y droxy phen y lpro p y 1 alcohol can be resolved into its optically active constituents by means of d- or I-tartaric acid. The dAdB salt has m. p. 86O the dAlB salt m. p. 86' the lAdB salt m. p. 85-87' and the ZAZB salt m. p. 92'. The d-base has m. p. 217" and aD 33-75" whilst the I-base has m. p. 218' and aD 30'. Tile action of the latter in raising the blood pressure is two to three times as strong as the racemic base. EUG. GRANDMOUGIN (Ber. 1914 47 384).-The author agrees with Lesser and Weiss (this vol.i 180) that Dorsch's tri- and tetra-bromoanthranilic acids should be cancelled. The substance obtained by Dorsch was tribromo- aniline. J. C. W. G. D. L. J. C. C. Halogen Substituted Anthranilic Acids. Perkin Reaction Reply to the Criticism of Meyer and Beer. ARTIIUR MICHAEL (Amer. Client. J. 1913 50 411-414).-The work of Meyer and Beer (A. 1913 i 617) is discussed and it is stated that their results do not disprove Michael aud Hartmann's view that the first phase of the Perkin r e a h o n ccjnsists of a n interaction between the aldehyde and anhydride (A. 1901 i 358) but that they afford new fhcts in confirmation of it. E. G. The Behaviour of m-Nitrocinnamic Acid Compared with the ortho- and para-Acids. FRIEDRICH WOLLRING (Ber. 19 14 47 108-1 1 l).-An account is given of experiments with derivatives of m-nitrocinnamic acid which are in many respects identical with those 2.42i.280 ABSTRACTS OF CHEMICAL PAPERS described by Reich and Koehler (this vol. i 41) and support the view that the nitro-group in the meta-position does not weaken the attach- ment of bromine atoms in the side-chain as is the case in the ortho- and para-eeries. ap-Dibromo-P-rn-nitrophenylpropionic acid m. p. 175" gives a sodium d t with 2H,3 a caEcium salt with 4H,O a methyl ester m. p. 91-92' and an ethyl ester m. p. 86-87' which is hydrolysed to m-nitrocinnamic acid by heating with water at 200' for a few hours When heated with alcoholic potassium hydroxide (2 mols.) the ester yields a-bromo-m-nitrocinnamic acid and also the allo-variety which is transformed in to the stable acid by sublimation in vacuum. The sodium and barium salts and the ethyl ester long needles m.p. 74" of the stable acid and the methyl ester m. p. 82-43' and the ethyl ester a n oil of the labile acid were isolated. A smaller quantity of alkali yields in addition a mixture of these ethyl esters whilst an excess of alkali yields m-nitrophenylpropiolic acid the barium salt of which decomposes on boiling with water into ~m-nitropheoylacetylene. On submitting the sodium salt of the above dibromide t o steam distillation w-bronto-m- nitroallostyyene was obtained as a n oil which is transformed into the stable isomeride m. p. 78-79' on distillation in vacuum. J. C. W. The alto-Nitrocinnamic Acids. FRIEDRICH WOLLRINU (Ber. 1914 47 lll-l15).-Attempts have been made to convert the stable m- and pnitrocinnamic acids into the labile allo-modifica- tions by submitting them to the action of ultra-violet light the method which Stoermer successfully employed in the caw of the ortho-isomeride (A 1912 i 974).A transformation of about 22% was effected in the case of the meta-compound but p-nitrocinnamic acid was extensively decomposed and yielded only minute quantities of the labile acid. The latter was prepared however by the nitration of aZZo-cinnamic acid. m-Nit rocinoamic acid v;as dissolved in alcoholic ammonia and exposed for 100 hours t o the light of a mercury lamp in quantities of about 5 grams in 20 C.C. After evaporating a part of the solvent and removing some flocculent products of decomposition by the addition of water the acid was fractionally precipitated by hydrochloric acid the last fractions yielding m-nitroaliocinnamic acid.This forms small needles m. p. 158O and is re-converted into the stable acid by illumina- tion in chloroform with a trace of bromine. The ethyl ester is a n oil. The dibromide ap-dibromo-p-m-nih-oallophenylpropionic acid was obtaitled by dissolving the acid in bromine as a semi-solid mass which was a mixture of two forms of the derivative one with m. p. 12l0 and the other a n oil which was extracted by cold benzene and which clianged into the crystalline form after a few weeks m-Amino- allocirtnccmic acid was prepared by adding a solution of the ammonium kalt of the nitro-acid to ferrous sulphate rendered alkaline by baryta and warming. It forms sparingly soluble yellow crystals m.p. 193y and i t s hydrochloride is considerably esterified merely by boiling with methyl or ethyl alcohol the esters being oils. The acid was diazotised and boiled with. water when m-hydroxyallocinnamic acid wasORGANIC CHEMISTRY. i. 282 ohtained as an oil which yielded P-m- hydroxyphenylpropionic acid on reduction with sodium amalgam. allo-Cinnamic acid was nitrated by fuming nitric acid free from nitrous fumes at 0-5' and the solution of the product in ammonia was fractionally precipitated. The first fractions yielded o-nitroallo cinnamic acid and the later fractions p-nitroallocinnarnic acid which forms yellow crystals m. p. 143'. The crude mixture of isomerides was reduced as above when excess of ammonia precipitated carbostyril due t o the allo-o-amino-acid.p-Aminoallocinnamic acid was isolated from the filtrate in yellow needles decomp. 103-104°. The hydrochtoride crystallises in spikes. J. C. W. Some Derivatives of Cinnamic Acid. H. RUPE 33. STEICIER and F. FIEDLER (Ber. 1914,47,63-75).-Ethyl P-hydroxy-PP-diphenyl- a-methylpropionate OH*CPh,*CHMe*CO,Et was obtained by boiling a mixture of benzophenone ethyl bromopropionate and metallic zinc with a mixture of benzene and toluene for a n hour with special precautions and then acidifying with ice-cold dilute sulphuric acid. The ester forms needles or colourless stout prisms m. p. 101-102° and dissolves in sulphuric acid to a deep green colour. It can be hydrolysed by heating for three hours with hydrochloric acid D 1.19 at 1 50° giving /3-hydroxy-PP-diphenyl-a-methylpropionic acid colourless microscopic needles m.p. 182'. The ester was successfully converted into p-phenyl-a-methylcinnamic acid CPh,:CMe*CO,H by simultaneous dehydration and hydrolysis induced by treatment with diluted sulphuric acid in boiling acetic acid for three to four hours; the product forms colourless prisms m. p. 163O gives a deep green solution in sulphuric acid and forms salts which are all sparingly soluble. All attempts to obtain the chloride of P-phenyl-a-methylcinnamic acid for example by warming with thionyl chloride resulted only in the formation of 3-phenyZ-2-methylindone C H < ~ ~ ~ > C M e reddish-yellow leaflets m. p. 86-87 ; semicavbaxone tetragonal platelet^ m.p. 200-501°. Ethgl P-hydroxy-p-~iLcn~l-a-methyl- n-butyrate OH CPh Me. CH hIe-CO,Et R pleasant smelling oil b. p. 144-145'/13 mm. can be dehydrated by boiling for six hours with 85% formic acid giving ethyl a/3-dimethyZ- cinnamate n pleasant smelling yellow oil b. p. 129.5-130°/12 mm. which was accompanied by a small quantity of the free acid and dimethylstyrene. Hydrolysis of this ester by potassium hydroxide yields a/3-dimethylcinnamic acid a8 n mixture of two forms a solid needles m. p. 112-113' (13% of the produck) and a viscous yellow liquid (87%) which distilled with some decomposition at 107- 1 1 4 O / 0.1 mrn. (compare Dain A. 1909 i 435; Raikow A. 1888 369). The solid acid is the more stable and begins to liberate carbon dioxide appreciably at 202O ; it is therefore regarded as the trans-isomeride whilst to the liquid acid which gives appreciable ovolution of carbon dioxide a t 131° and for which the decomposition curve is somewhat less regular is ascribed the cis-configuration but its purity is uncertain.The solid acid gave an ethyl ester b. p. 130°/12 turn. identical with the parent ester and a dibomide colou~~less needlee decomp. at 110'.i. 282 ABSTRACTS OF CHEMICAT PA4PERR. Hydrolysis of the parent ester by formic acid gave only the solid isomeride. The menthyl ester of the liquid ap-dimethylcinnamic acid was obtained by direct esterification aided l y hydrogen chloride and constituted a colourless oil b. p. l98"/14 mul. ; the liquid acid also gave a hydrochlol-ide crystallising in needles. Hydrogenation of either of the preceding isomerides by hydrogen and colloidal palladium or less well by sodium amalgam gave rise to P -phen yl-a -metlqZ-n- bu tyric acid CH F hMe* CHMe- CO,H colou rless needles m. p.130-1315' An attempt to converb the liquid acid into the solid isomeride by the action of sulphuric acid WAY unsuccessful on account of the formation of an indone derivative m. p. near 70"; oxime m. p. near 180'. Ethyl P-hydl.oxy-P-p-toZ?/Z-a-m~~h~~b~~~ y m t s C,,H,Mo*C Xe(OH) * CHMe* CO,Ett obtained by the interaction of p-tolyl methyl ketone ethyl a-bromo- propionate and zinc in banzone solution is a pale yellow liquid b. p. 149-150°/10 mm. It is dehydrated by boiling with 85% formic acid for three hours yielding ethyl ap-p-triinethylcinnamate a yellow liquid b.€1. 141-141*5°/11 mm. together with il quantity of ap-p-trintetliyl- cinruxmic uci j C,H,Me*Chle:CMe*CO,H needles from light petroleum or plates from alcohol m p. 1 6 3 O which can also be obtained by hydroiysis of the ester with potassium hydroxide solution. I n the synthesis of this acid the corresponding liquid modification was produced in insufficient quantity for investigation. The crystals of up-p-tri- methylcinnamic acid belong to the rhombic system (a b c = 0.786 1 1.223). Hydrogenation of a ~ - p - t r ~ m e t h y l c i n ~ i ~ ~ i c acid by hydrogen and colloidal yallsdirim produced p-p-tolyl-a-),i,etlryl-l~-butyl.ic m i d colourless needIe2 111. p. 11 3-1 14'. (',l-I,B4e*CHI\ITe*CIIMe.C02H D. F. T. Abietic Acid and Some of it8 Saltec.EMIL OSCAR ELLINUSON (J. Amer. Cl~em.. SOL 1914 36 325-3:!5).-Pure abietic acid was obtained from colophony by extraction with alcohol followed by recrystallieation from the same solvent. The acid formed colourless triangular plates which always contained traces of a viscid substance the presence of which is possibly due to some change in the acid itself. The melting point which is iufluenced by the rate of heating is near 152O if the temperature is raised by approximately one degree per minute. The wide discrepancies as to the m. p. as recorded by various investigators are considered t o indicate the existence of isomerides of different properties. After fusion the acid is reddish-brown and evidence of chemical change is forthcoming; for example the heat of combustion of the acid after fusion is somewhat less then that of the unfused acid.Cryoscopic and ebullioscoyic experimen tjs in various solvents gave results which were far from concordant the apparent molecular weight ranging from 200 in boiling pyridine to 500 in freezing benzene. Sodium and potassium abietates were prepared by direct neutralisn- tion of the acid with the corresponding alkali; the silver (white),ORGANIC CHEMISTRY. i. 283 copper (pale blue) calcium barium strontium cobalt (lavender) nickel (greenish-yellow) iron (light brown) zinc chromium (greenish-yellow) aluminium manganese (pale pink) and cadmium salts were obtained by precipitation of solutions of salts of the respective metals by a solution of the alkali salt of the acid. The stannic salt was instantaneously produced on mixing stannic chioride and cupric abietabe in benzene solution the solution of tin abietnte being filtered from the precipitated copper chloride.The abietatcs of the heavier metals all contained an excess of abietic acid. D. F. T. Preparation of Derivatives of p-Aminopheoyl Salicylate containing Sulphur. ISAK ABELIN EMIL BURGI and MENDEL PERELSTEIN (D.R..-P. 2681 74).-p-Sulphonzet?~ylaminophenyZ snlicylate O€I~C,H,*CO*O*C,H,~NH.CH,.O.SO K m. p. 134-1 36' (decomp.) is obtained on acidifying aqueous solutions of its salts of which the sodium salt is prepared by heating an aqueous suspension of p-amino- phenyl salicylate with 8 to 20 parts of formaldehy4e sodium hydrogen sulphite. It crptallises in white needles that are readily soluble in water which property enables it to be used in therapeutics where the insolubility of phenyl salicylate (salol) is a didvantage.Tho potassium salt is prepared in an analogous manner and has similar properties. An alternative methcd of prepmation is t o employ sodium hydroxymethylsulphonate instead of the formaldehyde Pinacol-Pinacolin Rearrangement. Preparation of Benzoyl- formic [ Phenylglyoxylic] Acid and Some of its Derivatives. S. F. ACREE (A7r~er. Chem. J. 1913,50 389-395. Compare A. 1903,i 724 ; 1904 i 742 ; 1905 i '316).-Ph~nylgly~xylic acid can be readily obtained in good yield tjy the interaction of cold dilute solutions of mandclic acid and potassium permangannte. The chloride b. p. 125'/9 mm. can be prepared by warming the acid with thionyl chloride a t about 40° and when treated with alcohol yields the corresponding ethyl ester.By the action of magnesium phony1 bromide (3 mols.) on ethyl phenylglyoxylate (1 mol,) a product is obtained which on decomposition with cold dilute sulphuric acid yields benzpinacona. When ethyl phenylglyoxylate (1 mol.) is treated with magnesium phenyl bromide ( 1 mol.) and the product decomposed with water an excellent yield of ethyl benzilate is obtained. A similar experiment was made with ethyl phenylglyoxylate and magnesium p-tolyl bromide with a view t o obtaining ethyl phenyl-p-tolylglycollate ; most of the ethyl phenylglyosy late was recovered unchanged but a small quantity of an ester b. p. 210-212'/15 mu. was isolated. Some New Derivatives of Di- and Tri-hydroxybgnaoic Acids.FRANZ TON HEMMELMATR ( Monatsh. 1 9 14,3 5,1-8. Compare A. 1911 i 953; 1912 i 977).-The hydrochloride of 3-bromo- 5-amino-p-resorcylic acid is most readily obtained by the reduction of an acid alcoholic solution of 3-bromo-5-nitro-P-resorcylic acid with dilute stannous chloride solution. It forms white needles which darken and slowly decompose abova 200' and are not melted at 275'. When boiled with water i t is partly decomposed with evolution of compound. J. c. c. E. G.i. 284 ABSTRACTS OF CHEMICAL PAPERS. carbon dioxide. ?,-Bronio-5-amino-P-reso~.cyEic acid colourless prisms which decompose slightly without melting at 380° is prepared by the action of warm water on the chloride. 3-Bromo-5-amino-~-resorcylic acid hydrobromide colourless crystals is obtained by reducing the nitro-acid by tin and hydrobromic acid.When dissolved "-' in warm dilute hydrobromic acid and treated with OI~./) potassium nitrite i t yields bromodiazo-P resorcylic acid ~~1 .N :N (annexed formula) dark orange-yellow crystals which \/ explode when heated and which are converted by successive treatment with potassium hydroxide and alkaline stannous chloride solution into 3-bromo-P-r~swcylic acid brown needles m. p. 202'. The latter is decomposed by boiling water to about the same extent as P-resorcylic acid so that the stabilising influence of fhe bromine atom in the meta-position to the carboxyl group appears to be neutralised by the proximity of the two hydroxyl groups. Arninogentisic acid hydrochloride colourless plates is obtained by the reduction of nitrogentisic acid by stannous chloride and dilute hydro- chloric acid.Protracted treatment with water decomposes it com- pletely into aminogentisic acid which decomposes at 204' after previous darkening. The action of methyl sulphate on hydroxyquinolcarboxylic acid has been investigated by Bargellini and Martegiani (A 1912 i 9Sl) who thereby obtained asaronic acid. The author finds however that the main product of the action is h y d ~ ~ o x y q u ~ ~ o ~ c a r b o x y ~ ~ c acid dimethyl ether brown needles m. p. 202O (decomp.). Sodium methoxide and methyl iodide in methyl-alcoholic solution convert this substance as also hydroxyquinolcarboxylic acid into the corresponding methyl ester colourless needles m. p. 95'. Acetylsalicylic Acid.HEINRICH VON ERANNICHFELDT (Ber. 1914 47 156-159).-Phenol and p-hydroxyacetophonone have been isolated a s the products of the distillation of acetylsalicylic acid with lime. The acid is therefore established as 2-hydroxy-5-acetyl benzoic acid as the discoverers Bialobrzeski and Nencki suggested ( A . 1897 i 531). The occurrence of phenol was traced to the action of lime on the p-hydroxyacetophenone and this unexpected reaction will be applied to other ketones. When the acid was treated with the required amount of chloro- acetic acid and potassium (but not sodium) hydroxide (compare R. Meyer An? 1913 i 1344) a small yield of 2-carboxy-4-ace~ylphenoxyacetic acid C02H*CgH,Ac=O*UH,.C0,H was obtained. The compound forms yellow scales m. p. 179" which give a reddish-brown colour with alcoholic ferric chloride traces of acetylsalicylic acid producing a violet coloration.Acety Isalicplic acid was also converted into the ethyl ester white needles m. p. 70-71° and by means of methyl sulphate followed by hydrolysis of tho ester by calcium hydroxide into the methoxy-deriv- ative OMe*C,H3Ac*C02H. The latter formed white needles m. p. 152' and yielded an ethyl ester pale yellow prismatic needles m. p. 41-4a0 and by means of diazomethane the methyl ester in 1 H. W. slender white needles m. p. 96'. J. c. W.ORGANIC CHEMISTRY. i. 285 Ketens. XXV. The Action of Acid Chlorides on Dipbenyl- keten. H. STAUDINGER 0. GOHRING and M. SCROLLER (Rer. 1914 47 40-48. Compare Staudinger Anthes and Schneider A . 1913 i 1339) -It is found that many acid chlorides condense with diphenyl- kuten a t the ethylenic linking This is of interest because although acid chlorides have been found capable of condensation a t a carbonyl group (Staudiager A.1909 i 1905) no such effect has previously been produced a t an ethylenic linking. The method was to enclose the diphenylketen and acid chloride in separate sealed test glasses and to allow interaction by breaking them inside n sealed bomb tube containing an atmosphere of carbon dioxide. If 110 chemical change occurred in twenty-four hours in the cold the tube was heated in a water-bath or in a bomb furnace. Diphenylketen and oxalyl chloride react in the cold giving diphenyl- malonyl chloride COCI*CPh,*COCl colourless crystals b. p. 5 1 -5-52 '5" h. p. 183-l84'/13 mm.; di-anilidc colourless crystals m. p. 187-1 88". The chloride when heated with alcohol produced crystalline methyl diphenylmulonate m. p. 94-95' but its considerable resistance to the action of water was in accord with the usual effect of the phengl group on the stability of an acid chloride (compare Schmidlin and Hodgson A. 19OS i 170). Carbonyl chloride gave with diphenylketerr the same product as was obtained with oxalyl chloride but a temperature of 120-130' was necessary. I n an analogous manner oxalyl bromide gave diphenylnzalonyl bromide m. p. 88-90' and ethyl chloroglyoxylate yielded ethyl diphenyZmalony2 chloride COCl*CPh,*CO,EEt m. p. 74-75". Ethyl chloroformate which might have been expected t o give rice to the same product as ethyl chloroglyoxylate actually gave rise a t looo to a slow polymerisation yielding a yellow crystalline substance m.p. 187-188"; t h i s is not identical with the dimeric tetraphenyl- cyclobutanedione described earlier (Staudinger A. 191 1 i 306 ; compare also Staudinger and Kon A. 3911 i 876). Chloroglyoxglanilide and chloroformanilide did not react in t h e expected manner with formation of diphenylmalonanil ; the former gave a somewhat complex change at 1 00" diphenylacetyl chloride oxanilide and ciiphenylcarbamide being obtained whilst the latter hubstance parted smoothly with the elements of hydrogen chloride producing phenylcarbimide and diphenylacetyl chloride. The co diphenyZrnalonanil CPh,<co>NPh which failed to appear as the product of the interaction of the last two reagents with diphenylketen was obtainable as colourless crystals m.p. 125-126' by heating phenylcsrbimide with diphenylketen a t 220° although at 150' the only change observed was the polymerisation of t h e diphenylketen to tetraphenylcyclobutanedione. Dtphenplmalonanil when heated with aniline a t 200' becomes converted into the diphenylmalonanilide described above but is remarkably stable towards mere heating and decomposes slowly with regeneration of its components at 300'. Thiocarbonyl chloride failed to react in the cold and on warming caused resinification. Bromoacetyl bromide phthalyl chloride cyanogen iodide and triphenylmethyl chloride gave a similar result. Acetyl chloride reacted first a t loo' the products being diphenpl-i. 286 ABSTRACTS OF CHEMICAL PAPERS.a c e q l chloride and a resinous mass the latter being probably formed by the polymerisation of the simple keten which had been primarily pro- duced from the acetyl chloride. Succinyl chloride gave the same products. Benzoyl chloride and bromide behaved like ethyl chloroformate inducing polymerisation to the substance m. p. 188'. It has already besn shown that the action of phosphorus penta- chloride on diphenylketen yields diphenylchloroacetyl chloride ; phosphorus trichloride merely gives rise to the dimeride m. p. 18S3 together with resinous substances. Sulphuryl chloride gives similar products t o phosphorns pentachloride whilst thioriyl chloride produces chlorodiphenylacetyl chloride together with sulphur dioxide and sulphur. I n the case of the last two reagents it is possible that the molecule of halogen compound first unites at the characteristic keten grouping the resulting compounds then losing sulphur dioxide and SO respectively the latter of which resolves itself into sulphur dioxide and sulphur.D. F. T. Methylation of Ethyl Diacetylsuccinate. RICHARD WILL- STATTER and CHARLES HUGH CLARKE (Ber. 1914 47 291-310)- Ethyl diacetylsuccinate having been used by Knorr and acetonyl- acetone by Paal as the starting point in the synthesis of substituted pyrroles the authors have attempted to obtain mono- and di-aikyl derivatives of these compounds with a view to the synthesis of tri- and t etra-substitu t ed py moles. Under the ordinary conditions for alkylating ethyl acetoacetlate the methylation of ethyl diacetylsuccinate follows a complicated course.The furan derivative of ethyl carbopyrotritarnte and the lactone of ethyl isocarbopyrotritarate are formed as also are ethyl 0 0-dimethyl- diacetylsuccinate and ethyl C-methyldiacetyls~iccinate the latter then undergoing change in three directions (1) By alcoholysis it loses a carboxjl group and yields ethyl a-xcetyl-P-methylsuccinate C02Et*C31cAc*CHAc*C0,Et + EtQH = ISIe-CO,Et + CO,Et*CHMe*CHAc*CO,Et. (2) Part undergoes further mcthylstion hydrolysis yielding s-dimethyl- succinic acid. (3) Condensat'ion to a cyclopentenone derivative occurs thus CO,Et*CMeAc*CHAc*CO,Et = The compound obtained by Dietzel (A. 1889 593) dong with methyl- pyrotritaric acid by distilling methylmethronic acid is not a dimethyl- cyclopentenone but trimethylfuran whilst the so-called methylkuto- pentamethylene from methronic acid is dimethylfuran.Ethyl hydrogen a-acetyl-P-methyleuccinate CO,Et*CHAc* CHMw CO,H forms prisms m. p. 66-67'. C0,Et*CHAc*CHJle*C02Et is a colourless moderately mobile oil b. p. 94-85O/0*07 mm. l>i7'5 1.0620. Hydrolysis and removal of carbon dioxide from the ethyl dimethyl- cydopentenonedicarboxylate yield 2 3~dimethyZ-A1-cyclopenten-6-one C H M e < ~ ~ ~ - ~ ~ ~ a mobile oil b. p. 67-68'/9 mm. The diethyl ester,ORGANIC CHEMISTRY. i. 287 Methylation of the disodium or dipotassium salt of ethyl diacetyl- succinate in ethereal suspension by means of methyl sulphate a t the ordinary temperature proceeds readily and exclusively a t the oxygen atom. The ethyl dimethyldiucetylsuccinate thus obtained CO,Et*C( :CMe*OMe)*C( :CMe-OMe)*CO,Et forms cis- and trans-isomerides (1) a colourless viscous oil b.p. 134.5-136.5O/0*2 mm. DY 1.1214 which does not react with hydroxyl- amine in acetic acid solution,-but unites with bromine in alcohol ; ( 2 ) rhombohedral almost cubical crystals m. p. 106'. The action of methyl sulpbate in presence of boiling xylene yields only oxygen- substituted derivatives mixed with ethyl carbopyrotritarate. The two dimethyldiacetplsuccinic esters may also be obtained by methyl- ating with diazomethane but the action is very slow. Ethyl dipopion ylsuccinate C0,E t *CH (COE t ) *CH( COE t )*CO,Et forms rhomb-shaped plates m. p. 87' and gives no reaction with ferric chloride. By dissolution in dilute sodium hydroxide solution and precipitation with ice-cold suiphuric acid it is converted into an oily enolic form which is re-converted into the ketonic modification when distilled in a vacuum. With hydroxylamine it gives ethyl 1-hydroxy- 2 5-diethylpyrrole-3 4-dicurboxylute C,,H,,O,N a viscous oil b.p. 205-206°/0.05 mm. whilst ammonium acetate converts it into ethyl 2 5-diethylpyrvole-3 4-dicai*boxylate C,,H,,O,N an oil b. p. 170"~' 0.025 mm. Metbylation of the disodium compound of ethyl dipro- yionylsuccinate in ether by means of methyl sulphate yields besides fiiran derivative only the 0 0-dimethyl ether C,,H,,O as an oil b. p. 130-135'/0~1 mm As regards its behaviour on methylation ethyl isocarbopyrotri- tarnte occupies a position intermediate between ethyl acetoacetate and ethyl diacetylsuccinate. Treatmeut of its dry sodium salt with methyl sulphate always yields a mixture in about equal proportions of the carbon-substituted (formula I below) and of the cis- and trums- modifications of the oxygen-substituted methyl derivative (formula 11 below).From these the corresponding mono-alkylated ethyl diacetyl- succinates may be obtained by treatment in the cold with sodium ethoxide which is simply added to the molecule. YMeAc-CO CO,Et*?MeAc . CO,Et*C:CMe*ONa ' >O (I) + NaOEt = c(C0,E.t) CMe OMw CMe $+-CO OMe* CMe ?*CO,Et CO,Et*CCMe>* ('I) 4- NaoEt = ONa*CMe:C*CO,Et' These sodium salts cannot be alkylat,ed in the same way as ethyl acetoacetate since they readily lose an acetyl group by alcoholysis and pass into homologues of the monoacetylsuccinic ester.Thus on heating with methyl iodide CO,Et*YMeA c C0,Et *QHMe C0,Et *C CMe* ONa + Et*oH -+ Me'Co,Et + CO,Et.C:CMe.ONa' CO,Et*yHMe CO,Et*CMe Ac' and this +Me1 -+-i. 288 ABSTRACTS OF CHEMICSL PAPERS. Under milder conditions of methylation for example with methyl sulphate in the cold replacement of the sodium occurs giving CO,Et*CllleAc*C( CO Et) CMe*OMe. Ethyl C-rnethylisocccrbopyrotritccrate (formula I above) is a colourles~ slightly viscous oil b. p. 142-143'/9 mm. Dfo 1.1468. The cis- and trans-modifications of ethyl O-methylisocarbopyro- triturate (formula 11 above) have the properties a-form domed hexagonal prisms m. p. 63" ; @-form qurrdratic plates m. p. 95'. Ethyl C-ethylisocwBopprot&arate C,,H,,O obtained by means of ethyl sulphate is a colourless oil b. p.143-144'/9 mm. Di5 1.1133. Ethyl diacetyl-C-methylsuccinate C13H2006 is a n oil b. p. 150-1 6b0/ 11 mm. Di5 1.1168 and gives a reddish-violet coloration with ferric chloride. The corresponding 0 0-di~aethylauccinccte C14H220tj has b. p. 160-161°/10 mm. Di5 1.1022 and the 0 0-diethplsuccinate C,,H,,06 is a moderately viscous oil b. p. 163-164'/14 mm. Ethyl diacetyl-C-ethylsuccirtate C,,H2,06 b. p. 158-163'1 10 rum. gives with methyl sulphate a O-rnethyl derivative b. p. 166-157"/9 mm. The a-form of ethyl 0-methylisocarbopyrotritarate m. p. 63' gives with sodi u r n ethoxide ethyl O-methpZ~icccetylsucci.rLate Cl,H,,O6 as a viscous oil b. p. 164-165'/13 mm. which forms a violet coloration with ferric chloride Since mono-alkylated ethyl diacetylsuccinntes cannot be further substituted a t the carbon atom alkylation of ethyl afij-diacetylbutyrate has been resorted to in order to obtain homologues of acetonylacetone.I n this cape the alkyl become3 attached to the carbon atom giving derivatives of dimethylacetonylace tone which Ciamician and Sil ber obtained from methyl ethyl ketone and converted into tetramethyl- pyrrole (A 1912 i 537). The methylated and more especially tho ethglated diacetyl butyric ester with which conversion into furan derivatives is no longer possible readily condense to cycZopentenones. Since this ring closure occurs i n a n alkaline medium methylation always yields a mixture of ethyl ap-dincetyl-a-metbylbutyrate and ethyl 2 3 4-trimethyl-A~-cyclopenten-5-one-3-carboxylate which can scarcely be separated by fractionation If this mixture of esters is subjected to ketonic decomposition in alkaline solution condensation to 2 3 4-trimetbyl-Al-cg/clopenten-5-one advances further and the latter cannot be separated from the dimethylacetonylacttone. Ketonic decomposition by means of dilute sulphuric acid or hydrobromic and glacial acetic acids results in the loss of the greater part of the diketone which is converted into tetramethylfuran this being distinguished from its lower homologues by the greater stability of the furan ring.colourles~ mobile oil b. p. 78"/11 mm. Dil 0,939 and gives a semicarbuzone C,H,,ON m. p. 209'. CH,-~HMe obtained CHMe*C HMe' by hydrogenating the ketone in presence of platinum is a liquid 1 2 3-Trimethylcyclopentccn-4-ol OH*CH<ORGANIC CHEMISTRY. i.289 b. p. 68-70'/12 mm. with an odour resembling that of menthol. Its naphthyluyethane C,H,,-O-CO~NH-C,,H7 has m. p. 11 1-1 12'. Ethylation of ethyl ap-diacetylbutprate by means of ethyl iodide and sodium ethoxide gives a mixture two-thirds of which consists of cyclic condensation product. Treatment of the mixture with aqueous barium hydroxide yields almost pure 2 4-dirnathyZ-S-etAyZ-A*-ryclo- pen~en-5-one C,H,,O b. p. 88-89'/12 mm. which forms n semi- carbasone C10H170N3 m. p. 158'. Methylcarbonato-derivatives of Phloroglucinolcarboxylic Acid and of Phloretic Acid. EMIL FISCHER and HERMANN STRAUSS (Ber. 1914 47 317-322. Compare A 1913 i 731 9 76 I 35 2).-The preparation of trimet h ylcar bona t o-deriva tive of phloroglucinolcarboxylic acid presents unusual difficulties since in aqueous alkaline solution only a monomethylcarbonato-derivative is obtained (A 1910 i 258) whilgt in the presence of dimethylaniline the formation of trimethylcarbonato-compound is accompanied by the production of considerable quantities of a neutral intermediate compound.The nature of the latter has now been examined and a ready method for converting it into the trimethylcarbonato-derivatives is described. ~rirnethylcarbo~loiol~lorogl~cinolc~r~oxy Zic [ a 4 6 -trimeth ylcarbonato- benzoic] acid m. p. about 123' (decomp.) is obtained in 86% yield when a solution of phloroglucinolcarboxylic acid in benzene is treated with methyl chloroformate in the presence o€ dimethylaniline ; the crude product is treated with potassium hydrogen carbonate in aqueous acet.one solution whereby the intermediate compound is decomposed and the acid is ieolated by additiou of hydrochloric acid and extraction with ethyl acetate. It can be more readily obtained from mono- methy lcarbonatophloroglucinolcar boxy lic acid.T. H. P. The ztbove-men tioned intermediate product C,H,( 0. CO,Me),* CO* 0 CO,Me m. p. 81-82' is contained in considerable quantity in the benzene solution obtained after the action of methyl chloroformate and dimethylaniline and may be obtained in the crystalline form when this solution is simultaneously shaken with dilute sulphuric acid and much ether. It is scarcely affected by cold aqueous solutions of baseP probably on account of its sparing solubility in water.2 4 6-1'rimethylcarbonatobenzoyl chloride acid has been obtained in the solid state m. p. about 53-55'. Phloretic acid [P-p-hydroxyphenylpropionic acid] obtained from phloridzin by the method of Cremer and Seuffert (A 1912 i 885) is transformed by methyl chloroformate in aqueous alkaline solution into P-p-methylcarbonatophenylpropionic acid fine needles or thin plates m. p. 83-84'. For the similar product obtained from synthetic p-bydroxy-a-phenylpropionic acid Sonn (this vol. i 184) gives m. p. 86-87'. Phosphorus pentachloride in the presence of' chloroform converts it into the corresponding chloride which can be distilled without decomposition under greatly reduced pressure and has b. p. about 120'/0*13 mm. When cooled from - 40' to -50' it slowly solidifies to a crystalline mass m.p. about 10-12'. H. W.i. 290 ABSTRACTS OF CHEMICAL PAPERS. [Resorcinolbenzein and Fluorescein.] F. KEHRMANN (Bey. 1914 47 84-87).-A final contribution by the author t o the controversy (compare A 1913 i 1352) with von Liebig (compare this vol. i 49 ; A. 1913 i 865). J. HEHZIG and R. WACHSLER (Monntsh. 1914 35 77-84).-Previous work on the constitution of galloflavin (Herzig Erdos and Ruzicka A. 1910 i 676) has been greatly hampered by the poor yields obtained in converting galloflavin tetramethyl ether into isogalloflavin trimethyl ether. An improvement has now been effected by the preparation of isogalloflavin and the conversion of the latter itito its trimethyl ether with intermediate formation of the tetramethyl ether the yields in each of the processes beiug very good.When galloflavin is dissolved in 10% aqueous potassium hydroxide i t may be recovered unchanged by immediate addition of acid ; after some time addition of acid causes no precipitate but a solution is formed which when warmed deposits isogalloflavin. The identity of the latter follows from its conversion into isogalloflitvin tetramethyl ether tn. pa 232-233' and transformation of the latter by potassium hydroxide and methyl sulphate itito the ether estar C,,H20,(011iIe)G m. p. 92-95'. Acetic anhydride and sodium acetate convert isogalloflaviu into triacetylisoguZlo~avin m. p. 220-223' (decomp.). Acetic acid is lost a t the m. p. the carboxyl group unlike that in isogalloflavin trimethyl ether being apparently stable. The molten substance after renewed acetylation is re-Zonverted into the original compound.The presence of a carboxyl group i n triacetylisogalloflavin cannot thus be directly proved but is rendered probable from the fact that diazo- methane converts i t into a substance C,,H,O,(OAc),*OMe m. p. [With TRENKLE.]-T~~ almost quantitative production of isogallo- flavin trimethyl ether from the tetramethyl ether is secured by dissolvicg the latter in methyl alcohol and cautiously warming with potassium hydroxide and water ; the reaction mixture is quickly cooled poured into concentrated sulphuric acid and cautiously diluted with water. The method is much less successful when applied to the preparation of isogalloflaviu trimethyl ether from galloflavin tetramethyl ether.Attempts have been made to obtain methyl ethers of still unchanged galloflavin by the rapid methylatiou of the latter immediately follow- ing its solution in potassium hydroxide. I n this manner methyl sulphate yielded a small smeary precipitate (which gave isogalloflavin tetramethyl ether with diazomethane) isogalloflavin trimethyl ether a substance which with diazome thane gave isogalloflavin te t rame t hy 1 ether and the ether ester C1,H,0(O~e),(~02Me)2 together with syrupy amorphous products which could not be distilled. '' Paired " Glycuronic Acids YOSHTTA SERA (Zeitsch. physiol. Chem. 1913 88 460-464).-When the urine of a rabbit fed with orcinol is treated with lead acetate filtered and treated with basic lead acetate a precipitate is obtained which after decom- position with hydrogen sulphide yields a solution which gives with barium carbonate bccrium orcinolglycuronate Ba(Cl,H,70,) The D.F. T. Galloflavin. 21 6-2 199 H. W.ONGAKIC CHEMISTRY. i. 291 salt has [.ID -73.58' (in aqueous solution) and yields orcinol and glycuronic acid when hydrolysed with sulphuric acid. It is not hydrolysed by emulsin and the author also finds that vanillin- glycuronic acid is also unacted on by emulsin (compare Hildebrandt Beitr. chem. Physiol. Path. 1906 7 438) so that there is no reason to suppose that either of these acids is of the nature of a glucoside. R. V. S. Constitution of Two Nitro-nt-tolualdehydes. FRITZ MAYER (Ber. 1914 47 406-411).-It has long been known that t h e nitration of m-tolualdehyde yields two products m.p. 64' and 44' which have been regarded as 4-nitro-m-tolualdehyde and 2-nitro-?a- folualdehyde respectively. The author now finds that by oxidation with 1% potassium permanganate the aldehyde m. p. 44O yields 4-nitro-m-toluic acid m. p. 134' and is therefore 4-nitro-m-tolualde- hyde whilst the aldehyde m. p. 64' yields 2-nitro-m-toluic acid m. p. 219' and is therefore 2-nitro-m-tolualdehyde. Consequently it follows that the series of compounds prepared by the author ( A . 1912 i 478) from the supposed 2-nitro-rn-tolualdehyde (in reality the 4-nitro-compound) are 6-amino-3-methylbenzaldoxime 6-iodo-&methyl- benzaldehyde 6-iodo-3-methylbenzylideneaniline 3 2'4ialdehydo-4 4'- dimethyldiphenyl and 2 7-dimethylphennnthraquinone ; the last substance is identical with Liebermann's 2 7-dimethylphenanthra- quinone m.p4 224' (A 1911 i 656). Starting from 2-nitro-m-tolualdehyde m. p. 64' the following aeries of compounds has becn prepared by reactions similar to those already recorded (loc. cit.) 2-amino-3-nzethylbenz~ldoxi~n~ m. p. 134' ; 2-iodo- m-tolualdehyde m. p. 55-56' ; 2 2'-diaZdehydo-6 6'-dimetl~yEdi~henyl m. p. 118'. The unsatisfactory yield in the last reaction is i n accord with the author's experience that in Ullmann's reaction with copper powder the yield is bad or good according as the halogen atom is situated between two positive or two negative groups. 6-lodo-3-methoxybenxaldehyde m. p. 1 14-1 15' prepared from 6-amino-3-methoxy benznldoxime is converted through the benzyl- ideneaniline into 2 2'-dialdehydo-4 4'-dimethox?/di~he.nyl ru.p. 123-124' which reacts with boiling aqueous alcoholic potassium cyanide to form 2 7-dinzethoxyphenanthrapuinone m. p. 2 14-2 15' dark red powder. c. 5. Alkylation of the cycZoPentanones and Rupture of the Cyclic Chain of 1 3-Tetra-alkyl Derivatives by Sodamide. A. HALLER and R. CORNUBERT (Compt. rend. 1914,158 298-304).- The direct alkylation of cyclopentanone in ethereal solution by means of sodamide and methyl iodide gives but a very small yield of methyl- cycZopentan-2-one the major portion being converted into condensation products (compare Godchot and Taboury A. 1913 i 873). 1-Methyl- cycZopentan-2-one prepared from ethyl cyclopentanonecarboxylate can however be readily successively methylated by the action of sodnmide followed by methyl iodide in ethereal solution.By this method the authors have prepared 1 3-dintethyEcyclope.ntan-2-one b. p. 145-146' (corr.) DP 0-8898 n 1.4321.i. 292 ABSTRACTS OF CHEMICAL PAPERS. 1 1 3-TrimethylcycZopentan-2-one b. p. 151-152' (corr.) Di0 0*878l nz 1.4306 (compare Blanc A 1907 i 710). 1 1 3 3-Tetramethylcyclopentan-2-one b. p. 155-156' (corr.) Di0 0.8653 ng 1.6288. In this series the boiling point rises steadily with the introduction of each methyl group whilst the density and refractive iudex steadily decrease. The ethylation of cyclopentanone yielded only a small quantity of a mixture of methylethyl- and methyldiethyl-cyclopentanones together with a large quantity of condensation products and was not proceeded with.The allylation of 1-methylcyclopentan-%one yielded 1 -methyldiaZlgZ- cyclopentan-2-one [(C3Ht)2= 1 3 or 3 31 b. p. 130'/16 mm. (corr.) Uy 0.9251 YL 1,4823 in which the distribution of the ally1 groups between the positions 1 and 3 has not beea determined. On warmiDg this substance with sodamide in xylene it undergoes decomposition giving a substance distilling a t 135-190'/16 mm. and containing nitrogen. 1 1 3 3-Tetramethglcyclopentan-%one when heated with soditmide in boiling toluene for seven hours is decomposed giving aa8-trimethyl- hexctmide CH,*CHMe*CH2*CH,-CA!te2*CO*NH2 white plates m. p. 123' the cotistitution of which was determirled by preparation as f 01 lows. Phenyl isopropyl ketone warmed in benzene solution with sodamide and then with isoam yl iodide yielded cli?izet?~ylisoamylncetoplienoize [phenyl aay-tvimethylamyl ketone] b.p. 160-151°/16 mm. (corr.) Df' 0.9361 rtg 1*5007,.giviog an oxime m. p. 131'. This ketone on warming with sodamide in toluene yielded the required amide as above which on decomposition with sodium nitrite and sulphuric acid gave aa8-trimethylhexoic acid b. p. 127'/16 mm. (corr.). W. G. Preparation of Semicarbazones and Semicarbazidesemi- oarbazones of cycZoHexenones. IPPOLIT MACUREVITSCH (J. 1Zuss. Phys. Chem. Soc. 1913 45 1925-1936).-With the exception of camphorphoronesemicarbazidesemicarbs-one no products of reaction of 2 mols. of semicrirbazide with unsaturated hydroaromatic ketones have previously beea prepared. The author finds however that the formation of semicarbazidesemicarbazonos takes place with unsaturated A*-cyclic ketones in the same way as with unsaturated Aa-aliphatic ketones.I n consequence of the inconstancy of their decomposition temperatures the semicarbazones are inapplicable to the characterisa- tion of unsaturated A1-cy clic ketones. For all the semicarbazones examined the decomposition temperatures vary within narrow and almost identical limits and the same is the case with the semi- carbazidesemicarbazones for which the temperatures are somewhat higher. When the cyclic ketone contains an iso-radicle as substituent t h e conditions employed for obtaining semicarbazidesemicarbazones yield also a large proportion of the setnicarbazone. Semicarbazidesemicarbazones may be obtained by treating the cyclic ketone (1 mol.) in cold aqueous alcoholic solution with semicarbazide hydrochloride ( 2 mols.) in presence of sodium acetate.Their formationORGANIC CHEMISTRY. 1. 293 occupies about a fortnight and may be ascertained by boiling a small quantity of the precipitate formed with absolute alcohol in which they are insoluble ; the completion of the reaction occupies a considerable period Owing to their difficult solubility in all the ordinary solvents and to their tendency to decompose when boiled for a long time with a solvent they are best purified by washing on the filter successively with hot water boiling absolute alcohol and anhydrous ether. Their formation may tie represented as follows C H R 2 < ~ ~ ~ ~ f ; ; s c r r + 2ZJH2*NH*CO*NH = CH,*CR,( NK-NH*CO*NH,) CHR2<CH2-C (:N.NH.Cc). NH2)>CH2 (I) Or CHR~<CH~*C(:IY.NH*CO.NH,) CH2- CHR1>CH*NH*NH*CO*NH2. Or the second semicarbazide residue may be taken up at the double linking of the first semicarbazide residue so that four constitutions are possible. The results of Kupe and Kessler (A. 1910 i 15) and of Harries (A. 1904 i 427) render formula I. the most probable. 2-Methyl - ill- cyclohexen - 6-one semicarbazone has m. p. about 174-176' (decomp.). Vorlander and Gartner (A. 1899 i 259) gave m. p. 199-201'. 2 4 - Dimethyl - A1 - cyclohexen-6-one semicarbazone has m. p. 168-171" (decornp.). Knoevenagel (A 1897 i 609) gave m. p. 179-180' and 174-174.5". 2-Methyl-4-ethyl-~1-cyclohexen-6-one semicarbaeom C,,H,,ON forms snow-white nacreous plates m.p. 162-168' (decomp.). 2-Methyl-4-yr0py2-A~ - cyclohezen-6-one sevticurbazone CllHIgC)N forms colourlese crystals m. p. about 150-153' (decomp.). 2-,Meti~~Z-4-iso~ro;Ilyi-hl-c~clohexen-6-one sernicui-baxone C,,HIgON3 decomposes at about 164-167'. 2-Methyl-4-isobutyl - Al - cyclohexen-6-one sernicmrbazone C,2H210N3 forms colourless nacreous scales m. p. about 163-167' (decomp.). 2 -Methyl-~ll -cy clohexen-6 -one senzicurbaxidesemical.bazone C9HI8O2NB forms a pale yellow microcrystalline powder decomposing at 174-179°. 2 4-Dirnethpl-Al-cy clohexen-6-one semicar3asidesemicarbaxone) ClOH2OO2% forms a snow-white microcrystalline mass decomposing at 182-1 85'. Attempts to purify this compound by dissolving it i n hydrochloric acid precipitating it by means of potassium carbonate and washing with water alcohol and ether resulted in marked decomposition.2- Methyl-4 - et?iyl-A1- cy clohexen - 6 - one senzicarEaxidesemicarbazona C,,H,,02NG forms small sno w-white crystals decomposing at 183-186'. 2-Methyl -4-propyl-A1-c yclohexen-6 -one semicar bazidese?rtical.bazone C12H2402N6y forms snow-white crystals decomposing a t 183-186'. 2-Methy2-4-isopropyl-A1~cyclohezen-6-one semicarbazidese~nica~bazone C,,H,,02N6 forms snow-white crystals decomposing at 186.5-1 90'. 'z - 121eti~yl-4-isobutyl-A1-cyclohexe~~-6-o~~e semicurtrazLdGsen~i~~~~~~zo~~C13H2602N6 decomposing at 185-188' mas not obtained quite pure VOL. CVI. i. GL'i 294 ABSTRACTS OF CHEMICAL PAPERS. The alcoholic solution yielded snow-white crystals of the composition C12H2P39 T.H. P. Action of Phenacyl Bromide on Thioresorcinol. CESARE Compare Posner A 1908 FINZI (Gazxetta 1913 43 ii 643-654. i 21).-[With IDA P~~~~~'~~.]-m-Diphenacylthiolbenzene C,H4:(S*CH2*COPh) is obtained in 85% yield by the interaction of thioresorcinol sodium hydroxide (rather more than 2 mols.) and phenacyl bromide (2 mols.); it forms silky needles m. p. 95' and is very stable being hardly decomposed by boiling alkalis. Its dioxime C,,H,,0,N,S2 forms tufts of needles m. p. 116'. m-Diphenacylthiolbenzene yields with phenylhydrazine a yellow amorphous product but the di-p-bromo- phenylhydrazone C,,H,,N,S,Br crystallises in tufts of needles m. p. 167-1 68'. When m-diphenacylthiolbenzene is treated with 90% nitric acid a t the ordinary temperature a naononitro-derivative C,,H170,S,*N0 is produced ; it crystallises in yellow prismatic tablets m.p. 166-16 7". obtained by the action of bromine In chloroform solution crystallises in colourless leaflets m. p. 132'. When diphenacylthiolbenzene is oxidised with hydrogen peroxide in acetic acid the sulphoxide C,,H,,O,S is obtained ; it forms small colourless prisms m. p. 149" and when treated (in chloroform solution) with gaseous hydrogen bromide an unstable perbi*omide is obtained. m-Diphenacyltl~ioZbenzer~esuZphone C,,H,,O,S can be obtained by the oxidation of m-diphenacylthiolbenzene either with an excess of hydrogen peroxide or better with potassium permanganate ; it crystallises in long colourless prismatic needles m. p. 175'. The sulphone can be methylated by boiling with methyl iodide and sodium methoxide in alcoholic solution. It yields a dioxime C22H2006N2S2 m.p. 203". Dibromo-rn-dipiLenacyEtAioEbenxene C22H160282Br2 R. V. S. Unsaturated P-Diketones. H. HIEMESCH (Ber. 1914 47 115-116. Compare Ryan and Dunlea A 1913 i 1067).-The influence of a second carbouyl group in the P-position on the properties of unsaturated ketones is being studied. Attempts had been made to condense ethyl cinnamate with acetophenone but without the success which Ryan and Dunlea achieved. Their product a€-diphenyl- A - pentene-ye-dione was obtained however by condensing cinnamoyl chloride with sodiobenzoylacetone and shaking the oil left after extrac- tion with ether with concentrated hydrochloric acid. With phenyl- hydmzine it yielded a compound which crystallised in slender white needles m.p. 139-141'. J. C. W. Lapachonone. IV. C. MANUELLI (Atti 2". Accad. Lincei 1913 [v] 22 ii 686-691. Compare A 1901 i 216).-0xidation of lnpachonone by means of boiling dilute nitric acid yields phthalic acid but 50% nitric acid in the hot although I t gives principally phthalic and o d i c acids yields also (1) a nitrodihydroxyqzcinone derived from an oxidation product of lapachonone C,,H,,O,*NO which formsORGANIC CHEMISTRY. i. 295 vermilion crystals m. p. 206" forms a semicarbuxone C,,H,,O,N m. p. 260' (decomp.) and a dehydrated acetyl derivative C,,H,,O,N m. p. 116-1 1 7 O and corresponds with the bromodihydroxyquinone C15H1504Br obtained by brominating lapachonone suspended in water ; (2) a small proportion of a white compound m.p. 217'. Oxidation of lapachonone with sodium dichromate gives in the hot phthalic acid and in the cold (1) a yellow substance apparently a mixture and (2) the ConLpound (C13H1305)2 which forms shining white prisms m. p. 258' yields a diacetyl derivative (Cl5Hl5V3)? m. p. 225-226' and forms phthalic acid on oxidation with dilute nitric acid. T. €3. P. Cedron. J. HERZIG and F. WENZEL (Monatsh. 1914 35 63-76). -The product of the action of ferric chloride on trimethylphloro- glucinol described by Weidel and W e n d (A. 1898 i 580) has been further examined by CeEelsky (A 1900 i 225). The work of the latter has been repeated,and the conclusions differ in many respects from those previously recorded. Cedron C,,H,,O (instead of C,,H,,O,) is formed from 2 molecules of trimethylphloroglucinol by the loss of four atoms of hydrogen and is readily reduced to the original substance It yields two isomeric dimethyl ethers which are not interconvertible and in which the methoxy-groups are evenly distributed between the two nuclei.It also gives two isomeric diacetyl derivatives whilst the presence of two hydroxyl groups is also shown by Zerewitinov's method. Up to the present tautorneric reactions of the other four oxygen atoms have not been observed. Two possible formulE are proposed for cedron (I and II) to the second of which slight preference is accorded as >GO CO-CHXe (1. ) o.<:&:!!;J> c<g;;>c<c (OH) C&Ie CH2- C(OH)-CH/- \cNe-co \CO-CMe/ \CH~C(OH)/ \-CH,-/ (11.) CMeH \CO oc/ \CMe explaining better the absence of tautomeric reactions.[With A. G~~~.]-Cedron tlie preparation of which from rnesitylene is described in detail has m. p. 280-282O which when the substance is preserved sinks to 26O-27Oc. A reason cannot be assigned for the change but the product has the same qualitative reactions as cedron m. p. Z8~-282' and yields the corresponding derivatives in the same yield. Ceiielsky records 305' (decomp.) as m. p. of cedron ; this value has not been attained by the present authors and search for a second compound in cedron has been uueuccessful. With cold potassium hydroxide cedron yields t_he salt C,,H,?O,K from which cedron is regenerated by acid. Cetielsky describes a tri-potassium salt. It does not react with methyl iodide or methyl sulphate.Diazomethane converts cedron into a mixture of two dimethoxy-compounds which can be separated by cry stalliaat ion from x 2i. 296 ABSTRACTS OF CHEMICAL PAPERS. ethyl acetate into two forms m. p. 253-256' and 211-214' rerpectively ; the mixed m. p. is 215-232' and remains unchanged after the substances have been intimately mixed during several weeks. The methyl ethers are stable towards acetylating ageuts. When cedron is treated for a few seconds with boiling acetic anhydride and sodium acetate two ocetyl derivatives m. p. 268-270° and 195-197' respectively are obtained. Protracted action leads to the formation of substances of high melting or decomposition point,. When either of the above dimethoxy-compounds is intimately mixed with zinc dust and anhydrous sodium acetate and boiled with aceiic anhydride monomethoxydiacet~ltr~r~aethy~i~loroylucinol m.p. 66-68' is obtsined in almost quantitative yield. I n a similar mariner cedron? when subjected to reducing acetylation gives triacetyl- trimethy~hloroglucinol m. p. 165-167'. H. W. Action of Sodium Hydroxide on Tetrabromo-o-benzo- quinone. C. LORING JACKSON and A. H. FISKE (Amer. Chem. J. 191 3 50 341-3SO).-In an earlier paper (11.) 1909 i 657) the authors have shown t h a t when tetrabromo-o-benzoquinone is treated with Fodium hydroxide tetrabromocatechol is produced together with one or more acids according to the strength of the sodium hydroxide used. A further study of these reactions has now been made. As stated by Zincke (A. 1887 SOSj the first effect of a solution of alkali hydroxide on tetrabromo-o-benzoquinone is the formation of an unstable green solid.By the further action of sodium hydroxide of N-concentration a n acid m. p. 217" (decomp.) is produced ; with a ~olotion containing 60 grams per litre two acids are obtained m. p. 207' (decomp.) and 131'; whilst with a solution containing 200 grams per litre an acid m. p. 174' (decorup.) is formed. The only one of these acids which has been thoroughly investigated is t h a t of m. p. 207' (decomp.) which has been found to be the C,H ,O,Ac,*O Me tribromocurboxyEyclopent&one e&r of hydroxgoxalacetic acid CO-f B P CO,H CO,H*CH(CO-CO,H)-O*CH<CBr (3Br 9 it crystallises in pale yellow needles and yields apyridine salt m. p. 122-123'. When a strong aqueous solution of this acid is treated with bromine carbon dioxide and a little oxalic acid are produced together with ~~eptabrornomath~yldiacetyl [trzbronzonzethyl uPPP-tetra- bromoethyl diketone] CBrs*CHBr*CO-CO*CBr3 m.p. 97-98' which crystallibes in #bright yellow plates and is gradually decomposed by sodium carbonate solution with formation of bromoform (2 mols.) sodium oxalate (1 mol.) and sodium bromide (1 mol.). If bepta- bromomethyldiacetyl is heated with water in a sealed tube at loo" a compound m. p. 71-72' is obtained which forms long slender pale yellow needles. By the action of methyl alcohol on heptabromo- diace tgl i t s methyl hemiacetal CBr *C (OH) (OMe) CO*CHBr CBr m. p. 100-101" is produced which crystallises in colourless prisms. The corresponding ethy? henLiacetal has m.p. 93-54O. If a dilute solutiol; of the tribromocar.boxycyclopente~one ether ofORGANIC CHEMISTRY. i. 297 hydroxyoxalacetic wid is treated with brominp the heptubronbo- keto-eec.-ccm yl ether of glycollaldehyds CBr,*CO*CH(O*CH,* CHO) *CHBr *CBr m,. p. 96-97' is tormed which crystallises in short stout white prisms and is converted by sodium carbonate solution into the Itmabromohydroxyketo-sec.-amyl ether of glycollaldehycls m. p. 7 1-72' which forms white crystals The acid m. p. 121' crystallises in white rhombic prisms and probably has the composition C,,H,07Br,. The acid m. p. 174" (decomp.) seems to be the dibromohydroxy- carboxycyclopentane orthodiether of Rihydroxy~soc~otonolactonecocrboxyl~c C(OH)(C02H)*~€€*O*$XC(C02H) acid CBr< CBr-CH.O.CH-(VO>O ; it forms pale granules and when treated with bromine and water yields hepha- bromomethy ldiaeetyl.The acid m. p. 217' (decomp.) probably has the composition C,,H,09Br ; i t crystallises in yellowish-white prisms and when treated with bromine and water furnishes a compound m. p. 156". E. G. Octaiodo-p-quinhydrone. C. LORING JACKSON and E. K. BOLTON (J. Amer. Chem. Xoc. 1914 36 301-308).-Although the crystals of octaiodoquinhydrone obtained by the action of sulphurous acid on a benzene solution of iodoanil (compare Jackson and Bolton A. 1912 i 476; Torrey and Hunter i b d 475) are in appearance very similar t o those of iodoanil itself their behaviour towards organic solvents and sodium hydroxide demonstrates that t,hey are readily resolved into iodoanil and tetraiodoquinol.The apparent greater stability of octaiodoqiiinhydrone relative to the unknown corresponding octachloro- and octabromo-compounds is considered to harmonise with Richter's method of formulation of such substances (A. 1911 i 136) the substance at present under discussion being represented a s 0 C,T,:OH.O* C614. D. F. T. Preparation of Nitrogenous Condensation Products of the Anthraquinone Series. PARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 268454).-When 1 8-diaminonaphthalene is heated with I-chloroanthraquinone in amyl-alcoholic solution in the presence of copper salts and an acid-fixing agent (such as sodium acetate) 8-amino-1 -anthraquinonylaminonaphthalene (m. p. 2 15') is produced. If however the condensation is effected in a solvent of high boiling point (such as nitrobenzene) or if the above substances are heated alone or in a solvent of high boiling point new compounds are obtained which give vats and form the starting points for the preparation of colouring matters.The condensation product obtained from the above materials has m. p. 330-340'; that ultimately obtained from 4-chloro-1-methylanthraquinone and 1 8-diamino- naphthalene melts a t about 280' and that from 4-chloro-1-amino- anthraquinone has m. p. above 290'. J. C. C.i. 298 ABSTRACTS OF CHEMICATi PAPERS. Preparation of Sulphuric Acid Compounds of 1 4-Diamino- anthraquinone and its Nuclear Substitution Products. FARBENFABRLKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 268592j.- When 1 4-diaminoanthraquinone (5 parts) is warmed with fuming sulphuric acid (45% SO, 100 parts) at 50-60' until a sample is soluble in ammonia and the mixture then diluted with water until the sulphuric acid is about 80% strength a compound separates in red crystals m.p. above 300° which has probably the constitution C6H4<~~>C,H,(N:S0,),. On warming with dilute sulphuric acid hydrolysis takes place; on treatment with nitric acid and subsequent hydrolysis 6-nit9.o- 1 4-d~am~noanthra~u~none is obtained and on warming with aqueous sodium hydroxide 4-amino-1 2-dihydroxy- anthraquinone (a-aminoalizarin) is produced. Similar compounds are obtained from 2-bromo-1 4-diaminoanthraquinone and 2 S-dichloro- 1 4-diaminoantbraquinone. J. C. C. Euxanthic Acid. J. HERZLB and R.STANBER (Monatsh. 1914 35 47-61).-The observations of Herzig and Schonbach on the methylation of quercitrin (A. 1912 i 707) have led the authors to investigate the action of diazomethane on euxanthic acid in the hope of obtaining a convenient method for the prepara- 0 tion of 1-methyleuxanthone (annexed formula) /\/\/\ The action appears to fulfil the desired conditions I I 1 IOH but the further hope of finding decisive evidence \/\/\/ for the formula C,,H,,O, for euxanthic acid has When euxanthic acid is dissolved in methyl alcohol and treated with an ethereal solution of diaxomethane white needles or leaflets m. p. 154-137' (decomp.) are obtained which have the composition C,,H150,(OMe),. To a certain extent an amorphous substance is formed as by-product and this can be made the chief product of the reaction if methyl alcohol is omitted.It appears to be a tetramethoxy-derivative of the anhydro-compound C19Hl,0,(OMe)4 (compare Spiegel A. 1883 219 ; Graebe Aders and Heyer A. 1902 i 39) and is fairly stable towards boiling water. The crystalline trimethoxy-compound is readily soluble in water and the solutions after evaporation yield an amorphous substance C,,H,,O,(OMe),. When covered with methyl alcohol i t regenerates the crystalline compound Cl,H,,0,(OMe)3 ; the same behaviour is shown by the amorphous product obtained when the crystalline trimethoxy- compound is melted. The amorphous product combines more slowly with ethyl alcohol to yield a subcrtance m. p. 124-127' (decomp.) which can also be obtained by repeated crystallisation of the trimetboxy-compound from ethyl alcohol.Analyses agree with a formula 2C,,H,,O,(OMe)~,H,O,EtOH. When crystallised from methyl alcohol or melted and ditjsolved in the same solvent it regenerates the trimethoxy-compound. Methyl euxanthate m. p. 214-216' (Graebe Aders and Heyer Zoc. cit. give 218') is also converted by diazamethane into the. OMe CO not been realised.ORGANIC CHEMISTRY. i. 299 crystalline and amorphous products which are obtained from euxanthic acid. The potassium salt C,,H,70,,K (compare Graebe Aders and Heyer Zoc. cit.) is unaffected by a methyl-alcoholic solution of methyl iodide at 100' ; a t 140-150° euxanthone m. p. 236-237O is formed whilst a t 110-130° the main product is methyl euxanthate. 1-Methyleuxanthone m.p. 236-239O is obtained by the action of warm 10% sulphuric acid on the amorphous substance C,,H,,O,(OMe) or more conveniently by dissolving the latter in concentrated sulphuric acid and pouring the solution on to ice. It can also be prepared from the crystalline methoxy-compound. I n continuation of the work on the methylation of glucosides (A 1912 i 707) the authors have studied the action of diazomethane on sucrose but with negative results. With glycurone however a syrupy mass is obtained which appears to contain as a maximum two methoxy-groups for each glycurone molecule. H. W. Preparation of Purpurogallin. (2. GRAEBE (Ber. 1914 47 337-338. Compare Nierenstein and Spiers A. 191 3 i 1367 ; Herzig this vol. i 60).-Purpurogallin has been most conveniently prepared by the oxidation of pyrogallol with sodium nitrite and acetic acid (Perkin and Steven T.1903 83 197). The author finds that the yields are considerably improved if formic acid is substituted for acetic acid. I n a series of comparative experiments the maximal yield of purpurogallin was 20% in presence of the latter 30-31% in presence of the former. The order of addition of the reagents is without influence on the result. Replacement of organic acids by hydrochloric or sulphuric acid leads to much smaller yields. A further improvement consists in carrying out the reaction with complete exclusion of air. Under these conditions purpurogallin is immediately obtained in the pure state m. p. 274O and this result is obtained with acetic as well as with formic acid.H. W. Purpurogallin. J. HERZIG (Ber. 1914 47,38-39).-The author has been unable to repeat the preparation of a phenylhydrazone of tetra-acetylpurpurogallin as described by Nierenstein and Spiers (A 1313 i 1367) his only product being purpurogallin itself. The failure is attributed either to insufficient detail in the description of the procedure or to a lack of identity between specimens of purpurogallin of different origin D. F. T. Oxonium Salts. Additive Compounds of Cineole. I. I. BELLUCCI and L. GRASSI (Gaxxetta 1913 43 ii 712-735).-This paper records the results of the thermal analysis of the binary systems formed of cineol and a number of aromatic substances containing m e or more phenolic hydroxpl groups. Cineole and phenol form a compound in equimolecular proportions m.p. 8". Cineole and a-naphthol form a compound also in equimolecular proportions m. p. 75". The eutectic temperatures lie at 60' and 6'.i. 300 ABSTRACTS OF CHEMICAL PAPERS. Cineole and P-naphthol form a compound in equimolecular proportions m. p. 48". The eutectics lie a t 43.5" and 3.5'. Cineole and o-creeol form a compound in oquimolecular proportionp m. p. 50". Cineole and m-cresol form a compound in equimolecular proportions m. p. -5'. Cineole and p-cresol form a compound in equimolecular proportions m. p. 1.5'. Cineole and o-nitrophenol do not form any compound; the eutectic lies at 6'. Cineole and m-nitrophenol do not form any compound; eutectic temperature 15'. Cineole and p-nitrophenol do not combine ; there is an eutectic at 16'.Cineole and o-aminophenol do not combine; the eutectic lies st 0'. Cineole and m-aminophenol do not combine ; the eutectic lies at 3". Cineole and catechol form a compound in equimolecular proportions m. p. 39'. Cineole and resorcinol form a compound in equimolecular proportions m. p. 89". The eutectics lie a t 73" (40% cineol) and 2". Cineole and quinol form a compound in the proportion of 2 mols. cineole to 1 mol. quinol m. p. 106.5". Cineole and guaiacol form a compound in equimolecular proportions m. p. 5". Cineole and salicylic acid do not combine. The eutectic temperature is 11". Cineole and m-hydroxybenzoic acid do not combine. The eutectic temperature is 13". Cineole and p-hydroxybenzoic acid form a compound which decomposes before melting but this system could not be investigated beyond 60% of p-hydroxybenzoic acid as the temperatures then reached are above the b.p. of cineol. Cineole and methyl salicylate form a compound in equimolecular proportions m. p. - 15". Cineole and phenyl salicylate do not com- bine. The eutectic temperature is 13". Cineole and naphthyl salicylate do not combine. There is an eutectic a t - 5". Cineole and thymol form a compound in equimolecular proportions m. p. 4.5". There are eutectics at 31" and 2". The eutectic temperatures are 103" and 2". R. V. S. Esters of Chromic Acid. HEINRICH WIENHAUS (Ber. 1914 47 322-331).-With the possible exception of the compound obtained by Gomberg (A. 1902 i 600) by the action of silver chromate on trjphenylmethyl chloride esters of chromic acid do not appear to have been described.The author finds that they can be readily prepared by shaking a tertiary alcohol dissolved in light petroleum or carbon tetrachloride with a n aqueous solution of chromic acid or preferably with an excess of solid chromium trioside. The ester remains dissolved or suqended in tbe orgariic solvent from which it can be readily obtained by evaporation. According to analyses and molecular weight determinations the esters are normal compounds of chromic acid H,Cr04. They are saponified with difficulty by aqueous alkalis readily by alcoholic solutions of the latter. With hydrogen peroxide and ether they do not yield the characteristic test for chromic acid whilst also esters of perchromic acid have not been obtained as yet. The farmation o€ these substances may also be used t o investigate the tertiary alcoholic nature of a given compound.For this purpose the compound under investigation is dissolved in light petroleum orORGAKIC CHEMISTRY i. 301 carbon tetrachloride and shaken with chromium trioxidc; if a pure red coloration is developed which persists after some time the presence of a tertiary alcohol may be regarded as established; on the other hand should the solution rapidly become discoloured the absence of a tertiary alcohol cannot be regarded as proved since many of the latter substances are somewhat readily oxidised. I n general tertiary alcohols do not readily form crystalline derivatives so that the formation of a solid chromic ester may frequently be utilised for their isolation in the pure state.The best results have been obtained in the terpene and sesqui- terpene series. a- and /3-Terpineol .p-menthan-S-ol and p-menthsn-1-01 (Wallach A. 1911 i 470) give liquid chroniates of small stability the initially yellow then red solutions becoming rapidly brown. By rapid evapora- tion of its solution p-menthun-1-ol chromate (Cl,,H19)2Cr04 can be obtained as a dark brownish-red oil. MethylJenciLyl chromate (Cl,H19)2Cr04 is readily obtained in mine- red needles or prisms which can apparently be preserved indefinitely in the dark. It has m. p. 130' (decornp.) [.ID -30.0' in carbon tetrachloride solution (the rotations recorded are all for the Li red line). Detorminations of molecular weight are rendered difficult by the gradual decomposition of the dissolved ester but yield results approximate to those required by a normal ester of chromic acid.An ethereal solution of methylfenchyl chromate is unchanged by agitation with a 30% aqueous solution of hydrogen peroxide. A solution of methylfenchol in light petroleum is not coloured when shaken with a n aqueous solution of chromic acid and hydrogen peroxide unless very concentrated; in that cape i t acquires a deep blue colour. Similar results are obtaiued with solutions of perchromic acid obtained from the salt K,Cr08 and dilute sulphuric acid. I n the preparation of ruethylfenchol by the action of magnesium methyl iodide on fenchone considerable difficulty is experienced in isolating the tertiary alcohol. owing to tbe ketone being regenerated on decomposition of the product with water (Wallach 2nd Wienhaus A .1907 i 541). The separation is however readily accomplished by converting the alcohol into the above chromate from which it can be regenerated by saponification or by fission with zinc dust and acetic acid or with finely-divided palladium and hydrogen. Ethylfenchol is obtained by the action of an ethereal solution of magnesium ethyl iodide on fenchone together with fenchyl alcohol ethare and ethylene whilst considerable quantities of fenchone are regenerated (compare Konovalov A. 1907 i 171). When dissolved in light petroleum and shaken with a solution of chromium trioxide in dilute sulphuric acid it yields ethylfenchyl chromate cinnabar-red powder or needles which blackens without melting a t 140" and at a higher temperature becomes lighter and finally greyish-green.When dissolved in carbon tetrachloride it has [.I+ 22.5O. Methylbornyl chromate pale orange needles is prepared in the same manner as the methylfenchyl compound. It hecomes discoloured at 105O arid is ltevorotatory iu carbon tetrachloride t.olutioo. Cedrol chromate (C15H25)2C~04 yellowish-red primis has m. p. 115'i. 302 BBSTRACTS OF CEEMICAL PAPERS. after darkening at looo. I n carbon tetrachloride solution i t has Ledol needles m. p. 105' behaves similarly to cedrol -yielding a chromate ( C,,H,,),CrO wine-red apparently monoclinic prisms m. p. 92' [a] + 30.0' when dissolved in cnrbon tetrachloride. Patschali-cam phor yields a stable red chromate thus establishing its tertiary alcoholic character whereas guaiacol (compare Gandurin A.1909 i 98) is fairly readily oxidised which points to the possibility that i t contains the secondary alcoholic group. Attempts to esterify the tertiary alcoholic groups of more highly oxygenated compounds such as pinacone terpin fenchone-pinacone a-hydroxyisobutyric acid and benzilic acid with chromic acid have not been completely successful. Certain hydroaromatic secondary alcohols (cyclohexanol menthol fenchyl alcohol borneol and isobosneol) when dissolved in carbon tetrachloride gave yellow to deep red solutions when shaken with chromium trioxide ; after a few seconds however brownish-red particles separated in quantity owing to complete decomposition. A solution of thymol was coloured blue ; eugenol solution reduced chromium trioxide without becoming coloured.The Constituents of Essential Oils. Nopinane /3-Dihydro- limonene and Carane. F. W. SEMMLEB and J. FELDSTEIN (Ber. 1914 47 384-389).-In order to obtain a complete knowledge of the physical data of the basal hydrocarbons of the terpene series some members i n which the ring is fully saturated have been prepared. Wolff's method (A. 1912 i 988) was employed namely the conver- sion of the correpponding ketone into the hydrazone by heating with hydrazine hydrate in a sealed tube followed by the action of sodium ethoxide under pressure. Nopinonehydrazone C9H,,N2 has m. p. 42-43' and nopinane (1) has b. p. 149'/747 mm. Dii 0.8611 n. 1.46141 aD L-0'. P-Dihydro- kimonene (11) from dihydrocarvone has b. p. 168-169'/750 mm. Carane (111) has b.p. 49-5OC/ 9 mm. 165-166'/750 mm. with slight rearrangement DZ 0.8381 nD 1.45823 aD - 34'. An account of the application of this method to pulegone and tanacetone will appear in another place. Pulegone- hydrazone has b. p. 129-131°/20 mm. Dg 0,9563 nD 1,49261 and dihydroterpinolene (IV) has b. p. 169-170'/748 mm. 0.8189 nD 1.46823. Tanacetonehydrazone has b. p. 128-129O/18 mm. DE 0.9502 n 1.4965 and tanacetane (V) has b. p. 156-157'/747 mm. Me C C H CMe CMe CHMe [a] + 7 9 . 4 O . H. W. 0.8217 n 1-45673 aD k0'. DZf 0,8158 n D 1.44121. H \/ \/ \/ (1.1 (11. ) (111.) (IV.1 (V.) =2 €€Me \/ HMe HMe \/ J I i I T C AORGANIC CHEMISTRY. i. 303 A table of rotations and dispersions is given. The increment in molecular dispersion M - Ma varies from 1% in the case of P-dihydro- limonene to 9% in tanacetane in which a three-membered ring is attached to a five-ring and 10% in cnrane in which a three-membered ring is joined to a six-ring.The increment exhibited by compounds containing a cyclopropane ring is therefore due to that ring. alone and not to any neighbouring ketone or other group (compare Ostling T. 1912 101 457). J. C. W. System Sulphur Dioxide-Camphor. I. BELLUCCI and L. GRASSI (Atti R. Accud. Lincai 1913 [v] 22 ii 676-680).-Thermal study of this system revealed no appreciable superfusion and indicated the formation of the two compounds 2S0,,CloH,,0 m. p. - 45" and SO,,CloH,,O m. p -224'. The acceleration produced in the formation of sulphuryl chloride from sulphur dioxide and chlorine by the addition of camphor must therefore be attributed to the interaction of the camphor and sulphur dioxide.The purified sulphur dioxide employed solidified completely at - 76" (compare Polak- van der Goot A. 1913 ii 946). T. H. P. Structure of Dibromomenthone and a New Synthesis of Buchu-camphor. GUIDO CUSNAWO (Atti R. Accad. Lirtcei 191 3 [v] 22 ii 569- 575).-The dibrornomenthone of Beckmann and Eickelberg (A. 1896 i 313) can be prepared from 4-bromomenthone by treating its chloroform solution with bromine. When this dibromomenthone is dissolved in 2.5% potassium hydroxide and ths solution saturated with carbon dioxide buchu-camphor (Semmler and McKenzie A 1906 i 373) is precipitated. I n addition a compound crystallising in large prisms m. p. about 85O and a carboxylic acid are obtained.A monobronzo-buchu-camphor can be obtained by acting on a chloroform solution of the substance with the calculated amount of bromine dissolved in chloroform ; it forms rhombic or hexagonal tablets rn. p. 85". This monobromo-compound yields hydroxythymo- quinone when it is dissolved in 2% potassium hydroxide and the solution subsequently acidified and distilled with steam. When heated with acetic anhydride and sodium acetate the dibromo-derivative is not only acetylated but also loses HBr yielding a substance C1,H1,O which forms colourless or slightly yellow prisms m. p. 106-107'. One of the bromine atoms of the dibromomenthone mentioned above can be substituted by the radicles of amino-bases. 'The anilide CloH160Br*NHPh prepared by heating dibromomenthone (1 mol.) with aniline (2 mols.) for half an hour at loo' forms lemon-yellow prisms which soften a t 190° melt at 195" and at a higher temper- ature the liquid deposits thymol.C,,H~,O Br*NH*C6H4Me forms pale yellow needles. The pipei*idide U,oHl,OBr*C,NH, crystal- lises in colourless prisms m. p. 127-129'. Hydroxylamine and dibromomenthone yield in addition to the product obtained by Beckmann and Eickelberg (Zoc. cit .) the P-luydroxylunuhe Cl0Hl6OJ3r*NH*OH which forms colourless crystals m. p. 158-160" and has the reactions The p-toluidide,i. 304 ABSTRACTS OF CHEMICAL PAPERS. of a P-hydroxylamine. A substance m. p. 65' crystallising in white needles is also produced. From the P-hydroxylamine the isonitro- arnine C,,H,,BrO*N,O,H can be obtniued ; i t is a n unstable substance crystallising in long colourlees needles and yields buchu-camphor when warmed with potassium hydroxide.In the preparation of the isonitroamine a colourless crystalline substmzcs m. p. 95' containing bromine and nitrogen is produced. I n view of the reactions recorded i n this paper the author considers t h a t the dibromomenthone has the constitution of 2 4-dibromo- 3-men thanone. R. V. S. Action of Aluminium Chloride on Turpentine. WJLHELM STEINKOPF and MICHAEL FREUND (Ber. 1914 47 411-420. Com- pare Aschan A 1902 i 749 ; Eagler and Routala A. 1910 i 2 160).-French turpentice DF 0.8680 aD - 29.45' in 1-dcm. tube 95% of which has b. p. 152-167' i s slowly treated with aluminium chloride at O' and the mixture is kept for twelve hours at the ordinary temperature (the longer the mixture is kept the more extensive is the polymerisation and the less is the quantity of residual liquid).The liquid portion after being decanted and purified yields by distillation in addition to unchanged turpentine a fraction b. p. 62-140°/14 mm. D 0,9129 a fraction b. p. 140-203' 14 mm. D 0.9487 and a residue of yellow colophony (CloT3!6)z m. p. 77-78'. The viscou. portion yields after purification a fraction b. p. 62-140'/14 mm. D 0,9119 a fraction h. p. 140-203'/14 mm. D 0.9503 and a yellow residue m. p. 77-78". Similar results are obtained when pure I-pinene is treated with aluminium chloride. I n some experiments in order to obtain a s much as possible of the more volatile depolymeriaation products (b. p. up to 250') the turpentine and aluminium chloride after the initial vigorous reaction are boiled so long as gas is evolved the liquid portion is then poured off and the viscous residue again heated and so on.The gaseous produ2ts thus obtained do not contain acetylene or hydrogen and consist mainly of saturated paraffin and cyclic hydrocarbons. The liquid product has DP 0.8821 begins to boil at 20' bas an odour of petro- leum and contains benzene and about 25% of unsaturated coustituents. After the removal of these the residual liquid consisting of saturated hydzocarbons is separated into 31 fractions boiling between 30' and 249 . The b. p. density refractive index and percentage of carbon and hydrogen of each fraction are tabulated and compared with the corresponding constants of paraffin and naphthene hydrocarbons.The results indicate that the most volatile portions (fractions 1 and 2) of the depolymerised liquid consist of almost pure pentane and isopeDtnne ; then naphtbenes begin to appear and become the main constituent in fraction 5. Fraction 13 b. p. 115-120' is almost pure octanaphthene. The nitration of fraction 22 b. p. 165-172' yields a tertiary nitro-compound C,,U,,O,N b. p. 1 1S-12Oo/12 mm. Dm 1.0299 1% 1.46572 which is apparently nitrodecanaphthene (Engler and Halmai A. 1910 i 160). The liquid h. p. above 250' I):' 0.9609 is dark brown and viscous. After further treatment with aluminium chloride and removal of ttieORGANIC CELEMISTRY. i. 305 portion boiling below 250° a yellow liquid is obtained which has Di5 0.9535 92 1.51048 and is quite analogous to the various artificial and natural lubricating oils.The experiments show that unsaturated cyclic hydrocarbons like the terpenes yield by treatment with aluminium chloride the same or similar mixtures of hydrocarbons as do olufines such as pentene or hexene. c. s. Nitrocamphene. 11. New Connexions between the Camphene and the Camphane Series. P. LIPP (Annalen 1914 402 343-364. Compare A. 1913 i 1077).-The course of the conversion of nitrocamphene (Jagelki's camphenilo nitrite) into tricyclenic acid by weans of sulphuric acid (Bredt and May A. 1910 i 32) has been examined and a previous statement of the author (Zoc. cit.) corrected. The nitrogen is eliminated in the form of hydroxylamine which suggests the intermediate formation of a hydroxamk acid.The first product of the reaction which can be isolated is however the neutral sulphuric ester C,,H,,O,NS m. p. 127" (decomp.). The ester is readily hydrolysed by warm water yielding a hydroxy-hydroxamic acid Cl,H1703N m. p. 163-164" (decomp. corr.) which is not camphenylhydroxamic acid as stated previously (Zoc. cit.) but hydrosyapoc~nzphccneiiydroxamic acid 0H.N :C(OH)* C- ' CMe,--CH since it is converted into keto- pink acid and Bredt and May's hydroxyqocamphanecarboxylic acid 111. p. 340-242' (corr.) (Zoc. cit.) by cold 25% hydrochloric acid and &odium nitrite. The latter acid is undoubtedly a camphane derivative and siuce it is highly improbable that the change from the camphene t o the camphane nucleus is effected by the nitrous acid in the preceding reaction the only alternative explanation is that the nuclear trans- formation is accomplished during the addition of the sulphuric acid to nitrocamphene in the formation of the neutral sulphuric ester.The formation of this ester is remesented bv the scheme \ CH(OH)*CH \CH,--CH,/ c9H14<g;SrNOH and the nuclear transformation by the annoxed diagram CH,-CH-CH CH,-CH-CH + UH,-C- CH*OSO I I C'(:NOH)-O \ C: C H * NO Hydroxyupcarnphanehydroxamic acid condenses with acetone to form a subsdunce C13.H2103N m. p. 309-210° (corr.) and yields hydroxylarniue and tricyclenic acid by boiling with dilute sulphuric acid. A similar exallople of the transformation of the camphene into thei. 306 ABSTRACTS OF CHEMICAL PAPERS. carnphane nucleus is t o be found in the action of fuming hydro- bromic acid on nitrocamphene.The transformation is effected during the addition of hydrogen bromide to the nitrocamphene then follows the change *CH,*NO -+ OH*?NOH aid the hydroxyl group is replaced by bromine the product being bromoapocamphaizehyd.r.ozcx;.nLyl bromide 0H.N :CBr*U- CMe,\CH,m. p. 132-133" (corr.) The proofs of this formula are the following By heating at 100' under pressure with fuming hydrochloric acid the bromide yields hydroxyl- amine and mainly an unexamined neutral szcbstance m. p. 150-152O. The two bromine atoms function differently. Only one is displaced by the action of ethereal aniline or ammonia bromoapocanzphanean&Zino- oxims C1,H,,ON,Br m. p. 153.5-1545O (decomp.) and brornospo- ca~p?~anenmidoxime C10H,70N2Br decomp.156O being formed ; the latter is converted into hydroxyapoccbmphaneamidoxime C10H1802N9 m. p. 180-181' (decomp. corr.) by boiliag water. Both halogen atoms are displaced when bromoapocamphanehydroxamyl bromide is treated with cold methyl-alcoholic potassium hydroxide whereby methyl rnethoxyapocump?~anehydroxc6rnate C1,H,,O,N m. p. 102 5-1 04' (corr.) is produced; by brief boiling with 50% sulphuric acid the methyl ester yields tricyclenic acid and hydroxylamine. The final proof of the constitution of bromoapocamphanehydroxamyl bromide is furnished by reduction with .zinc dust and glacial acetic acid whereby the nitrile m. p. 17 1-1 72' (corr.) of upocampbanecarboxylic acid and a little w-aminocamphane are produced. Aqueous hydroxyapocamphaneirnidoxime hydrochloride and a slight excess of sodium nitrite yield nitrous oxide and hydroxycamphenilano- nitrik m.p. about 145' (decomp.) (annexed CH,--~H-CiMe formula) which is very stable towards oxidising agents or phosphorus pentachloride CH,-IH-~(OH).CN can be converted into an isonteride m. p. 165-1 70' and yields camphenilone and hydrogen cyanide by fusion. Like other nitromethylene derivatives nitrocamphene reacts ad- ditively with potassium cyanide in boiling alcohol the product after treatment with carbon dioxide yielding a compound C,,H,,O,N Additive Reactions of Caoutchouc. Elucidation of its Constitution and a Theory of Vulcanisation. F. KIRCHHOF (KoZEoid. Zeitsch. 19 14 14 35-43).-The increase in weight of thin films of caoutchouc on exposure to oxygen and to bromine and sulphur chloride vapour has been determined in a series of experiments in which the caoutchouc was weighed at the end of measured time intervals.The weight-time curves obtained in this way indicate an absorption of sulphur chloride which lies between the values required by the formulae~WloH,6,S2C12 and ( CloH16)2,S2C12. Since hydrogen chloride is evolved during the absorption process it is probable that the formula Cl,,H16,S2C12 represents the composition of the compound ,CHBr*CH \cH,-cH,/ I VH2 I m. p. 165-166O. c. s.ORGANIC CHEMISTKY. i. 307 which is formed. This conclusion is confirmed by the results obtained in the estimation of the combined sulphur. The curves representing the data obtained with bromine vapour a t 18' point to the formation of the dibromide C1,H,,Br but the corresponding data obtained in experiments a t 80' shorn t h a t the final increase in weight is less than that required by the formula for the monobromide C,,H,,Br.If the additive product obtained at 18" is heated on the water-bath hydrogen bromide is evolved and the monobromide is formed. Experiments with oxygen a t 75-80' have given indefinite results and it was found that different samples of caoutchouc behave very differently in regard to their rates of oxidation. Other observations relate to the changes which occur in the viscosity of solutions of caoutchouc during the addition of sulphur chloride. The initial slight fall i n the viscosity is succeeded by a rapid rise which continues until ultimately the solution gelatinises.Gelatinisation occurs much more quickly in light petroleum as com- pared with benzene solutions. The later part of the paper is speculative in character and deals with the constitution of caoutchouc and the changes which occur during the additive reactions on the basis of the above observations. €1. M. D. Synthetic Caoutchouc from Isoprene. G. STEIMNIG (Ber. 1914 47 350-354).-From experiuiciits on L L ~ diozonides (analyses molecular weight velocity of decomposition by boiling water nature of decomposition products) of Para caoutchouc and of the caoutchoucs prepared by autopolymerisation of isoprene and from isoprene by the acetic acid process Harries (A. 1912 i 706; 1913 i 284) has been led t o assume the identity of the three products.The author has applied the same method of investigation to the caoutchoucs obtained (1) by heating isoprene in the presence of ozvnides or peroxides and (2) by the action of sodium in the presence of carbon dioxide on isoprene. The ozonides are found to yield succinic acid and acetonyl- acetone in addition to lsvulinaldehyde and laevulic acid. Hence the caoutchoucs must contain 1 6-dimethyl-1 5-cycZooctadiene QH2* CMe CH*$!H CH,*CMe:CH*CH,' in addition to 1 5-dimethyl-1 5-cycEooctadiene the amount of the former being estimated a t about 20%. The two substances may be regarded as formed by the unsymmetrical and symmetrical condensa- tion respectively of two molecules of isoprene. Subsequently caoutchouc obtained by the autopolymerisation of isoprene has been re-investigated with the result that approximately the same quantities of succinic acid and acetonylacetone have been found among the products of de- composition of the ozonide as are yielded by other artificial caoutchoucs.Natural caoutchouc on the other hand does not yield a derivative of 1 6-dimethyl-1 5-cycZooctadiene and the incomplete identity of the artificial caoutchoucs with the natural product receives an explanation. The artificial caoutchoucs are purified by repeated treatment with a mixture of benzene and acetone ozonised in chloroform solution andi. 308 ABSTRACTS OF CHEMICAL PAPERS. the purified ozonida is decomposed n i t h boiling water. The resulting solution is concentrated in a vacuum until the laevulic acid commences to volatilise and then cooled when succinic acid separates.The aqueous distillate is treated with a n excess of phenylhydrazine acetate which causes a separation of the oily diphenylhydrazones of lsvulin- aldehyde and acetonylacetone. The two producw can be identified by addition of dilute sulphuric acid and distillation with steam. Lsvulin- aldehyde is thereby recognised by the formation of the non-volatile phenylmethyldihydropyridazine rn. p. 197" (compare Harries A 1898 i 333) whilst the presence of acetonylacetone follows from the formation of the volatile 1-phenylamino-2 5-dimethylpyrrole m. p. 90-92' (Knorr A 1885 995). H. W. S y n t h e t i c Resins. Condensation Products of Phenolic Substances by Aid of Hexamethylenetetramine. L. V. REDMAN A. J. WIETH arid P. P. BROCK (J.had. Erbg. Chem. 1914 6 3-16). -The authors give a synopsis of previous work on the condensation of salicylates hydroxybenzy 1 alcohols aromatic hydrocarbons etc. with formaldehyde and record the results of their study on the reaction and the products which are formed when dry hexamethylenetetramine is made t o react with anhydrous phenol. The resins formed by this reaction possess higher dielectric properties and are of more uniform character than the resins formed in the wet way and are more suitable for use in the electrical varnish glue moulding and other industries. w. P. s. Sphingosine. 11. The Oxidation of Sphingosine and Dihydrosphingosine. P. A. LEVENE and C. J. WEST (J Biol. Chem. 1914 16 549-553. Compare A. 1912 i 284 575).-On oxidation o€ sphingosine and dihydrosphingosine in the form of their sulphates by chromic acid in acetic acid solution the authors have obtained from the first a tridecoic acid m.p. 47-47*5" and from the latter a pentadecoic acid m. p. 60-61'. Their results are not in entire agreement with those of Lapworth (compare T. 1913 103 1029). On the basis of their results the authors suggest for sphingosine the formula C,,H,,*CH:CH*CH(OH)*CH(OH)*CH2*NH2 the exact arrangement of the two hydroxyl and the amino-group not being however definitely fixed. W. G. Digitoxin and Gitalin. H. KILIANI (Arch. Pharrn. 1913 251 562-587).-Attempts t o convert gitalin into anhydrogitalin by treatment with absolute alcohol or glacial acetic acid have been unsuccessful (compare Kraft A. 1912,1 374). The addition of ether to a solution of gitalin in six parts of methyl alcohol and chloroform (equal vol.) causes the precipitation of about 25% of anhydrogitalin ; under Eirnilar conditions Merck's digitoxin yields about 90% of digitoxin but no anhydrogitalin.The hydrolysis of digitoxin is best effected by boiling for fifteen minutes with ten parts of 50% alcohol containing 1 C.C. of hydro- chloric acid (U 1*19) and then adding water whereby about 41% of digitoxingenin is precipitated and digitoxose remains in the filtrate.ORGANIC CFIEMISTRY. i. 309 Digitoxose is decomposed extremely etsily by hot acidd even when very dilute. Although it is a tetrose it behaves like Larabinose in Bial’s reaction. It does not yield furan by Giinther Chalrriout and Tollons’ method and can also be distinguished from arabinose by the ph lo rogl uci no1 test.The following salts are suitable €or the identification of digitoxonic acid (A. 1909 i 5 5 2 ) copper salt a green very hygroscopic syrup obt;tinecl by heating the syrupy lactone (Zoc. cit.) with freshly prs- cipitated copper hydroxide (not the carbonate) ; quinine salt m. p. 164O long stout needles or thin prisms prepared by warming a n aqueous solution of the lactone with an alcoholic solution of qiiinine ; brucine salt C6H,,0,,C,,H,60,N,,3E[,0 m. p. 1 2 4 O stout prisms prepared from the lactone and brucine in water the salt being pre- cipitated from the solution after concentration by alcohol and et,her. The author and also other investigators have shown that digitoxin (one sample extracted from the leaves by water or dilute alcohol other samples purchased from Merck in 1894-5) is obtained in a hydrnted form by crystallisation from 85% alcohol.Now it is found that digitoxin (from Merck 1911-12) after being purified by the methyl alcohol-chloroform method mentioned above crystalliseq practically anhydrous from 85% alcohol a result confirming Kraft’s observation (Zoc. cit.). The author is of opinion thsrefore that there must be two kinds of digitoxin only one of which can be hydrated. c. s. E. L ~ E R (Compt. rend. 1914 158 185-188. Compare A 1912 i ‘708).- By the action of acetic anhydride and sodium acetate on hornonatdoin the author has obtained three scetyl derivatives two crystalline and one amorphous each contining five acetyl groups (compare Tschircli and Klaveness A.1301 i 39Y) and these he considers to be derived from isomeric homonataloins the isomerisation t:rking place during the aeetylation. H e supports Robin5on and Sirnonsen’s formula for the methyl ether CE-I co CH of the alorniodiu of T.,1905,95,1085) HO*CH,*CI 11 ‘C*CH,*OMe having obtained a crystalliiie penta- bromo - derivative from it. As a result of this wlJrk he now assigns theannexed cm-titu- tiori t o homonataloin nataloin being its homologue in which tho group *CH,OH is replaced by *CH,*CH,OH. Bile Pigments. V. Constitution of Bilirubic Acid and Bilirubin. HANS FISCHER and HEINRTCH ROSE (Zeitsch. physiol. Chem. 1914 89 255-271. Compare A. 1913 i 71).-When trimethylpyrrolepropionic acid is treated with a concentrated solution of sodium &rite the oxime of phonopyrrolecarboxylic acid is produced.This renders probable a formu1.t for bilirubic acid which the authors had regarded as unlikely because bilirubic acid was The Constitution of Homonataloin and Nataloin. Ho.c//\/\/\\co.CEI;[CR.O[-I],*C=O nataloin (c)mpale \/\/A/ CH CO CH W. G. VOL. CVI. 1. Yi. 310 ABSTRACTS OF CHEMICAL PAPERS. found not to be acted on by sodium methoxide. They now find however that potas>ium methoxide effects the expected decomposition trimethylpyrrolepropionic acid and tetramethyl pyrrole (identi6ed as picrate) being formed. Ethyl 3-hydroxy-5-methplpyrrole-4-carboxylate (compare Benary and Silbermann A. 1913 i 651) is destroyed by sodium methoxide and OB reduction with Mec--gEt Me~-~*[CH,],*CO,H acetic acid and hydriodic H0.C C-CH,-C CMe acid does not yield 2- methy lpyrrole.I n consequence of these NH results the constitution of bilirubic acid is expressed by the annexed formula When bilirubin is reduced with hydriodic acid and acetic. acid cryptopyrrole (identified as picrate) and isophonopyrrolecarboxylic acid (identified as picrate) are produced. Bilirubic acid behaves similarly. When bilirubin is treated with sodium methoxide trimethylpyrrole- propionic acid is formed. When potassium methoxide is used however in addition to trimethylpyrrolepropionic acid phyllopyrrole is obtained. The significance of these results in regard t o the constitution of hemibilirubin and of bilirubin is discussed and probable formuls are o-+-Broniides of Thymol and of o-isoPropylpheno1 and their Conversion into Coumaran Derivatives.11. K. FRIES W. GROSS-SELBKCK and 0. WICKE (AnnaZen 1914 402 261-331. Cornrare Fries A. 1910 i 333).-The siibatnuce previously called 1 4 6-tribromo-5-rnethyl-Z-br omomethylcoumarone (loc. cit.) exhibits behaviour inharmonious with this formula. Thus it is readily autoxidised in boiling benzene in a curlent of dry air yielding the bromide C10H502Br3 m. p. 137' colourless needles of 4 6-dibromo-5- met ?b y Ecounaar on e- 2 -car b ox y tic acid C,H 31 e B rZ<' C H rn . p . 272" (met?Lyl ester m. p. 154'; eth$ ester m. p. 123"; anilide m. p. 210'). Since i t is known that keten-haloids frequently aiitoxidise in the sense CH,:CBr -+ CHzBr*COBr the substance previously called 1 4 6-tribromo-5-methyl-2-bromomethylcoumarone is now re- garded as 4 6 clibromo-5-met?~yl-2-dibromoma~?~yle~iecoumccran C6HMeBr,< O>OH,.This formula is supported by other evidence. For example it can be bhown that the particularly reactive bromine atom in p /3 3 5-tetra- bron~o-2-bydrox~-4-methyl-a-bromomethylstyrene (from which the tetra- bromocouniaran is prepared ; Eoc. cit.) is the one in the bromomethyl group because when this bromine atom is replaced by a hydroxyl group a stable alcohol is produced (see below) from which a coumaran derivative caiinot be prepared. The conversion of 4 6-dibromo-5-methyl-2-dibromomethylenecou- maran iuto 1 1 4 6-tetrabromo-5-methy1-2-methylenecoumaran m. p. \/ \/ NH given for these compounds. R. v. s. 0 C( 'CBr,)ORGANIC CHEMlSTRY.i. 311 140° can be effected not only by hydrogen bromide (loc. cit.) but also by merely keeping the substance at its m. p. 179'. This intra- molecular change is peculiar but the constitution of the transformed product is established not only by the evidence already recorded (loc. cit.) but also by the fact that 1 4 6-tribromo-l-acetoxy-5-metl~yl- 2-methylenecoumaran obtained fram i t by means of d v e r acetate yield3 4 6-dibromo-5-methyl-2-metbylenecoumaran- 1-one by hydrolysis und simultaneous loss of hydrogen bromide. The transformed product might possibly be 1 4 6-tribronio-5- methyl-2-bromomethylcoumt.trone (the formation of the di bromomethyl- methylenecoumaranone from this is readily explicable in the light of Straus's researches on the behaviour of the keto-haloids of unsaturated ketones [A.1912 i 9891) but if such mere the case certainly the alcohol c6HD6eBr2<C(CH2*oH~~~~r should be capable of existence whereas actually only the coilmaranone can be obtained by means of silver acetate and subsequent hydrolysis. Moreover such a cons tit ution of the tetra bromocou tu aran leads to u n te ua ble conclusions in connexion with 4 6-dibromo-5-ruethyl-?;-bromomethylcoumaran (eee below). By heating with alcohol a t IOO' 1 1 4 6-tetrabromo-5-methyl-2- methylenecoumaran is converted into 1 4 6-tribromo-l-etho~y-5-~~yZ- 2-methylenecoumaran c6HMeBr2< C(:CH$>CBr*OEt m. p. 115" from which 4 6-dibromo-5-methyl-2-methylenecoumaran-l-one is ob- tained by treatment with cold concentrated sulphuric acid.The lactone reacts with boiling methyl or ethyl alcohol in the presence of a little dilute hydrochloric acid to form 4 6-dibronzo-l l-dirnethozg5- msthyl-2-methyZenecoumarun Cl2Hl20,l3r m. p. 97" colourless needles or the corresponding cliethozy-cotnpound m. p. 66 -68'. /3 p 3 5-Te trabromo-2 -hy drox y-4- me t hy 1 -a- bromome th y lstyrenc which contains its reactive halogen atom in the bromomethyl group reacts with methyl alcohol at 100' to form p p 3 5-tetrabrom- 2-hydrox~-4-~methyE~-ethoxymethylstyrcne m. p. 0 7" (ucatccte m. p. 60°j and with silver acetate in hot glacial acetic acid to form /3:P:3:5-telru- bromo-2-~yd~oxy-4-m~thyZ-a-acetoxyn~~t~~yZ~tyrene m. p 142' the hydrolysis of which by boiling aqueous alcoholic potassium hgdroxidu yields /3 p 3 5-tetrabronzo-2-hyd~ox~-4-methyl-a-~y~~rox~~~t~i~l~rn. p.85-88' (clicccetute m. p. 85'). /3 ,d :3 :5-Te trabromo-2-hydroxy-4-met hyl-a-bromomet hylstp rene reacte with bromine not a t the ordinary temperature but a t 100' to form an unstable +-bromide from which by lyss of hydrogen bromide is obtained p 3 ~-zribromo-a-l~ydrox~-4-nietil?/l.a-tl.ibromorrLeth?/lstyrene OH*CC,HMeBr2-C(CBr3):CHBr m. p. 126-127O stout prisms. The lutter forms an acetate m. p 150° and in alcoholic solution is converted by concentrated aqueous potassium hydroxide into a by-product m. p. 159O and a main product m. p. 184O which is 1 1 4 6-let~abromo- 5-methyl-2-bromomethylenecozlu~aran C H M eBr2<'(:'Il '8>CBr and is also obtained by the bromination of 1 1 4 6-tetrabrorno-5-plethyl- 2-methylenecoumaran or of 4 6-dibromo-5-methyl-2-bromomethyl~ne- Y 2312 ABSTRACTS OF CHEMICAL PAPERS.coumaran (see below). 1 1 4 6-Tetrubromo-5-methyZ-2-dibromomethylene- counzaran C,oH,OBrG m. p. 198' is obtained by the bromination of 1 1 4 6-tetrabromo-5-methyl-2-methylenecoumxran or the ccrrre- sponding 2-br omomethylene derivative at 50-60'. By heating with copper powder a :,El /? 2 6-pentabromo-3-hjdroxy- l-n1ethyl-a-bromometl~yl-4-ethyl benzene loses two atoms of bromine and yields a substance which is regarded as p 3 5-tribromo-2-hydroxy- 4-meti~yZ- ~-bromometJtyZstyi*ene OH-C,HMeBr,* C( CH,Br) :CHBr m. p. 107' since i t still contains a reactive bromine atom. The substance forms an ucetyZ derivative m. p. 105' and in consequence of the presence of the reactive bromine yields p 3 5-tribromo-2-hydroxy- 4-.methyl-a.naethoxynzethylsty~cne ~ C,,H,,O,Br m.p. 104' the corre- sponding ethoxy-derivative m. p. 71" and anzlino-derivative m. p. 96O (diucetgl derivative m. p. 167') by heating with methyl alcohol ethyl alcohol and aniline respectively. By treatment with silver acetate aud boiling glacial acetic acid p 3 5-tribromo-2-hydroxy-4-methyl- a-brornoniethylstyrene yields /3 3 5-tribrorno-2-hydroxg-4-nteth?/l- a-acetoxymetJrp?stgrene OH*C,HMeBr2* C( :CHBr) * CIII,.OA c m. p. 1 29' stout prisms from which the aZcohoZ C,,H,O,Br m. p. 126' (rlictcetutr m. p. 63O) is obtained by boiling aqueous alcoholic potmsium hydroxide. By treatment with aqueous potassium hydroxide the alcohol is changed to 4 6-dibromo-1 -hydroxy-~-n~ethy~-2-nzet~g~enecoumcc C,HMeBr,< 2,>CH*OH m.p. 151" and p 3 5-tribromo-2-hydroxy-4-methyl-a-bi~omometh;l- styrene to 4 6-dibromo-5~methyl-2-bromomet hylenecournaran m p. about 140'. The last substance does not contlain bromine reactive to silver acetate and is identical with that obtained by the reduction of 4 6-dibromo-5-methyl-2-dibromomethylenecout~aran ; like this com- pound it is changed by fusion t o the isomeric 1 4 6-tribroino- 5-methyl-2 - meth~lenecouniuran C,H MeBr,<'( H$>C l i Br m. p. 1574 which contains reactive bromine. This bromine is displaced by heating with alcohols aniline and silver acetate 4 6-dibtorno- 1 -nzethoxy-5 -rnetJql-2-snet~ylen,ecou?naran C(:CH ) O,HMeBr,<C(:CH~>CH~OMe m.p. lOl' and the corresponding ethoxy-derivative UJ. p. 65-66' unilino-derivative m. p. 143' and acetoxy-derivative m. p. 13 1-1 3Z0 being produced By hydrolysis the last substance yields 4 6-dibromo- l-hpdroxy-5-ruethyl-2-methylenecoumsn m. p. 15 lo which is identical with the compound mentioned above and is oxidised to 4 6-dibromo- 5-methyl-S-methy lenecoumaran-l-one by chromic and acetic acids. By reduction with zinc dust and alcoholic hydrogen chloride 1 4 6- ti ibromo-5-methyl-2 methylenecoumaran is converted into 4 6-dibromo- 5-me~f~yl-2-~~~etlrylenecoumaran m. p. 74' colourless needles and by brominatiou in chloroform at 100' into 1 4 6-t~ibromo-5-methyl-2- dibroi?zomethyZenecournar~n m. p. 177' which contains a reactive bromine atom in position 1 and therefore yields a corresponding methoxy-derivat ive C11HS02Br4 m.p. 194" etLox.y-derivative m. p. 132' ardilino-derivative no. p. 160° and acrtoq-derivative m. p. 161' ;ORGANIC CHEMISTRY. i. 313 by hydrolysis the last is converted into 4 6- jib^-onzo-l -hyJ~oxy-5- metl~yl-2-dibronaomethyZenecoumcimn m. p. 185O. 2-Hydroxy-a-methylstyrene (B6hal and Tiffeneau A. 1908 i 26 1 ) rapidly polymerises by treatment with ethereal hydrogen chloride an(] yields a bimolecular form C,,H,,O m. p. 97' small plates which is depolymerised by heating fornis a n acetyl derivative C,,H,,O m. p. 96-97'' and methyl ether C,,H2,0 m. p. 115-117" prisms and is converted by bromination in chloroform at about 50' into a tetrubronzo-derivative C,,Hi60,Br m. p. 149O stout prisms (acetyl derivative C20H180!Br4 m.p. 159-1 60'). By brominntion in chloroform in a freezing mixture and finally at the ordinary temperature 2-hydroxy-a-methylstyrene yields n penta- bromo-$-bromide which behaves in general like the hexabromo-$- bromide obtained from 2-hydroxy-a 4-dimethylstyrene (Zoc. cit.) a p 3 5-Tet~abrorno-2 -hydroxy-a-bromometh?/l-l -ethylberizene OH*C6H2Br2*CBr( CH,Br) m. p. 1 2 6 O prismatic crystals forms an ucetyl derivative 111. p. 137' and is converted by aqueous acetone into a red very unstable methyl- enequinone which almost immediately changes to p 3 5-tribrorno-2- hydroxy-a-bromomethylsty-ene OH*C,H,Br,*C( CH,Br):CHGr m. p. ill' colourless crystals (uc?tyZ derivative m. p. 102'). By the substi- tution of the reactive halogen in the bromomethyl group the last substance yields a methoxy-derivative OH*C6H2Br,*C( CH Br)*CH,-OMe m.p. 81' (acetyl derivative m p. 95-96') nnilinoderivative m. p. 131' (diucetyl derivativs m. p. 154O) and acetoxy-derivative ; by the hydrolysis of the last substance is obtained ,& 3 5-tribromo-2-hydroxy- a-hydroxymethylstyrene OH*C,H,Br,*C( :CHBr)*CH,*OH m. p. 1 30° which is converted into 4 6-dabromo-1 -hydroxy-2-methy2enecoumaran m. p. 130-132O (see below) by prolonged boiling with dilute sodium hydroxide. Alcoholic /3 3 5-tribromo-2-hydroxy-a-bromomethylstyrene is con- verted by concentrated aqueous potassium hydroxide into 4 6-dzbromo- C(:CHBr)>CH m. p. 140' 2- bromomethylenecounzu~an C6H2 Br,< 0 which does not contain reactive bromine but is changed by fusion or by hydrogen bromide in hot glacial acetic acid into the isomeride 1 4 6-tribromo-2-met~~ylenecoumcirccn m.p. 1 2 4 O ; this contains reactive bromine and therefore yields a methoxy-derivative C,H2Br,<~(:CH2)>CH*OMe m. p. 7 2 O unilino-derivative m. p. 140-141' and acetoxy-derivative m. p. 95'. By hydroljsis the last substance yields 4 6-dibromo-1- hydroxy-2-methylenecourrl~ran. 'J'he reduction of ethereal 1 4 6- tribrorno-2-methylenecoumaran by zinc dust aid alcoholic hydrogen chloride yields 4 6-dibi.orno-2-iize~hy~eriecoumuran C,H,0Br2 m. p. 72' whilst the brorriination of the tribromomethylenecoumaran yields 1 4 6-t~ib~onzo-2-dib~omo~nethy~enecou~narcm m. p. 1 2 8 O which reacts instantly with silver acetate By bromination in chloroform at looo a p 3 5-tetrabromc-3- hydroxy-a-bromomethyl-1-ethylbenzene yields a p p 3 5-penta.i.314 ABSTRACTS OF CHEMICAL PAPERS. brbnz 3- 2 -hyLl y.o,q-a- bronzonzet f q l - 1 -ethylbenzene 0 H U,H2Br,*CRr( CH2Br)*CHBr2 m. p. 113-114' colourless plates (ucetyl derivative m. p. 138). This hexabromo-$-bromide is changed (1) by copper powder in the ethereal solution t o /.3 3 5-tribromo-2-hydroxy-a-bromnmethylstyrene ni. p. 11 1" ; (2) by aqueous acetone to /3 p 3 5-tetmbromo-2-hpdro~y-a- bromosnethylstyrene m. p. 124" (acetyl derivative m. p. l04") and (3) by dilute aqueous alkalis to 4 6-dibromo-2-dibromo~~zethylenecoumaal*an m. p. 170". /3 /3 3 5-Tetrabromo-2-hydroxy-a-bromomomethylstyrene which contains a reactive halogen in the bromomethyl group yields a methosy-derivatire OH*C,H2Br,*C( :CBr,)*CH,*OMe m.p. 145" and ncetoxy-derivative m. p. 94" the latter forming by hydrolysis the corresponding alcohol C9H6O8Br4 m. p. 154" (diacetute m. p. 103'). 4 6-Dibromo-2-dibromomethylenecoumaran which is also obtained by the action of aqueous alcoholic alkalis on the preceding tetra- hromohydroxybromomethylstyrene does not contain reactive bromine llut i s changed by fusion into the isomeride 1 1 4 6-tetrubromo- 2-niethyZenecouma~an nl. p. 130-131" which is reactive and is more ( onveiliently obtained by the bromination of 4 6-dihromo-2-bromo- methylenecoumaran in boiling chloroforni. 4 6-Dibromo-2-dibromo- methylenecoumaran is reduced to 4 6-dibromo-2-bromomethylene- coumaran by zinc dust and hydrogen chloride in alcohol ic-ethereal ~olution and is readily autoxidised in boiling benzene whereby bydrogen bromide is evolved and the hy-ontide m.p. 144" of 4 6-dibromocoumc~rone-2-ca~boxylic acid m. p. 277' is obtained. The acid forms a methyl ester m. p. 155O and ethyl ester m. p. 106". 1 1 4 6-Tetrabromo-2-methylenecoumaran forms 1 4 6-tribromo- 1 -met?~oxy-3-met~~yle~zecoumara~ m. p. 11 5' and the etlioxy-derivative m. p 140" by treatment with methyl and ethyl alcohol respectively at 1 OO" and is converted into 4 6-dibrorn0-2-rnetl~ylenecounznrnn-1-one m. p. 146" faintly yellow crystals by treatment with d v e r acetate and boiling glacial acetic acid and subsequent hydrolysis of the product. The lactone dissolves rapidly in warm dilute sodium hydroxide and is recovered by acidification ; unlike 4 6-dibromo- 5-methyl-2-methylenecoumaran-l-one it does not form ortho-esters with alcohols.It is noteworthy that all the preceding derivatives of styrene and coumaran which contain reactive bromine do not develop a coloration with concentrated sulphuric acid whilst the oxygenated derivatives obtained therefrom by replacing the reactive bromine by the methoxy- ethoxy- or acetoxy-group produce deep blue or bluish- Crystalline Oxoiiium Carbonates. (Preliminary Communi- cation.) F. KEHBMANN and ADOLF BORN (Bey. 1914 47 82-84).- If at the ordinary temperature a saturated aqueous solution is prepared of the chloride of the trimethyl ether ester of the fluorescein com- pound obtainable from cresorcinol and phttialic anhydride namely violet colorations with this reagent.c. s.ORGANIC CHEMISTRY. i. 315 carbon dioxide for ren*minutee,'followed by the addition of a n equal bulk of saturated potassium hydrogen carbonate solution causes the separation of golden-yellow crystals. The new substance gives a yellow aqueous solution with a bitter taste similar t o that of the chlaride ; the solution is alkaline to litmus and although fairly st'able at Oo decomposes rapidly on warming. Even in the dry condition the substance undergoes decomposition in the courw of twenty-four hours water of crystallisation which is probably present producing apparently a similar hydrolysis to that which occurs in solntion. From its analysis the salt appears to be a hydrogen ccwbonate C H Me(OMe) >O*CO,H ; C O ~ M ~ * C ~ H ~ * C ~ C H ~ ~ I ~ (OhTe) the existence of the corresponding normal carbonate is possible for on boiling the solution a portion of the carbon dioxide is retained more tenaciously than the rest and the solution becomes more strongly a1 kaline.I n a n analogous manner but by salting olit with solid potassium hydrogen carbonnte yellow leaflets of a carboqtccte can be obtained from the chloride of the methyl ester of fluorescein dirnethvl ether C H.(OMe)yO C02Me*C,H4*C<CGHd OMe) C1. This carbonnte which dissolves in mineral acids with effervescrnce is less stable than the precedinq one. 6 3( Naphthaflavones and Naphthathioflavones. SIEGFRIED RUHEMANN (Ber. 1914 47 119-185).-The preparation of p- substituted cinnamic esters by the condensation of the naphthols or naphthyl mercaptans with ethyl phenylpropiolate is not so simple as in the (laseof phenol and phenylinercaptan ( A .1913 i 891 1374) partly owing t o the di6culty of preparing the pure sodinm compounds and partly owing t o the poor yields. The condensation to flavones is easily effected. pa-Naphthoxycinnamic acid (T. 1900 77. 989) was treated in benzene with phosphorus pentachloride followed by aluminium chloride and converted into a-naphthaflavone (Kostanecki A 1898 i 373). I n the same way (Zoc. cit.) p-naphthol waq transformed into ethyl /3p-naphtlihoxyciitnnrnate C,,H,*O* CPh:CH C02Et which forms colou r- less shining leaflet? m. p. 161-162° b. p. 285-?90°/23 mm. /3P-Naphthoxycinnamic acid forms colourless needles decornp. 16 4O and furnishes an almost quantitative yield of A/\ P-naphthaflavone (annexed formula) which crys- 1 1 tallises in colourless needles m.p. 164-165O and \/\/\O gives a colourless solution with intense blue Similarly ethyl p-a-?za~iithylthioZcin?zamccte b. p. 278-280°/12 mm was hydrolysed to P-a-naphthpl- thiolcinnamic acid which was obtained in colourless needlee m. p. (20 ICPh fluorescence in concentrated sulphuric acid. \/ cHi. 316 ABSTRACTS OF CHEMICAL PAPERS. 1S3-184' and condensed t o a-naphthathioJaaone ,'\A (ailnextd formula). The latter forms almost I 1 colourless leaflets m. p. 182O and in contrast t o \/\/\CO the benzothioflavones it exhibits a faint green S' ICH fluorescence in sulpliuric acid. Ethyl PP-naphth?J- thiokcinnccnzate was also obtained in colourless needles m.p. 102-103'. ~~-N~pht/~yEtI~ioZcinsaamic acid forms yellow prisms m. p. 165-166' and is converted irLto P-naphtir~/llhioZstgr~ne C,,H,*S*CPh :CH yellow needles m. p. 84-85' b. p. 238-235O/12 mm. on distillation in vacuum and into P-nnpl~t~ccthi~fEnvone colourless needles m. p. 155O by the above method. J. C. W. \/ cpll 3 -Aceto - 2 5 - thioxen [3 -Acetyl - 2 5 - dimethgltbiophen]. (Mlle.) F. ZILBERFAHB (J. I h s s . Yhps. Chem. Soc. 1913 45 1936-1 940).-Two acetylthioxens are already known that obtained from coal-tdr thioxen b. p. 223-224' D" 1.091 giving a n oxime m. p. 65' and 2-acetyl-3 5-dimethylthiophen b. p. 226-228' the oxime of v;hich has m. D. 70'. CMe:gAc CMe:CH obtained by acetylating 3-Acetyl-2 b-dimethy/kthiop,hen S< the 2 5-dimethylttiiophen prepared by the action of phosphorus trisulphide on acetonylacetone is a colourless liquid b.p. 223-284.5' Di3'5 I 4979 D:' 1.0973 ng'5 1.5441. Its semicarbazone CgHl30N,S 111. p. 197' and its oxime C8H,,0NS m. p. 83' were prepared. Hence the thioxen from coal-tar cannot be either 2 :5- or 3:5- dimethyl thiophen. T. H. P. Harmineand Harmaline. 0. FISCHER [with (Frl.)L. ANaERMANNand E. DIEPOLDER] (Ber. 1914 4 7 99-107).-Hitherto no direct evidence of the existvnce of a pyridine and a pyrrole nucleus in the molecule of harmine has been obtained although the various formuls advanced by 0. Fiecher and by Perkin and Robinson (T. 1912 101 1775) and Hasenfratz (A . 19 12 i 383,797) incorporate those systems. By heating harminic acid or what amounts to the same apoharminecarboxylic acid with dilute nitric acid in a sealed tube at 180-200' oxidation to isonicotinic acid (4-pyridinecarboxylic acitr) has been effected.The product was isolated by decomposition of the copper salt and completely identified with material prepared by Weidel's method (m. p. platini- and auri-chlorides). Tha nitrogen of the pyrrole nucleus cannot there- fore be ortho t o the pyridine ring as a nitropyridinecarboxplic acid might have been expected in that case. Attempts have also been made to prove the presence of the pyrrole nucleus by conversion into a dioxirne according to Ciamician and Zanetti but without success. Harmine does not react with hydroxylamine and harmaline only forms a n additive compound. Furthermore the formation of a bisazo-derivative of harmaline ( A 1912 i 645) would suggest that the methyl group is attached to the pyridine rather than to the pyrrole nucleus.The formula for harmine which agrees most nearly with the accumulatedORGANIC CHEMISTRY. i. 317 evidence including the fact that it gives the quinophthdone reaction is the one annexed. When harmalino is heated with methyl iodide and methyl alcohol methylharmaline Me!,,:CH I* >NH hydriodide separates but the highly con- ceutrated mother liquor deposits dimethyl- harmaline iodide C,,H,,ON,I,~H,O in stout yellow crystals m. p. about 220'. The primary iodide mas coDverted into rneth@armccline hpdrochloride Cl,H1701T2C1,4H,0 which formed twinned crystals with pearly lustre decomp. 265'. From this the picrate slender yellow needles m.p. 216O the nitrate s t m t yellow shimmering prisms or tablets decomp. over 230° the awichloride reddish-violet needles decomp. 1 5 3 O and the pZatinichZoi*ide orange leaflets decomp. 220° were prepared. The hydrochloride was also reduced by means of sodium in amyl alcohol to methyldihydl.oharmaline C,,H,,ON which was obtained in almost colourless leaflets m. p. 173-174O. The hydyochloride forms slender white scaleF decomp. 142-146'. With methyl iodide i t yields diniethyldihydroharlal~n~ iodidrr C,,H,,ON,I' in colourless crystals m. p. 203'. Unlike the above dimethylharmaline iodide i t does not produce trirnethylamine when heated with sodium hydroxide but yields a substance of the composition of dimethylharmclline ammonium hydroxide C15H2202N2 which forms colourless needlcs m.p. 129' from light petroleum. When treated with hydroxylamine harmaline jields a coinpound C,,HI7O,N,. which is insoluble in alkalis but soluble in mineral acids and forms colourless needles m. p. 180'. Renzylideneharmine and benzylidenediharmaline (Perkin and Robinson) were also prepared. Dihydroharmaline also condenses with benzaldehyde giving benzylidene- bisdiiiydrohar~aaline C,,H,,O,N in colourless flakes the hydrochloride forming very slender needlel.. OMe/\ I 1 \ A * C H N J. C. W. Strychnos Alkaloids. XX. Oxidation of Acetyl- brucinolone. HEHMANN LEUCHS and HUBERT RAUCH (Bcr. 1914 47 370-380).-Two acids acetylbrucinolic acid and a dibasic acid C23H24010N2 were obtained by the oxidation of acetylbrucinolone ( A 1912 i 210 898).The latter has now been hydrolysed and besides acetic acid oxalic acid and a n amino-acid C,,K,,O,N have been isolated from the products. This similar behaviour of the two acids points to the conclusion that the addition of oxygen to acetyl- brucinolone has taken place at the saue part of the molecule. The formation of two acids presupposes that the ethylene linking which is attacked must be in two different positions. Thus the grouping (I) leads to acetylbrucinolic acid and (11.) to the dibabic acid. This difference is not due t o displacement of the ethylenic linking during oxidation but to the presence of a n ieomeride for pure acetj lbrucinolone prepared from brucinoline hydrate I. only yields acetylbrucinolic acid. Atterupts were therefore made to purify ~cetylbrucinolone either by destroying one isomeride or by causing ai.315 ABSTRACTS OF CHEMICAL PAPERS. displacement of the double linking into a comnion position. Success way attained by heating the crude product with alcoholic ammonia. Pure brucinolorje was thus obtained and the results indicated that in all probability the process was mainly that of the displavement of the bond in the isomeride. The barium silt of the acid C,,H,,O,,N,(loc. cit.) was heated with hydrochloric acid when the barium chloride which crystallised was converted into the sulphate and filtered. The filtrate deposited the hydrochloride of an amino-acid C',,H,,0,N2,2HCI on freezing and also contained oxalic hut no lrialouic acid. A by-product was also obtained from the last mother liquors in shiuiug broad needles decomp.about 272O when the whole filtrate was evaporated and the oxalic acid extracted with ether. The above hydrochloride forms hexagonal prisms m. p. 235-236' with gas evolution hnd does not give the brucine reaction or precipitates with ferric mercuric or platinic chlorides. The free base could not be isolated but a compound C26H2707N3 with phe rI yt car bi a i d e was obtained in s m a1 I colourl esa prisrn~ decomp towards 2 loo which give the brllcine reaction and dissolve in alkalis. Crude brucinolone is yellow but the pure sub~tance prepire11 by adding the requi-ite amount of sodium hydroxide to bruciuolinri hydrate I. and dehydrating the amino-acid SO obtained a t 135" in vacuum over phosphoric oxide is colourless and has [a] - 37".Pure brucinolone was acet(y1ated and then oxidised by permanganate in acetone as in A. 1912 i 211. The extraction of t h e products was carried ont in a modified way when a small amount of a neutral oxidation pvoduct 11.. C,,H2,O,N2,4H20 of acetylbrucinolone wits i$olated. It lost 4H,O a t 130' in vacuum over sulphuric acid and then had m. p. 175-180° but reabsorbed 1H20 in the air. It gives the brucine reaction. Crude acetylbrucinolone was heated with methyl-alcoholic nrnm0ni.t a t 95" when the tube soon became full of colourless crysttls OF pure brncinolone. The mother liquor contained a base which was isolatetl RS the AydrocJiloride C2,H,50,N,,HC1 in the form of rectangular prisms m p. 320' (decomy.). The free Ease crystallises in fout-sideti tablets from echyl acetate m.p. 280' (decornp.) and is alkaline to litmus and turmeric. J. C. W. Pyrrole. HANS FISCHER and W. ZINNERMANN (Zeitsch. phpio?. Cherre. 191 4,89,163-169).-Tetramethylpyrrole reacts with hyciroxgl- 7Me:CMe CMe:CMe amine according t o the equation >NH + 2NH2*OH= 7HMe*CMe:NOH CHMe*CMe NOH +NH (compare Ciamician and Zsnetti A . 1890 264 1155 ; 1891 1502),:the dioxime obtained being iJentical with that of Ciamician and Silber (A. 1912 i 174 538). Hydroxylamine acts on porphyrinogen as an oxidising agent meso- porphyrin and ammonia being formed. When ethyl 2-methylpyrrole-3-carboxylate and acetone are heatedORGANIC CHEMISTRY. i. 319 together iu presence oE a little CO,Et*g-EH HE -g*CO,Et hydrochloric acid a condeosa- MeC C C CXe tion product of the annexed formula is formed.The sub- stance has the composition and molecular weight required by this formula and gives the Ehrlich aldehyde reaction in the warm (but not in the coldj. When 5-acetyl-2 4-dimethylpyrrole and formaldehyde are heated at 130' for five hours a substance C1,Hi,O,N is obtained ; i t crystallises in compact prisms m. p. 136-138". On heating with sulphuric acid and water on the water-bath for two hours i t yields 2 4-dimethyl- p yrrole. Acetaldehyde reacts in the same circumstances as formaldehyde yielding a substance C,?,,ON,2 MeCHO m. p. 142'. When 3-acetyl-2 4-dlmethylpyrrole is treated with pyridine and cyanogen bromide two substances are formed of which the chief product bas the formula O,,H,,ON,.It crystallises in compact prisms m. p. 20S0 and is probably a cyanamide derivative. \A /\/ NH CMe NH R V. S. Bases Formed by the Alkylation of P y r r o l e s . I. G. PLANCHER and C. RAVENNA ( A t t i R. Accacl. Lincci 1913 [v] 22 ii 703-707).- It has been shown by Plancher and his pupils (1897-1908) that the action of methyl iodide on sodium pyrrolecnrboxylate yields a pentamethylpyrrolidine and from this or from 1-methylpyrrole hy mothylat ion pent~methylmethylenepyrroline is obtained Further methylation then gives pentamethylisopropylidenepyrroline and if as has been supposed the constitution of this compound is represented by It i t the formula should be obtainable from either 2 5-dimethylpyrrole or 2 4 5 - trimetJiyIpyrrole or 2-methyl-5-isopropylpyr role.I n the present paper the action of methyl iodide on 2-methyl-5-iso- propyl pyrrole is considered. With excess of methyl iodide a base C,,H,,N is formed giving an aurichloride C,,H,,N,HAuCI m. p. 86-87" which is not identical with the aurichloride m. p. 99*5-100*5° prepared by Anderiini (A. 1890 1431) whose results were con6rmed by the authors. With deficit of methyl iodide a mixture is obtained giving on purification a base C,,H,,N the aurichloride of which has m. p. 95'. It seems probable that Anderlini's product is not quite pure and that the purest product is that obtained from 2-methyl-5-isopropyl- pyrrole. Preparation of pentamethylisopropylidenepyrroline in some other way is hence desirable. If the bases obtained by the above two methods prove to be identical the constitution would be demonstrated since the prepara- tion from 2 -methyl-5-isopropylpyrrole would fix the positions of one methyl and of the isoproppl group.I n order to determine the positions of the other methyls attempts h4ve been made to prepare more highly rnethylated bases from Korschun's 2 3 5-trimethylpyrrole ( A . 1905 CMe,- CMe C ( C J1 e,). CMe' C(:CMe,)*yMe or NMe< NMe<Cbge=z=CMei. 320 ABSTRACTS OF CHEMICAL PAPERS i 373) and from 2 :5-dimethylpyrrole. The first of these when heated with methyl iodide methyl alcohol and potassium carboDate in B sealed tube for ten hours at 140’ gives a base C,,HI7N correspond- ing in composition with Ciamician and Anderlini’s l-methyltetramethyl- enepyrroline (A. 1889 5 S ) and forming a n aurichloride rn.p. 100’. Similar treatment of 2 5-dimethylpyrrole yields a semi-solid hydro- chloride which gives indications of the presence of a base C,H,,N a small proportion of a picrate m. p. 168O being obtained. This experiment is being repeated. T. H. P. Bases Formed by the A l k y l a t i o n of Pyrroles. 11. G. PLANCHER and T. ZAMBONINI (Atti R. Accad. Lincei 1913 [v] 22 ii 708-712. Compare preceding abstract).-The interaction of 2 3 4 5-tetramethylpyrrole and methyl iodide in presence of potassium carbonate and methyl iilcohol in a sealed tube at 110’ yields (1) pentamethylmethylenepyr rolino which has a sweetish faintly gersnic odour recalling that of the analogous indole derivative obtained by Fisclier ; its deliquescent hydrochloride m.p. 12P its orange-yellow picrate m. p. 148O and its aurichloride C,,H,,N,HAuCI m. p. 101-102’ decomposing a t 220° were prepared. Cl o%N ~,H,OP (2) Pentamethylpjrrolenine b. p. 70-90°/26 mm. which has a n odour intermediate to those of camphor and menthol and gives a pale yellow picrate m. p. 168-169O. The colours of these two picrates are precisely similar t o those of the corresponding indole derivatives trimethyl- indolenine and trimethylmethyleneindoline. The action of magnesium methyl iodide on 2 3 4 5-tetrametbyl- pyrrole yields only pentamethylpyrrolenine which is the first of these bases to be obtained pure. The esters of pyrrolecarboxylic acids with a methyl group in the 1-position do not uudergo corn plete methylation even under prolonged treatment with methyl iodide at a high temperature.Thus ethyl 2 5-dimethyl-1-ethylpgrrole-3 4-dicnrboxylat~e and ethyl 1 2 5-tri- methyl-3 4-dicarboxylate do not lose their carbethoxyl groups but are simply hydrolysed whereas Korschun’s ethyl 2 3 5-trimethyl- pyrrole-4-carboxylate (A. 1905 i 373) and esters of other secondary pyrrole derivatives yield secondary tetramethylpyrrole. Fut ther 1 2 5-trimethylpyrrole remains unaltered even when heated for fifteen hours a t 260’ with sodium methoxide. It seems cert,ain then t h a t pyrrole derivatives are acted on by sodium ethoxide only mlien the irninic hydrogen is iiot substituted. Again organo-magfiesium compounds are without actiou on 3 5-dimethyl-1.etbylpyrrole. CgH15N>C6H307N3 T. H. PORGANIC CHEMISTRY.i. 321 Action of Chloroform on Tetramethylpyrrole. 111. G PLANCHER and T. ZAYBONINI (Atti R. Accccd. Lincei 1913 [v] 22 ii 7 13-7 16. Compare preceding abstracts).-The results obtained by Planchcr and Punti in their studdy of the action of chloroform on 2 5-dimethylpyrrole (A 1910 i 132) indicate that with tho pyrroles j u s t as with the indoles the initial action of chloroform is perfectly analogous to that of the alkyl iodides a dichloromethylpyrrolenine being formed ; this cotupound subsequently loses a molecule of water yielding a chloropyridine derivative. I t is now found that a similar reaction occurs with 3 3 4 5-tetritchloropyrrole and chloroform. 3-Dicl~lovomethyl-2 3 4 5-tetramethylpywotenine CMe:vMe N'C,\le*CAle-C HCI obtained by the action of chloroform on 2 3 4 5-tetrachloropyrrole in presence of alcohol and aqueous alcoholic potassium hydroxide forms bard coiourless crystals m.p. 86-87' which tend to turn red and lose hydrogen chloride in the air ; it forms an orange-red picrate m. p. about 189O and with nitrous acid gives pale yellow scales tn p. 155". The mot her liquors contain other bases t o be examined later. When treated with sodium ethoxide 3-dichloromethyl-2 :3 4 5-tetra- as a n oily liquid forming apicrccte m. p. 124'. C Ve'CMe 3-Chloro-2 4 5 6-tetrumethylpyridine N G C ite:- cc,> c Me obtained by the action of aqueous alcohol on the dichloromethyltetra- methylpyrrolenine has an odour resembling that of quinoline and gives a picrate CgH1,NC1,C6H3O7N3 in dark yellow scales m.p. 152'. T. H P. Complex Compounds of Organic Salts with Some Organic Bases. G. Ross1 (Gazxetta 1913 43 ii 654-665).-This paper describes the results of measurements of the electrical conductivity of solutions containing water pyridine and the following salt3 (taken one at a time) nickelous nitrate cobaltous nitrate sodium bromide copper acetate and also of solutions containing water hexamethyl- enetebramine and each of the following salts cobaltous nitrate nickelous nitrate copper acelate. From the experiments it appears that pyridine can unite with certain cations giving complex cations which are stable below 40". With water these complex cations behave like simple cdtions giving unstable hydrates of the type nPy*R,n'H20 which are resolved into water and complex cations nPay*R at a temperature below 40'.Hexaruethylenetetr,tmine does not form complex ions but when it combines with salts i t behaves like w&er of crystallisation. R. V. S. Two Compounds of Zirconium Chloride with Pyridine. ED. CHAUVENET (Coinpt. rend. 1914 158 128-1 30) -In addition to the COUApoUnd Zi C1,,2C,H5N prepared by hlnttilnws (compare A . 1899 ii 295) the author has obtained u conzpound Z:C1,,4C5H,N byi. 322 ABSTRACTS OF CHEMICAL PAPERS. saturating pyridine with zirconium chloride and allowing the solution to evaporate in a dry atmosphere. The crystals are freed from excess of pyridine by washing with light petroleum which however tends to remove small quantities of the combined pyridine. The crystals are prismatic and act energetically on polarised light.They possess a high dissociation pressure at the ordinary temperature. From a study of the heat of fixation of the pyridine molecules the anthor shows that a third compound cannot exist between the two described. The com- pound ZrCI4,4C,H,N decomposes slowly a t the ordinary temperature and rapidly a t 50Oto give ZrC1,,2C,H5N. The heats of fixation of the two and four molecules of pyridine are respectively 54 Cal. and 70 Cal. or for one molecule 27 Cal. in the one case and 17.5 Cal. in the other. W. G . 2-Acetyl-1-methylindole. OTTO DIELS and WALTRER DURST (Ucr. 19 14 47 284-2t,O).-2-Acetyl-l-methglindole bas a physiological effect resembling that of morphine but is only sparingly soluble so that the authors have now int’roduced a n aminogroup into tbe molecule with the object of obtaining a compound giving more soluble s d t s . The new compound has however no physiological action.Diacet yl- p-miti-ophen ylmethylhydraxone COMe-CMe:N*N Me* C6H4-N0 obtaiued by nitrating diacetylphenylmethylhydrazone (see Diels and Kollisch A 191 1 i 230) forms brownish-yellow needles exhibiting orange-blue dichroism m. p. 157-158’. On reduction it undergoes decomposition yielding p-phenylenemethy ldiamine. nit sting 2-acetyl-1-methylindole or better by the indole-transforma- tion of diacetyl-p-nitrophenylmethyl hydrazone forms dark brown needlee m. p. 1999 Eeduction of this nitro-derivative by means of stannous chloride and hydrochloric acid yields the c?dorsindo&te base in the form of olive-brown needles with a marked bluish reflection. 5-Anaino-2-acetyl-l-metl~ylindole NH,*C6H,<NMe>CX~~ -CH\ prepared by reducing the corresponding nitro-compound in moist ethereal solution by means of zinc dust.forms olive-green leaflets m. p. 173’. The hydrochloride gives an intense blue coloration with ferric chloride in aqueous solution and with nitrous acid forms a diazonium salt which with lt-salt yields a fine red azo-colouring matter. T. H. P. Isatin and Allied Compounds. I. W. BORSCHE and W. JACOBS (Ber. 191.1 47 354-363).-The yroFerties assigned by Gysae t o “ieayhenic acid,” the condensation product of isatin and phenylacetic acid are not in agreement with the proposed constitution (A 1894 i 29). The substance is now identified with 2-hydroxy- 3-phenylquinoline-4-carboxylic acid (Hubner A.1908 i ZS8j. This reactiorl of ikatin has teen extended to other acids with an activeORGANIC CHEMISTRY. i 323 methylene group particularly malonic acid. A similar condensation takes place but the carboxyl group which should be in position 3 is at the same time destroyed. Thus isatin and rnalonic acid yielded 2-hydroxyquinoline-4-carboxylic acid. Tbis was identified with the product obtained by Camps' method (A 1900 i 310) from N-atetyl- isatin. The attachment of malonic acid to isatin does not take place at the nitrogen atom since N-methylisatin also reacts. The ease with which the pyrrole ring passes into another cyclic system led the authors to attempt the rearrangement of isatoxime. Neither by means of dilute mineral acids alkalis nor by acetic anhydride could any change be effected and the expectation that a quinoxaline or quinazoline would result by the Beckmann transformation was also unfulfilled the product being o-c-janophenylcarbimide or o 0'-dicyano- carbanilide.The identity of '( isaphenic acid " was established by converting the substance into 2-chloro-3-phenylquinoline-4-carboxylic acid and the 2-hydroxyquinoline-4-carboxylic acid obtained by heating isitin with malonic acid and glacial acetic acid first at loo' then a t 120° was identified by conversion into the chloro-acid and the esters the latter by direct means using srilphuric acid. 5-Bromoisatin prepared by adding bromine in glacial acetic acid to a boiling solution of isatin in the same solvent yielded with malonic acid grey insoluble high melting 6-bromo-2-hy&roxyquinolinc-4-carboxylic acid which was analysed ' as the ethyl ester C,,H,,O,NBr colourless needles decomp.about 220'. Similarly 5 7-dibromoisatin formed 6 8-diborno- 2-hydro~yquinoline-4-carbox~lic acid as a yellowish- white powder which did not melt. N-Nethylisatin \vas also condensed with rualonic acid in glacial acetic acid and the solution obtained was diiuted and allowed to evaporate. 'I'he product which was probably o-sneth?lluminophenyl- funlark acid C,,HI1O,N formed colourless crystals m. p. 163-164' and the monomethyl ester crystallised from ether in colourless prisms UJ. p. 131-132'. Experiments have already been commenced with the aim of COB- densing N-methylisatins with acetophenone to 2-phenylcinchonic acid a l k j l haloids but the only products which have been isolated as yet are apparently compounds with two molecules of the ketone through the loss of two molecules of water.Thus N-methylieatin was dissolved in 33% potassium hydroxide and heated with alcoholic acetophenone for two days when the solution was diluted and the concentrated filtrate from neutral substances was acidified. A small amount of a n acid C2,H2,0,N was obtained as a blood-red crystalline powder m. p. 2 40-2 4 2' (decom p. ). Sirnil arl J 5 - bromo-N-~~ethyZisatira C,H60,N Br slender red needle.. m. p. 172-173° obtained by direct bromination or methylation with methyl sulphate formed a red acid C,,H,,O,NBr 111. p. 253-254'. J. C. W. Preparation by Catalysis of Decahydroquinoline and 2 -Me thyldecab yd roquinoline.PAUL S A B ATIER and M MURAT (Comppt. rend. 1914 158 309-311. Compare Ipatiev A. 1908 i 332).-By bubbling hydrogen through quinoline at 100' and passingi. 324 ABSTRACTS OF' CHEMICAL PAPERS. the issuing gas on to very active nickel at 130-140' a good yield of decahydroquinoline b. p. 204-207" is obtained. 2-Methylquinoline can be similarly hydrogenated using active nickel at 180° and gives 2-rnethyldecahgdroquinoline C,,HI9N a colourless liquid b. p. 2 1 6.1 752 mm. D 0.9489 Dto 0.9308 n 1.497. It is soluble in water alcohol and ether and like decahydroquinoline i t turns litmus blue fumes in air and fixes carbon dioxide giving a solid carbonate. The following derivatives have been prepared hydrochloride a very deliquescent crystalline powder m.p. 284" ; plntinichloride de- liquescent brown crystals ; mid oxalate colourless deliquescent needles ; dichromate greenish-yellow ; picrate yellow plate. m. p. 134" ; methiodide m. p. 230' ; phenylurethccne a white crystalline powder 111. p. 148'. W. G. Preparation of Hydroxyanthrapyridones. FARBENFABRIKEK VORM. P~~IEDR. BAYER & Go. (D.R.-P. 268793).- Chlozoanthra- pyridones iu which the chlorine is contained in the pyridone ring when treated with alkali hydroxides yield hydroxyanthrapyridones. Hydroxy N-nzeliLylnnt~ra~yridone yellow needles m. p. 280° is obtained by boiling an alcoholic solution of chloro-N-methylanthra- pyridone with alcoholic potassium hydroxide or by heating the chloro- derivative with aqueous potassium hydroxide in an autoclave.Similarly 4 - bro moh y droxy- 1 -N -me thylanthrap yridone h y droxy- 1 -N- p - tolylacnthra~y?.idone and hydyoxyanthrapy*idone are cbtained from the correspor .ding chloro-derivatives. Dichlorodi-N-nie thylanthrltdipyridone also yields the corresponding hydroxypyridone dei ivittive. J. C. C. Propiorhodanines. BROR HOLMBERG ( B e y . 1914 47 159-1 65). -Some condenbations of P-iodopropionic acid with di thiocarbamates ammonium thiocarbarnato and potassium trithiocarbonate are described. A solution of sodium P-iodopropionate was left with ammonium dithiocarbamate for twelve hours then acidified with hydrochloric acid when P- thiocarbacm?/lthiol~ro(lionic acid NH,.CS*S.CH,*CH,*CO,H was precipitated. It crystallised in very pale yellow tablets m. p. about 125" but was not purified.A different product was obtaiued by leitving the mixture for two days namely thiocarbonylbis- P-thiolpropionic acid (see below). Unlike thiocarbamylthiolacetic acid (A 1909 i 286) the above lactic acid was riot dehydrated by boiliDg iu aqueous solution but required acetic anhydride. The ,cs- yH crystallised in long SCCH2*CB,* C 0 product propiorhodanine yellow prisms m. p. 120-121'. Aniline carbon disulphide and aqueous potassium hydroxide were stirred together and the filtrate from diphenylthiocarbamide was left with sodium P-iodopropionate for two days. Actrtic acid precipitated p-tiiioccLrburcilitlopyopionic acid C,,H,,O,NS which crystallised from alcohol iu small colourless prisms m. p. 153-154". Acetic anhydride dehydrated it to N-phen.ylproiuzorhocl~~nine C,oIl,O NS which formed yellow prismaticORGANIC CHEMISTRY i.325 needles m. p. 173-173.5O. It did not react with benzaldehyde but it corn b ined with alco ho 1 forming 2-thiol-2 -ethoxy-5 -phcny&enthia zolid - 4-one CO<C~,.CH,. 8 in shining colourlese short prisms m. p. 85-85.5". Ammonium thiocarbamate and sodium P-iodopropionate were left for a day and then acidified when Lmglet's carbdmyl-P-thiolpropionic acid (A. 1892 i 440) was gradually deposited. A solution of potassium trithiocarbonate obtained by shaking potassium sulphida with carbon disulphide was also left with sodium P-iodopropionate and converted in to th iocarbon ylbis-B-thioZp ropionic mid CS( S-C H,*CH,* CO,H),. This forms thin golden-yellow leaflets m. p. 109.5-1 loo and bahavev like the corresponding trithiocarbodiglycollic acid (A 1905 i 323) on heating in neutral alkaline or ammoniacal solution b a t i t is decom- posed by aniline into P-thiolpropionic acid and diphenylthiocarbamido and not into phenylpropiorhodunine.The barium salt forms yellow prismatic needles with 4H,O. [Preparation of Derivatives of p-B henylenediamineaul- phonic Acid.] FARBWEHKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 268794. Compare this vol. i 881.-Instead of condensing p-auiinodiphenylaminesul phonic acids with 4-chloro- 1 3-dinitrobenzene aminophenylnaphthylam~nesulphonic acids or their derivatives may be condensed to give similar products. 5-op-Diniti~oanzlino-2-P-1~~~pf~tI~yl- arninobenzeneaulphonic acid C H,(N0,)2*NH*C,,H3(S0,H)*NH*C,oH~ is prepared in this way from sodium p-aminophenyluaphthylamine 0- sulphonate.J. C. C. Action of Sodium Paroxide on Benzidine in the Presence of Ethyl Alcohol. G. Rossr (Gcczzetta 1913 43 ii 671-673).-Wheu a boiling alcoholic solutioti of benzidine is cautioudy treated (explosions may occur) with sodium peroxide glyoxime N-pheriyl ether yPh>CH*CEt<) 0 -- is produced; the substance has already been obtained in various other ways. E. BOVINI (Atti Iz. Accad. Lincei 1913 Lv] 22 ii 460-165).--In this paper a numbdr of hydrazones derived from acstophenone and benzopherione are described. Some of thelu are already known ; none is phototropic. Acetophenone-p-tolylhptrazone C MePh N N H* C,€I,BIe for ma colo ur- less needles m. p. 122'. Benzo~i~arnone-p-tolylk ydi*azone CPh , N N H C H Me cry s talli s as i u pale yellow prisms m.p. 90". Benxophenone-P-na~f~t~~yl/Lydrazo~~e CPh,:N*N H*C,,H forms colour- less crystals m. p. 159.3-160.5°. Benaophernone~henylme th ylh yd raxone C P h, N N NePh forms y ello \v crystals m. p. 81-82O. U e i ~ z o ~ i ~ e ~ z u t ~ e p l ~ ~ t ~ g l b ~ . r i z y E h y d ~ a e o ~ ~ s CPh,:K*NPh*CH,Ph crystal- VOL. CVI i Y N Ph-? (S H) 00 E t J. C. W lS Ph R. V. S. Phototropy of Hydrasones. lices 111 pale yellow scdes m. p. 105-106". R. v. s.i. 326 ABSTRACTS OF CHEMICAL PAPERS. Phototropy. F. BOVINI and F. GRAZIAN (Guxzetta 1913 43 ii 674-692).-1n this paper are described a large number of hydrazones derived from clipheuyl- ditolyl- phenylmethyl- phenylbenzyl- and phenyl-P-naphthj I-hydrazines ; none of them is phototropic.Of them the following have iiot been prepared previoosly. Anisulde?d Ydedi~~~ierLylhydraxone OMe* C,H;CH K *N Ph has m. p. 7 6". Benxuldehyde-p-ditol?/lliydrazone CH Ph N*N( C,H,Me) forms small yellow prisms m. p. 99'. Anisaldehyde - p - ditol$lhydrazone OMo*C,H,*CH:N*N(C,H,Me) forms slightly yellow flattened needles m. p. 128'. CwminaldelLyde-p-d~t~lyl)t~dr~zone C,H,PiP*CH :N*N( C,H,l\ile)2 cry- st'allises in loug silky needles m. p. 104'. Cinizc~rnaldehyde-p-diloE ylhydyazone CHPh CH-CH :N*N( C6H,Me) forms deep yellow flatt'ened needles m. p. 143'. Xalicyluldehyde-p-ditolyliLydraxone 0H.C H *CH N*N( C,H,Me) is a greenish-yellow crystalline powder m. p. 1"2t0. ~i~eronaldehyde-p-ditol~lhyclrcLzone CH2:O2:C6H;CH :N*N( C,H4Me)2 crystallises in colourless leaflets m.p. 134". slightly yellow needles m. p. 54'. crystallises in minute deep yellow needles m. p. 114O. greenish-yellow leaflets m. p. 128'. coloxless needles m. p. 122'. Cumina ldehycle)~he.lzyliiaeth ylh ydrazone C6H4Pi p C H :N *N MePh forms CinPzamaldelrt ydephenylmet?L ylh?/draxone CHPh C H CH N *N MePh p- To1ualdehydq)hen ylweth yE?t ydmxone C,H,ISle*CH N NNeP h forms VaizilZinz~henyZmelhylhyd?.azone OMe* C,H,( OH) * CH N*N MePh forms Cinna~nuldeh~ldep~~~~~y~~enzylli ydraxone CHPh :CH *CH N *NPh*C H,Ph is a lemon-yellow crystalline powder UI. p. 167-168". Pip;ronddeh ydeplten 91 benxylh y drazone CH, 0, C,H,*CH N*NPh*CH,Ph forms slightly yellow needles m. p. 124'. p-Tolualdeliydep?ten?/Zbenzyl?tydraxone C,H,R~e*CH:N*NPh*CH,Ph crystallises i u silky needles m.p. 123-124'. Phenyl-P-nayhthylhyd~.azine can be prepared by reducing with zinc and acetic acid the corresponding nitrosoamine described by Streiff (A. 1881 176). Benzuldehydephenyl-/3 naphthylhydruxone CHPb :N*NPh*C,,H7 forms yellow needles m. p. .92-93'. 9 nisaldeh ydepheny Z-P-naphth ylhydraaoue OMe*C,H,* CH:N*NPh*Cb,H CGH4Prs*CH :N*NPh*C,,H7 forms large prismatic needles m. p. 116-117 . Cuminaldehydephen yl-/3-nap?ithyl?tydrazone forms small needles m. p. 118'. 0inizamaldehyde;uhun yl- P-naphth ylh ydraxone CHPh:CH *CH:N *NYh-CloH7 forms minute pale yellow acicular crystals m. p. 156'.OBGANIC CHEMISTRY. i. 327 p-l’oZuaZde~~ydephenyl-P-?~cllv~thyZrlLydrazone forms J ello w acicular crystals m. p. 1 5 4 O .R. V. S. Constitution of the Colouring Matter of Blood. Coloured Dipyrrylmethane Derivatives. 0. PILOTY J. STOCK and E. DORMANN (Bey. 19 14 47 400-406).-The colour of the following substances like t h a t of dehydrobilic acid (Piloty and Thannhauser A. 1912 i gas) is due possibly to the presence of a system of conjugated double linkings. Di(4 ; 5-dirneth~/l-3-eth~/lp.~rryl)methccpze GMe-CEt CEt ?Me In. I;. 99*5-100° brown rhombic leaflets with a bronze lustre (Ayd~o- chloride C,,H,5N2CI m. p. about 206O long green prismatic leaflets) and chlwodz (4 5-d imeth yZ-3 -eth y l p yrryl) methane f?le CEt~C.CHCl CeCEt*sUe CMe-NH NH CMe’ yellow felted needles subliming almost without decomposition are produced by gently warming haemopyrrole-6 chloroform alcohol and aqueous potassium hydroxide (1 I) and are separated by means of the insolubility of the hydrochloride of the former in cold dilute hydrochloric acid.By a similar reaction phonopyrrolecsrboxglic acid-a yields di(4 5- dimeth~~l-3-o-carbox~~lethy~pyrr~Z)methcclne CMe-NH >c CH:C<N=;CMe CIMe*C(CH2*CH2*C02H)~~.c~ I I :c< C( CH,-CH,*CO,€I):~Ale m. p. 240° red prisms with a faintly green lustre which forms a hydro- chZoride C,,H,,O,N,CI decomp. about 2 1 5 O brick-red prismatic reedles with a green lustre. The absorption spectra of the preceding coloured substances present some similarity to that of bilirubin but none t o that of the colouring matter of blood. c. s. Fimion of the Diketopiperazine Ring by Electrolytic Reduction. GEO. W. HEIMROD (Ber. 1914 47 338-350).-3!he author has studied the electrolytic reduction of glycine anhydride and similar substances and finds that amino-aldehydes are thereby pro- ClVte--NH/ N- CMe’ .- duced owing to disruption of the ring for example CH2<EE:z>CH2 + 413 = 2NH2*CH2*CH0. Since in general the -CO*NH- group is electrolytically reduced to the group -CH,*NH he is led to discuss the possibility that the constitu- tion of diketopiperazine may be more correctly represented by the formula CH2<CO)<NH>CH NH CO- or that in solution a n equilibrium may exist between this form and that usually assumed. A solution of glycine anhydride in hydrochloric or sulphuric acid is scarcely reduced by sodium amalgam. Aluminium amalgam is also without effect. Electrolytic reduction is effected in a divided cell the anodei.328 ABSTBACTS OF CHEMICAL PAPERS. (platinum lead or Acheson graphite) being immersed in a porous pot. Cathodes of platinum platinised platinum copper silver gold lead cadmium palladium and mercury have been tried but of these only the last mentioned gave useful results. Considerable irregularities have been encountered which can only be avoided by a most careful purification of the metal from grease. The cathode solution consists partly of a suspension partly of a solution of the anhydride in sulpburic or hydrochloric acid and as a result of a large number of experiments 2,V-hydrcchloric acid is found to yield the most satisfactory results. Even in this case the current yields are very poor and the excess voltage required i s high.The temperature is maintained at - 5' to 0'. The solution obtained by the reductiori of glycine anhydride after concentration and treatment with phenylhydrazine and acetic acid yields the osazone of a-aminoacetaldehyde m. p. 175.5' ; Neuberg (A. 1908 i 323) gives 176". Glycine alanine anhydride CHMe<CO.NH>CH NH*CO gives a solution which readily reduces ammoniacal silver oxide and Fehling's solution and yields a n oazone. An attempt to purify the latter was not made since i t probably conbists of a mixture of the osazones of amino- acetaldehyde and a-a m ino propaldeh yd e. Alanine anhydride (compare Fischer A. 1906 i 145) is prepared by the condensation of a-bromopropionpl bromide with alanine and esterification of tho product with alcohol and hydrogen chloride. Ethpl b~ornopropionylnrinopro~~~o~tu~~ so obtained crystallises in long needles m.p. 1 3 9 O and is converted by alcoholic ammonia at looo into alanine anhydride On reduction aud treatment with phenyl- hydrazine i t yields the osazorie of rnethylglyoxal m. p. 154*8O for which Nef (A 1905 i 2) gives m. p. 149-154'. C-Phenylglycine anhydride is ill-adapted for electrolytic reduction on account of its practical insolubility in water and dilute acids. An attempt to isolate the osazone was not made but t h s solution was found to reduce ammoniacal silver oxide and Fehling's solution. Sarcosine anhydride CH,<NMe.CO Co"Me>CH2 is prepared in the fol- lowing manner A 40% solution of formaldehyde (1.5 mols.) is allowed to react with molecular quantities of potassium cyanide and methyl- amine hydrochloride.The nitrile formed is extracted with ether and hydrolyked with concentrated hydrochloric acid. The solution is evaporated in a vacuiim treated with barium hydroxide and excess of the latter removed by carbon dioxide. The filtered tiolution is cvapo- rated t o dryness and the sarcosine extracted with absolute alcohol and converted into the anhydride by heating at 215-220'. On reduction and subsequent treatment in the usual manner a n osazoue m. p. 168-175' is obtaiued which is apparently identical with that ob- Pyrimidines. LXVI. The Formation of Pyrimidines from Ethyl Aminomalonate and Aminomalononitrile. TREAT B. JOHNSON and BEN H. NIC~LET (J. Airier. CI~ern. Sue. 1914 36 345-355. Compare Johnson this vol.i 366).-As tained from glycine anhydride H. w.ORGANIC CHEMISTRY. i. 329 an outcome of the recent paper in which i t was snggested (Zoc. cit.) that the purines in plants may be formed from pyrimidines of the barbituric acid series such as dialuric acid and uramil the authors consider the possibility that hydrogen cyanide may be t,he parent substance from which these are derived. It is already known tbat hydrogen cyanide can polymerise t o aminomalononitrile (compare Ram- berger and Rudolf A. 1902 i 364) and the results now published show that i t is possible to convert this into pyrimidine substances. Ethyl arninomalonate was prepared by reducing ethyl nitroco- malonate with hydrogen sulphide in the presence of an equimolecular amount of potassium hydroxide the process being less troublesome than reduction with aluminium amalgam (compare Piloty and Nere- sheimer A 1906 i 146) ; ethyl nitromalonate resisted reduction in this manner.When ethyl aminomalonate which is isolated as the hydrochloride is shaken with a n aqueous solution of sodium hydrogen carbonate and a benzene solution of ethyl chloroformate ethyll carb- ethoxyaminomalonate CO,Et*NH*CH(CO,Et) is obtained in colourless needles m. p. 63". The ester condenses also with ethyl benzopldithiocarbamate in alcoholic solution giving ethyl benxoyllthiocarbarnicEornaZonate NHBz*CS*NH=CH( CO,Et) rectangular plates m. p. 123'. With thiocarbamide in alcoholic solution containing sodium ethoxide ebhyl aminomalonate reacts in the usual manner of malonic esters condensing t o 2-thiouramiZ CS<NH.C,>CH*NH NH*CO a yellow powder which is unaltered a t 300'.When warmed in aqueous solution with potassium cyanate this thiouramil undergoes condensation and the addit ion of hydrochloric acid precipitates 2-thio- +-uric acid cs<NH*co NH'Co>CH*NH*CO *N H &H,O R practically colourless crystalline powder which on loss of its water of crystallisstion becomes deep purple ; it decomposes above 300'. The anhydrous substance gives a deep green solution in alkali the colour being changed to red by acetic acid and destroyed by hydrochloric acid which precipitates the substance. It was not fonnd possible to cause tbis substance to pass into thiouric acid. Ethyl nitrosomalonate condenses with thiocarbamide in alcoholic solution containing sodium ethoxide with formation of 8-thiovioluric acid CS<NH.CO>C:NOH a yellow powder which does not melt below 300'.Potassium cyanate in concentrated aqueous solution immediately condenses with the hydrochloride of ethyl aminomalonate giving ethyl carbamiciomalonate N H,* CO*NH* CH (C0,E t) octahedral crystals m. p. 1 7 3 O which did not condense further with carbamide to give $-uric acid. A mixture of aminomalononitrile and thiocarbamide in alcoholic Folution containing sodium ethoxide when heated for several hours undergoes condensation t o 4 5-diamino-2-thiotetrul~ydro-6-pyrimidone NH*CO a colourless substance which decornpised when heated. D. F. T.i. 330 ABSTRACTS OF CHEMICAL PAPERS. Researches on Pyrimidines. LXVII. The Condensation of Thiocarbamide with E thy1 Allylacetoacetate.TREAT B. JOHNSON and ARTHUR J. HILL (J. Amer. Chem. Soc. 1914 36 364-372),- On account of the abnormal behaviour of ethyl allylmalonste ethyl diallylmalonate and ethyl benzg lallglmalonate towards thiocarbamide (Johnson and Hill A. 1911 i 502) as compared with carbamide the authors have chosen ethyl allylacetoacetste as a /?-ketonic ester for an investigation of the bebaviour towards thiocarbsmide. When heated with thiocarbamide in alcoholic solution containing sodium ethoxide for ten hours ethyl allylacetoa,cetate is converted into 2-thio-4-methyl-5 -a1 lyltetrah ydvo-t%pyrimidQne CS<NH-C'~CoCIJ,*CH:CH SH*CMe flat prisms m. p. 187'; this substance reacts in a n alcoholic solution containing a molecular proportion of sodium ethoxide with methyl iodide producing 2-me~hylthiob-4-methyl-5-allyldihydro-6-p~rinaidone SMe*C<E%g>C*CH,*CH CH colourlees flat prisms m.p. 189-191'. Both this methyl derivative and the parent thio-compound are hydrolysed by aqueous chloroacetic acid giving 2 ; 6 -diketo-4-naethyl-5-allyltetrahydropyrimidine NH-co>C*CH2*CH:CH H*CMe barrel-sbaped prisms m. p. 218'. Heating with hydrochloric acid converts both the last-named substance and also 2-methylthiol-4-methyl- 5-allyldihydro-6-pyrimidone into 2 6-dirEeto-4-methyZ-5-@-cAEoropropy~- tetTahydrop?lrimidd.e CO<zEl,,:>C*CH2* CHClMe rosettes of minute prismg m. p. 233' (decomp.) whilst 2-thio-4-methyl-5-allyl- dihydro-6-pyrimidone under similar but more prolonged treatment ovate prisms m. p.218-220' (decomp.) without loss of sulphur. The last product exhibits interesting behaviour when heated with a n alcoholic solution of a n equimolecular quantity of sodium ethoxide forming a bridge between the 2 and 5 positions the resulting substance C-S*CHMe*CH /NH--CO -C \ needles ni. p. 225-227' being the first member %-+"~ of a new class of pyrimidines and the name 2 5-cyclopropyZt~~ioZ-4-met?~yl- dihydro-6-pyrimido1te is given. When heated with hydrochloric acid the bridge undergoes fission a t the C-S bond with formation of tbe 2-tbio- 4-rnethyl-5-@-chloropropyltetrahyd ro-6-pyrimidone described above. By heating an aqueous solution of 2-ethylthioldihjdro-6-pyrimidone and chloroacetic acid for a n hour uracil c m be obtained. D. F. T. Researches on Hydantoins.XXVII. Synthesis of' Hy- dantoin- 4-carboxylamide. TREAT B. JOHNSON and BEN H. NICULET (J. Amer. Chem. Soc. 191 4 36 355-364).-Nitromalon- amide (Ruhernann and Orton T. 1895 67 l O O 2 ) of which theORU A NIC CHEMISTRY. i. 331 m. p. ia said to vary between 168' and 182' with the rate of heating was obtained by the gradual addition of finely divided malonamide t o seven times its weight of fuming nitric acid (D 1.5-1.55) cooled in a freezing mixture. It was reduced by aluminium amalgam in ammoni- acal aqueous solution ,giving aminomalonamide NH,*C H(CO*NH,) which when warmed with barium hydroxide solution is converted into barium aminomalonate colonrless prisms. By heating at 100' with 85% formic acid aminomalonamide gives the formyl derivative (com- pare Conrad and Schulze A 1909 i 213) whilst treatment with ethyl chloroformate and alkali produces car6etl~oxyarninomaZonarnide CO,Et*NH*CH(CO*NH,) rosettes of colourless leaflets m.p. 178' which readily undergoes internal condensztion in warm alkaline alcoholic solution with formation of hvdantoin-4-carbox.&-~nids hexagonal prisms or thin plates m. p. 249' (decomp.); this did not give rise t o uric acid when heated with carbamide. Aminomalonamide reacts smoothly with cyanic acid in cold aqueous solution giving carbarnidonaulonamide NH2-CO*NH-CH(CO*NH2)2 prismatic needles decomp. a t 200-285' which when wsrmed a t 100' with barium hydroxide solution is converted into the barium salt (with 2H,O) of carbamidomalonic acid. When treated with ethyl ncetyl- dithiocarbamate COMe*NH*CS,Et aminomalonamide yields acstyL t hiocar bnmidomalona mide N H A c CS N K C H ( GO N H ) 2 fine need lea m.p. 254' (decomp.) which on hydrolysis with hydrochloric acid pro- duces 2- thiohydnntoin. Ethyl benzoylthioncarbamate NHBz* CS*OEt in a similar manner converts aminomalonamide in to benxoylethyl-+- carbarnidomalonamide NHBz-C( OEt) :N*CH(C3*NH2) colourless hair- like needles m. p. 230-240' (decomp.). Chromoisomerism of Onium Compounds. Met hylphen- azonium Iodides. I. F. KERRMANN and A. DANECKI (Ber. 1914 47 279-2841. -This paper constitutes an initial reply to Hantzsch's criticisms (A. 1913 i 393 903 ; this vol. i 91) on the authors' previom results (A. 1913 i 298 522 1241). D. F T. The following methylphenazonium iodides have been prepared (I) The normal iodide C13€€11N2T in dark brownish-red flat needles (11) The periodide of a partly-quiuonoid complex or leaves showing steel-blue reflection.C13H11N213~C13H13~2' + 2H20 (or +EtOH) which forms large blackish-green needles with a bluish reflection and is obtained only in presence of escess of hydrogen iodide from the holoquinonoid salt; one-half of the latter is reduced to t h e leuco-compound with liberation of 2 atoms of iodine which combine with the non-reduced half to form the tri-iodide. These two iodides (I) and (II) have been repeatedly prepared and analysed and there is no doubt that they are neither chromo-isomeric nor even isomeric. (111) The meriquinonoid iodide C,3H11N,I,Cl,Hl,N,T. + H20 which forms greyish -green crystals. (IV) Various periodides obtained by the action of iodine-potassium iodide solution on the normal iodide (I).T. H. P.i. 332 ABSTRACTS OF CHEMICAL PAPERS. [Constitution of Benzoylhydrazicarbonyl.] R. STOLLP (Ber. 19 14 47 427).-Frennd acd Kuh propooed the dihydro-oxadiazole formula of benzoylhydrazicarbonyl in 1890 not Rupe and Gebhardt in 1899 as stated previously by the author (A. 1913 i S9S). c. s. Carbazoles of the A n t h r a q u i n o n e Series. FRITZ ULLMANN and ERICH ILLGEN (Ber. 1914 47 380-383).-Since the acridone derived from 1-aminoanthraquinone (A 1911 i 489) is not sensitive towards alkalis as is the isomeride from 2-aminoanthraquinone (A. 1911 i 46S) the authors have attempted the synthesis of crrrbazoles derived from the former base. 1 3-Dibromo-3-aminoanthraquinone was boiled with potassium acetate and aniline when a 97% yield of 3-bromo-2-amino-I-anilino- anthraquinone was obtained in long dark red needles m.p. 20s' (corr.) It was treated with isoamyl nitrite in glacial acetic acid when the red solution became pale and on cooling deposited 3-bromo- N-phenyE-2 I-azirninoanthraquinone (1.) in yellow needles ni. p. 315-316O (corr.). This was gradually added t o gently boiling dipheny lamine and condensed to 4- bromo- 1 ~-phthaZoylcccrbazoZe (11.). The latter forms brick-red shining leaflets m. p. 304" (corr.) gives a cornflower-blue solution in cold sulphuric acid which becomes violet on warming and dyes cotton pale brown in the red alkaline hyposulphite vat. A new method for the preparation of azimines mas investigated in the case of 1-chloroanthraquinone.This substance was boiled with aziminobenzene potassiurh acetate and a little copper acetate in nitrobenzene when l-anthrapuinonylbcrnzotriazole 111 was obtained i n pale yellow leaflets 113. p. 269" (corr.) which were added to boiling diphenylarnine and converted into 1 2-~)hlhaEoylcarbazoZe I V. This compound forms brick-red needles m. p. 255' (corr.) dyes cotton pale orange and colours sulphuric acid blue. J. C. W. Anomalous Solubility of Uric Acid (Colloidal Uric Acid). P. GUDZENT (Zeitsch. physiol. Chem. 1914 89 253-254).- An additional argument against the existence of a colloidal form of uric acid (compare Schade arid Bodeo A 1913 i 404) is to be found in the fact that if solutions prepared according to the directions of theee authors are subjected to ultrafiltration no change can be detected in the smountGof total nitrogen in them.R. v. s.ORGANIC CHEMISTRY. i. 333 Quadriurates. CV. E. RINGER (Zeitsch. physiol. Chem. 19 14 89 321-334).-Polemical. The author is in agreement with Kohler (this vol. i 94) that chemical compounds having the compo4tion of quadriurates do not exist but points out that his view was and is that such quadriurates exist as solid solutions. Synthetic Glucosides of t h e Purims. EMIL FISCFIER and BURCKITARDT HELVERICH (Rei.. 1914 47 2 10-235).-Several gluco- side+ of the purines have been synthesised by the interaction of acetobromoglucoee or allied compounds with the salts of the purines with the heavy metals especially silver.The possibility of the formation of isomerides renders the purification of the tetra-ncetyl- glucosides rather difficult and hydrclysis to the free glucosides witbout further decomposition into the purine and sugar also requires special precautions in many cases. Besides the difficulty of obtaining a suitable salt of uric acid the isolation of a glucoside would be especially opposed by the above obstacles. The glucosides of hypoxanthine xanthine guanine and adenine were prepared by indirect methods from trichloropurine or dichloroadenine. It is expected that the combinatioii of the purine-glucosides with phosphoric acid and therefore the syntbesis of nucleotides will soon be accomplished. The silver salt of theophylline was boiled with acetobromoglucose in dry xylene for one minute when tetr~-ncet~lt7~eophylline-d-glucoside C7H~02N4,C,H70,Ac was obtained in long flat prisms by the addition of light petroleum t o the filterate.The componnd seems to exhibit dimorphism for i t has m. p. 147-149' (corr.) when crystallised from alcohol and m. p. 168-170° (corr.) from water although the two specimens have [a] - 12.21' and - 12-36' in acetylene tetrachloride respectively and both yield the same theophylline-d-glucoside. The latter was prepared by saturating a methyl-alcoholic solution of the acetyl derivative with ammonia at Oo when an ammonia compound of the glucoside crystallised which was filtered and dissolved in methyl alcohol. The solution was evaporated in vacuum and the thsoph9Zline- d-glucoside mas obtained as a heavy powder consisting of rhorirbic plates m.p. 278-250' (corr.). It crystnllises with 2H20 from hot water has a bitter taste and very powerful diuretic action and does not reduce Fehling's solution. The dry substance has [a] -2*33' - 2.28O in water but + 1*OS0 1.09' in N-hydrochloric acid. Neutral- isation of the acid solution reverFes the rotation but the rotation of an alkaline solution gradually falls from - 3-48' probably owing t o disruption of the purine nucleus. The glucoside is readily hydro1 ysed by hot N-hydrochloric acid but emulsin and yeast are without action. The dextrose residue is probably in position 7. I n the same way the galactoside [a] +23*4O and the rhamnoside La] -76.5' of tbeophylline have been prepared. Ttt7.a-acetyZtheob?.omine - d - gkcoside C7H7O2N4,C6H7O5Ac4 forms colourless needles [a] - 18.42' in acetylene tetrachloride but is readily resolved into i t s components even in hot water.For the hydrolysis with ammonia great care was necessary but theobronzine d- gZucoside was isolated in small bitter prisms with 1H,O [UK -49.58' R. V. S.i. 334 ABSTRACTS OF CHEMICAL PAPERS. (ten minutw after solution in water). Tt is gradually hydrolysed in water and therefore reduces Fehling's solution. Tetra-acetylchloro- theophylline-n-glucoside C7H602N,Cl,C,H70,Ac forms flat prisms m. p. 166-16'io(corr.) [a]? - 15-47'' - 1595'in toluene and chloro- theophylline-a-glucosida crystallises with lMeOH or 1H20 in bitter prisms m. p. 159' (corr) [a] + 18*88' 18.35' in water and does not reduce Fehling's solution. Tetra-acetylhydroncycafeine-d-glucoside forms very slender needles rn. p.235' [a] + 1.*36' l*Sl' in acetyl- ene tetrachloride but it could not be hydrolysed without complete resolution into the components. Tetra-acetyltrichlovopurine-d-glucoside C5N,Cl,,C6'Er1705Ac crystal- liees in long prisms m. p. 168-169' (corr.) [.] - 26*68O [a] - 26.02' i n acetylene tetrachloride. Tetra acetyldichloroadenine-d-glucoside forms pale yellow curved needles m. p. 213-215'(corr.) [a] - 16*41' - 16-52' in acetylene tetrachloride and is hydrolysed by ammonia to di~hloroadenine-d-glucoside which crystallises in very sparingly soluble slender needles m. p. 250' (corr.) [a] +8.3" 9.2' in water. The latter was shaken with hydriodic acid and phosphonium iodide at O' when i t formed a pale yellow solution.This was poured into ice water treated with lead acetate filtered then silver nitrate was added to remove the remaiuing hydriodic acid and finally the solution of the lead salt was decomposed by hydrogen sulphide. The crude glucoside obtained on evaporating the filtrate was converted into the picrate which formed long yellow tablets m. p 250'. Adenine-d-glucoside was obtained in long flat prisms which melt a t 210" with gas evolution then crystallise and melt finally st 275' (decomp.) ; - 10 5' in water +5-67' in N-hydrochloric acid. It has a slightly bitter taste forms precipitates with phosphotungstic acid and silver nitrate and is only s!owly hydrolysed. It was treated with an excess of nitrous acid and hgpoxanthine-d-glucoside was isolated from the product through the lead salt in the form of long needles m.p. 245' [a12 - 34.5' in AT-sodium hydroxide + 12.92' in N-hydro- chloric acid. Dichloroadenineglucoside was shaken with zinc dust and water in a sealed tube a t 140' and reduced to chloroadenine-d-glucoside C511,N5Cl,C,H1,05. The latter forms sparingly soluble sheaves of needles [a] -7*66' [a]g -7.69' in water. It mas treated with nitrous acid and the crude syrupy chlorohypoxanthineglucoside was heated with alcoholic ammonia a t 145-1 50° when by the intervention of the lead salt a small amount of not quite pure guanine-d-glucoside C,H,0N5,C6H,,05 was obtained in slender glisterriog needles m. p. 298' (corr.). J. C. W. c H9O,N,,C,H70,Ac C5H2NSCI 2% C,H70 Transformation of Diphenyldibenzylidenehydrotetrazone into Dehydrobenzaldehydephenylhydraxone and into Benzil- osazone.R. CIUSA and B. TOSCHI (Atti Id. Accad. Lincei 191 3 [v] 22 ii 489-494).-l'he authors siiggest a mechanism for this transf'orm- ation and suggest that a similar explanation may apply t o the reactionORGANIC CHEMISTRY. i. 335 of diphenylamine with oxidising agents in sulphuric acid solution to the benzidine and Fernidine transformations and to others. When the substance C H 0 N (m. p. 236-238') obtained from the nitroso-derivative of gs8nz2~l~eheyde-p-nitrophenyl hydrazone (Barn- berger and Pemsel A. 1903 i 285) is heated with benzoyl chloride at 130-135' a substance C40K3004NS rn. p. 259' is obtained ; it is not a ben zoy 1 derivative. Constitution of Bisazophthaleins and of the Coloured Salts of Phenolphthalein.P. SCHESTAKOV and TH. NOCKEN (Bar. 1914 47 331-336).-Derivatives of the quinone form of phenolphthalein have not yet been obtained from the coloured solutions of phenolphthalein salts since the reagents which have been used are those which react with the portions of the molecule which by their change determine the structure of the tautomeric form. Such deriv- atives are only to be expected when reagents are used which cause the substitution of hydrogen atoms in the quinone- or phenol-rings and do not react with the oxygen groups. The authors have therefore investigated the action of benzenedi- azonium chloride on an alkaline solution of phenolphthalein and have obtained dibenxeneaxophenolphthaZein (formula I) in 40% yield the R.V. S. C,H C6H,*OH C6H C6H,*OH c0<-0>0<(4 H,( N,Ph) 0 H CO<-O2C<C,H2( OH) (1. ) (11.1 constitution of which follows from its reduction to the corresponding diamino-compound and conversion of the latter into pyrogallol-phnol- phtha2ide (formula 11). It is therefore probable that the derivatives prepared by Odd0 (A. 1913 i 1111) from phenolphthalein and diazotised solutions of p-toluidine and o-nitroaniline respectively con- tain the substituents in the same ring and not as previously assumed in different rings. Dibenzeneazophenolphthalein . yellow crystalline substance m.. p. 189-190° is prepared by adding a diazotised solution of aniline (2 mols.) t o a solution of phenolphthalein (1 mol.) in aqueous sodium hydroxide and subsequent acidification with hydrochloric acid.When reduced with sodium thiosulphate in alkaline solution or better with a slight excess of tin and bydrochloric acid it gives diaminophenol- phthaleia (compare Gattermann and Barnberg A. 1899 i 514; Oddo Zoc. c i t . ; Meyer and Hantzsch A. 1907 i 933) which when diazotised and poured into a boiling aqueous solution of copper sul- phate yields pyrogallolphenolphthalide. The latter forms a yellowish- brown hygroscopic mass m. p. above 300° and has not been isolated in the pure condition. Boiling acetic anhydride and sodium acetate convert it into a tetra-acetyl derivative which separates from alcohol as a colourless mass m. p. 84-86' from aqueous alcohol in crystals m. p. 145O. H. W. Changes in the Physical Condition of Colloids. XVII.Optical Rotation of Protein Salts. WOLFUANG PAULI MAX SAMEC and ERWIN STNAUSS (Biochem. Zeitsch. 1914 59 470-495).-8 salt- free solution of native protein prepared by prolonged dialysis under- goes no change of optical rotation on the addition of a neutral salt ori. 336 ABSTRACTS OF CHEMICAL PAPERS. of an acetate-acetic acid ‘( buffer ” mixture up t o the isoelectric point From the last fact it will be noticed that small changes in the condition of ionisation of the proteins have but little effect on the rotation which is in marked contrast to the effects already observed on viscosity and precipitability by alcohol. On addition of acids the rotation is increased up to a certain maximal point ; addition of more acid (provided that not sufficient to cause proteolysis is added) causes no further chango.This point of maximal rotation corresponds with that of maximal viscosity and minimal precipitability or as has already been shown the point of maximal ionisation of the acid protein. The depression of the ionisation by addition of further acid affects the viscosity and precipitability but not the rotation. This constan t depends therefore on the formation of a protein acid salt and is independent of the ionic dissociation of the latter. The general action of all acids is similar but the amount of change in rotation produced by each individual acid varies and depends on the character of the anion and not on the strength of the acid. The order of action of the acids is hydro- chloric>oxalic and moncchloroacetic>sulphuric and tric~loroncetic acids (the latter two about eqiial).There is a marked parallelism between the viscosity and rotation effects due to theFe acids. Alkalis also cause increased rotation and again there is a marked parallelism between rotation and viscosity changes produced. I n this case the amount of change produced depends on the strength of the alkali. Addition of normal salts t o acid proteins prodrices a depression of the rotation and again there is a marked parallelism between viscosity and rotation changes. I n the case of the alkali proteins no change is produced in the rotation by the salts of alkalis whereas the salts of alkaline earths diminish the rotation. The anions here have little action. I n all t’heFe reactions of normal salts there is a parallelism between the optical changes produced and the changes in the coagulation temperatures.These actions are possibly due to the production of salt complexeP. Caffeine and theoyhyllino produce a marked increase in the rotation just as they do in the viscosity of the proteins. These changes are apparently due to the formation of a complex of the protein with the purine base. The action of acids on gelatin was also investigated and it was found that whereas this protein undergoes the most marked changes in hydration (recognised by the water imbibition and viscosity) under influence of acids and alkalis its optical rotation is but little changed. This fact is ascribed to the presence of large quantities of the optically inactive glycine in gelatin. The authors discuss in some detail the CRUFBS of the change in rotation on formation of salts from neutral proteins and call attention to the possible tautomerism in the molecule.S. B. S. The change depends on the anion. Historical Notes on Egg-albumin and Peptone Solutions. L. BERCZELLER (Kolloid. Zeztsch. 1914 14 1-2).-A reference t o early discussions (1870) on the nature of the peptonisation process. H. &I D.ORGANIC CHEMISTRY. i. 337 The Nucleo-protein (Hammarsten) from the Ox-pancreas. I. MARTIN KNOPF (Zeitsch. plhysiol. Cheiri. 1914 89 170-174) - According t o the analyses of other workers the nucleo-protein separated from the pancreas by Hammarsten's method contains 4.5% of phosphorus. As guanylic acid contains 8.5% of phosphorus the nucleo-protein in question should contain nearly 50% of gusnylic acid if this latter substance is the only phosphorus-containing component of the nucleo-protein.No observer has obtained more than 12% of guanylic acid from the nucleo-protein and with the guanine estim- ations in t h e present research the figure was smaller ; there are no grounds for believing that this is due to loss of material during the manipulations. It cannot therefore be doubted that the nucleo- protein contains other pbosphorised constituents and one was obtained of a very soluble nature in the mother liquor after removal of the potassium guanylate it has not yet been obtained free from protein but further work is in progress. W D. H. The Partial Enzymatic Hydrolysis of Yeast Nucleic Acid WALTER JONES and A.E. RICHARDS (J. Biol. Chem. 1914 17 71-80) -Thymus-nucleic acid yields on hydrolysis phosphoric acid guanine adenine cytosine thymine and a hexose. Yeast-nucleic acid yields the same except that uracil and pentoso replace thymine and hexose respectively. The strbcture a t tho OH 0 0 OH base of the complex in both cases appeara to be o ~ . o . ~ . o . p . o . ~ ~ that annexed. Bang's discovery of guanylic acid in animal tissues (yielding phosphoric acid ' . . . . i i gudnine and pentose otllg) was followed by the work of Levene and Jacobs who showed that by the loss of phosphoric acid the crystalline compound guanosine (guanine + pentose) could be obtained. Guanylic acid is thus a mouo- nucleotide whereas the yeast acid is a tetr+nucleotide the four oxygen atoms placed lowermost it1 the above formula.being united respectively to the four basic groups. If cleavage took place vertically four mono- nucleotides should be obtained one of which would be guanylic acid. To obtain this acid from the yeast acid would therefore be a confirma- t i o n ~ € Levene and Jacobs' view of its structnre. The action of extract of pig's pancreas is variable according to the time it is kept a t 40° so that the enzymes in i t are gradually destroyed but the first action of the fresh extract is to split the yeast acid into two di-nucleotides one of which contains guanine and cgtoiue aud the other adenine and uracil. Bath of these compounds (each containing one purine and one pyrimidine base) were separated ; the enzyme rebponsible for this cleavage is termed tetra-izuclease.Continued action of the extract decomposes the two di-nucleo tides into their constituent mono- nucleotides (one of which is guanylic acid) and these in turn are converted into nucleosides (that is base + pentose) from which the free bases are finally produutd. The task set out upon was thus accomplished but owing to the uncertainty of the condition of the enzymes in the extract ttic final outcome i3 uticertaiu also and only occasionally successful. There is however another method which lid3 LIO element of chance in it at all and that is to allow peast to act on thei. 338 ABSTRACTS OF CHEMICAL PAPERS. yeast-nucleic acid; guanylic acid is then always obtained as an end product aud it was thoroughly identified with Baug's acid.W. D. H. The Changes in the Physical Condition of Colloids. XVI. Deaminogelatin. LEOPOLD BLASEL and JOH. MATALA (Biochem. Zeitsch. 1914 58 417-450. Compare Pauli A 1913 i 108)- The substance employed for these investigations was obtained from gelatin by treatment with nitrous acid according to Skraup's method. I t s behaviour towards acids and alkalis was compared with that of the proteins from which it differs chemically in that the terminal amino-groups have been removed. It was treated in solution with hydrochloric acid in varying concentrations and the hydrogen and chlorine ion concentrations in various dilutions were measured. The results indicate a distinct amount of combination between the protein derivative and the acid although the amount is less than in the case of the natural proteins. This fact is of interest in view of the absence of amino-groups.There is however a marked difference between the corn bination of deaminogelatin and of natural proteins with acids. I n the case of the latter there is a large increase in the viscosity of the solutions with addition of small amounts of acids. which increases up to a maximum. Addition of acids. beyond this maximum causes a diminution of viscosity. The point of maximum viscosity corresponds with the point of maximum difference between the amounts of combined hydrogen and chlorine ions. This is explained by Pituli by assuming the combination of the hydrochloric acid to form a chloride giving rise to protein and chlorine ions the former of which give rise t o the high viscosity of the solution.Addition of excess of mineral acid depresses the dissociation of the protein salt and diminishes the number of protein ions. A similar phenomenon as regards viscosity was not observed in the case of deaminogelatin. In the case of the latter substance however the point of maximum difference between the bound hjdrogen and chlorine ions corresponds with the point or" minimal precipitability by phenol as in the case with the natural proteins. The precipitability by phenol is increased by the addition of neutral salts which depress the electrolytic dissociation of the salt. The behaviour of dearninoglutin towards alkalis is similar in many respects to that of the natural proteins the viscosity passing through a maximal point with addition of increasing amounts of alkali hydroxide the maximal point again corresponding with the largest amounts of protein ions in solution.Electrometric measurements indicate a binding of the hydroxyl ions (namely combination with hydrogen set free from the carbosyl group of the proteins by the alkali). There is in this case no maximal precipitation point for phenol less and less precipitate being obtained as the amount of alkali is increased The authors give an account of the precipitability of alkali deaminogelatin by phenol in the presence of salts. Here various minimal points can be observed but the phenomena appear to to somewhat complex and are not yet explained in a satisfactory manner. S B. S.ORGANIC CHEMISTRY. i. 339 Cerebrosides of the Brain. IV.a n d V. H YHIERFELDER (Zeitsch. p h y ~ i ~ l . Chem. 1914 89 236-248 247-250. Compare A. 1913 i 747).-1V. This paper deals with the more readily soluble portions of the mixture previously mentioned (Zoc. cit.) after the cerebrone and kerasin fractions have been removed. By fractionations with various bolvents it is possible to isolate from it a substance free from sugar as well as products containing sugar (cerebrosides closely related to cerebrone and kerasin). The su€stance which contains no sugar begins to melt above SO' and has [a]? - 3.38' (in 8% solution in chloroform and methyl alcohol) and contains about 77% C 12.5% H and 2.3% N. Acid hydrolysis yielded sphingosine sulphate dimethyl- sphingosine sulphate sugar derived from admixed cerebroside and kerasinic acid (compare Zoc.cit.). Acetylstion yields an acetyl derivative m. p. 104'. The substance is probably a compound of sphingosine with kerasinic acid or a mixture of compound3 of sphingosine with various fatty acids similar to kerasinic acid. V. A hexa-acetykerebyone can be obtained from crystalline cerebrone with acetic anhydride and sodium acetate. Ti; becomes damp a t 31° and is quite liquid a t 40-41'; [a]:-3' (iu lO.lo/ solution in chloroform and methyl alcohol). A pentcc-acetylkeraain can be obtained in the same way. A summary is given of tha conclusions which can be drawn as to the constitution of cerebrone and the cerebrosides in view of the results hitherto obtained by the author. R. V. S. Nomenclature of Enzymes. EDMUND 0. VON LIPPMANN (Chern. Zeit.1914 38 81. Compare A. 1903 i 304).-The author points out that considerable confusion is caused by the arbitrary system of nomenclature adopted for enzymes and that a rigid system is impossible so long as the name is derived from one word. He proposes to compound the name from two words the first of which indicates the substance acted on the second the sole or most characteristic product formed. Thus amyloglycase yields glucose from starch amylomaltase gives maltose from starch lactoglycase forms glucose (and galactose) from lactose. H. W. Chemical Constitution of Invertase. I. J. AT. NELSON and SIDNEY BOXN (J. Amar Chem. Xoc. 1914 36 393-403).-The results of this investigation generally confirm those of O'Suliivan and Tompson (T. 1890 57 834). The invertase was obtained by the autolysis of 91 kilos oE pressed yeast the 22-27 litres of liquid obtained being treated with alcohol and the precipitate puri6ed by several stages including re-solution and re-precipitation and finally ending with dialysis and re-precipitation.The yield of purified invertase amounted to approximately 200 grams. The product was a colourless powder which gave a slightly opalescent solution in water and responded to the biuret Millon and xantho- proteic tests although it gave no precipitate with phosphotungstic acid mercuric acetate or lead acetate. I t s solutions did not coagulate on heating and could not be salted out by magnesium ammonium or ziuc sulphates. The average content of uitrogen,i. 340 ABSTRACTS OF CHEMICAL PAPERS. phosphorus and ash was 1.3 0.3 and 0.9% respectively.towards sucrose was The activity OG= 37 mins. at 37' (see OSullivan and Tompson The polysaccharide of the invertase (yeast gum) mas separated from invertase solution by precipitation with Fehling's solution (Salkowski A 1900 i 180); after purification by repeated re-precipitation by alcohol from aqueous solution it was found to be free from nitrogen and ash but to contain practically all the phoaphorus originally preseot in the invertase. The action of acetyl bromide and of acetic anhydride on invertase gave colourless amorphous products of m. p. 198' (decomp.) and 184-198' (decomp.) and of acetyl values 44.4% and 42.5% respectively. The latter product after hydrolysis yielded a considerable quantity of mannosazone on treatment with phenylhydrazine acetate.Although a 10% solution of invertase is not affected by the usual protein reagents after hydrolysis with dilute sulphuric acid a t 100' and neutralisation copious precipitates are formed on addition of phosphotungstic acid phosphomoly bdic acid or mercuric chloride whilst the hydrolysed solution also gives a small amount of gelatinous precipitate on treating with a solution of ammonium magnesium or zinc sulphate. Evidently therefore the properties of the protein are effectually masked in the invertme itself. The polysaccharide of invertase is unaffected by ptyalin pancreatic amylase or castor bean lipase. D. F. T. Conditions of Action of the Salivary Diastase. L. MICIIAELIS and H. PECHSTEIN (Biochem. Zeitsch. 1914 59 77-99).-1n complete abseuce of salts diastase is inactive.It forms double compounds with a large number of' salts each one of which has its own character- istic properties which are due almost entirely to the anion. All such complexes possess diastatic properties but differ from one another ( a ) in the affinity of the salt to the diastase which mill eiIect the completeness of the combination ( b ) in the magnitude of its action on starch or in other words the affinity of the salt-diastase compound for starch ( c ) in the acid dissociation constant and consequently i n the isolectric point and the [H'] concentration of optimal activity. The diastase complexes are active in the form of their anions. As regards the affinity of diastase to salt the latter cau be divided into three classes (1) nitrates with very great affinity (2) chlorides and bromides with smaller but still great affinity (3) bulphates phos- phates and acetates with low affinity.As regards the action of the complexes on starch they can be arranged in the following order Chlorides bromides>iodides ni trat es)sulpha t es acetates and yhos- phates. 'These results are arrived at by investigating the action of salts separately and combiiied on the activity of didgsed saliva. The results in mixtures were not necessarily additive as the addition of a salt of great afKnity yielding a less active diastatic complex to a more active complex formed from a salt of smaller affinity would diminish tlie activity of tlio latter. The isoelcctric point of all the complexes lies between and It was not possible to deteruiirie this point with such accuracy as in the case of other ferments as it varied loc.cit.)ORGANIC CHEMISTRY. i. 341 with the different complexes (for phosphate acetate sulphate p = 6.1-6.2 ; for chloride and bromide 6.7 ; for nitrate 6.9). The more acid therefore is the point of optimal action the less the affinity of the anion for the diastase. S. B. S. The Emulsin-like Ferments. L. ROSENTHALER (Biochem. Zeitsch. 1914 59 498).-A reply to a criticism of Bayliss (this vol. i 919) who ascribes to the author's so-called cr-emulsin the property of synthe- siaing a glucoside. The author has only ascribed to the ferment t.hus designated the property of causing the formation of the cyanohydrin from benzaidehyde and hydrogen cyanide.P. RONA and Z . BIEN (Biochem. Zeitsch. 1914 59 100-112).-The point of optimal activity of the blood esterase of rabbits lies at about [H']= the anions of the ferment being the active agents. The acid dissociation constant is about 10-6. The esterase differs therefore from the liyase of the stomach and probably also that of the small intestine. The rate of activity on various esters varies and is probably a function of the chemical constitution of the latter. s. B. s. S. B. S. The Esterase of Blood. V. I. Fermentation Equilibria. 11. Division and Displacement in an Alcoholic Medium containing Dextrose and Two Glucosidases. EM. BOURQUELOT and M. BRIDEL (Compt. rend. 19 14 158 370-373; J. Pharm. Chirn. 1914 [vii] 9 155-158).-1n the action of a-glucosidasc on a solution of dextrose in dilute alcohol the equilibrium is reached when the ratio of combined dextrose to free dextrose isas 32.6 67.4.With P-glucosidase the ratio is 23-39 76.61. If the two ferments are allowed to act simultaneously on the same solution of dextrose in alcohol or iE the second ferment is introduced after equilibrium has been reached with the first the final equilibrium is reached when the amount of free dextrose bears respectively the above ratios to the two forms of combined dextrose each ferment being without action on the glucoside spthesised by the other. The Effect of Acids and Alkalis upon the Catalase of Take- diastase. RAY E. NEIDIG (J. Arner. Chem. Soc. 1914 36,417-429). -Euler (A*$ 1905 i 400) has obtained results on the inhibition of various catalases by acids indicating that the catalases of various origin are not identical.The author is extending this examination to the cntalase obtainable from lower fungi and has selected commercial taka-diastase obtained from AspeYgilZus oryxae as especially suitable for this purpose. The activity of the catalase was measured by the rate of decom- position induced in hydrogen peroxide. The results indicate that the inhibiting effect of acids and alkalis follows the order of their dissocia- tion constants. Neutralisation of the solution after fifteen minutes contact with acid or alkali does not restore the original activity of the enzyme whilst it is found that although with alkali hydroxides the effect is proportional to the period of contact the time of contact with sulphuric or hydrochloric acid has little or no influence on the activity of t h e enzyme.W G. D. F. T. VOL CVI. i. u ui. 342 ABSTRACTS OF CHEMICAL PAPERS. ‘‘ Glyoxalase ” a Ferment which Converts Methylglyoxal into Lactic Acid. H. D. DAKIN and H. W. DUDLEY (Biochm. Zeitsch. 1914 59 193-194).-The authors claim priority over Neuberg for the discovery of this enzyme. They also state that the ‘ l glyoxalase ” is not identical with aldehydemutase and state reasons for maintaining their nomenclature assigning the name glyoxalase to ferments which convert glyoxals into hydroxy-acids. C. NEUBERG replies affirming his former conclusions. Experiments on the Adherence of Arsenic Acid to the Aromatic Nucleus. E. SCHMITZ (Ber. 1914 47 363-3’70).-Al- though free arsanilic acid or an alkaline solution is stable towards heat solutions of the monosodium salt (‘ atoxyl,” NH,*C,H,*As03HNa,4H20 cannot be sterilised without decomposition into arsenic acid.Solu- tions of arsanilic acid with various proportions of alkali havs there- fore been heated at looo or in an autoclave et 130° and the amount of free arsenic acid estimated as magnesium pyroarsenate the un- changed arsenic acid being precipitated by acid in a freezing mixture and the last traces removed as the resorcinol azo-dye. It; was found that the replacement of the second hydrogen by an alkali metal even lithium gave stable solutions Carbamide also stabilised the solutions of sodium arsanilate. The maximum instability was found in a solu- tion containing sodium to arsanilic acid in the proportion 8 10 whereas complete stability was reached when the proportion was 15 10.That the amino-group also plays an active part was shown by the fact that the sodium salts of substituted amino-compounds (acetyl- chloroacetyl- benzoyl-derivatives the carbamide resorcinol azo-dye phloroglucin- aldehyde compound and sodium acetanthrnnilarsinate) all gave stable solutions. The cause of the decomposition must therefore lie with some interaction between the amino-group and the second hydroxyl group of the arsenic acid residue. Perhaps a free hydrogen atom in the para-position is a criterion for sodium p-phenolarsinate is also unstable whereas the disodium salt or sodium p-methoxyphenyl- arsinate is stable. I n arsanilic acid itself it may be that the formation of an inner salt ueutralises the groups in question for free p-phenolarsinic acid in which this is impossible is very unstable in solution.J. C. W. Preparation of Acyl Derivatives of p-Aminophenylarsinic Acid. CHEMISCHE FABRIE AUF ACTIEN (VORM. E. SCHERINO) (D.R.-P. 2 68 983).-p-lodoacat ylaminop~e~zyEars~n~c acid CH,I*CO*NH*C,H,*AsO(OH) prepared by treating sodium p-aminophenylarsinate with iodoacetyl chloride or iodoacetic anhydride forms whito needles m. p. 196’ (decomp.). p-lodopropionylaminophenylarsinic acid white needles m p. 224’ (decomp.) is similarly prepared from iodopropionyl chloride. Aromatic Arsenic Compounds. V. p-Iodoso- and p-Iodoxy- phenylarsinic Acid. P. EABRER (Bev. 1914 47 96-98. Compare A. 1913 i 413 ; 1912 i 740 929).-pIodoso and p-iodoxy-phenyl- S.B. S. J. C. C.ORGANIC CHEMISTRY. i. 343 arsinic acids can both tie obtained directly or indirectly from p-iodoyhenylareinic acid (Blameli and Patta A. 1909 i 543). Chlorine is led into a cooled solution of p-iodophenylarsinic acid in acetic acid when phenylarsinic acid p-iodochloride ICl,*C,H,~AsO,H crystallises. This is a yellow substance always giving an odour of chlorine. When treated cautiously in aqueous suspension with sodium hydroxide solution it is converted into p-iodosophenylarsinic acid IO-C6H,*AsO3H2 a colourless crystalline powder of ma1 ked oxidising power which decomposes explosively when heated. Oxidation of p-iodophenylarsinic acid or of p-iodosophenplarsinic acid in ice-cold N-sodium hydroxide solution by chlorine yields p-iodozy- phenplarsinic acid as a colourlesp granular solid.It is a stronger oxidieiog agent than the p-iodoso-compound. p-Iodo- p-iodoso- and p-iodoxy-phenylarsinic acids have almost equal toxic effects on mice but the two former unlike the iodoxy-compound affect mice with jaundice. D. F. T. Derivatives of Naphthylarsinic Acid. N. ANDREEV (J. Buss. Phys. C'hem. Xoc. 1913 45 1980-1985).-l-Nit~~onaphthyl-4-arsinic acid NO,*C,,H,*AsO(OH) obtained by nitrating a-naphthylarsinic acid forms pale yellow needles and is converted into a-nitronaphthalene by heating with concentrated hydrochloric acid at 120° into a-naphthol by fusion with potassium hydroxide and into 1 4-chloro- nitronaphthalene by treatment with phosphorus pentachloride. J u s t as with m-nitrophenylarsinic acid the arsenic in 1-nitronaphthyl- 4-arsinic acid is so stably connected with the naphthalene that it is not replaced by iodine and only slightly by bromine; on the other hand the arsenic of p-nitrophenylarsinic acid is readily replaced by either bromine or iodine.Reduction of the nitronaphthylarainic acid to the corresponding amino-derivative is rendered difficult by t h e ease with which the arsenic grouping undergoes reduction. DiaminoarsenonapiLthuZene hydrochloride H C1 ,NH,-CloH,*Ae As*C1,H;NH,,HCI obtained by reducing 1-nitronaphthyl-4-arsinic acid in methyl-alcoholic solution by means of stannous chloride and hydrochloric acid forms a fine pale jellow precipitate and both the hydrochloride and the free base readily oxidise in the air especially if the latter is moist. l-Aminonapl~thyZ-4-ursinic acid NH,*C,,H,-AbO(OI) is prepared by fusing a-naplitbylamine arsenate or better by heating a mixture of a-naphthylamine and arsenic acid gradually to 175" (compare Adler and Adler A. 1908 i 492) the yield being very greatly diminished if traces of moisture are present. Diazotisation of the amino-acid yields the hydrochloride of the aminoazo-compound A ~ O ( O H ) ~ C l o ~ ~ ~ N 2 ~ C l ~ ~ ~ * ~ H ~ HCI as a dark raspberry-red precipitate. HCI,NH,*C,oH,(OH)*As:As*CloH5(OH)~NH2,€LCl obtained by nitrating Adler and Adler's hydroxynaphtbylarsonic acid (Zoc. cit.) and reducing the product by means of stannous chloride and hydrochloric acid forms a fine brownish-yellow powder. Diaminodih ydroxprsenonaphtha lene din ydrochloride T. H. P. a u !i. 344 ABSTRACTS OF CHEMICAL PAPERS. S p l i t t i n g oP Arseno-compounds by Methylation. A. BERTHEIM (Ber. 1914 47 271-277).-The action of methyl iodide on arseno- compounds results in the formation of a quaternary arsonium iodide and a primary arplarsine di-iodide thus ArAs:AsAr + 3MeI = As&!e,ArI + ArAsI,. The tertiary aryidimetbylarsine AsMe,Ar must be assumed to bo nn intermediate product and the true addition which represents a trans- formation from the primary to the quaternary series extends only t.0 one half of the molecule which is resolved at tho double linking. The reaction is iutermediate t o those of methyl iodide on arsenic and on the cacodyls AsR2*AsR + 2MeI = AsMe,R,I + AsR,I (com- pare CahourP Annulen 1863 122 198 206). The yellow oily compounds obtained by Auger (A. 190.1 i 724) by the action of sodium hypophosphite and sulphuric acid on methyl- and ethyl-arainic acid are similarly decomposed on metbylation and must therefore be regarded as arsenomethano etc. The actions of ethyl iodide and higher homologues on arseno- compounds are more complicated. When heated in a sealed tube at looo arsenobenzene and methyl iodide yield phenyltrimethylarsonium iodide the corresponding periodide and phenyldi-iodoarsine AsPhI,. Arsenobenzene and ethyl iodide give (1) iodoarsenobenzene (2) a quaternary iodide probably phenyltriethylarsonium iodide (3) phenyl- di-iodoarsine and (4) a colourless oil of strong cacodyl-like odour which is apparently a second or tertiary compound or a mixture of these. p-Arsenotoluene and methyl iodide yield p-tolyltrimethylarsonium iodide m. p. 274-2'75' (frothing) (compare Michselis A 1902 i 411) and p-toiglarsenic oxide C,H7*As0. p p'-Di-iodoarsenobenzene and methyl iodide give (1) p-iodoplhenyl- trametlbylarsonium iodide C6H,I*AsMe,I which contracts considerably above ZSS' and melts and boils at 300' aud (2) tho corresponding substituted arsenic oxide. p-Anisylarsinic acid prepared by methylating hydroxyphenylarsinic acid bas m. p. 179-180° but softens much below this temperature. Michaelis (A. 1902 i 411) gave m. p. 203'. p 11'-Dimethoxyarsenobenzene and methyl iodide yield ( 1) p-anisyl- ti.iniethykc~rsoieium iodide OMe*C,Hp*AsMe,I m. p. 213' with previous sof teniag and (2) p-anisy ldi-iodoarsine. As + 4MeI = AsMe,T Ad T. H. P. Compounds of Chlorine Bromine and Iodine with Diamino- dihydroxyarsenobensene and Silver. J. DANYSZ (Compt. rend. 1914 158 199-201).-The compounds referred to are obtained by adding drop by drop a solution of the silver haloid in aqueous potassium cyanide to a solution of diamirio;lihydroxyarsenobenzene hydrochloride until a permanent precipitate is just formed This is just redissolved by addition of hydrochloric acid and the silver halogen compound is precipitated as its sulyhate by addition of sulphuric acid. The last traces of potassium cyanide are removed by washing with a solution of potassium chloride. I n the formation of these compoundsPHYSIOT,OGICAT CHEMISTRY. i. 345 one molecule o€ the silver haloid reacts with one molecule of the arsenobenzene. The compounds obtained vary in colour from orange- yellow to deep brown and the chloro-compound is less active as regards antiseptic and therapeutic properties than the iodo- and still less so than the bromo-compound. The toxicity of the bromo-compound is almost the same as t h a t of salvarsan itself whilst its sterilising power in vitro and in vivo is much greater. W. G. Preparation of Arsleno -m etallic Derivatives Containing Noble Metals. FARBWERKE voR& MEISTER LUCIUS & BRUNING (D.R.-P. 268220 268221).-Aqueous solutions of the salts of 3 3’- diamino-4 4’-dibydroxyarsenobenzene and of gold or the metals of the platinum group are mixed whereby additive compounds are obtained in which the metal is not precipitated by the ordinary reagents. The compounds are separated by evaporation in a vacuum or by precipitation with alcohol and ether or alcohol and acetone. The second patent describes similar compounds obtained from the sodium formaldehydesulphoxylate compound of 3 3‘-dinmino-4 4’- dihydroxyarsenobenzene employing copper silver gold and platinum salts. J. C. C.

ISSN:0368-1769    

DOI:10.1039/CA9140600245

出版商:RSC    

年代:1914

数据来源: RSC