摘要:

ii. 284 ABSTRACTS OF CHEMICAL PAPERS. A n a1 y t i c a1 Chemistry . Recent Advances in Forensic Chemistry. MAX DENNSTEDT (Ber. 1911 44 5-38).-A lecture delivered before the German Chemical Society. c. 5.ANALYTICAL c! HEM IYTRY. ii. 225 Volumetric Analysis with Small Quantities of Liquid. F. PILCH (Monatsh. 1911 32 Zl-f?l)).-A special form of apparatus is described which consists essentially of t w o burettes opening directly into a reaction chamber of 20 C.C. capacity. Each burette is about 40 cm. long and has a capacityof 3 c.c.; each cubic centiinetre is divided into 100 parts and the accuracy of measurement is 0.001-0.002 C.C. A Nernst micro-balance is used for weighing out the substances (0.5-2 rug.) to be introduced into the reaction chamber. Experiments are given showing that accurate results may b3 obtained in iodimetry volumetric determinations with silver nitrate acidimetry alkalimetry and in the estimation of nitrogen by the Kjeldahl process.I n the last process the ammonia is distilled directly into acid contained in the reaction chamber. T. Y. P. A Micro-filter for the Treatment of S m a l l Q u a n t i t i e s of Precipitate. JULIUS DONAU (Monutsh. 19 11 32 S 1-4 I ).-The preparation from thin platinum foil arid asbeatos fibre of a moditied Gooch crucihle is given. The crucible weighs only 0.02 gram and can be used with the filtering tube previously described (Abatr. 19 LO ii 152). Accurate results have been obtained in the gravimetric determina- tions of antimony arsenic tin iron potassium silver and copper the weight of substance taken varying from 1-3 mg.T. S. Y. A Simple Flask and an Arrangement for Carrying Out Chemical Reactions. EUGEN SPITALSKY (Chem. Zed. 19 1 1 35 175).-The apparatus is intended t o prevent any loss caused by spirting when the reaction is somewhat violent. A flat-bottomed flask having it very narrow opening into a bulb.shaped neck serves as reaction fldsk and the very small amount of liquid which is carried off by t h e gases is retained by means of a glass ball or preferably a round porcelaiu sieve placed over the constriction. When the liquid is heated to boiling any liquid condensed in the neck runs bdck into the flask and rinses the porcelain sieve thus absolutely preventing loss of substance. The apparatus can also be used for carrying out reactions which take some time to finish such as the iodometric estimation of chromic acid or the determination of the iodine number of fats.By carefully pouring a little water or chloroform on t o the porcelain sieve or glass ball a seal is formed which prevents any volatilisation of the iodine. L. DE K. The Yellow Colour of Alcoholic Potash. R. GAZE (Chem. Zentr. 1910 ii 1499-1500 ; from Apoth. Zed 1910 25 668-669). -The best method for the preparation of colourless alcoholic potash consists in placing a cooled solution of 66 grams of potassium hydroxide (purified by alcohol) in 66 grams of water in a litre flask and with constant shaking slowly adding absolute alcohol to the mark. The solution when prepared should be kept in a white glass vessel in the light.To decolorise yellow or brown alcoholic potash it shouldii. 226 ABSTRACTS OF CHEMICAL PAPERS be left in contact with fresh animal charcoal for twelve hourd being frequently shaken N. c. Method for Complete Destruction of Organic Matter in the Detection of Mineral Poisons. PIERRE BRETEAU (Compt. rend. 191 1 l52,199-200).-Three hundred grams of the material are gently warmed with 300 C.C. of pure sulphuric acid (D 1.84) in a 2-litm Jerla flask and the mixture treated with a current of oxides of nitrogen which are best prepared hy passing sulphur dioxide into 500 C.C. of nitric acid contained in a Durand wash-bottle. The gas is fleed from spray by passage through cotton wool. The temperatrire is gradually raised and the process completed as in the Kjeldshl estimation of nitrogen. If necessary 50 C.C.of sulphuric acid are added to com- pensate for loss by evaporation. When the liquid has become colourless it is concentrated in a platinum dish and treated in the usual way. The process is complete in about four hours; the above- mentioned quantity of nitric acid is sufficient for four or five operations. Simple Method of Applying Boedeker's Reaction. JATME FERRER HERNANDEZ (Aizal. Pis. Quirn. 1911 0 16-17).-Test papers are prepared by soaking in 6% zinc sulphate and then in 10% sodirim nitroprusside. They keep well i n the dark and are sufficiently sensitive. w. 0. w. One part of sodium sulphite in 2500 can be detected. G. D. L. The KjeldahI Nitrogen Process. WILLEM VAN RYN (Pharm. Weekblad 1911,48,27-28).-If i t should be necessary to temporarily stop the heating with sulphuric acid the Kjeldahl flask may be fitted with a perforated rubber cork through which passes a tube beut a t right angles and furnished near it3 lower end with a glass bulb.The end of the tube is made to dip into a small quantity of sulphuric acid. As the flask cools the acid is drawn up into the bulb and the air which follows has to bubble through the acid and is thus freed from water The Estimation of Small Quantities of Ammonia. PAUL ART~VIANN (Chem. Zeit. 191 1 35 50-51 64-65).-For qiinntitieq Bot exceeding 2 mg. of ammonia per litre the colorimetric (Nessler) process is the best. For larger quantities the iodometric method (addition of sodium hypobromite estimating the excess iodometrically) is more suitable.I n some cases a preliminary distillation with addition of magnesia is resorted to. I n the presence of nitrites these are rendered harmless by means of potassium permanganate and a little dilute sulphuric acid. The excess of permanganate is reduced by means of ferrous sulphate any excess of which is oxidised by cautious addition of permanganato. To remove the iron and manganese the liquid is made alkaline with sodium hydroxide and shaken with a little barium carbonate. After making np to R definite volume with ammonia-free water the solution is :dlowed t o settle and an aliquot p w t is then poured off and treated with Iijpbromite. L. DJS K. vapour and any ammonia. L. DE K.ANALYTICAL CHEMISTRY 4 ii. 227 Estimation of Nitrates in Vegetable M a t t e r .KARL .KROG and JOHN SEBELIEN (Glum. Zeit. 191 I 36 145-146).-1n order t o be able to apply successfully the recent ‘‘ nitron ” processito the estimation of nitrates in such vegetable substances as turnips for instance it is necessary to remove some of the interfering organic matters. A liquid ready for treatment with the ‘‘ nitron ” reagent may be obtained by macerating 10 grams of the material with a mixture of 300 C.C. of alcohol and 200 C.C. of water; 250 C.C. of the extract are then evaporated to about 80 C.C. to expel the alcohol the liquid is treated with a little purified animal charcoal and the filtrate and washings are concentrated to 25 C.C. After adding the reagent and cooling in iced water for two hours the separation of the “ nitron ” nitrate will be complete.L. DE K. E s t i m a t i o n of Phosphoric Acid in Superphosphates and Bone-Meals. ZYGMUNT ROMANSKI (Chern. Zeit. 191 1 35 163-164). -Fitty C.C. of the prepared solution (= 1 gram of superphosphate or 0.5 gram of raw phosphate) are mixed with 50 C.C. of magnesium solution and 30 C.C. of 10% ammonia are added. (When dealing with raw phosphates a sufficiency of 20% ammonia is used t o neutralise the acidity.) After remaining for an hour with frequent stirring another 20 C.C. of 10% ammonia are added and the whole is left overnight. The precipitate is now collected in a Neubauer crucible washed first with ammoniacal water then with alcohol and finally with light petroleum (D 0-64). It is then dried in a vacuum and weighed or i t may be dried in a n oven a t a temperature not exceeding 40’.The weight multiplied by 28 or 56 respectively = % of phosphoric acid in the sample. The acid magnesium solution is prepared as follows 300 grams of magnesium chloride and 400 grams of ammonium chloride are dissolved in 7 litres of water. One litre of 20% ammonia is added and then 1000 grams of citric acid. L DE K. The Estimation of Silver by Electro-Deposition f r o m an Ammoniacal Solution of the Oxalate. FRANK A. GOOCH and J. P. FEISER (Amer. J. Sci. 1911 [iv] 31 109-11l),-Twenty-five t o 50 C.C. of the silver nitrate solution (containing about 0.25-0.50 gram of silver) are precipitated with ammonium oxalate and the silver oxalate is redissolved by adding ammonia. From this solution after diluting to 100 c.c. the metal is deposited electrolytically using a current of 0 25-1.5 ampere and 4-7 volts.The cathode with the deposited silver is dried over a low flame and then heated t o incipient redness. The operation takes from twenty-five t o thirty minutes. The beet form of apparatus appears t o be a gauze cone set point down- \\-ikrdS and so placed with relation t o an annular platinum band used as the anode t h a t the end of the axis where the centrifugal effect of rotation is least shall not receive much of the deposit. The silver nitrate may be also precipitated by hydrochloric acid. The silver chloride is then dissolved i n ammonia and elecriolysed in tile presence of ammonium oualate L. DE I<.ii. 228 ABSTRACTS OF CHEMICAL PAPERS. The W a r t h a - P f e i f f e r Method of E s t i m a t i n g the H a r d n e s s of N a t u r a l waters. J.M. SILBER (ATcIL. Hygiene 1911 73 171-182).-The ordinary soap method fails to give accurate results in presence of magnesium salts or of dissolved carbon dioxide. Wartha's method as modified by Pfeiff'er works satisfactorily (com- pare Pfeiffer Zeitsch. mngew. Chem. 1902 9 128). Complications arise when the saline matter consists chiefly of the sulphates and chlorides of calcium and magnesium but these are obviated by scme modifications in procedure suggested by the author for details of which the original paper must be consulted. It is clsimed that with these modifications the method is easy rapid and accurate. E. J. R. Pb ysico-chemical Estimation of Calcium in Wine. MARCEL DUBOUX (Chew. Zentr.1910 ii 1566-1567 ; from Schweix. IVoch. Chem. Phccrnz. 1910 48 592-594).-Calcium cannot be estimated directly in wine by measuring the conductivit,y of the latter owing t o the presence of substances which inteifere with the estimation. It is necessary t o separate the calcium from the other electrolytes by treat- ing 50 C.C. of the wine with 2 C.C. of dilute sulphuric acid and 100 C.C. of 35% alcohol; after the lapse of two hours the precipitated calcium sulphate is collected on a filter washed with 70% alcohol and then dissolved in about 30 C.C. of water. The solution is now titrated with N/1-potassium oxalate solution which is added drop by drop and the conductivity is determined after the addition of each drop. The precipitation curve of the calcium oxalate consists of two straight lines connected by a short curve; the intersecting point of the two straight lines when these are extended corresponds with complete precipita- tion of the calcium oxitlate.It is recommended that 1.5 minutes be allowed t o elapse after the addition of a drop of potassium oxalate Quantitative Separation of Barium S t r o n t i u m and Calcium. J. L. M. VAN DER HORN VAN DEN Bos (Chem. TVeekbZad 1921 8 5-10).-1n e5timating barium strontium and calcium in a mixture of their salts the barium is precipitated from the boiling solution by addition of a few drops of glacial acetic acid and a slight excess of ammonium chromate solution the clear liquid decanted through a Gooch crucible the precipitate washed by decantation several times with a dilute solution of acetic acid and ammonium chromate trans- ferred to the crucible and mashed with warm water until the filtrate does not react with silver nitrate The crucible is heated to low redness.To estimate the strontium the filtrate from the barium chromate is concentrated to remove excess of acetic acid diluted with a small quantity of water and made neutral or slightly alkaline with ammonia treated with ammonium chromate and evaporated nearly to dryness. After cooling the residue is triturated with 50% alcohol and the alcohol decanted through a Gooch crucible the process being repeated until the alcohol is almost colourless. The precipitate is then trans- ferred t o the crucible and washed with 96% alcohol. It is then dried in a n air-oven a t SO-90° and weighed. solution before the conductivity is measured.w. P. s.ANALYTICAL CHEMISTRY. ii. 229 The author suggests estimating the calcium in the filtrate from the strontium chromate by precipitation as calcium oxalate and titration with permanganate but has not tried the method. The mashing of the strontium chromate with alcohol is a slow process and the percentage of strontium present in the mixture must be low. A volumetric method of estimating the three metals is recommended. The solution employed contained 0-157 gram barium 0.1 31 7 gram strontium and 0-1071 gram calcium. To estimate the barium it is diluted to about 300 c.c. boiled acidified with acetic acid and treated with 50 C.C. of 0*20SS/N-potassium dichromate solution with constant stirring the dichromate solution containing sufficient ammonia to produce a yellow colour.After cooling the liquid is diluted to 500 c.cb the barium chromate allowed to settle and 100 C.C. of the clear liquid decanted through a filter. To the filtrate is added a solution of potassium iodide in hydrochloric acid and the liberated iodine ie titrated with thiosulphate. To estimate the strontium 350 C.C. of the solution are evaporated with 10 C.C. of 0*2088/N-potassium dichromate solution coloured yellow with ammonia and when almost dry triturated with 50% alcohol. It is then diluted with 50% alcohol to 250 c.c. allowed to remain for half an hour with occasional shaking to facilitate solution of the potassium dichromate 100 C.C. decanted through a filter and treated with a solution of potassium iodide in hydro- chloric acid.After two or three minutes the solution is diluted with water and titrated with thiosulphate. For the estimation of the calcium 125 C.C. of the filtrate from the strontium chromate are diluted boiled made slightly alkaline with ammonia and precipitated with ammonium oxalate. The precipitate is allowed to settle and washed by decantation with warm dilute ammonium oxalate to remove the chromate. After washing out the excess of ammonium oxalate with warm water the residual calcium oxalate is titrated with potassium permanganate. The fact that oxalic acid is readily oxidised by warm acid solutions of chromates precludes estimating the calcium by titration of the excess of ammonium oxalate added. Waldemar Fisher’s Modification of Volhard’s Method for the Volumetric Estimation of Manganese and its Comparison with other Well-known Methods.EDWARD CAHEN and HARRY F. V. LITTLE (Analyst 1911 36 52-59)-Fisher’s method is the best of all the modifications of Volhard’s method from time to time proposed. The authors’ method which is practically the same as that of Fisher is as follows The neutral solution of manganese salt contain- ing 10 grams of zinc sulphate is diluted to 500 C.C. and heated to boiling. One gram of pure zinc oxide is added and the liquid titrated with permanganate until slightly pink. The liquid is then cooled somewhat and 1 or 2 c,c. of glacial acetic acid are added. The titration of the colourless solution is then continued until the pink AUGUST KAPSSER (Chm.Zeit. 1911 35 94).-Some practical hints as to the assay of these ores are given. A. J. W. colour is permanent. L. DE K. Aasay of Bog Ores. VOL C. ii. 16230 ABSTRACTS OF CHEMICAL PAPERS. The analysis should be performed on the sample dried for five hours at looo and it must be remembered that the powder is very hygro- scopic. The organic substances may be destroyed either by ignition or more conveniently by treating the hydrochloric acid solution with potassium permanganate. The iron is then titrated by Reinhardt’s (stannous chloride) method. It is recommended that the analysis should be done in duplicate that is both by the ignition and the permanganake process. L. DE K. Deposition of Metallic Chromium in the Electrolytic Eetimation of Manganese by Engel’s Method.J. K~STER (Zeitsch. EZektrochem. 191 1 17 57-58).-The deposit of metallic manganese formed on the catliode according to 0 t h (Abstr. 1909 ii 703) is shown t o consist mainly of chromium It is only formed when the electrolysis is carried out with too large a current density. T. E. Analysis of Molybdenum Glanz. WALDEMAR TRAUTNANN (Zeitsch. angew. Chem. 191 1 24 207).-The process described previously (Abstr. 1909 ii 942) requires a slight modification when dealing with ores containing zinc blende. The solution of the molybdenum in ammonium E;olysulphide should be heated to boiling so as to render the zinc sulphide filterable. The filtrate is then acidified to precipitate the molybdenum trisulphide. After converting this into the trioxide and weighing it should be tested for impurities to be deducted from the total weight.The oxide is fused with potassium hydrogen sulphate the mass is dissolved in hot water and precipitated by ammonium carbonate. The precipitate consisting of alumina and silica is washed with ammoniacal water containing a little ammonium nitrate ignited and weighed. L. DE K. Estimation of Tungeten. 16. MDIVANI (Bull. Soc. chirn. 19 11 [iv] 9 122-124; Bull. SOC. chim. Belg. 1911 25 41-42).-The solution should contain the tungsten as ammonium tungstate or as a potassium or sodium salt. Fifty C.C. of the solution representing about 0.1 gram of tungsten trioxide are mixed with 20 C.C. of recently-prepared tin solution containing 50 grams of crystallised stannous chloride per 200 C.C. of strong hydrochloric acid.After boiling for two minutes the blue precipitate is washed with hot water (first by decantation) collected ignited and weighed as trioxide. Experiments have shown it to be absolutely free from tin. The presence of ferric chloride does not interfere with the reaction. L. DE I(. A Reaction f o r Uranium Salts. J. A. SIEM~SEN (Chem. Zed. 1911 M 139)-Any salt of uranium when mixed with a solution of ethylenediamine at once yields a bright yellow crystalline salt soluble in excess of the reagent. The reaction is almost as delicate as the ferrocyanide or hydrogen peroxide test. L. DE K.ANALYTICAL OHEMISTRY. ii. 231 The Separation of Titanium from the Heavy Metals. KABL BOBNEMANN and H. SCHIRMEISTER (Metallurgie 1910 7 723-729. Compare Abstr. 1910 ii 1073)-Titanium is readily separated from copper or nickel by precipitation as orthotitanic acid by means of ammonia.Organic acids hinder the precipitation of titanium and therefore cannot be used for its separation from iron but the con- version of the iron into ferrocyanide is found to answer the purpose the iron being previously reduced to the ferrous state. From 0.3 to 0.5 gram of the substance is dissolved and the solution which must not be too acid is diluted to 500-600 C.C. and warmed to 50° with 20-30 C.C. of a saturated solution of sodium hydrogen sulphite until free from ferric iron. After warming to 40° 70-100 C.C. of a solution of potassium cyanide in concentrated ammonia are added with stirring and the solution is boiled until the precipitate is pure white and the solution pale green.The solution is filtered out of contact with air and the precipitate is washed with an ammoniacal solution of ammonium sulphite and then with hot water. The iron in the filtrate may be estimated after evaporation to dryness with sulphuric acid by dissolving in water precipitating with ammonia and dissolving and titrating the precipitate. Iron may be titrated with permanganate after reduction with stannous chloride if the quantity of titanium present is less than that of the iron mercuric chloride and a solution of manganous sulphafe and phosphoric acid being added. When the proportion of titanium is larger the greater part of the excess may be removed by precipitating the iron by Classen’s hydrogen peroxide method. Titanium and iron may be titrated together after reduction with zinc and the titanium is then obtained by difference.C. H. D. Qualitative Reactions of Oil of Turpentine Pine W o o d Oil and Resin Spirit. CARLO GRIYALDI (Chem. Zeit. 1911 35 52).- Gross adulteration of oil of turpentine with pine wood oil or with resin spirit may be detected by shaking 4 C.C. of the sample with 200 C.C. of a solution of 27.5 grams of mercuric acetate in n litre of water for an hour; 160 C.C. of diluted nitric acid (3 parts of nitric acid 1) 1.4 and 1 part of water) are then added and the whole is again thoroughly shaken. Pure oil of turpentine gives a clear solution but if adulterated with either of the above substitutes to a considerable extent a turbid liquid is obtained gradually yielding a flocculent deposit. In doubtful cases a larger quantity of the sample may be operated on.L. DE K. Direct Estimation of Caoutchouc in Vulcanised Rubber Materials. GERHARD H~~BENER (Chem. Xeit. 191 1 35 113-1 15).- Asphaltic or bituminous substances interfere with the estimation of caoutchouc in vulcanised rubber by the tetrabromide method as they yield insoluble bromides and cause the results for the caoutchouc to be too high. The bitumen bromide may however be removed by extracting the mixed bromides with a mixture consisting of equal parts of absolute alcohol and carbon tetrachloride ; the caoutchoucii. 282 ABSTRACTS OF CHEMICAL PAPERS. bromide is insoluble in this solvent. Paraffins and resins also yield insoluble bromine compounds and it is probable that these would be removed by the alcohol-carbon tetrachloride mixture ; in any case paraffins and resins if present in the rubber material can be eliminated by extraction with acetone previous to the bromination.w. P. s. Estimation of Sucrose in Beet Sugar Factory Refuse by Clerget’s Process Using Invertase as Hydrolyst. JAMES P. OGILVIE (J. Xoc. Chem. Ind. 191 1 30 62-64).-Distinctly higher results are obtained in estimating sucrose in beet molasses by Clerget’s process using invertase as a hydrolyst than are found by the ordinary Herzfeld modification in which concentrated hydrochloric acid is employed as the hydrolyst. But if in the Herzfeld process the error due to the influence of the optically active non-sugar substances is obviated by using the direct acid polarisation instead of the usual alkaline (basic lead acetate) polarisation the results do not differ appreciably from those obtained by means of invertase.From this it would appear that invertase is a selective hydrolyst inverting only the sucrose (and raffinose if present) without affecting the non-sugar substances. Pellet’s method of obviating the error due to the influence of optically active non-sugar substances by taking the direct polarisn- tion in a solution acidified with sulphurous acid gives the same results as the method proposed by Andrlik and S t a d k in which concentrated hydrochloric acid and urea are used. As a practical method Pellet’s sulphurous acid process is now recommended as preferable to the Andrlik and Stanrjk procedure by reason of its simplicity and several other apparent advantages.w. P. s. Estimation of Formic Acid in Foods. HEINRICEI FINCKE (Zeitsch. Nahr. Genussm. 1911 21 l-l5).-The author has sub- mitted the process described by Auerbach and Pluddemann (Abstr. 1909 ii 355) to a critical examination and finds that it yields trust- worthy results. When only a few estimations of formic acid have to be made it is more convenient to collect the precipitated mercurous chloride on a filter and weigh it as in this case there is no need to prepare the standard solutions required if the estimation is carried out volumetrically. In separating formic acids from foods the material should be acidified with an organic acid (mineral acids must not be used as they may cause sugars present to caramelise and yield volatile products which reduce mercuric chloride) and submitted t o steam-distillation until about 1500 C.C. of distillate have been collected.When aldehydes are present the vapours from the distillation flask must be passed before entering the condenser through a flask con- taining water and calcium carbonate; the formic acid is retained in this flask whilst the aldehydes pass over into the distillate. Sulphur dioxide if present is removed by treating the neutralised and evaporated distillate with hydrogen peroxide and sodium hydroxide for four hours a t the ordinary temperature; the excess of hydrogen peroxide is then destroyed by the addition of freshly precipitated mercuric hydroxide. Salicylic acid yields an insoluble compoundANALYTICAL CHEMISTRY.ii. 233 when heated with mercuric chloride in the presence of sodium acetate but the formation of this compound is prevented by the addition of sodium chloride. Generally the amount of sodium chloride (15 grams per litre) contained in the mercuric chloride solution employed is sufficient for this purpose but for the estimation of formic acid in foods containing large quantities of salicylic acid it is recommended that the neutralised distillate be concentrated and that 1 gram of sodium chloride 2 grams of sodium acetate and 0.5 gram of mercuric chloride be added for each 50 C.C. of the concentrated distillate obtained w. P. s. Estimation of Total Fatty Acids. P. SIMMICH (Zeitsch. Nalw. Genussm. 1911 21 38-44).-As incorrect results are obtained if fatty acids are dried in their free state before being weighed the author recommends that in the estimation of the total fatty acids in fats oils and soaps the fatty acids (liberated from the saponified fat in the usual way) should be separated by means of a mixture of ether and light petroleum; the ethereal solution is then neutralised by the additioii of N/2-potassium hydroxide solution and the solvent is evaporated in an atmosphere of hydrogen. The residue of soap is finally dried at a temperature of looo under reduced pressure and weighed.The weight of the fatty acids is found by subtracting from the weight of the soap 0.01307 gram for every C.C. of N/Z-potassium hydroxide solution used for the neutralisation. w. P. s. Separation of the Liquid Fatty Acids (Unsaturated) from the Solid Fatty Acids (Saturated) in Natural Mixtures of Fatty Acids.11. PIETRO FALCIOLA (Gccxxetta 1910,40 ii 425-435). -See this vol. i 174. Employment of the Electrometric Method for the Estima- tion of the Acidity of Tan Liquors. HENRY J. S. SAND and DOUULAS J. LAW (J. sbc. Chem. Irzd. 1911,30 3-5).-The estimation of the acidity of tan liquors is rendered difficult by the dark colour of the liquors masking the colour change of the indicator used. The authors suggest the titration of the liquors by the electrometric method. The hydrion concentration is determined in the usual manner by means of a hydrogen electrode specially designed for convenient manipulation. It is convenient to use the normal calQmel electrode as a standard and the liquor which is being titrated is taken as neutral when the end-voltage is 0.69 volt Experiments in which varying known quantities of acetic lactic or butyric acids were added to tan liquors and the acidity then measured by the above method gave satisfactory results.I. T. S. P. Index of Oxidation of Milk. TEMISTOCLE JONA (Gazxetta 1910 40 ii 414-418).-The index of oxidation of milk is the number of cubic centimetres of N/l 0-permanganate required to oxidise a given volume of it under certain conditions and is constant unless the milk be watered or deprived of cream (Comanducci Proc. Sixth Colzgret~s of Applied Chem. 5 606). In addition to the above index the authorii. 234 ABSTRACTS OF CHEMICAL PAPERS. determines in a similar manner the index of oxidation of the whey obtained by treating the milk with acetic acid at the b.p. and subsequently filtering. By means of the double index so obtained it is possible to differentiate between watering and the separation of cream for the former lowers the index for the whey only The two indices have been determined for the milk of two hundred cows of the Pavia district as also the variations caused by definite admixtures of water or losses of cream so that not only the nature but also the probable extent of frauds on milk practised in that city can be determined. R. V. S. New Method of Estimating the Lactose and Fat in Milk. TEMISTOCLE JONA (Gasaetta 1910 40 ii 419-424. Compare preced- ing abstract).-The reduction of perrnanganate by milk is due solely to the fat and lactose contained in it. Hence from the amounts of reduction effected by the milk and by the whey respectively it is possible to estimate these two constituents.With genuine milk or milk merely deprived of cream the results obtained are accurate; watered milk yields only approximate figures for the lactose if the water added contains substances which reduce permanganate but the approximation suffices for many purposes. As the mean of his estimations the author finds that 1 C.C. of N/10 permanganate is equivalent to 0.0049 gram of fat. Experiments with milks further show that 1 C.C. of N/10 permanganate is equivalent to 0.001401 gram of lactose hydrate whilst from experiments with pure aqueous lactose solutions the factor 0-001460 is obtained. R. V. S. Refractive Constants of Vegetable Oils.ISIDOR KLIMONT (Zeitsch. angew. Chern. 1911 24 254-256),-The values of sp. gravities refractive indices,'specific refractions (n - l/d) saponification numbers iodine numbers and mean molecular refractions have been determined for different samples of the following oils linseed cotton rape hoof hedge mustard maize olive soja sesame and earth nut. The specific refraction appears to be independent of the iodine number and is practically constant namely 0.51. The mean molecular refrac- tion varies with the Paponification number. The molecular refraction of itself is of but little value but is useful when compared with other constants. It is shown that determinations of specific gravity by the pyknometer or by the hydrometer do not affect thevalue of themolecular refractiop to any large extent and that even a few degrees difference in temperature a t which the determinations are made has only a small effect on the final value.J. J. S. [Detection of Ferricyanides.] 40 481-482).-See this vol. i 185. Assay of Cinchona Bark. CARLO GASTALDI (Gaxxetta 19 10 Estimation of Quinine and Total Alkaloids. VIGNERON (J. Pharm. Chim. 1911 [vii] 3 103-108). -The methods described are simplifications of the processes described in the French Codex and are recommended as affording results which are accurate enough for practical purposes.ANALYTICAL CHEMISTRY. ii. 235 The bark is extracted with 0.01% hydrochloric acid and the extract concentrated so that 100 C.C. contains the alkaloids of 20 grams of bark An aliquot portion of this concentrated extract is precipitated with a definite quantity of a solution of ammonia and sodium hydroxide previously saturated with (1) the total alkaloids of the bark under examination and (2) quinine by a special process.The precipitated alkaloids are washed slightly dried below 45O dissolvQd in a mixture of ether and chloroform and the residue from this solution dried and weighed as the “total alkaloids.” For the estimation of quinine the precipitate of total alkaloids is dried the quinine washed out with ether dissolved in dilute sulphuric acid and precipitated dried and weighed as the chromate. Full directions are given in the original as to the quantities of materials to be used and ihe precautions t i be adopted in Earrying out the prescribed operations.T. A. IT. Precipitation of Cocaine Solutions with Platinum Chloride. MAXNYHANN and RICH. BJORKSTEN (Yharm. 2entr.-h. 1911,52,75-74). -The cocaine solution (about 20 c.c.) is acidified with 2 C.C. of hydro- chloric acid (D 1*125) a sufficiency of platinum chloride is added and then treble the volume of alcohol. When fully deposited the compound is collected on a weighed filter mashed with alcohol dried at 1 0 5 O and weighed. As the salt is not absolutely insoluble a correction should be made by adding 0.022 gram for each 100 C.C. of filtrate. I n the presence of atropine the method cannot be applied. Boric acid does not interfere to any extent but in the presence of sodium chloride the The compound has the composition ( C,7H,10,N),,H,PtCI,. precipitation is very incomplete.L. D E K . Saponin Reactions. C. REICHARD (Pharm. 2entr.-h. 1910 51 1199-1204).-A large number of tests are given of which the following are the most characteristic. Xodium nitropusside in aqueous solution is a t once reduced on adding saponin when a flesh-coloured liquid is formed which dries up to a dark green residue. This reaction neatly distinguishes saponin from alkaloids. Diphenylamine Test.-Solid diphenylamine is moistened with a few drops of colourless 25% nitric acid and a few drops of sulphuric acid are added. The liquid is then divided into two parts and to one of these is added a little saponin. After about half an hour the reagent should be Btill colourless or but very faintly green whilst the saponin mixture has assumed a beautiful yellow colour.Titanic Acid Fest.-Pure titanic acid is heated with sulphuric acid until the liquid does not adhere obstinately to the glass. If now a little saponin is added a violet coloration appears but this soon fades. Nercurammoniurnm Chloride Test.-When a mixture of equal parts of white precipitate and saponin is moistened with water and allowed to dry nothing takes place but if now the mass is moistened with potassium hydroxide the edges turn yellow then grey,and after a few hours the mass has completely blackened. L. DE K.li. 236 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Tannin by means of Casein. MASIMILIAN NIERENSTEIN (Chem. Zeit. 1911 35 31).-Fat-free casein may be employed in place of hide-powder for removing tannin from solutions containing the latter together with gallic acid and sugars.One hundred C.C. of the solution are shaken for ten minutes with six gram8 of casein a further quantity of three grams of casein is added and the mixture is filtered. The estimation is then proceeded with in the usual way. w. P. 8. The Degree of Aocuracy with which Proteins can be Estimated in Milk by Formaldehyde Titration. H. DROOP RICHMOND (Analyst 191 1 36 9-1 l).-The author has applied this process to a number of samples of fresh milk with the object of ascertaining the agreement between duplicate estimations and the constancy of’ the factor for calculating the proteins from the aldehyde figure obtained. As mentioned previously (Abstr. 1906 ii 634) strontium hydroxide is preferred for use in the titration owing to the fact that when this substance is used the acidity of formaldehyde does not increase with dilution.The method employed is as follows To 10 c.c of the milk are added 1 C.C. of a 005% p.henolphthalein solution and the milk is neutralised with N/ll-strontium hydroxide solution ; 2 C.C. of a 40% formaldehyde solution are then added and the titration is continued until a pink coloration is obtained. After deducting the acidity of the formaldehyde solution the latter titration represents the aldehyde figure. The proteins were also estimated by Kjeldahl’s method using the factor 6-38 to convert the nitrogen found into protein. From the results obtained the factor 0-170 is calculated as tqhe most probable figure to express the relation between -the proteins and the aldehyde figure. The difference between the amounts of proteins found by the aldehyde method and by the Kjeldahl method varied from + 0.20 to - 0.13%. w. P. s. Micro-chemical Detection of Albumin. THOMAS BOKORNY (Chem. Zed. 1911 35 69-70).-The true albumin in proteosomm may be coagulated and recognised under the microscope by immersing them for half an hour in a solution containing 8% of acetic acid 4% of The Estimation of the Enzymatio Activity of Nuclease by the Optical Method. GIACOMO PIaHmI (Zeitech. physiol. Chern. 1910 70 85-93).-The activity of nuclease in blood-serum and various tissue extracts may be investigated not only by estimating the cleavage products chemically but also by the polarimeter ; nucleic acid is dextrorotatory ; as it i s broken up into its cleavage products this power disappears and the rate of fall in the dextrorotation measure8 the activity of the nuclease. The present research deals only with the nuclease of blood-serum. sodium chloride and 0.5% of caffeine. L. DE I(. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9110005224

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 237 General and Physical Chemistry. Spectroscopy of Oxygen. HEINRICH KAYSER (Ann. Pliysik 131 1 [ I V ] 34 498-504).-The author criticises statements made by Steubirlg (Abstr. 1910 ii 913) relative to the constitution of banded spectra and disputes the validity of the conclusions drawn from the observations on the fluorescence and band spectra of oxygen. I n reference t o the f i r d t ultra-violet spectrum which has generally been attributed to water but which Steubing supposes t o be characteristic of oxygen the author points out t h a t this is not only exhibited by Geissler tubes containing oxygen but also by tubes containing any other gas. Although i t is not quite certain t h a t this banded emission spectrum is due to water available observations demonstrate positively that i t cannot be ascribed to oxygen.The Structure of Certain Spectral Lines and the Zeeman Effect in Weak Magnetic Fields. HARALD LUNELUND (Ann. Ph~lsik 191 1 [iv] 34,505-542).-The utility of the Heraeus amalgam lamp as a means of producing line spectra and the behaviour of some of the finest lines in weak magnetic fields have been investigated. With a small current (3 amperes) good results are obtained for the mercury spectr um and the strongest cadmium lines appear quite sharply but the amalgam lamp cannot be recommended for the examination of the spectra of bismuth and lead. OF the various lines examined the mercury line X = 4916 the cadmium line X = 6439 the zinc lines X=6362 4810 4722 and 4680 and the lead lines h=5190 5006 4168 4062 and 4020 appear to be simple.I n a weak magnetic field the components of the mercury lines X = 5750 5769 5461 and 4359 ; of the cadmium lines X = 5086 and 4800 and of the bismuth line X=4722 were found to undergo resolution. One of tho components of the mercury line A = 5'790 iiudergoes a displacement which is proportional to the square of the strength of the applied field. In the case of the line X = 5461 one of t h e components shows remarkable changes i n the distribution of the intensity as the strength of the field is altered. Absorption-Spectra. 111. F. H. EYDMAN jun. (Chem. Weekblacl 1911 8 123-131).-A criticism of the methods employed by Formhnek and by Hartley in their experiments on absorption-spectra. H. M. D. H. M. D. A. J. W. Permeability to Light of Mixtures of Several Light- absorbing Substances [Spectroscopic Evidence for the Formation of New Compounds]. OTTO RUFF (Zeitsch.physihd. Chem. 1911 76 21-57).-Whon t o a solution of nitrogen sulphide (N4S4) in liquid animonia increasing amounts of hydrogen sulphide are added the absorbing power of the solution for light of a definite wave- length goes through a number of maxima and minima. The occurrence of such maxima and minima is ascribed to the formation of a series of new compounds since it can be shown mathematically that i f certain VOL. c. ii. 17ii. 238 ABSTRACTS OF CHEMICAL PAPERS. conditions hold such maxima and minima must always be observed when two coloured substances or a coloured and a colourless substance interact in solution t o form new substances ; further from the position of the maxima and minima certain conclusions can be drawn as to the composition of the new compounds.The subject is treated mathematically on two separate experimental conditions (1) when the concentration of one of the reacting substances is kept constant and that of the other is varied ; (2) when both concentrations are varied but the sum is always kept constant. The following types of reaction are discussed on both assumptions (a) nA + B ac + bd ; (c) the coupled reaction W A + B Z C and nA + C ZZ D and the results to be expected when one new compound is formed are deduced. If several new compounds may be formed it is shown that the number of limiting values for the absorption cannot exceed the number of new compounds but may be less.The position of the limiting values gives only approximate information as to the composition of the compounds. The observations with mixtures of nitrogen and hydrogen sulphide indicate the presence in liquid ammonia of a number of compounds (NH,),S (NH,),S (NH,),S (NH,),S and compounds containing still more sulphur. Measurements with mixtures of cobalt and nickel chlorides and of methylene-blue and azobenzene showed no indication of chemical combination. Rlixtures of helianthin and azobenzene and of methyl- orange and methylene-blue gave curves with one maximum or one minimum indicating chemical interaction. Finally no evidence of chemical combination was obtained in a highly diluted solution of bromine and iodine. G. S. Duration of Phosphorescence of Uranyl Salts.JEAN BECQUEREL (Compt. yend. 1911 152 51 1-513).-With the majority of phosphorescent substances the duration of phosphorescence increases as the temperature is lowered. This is also the case witti certain uranium salts especially those of organic acids such as the acetate tartrate and oxalates which show a much more prolonged phosphor- escence at the temperature of liquid nitrogen than a t the ordinary temperature. Uranyl nitrate however shows no difference in the duration or intensity of luminosity a t - 190Oand at the temperature a t which the fused hydrated salt crystallises. The sulphates and double sulphates are perhaps slightly more luminous at low temperatures but do not show more prolonged emission. The observations agree with those already published (Abstr.1906 ii 630) and confirm the view thab phosphorescence is localised i n the Actino-dielectric Action in the Phosphorescence of the Alkaline-earth Sulphides. C. RAMSAUER W. HAUSSER and KOBERT OEDER (Ann. I’hysil 1911 [iv] 34 445-454).-The actino-dielectric action observed by Lenard and Saeland (Abstr. 1909 ii 283) has been further examined under more favourable conditions in the case of calcium sulphide containing bismuth as metallic ‘‘ impurity.” When the phosphorescent substance is under the C ; (b) ccb + cd uranyl radicle. w. 0. w.GENERAL AND PHYSICAL CHgMISTRY. ii. 239 infludnce of an electric field the photo-electric effects which are observed on exposing to the exciting light for successive short intervals of time and on reversing the field of force indicate that the actino-dielectric action is of tho nature of a dielectric displacemeht.The actino-dielectric effect increases with the time of exposure of the calcium sulphide to the exciting light at first rapidly and then more slowly but even after an hour i t has not attained a limiting value. It increases much less rapidly than the intensity of the exciting light and approximates to a maximum as the light intensity is increased. The effect is also dependeut o n the wave-length of the light which falls on the substance. The curve which is obtained by plotting the actino-dielectric effect as a function of the wavo-length exhibits a pronounced maximum a t nboiit X = 600pp tz minimum at about X = 5OOpp and as the wave-length further dirninishes thc dielectric effect increases rapidly.H. M. D. Optical Send tisation. CHR. WINTHER (Zeitsch. wiss. Photocl~em. I91 1 9 205-228).-By means of experiments with Eder’s solution and with photographic plates the author has examined the sensitising action of ferric chloride eosiri erythrosin acridine and cyanine. If a n aqueous solution of ferric chloride prepared in the dark is added t o Eder’s solution the resiilting liquid can be kept for months in the dark without separation of mercurous chloride. On the other hand if the.ferric chloride solution is insolated for a very short interval before being added t o the Eder’s solution reduction takes place and merciirous chloride is precipitated. From this it follows that pure aqueous solutions of ferric chloride (or sixlphate) are photo-sensitive.To ascertain the photo-chemically active constituents in the other cases examined the substances concerned were subjected either singly or in pairs t o a primary insolation before being brought together in the datk. Primary insolation of eosin eosin + ammonium oxalate and erythrosin + ammonium oxalate gave no result whereas insola- tion of eosin + mercuric chloride and of erythrosin + mercuric chloride resulted in the precipitation of calomel. A very slight precipitate was also obtained after insolation of erythrosin alone. From experiments carried out on these lines it is found that tho photo-chemically sensitive constituents aro complex compounds formed by combination of the mercuric salt with the colouring matter. Other observations show that a solution of acridine chloride is sensitiaed by the addition of ammonium oxalate and that cyanine yields an extremely sensitive precipitate with mercuric chloride.I n the case of the photographic plate t h e sensitising influence of eosin and the development of the latent image by mercurous nitrate have been investigated. H. M. D. The Theory of Colour Sensitivenees. CHR. ~VINTHER (Zeitsch. eoiss. Photochem. 191 1 9 229-236).-A theoretical paper in which the connexion between the nature of the photo-chemically active rays ahd t h a t of the sensitive substance is discussed in reference to Grotthuss’s theorem according to which chemical action is brought about only by the absorbed rays. 17-2ii. 240 ABSTRACTS OF CHEMICAL PAPERS. I n photo-chemical reactions in which oxidation and reduction occur as in the action of light on Fehling's solution the primary photo- chemical effect consists in the removal of an electron from a substance which is thereby oxidised.The free electron then enters into com- bination with a second substance which undergoes reduction. Accord- ing to this view the colour sensitiveness of the active mixture o r complex is determined by the absorption of the oxidisable substance. Examples of this are found in the oxidation of iodine sulphur and siilphite ions and of pyrogallol cuprous chloride and ferrous salts. It is further supposed t h a t all oxidisable substances which exhibit selective absorption must be more or less photo-sensitive,and in this way the author draws the conclusion that the converse of Grotthuss's theorem holds good for photo-chemical changes in which oxidation is involved.Since the action of the active light consists in setting free an electron i t follows that the photo-sensitiveness must be approximately proportional to the reduction potential of the oxidisable substance. If no rediicible substance is present in the medium which is acted on by the light rays the primary photo-action leads quickly to a stationary condition which depends on the intensity of the light. When the light is removed the system returns more or less quickly to its original condition. I n presence of an oxidising agent the progress of the complete photo-chemical change is determined by the relative rate9 a t which the electrons are set free by the primary photo-action and taken up by the oxidisable substance in the secondary action.It follows from this that every photo-chemical oxidation-reduction reaction in which the oxidisable substance is reduced more slowly than free oxygen must be retarded by t h e presence of free oxygen. On the basis of these views the author describes R method of classifying different photo-chemical sensitisers. H. 35. D. Nitrification by Ultra-violet Light. DANIEL BERTRELOT and HENXY GAUDECHON (Compt.rend. 1911,152,522-524. Compare Abstr 1910 i 349 543 ; ii 564 606).-Although ultra-violet light does not bring about direct combination between oxygen and nitrogen yet the rays are able t o effect the nitrification of many organic compounds and ammonium salts in this respect as in others showing a remark- able similarity to the action of natural ferments.In the experiments the substances mere exposed in presence of air or oxygen to the light from a 110-volt lauip a t a distance of 3-6 cms. for three to nine hours at temperatures not exceeding 35-50'. Under these conditions a 4% solution of ammonia showed the reactions of a nitrite but remained free from nitrate. Ammonium hydrogen carbonate ammon- ium chloride and sulphate in aqueous solution underwent oxidation in the same way as did also compounds such as methylamine ethyl- amine ethylenediamine guanidine acetoxime hydroxylamine acet- amide acetonitrile etc. The conversion of carbamide in to ammonia under the action of the light (Abstr. 1910 ii 814) is only the first stage in its oxidation t o a nitrite.As in the case of fermentation nitrification is prevented by the presence of acids. Similarly the process is a reversible one; thus a concentrated solution of ammonium nitrite is decomposed on exposureGENERAL AND PHYSICAL CHEMISTRY. ii. 241 with liberation of nitrogen. first converted into the nitrites oxygen being evolved. Ammonium or potassium nitrate are W. 0. W. Ultra-violet Radiations. ANTOINE GUNTZ and JULES MINGUIN (Compt. nmd. 1911 152 373-373).-Using a 3.5 ampere 220 volt silica mercury lamp at distances fiom 15 to 6 cm. three classes of action on substances were observed. (1) Mechanical effects tl-Eenzyl- idenecamphor in good crystals got warm and after two hours exposure the crystal faces became dull and showed under the micro- scope corrosion figures similar to those obtained with solvents such as toluene.These Pctions are due to the rays and not to heat. (2) Cliemical effects A crystal of sugar-candy warmed withoiit melting and rapidly turned dull and yellow showing corrosion figures under the microscope. Seven grams gave with Pehling's solution 0.107 gram of a reducing substance and dextrose w t s characterised by i t s osazone. (3) Changes of state Anthracenc in benzene solu- tion deposited its polymeride para-anthracene melting at 375" arid indene was resinified. White phosphorus alone and in solution in carbon disulphide was transformed into the red variety. A crystal of transparent sulphur became opaque and powdered under slight pressure. Solutions of sulphur in benzene and carbon disulphide deposited the insoluble modification.F. S. Photo-kinetics of Bromine Substitution. I. The Course of the Photo-reaction. LUUWIK BRUNER and S. CZARNECKI (Bull. Acad. Sci. Cracow 1910 516-559. Compare Abstr. 1909 i 900; ii 951). -Further investigation of the photo-brontination of tolucne has shown that consistent results cannot be obtained in differertt experiments on account of the enormous influence exerted by traces of oxygen. I n presence of small quantities of iodine (0.0004 to O.OC3 mol. per litre) the dikturbing effect of traces of oxygen is eliminated and experiments have been made in these circum- stances to determine the nature of the photo-broinination process. The rate of disappearance of bromine in a particular experiment is constant and this is attributed t o the increasing transparency of the solution towards the active light rays which counterbalances the effect of the diminishing bromine concentration.I n experiments with different quantities of toluene in an inert solvent the velocity is proportional to the concentration of the toluene. For variations in the amount of added iodine the velocity diminishes as the amount of iodine increases. Between 1" and 33" the temperature-coefficient of the reaction is 1-55 which is much greater than for most photo-chemical reactions although only about half as large as the coefficient of the side-chain substitution when this takes place in the dark. The nature of the solvent in which the toluene is dissolved has also an influence on the rate of the photo-reaction.I n carbon tetrachloride and carbon disulphide the velocity is nearly the same but is almost three times as great in benzene. I n an ionising solvent like nitrobenzene tbe reaction proceeds muchii. 242 ABSTRACTS OF CHEMICAL PAPERS. more slowly and until the intensity of the light reaches a certain value it appears not to take place a t all. Comparative measurements of the velocity of the photo-reaction have also been made with the homologous and with various sub- stitution products. The photo-sensitiveness of the hydrocarbons in- creases in the series toluene rn-xylene 0-xylem p-xylene ethyl- benzene isopropylbenzene cymene. On the other hand nuclear-sub- stituted halogen derivatives are much less photo-sensitive than toluene. From experiments io which rays from a mercury arc lamp were used as exciting agent it seem probable that each kind of light which is absorbed is equally effective in connexion with the photo-bromina- tion process independent of its wa-ve-length. H.AT. D. Photo-kinetics of Bromine Substitution. 11. The Course of and the Factors which Influence the Photo-chemical After-effect. LUDWIK BRUNER and 511. EnIrocIksiir (BUZZ. Acad. Sci. Crncow 1910,560-593. Compare preceding abstract).-Experiments have been made to determine the nature of the after-effect which has been found t o accompany the photo-bromination of toluene. These show that tho presence of oxygen during the photo-bromination is necessary for the rapid subsequent reaction which is observed in the dark. This after-reaction is of the auto-catalytic type and is probably due to oxidation products of bromine which are produced during the photo-bromination process in the presence of oxygen.When t h e partIy photo-brominated toluene is heated for two hours at looo or is kept for fifteen t o eighteen hours at the ordinary tem- perature the catalyst is destroyed for no after-effect is observed when more bromine is added. The addition of oxidisable substances such as hydrogen bromide and iodine to the solution either before or after the photo-bromination also brings about the disappearance of the after-reaction. Certain observations relating t o the bromination of toluene in the dark without previous insolation are supposed to be due to the presence of this catalytic agent. I n very dilute solution the bromine enters only the side-chain and this reaction is auto-catalytically accelerated.If oxygen is excluded or the solution is saturated with hydrogen bromide or if a trace of iodine is added the side-chain substitution reaction does not take place. In agreement with this view it has been found t h a t the treatmect of the toluene solutions with ozonised oxygen facilitates enormously substitution in the side-chain. The action of bromine on such solutions gives the side-chain subfititution product even in the dark and in concentrated solutions and the reaction proceeds with great rapidity. H. M. D. Comparative Action of Ultra-violet Light on Straight Chain and Cyclic Orgdnic Compounds. Mineral Salts in Aqueous Solution. DANIEL BERTHELOT and HENRY GAuDEcIroN (Conapt.rend. 191 1 152 376-378. Compare this vol. ii 86).-Cyclic compoundp so long as they are not completely saturated are extremely stableGENERAL AND PHYSICAL CHEMISTRY. ii 243 towards ultra-violet light. Thus pyridine undergoes no change whilst piperidine decomposes with liberation of hydrogen under the action of the light. Cyclic compounds containing a side-chain such as cinnamic acid undergo slight decomposition but to a much less extent than corresponding aliphatic compounds. Ultra-violet light is as it rule without action on aqueous solutions of metallic salts. Ferrous bulphate solutions however a t orice give a rust-coloured precipitate! probably of a basic sulphate. Advantage may be takeu of this reaction to purify salts of nickel and cobalt from m a l l quantities of iron.Ferric sulphate gives no precipitate when pure but if nickel or cobalt sulphates are present a precipitate is forrri ecl. w. 0. w. Action of Ultra-violet L i g h t on Diastases. If. AGULIION (Compt. ?*end. 191 1 152 399-401. Compare Green Abstr. lS96 i 110 ; lSSS ij 399 ; Ceiriovodeanu arid Henri hbstr. 1909 ii S22 ; 19 10 ii 332).-The diastatic activiLy of yeast sucrase comrriercial diastase and pancrentiri emulsin pepsin rennet and untnlase (from the pig) is diminidled to a greater or less extent by exposure to tho light fKom a qii:rrtz-mercury lamp. Light oE wave-length exceecliag 3028 Angstrom unirs has practically no action on the enzymes. When a 1% solution of emulsiii is exposed to ultra-violet light a flocculeut precipitate appears ; all the enzyme however remains in solution.l h e presence of proteins or colouring matter in the diastase prepara- tions protects them to a certain extent from the action of the light. w. 0. w. r 1 I n v e s t i g a t i o n s on the Radium Contents of Rocks. 11. ERNST II. BBCIINER (Proc. K. Akad. Wetensch. Anzstertlam 191 1 13 818-819. Compare Abstr. 1910 ii 1025).-Measurements of the amount of radium in eleven specimens of sedimentary rocks of different geological periods (four of marble six of limestone and one of chalk) showed with the exception of one carboniferous limestone containing three times the mean quantity of radium very little individual diff’erences from the mean quantity (1.4 x 10-l2 gram of radium per gram) This mean is in good agreement with the mean of the values found for limestone by other observers but is much less than that from Joly’s data (3-3).Excluding granites which have a high radium content and of which a particularly large number have been investigated the mean for sedimentary rocks is somewhat higher than the mean for igneous rocks. The Radium-content of Salts of Potassium. JOHN SATTERLY (Proc. Camb. Phil. Xoc. 191 1 16 67-70).-Previous determinations by the emanation test of the radium content of potassium salts having been made without boiling the radium in a series of Campbell’s specimens mas measnred by boiling the solutions to expel the emanation. gram of radium per gram of salt but the amount varied and bore no relation to the percentage of potassium present. This amount of radium is only ono ten-thousandth part of what would be necessary to produce the F.S. The average amount founcl mas 3 x observed radioactivity of the salts. E’. s,ii. 244 ABSTRACTS OF CHEMICAL PAPERS. Action of Sljght Rise of Temperature on the Induced Radioactivity. EDOUARD SARASIN and Tri. TOMMASINA (Compt. rend. 191 1 152 434-436).-It is stated that the experiments described show that an elevation of Z O O or 30' increases the radi0activit.y of a metal rendered radioactive by exposure t o radium. Three concentric bells of metal gauze within a bell of sheet metal were placed inside an external bell containing a salt of radium for some weeks. The gauze and inner bells showed a feeble residual activity whilst the external bell showed a very strong residual activity which decayed to only three-fourths of its initial value in a day and then remained constant.Placing this bell on a radiator to increase its temperature 12O increased its activity strongly but this returned t o its initial value a t the ordinary temperature. A new metal bell exposed directly to radium showed superimposed on the decay curve of its radioactivity the same increases of activity due t o rise of temperature. All experiments with glass surfaces gave only null results. F. S. Behaviour of Lead Chloride from Pitchblende towards Magnesium Phenyl Bromide. GEORCI EBERT (Chem. Zentr. 19 10 ii 1128 ; from Ion 1910 2 277-283).-Determinations of the equivalent of the lead from active lead chloride which had been treated with magnesium phenyl bromide (Hofmann and Wolfe Abstr.1907 ii 521) which effects a concentration of the active material showed the presence of a substance with an equivalent less than that of lead. I n order t o concentrate the radium-D further the sulphate was sublimed. The sublimate is distinguished from lead sulphate only by i t s volatility and by its lower equivalent. Its analytical reactions are those of lead. The a-activity js strong from the first a,nd after four weeks is unmeasurably strong. The P-activity is feeble at first but after four weeks rises t o 14 uraniiim units. No emanation could be detected after eight weeks. I?. s. Ionisation of Gases by Chemical Change. H. BRERETON BAKER (Reprint of Royal Institution Lecture delivered March 11 1910).-The term " electromerism " is proposed instead of '' ionisa- tion " as used in connexion with the conduction of electricity throiigh gases in view of the fact that the nature of the ions is different in gases to those of liquid electrolytes. Radium bromide in an open silica tube sealed up with a mixture of very pure and dry hydrogen and oxygen causes no combination although the combination of 1/5000th part could have been detected.Very dry air does undergo electromerism under the action of radium bromide. Carbon monoxide and oxygen whether moist or dry do not contract under the action of radium. Hydrogen and nitrous oxide dried ouly by passage through phosphoric oxide cc;mbine in a Jena tube with great uniformity when heated at 530'. When lime or thoria is present the starting point of the reaction occurs at lower temperatures.When 2 mg. of radium bromide are heated in the mixture the latter explodes when the combining temperature is reached. Hydrcgen sulphide and sulphur dioxide dried only by calcium chloride do not react a t the ordinary temperature but in presence OFGENERAL AND PHYSICAL CHEMISTRY. ii. 245 liquid water decomposition into sulphur and water takes place. I n presence of 2 mg. of dried radium bromide after six hours decomposi- tion is complete the whole of the water and sulphur condensing in the small tube containing the radium bromide. Ten mg. of radium bromide exposed to an atmosphere saturated with water-vapour at 0" for two days collected 1.5 mg. of water on its surface. Probably the water vapour condenses in liquid drops on the electromers (ions) and in these drops the chemical action occurs.If this deposition of liquid drops occurs with minute quantities of water the influence of moisture on chemical change is explained according t o Sir J. J. Thomson's theory since the electromers are present in ordinary gases. The Mobility of the Positive Ion in Gases at Low Pressure. GEORGE W. TODD (Proc. Camb. Phil. SOC. 1911 16 21-25*).-By means of a modification of Rutherford's alternating field method the mobilities of the positive ions in air hydrogen carbon dioxide and ethyl bromide have been measured a t varying pressures down t o from 5 mm. t o 1 mm. in the different cases. I n all cases the product of the pressure of the gas and the mobility cf the ion mas constant showing that the positive ion unlike the negative ion is inseparable from the gas molecules attached to it at higher pressure at all pressures down to a few millimetres. The Mobility of the Positive Flame Ion.S. G. LUSBY (Proc. Camb. Phil. Soc. 1911 16 26-34).-The velocity of the positive ions produced by introducing a salt bead into a Bunsen flame has been measured by H. A. Wilson's method. Various salts of the metals of the alkali and alkaline-earth families of elements were investigated and tbe same velocity was found for all namely 290 cm. per second under a potential gradient of 1 volt per cm. at a tem- perature of 145OOA. Potassium permanganate was found t o be a n ideal salt for the measurements the changes of its chemical com- position by heat not affecting its ions but a variety of salts were employed and all gave t h same result.It is calculated that a positive ion of the same mass as the hydrogen atom should have a mobility very near t o t h a t found i n the experiments which points t o the conclusion t h a t the positive flame ion has the same mass as the hydrogen atom. The mobility should vary as the square-root of the absolute temperature and this theoretical deduction is being tested F. S. F. S. F. S. The Ionisation of Heavy Gases by X-Rays. R. T. BEATTY (Proc. Camb. Pld. Soc. 191 1 16 46-47).-The sudden increase in the ionisation produced in and the absorption of X-rays by heavy gases such as nickel carbonyl hydrogen arsenide and hydrogen selenide when the X-rays attain a certain degree of penetrating power is connected with the production of secondarj- X-rays characteristic of the heavy element and of an increased production of P-rays which ionise the gas.The production of P-rays was put into evidence by plotting the curves connecting ionisation with the pressure of hydrogen * and Le Bndium 1911 8 113-115.ii. 246 ABSTRACTS OF CHEMICAL PRPEHH. selenide ionised by X-rays sufficiently penetrating to evoke the selenium secondary X-radiation. The ciirve at low pressures was convex to the axis of pressure but by lining the ionisation chamber with selenium a linear curve was obtained. I n the latter case any P-rays striking the walls before using up all their energy in ionisation are balanced exactly by P-rays coming from the selenium. From similar curves when a i r wab used in the ionisation chamber it was f o n d that the relative ionisation of hydrogen selenide was 30 for the secondnxy X-r adia tions of iron nickel copper zinc and selenium but increabed greatly for the rays of strontium molybdenum silver tin and iodine attaining the maximum value of 286 for the last.Similar results were obtained with nickel carboriyl and hydrogen arsenide. F. S. The Discharge of Positive Electricity from Sodium Phos- phate Heated in Different Gases. FRANK HORTON (PYOC. Cm16. Phil. Soc. 191 1 16 89-lOl).-The leak of positive electricity from a n anode consisting of a platinum strip coated with sodium phosphate and heated by a current in a n apparatus carefully freed from all carbon by nitric and chromic acids was measured by a sensitive gdvano- meter i n oxygen carbon monoxido and hydrogen at various pressures.The leak was greatest in hydrogen and least in oxygen but in all cases varied with the time on changing the gas in the apparatus before coming to a steady value. On changing from hydrogen or carbon monoxide to oxygen the leak decreased whilst on changing t o carbon monoxide the leak increased. The conclusion is drawn that the gas molecules diffuse into the anode and take an active part in carrying tho current from its surface. F. S. Obaervations on the Ions and Fog-nuclei which are Pro- duced in Gases by Ultra-violet Light. STANISLAUS PACHS ( A m . Z'lqsik 191 1 [iv] 34 469-497).-Measurements of the potential differences required t o produce saturation currents in dust-free air subjected to the action of ultra-violet light indicate that the velocities of the least mobile positive and negative b n s a r e respectively 0*0022 and 0 0033 cm.per second for a fall of potential of one volt per cm. I n reference to the nature of the fog-nuclei which are simultaneously produced by the action of ultra-violet light experiments haye beeu made with several gases which were subjected t o adiabatic expansion after saturation with the vapours of different liqhide. These condensation nuclei are fouud in dry a r carbon dioxide oxygen and nitrogen but not in hydrogen. The absence of the effect in hydrogen is due t o the very small extent to which this gas absorbs the ultra-violet rays. Expansion experiments i n which the gases were passed over water benzene chloroform and a 5% aqueous hydro- chloric acid solution gave similar results.Other experiments with a i r show that the period of illiimination is without appreciable influence on the formation of the condensation nuclei. These persist for a considerable time and could be recognised at the end of an hour. Bubbling through distilled water or cooling to -80' has no effect on the nuclei but they are found to be destroyed by heating above 180".GENERAL AND PHYSICAL CHEMISTRY. ii. 247 From these observations the author draws the conclusion t h a t the formation of the nuclei cannot be due to chemical changes as has been supposed by certain observers. On the other hand the facts are consistent with the assumption that the action of the ultra-violet light consists in produciDg larger molecules of the gas by a process of polymerisation.H. M. I). Electrical Conductivity of Non-aqueous Solutions. VII I. Aluminium Bromide a n d Nitrobenzene. WLADIMIR A. PLOTNT- KOFF (J. Buss. Phys. Chem. Xoc. 1910 42 1589-1596)-C01~- ductivity measurements of solutioris of aluminium bromide in nitro- benzene a t 18’ shorn that the specific conductivity a t first rises rapidly with the concentration to reach a mnximnm a t 19”/ after which it falls the conductivity curve being almost symmetrical. The molecular conductivity increases continuously with the dilution. For the dilution + = 1190 (c.c.) p is about 3.5 calculated for the mole- cule AlBr ; pa is approximately 4.5. The conclusion is drawn that alumiriiuin bromide is moderately highly ionised in nitrobenzene.The molecular weight of aluminium bromide is only about half as large in nitrobenzone as in carbon disulphide. ‘l’tie conductivity of these solutions is probably due to ionisation OF the complex AI,Br,,2CGH,*N0 the constitution of which is discussed. Electrical Conductivity of Bolutions in Eeters with Small Dielectric C o n s t a n t s . AL. N. SACHANOFF (2 IZuss. Phys. Cheni. Soc. 1910 42 1363-1 37O).-Walden’s measuremerits of the con- ductivities of solution’s c;f salls in liquids with relatively high dielectric constants (9bstr. 1906 ii 149) indicated the dominating influence of the dielectric constant on the dissociating power of the solvent arid the general independence of this power of the chemical nature of tho solvent. With solvents having low dielectric constants however the author has shown t h a t the dissociating power depends especially on their chemical nature (compare Abstr.1‘310 ii 1027). The present paper gives the results of measurements of the con- ductivities of solutions of various szlts in isoamyl acetate methyl benzoate and imam yl benzoate the respective dielectric constants of which are 4.79 6.63 and 4.99. I n all caseq the molecular conduc- tivities are very small so that the diwocinting powers of the esters with low dielectric constants are inconsiderable and are indeed much less than those of primary amines with identical dielectric constants I n a few cases the molecular conductivity increases slightly with increase of dilution but more often it diminishes. The conclusion is drawn that in general when the dielectric con- stant is low the chemical character of the solvent is the most important factor in determining the dissociating power the magnitude of the dielectric constant playing a secondary part.When however tho dielectric constant is couipnrstively high i t exerts a dominating influence on the dissociating power which is then only slightly affected by the chemical nature of the solvent. The Nernst-Thomsou law is only valid for solvents with relatively high dielectric constants. T. H. P. T. H. P.ii. 248 ABSTRACTS OF CHEMICAL PAPERS The Theory of Electrolg tic Dissociation taking into Account the Electrical Energy of the Ions. F. A. KJELLIN (Arkiv. g e m . Min. Geol. 1911 4 No. 7 1-23).-Taking the electrostatic repulsions and attractions between the ions in a solution as the basis it is shown that the electrical energy of the ions diminishes with increasing dilution finally attaining a t infinite dilution a value which corresponds with the transference of electrons from atoms of the one sign to atoms of the opposite sign.From a consideration of the variation of the electrical energy with change in volume the total energy of the ions being independent of the volume the conclusion is drawn that the kinetic energy of the ions varies with the volume of the solution. The application of the tlieoreni that the gas pressure depends on the kinetic energy of the particles then leads to a n equation of condition for the dissociation of a binary compound into univalent ions. From this equation of condition is deduced an expression for the dissociation equilibrium which is found to give extremely good constants for the binary electrolytes sodium chioride potassium chloride magnesium sulphate zinc sulphate and copper sulphate. The equation of condition is ( p + a / ~ - ~ ~ ) P = $C where Y is the volume of solution containing 1 gram-ion and C is a constant ; y is the effective pressure of the ions and is given by the relation y - P +cb/yF where P is the pressure exerted by the ions on the walls of the containing vessel according to the kinetic theory and a = l*SOZZ[ K being the unit pressure due to the repulsive force betKeen the positive ions when there is 1 gram-ion per unit volume. When the dilution becomes infinitely great .$C =pa V .The equation for the dissociation equilibrium is {(pm.Vm )/'ZZY'} log Ci - ( 4 ~ ~ / 2 * 3 0 2 5 Z i ' T ) ~ ~ - log C,=log k where C.i is the concentration of the ions Cs that of the undissociated salt and /% is a constant.It is further shown that if it isassumed that in the combination of a metal with a non-metal there is a transference of electrons from the atoms of the metal to those of the non-metal that is that the forces holding the atoms together within the molecule are of an electrostatic nature then if the molecules are surrounded by a dielectric with a bigher dielectric constant than that of a vacuum or of the ether the electrostatic forces tend to force the solvent in between the atoms thus causing electrolj6c dissociation. By the application of similar reasoning t o the change of a metal into ions a simple explanation is given for the influence of different media on the potential difference between a metal and a solution of its salt. It is also shown how the equation of condition may be applied to calculate the value of the so-cslled electrolytic solution pressure.T. S. P. Electromotive Force Produced in S o l u t i o n s by Centrifugal Action. RICHARD C. TOLMAN (J. Amer. Chenz. Soc. 1911 33 121-147).-Colley has sliomn that when an electric current isGENERAL AND PHYSICAL CHEMISTRY. ii. 249 passed through a solution of silver nitrate or cadmium iodide in a vertical tube with a silver electrode a t each end the existence of a difference of potential between the electrodes can be detected which is due t o the effect of gravitation.Des Coudres carried out similar experiments in which centrifugal force was substituted for gravita- tion and by this means obtained a much larger E.LW.8'. It is now shown that it is possible t o derive a relation connecting the E.M.F. produced by the action of gravity with the transference number of the electrolyte both from thermodynamic and from kinetic considerations and it is pointed out in connexion with the latter t h a t the production of a n E.M.F. by centrifugal force is a proof of the presence of free ions in a solution of an electrolyte or at least of a certain degree of polarisation in the molecules. An account is given of a method for determining transference numbers by centrifugal experiments. It consists in the measurement of the E.M.F. between electrodes placed at the central and peripheral ends of a rotating tube containing the electrolyte. The apparntus is described with the aid of diagrams.An equation is given connecting the E.M.F. and the transference number of the salt with the rate of rotation the density of the solution and the molecular weight and '' partial " specific volumes of the substances involved. Measurements have been made of the E.M.F. produced by the rotation of molar solutions of the iodides of potassium sodium lithium and hydrogen. The E.M.F. was found to increase in pro- portion to the square of the rate of rotation The transference numbers were calculated and were found to agree fairly closely with those obtained by other methods. X. G. Experiments with Gas Cells Yielding Current at High Temperatures. A.BEUTNER (Keitsch. Elektroclhem 19 11 17 91-93).-This is an attempt to construct a gas cell which will yield an appreciable current. The electrodes consisted of platinum tubes closed a t one end by palladium foil. The closed ends were immersed in a fused mixture of sodium chloride and potassium fluoride or of sodium and lithium chlorides and one tube filled with hydrogen and the other with air. The E.X.F. a t 760' was 0.95 volt and this fell very rapidly when a current was taken from the cell partly owing to the small permeability of palladium for oxygen and partly to the depolarisation of the hydrogen electrode by atmospheric oxygen dissolved i n the electrolyte. By passing a current of carbon dioxide through the electrolyte the depolarisation of the hydrogen electrode is much diminished and the B.A4.F.falls much less rapidly. When nickel tubes were used as electrodes the results were similar but quantitatively much worse. T. E. Rate of Discharge of Galvanic Cells. I. D. REICHINSTEIN(~eitsC~. Elektrochem. 1911,17,85-90).-The cells consist of a small electrode of copper zinc or nickel immersed i n a suitable solution and a large lead peroxide accumulator plate in sulphuric acid ; the solutions are separated by a porous pot and t h a t surrounding the metallic electrode is well stirred. The current taken from the cell is varied and theii. 250 ABSTRACTS OF CHEMICAL PAPERS corresponding potential of the metallic electrode is measured. With copper in N-copper sulphate the potential with a current of 0-133 ampere per 5 sq.cm. was 0.817 volt less than on open circuit. Such a large difference cdnnot be ascribed to increased concentration of copper ions a t the surface of the eloctrode. The addition of sulphuric acid to the copper sulphate solution diminishes the fall in a very marked way. Very similar results were obtained with zinc in normal nud acid sodium sulphate solutions. Nickel in 20% sulphuric acid behaves qualitatively in the same way. The decrease of potential is however very much more rapid and the nickel becomes passive with a very small current. If a chloride is added to the sulphuric acid this does not occur. T. E. Electrophoresis of Lampblack. ALBERT REYCHLER (BUZZ. SOC. clha. Bslg. 1911 25 81-85).-The first part of the paper consists of a reply to Spring (this vol.ii 15). The becond part contaius an account of further experiments with slightly alkaline suspensions (n/410- n/1100) of lampblack the preparation of which is described in detail. The apparatus used to investigate the electrophoresis of such suspensions was similar to that used by Coehn (Abstr. 1909 ii Sal) except that the upper portions of the U-tube were connected by R horizontal tube. The experiments were carried out in two ways. (1). The suspension filled the lower part of the U-tube to the height of the stopcocks. Above the stopcocks was a dilute solution of potassium hydroxide containing the electrodeq but not reaching t o the level of the horizontal tube. The phenomenon then observed was one of anaphoresis. (2). 'I'he arrangement was similar to that in (l) except that the potassium hydroxide solution above the stopcocks also filled the horizontal tube. These results may be exp1aine.d as follows During the electrolysis the migration of potassium hydroxide from the anode through the suspension to the cathode carries with i t some of the water.In ( 1 ) the adjustment of level by means of the hydrostatic pressure forces the suspension towards the anode without destroying the surfaces of separation. The phenornenon thus appears to be one of anaphoresis. I n (2) the adjustment of level takes place through the horizontal tube and tho process becomes one of cataphoresis. This explanation assumes that the lampblack is completely indifferent to the action of the current. There is reason to believe however that it is slightly acid in nature so that in an alkaline medium the Value of Magneton Deduced from the Coefficients of Mag- netisation of Solutions of Iron Salts.PIERRE WEISS (Compt. y e d 1911 152 367-369. Compare this vol. ii 91 183).-From the data of Pascal and others the author deduces the value 1122.1 for the magnetic saturation of magneton in magnetic substances. The effect was then cataphoretic. anaphoresis would be increased. T. s. P. w. 0. w. The Magnetisation of Ferro-magnetic Substances above the Curie Point. PIERRE WEISS and G. Fogx (Arch. Sci. phys. nat. 191 1 [iv] 31 89-1 17. Compare this vol. ii 183j.-MeasurernontsGENERAL AND PHYSICAL CHEMISTRY. ii. 251 of the magnetic susceptibility of iron nickel cobalt magnetite and nickel iron alloys have been made at high temperatures by mezns of the apparatus described previously.hlagnetiastion temperature curves are clrawri which show the behaviour of the different substances. From the data for the various alloys at constant temperature the conclusion is drawn that a definite compound of the composition Fe,Ni is proved. At this point two magnetisation curves intersect and i t is supposed that these correspond with two series of solid sol u tiona. H. M. D. The Magnetic Susceptibilities of Certain Compounds. A. E. OXLEY (Proc. Camb. ZJhiZ. Soc. 1911 16 [l] 102-111).-Thc magnetic susceptibilities of iron cwbouyl nickel carbonyl potassium ferrocyanide and potassium ferricyanide were found to be respectively - 4.00 x 10-7 - 4.81 x 10-7 - 4.23 x 10-7 and + 93583 x a t 19'.The great difference between the values for the ferrocyanide and the ferricyanide is attributed t o the presence of the molecules of water of crystallisation in the crystals of the ferrocyanide. The low suscepti- bility of the two metals in the carbonyl compounds is also supposed to be corinected with the high apparent valoncy. From measurementH between - 60' and + 15" i t has been found that the susceptibility of the carbonyls and of the ferrocyanide is nearly independent of the temperature whereas that of th5 ferricyanide diminishes as the temperature rises. H. M. D. Magnetic Constants of Feebly Magnetic Alloys. TULLIO GNESOTTO and BfARIA BINaHINoTro ( i h o v o Cim. 1910 Lv] 20 ii 384-441).-'l'he authors have measured t,he coefficient of magnetisatiou and the susceptibility of bismuth tin cadmium and lead and of the various alloys of each of the six different pairs of these metals.The su-ceptibility of those alloys which do not contain bismuth is a linear function of their composition as mas to be expected according to Curie's law. The magnetic properties of alloys containing bismuth may serve however t o elucidate their constitution. Eight of the tin-biemnth alloys mere examined ; those containing much bismuth have n susceptibility much lower than that of pure bismuth whilst thoso rich in t i n are more pzramametic than tin itself. The alloy containing 10% of bismuth is amagnetic. The cadmium-bismuth alloys (of which twelve were investigated) all have a lower susceptibility than mould be the cace if the variation were linear.The two lead-bismuth alloys examined had su.;cepttbilities far lower than they would have if the variation were a linear function. a. R. v. s. Use of the Magnetic Field a9 a mean3 of Determining Constitution in Organic Chemistry. VII. PAUL PASCAL (BUZZ. Xoc. ch,im. 1911 [iv] 9 134-139). Compare hbstr. 1910 ii 100 179,580; this VO~. ii,91,183).-1n this part Lhe influence of oxygenated functions on molecular magnetic susceptibility is discussed. This in- fluence depends on (a) the mode of saturation of tho oxygen v:ilenciea ( b ) the structtire of t h e rest ofthe molecule. The values assigned to the various effects included under (a) have been given already (Abstr.,ii. 252 ABSTRACTS OF CHEMICAL PAPERS. 1909 ii 859 ; 1910 ii loo) and they apply both to saturated normal aliphatic substances and to polymethylenes free from side-chains.As regards effects included under ( b ) it is found that a branched-chain compound has always a higher magnetic susceptibility than the normal isomeride. The presence of a tertiary carbon atom in position a y 6 or E with respect to the oxygen atom raises the susceptibility by - 13.5 x in position p the effect is -5.0 x 10-7; in [ or q it is - 8.0 x lo-’ and in 8 i t is nil. The corresponding values for a quaternary atom are - 16 x 10-7 - 5 x - 10 x 10-7 and nil. These results can be extended t o closed-chain compounds with the convention that a cyclic carbon is regarded as tertiary if it carries no side-chain and as quaternary if i t does. The influence of the nucleus is confined t o that of the carbon atom joined directly to the oxygen and other side-chains produce no effect.The study of magnetic siisceptibility throws very little light on the internal structure of oxygenated aromatic compounds since the results are the same for diagonal linkings as for alternate single and double linkings. The application of these rules is illustrated in the original in the case of as-diphenylpentadienone where the calculated value is - 1469 x 10-7 and the value found is - 1462 x lW7. The magnetic susceptibility of furfuraldehyde is - 492 x 10-7 whilst that calculated on the assump- tion that there are two diagonal linkings is - 496.5 x 10-7. This view of its structure is in barmony with the results of Marquis’s nitration experiments (Abstr.1901 i 222 ; 1903 i 50; 1905 i 224). T. A. H. Use of the Magnetic Field in Determining Constitution in Organic Chemistry. VIII. PAUL PASCAL (Bull. SOC. chirn. 1911 [iv) 9 177-182).-The discussion of the influence of oxygenated functions on magnetic susceptibility (preceding abstract) is continued. Investigation of isosmyl ether phenyl ether benzophenone xanthone and similar symmetrical substances shows that in these cams the disturbing influence of tertiary and quaternary carbon atoms on magnetic susceptibility is eliminated whence the following ‘rule is deduced when an open-chain compound contains an oxygen atom joining two identical groups or when a carbonyl group mites two identical radicles the influences of tertiary or quaternary carbon atoms in the radicles mutually destroy each other.The magnetic susceptibility of anthraquinone is best explained by referring this substance to anthracene amd supposing it t o contain four binuclear and eight uninuclear carbon atoms which is tantamount t o accepting the representation of this compound and also that oE phenanthraquinone by diagonal linkings. The inflaence of a methoxyl group is equal to + 5 x 10-7. A long list of calculated and experimental values for the magnetic susceptibility of oxygenated compounds is given showing good agreement between the two sets of values. T. A. 13. Modification of the Reichert Thermoregulator. E. FONTAINE (Ann. Cihim. anal. 191 1 16 52-53).-1n the ReichertGENERAL AND PHYSICAL CHEMISTRY. ii. 253 thermoregulator the level of the mercury is altered by means of a screw at the end of a horizontal side-tube.I n the present modification the outer half of the side-tube in bent upwards parallel with the main tube of the regulator and contains a cylinder of wood which does not touch the walls. The position of the cylinder in the mercury and therefore the level of the mercury in the main tube can be altered by means of the screw Conduction of Heat Through Rarefied Gases. 11. FREDERICK SODDY and ARTHUR JOFIN GERRY (Yroc. IZoy. SOC. 1911 A 84 676-585. Compare Abstr. 19 10 ii 180).-Measurements of the conduction of heat in argon helium and hydrogen a t very low pressure from an electrically heated platinum strip stretched through a long exhausted tube have been continued at various temperatures of the strip and the surrounding bath in order to test the theory that for the light gases the interchange of energy is imperfect after a single impact with the suiface.The experiments were performed with the temperature of tha bath from - 185' to 187O and of the strip from - 120' to 264'. I n an addendum a correction is made in the results owing to the pressure measured in the guage not being the same as the real pressure in the tnbe containing the heated strip on account of the difference of temperature between them (Knudsen). The theoretical values for the conductivity calculated from the kinetic theory are also multiplied by a correcting numerical factor (Smoluchowski). The corrected results for the ratio of the observed to the calculated con- ductiviby show that in heliiiin and hydrogen the ratio is highest at the lowest temperature and decreases with rise of temperature.For argon the influence of temperature is small and irregular. Hydrogen showed the same value of the conductivity whether the heated surface was of palladium or platinum. The reason why the heat conductivity of gases especially of the lighter gases is less than that calculated from the kinetic theory remains undecided. G. S. F. S. Specific Heats of Bargtes Witherite Fused Lime Quartz and Chalcedony at High Temperatures. P. N. LASCIITSCHENKO (J. Russ. Phys. Client. SOC. 1910 42 1604-1614).-The specific heat of barytes increases practically linearly with rise of temperature from 0,1137 a t 150' to 0.1486 at 1050' this result being in agreement with the absence of any indication of polymorphism in barium sulphate.In the case of witherite the specific heat rises from 0.1158 at 250' to about 0.13 at 615' then remains almost constant up to SOO" becomes 0.1429 at SlO' again increases slowly to about 0.16 a t 910' and falls from 0.1620 at 1030' to 0.1500 at 1060'. These results indicate a molecular transformation of witherite at 800'; the heat of transformation is found to be 1.76 Cal. per 1 gram.-mol. With lime fused in a Moissan electric furnace the specific heat is 0.172 at 190° 0.181 a t 375" and 400° 0.190 at 415' after which i t increases gradually to 0.193 at 590" and 680". Fused lime hence undergoes t ramformation a t 400-415' the heat of transformation being 0.29 Gal. per gram.-mol. The specitic heat of chalcedony increases from 0.1930 at 139' to VOL.c. ii. 18ii. 254 ABSTRACTS OF CHEMICAL PAPERS. 0.2039 at 224O 0.2484 a t 230° 0.2485 at 24'7O and 0.2530 at 442'. The heat of the transformation which occurs a t 224-230° is 0-523 Cal. per 1 gram.-mol. of silica. With quartz the specific heat increases slowly from 0,2250 at 200" t o 0.2350 at 580'. A t 600' i t becomes 0.2400 the heat of the trans- formation a t 550-600° being 0.181 Cal. per gram.-mol. of silica. The specific heat then rises to 0.2480 a t 6503 and beyond 700" diminishes slightly 'r. Ir. P. Convenient Attachments for a Melting-point Apparatus. ATHERTON SEIDELL (J. Anzer. Cliem. Xoc. 191 1 33 83-84).-h new form of melting-point apparatus has recently been described by Blenge (BUZZ. No.70 Hyg. Lub. U.S.P.H. and M.H. Xeru.). The bath requires t o be stirred continuously during a determination and the heat must be so applied that the temperature rises a t a certain constant rate before the m p. is reached and at a slower constant rate whilst the compound is melting. I n order to facilitate these operations a simple attachment driven by a small water-motor has been constructed to move the stirrer automatically and an arrangement has been devised to ensure constant heating by the Bunsen burner. The latter device consists of a piece of wire gauze fixed in a horizontal poition about a n inch above the burner and an ordinary lantern chimney to surround the flame. The upper end of the chimney is nearly closed with a piece of asbestos board provided with a hole through which the bath of the melting-point apparatus passes.E. G. Laws of Distillation of Liquid Binary Mixtures. C. MARI LLER (Bull. Assoc. c?Lim. Sucr. Dist. 191 1 28 473-490 537-559).-A mixture of two mutually insoluble liquids boils when the sum of the vapour pressures (P,+P,) equals the external pressure that is a t a temperature which may be lower than the boiling point of both liquids separately. The distillate contains the two liquids in the constant proportion M,Pl ilf2P2 where Ml and M2 are the molecular weights of the two liquids. This formula established by Regnarilt and by Gernez holds very closely for mixtures of carbon disulphide and water. Any subs'ance such as water with a product ilfY which is small appears in a mixed distillate in relatively small amount.The proportions in a distillate can be varied at will by distilling under increased or dirninibhed pressure a fact which finds technical application in the distillation of brandy where a high pressure leads to increased bouquet The proportions are also altered by the presence of dissolved solids which diminish the vapour pressure of their solvents. In the case of completely miscible liquids such as water and alcohol Duclaux established that da/dw = Ka/(a + w) where da a are the pro- portions of alcohol and dw w the proportions of water in vapour and liquid phases respectively. I n ascending the series from methyl t o octyl alcohol K increases that is methyl alcohol is the most difficult alcohol t o dehydrate by distillation. The ratio da/a diminishes t o a value very near 1 as the strength of ethyl alcohol approaches 95% so that the last traces of water are difficult to remove by distillation...GENERAL AND PHYSICAL CHEMISTRY. 11. 255 If the volumes A w of the vapours of alcohol and water are considered instead of cla dw the constant K milst be multiplied by a factor to take account of the various densities. The modified constant has a value about 4.8 for the first three soluble alcohols and 8.0 for the next three partly soluble alcohols in the aliphatic series. The author deduces theoretically that in the range of con- centratiofis for which Duclaux’ equation holds the vapour tension of the water is the same as the tension of pure water and the boiling point of all these water-alcoholmixtures must be below that of water.The tension of the alcohol however is approximately proportional to its concentration. The volumes of each substance in the vapour phase are strictly proportional to the rapour pressures so that by determining the composition of the distillate the vapour pressures in the original mixture can be deduced. Experimental data for ethyl alcohol show that in fact the vapour pressure of the water is not affected until the proportion of alcohol exceeds 20% by volume. Further addition of alcohol increases the vapour tension of the water a maximum increase of 6% being attained at 40% alcohol after which a progressive decrease occurs. I n rectifying alcohol the depth of liquid in the retort appears to have no influence on the strength of the distillate but rapid evaporation or eTaporation from a small surface or under reduced pressure gives a distillate richer in water than slow evaporation or evaporation in a current of air. Violent ebullition by radiant heat was avoided in the author’s experiments.Sodium hydroxide copper sulphate potassium carbonate potassium alum or potassium sodium tartrate may bring about a separation into two phases. So long ps two phases exist the distillate is of constant composition but8 single phase mixtures containing salts may yield a distillate which is richer or poorer than tho residue according to the various concentrations. Methyl alcohol behaves similarly to ethyl alcohol but is generally more difficult to dehydrate by distillation. Propyl alcohol-water nrixtnres resemble hydrogen chloride giving a certain constant boiling mixture for each pressure.A t 760 mm. this mixture contains 77% of propyl alcohol. All other mixtures tend to attain this composition on boiling. The higher alcohols behave normally up to the limit of their solubility but when two phases are present a distillate of constant composition is obtained. Formic and acetic acids are concentrated by evaporation whereas propionic and butyric acids give constant boiling mixtures with water above which strength the pure acids become tail products of the distillation. The usual evaporation formula does not hold for dilute solutions of acetic acid which is supposed to be partly polgmerised in the gaseous phase. Mixtures of ethyl alcohol with benzene or ether and of benzene with acetic acid behave similarly t o ethyl alcohol-water mixtures.Ethyl alcohol with carbon disulphide or acetonitrile and methyl alcohol with acetonitrile behave like propyl alcohol-water mixtures there being in each case a constant boiling mixture. R. J. C 18-2.. 11. 256 ABSTRACTS OF CHEMICAL PAPERS. Cornposition and Vapour Pressure of Solutions. IV. Change in Composition of Mixtures of Constant Boiling Point. M. S. VKEVSICY (J. Auss. Phys. Chern. Soc. 1910 42 1349-1 355).-The author extends his previous theoretical considera- tions (Abstr. 1910 ii 1038) to the cases of binary liquid mixtures forming constant-boiling mixtures possessing (1) a maximum and (2) a minimum vapour pressure. It is shown that if on raising tho temperature the proportion of the component A in the vapour increases then in case (1) the proportion of this component and in case (2) that of the other component increases in the mixture cf constant boiling point.By means of t,he results of Roscoe’s measurements of the com- positions of aqueous hydrochloric hydrobromic hydriodic and formic zcids having constant boiling points (Aiziznleiz 1860 116 203 ; 1863 125 32l) and of Thomsen’s values for the heats of dilution of theso acids with water ( l’herrn ochenz ische Uiat ersuchungen) the f ol !o rv i n g ‘ger,eral conclusions are attained. Rise of temperature of a solution having a maximum (minimum) vapour premuro produces i n the mixture of constant boiling point a n increase in the proportion of t h a t com- ponent the evaporation of which involves the greater (less) expenditure of energy.T. 13. P. New Rectification Tubes. 31. EMMANUEL POZZI-ESCOT (Bull. Assoc. chim. Sucr. Dist. 19 1 1 28 501 ).-The laboratory still-heads shown in the annexed illustration are self-explanatory. The form A is more efficient than B for the same number of bulbs 1%. J. C. An Electrically Heated Vacuum Frac- tionation Apparatus. H. S. BAILEY (J. Anzer. Chew. Soc. 19 1 1 33 447-450).-h special appa-rstus for the fractiopal distillations of es- sential oils is described. The bottom of the flask is made as narrow as possible so that on work- ing with 50 C.C. portions all but the last 5 C.C. The heater is a coil of German silver or nichroine The apparatus is so designed t h a t the successive fractions may bo may be dihtilled.wire sealed into the narrow portion of the flask. collected without releasing the vacuum. T. s.. P. “ Simple ” and Complex ‘‘ Syatems ” of Thermodynaniical Chemistry. JOI~ANNES J VAN LAAR (Zeitsch. plqsikal. Chern. 191 1 ’76 67-74).-The ‘‘ simple ” system of thermodynamic chemistry recently put forward by Washburn (Abstr. 1910 ii 391) possesses no substantial advantage over the other methods depending on cyclical processes and in the author’s opinion is much inferior to the method based on thcrmoclyna.mic potential. Some details of b’ashburn’s paper are also adversely criticised. G. S.GEKERAL AND PHYSICAL CIIEBIIS'I'KY. ii. 257 The Heat of Solution of Fused Mixtures of Potassium and Sodium Nitrate. JAN YON ZAWIDZKI and A. SCHAGGER (Chem. Zentr. 1910 ii 1025 ; from li'osmos 1910 35 IZaclzisxewski Testtciiad 498-505).-The heats of solution in water of mechanical and of fused solidified mixtures of potassium and sodium nitrate have been measured.I n both cases the observed heats of solution are in agreement with those calculated from the values for the pure substances according t o the mixture rule. Since the two nitrates form a complete series of mixed crystals it follows t h a t the heat of formation of the mixed Relations between the Density Temperature and Pressure of Substances. ~ ~ I C I I A R D D. KLEEMAN (I'hil. kfccg. 1911 [vi] 21 325-311. Compare Abstr. 1910. ii 22) 492 600 938; this vol. ii 34 97).-Further relationships between the pressure volume tem- peiature and the latent heat of vaporisation a r e deduced from tho assumed law of molecular attraction.It is also shown that this lam leads to the theory of corresponding states and that t h e equation corresponding with this theory must apply t o all states OF matter. crystals must be extremely small. 11. 1\1. D. 13. 31. D. Dilatometric Investigations of Hydrolytic Decompositions. GINO GALEOTTI (Zeitsch. physikal. Chem. 1911 '76 105-126).-'l'he hydrolytic decomposition of sucrose ethyl acetate starch peptone and proteins is accompanied by a diminution of volume independent of whether the change is effected by acids or by enzymes. The rate of change of volume proceeds p3rallel to the rate of the reaction and in certain cases (hydrolysis of sucrose and of etbyl acetate) it has been found possible to determine the rate of reaction by rrieasuring the volume change.The diminution of volume takes place independently of whether pressure accelerates or retards the reaction. From the results the conclusion muat be drawn t h a t water occupies a smaller volume in the Viscosity of the Liquids ussd for the Mechanical Separation of Minerals. ENRICO CLERICI (Atti h?. 1:ccad. Lincei 1911 [v] 20 i 45-50) -The author has detormined the ' viscosity of sixteeu liquids used for this piirpose including the solutions of barium mercuribromide thallium formate thallium rualonate and the mixture K. v. s. EMIL BOSE and ~IAHGRETE BOSE (YlLysiknZ. Zeitsch. 191 1 12 126-1 %).-l'he observations of Boje and llauert (Abstr. 1909 ii 645) relating t o the viscosities of liquids when in a condition of '' hydraulic" flow are subjected t o analysis.For the same liquid the times (2) required for the discharge of a given volume thrmgh the same tube a t different pressures can be rapresented by The connexion between t h e density the Poiseuille coefficient of viscosity and the '- critical ') time of discharge is found to be the same for the other liquids examined as for vwter. combined state than when it forms part of the solvent. G. s. of the two last proposed by him. The Turbulence Viscosity of Different Liquids. log. i / ~ = A + n log. p + C(10g. + D.(log:p)3. H. .M. D.ii. 258 ABSTRACTS OF CHEMICAL PAPEHS. Van der Waals' Theory of the Liquid State from the Stand- point of Viscosity Phenomena. MARYAN SMOLUCHOWSKI (Chem. Zentr. 1910 ii 1015 ; from Kosmos 1910 35 Rccdxisxewski Festband 543-549).-The theory of van der Waals is examined with reference to the viscosity of liquids.It is shown that the theory of corresponding states oEers no explanation of bho relationships between the viscosities of different liquids. Prom the measurements of Warburg and Sachs of the increase in viscosity with increase in pressure the author calculates the change in viscosity with the temperature at constant volume in the case of benzene and ethyl ether. This is not in agree- ment with the requirements of the generalised van der Waals' theory. H. M. D. R. MAGINI (Atti 22. Accad. Limei 1911 [v] 20 i 30-37. Compare Abstr. 1910 ii 932).- The author's measurements of the surface-tension of water by the method of maximum pressure of small bubbles show that the surface- tension when the water is first brought into contact with air is 73.692 dynes per cm.at 1 8 O whilst after complete aeration it has decreased to 73.065 dynes per cm. at which value it remains constant ; the difference exceeds the limit of experimental error of the method This water of const.ani; surface-tension serves as a control of the accuracy of the experimental method. Equimoleculnr solutions of maleic and fumaric acids affect equally the surface-tension of ethyl alcohol (95%). The surface-tension of absolute ethyl alcohol is 23.33 dynes per cm at 1 5 O and is a linear function of the temperature down to the m. p. R. V. S. Measurements of Surface-Tension Observations on the Surface-Tension of Liquid Sulphur. W. A. DOUGLAS RUDGE (Proc.Canzb. Phil. Xoc. 1911 16 [i] 55-63).-Measurements of the angle of contact between glass and drops of liquid sulphur have been made a t different temperatures. The angle of contact changes when the temperature reaches 1 8 5 O and again a t 256' the observed angles at 130° 190° and 260' being 60° 43.4' and 26.6'. From the rise of the liquid in a capillary tube a t 133' the surface- tension was found to be 11.56 dynes per cm. At higher temperatures the capillary behaviour is somewhat anomalous but there appears to be no sudden change at the temperatures at which the angle of contact of the liquid drops exhibits variations. Adhesiveness. MAURICE HANBIOT (Compt. rend. 19 11 152 369-372. Compare this vol. ii 118).-When two plates of brown gold are heated below the temperature at which they rapidly pass into ordinary gold and then brought into contact strong adhesion takes place between them.The pheiiomenon is not due to electric or magnetic action and it appears to be possible for it to occur only during the actual transformttion of one variety of gold into the other. Adsorption from Solution. ROBERT MARC (Zeitsch. physikal. Chern. 1911 76 58-66).-Remarks on the recent paper on this H. M. D. w. 0. w.GENERAL AND PHYSICAL CHEMISTRY. ii. 259 subject by Schmidt (Rbstr. 1910 ii 1041). The author agrees with Schmidt thnt there is an upper limit of adsorption but points out that the greater part of the experimental curve obtained by Schmidt is represented at least as well by the usual logarithmic adsorption formula as by that of Bchmidt whereas the latter is quite inapplicable for slight adsorption.It is suggested that the adsorption curve obtained by plotting amounts adsorbed as ordinates against concentra- tions as abscisss is discontinuous ; above a certain coricentrntion i t becomes practically horizontal and can thoref ore riot be represented The Adsorption of Sugar in Aqueous Solution. GEORG W~KGNEE and FRERIK BUI~MEISTE~~ (Zeitsch. Chem. Iml. Kolloitle 191 1 8 126-1 35).-Experirueiital data are recorded which show that sucrose and lactose are removed from aquoous solutions of different concentrations by animal charcoal in accordance with an expoueiitial adsorption formula. The magnitude of the adsorption is approximately t.he same for the two sugars. The adsorption is probably due to a reduction of the surface-tension at the surface of contact between the aharcoal and the solution and although the sugars increase the surface-tension of water at the air contact surface this is not the case for other contact surfaces as is shown by reference to data for the surface-tension of solutions in contact with mercury.Lactose is also absorbed by animal charcoal from milk but to a smaller extent than from pure aqueous solutions. This is attributed to the emulsoid character of milk which brings other surface contact factors into play. Solid Solutions in the Dissociation Oxides. LOTHAR WOHLEE (Zeitsch. EZektvochem. 191 1 17 98-103).-The author maintains that the changes in the dissociation pressure of an oxide at constant temperature are due to the formation of solid solutions and not as Allmand (Trans. 1910 97 618) has supposed to changes in the size of the molecules.T. E. Methods of Investigation of Capillary Chemical Problems. P. P. VON WEIMARN (Zeitsch. Chem. hut. Kohide 2911 8 133-138). -Polemical against Yawloff ,(Abstr. 1910 ii 1043). The author maintains the correctness of his views relative to the nature of the surface layers of crystalline substances and points out that these are in agreement with all experimental observations. Capillary Analysis of Colloidal Solutions. FRITZ F~CHTEE and NAIMA SAHLBOM (Chein. Zentr. 1910 ii 1088-1089 ; from Vtrh. Nccturf. Ges. in Basel 1910 21 1-24).-Most of the results have been published previously (compare this vol. ii 100). The positive colloids which have been found to be precipitated i n the capillary rise of solu- tions through strips of unsized paper are ferric chromic aluminium ceric cupric and ruthenic oxides and zirconium and thorium dioxides.The phenomenon varies with the kind of paper used and in the case of thin sheets it is only observable if evaporation of the water is prevented. The following negative colloids are not precipitated by a single formula. G. s. H. M. D. H. M. D.ii. 260 ABSTRACTS OF CHEMICAL PAPEKS. Prussian-blue cupric ferrozyanide uranyl ferrocyanide arsenic trisulphide antimony trisulphide selenium g.dd silver and vanadic acid. The potential difference which causes precipitation of the positive colloids has been measured for ferric oxide solutions and found to diminish as the concentration diminishes.The potential difference calculated from measurements of the limiting diameter of glass tubes which show the precipitation effect is in moderate agreement with the observed values. The capillary precipitation phenomena may be utilised for testing the progress of dialysis for comparing different kinds of ptip.r and for the investigation of the degree of hydrolysis of salt solutions. H. 31. D. Mixtures of Acetic Acid with Normal Liquids. L GAY (Cornpt. Tend. 1911 152 518-519. Compare Abstr. 1910 ii 935 1043)-The concliision previously arrived at on tlheoretical grounds t h a t for two fluid phases in osmotic equilibrium with a common constituent a t infinite dilution the variations in volume should be equal at the same temperature and pressure has now been experi-‘- mentally verified for mixtures of acetic acid with toluene ethylene dibromide and propylene dibromide.On the other hand mixtures of acetic acid with chloro- and bromo-benzene ethylene dichloride aud ethyl nitrate show an increase in volume smaller than t h a t observed on making the preceding mixttures. Acetic acid and ether show marked contraction on mixing. w. 0. TV. Diffusion [of Dissolved Substances]. RARTOLO L. VANZETTI (Il7u0vo Cim. 1910 [v! 20 ii 442-444).-Polemical. A reply to the criticism;3 of Scarpa (Abstr. 1910 ii 1044). Factors of import- ance in the author’s experiments are not allowed for by the foruiu18 used by Scarpa. The observed deviations cannot be due solely to false equilibrium because that does not explain the behaviour of the lithium and sodium salts and the fact that the deviations do not accord with theoretical expectations does not necessarily invalidate the author’s met hod.R. ’V. S. A New Didysor. RICHARD ZSIGMONDY and It. HEYER (ZeilscA. Chent. Ind. Kolloide 1911 8 123-126).-A new form of dialysor is described in which the dialysing membrane consisting of a thin sheet of collodion forms the ceiling of a shallow compartment into which water enters at the centre and is made to flow rapidly towards the circumference. The flow of water i3 maintained by the aid of strips of blotting paper which are supported a t the periphery of each radial section. With tbis apparatus it was found that the solution prepared by mixing 200 C.C. of water glass and 40 C.C. of concentrated hydro- chloric acid was practically free from chlorine after dialysis had proceeded for twenty hours.Comparative experiments in which the 6 ‘ star ” dialysor was filled with a collodion and a parchment membrane showed that the former acts much more rapidly than the latter. H. M. D.GENERAL AND 1’11 Y S 1 CA L C EI EM ISTR Y. ii. 261 Solubility Studies. WALTER HERZ (Zeitsclh. ccnon~. Chem. 191 1 70 70-72. Compare Abstr. 1910 ii 192)-The solubility of succinic acid in water is lessened by the addition of hydrogen chloride or bromide the effect being greater than that produced by alkali salts with the exception of lichium chloride. The two halogen acids are equal in their influence. The solubility of boric acid in water is increased to an equal extent by tartaric and racemic acids.C. H. D. P j e u d o - s o l u t i o n s or Apparant S o l u t i o n s According to Francesco Selmi. ICILIO GUARESCHI (Zeitsch. Chem. Itid. Kolloicle 191 1 8 113-123).-Quotations are given from various papers pnblished by F. Selnrii which show that this author was probably the first to recognise the special cliaracteristics of colloidal solutions and already in 1846-1847 applied the term pseudo-solutions to those solutions which are now distinguished as colloidal disperse systems. El. 11. I). The “Precipitation Coefficient” of P. P. von Weimarn. P. N. PAWLOFF (Zeitscli. Chem. Ind. Kolloide 1911 8 138-141 ; J Buss. Pliyls. Chem. Xoc. l910,42,1650).-According to von Weimarri the size of the particles of a precipitated substance is determined by a coefficient N - P / L where F IS the rate of formation of the cry~t:tlline substance and L the conceLtration of the solution from which pre- cipitation takes place.This conception of a precipitation coefficient is criticised and a simpler method of deducing the connexion between the degree of dispersity of a precipitate and the properties of the mother solution is indicated. According to this view the degree of clispersity of a precipitate a t a given temperature is determined by ( 1 ) the free energy at the surface of contact with the solution (2) the molecular weight of the dissolved substance (3) the concentration of the solution in contact with the actual precipitate and (4) the concentratioJ of the solution in contact with the macro-crystalline substance.H. AX. D. The “ Precipitation Cmfficient.” P. P. VON WEIMARN (Zeitsclb. Chent. Ind. Kolloicle 1911 8 141-143).-A reply to Pawloff (com- pare preceding abstract) in which the outlines of the author’s views are again brought forward. H. M. D. Mechanical Stimulus to Crystallisation in Supercooled Liquids. STEWART W. YOUNG (J. Amer. Che,m. Soc. 1011,33,148-162). -Ostw~tld has stated that when a liquid is cooled below its m. p. it remains through a certain range of temperature in the metastable state in which it cannot crystalliae spontaneously even under the influence of stirring but that as the supercooliag is increased the substance passes out of the metastable into the labile state in which the con- ditions are entirely changed and crystallisation must occur spon- taneoasly sooner or later.Numerous attempts have been made to determine the temperature a t which a given substance pnsses-from the rneta,table into the labile condition but without much success. Deii. 262 ABSTRACTS OF CHEMICAL PAPERS. Coppet (Abstr. 1901 ii 384) made a study of the spontaneous crystallisation of sodium sulphate and other substances as a result of which he was led to the conclusion that a definite metastable limit does not exist but that the transition from the metastable to the labile condition is very gradual. In a. series of cryoscopic experiments with water with the ordinary Beckmann apparatus it was found that much less supercooling was possible when a platinum or copper stirrer was employed than when a glass one was used.The simplest explanation of this seemed to be that crystallisation was promoted by the friction between the stirrer and the thermometer and that this varied with different stirrers. Experiments were next mado in which friction was generated between a movable rod and a fixed ring the liquid being stirred meanwhile by means of bubbles of pure hydrogen. Both rod and ring were made of various substances and the results showed that the effect of the friction was greater between rough than between smooth surfaces. I n another series of experiments friction was produced by the rotation of a rod with a conical tip which moved in a similarly formed conical bearing and the conclusion was reached that the factor which stimulated crystallisation was not pure friction but consisted of a succession of small impacts between points on the surfaces.Experiments were therefore carried out in which an apparatus on the principls of a stamp mill w a s employed which was worked by means of a small motor. The stamp consisted of a steel rod which carried a bit at the end and was allowed to drop through a guide and strike upon an anvil on which was cemented a flat disk. Both bit and disk could be changed in order to permit of experiments being made with any desired materials. Measurements mere made with water benzene arid a concentrated solution of calcium chloride hexahydrate and the relations between the number of degrees of supercooling and the impact values are shown by means of curves. The results show that it is no longer justifiable to assume the existence of a metastable limit since the whole unstable field is labile and crystallisation may be brought about in any portion of it by the production of sufficient mechanical shock.Interesting results were obtained with a solution of sodium sulphate this being a case in which the supercooled liquid can yield more than one phase. E. G. Habit of Crystals of Artiflcial Barytes. HILDA GERHART (I’sch. Jfin. Mitt. 1910 29 185-191).-The experiments were made with the idea of determining the influence of various salts in solution on the habit of the resulting crystals (compare Abstr. 1910 ii 276). The salts employed were barium chloride and one or other of the sulphates of iron sodium magnesium or ammonium or potash-alum either alone or with the addition of potassium nitrate.An excess of one salt (in some experiments the chloride and in others the sulphate) was placed in the solid form a t the bottom of a reagent-glass and covered with a thick layer of silica jelly; a solution of the other salt was placed over the separating layer and the whole kept a t an equableGENERAL AND PHYSICAL CHEMISTRY. ii. 263 temperature for some months. Crystals of barytes measuring LIP to 0.1 mm. across were formed mostly in the upper portion of t h e silica jelly ; these have the form of plates u(lOO) with irregular outlinee or of boat-shaped forms flattened parallel to b(010). The greatest influence in tho form of the crystals is produced by the presence of potash-alum arid potassium nitrate. The presence of sodium sulphate favours the growth of skeletal forms.L. J. S. Crystallisation Dissolution and Regeneration Poly- hedra of Potassium- and Ammonium- aluminium Alums in Aqueous Solutions containing Hydrochloric and Nitric Acid. ZYGMUNT WEYBERG (Chem. Zentr. 1910 ii 1036 ; from f!!os~/ws 19 10 35 Rccclzisxewski Yestlrmd 487-494).-SmalI quantities of hydrochloric acid have no influence on the crystalline form of t h e alums. When the acid concentration amounts to 6 grams per 100 prams of water the surfaces (211) and (201) appear on the crystals. With increasing concentration the surfaces ( 2 11) and (110) disdppear and (201) becomes more developed. In solutions which contaiu more than 25 grams of acid per litre crystals are formed which exhibit tho surfaces (loo) ( l l l ) and (311).Similar observations relating to the dissolution and regeneration of crystals indicate that in all cases the same modifications of the exposed form are determined by a given concentration of hydrochloric acid. Nitric acid has a similar action but more concentrated solutions are required to produce the same effects H. %I. D. Confirmations of the New Theory of the Phenomenon of Allotropy ANDREAS SMITS and H. L. DE LEEUW (Proc. li Aknd. FVetensch. Anzsterdam I91 1 13 822-829).-Observations relating to diiferences in the behavour of white phosphorus at its melting point are interpreted in terms of the theory that the liquid and solid consist of allotropic forms which are in dynamic equilibrium (compare Abstr. 1910 ii 195 400). A method of purifying white phosphorus is described in which the element ifi distilled and subjected to a series of fractional crystallisation processes in a highly exhausted apparatus.By this means a perfectly colourlesa coarsely crystalline product is obtained which on immersion of tho melting-point vessel i n a thermostat the temperature of which varied slowly was found to melt a t 44.0" within a range of 0*02O. This is regarded as the unary melting point. When the pure phosphorus is maintained in the liquid condition for some time the unary temperature is no longer found on solidification. The actual behaviour depends on the heat treatment and on the rate of cooling and the cooling and heating curves which have been obtained for white phosphorus under different conditions are considered to indicate a partinl conversion of white phosphorus into a n allotropic modification.11 M. D. Condensed Disperse Systems. P. N. PAWLOFF (J. Russ. Yhys. Chm. Soc. 1910 42 1631-1 649) -A mathematical paper in which the author deals with surface energy the degree of dispersion of theii. 864 ABSTRACTS OF CHEMICAL PAPERS. phase in the condition of most stable equilibrium formation of disperse precipitates i n solutions the equilibrium of the system drops + vapour nionotropic and enantiotropic substances position of the stable region of highly disperse crystalline condition among substances in other states and the surface energy of crystalline substances. The Deterinination of Three-Phase Pressures in the System Hydrogen Sulphide and Water. F. E. C. SCIZEFFEI~ ( PY-oc.II. Akad. Iveetensch. Amsterdccm 19 1 1 13 829-837).-Pressure measiirements at different temperatures have been made for the three-phase systems (SLV) (SL'V) and (LL'Y) where Xrepresents a solid compound L and L' liquid phases and V the coexisting vapour. The data show the exist- ence of a quadruple point at 29.5' and 22.1 atmosptieres. A comparison of the pressure-temperature curves for the systems (SLY) and (LL'V) with that representing the vapour pressure of pure hydrogen sulphicle The Equilibrium between Nitric Acid Nitrous Acid and Nitric Oxide. GILBERT N. LEWIS and ARTHUB KDGAR (J. An2er. Chem. Soc. 1911 33 292-299).-The results obtained by Saposchnikoff (Abstr. 1902 ii 16) for the equilibrium constants in the reaction 3HN0 = HXO + 2N0 + K,O and with acid concantra- tions ranging from 0-03rtT to 3*ON not being entirely concordant the authors have re-investigated the matter. The method ercployed consisted i n passing a stream of nitric oxide through a tenth-normal solutioa of nitric acid at 25' in a vessel which permits the measurement of the electrical conductivity of t,he solution.The conductivity is measured from time t o time until i t attains a constant value. Since t h e conductivity of the nitrous acid produced is almost negligible in the presence of the nitric acid and can readily be allowed for the change in conductivity is very nearly proportional t o the amount of nitric acid decomposed. The reactim is complete after about fifty hours and in five different experiments very concordant results were obtained.The value of the constant Ar=(HN0,)3/(H')(N0,') is found to be 0.0267 at 25". The value obtained by Saposchnikoff starting with nitric acid of the same concentration was 0.0175. IF however his results are re-calculated using the same value for t h e degree of dissociation of the nitric acid as that used by the authors the value becomes 0.020s. Some experiments made with 0-2N-nitric acid seem t o indicate a change in the equilibrium constant with the concentration. T. H. P. indicates t h a t they are nearly identical. 13. 11. I>. T. S. Y. A New Method for the Analysis of Some Binary Com- pounds Based on the Law of Mass Action. OTTO RUFF (Ber. 191 1 44 54S).-A claim of priority over Ostromissleneky (this vol. Chemical Formula3 of Certain Eutectics and Transition Points.ALEX. GORBOFF (J. Buss. Phys. Chern. XOC. ,1910 42 1517-1529).-The author applies the views previously expressed ii 195). c. s.GENERAL AND PHYSICAL CHEMISTRY. ii. 265 (Abstr. 1910 ii 111) to the data published for a large number of eutectic mixtures by various authors and derives formulae for the compounds which the Components of the eutectics form with one another. For the details of his conclusions the original must be consulted. T. H. P. Application of the Phase Rule to Stereoisomeric Com- pounds and the Recognition of Racemic Compounds ALBERT LADENBURG (Ber. 1911 44 676-680. Compare Abstr. 1310 i 696 769 also Roozeboom Abstr. 1899 ii 733).-To determine whether a given substance is a racemic or an inactive mixture a saturated solution is prepared which is optically inactive and a small quantity of one of the optically actire components is then added.If a mixture is present the solution remains inactive but if the racemic compound is present the solution becomes optically active (compare Laderib urg Trans. 1899 75 465; Abstr. 1899 ii 551). The phase rule only applies to stereoisomerides in the case of liquids if the various forms are taken as representing one component. Measurements of the vapour pressure and refractive index of various mixtuies of racemic and d-pipecoline show for liquids how closely the properties of the racemate approximate to those of its components. There is no doubt that liquid racemates exist. E. F. A. Velocity of Crystallisation and Dissolutiou. CARL L. WAGNER (ZeitsciL. Hektrochem.191 1 17 125-134) ; EOEERT MARC ( d i d . 134-139).-Wagner thinks that RIarc’s experimental results are not sufficiently accurate to decide whether the rate of crystallisation is of the first or second order. Marc replies t h a t iE the whole of the results are taken into accourit there can be no doubt that his interpretation of them ia correct (Abstr. 1910 ii 834; also 1908 ii 160; 1909 ii 798 983). T. E. Velocities of Reactions in Gss-Liquid Systems. J. BOSELLI (Compt. rend. 19 11 152 374-375 60%- 603. CompItre this vol. ii 196).-Experirnents on the rate of dissolution of oxygen and carbon monoxide have been made and the results found to confirm the conclusions arrived at in a previous paper. Two classes of reaction have also been‘ studied. Of the first the oxidation of and fixation of carbon inonoxide by hzmoglobin or the oxidation of potassiumpyro- gnllol and of ferrous oxalate may be taken as examples. The velocity of reaction in such cases is practically independent of the volume of liquid but varies considerably with the rate of agitation.The oxidation of dextrose in alkaline solution and of ferrous sulphate with and without a catalyst have been examined as instances of the second class of reaction. I n this group the velocities are proportional to the volume of liquid and independent of the speed of agitation. The rate of absorption of oxygen by hemoglobin is the same for warm-blooded vertebrates whether the substance is present in blood suspended as corpuscles in physiological salt solution or dissolved in water.It is independent of the reaction of the mediuui and is practically uninfluenced by temperature. The speed increases lessii. 266 ABSTRACTS OF CHEMICAT PAPERS. rapidly than the pressure of oxygen above the liquid and is proportional to the square-root of the rate of agitation. The same remarks apply t o the oxidation of pyrogallol and ferrous oxalate. The velocity of reaction between ferrous sulphate solutions and oxygen follows A rrhenius' law. Copper salts act as positive catalysts dextrose and sulplruric acid as negative ones The rate of oxidation of dextrose in alkaline solution is approximately proportional to the cube-root of the concentration of alkali ; ferric potassium tartrate acts as an accelernt iog catalyst up t o a certain concentration.w. 0. w. Velocity of Decomposition of Dissolved Dithionic Acid. JOSEPH A. MULLER (BulZ. Soc. chiin. 1911 [iv] 9 183-185).-ITt has been shown previously (Abstr. 1910 ii 154) that iodine acts slowly on sodium dithionate in prewnce of acid in accordance with the equation NaaSdOG + I2 + 2H,O = 2NaHS0 + 2HI. Investigation of this reaction shows that i t is nnimolecular in type whence it must he supposed that three successive reactions occur (a) liberation of dithionic acid ( b ) decomposition of the latter into sulphurous and sulyhuric acids ( c ) action of iodine on sulphurous acid. The time required for reactions ( a ) and ( c ) is negligible in coiiipsrison with that required for ( b ) so t h a t the velocity of ( b ) only is measured. A t 51.3' the constant of velocity of decompositiou of dithionic acid is 0.00836 under the conditions of these experiments. T.A. IT. Catalysis in a Homogeneous System. JOSEPH A. MULLER (Bull. Xoc. chirn. 1911 [ivJ 9 185-188). -Investigation of the influence of (u) change of temperature and ( b ) concentration of acid on the velocity of decomposition of dithionic acid by iodine (compare preceding ilbstract) shows that the velocity of decomposition increases (1) with increasing concentration of acid and (2) with rise of tempera- ture Further investigatioii of the states of ionisation of acid solutions of the same strengths and at the same temperatures as those used i n these experiments shows that there is no relationship between the concentration of hydrogen or chlorine ions and the velocity of decomposition. The conclusion is drawn therefore tJhnt t h e decomposition is due to the action of the non-ionised acid.Tho valiie of k as a function of the absolute temperature of the system is approximately given by the equation Ic = ~ ( a ~ y ' - l)/(hT- l) where n = 4.6 x lo-? a = 1.0023 b = 1.1458. T. A. U. Kinetics of the Transfarmation of Chloroalkylamines into Heterocyclic Compounds. HERBERT FREU~ DLI CH and A. KRESTOV- NIKOFF (Zeitsch. physikal. Chem. 191 1 '76 79-104).-The rate of transformation of 8-chlorobutylamine into pyrrolidine hydrochloride Cl.[CH,],*NH -+ C,NHS,HCI and of c-chloroamylamine into the isomeric piperidine hydrochloride Cl*[CH,],*NH -+ C,NH,,.fICI has been investigated the change being followed by titratiug the ionised chlorine with silver nitrate. The reactions proceed quanti ta- tively according t o the above equations in alkaline solution.I n acid or neutral solution 110 change occurs.GENERAL AND PHYSICAL CHEMISTRY. ii. 267 With excess of alkali the reactions are unimolecular and are only very slightly accelerated by greatly increasing the alkali concentra- tion. If t o E-chloramylamine hydrochloride an equivalent of alkali is added the reaction proceeds as if only the non-ionised amine is under- going change the hydrochloric acid distributing itself between amine and piperidine according t o the law of mass action. The Flower change when ammonia is used instead of alkali can be interpreted on the same lines. Neutral salts increase the rate of reaction somewhat ; alcohol retards it.The temperature-coefficient for 10" between 0' and 10" is 3.9 for the amylamine 3.6 for the butylarnine. The rate of ring formation is about seventy times faster for the butyla,mine than for tbe amylamine a result in accordance with Baeyer's tension theory . The general question of the transformation of labile bases iiito their isomerides is considered and i t is shown that when the base in question is strong ttie OH'-ion concentration of the base added should have a considerable influence and the reaction must be bimolecular whilst for weak bases the OH'-ion concentration should have compara- tively little influence and the reaction must therefore bo unimolecular. This is in entire accord with the results of previous observers who have used strong bases and of the present investigation as the amines in question are weak bases.The dissociation constant of c-chloro- amylamine a t 0' is about 3*10-4. G. S. The Dsvelopnlent of the Atomic Theory. 11. The Various Accounts of the Origin of Dalton's Theory. 111. Newton's Theory and its Influence in the Eighteenth Century. ANDREW N. MELDHUM (Mern. Manchester Phil. Soc. 1911 55 No. 111 1-12 ; No. .ZV 1-1 5).-Historical. Practical Method for Preparing Semi-permeable Membranes Applicable to the Determination of Molecular Weights. EUG~NE FOUARD (Comnpt. rend. 191 1 152 519-521).-A collodion cell prepared according t o the method of Roux and Salimbeni is filled with a solution of tannic acid and immersed in a gelatin solution. After this treatment it is impermeable to dissolved molecules but remains pervious t o water. To avoid distension of the fragile membrane under pressure it is deposited on a cylinder of metallic gauze terminating in metal sockets one of which is fitted with a stopper and manometer.Such a cell is superior t o de Vries' apparatus and may be used t o determine rnolecular weights by comparison of isotonic solutions. The pressure indicated by the manometer with non-isotonic solutions is always lower than the calculated va,lue van't Hoff's constant for substances of known molecular weight being about 20% less than the theoretical number. w. 0. w. Universal Chemical Language. WILIZELN Osi WALD (Zeilsch,. physikal. Chenz. 191 1 76 1-2O).-The author makes suggestions for the translation of chemical literature into the universal language Jdo a modified form of Esperanto. The most suitable equivalents in Idoii.268 ABSTRACTS O F CHEMICAL PAPERS. for the names of the elements and of inorganic and organic compounds arc discussed i n detail. G. S. Modified Boltwood Pump. ALLAN F. ODELL (J. Amer. Chem. Xoc. 1911 33 56)-A diagram is given of a modification of Boltwood's automatic Sprengel pump (Abstr. 1897 ii 205) which is just as efficient as the larger forms although occupying only one- third of the space and requiring only LOO graus of mercury for successful moiking. In t h e nianufactiired forms of the Boltwood pump tbe internal diameter cf the dropping tube often deviates considerably from thz-tt prescribed (2.5 mm.). It has been observed that low vacua cannot be obtained with tubes slightly wider tlian 2.5 mm.whilst tubes of smaller diameter than 2 mm. work very slowly. E. G. New Gas W a s h - b o t t l e s . FRITZ FRIEDRICHS (ZeitsclL. unal. Chenz. 191 1 50 175-176).-The gas inlet tube of the apparatus is expanded into a screw-like form nearly touching the sides of the cylindrical containing vessel so that there is formed a spiral channel about 125 cm. long through which the gas bubbles bave t o pass. Four diiferent forms of this wash-bottle are described and figured. L. DE K. Simple Device for Use in F i t t i n g Up a Series of Absorption Flasks etc. HANS RECKLEBEN (Chem. Zed. 191 1 35 279).-Tho device consists of a wooden lath or rod and a number of short lengths of wire; the absorption flasks wash-bottles or U-tubes used for purifying gases are bound to the lath by means of the wires a couple of turns cf the mire being sufficient for the purpose.The lath may be fixed in a clamp-stand so t h a t the series of fiilsks etc. attached to w. P. s. it can be arranged at any desired height. The Efflciency of Calcium Bromide Z i n c Bromide and Zinc Cbloride a s Drying Agents. GREGORY P. E A X T E R ~ ~ ~ R. D. WARREN (J. Arner. Cltesri. h'oc. 191 1 33 340-344).-Since hydrogen chloride cannot be dried with phosphoric oxide owiog to the formation of volatile phosphorus compounds i t is probable t h a t this will also be t h e case with hydrogen bromide. It is therefore necessary t o investigate the action of various anhydrous bromides as drying agents. The method used was as follows A measured amount of moist a i r was passed through a tube containing a layer of crushed fused bromide and then through a weighed phosphoric oxide tube.From the gain in weight of the latter and known volume of air passed over the bromide the pressure of the aqueous vapour in the a i r which was in equilibrium with the fused bromide could be determined. Similar experiments were made with zinc chloride in order to com- pare i t with sulphuric acid and calcium chloride as a drying agent for hydrogen chloride. As shown in the following tablep the first hydrate of ziuc bromide has an aqueous vapour pressure six times as great as that of calcium bromide a t the ordinary temperature so t h a t calcium bromide is a muchGENERAL AND PHYSICAL CHEMISTRY. ii. 269 better drying agent than zinc bromide.Zinc chloride is less well suited for drying hydrogen chloride than sulphuric acid but more so than calcium chloride. Vapour pressures in mm. of mercury of the lawer hydrates of CaBr,. .............. 0 -09 0.18 0'19 ZnBr ............ 0.28 1-16 6-34 0". 25". 50". ZnC1 ............ - 0.86 2-19 The weights in grams of residual water in one litre of gas dried a t 2 5 O by these salts and by cslciuta chloride and sulphuric acid a r e calcium bromide 0.0002 ; zinc bromide 0.001 1 ; zinc chloride 0 0008 ; calcium chloride 0.002 1 ; sulphuric acid 0*000003. VLADIMIR STAN~K (Zeitsch. Zuchrind. Bohrn 192 1,35,311-315).-The substance to be dehydrated which should be insoluble in ether is spread in as fine a state of division as possible on a gauze sheet which is immersed in ether in a large closed vessel with a capacity of 2-3 litres.The gauze rests on a wire basket filled with sticks of sodium hydroxide which is supported by a porcelain dish resting on the bottom of the vessel. The ether dissolves water from the substance becoming denser thereby and sinking so that it comes in contact with the sodium hydroxide and is dehydrated again Circulation is continuous and as the sodium hydroxide dissolves the lye falls to the bottom of the vessel; 52 grams of mashed beet containing 78% of water were dehydrated by this means in twenty-four to thirty-six hours When the substance is partly soluble in ether it is preferable to use an apparatus in which ether distilled from a flask is condensed rises through sticks of sodium hydroxide to dehydrate it and then flows down over the substance back to the distillation flask. T. S. P. Dehydration of Substances by means of Ether. E. F. A. Good Substitute for the Platinum Triangle. RAYMOND C. BENNER (J. Amer. Chem. Xoc. 1911 33 189-190).-Wire composed of an alloy of nickel and chromium is recommended as a substitute for platinum for making triangles. The alloy is specially adApted for the purpose owing to its resistance to oxidation at high temperatures and to its being unaffected by the ordinary fumes of the laboratory Platinum crucibles placed on such triangles were ignited side by side with others on platinum or pipe-clay triangles and all the crucibles showed the same loss of weight. M. EUMAWUEL POZZI-ESCOT (Bull. Asooc. chim. Sucr. Uist. 191 1 28 501-502).-A small mu& furnace made of sheet metal is supported on the tube of a single Bunsen burner. The arrangement gives temperatures up to 400° and is suitable for determining ash in plants e t a Lecture Experiment for Demonatrating Ghemiual Lpmia- escence. ARNOLD HECZRO (Chem. Zeit. 1911 35 199.)-A very distinct green luminescence is produced when moist air is allowed t o come in contact with a solution of qaagaesium phenyl bromide in anhydrous ether. The latter solution is most conveniently contained E. G. Laboratory Muffle Furnace. R. J. C. VOL. C. ii. 19ii. 270 ABSTRACTS OF CHEMICAL PAPERS. in a round-bottomed stoppered flask and the luminescence may be caused to appear by removing the stopper and breathing into the flask ; when the solution comes into contact with the moist side of the flask a green light is produced which fades away after a time. It may be reproduced by the introduction of a further quantity of moist air. Magnesium phenyl iodide exhibits a similar but less intense luminesceuce w. P. s. Lecture Apparatus. [Action of Acids on Pure and Impure Zinc.] FRITZ C'ASPARI (Chern. Zeit. 1911 35 183).-The apparatus described is intended for use in demonstrating the fact that dilute acids attack pure zinc but slightly if at all whilst zinc containing traces of other metals is readily attacked. It consists of a U-tube one limb of which is shorter than the other ; a tap is placed on the shorter limb a t about one-half its height and the whole tube except the portion above the tap is filled. with dilute sulphuric acid. A rod of pure zinc one end of which has been immersed in a solution of copper sulphate is placed in the shorter limb of the tube above the tap the end of the rod coated with copper- being uppermost. When the tap is opened slightly the acid comes into contact with the zinc but no evolution of hydrogen takes place until the acid rises sufficiently high to reach the end of the rod which is coated with copper; hydrogen is tben evolved rapidly. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9110005237

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

i. 249 Organic Chemistry. Action of Formaldehyde on Petroleum Distillates F o r m a - tion of Liquid Condeneation P r o d u c t s . ALEXANDER M. NASTUKOFF and K. L. MALJAROFF (J. Kuss. Phys. Chem. Joc. 1910,42 1596 -1 604). -On treating the fraction of ordinary kerosene of b. p 800-250° with its own volume of formalin and 0-75 time i t s volume of sulphuric acid the authors obtained in addition to solid condensation products also liquid condensation products of b. p. above 250". These products amounting t o 19% of the weight of the kerosene have very high formolite numbers (compare Abstr. 1904 i 801). The fraction of the liquid products b. p. 186-188O/50 mni. has the formula C15H25 the formolite number 105 Df:?; 0.8498 and ng 1.4703 ; its viscosity is 2.07 compared with that of t h e original kerosene fraction as unity or i n Engler degrees 6.57 a t 31'.The reaction of formation of these liquid products is regarded as a union of the methylene group of the formaldehyde with the -C:C- group of the original naphthene or olefine the instability of the trirnethylene ring thus formed leading t o the re-formlttion of a double linking. thus V I ~ -CH -E Me -sH -+ -bH>CHZ -+ -CH -CH The solid condensation products mentioned above are soliible in benzene toluene etc. and are termed soluble formolites. Methylisopropylethylene [a-Methyl-As-amylene]. A. GoiisIrr (J. Buss. Phys. Chena. SOC. 1910 42 1356-1 358).-Sy converting methylisobutylcarbinol obtained by the action of acetaldehyde ou magnesium isobutyl chloride into the corresponding iodide or chloride and treating the latter with alcoholic alkali hydroxide the author obtains an hexene C6H12 b.p. 57-58.5O/760 mm. D$ 0.6i06 rLg 1.3883. IF however t h e methylisobutylcarbinol is prepared by reducing mesityl oxide in aqueous ether by means of sodium the hexene has the constants b. p.57-59"/740 mm. Dy 0.6703 Y L ~ 1.3884. This hydrocarbon which gives isobutyric acid on oxidation and is probably 6-me thyl-Ab-amylene is accompanied by a small proportion of T. H. P. another possibly 6-methyl-Aa-amylene. T. I€. I?. Action of Hypochlorous Acid on Ethylene Hydrocarbone. [Mlle] A. UMNOVA (J. Kuss. I'hys. Chem. Soc. 19 LO 42 1530-1543). -The action of hypochlorous acid on PG-dimethyl - As - amyleoe yields (1) y-ch~o~o-~6-cl~metlr.?/l-a-a~nylr?ne i;H:,:CMe*CHCI*CHMe a colourless liquid b.p. 44-45O/30 mm D 0.9229 DF 0.9083. The corresponding alcohol PG-dimethy C-Aa-penten- y-02 CH,:CMe*CH(OH) CHMe is a viscous liquid b. p. 77-79'/21 mm. 154-156'/0rdinary pressure Dg 0.8599 Di0 0.8427 giving a n c~cetyl derivative CyHl,O b. p. 169-171". On heating with 0.5% sulphuric acid solution the VOL. c. i . ti. 250 ABSTRACTS OF CHEMICAL PAPERS. alcohol in converted into diisopropyl ketone. (2) The chlorohydvirt OH-CMe,*CHCl*CI'IMe which was not obtained pure and is apparently formed as an intermediate product. These results are analogous to those obtained by Lmoff (J. Buss. Phys. Cheva. Soc. 1881 16 469) Scheschukoff (Abstr. 1884 1276; 1885 645) and Kondakoff (Abstr. 1886 136) by treating various unsaturated hydrocarbons with gaseous chlorine.y-Chloro-/38-dimethyl-A~-amylene is also obtained by the action of chlorine on /.36-dimethyl-Ap-amylene. The action of hypochlorous acid on E-J88-trimet8hyl-A~-amylene yields (1) y-chloro-P66-ti.imsthyl-a.-a,,lylene CH,:CMe*CHCl*CMe b. . p. 53-54O/20 mm. D 0.9199 Di0 0.9042 n'$ 1.4473. The correspondiug alcohol CH,:CMe*CH(OH)*CMe,(?) b. p. 75-'77"/12 mm. 173-175°/ ordinary pressure D! 0.8685 Di0 0.8556 forms an cccetyl derivative CloHls02 b. p. 187-188' 83-85/20 mm. This alcohol could not be converted into the isomeric ketone by means of dilute sulphuric acid bo that its structure is somewhat uncertain. (2) Possibly a chlofo- hydrin which could not be isolated. y-Chloro-jj'88-trimethyl-Aa-amylene is slso obtained by the action of chlorine on p88-trioiethyl-A~-arnylene. 6-lodo-P-rnet?byZpentane C 13 Mel*CH,*CHRle prepared by the action of hydrogen iodide on methylisobutjlcarbinol has b.p. 75-77'/60 mtn. D 1,4412 D,2' 1.4201. 6-Methyl-AS-amylene CHRle:CH*CHMe obtained by the action of alcoholic potassium hydroxide on the pseceding compound has b. p. The action of hypochlorous acid on 6-methyl-Ab-amylene yields the chlorohydrin,OH*CHMe*CHCl*CHMe which was not isolated in a pure state but was converted by distilling with potassium hydroxide into a colourless liquid b. p. 99-100". 0 the oxide CHMe,*CI3< 1 CHMe' The corresponding P-melhylpentane-y6-diol has ni p. 48-49' b. p. 194-106". Course of the Intramolecular Transformations of Alkyl Bromides and the Question of the Cause of Equilibrium in Reversible Reactions.ARTHUR MICirAEL and HANS LEUPOLD (Annalen 191 1 379 263-333. Compare Faworsky Abstr. 1907 i 741).-The vapour densities of isobutyl bromide and tert.-butyl bromide have been determined by Blackman's and by V. Meyer's method. 'l'he results by both methods prove that at 184' only 3% of the isobutyl derivative but about 50% of the tertiary compound is dissociated. Using the Blackman apparatus the volume of vapour of tlie tertiary compound agreed with the normal vapour density during the first minute but gradually increased during half an hour owing to slow dissociation. The authors confirm Meyer and Pond's conclusion (Abstr. 1885 1033; compare Konowaloff ibid. 1886 9) that the dissociation is not aifected by the nature of the walls of the glass vessel or by tlie introduction of asbestos sand or powdered glass.When mercury is present a small aniount of a white solid probably mercuric bromide is formed i n the case of tho tertiary couipound but the 58-59' Ug 0.6874 DF 0.6695. CHMe,* CH (OH) *CH Me* OH T H. P.ORGANIC CHEMISTRY. i. 251 amount is so small that it does not affect the volume of vapour. An interesting observation was made during the determination of the vapour density of isobutyl bromide by Victor &%eyer's method. I n our experiment the stopper of the small Hofmann bottle stuck and the bromide was not vaporised until the liquid had been some minutes in the hot tube. The result indicated appreciable dis- sociation due t o the partial conversion of the iso- into the tert.-butyl bromide.Formation of the t e r t ary bromide cannot be detected after heating the isobromide at 80" fo three hundred hours or even after boiling (b. p. 91*2-91-5') for fifty hours. A t 92-95"? however in sealed tubes 3% is tranformed after thirty hours and at 110" the reaction proceeds fifteen times as quickly as at 92-95' The rato of trans- formation appears t o depend on the diameter of the tube in which the liquid compound is heated ; with narrow tubes the reaction proceeds much more slowly than with wider ones at all temperatures between 110 and 535". The velocity does not depend on the dimensions of the gaseous phase as stated by Eltekoff but on the size of the liquid surface. The reacti n proceeds much less readily when tcll the substance is in the form of vapour; for example when the isobutyl bromide is heated at 140' for fourteen hours in the form of vapour no appreciable amount of tertiary bromide is formed whereas after one hour a t the same temperature in the liquid form (diam.of tube 6 mm.) 55% of the tertiarycompound is formed. The equilibrium between the iso- and tert.-bromides is reached when 74% of tertiary compound is formed and this equilibrium holds for practically all temperatures between 140' and 262'. At the higher temperatures even a t SSS" decomposition occurs as proved by the darkening in colour arid the evolution of hydrogen bromide on opening the tubes but the amount of this decomposition does not appear to be appreciable (1% after two hours). The conversion of tert.-butyl bromide into the isobutyl bromide proceeds extremely slowly even after fourteen hours at 140' in the liquid condition the formation of the iso-compound could not be detected whereas the isobromide under similar conditions has reached the equilibrium point.The transformation of the tertiary compound begins at 184" and even after thirty-five hours only 7% is transformed into the iso-compound. At 2 3 5 O and 262" equilibriuni is attained after ten and two hours re3pectively and the equilibrium mixture has the same composition as when the isobromide is heated namely 74% of tertiary and 26% of isobromide. I n this reaction the liquid surface does not appear t o have any appreciable affect. The conversion of propyl into isopropyl bromide has been studied but as the temperatures required are much higher the results are not so favourable.The reaction begins at 184" and after one hour at 237' and 269" the amounts of isopropyl bromide are 17% and 20% respectively; as distinct signs of decomposition were observed attempts were not made t o determine the equilibrium point. The influence of the size of the liquid surface is observable but not marked and at 237O and 262' the transformation takes place more readily in the gaseous than in the liquid phase. This may be due to the partial decomposition of tihe propyl bromide (compare Aronstein Abstr. 1883 172). The $ 2i. 252 ABSTRACTS OF CHEMICAL PAPERS. transformation of isopropyl into propyl bromide takes place extremely slowly whether examined in the gaseous or liquid condition. The transformation of active amyl bromide into the tertiary com- pound takes place quickly at 184' and at this temperature is influenced to an appreciable extent by the dimensions of the liquid surface but at 237' the effect of this factor is not so marked. A t 1 8 4 O the velocity of transformation is much smaller with the vapour than with the liquid whereas at 237' and 262O the reverse is true.Transformation of inactive primary isoamyl bromide could not be detected at 262' and the investigation of Wichnegradsky's secondary isoamyl bromide (Awnaleti 1877 190 328) which is a mixture of secondary and tertiary bromide showed that the mixture is com- paratively stable as after ten hours at 184' only 6% of the secondary compound was transformed. Tertiary amyl bromide at 166' is fairly rapidly transformed into a mixture of secondary and primary active isoamyl bromides. The dimensions of the liquid surface have an appreciable effect and equilibrium appears to be attained when 12% of secondary and 7% of primary bromide are formed.The conclusion is drawn that dissociation does not play an important part in the transformations as many of these begin at temperatures a t which dissociation does not take place and in many cases the transformation proceeds more slowly in the vapour phase where dissociation is marked than in the liquid phase where the dissociation is less. The reactions are regarded as intramolecular changes and an attempt is made to explain the changes by reference t o Michael's entropy law to intramolecular neutralisation and to the relative afinities of the atoms.It is suggested that the influence of the liquid surface may be due to the fact that in the conversion of the liquid into vapoui. an inter- mediate state is formed which is extremely sensitive to energy changes. One of the most interesting points established is that the velocity of transformation of the butyl bromides is not in harmony with the dynamical views of equilibrium in the case of a balanced reaction. I n the case of iso- and tert.-butyl bromides equilibrium is reached at any temperature between 140' and 365' when 74% of tertiary and 26% of iso-bromide is present and hence the values of K and K' for the trans- formation of iso- into tertiary and tertiary into isobromide should be in the ratio 3 1 whereas the ratio is much greater.I t is shown t h a t Then a mixture of 74% tertiary and 26% isobutyl bromide is heated a t l l O o 140° or 237' no apparent change occurs in the liquid state but that at 337' in the state of vapour a diminution of tertiary bromide is noticed probably due t o decomposition. It is suggested that the equilibrium is static and not dynamic and t h a t it does not depend on the two velocity constants but merely on the relative amounts of the two bromides. Such a mixture may correspond with the maximum of entropy under the couditions of the experiment. Pull details are given for the preparation of the various alkyl bromides and methods have been worked out for estimating the amounts of the isomerides present in mixtures. teYt.-Eutyl bromideORGANIC CHEMISTRY.i. 253 can he estimated in the presence of the isobromide by shaking for fifteen minutes with fifty times its weight of water filtering and estimating the hydrobromic acid in the filtrate by means of standard silver nitrate and ammonium thiocyanate. A mixture of n- and iso- propyl bromide is shaken with N/tO-squeous silver nitrate solution for three hours when the whole of the iso-conipound is decomposed together with about 2.7% of the n-compound. With mixtures of primary secondary and tertiary isoamyl bromides the amount of tertiary com- pound can be determined by shaking with water and then the secondary by shaking with sil;er nitrats solution for three hours. J J. S. Boiling P o i n t s of Aqueous Solutions of isoPropyl Alcohol and of Trimethylcarbinol. ANTONY G.DOROSCHEWSKY and E. V. YOLJANSKY (J. 12uss. Phys. Chem. Soc. 1910 42 1448-1452). -For the b. p./760 mm. of isopropyl alcobol and ttimethylcarbinol the authors find the respective values 82*44* and 82-55' which are in good agreement with those obtained by Young and Fortey (Trans. 1902 81 735). The boiling points of aqueous solutions containing from 0 to 100% of isopropyl alcohol or trimethylcarbinol mere deter- mined at 700 mm. 760 mm. and 800 mm. the results being tabulated along with the corresponding values of dt/dp. For the aqueous solutions of these alcohols as with those of methyl ethyl and propyl alcohols the ratio of the absolute boiling points at two definite pressiires is constant. Thus with isopropyl alcohol the mean values of 17760 T/700 T/760 !Z'/SOO and T/SOO T/700 are 1.0060 0.9963 and 1.0097 respectively the limiting values being 1~0058-1~0063,0~9962-0*9966 and 1~0095-1*0100.For trimethyl- carbinol these ratios have the values 1.0059 (l.OO58-1*006O) 0.9963 (0.996L0.9966) and 1.0095 (2.0094-1.0096) (compare Abstr. 1910 ii 266). T. H. P. Oxide from Decaniethyleneglycol. I. V. EGOROFF (J. Russ. Phys. Chern. Soc. 1910 42 1655-1665).-Attempt.s to prepare the hydroxy-acid OH*[CH,],*CO H from ethyl sebacate resulted in the formation of a considerable proportion of the glycol OH*[CH Jlo*OH. I n order to convert this glycol into the unsaturated hydrocarbon CH2:CH.[CH2],.CH:CH2 (I} the corresponding dibromo-compound was treated with alcoholic potassium hydroxide solution and (2) the glycol itself was treated with sulphuric acid.But neither reaction gave rise t o the hydrocarbon the diethyl ether of decnmethylene glycol being obtained in the first case and an oxide in tbe second. a~-l)ibrornodecc6ne CH2Br*[CH2J,*CH 2Br has m. p. 27'. The diethyl ether of decamethyleneglycol OEt*[CH,],,*OEt is a n oily DecanaethyZene a&oxide CH,* [CH2],*CH< obtained by the action of sulphuric acid on decamethylene glycol has b. p. 197-199" D! 0.S694. The action of phosphorus pentachloride or yentabromide liquid b. p. 257-260" D! 0.8500. CH2*YH 0-CH,i. 2.54 ABSTRACTS OF CHEMICAL PAPERS. on the oxido shows that the latter readily undergoes conversion into the unsaturated alcohol OH-CH,*[CH2],*CH:CH*[CH2]4*CH,. I n t h e case of the pentachloride this alcohol is then transformed into an unsaturated halogen derivative but with the pentabromide the hydrogen bromide developed readily combines.with the unsaturated compound giving as-dibromodecane CloH2013r2 as a yellow oil. T. H. P. New Method for the Preparation of Ketone-Alcohols. OTTO DIEM and JACOB MARTIN JOHLIN (Bey. 1911,44 403-410).-Ketone- nlcohols of the type OK*CMeR*COMe are obtained i n the form < J f %heir phenylmethylhydrazones by the interaction of magnesium a1 kyl halides and diacetylphonylmethylhydrazone. The reaction takes place according to the follo~ving scheme COB!le*CMe:N*NMePh + RMgX + H,O -+ CMeR( OH)* CMe:N*NMePh. On boiling the phenylmethylhydrazones with water and benzaldehyde the keto-alcohols are obtained in the free condition. p-M etb y lbu tan-p-ol- y - one ( t rimethyl ket ol ) OX CMe,.C OMe is a colourless liquid h. p. 142'/750 mm. DI3 0.9595 (compare Schmidt and Austen Abstr. 1903 i 2 ) ; the pl~enyZnaetiL?/I?~~?/dl.azonc OH*CMc,* CMe N *NMePh is a yellow liquid b. p. 144-145"/12 Dim. D20 1,0179. y-Aleth?/Zpentun-y-oZ-~-o.lze (dimetiLyletlLyZ~e~ol) OH*CMeEt*COMe a colourless liquid b. p. 154'/750 mm. W3 0.9496 is purified by converting it into the semicarbaxone OH*CMeEt*CMe:N*NH.CO*NH m. p. 150" and distilling this in steam with phthalic anhydride; tbe p~en?llnaethyZ~ydruzone OH*CMeEt*CMe:N*NIePh is a yellow oily liquid b. p. 158-15!1°/12 mm. D13 1.0146. OH*CMePh*COMe p- Phew y Z but un- p-ol - y -one (pJheny Zdime thy Zka to Z ) forms a colourless oily liquid b. p. 122-123"/8 mm. DI7 1.0801 ; the yJieny Imetlqlhydrazone OH*CMoPh*CMe N-NMePh crystalliEes i n white prisms m.p. 68". Attempts t o prepare ketoses of the type OH*CRR'*CO*CH,*OH by brominating the above ketone-alcohols and replacing t h e bromine by the hydroxyl group were unsuccessf 111. The interaction of equal molecular quantities of ethyl oxalate /I-metbylbutan-P-ol-y-one and sodium ethoxide leads t o tbe formation of a compound which the authors consider t o be a Zactone of the CMe *CO following structure O<Co"_Co>CH2 ; it crystallises in prisms m. p. 1139 gives a dark purple coloration with ferric chloride and on treatment with diazomethane in ethereal solution yields a crystalline nzethyl derivative O<co-co CMe,*Co>CHMe having m. p. 89". When the condensation of /I-methylbutan-P-ol-y-one and cthyl oxalate is effected by means of two moleciiles of sodium ethoxide an >CH (?) is obtained ; isomeride having the formula C132<co this has m.p. 179" and reacts with diazornethane to form a methyl CMe(OH)*CO coOEGA N IC C EI EM 1 STKY. i. 255 derivative CIi,<co CMe(oH)'~>CHMe which crystsllises in slender needles m. p. YO' having the appearance of glass wool. Action of Ultra-violet Light on Glycerdl. HENRI EIERRY VICTOR HENRI and ALBERT RANC (Compt. rend. 1911 152 535-536. Compare Abstr. 1910 i 652) -When exposed to ultra- violet light in the presence of air glycerol is decomposed with pro- duction OE glyceraldehyde and other unidentified substances which combine with plienylhydrazine. If the decomposition takes place in presence of an alkali p-acrose is formed.In both cases the yields are small but may be improved by the addition of salts of iron cobalt and especially uranium which act as catalysts (compare Neuberg Abstr. 1'308 i 915 ; Eerthelot and Gaudechon this vol. ii 170). F. B. w. 0. w. Oxidation of Unsaturated Compounds with Organic Peroxides. I. NIKOLAUS PRILESCHAEFF (J. Buss. I'hys. Chcrn. rs'oc. 1910 42 13S7-141S).-1SIost of this paper has been already pub- llished (Abstr. 1910 i 86) the new work being as follows Measurement8s of the velocity of decomposition of benzoylhydro- !peroxide were made in chloroForm ether and carbon tetrachloride at 25'. I n the first two of these solvents the reaction is of the first order the values of K being 0.06507 (chloroform) and 0.06469 (ether). I n ,carbon tetrachloride the decomposition proceeds much more rapidly.Octylene oxide C,H13*CH<gH readily reacts with ncetyl chloride giving the compound C,H,,O,AcCl b. p. 11 7-1 18'12 1 mm. D 1.0066 Dig 0.9951. With zinc chloride the oxide readily undorgoes iso- merisation giving a compound b. p. 172-173' showing intense aldehydic properties and forming a sernicarbazone m. p. 67". The glycol C,H,,(OH)2 b. p. 135-136°/20 mm. formed on hydration of the oxide is a vaselin-like mass m. p. 45-46' and gives a diacetyl derivative b. p. 139-140°/24 mm. D 0.9874 Di! 09739. The interaction of diisobutylene and benzoylhydroperoxide results in the formation of the two oxides CMe,*CH,*C&lIe< I qud 0 CH CMe CMe,*CH<b . The glycol formed from deoylene oxide C,FIl&E3<zH' forms a vaselin-like mass and yields R diacetyl derivative C10H2002A~2 b.p. 163'/22 mm. D 0.9330 Di! 0.9195 Under the influence of zinc chloride the oxide undergoes isomerisation to a n aldehyde b. p. 209-210°/762 mm. or 125-126'/50 mm. Py-DirnethyI-A~-butylene and benzoylhydroperoxide yield Py-di- methyl AP-butylene oxide. ~imet~y~cyclo~i,exerte oxide '?H2.CH2*?h'e>~ prepared froin d i- methylqyclohexene and benzoglbydroperoxide has b. p. 1 50-151'/ CH2= CH ,.CMei. 256 ABSTRACTS OF CHEMICAL PAPERS. 756.6 mm. D 0.9340 Di6 0.9201 9 2 2 1.44676. The corresponding glycol C,H,,(OH) m. p. 92-92*5° gives a naonoacetyl derivative b. p. l%-129/22 mm. Di 1.0680 Di6 1.0645 ng 1.4689. These results show that benzoylhydroperoxide may be used as a reagent for hydrocarbons of the ethylene series and that under the conditions employed by the author it allows of the estimation of the double lin kings in a hydrocarbon with considerable accuracy.The character of the unsaturated complex present in the hydrocarbon is also indicated since under the isomerieing influence of acids oxides containing the group CH >O yield aidehydes =CH,*C€€O whilst tho-e containing -$?K- 0 - YH>O yield ketones -CH,*CO-. -CH Oxidation of phenylacety lene by means of ben zoylhydroperoxide yields phenylacetic acid. T wo-Component Systems. I. E ther-Hydrobromic Acid Ether-Chlorine and Ether-Bromine. DOUGLAS McTNTosEr (J. Amer. Cliem. Xoc. 191 1,33 71-75).-Studies of these two-component systems were made in connexion with the investigation of the com- pounds formed by organic substances containing oxygen with the halogens and halogen acids.The results are tabulated and plotted as curves. On adding liquid hydrogen bromide to ether the f p. ( - 118") is slightly depressed and then the compound C4Hl,,0,HBr separates ; further addition raises the m. p. and a t - 40" the ether hydrobromide melts. On adding more of the acid the f. p. falls until the eutectic point is reached when a mixture of solid hydrogen bromide and a compound separates; this occurs at about - 115" and the liquid contains 12% of ether. The f. p. then rises to -86O the m. p. of hydrogen bromide. Ethyl ether forms two compounds with hydrogen bromide namely C4HI00,HBr (Archibald and McIn tosh Trans. 1904 85 919) and C,Hlo0,2HBr in which the oxygen may be regarded as sexavalent; the latter compound has m.p. - 46O but the f.-p. curve shows no break a t this temperature. With chlorine ether yields the compound C,H,,OCI (Trans. 1905 87 784) which melts a t -51"; further addition of chlorine lowers the m. p. to - 103'. Ether unites with bromine to form the compound C,HloOBr2 (Zoc. cit.). The addition of bromine depresses the f. p. of this compound and a t - 119.5" solid ether and ether dibromide separate. The dibromide melts a t -3So and on adding more bromine t h e compound C4HIOOBr3 m. p. 2 3 O is produced (Schutzenberger Ann~den 1864 129 60). On continuing to add bromine the f . p. falls and at - 20" bromine and the tribromide separate. Influence of the Medium on the Formation of Oxonium Dibromides of Simple Ethers.WLADIMIH W. TSCHELINZEFF and W. K. KONOWALOFF (J. Russ. Phys. Chem. Xoc. 1910 42 3614-1630. Compare Abstr. 1909 i 353).-The authors have studied the formn- tion of the oxonium dibromide corresponding with ethyl ether in T. H. P. Pure chlorine mslts a t - 101.5O. E. G.ORGAn'lC CHEMISTRY. i. 257 benzene light petroleum (b. p. 81-82O/746-7 mm. Di0 0*7789) chloroform carbon tetrachloride ethyl bromide ethylene dibromide bromobenzene and carbon disulphide at 20° at which temperature the reaction occurs practically instantaneously in absence of solvent. The reactions were followed calorimetrically the heats of solution of ether bromine and the oxonium dibromide in the variOus solvents being determined separately. The results show that all these solvents exert intense retarding influences on the reaction.Such influence is condit,ioned by the friction between the molecules of bromine and ether and the solvent this being complicated by the different mutual actions occurring between the reacting and resultant compounds and the solvent. The formation of a new phase in the shape of a layer of the dibromide observed in four of the eight cases exerts only a very small influence on the subsequent velocity of the reaction. In the order of increasing magnitude of their retarding effects the solvents are carbon disulphide carbon tetrachloride ethyl bromide light petroleum ethylene dibromide chloroform benzene bromobenzene. T. H. P. Uranyl Nitrate and the Nature of its Ethereal Solution. PAUL LEBEAU (Compt.rend. 1911 152 439-441. Compare Lowenstein Abstr. 1909 ii 736).-Uranyl nitrate appears to form at least two compounds with ethyl ether these being deposited in crystals when an ethereal solution of the salt is dried over calcium nitrate and cooled at about - 10" and - 70' respectively. The dihydrate remains when the ether is removed from these compounds by a current of dry air. w. 0. w. Action of Magnesium and Aliphatic Halogen Derivatives on E thy1 Chlorocarbonate. I. MATSCHUREVITSCH (J. Russ. I'hys. Chem. Xoc. 1910 42 1582-15S9).-'l!he author has studied the formation of t rie thylcarbinol from magnesium ethyl chlorocarbonate and ethyl bromide (or iodide) and that of tripropylcarbinol from magnesium ethyl chlorocarbonate and propyl bromide. The results shorn that this method affords a good means of obtaining tertiary aliphatic alcohols.The following complex compounds formed in the second phase of the reaction (compare Reformatsky J. Russ. P h p . Chem. Soc. 1903 35 11b7; Houben Abstr. 1903 i 825) have been obtained (1) C7H,,*O*MgBr ; (2) CEt,*O*MgI,Et,O which mas obtained crystalline ; (3) when propyl bromide was employed the complex could not be isolated in a pure state. T. H. P. Preparation of Aluminium Chromium and Iron Formatee. GEORG MUTH (D.R.-P. 228668) -The usual method of preparing aluminium chromium and iron formates hy treating the metallic hydroxide with free formic acid is expensive and the following alternative is recommended. The metallic hydroxides in the form of a paste are treated with an aqueous solution of aluminium fluoride (FiO%) the calculated quantity of sodium formate added and thei.255 ARS'I'KilC'l'S OF CHEMICAL PAPERS. insoluble sodium :duminium fluoride separated by filtration ; the solution is concentrated and the product obtaiued in a pure condition Al,Z;" + M,F + 6H*CO,Na = AI,F,,GNaF + A12(C0,H) AlzF + Cr2E' + 6H*CO,Na= Al,F,,GNaF+ Cr,(CO,H),. E. M. G. M. Direct Esteriflcation by Catalysis ; Preparation of Benzoic Esters PAUL SABATIER and ALPHONSE MAILHE (Conzpt. rend. 191 1 152 358-261).-The reactions that take place when a. mixture of an :dcohol and acid are passed over a heated catalyst of the type MO may be represented by the equations ( I ) 140 + 2R*CO,II = (R*CO,),M + H,O = MO + R*CO*R + H20 + CO,; (2) MO + BC,,H2,,+1*OH ZZ J1(O*CnH2,,+i) + H,O ; (3) lK(0*C97,€i2~L-\-1)2 = MO + H,O + CnK2?% ; (4) M(O*C H2,t+l)Z + 2R*CO,H = MO + 2R*C0,*CnET91+1.The formation of an ester according to (4) is limited by decomposi- tion of the unstable salt by water whereby the alcohol is regenerated. All the possible products are formed when acetic acid and alcohol are acted on by thoria at 400". If the acid employed however is one t h a t does not readily decompose according to (l) the principal reaction is t h a t of ester formation ( 3 ) and (3) being negligible. Thus methyl ethyl propyl isobutyl isoamyl and ally1 benzoates are obtained in practically theoretical yield by passing a mixture of the acid (1 mol.) and the alcohol (12 mols.) over thoria at 350". The mixture of vapours is best obtained by allowing a solution of the acid in the alcohol to drop through a capillary tube. isoPropyl benzoate has a180 been obtained in good yield in spite of the readiness with which isopropyl alcohol forms propy lene.cycZoHexano1 gave a good yield of benzoate. Similar results have been obtained with the toluic acids but the method is less advantageous in these cases owing t o the sparing Direct Es teriflcation and Hydrolysis by Clatalysis. PAUL SABATIER and ALPHOKSE MATLHE (Compt. rend. 1911 152 494-49'7 Compare preceding abstract) .-Titanium oxide is even more effective than thorium oxide in bringing about esterification when the vapour of an alcohol and an acid ie passed over i t a t 280-300". This is especially the cace with acetic and propionio acids. The equilibrium limit of ester formation is very rapidly attained when the acid and alcohol are in molecular proportions.Thus with acetic acid and isobutyl alcohol 69.5% of ester was formed and with isobutyric acid and ethyl alcohol 71% was produced. These values are slightly higher than Menschutkin's for esterification at 155". The process is complete with large excess of acid or alcohol. This method cannot be applied to the preparation of formates owing t o the decomposition undergone by tho acid; it has been successful however in the case of the acetates propionates butyrates isobutyrates isovalerntes and bonzontes of methyl ethyl propyl butyl isobutyl isoamyl and benzyl alcohols. Benxyl isovnlerate bas b. p. 245'. The same syntheses can be cffected by thorium oxide below 300° but less advantageously. solubility of the acids.w. 0. w.ORGANIC CHEMISTRY. i. 250 Complete hydrolysis occurs when an ester is mixed with excess of water vapour and passed over titanium oxide at 280-300°. w. 0. w. Preparation of Derivatives of PP-Dialkylpropionic Acids. FARBENFABRIKEN voim FRIEDR. RAYER 6; Co. (DX-P. 22S667).- The preparation of some PP-dialkylpropionamides has been previously described ; it is now shown that therapeutically active amides can be obtained by the action of alkalicyanoacetic ester on halogenated dialkylcarbinols followed by hydrolysis and subsequent elimi tintion of carbon dioxide. Ethyl cyanoncetate (1 13 parts) was mixed with absolute alcohol (200 parts) and slowly treated with sodium ethoxide (23 parts Na) in the same solvent ; methylpropyl- cdrbinyl bromide (151 parts) was then added the mixture boiled until neiitral the alcohol removed by distillation and the oily ethyl methyll- 2?r~~?2/Zcarljoc?lcnoacetate [a-cyano-P-metA~ZI~exoate] C H CHMe CH (CN) CO,E t separated by treatment with water; it has b.p. 175'/35 mm. The foregoing ester was bgdrolysed with alcoholic sodium hydroxide and the a-cy~no-P-metI~yl~exoic m i d separated by the addition of acid ; this on prolonged warming with somewhat concentrated acid yielded a-~net~y~buty~.naa~onam~c acid CHMePr-CH(CO*NH,)*CO,H which at; n temperature of lSOo was converted by loss of carbon dioxide into P-)net?~?lZ-n-hexoanide C,H~.CHnle*CH,*CO.NH m. €1. 99O. F. M. G. 11. Direct Synthesis of the Glycerides. ITALO BELLUCXI and R.MANZETTI (Atti R. Accad. Lincei 1911 [v] 20 i 125-12S).-The authors find that the direct synthesis of the glycerides may be effected with nearly theoretical yield by heating together equivalent quantities of glycerol and the fatty acid at a moderate temperature under reduced pressure. I n these circumstances the water formed is removed aud the reaction rapidly proceeds to completion. I n an instance cited a yield of 95-98% of triolein was obtained in a few hours by heating together the theoretical quantities of oleic acid and glycerol under a pressure of 2 cm. the temperature being gradually raised from 160Oto 260° and special arrangements being made to prevent volatilisa- tion of the reagents. The glycerides obtained in this way are pure except for traces of glycerol and acid which can be removed readily by washing them with water and subsequently treating them in ethereal solution with calcium hydroxide.Condensation of Halogen Compounds with Ethyl PP-Di- methylglycidate. GEORGES DARZENS (Compt. rend. 19 11 152 443-446).-The action ol organomagnesium halides on ethyl PP- dimethylglycidate has not led to the isolation of any definite com- pounds. If the corresponding zinc derivatives are employed however esters of tho type CHMe,*CR(OH)*CO,Et are obtained. Thus on warming the ester with methyl iodide in toluene solution i n presence of the zinc-copper couple and treating the product in the usual may an 80% yield of ethyl a-hydToxy-ap-dimethylbzLt?lmte CHMe,.CMe(OH)*CO2Et R. V. S.i. 260 ABSTRACTS OF CHEMICAL PAPERS is obtained.This is a liquid with a camphoraceous odour b. p. 7 6 O / 90 mm. 175-173" under ordinary pressure. The wid resulting from hydrolysis has m. p. 70"; Perkin (Trans. 1896 69 l4S6) gives m. p. 75-77' but his compound may be isomeric with the author's. From ethyl P,j-dimethyl6.lycidate and ethyl iodide ethyl a-hydroxy- P-metl~?/l-a-et?~yIbut~r~te was prepared. This has b. p. 76"/16 mm. 180-181° under ordinary pressure ; the corresponding acid has m. p. 76O b. p. 140'/22 mm. Ally1 bromide gave ethyl a-hyclroxy- P-))iet~yl-a-uZlyZ6utymte b. p. 90'/2 1 nim. 19s-199" under ordinary pressure; the corresponding acid has m. p. 5 7 O b. p. 147"/2l mm. The molecular transformation involved in the formation of these substances may be explained by supposing that the glycidic ester first undergoes change into a pyruvic ester which then acts uormally with the zinc compound.Ethyl dimethylpyruvate was detected amongst the products of the reaction. w. 0. w. Action of the Chlorides of a-Alkyloxy-apids on Mixed a r g a n o - m e t a l l i c Zinc Compounds. EDMOND E. BLAISE m d L. PICARD (Compt. rend. 1911,152,446-447. Compare this vol. i 175). -A discussion of the action of organo-zinc halides on higher homo- logues of the acid chlorides dealt with i n a previous commnnication. a-Ethoxyhexoic acid on treatment with thionyl chloride furnishes a-ethoxyhexoyl chloride b. p. 69'/9 mm.; y-ethoxyheptccne b. p. 15 1'1 750 mm. results when this is acted on by zinc ethyl iodide. Esters of ~-nlkyloxy-aa-dialkyl acids are best prepared by treating ethyl oxalato with phosphorus pentachloride and allowing a zinc alkyl halide t o act on the product.The reaction proceeds in accordance with the equation OEt*CCI,*CO,Et + 2ZnRI = Z d + ZnCl + OEt.CR,-CO,Et. The ester is contaminated with ethyl oxnlxte which may be removed by shaking with ammonia. a-Ethoxpisohutyric acid OX t *CMe,*CO,H b. p. 9 9 O / 1 4 mm. was prepared in S4% yield by this process. a-Ethoxy- u ethy?butyric acid has b. p. 1205O/13 mm. It was not possible to prepare the chlorides of these acids by the action of thionyl chloride this reagent leading t o profound decomposition. w. 0. w. Synthesis of p-Hydroxy-a-ethylbutyric Acid. I. MATSCnURE- VITSCH (J Buss. Phys. Chern. Soc. 19 10,42 1576-1582).-P-Hydroxy- a-ethylbutyric acid previously prepared by Waldschmidt (Abstr.1878 136) and by Marshall and Perkin (Trans. 1891 59 870) may be obtained by Reformatsky's method by the interaction of acetaldehyde ethyl CL bromobutyrate and zinc Obtained in this may the acid has the properties given by Waldschmidt except that the silver salt is found to be uustable and readily soluble in water On distiilation the acid is converted into a-ethylcrotonic acid. T. H. P. TELEMACHOS KOMNENOS (Monatsh. 1911 32 77-SS. Compare Abstr. 1910 i 36 1 708).-An extension of the previous investigations. Succinic acid 2nd methyl hydrogen succinate are produced when ethyl succinate is added t o a warm solution of sodium methoxide in methyl alcohol. The hydrolysis and subsequent partial esterification are unexpected Interchange of Alkyl Groups in Acid Esters.ORGANIC CHEMISTRY.i. 261 since the prolonged heating of ethyl succinate with alcoholic sodium ethoxide does not cause hydrolysis but the formation of ethyl succinyl- succinate. Consequently ethyl succinate has been heated on the water- bath for forty hours with methyl-alcoholic sodium methoxide but here again hydrolysis occurs the chief product being sodium succinate ; a small amount of a substance m. p. 1 5 5 O probably methyl succinyl- succinate is formed. When ethyl phenylacetate is heated for two hours on the water-bath with methyl-alcoholic sodium methoxide methyl phenylacetate b. p. 2 1 5 O D15 1.050 is obtained together with n little phenylacetic acid. Under similar conditions ethyl benzoate is partly hydrolysed and partly converted into methyl benzoate.This last example is important in that it shows that the interchange of alkyl groups occurs in the esters of acids which do not contain an Theoretical Consideration of the Isomerism of Fumaric and Maleic Acids. BORIS GLASMANN (Pharm. Zen&.-h. 1 9 1 1 52 275-281).-The author suggests that the hypothetical ortho-di- carboxylic acid C(OH),*CH:CH*C(OH) may lose the elements of “-fiH and water in different ways whereby maleic acid ,C(OH) *CH fumaric acid 0 >O I ] are produced. It is shown that the preceding constitutions serve to account for the chemical behaviour of the two acids the conversion of the one into the other and their formation by the oxidation of furan derivatives; also an attempt is made t o explain the formation of racemic acid and of mesotartaric acid by the oxidation by potassium permanganate of fumaric acid and maleic acid respectively.It is remarked that in addition to maleic and fumaric acids yet a third acid having the constitution CO,H*CH:CH*CO,H may be derived from the hypothetical ortho-dicarboxylic acid ; for example ,CO -CH C( OH)*C €1 \C(OH),*CMe \C(OH)-CMe CO,H*CH:CMe*CO,H are proposed for citrnconic mesaconic and itaconic acids respectively active methylene group. c. s. o<C(OH),*CH’ \C(OH).CH’ the constitutions 0 J I 0’ >O / I and c. s. Chloral Chlorortcetate. EMILIO GABUTTI (Gcczzeltn 1911 41 i 11 1-1 12).-1n the description of this compound previously published (Abstr. 1900 i 370) the boiling point (224’/760 mm.) of the pure substance was omitted by a printer’s error.A direct comparison of the products respectively obtained by the method formerly given and by that of Wegsctieider and Spath (Abstr. 1910 i 155) has demonstrated their identity. R. V. S . Investigations on Complex Compounds. VII. Complexes of the Dioxime Series. LEO A. TSCHUGAEFF (J. 12uss. 1’1b98. Chem. ~ o c . 1910 42 1466-1487).-[With A. P o s i ~ ~ ~ l i o ~ ~ . ] - F u r ~ h e ri. 262 ABSTRACTS OF CHEMICAL PAPERS. investigations have been made on the diammino-base [Co2PyD2H,]O€€ (where P y = C,NH,) corresponding with dimethylglyoxime which separates in the form of sparingly soluble cinnamon-red crystals when the salts [Co3PyD2H,]X are treated with alkali hydroxide or ammonia. This base losos water forming tho anhydride on precipitation.The fact t h a t its molecular conductivity i s only p= 7.0 for a dilution of 1000 litres confirms the co-ordination formula ascribed to it. On solution in acids it again yields salts of the type [Co3PyD2H,]X. These transformations recall those occurring i n the magenta series and with other colouring matters of similar constitn- tion and it may be that the loss of water is preceded by the migration of the hydroxyl group of the base from the external sphere to the cobalt atom of the inner sphere thus creating the conditions for the loss of water and the formation of the anhydrous base. The latter I n accordance with this structure current only to a slight extent; the conductivity increases very con- ~M~:N(OH).,- ; ~ o - p ~ probably has the annexed structure.CMe==No/qo<No:cMe the free base conducts the electric siderably with the dilution but this is probably due to hydration of the anhydrous base. Aqueous solutions of the base exhibit a distinct alkaline reaction. [With I. KIRiEFF.1-The chloride and iodide of cobaltidihydroxyl- aminodimethylglyoxi~e were prepared. The chEoride [CoZNH,* OHD,H,]CI forms large yellowish-brown crystals readily soluble in water. The iodide [CoZNH,*OHD,H,]T forms dark yellowish-brown crystals and on dissociation yields two ions. These salts may be kept for a long time and even recrystallised without appreciable alteration. [With lv. TISCIITSCHENKO.]-T~~ compound formed by nickel with the dioxime of methylglyoxal exists in a dark red unstable form and a more stable orange one. These are possibly CMe--fi 1 1 H stereoisomerides in which the methyl groups of NO>Ni,:IN*OH the dioxime occupy either the annexed qn-position M0 CMe-CH I 1 co b c c ~ t ~ a n ~ m ~ n o c h ~ o r o ~ ~ e t ~ ~ y ~ g ~ y o x ~ m ~ n e obtained by the action of rnethylgl_voxime on purpureocobal t chloride forms a cinnamon-red crystalline precipitate stable towards acids.Cob~cltidiccmminomet~~~~gZ~oximine chloride [ Co2NH,D,H2]C1 ob- tained by the action of excess of ammonia on the preceding compound forms dark cinnamon-red plates. The corresponding iodide forms dark yellowish-brown crystals ; the ease with which this compound is formed from the chloride by the action of potassium iodide indicates that the iodine is present in an ionisable condition and this is confirmed by measurements of the electrical conductivity of the salt.The free base [Co2NH,D2H,]OH forms a dark brown solution exhibiting distinct alkaline properties. [With B. I?. AFANAsEEFF.]-.hvestigation of the decomposition of [Co2PyD,HI I p y PY N-OH or the anti-position. [ CoNH aC11D2H2],ORGANIC CWEhlISTRY. i. 263 the nickel compounds of glyoxime methylglyoxime dimethylglyoxime and methylethylglyoxime by hydrochloric hydrobromic nitric and acetic acids shows that tlic stability of these compounds increases with the complexity of the substituent groups of the glyosime. T. 11. P. Photochemical Synthesis of Carbohydrates from Carbon Dioxide and Hydrogen in Absence of Chlorophyll. WALTIIE:~ 1 - 6 ~ (Biochern. .Xeitsch. 1911 31 358-360).-8 criticism of the recent work of StoklasA and Zdobnic‘ky (this vol. i 178).S. B. 8. Investigations of the Phosphorus Compounds of Seeds Particularly Phytin. WLAD. VOL~BRODT (Bull. Acacl. Sci. Cracow 1910 A 414-511).-The author obtains from maize meal a solution which contains phytic acid ; on evaporation a yellow viscous mass is left When the solution is neutralised with barium hydroxide solution an acid barium phytate crystallises o u t ; this salt is white when dried in a stream of dry air but yellow i f dried more slowly. On analysis it was found that for 6 atoms of carbon only 5.5 of phos- phorus were present hence Posternak’s formula is incorrect. Neutrali- sation of the acid with sodium or barium hydroxides in presence of various indicators showed that more than four hydroxyl groups occurred in the molecule since more than four salts appeared to be formed.On heating with water to 1 5 5 O phytic acid decomposes with formation of phosphoric acid and inositol. Evidence was obtained of the presence of euzymes in t h e seed capable of splitting off phosphoric acid from the organic phosphorus compouil d s. E. J. 1:. Contardi’s Polyphosphoric Esters of Mannitol Quercitol Inositol and Dextrose. PAUL CARRE (Bull. Xoc. chim. 1311 Liv] 9 196-199. Compare Rbatr. 1905 i 814 and Contardi Rbstr. 1910 i 157 609).-The author has repeated C’ontardi’s experiments and finds that his supposed polyphosphoric esters of msnnitol quercitol inositol and dextrose arc in reality mixtures of phosphoric acid barium dihydrogen phosphate and the parent substances or their decomposition products.T. A. H. Digestive F e r m e n t s for Manninotriose and its Derivatives. HENRI BIERRY (Gompt. wnd. 1911 152 465-46’7. Compare l’auret Abstr. 1902 i 661 ; 1903 i 606).-The gastro-intestinal juice of JJeZix readily tiydrolyses stachyose or manninotriose one of the products of the partial hydrolysis of the sugar. I n the latter case the final products are galactose (2 mols.) and dextrose (1 mol.) but an intermediate biose (dextrose-galactose) appears t o be produced. The biose has not been i5olated; it cannot be lactose since lsctase is without action on it. The osazou0 of the trisaccharide undergoes hydrolysis in the same way. This compound 118s m. 1). 122-124° and not 192-194O as stated by Neuberg arid Lsc~timsnn (Abstr. 1010 i 325) Tanreti.264 ABSTRACTS OF CHEMICAL PAPERS gives 1 2 2' il.l"anninot.t.iosecarbamide C H,,O,, N COON H H,O 1.3 + 127*4O is also hydrolysod by the above ferment with formation of galactose. w. 0. w. Chemical Processes Occurring in the Preparation of Cellu- lose by the Sulphate Method. PETER KLASON and BROR SEGERFELT (Ad&. Kern. Min. Geol. 1911 4 No. 6 1-20).-!l!he so-called sulphate method for the preparation of cellulose from wood consists in treatment of the latter with a lye containing chiefly sodium hydroxide and sodium sulphide. The chemical reactions taking place consist for the most part in the transformation of the gum-like carbohydrates into saccharinic acids the latter neutralising the alkali. At the same time the lignin molecules are broken down into simpler ones which also dissolve in the alkali because they contain hydroxyl groups ; about one-fifth of the methoxy-groups in the lignin are also destroyed by saponification thus increasing the amount soluble in the alkali. The process of saponification in the boiling solutions give rise also to methyl alcohol methyl mercaptan and methyl sulphide the methyl.alcohol being formed in the greater quantity. With insufficient; quantity of alkali the quantity of methyl mercaptan increases ; increasing quantity of alkali favours the formation of methyl sulphide. Under the same conditions fir wood givesabout twice as much methyl mercaptan as pine wood. Wheat straw contains fewer methoxy- groups than the woods and gives less methyl mercaptan. Both rueta- and para-saccharinic acids are found in the liquors together with a new form of isosaccharinic acid to which the authors give the same sapin-isosaccharinic acid (sapin = fir); this latter acid constitutes the greater part of the saccharinic acids. Assuming thatr Nef's theory of the formation of the saccharinic acids is correct (Abstr.1908 i 5 ; 1910 i 711) this points to the chief constituent of the gum-like carbohydrates in pine wood being one of the following ketohexoses E-f ruc tose I-pseudofructose I - taga tose or d-sorbose. When the process of extraction is complete about half of the hydrogen sulphide originally present in the lye is chemically com- bined with the lignin in the black liquors. Because of this and because of the formation of volatile methyl-sulphur compounds the sodium sulphide present in the lye is only gradually changed into the active sodium hydroxide.This explains the protecting action OF alkali sulphide on the cellulose fibres. T. S. P. The Nitrogenous Products of Alkaline Hydrolysis of' Cellulose Nitrate. ERNST BEHL and ANDOR FODOR (Zeitsch. Schiess. Sprenystofwesen 1910 5 254-256 269-273).-A discussion of t h e results obtained by various workers on cellulose during the past ten years. It is shown that by the alkaline hydrolysis and reduction of collodion and cellulose nitrate aliphatic nitrogenous acids are produced their decomposition products being demonstrable as hydrogen cyanide liydroxylamine ammonia and nitrous acid. The formation of a polysaccharide by the condensation of n molecules of a hexose is stated to take place according to the formulaORGANIC CHEMISTRY.i. 265 R C ~ H ~ ~ O ~ - ( n - 1)H20 (compare Kiliani Abstr. 1908 i 320) and the expression (C,Hlo05)n as representing the cellulose molecule is to be considered erroneous. The action of an excess of sodium carbonate on an alcohol-ether solution of collodion wool yielded after two weeks' shaking together a colourless nitrogenous compound soluble in alkalis with a yellow coloration; after a further period of several weeks two other gelatinous dextrin-like substances were obtained. The action of sodium ethoxide on a highly nitrated cellulose in acetone solution resulted in denitration yielding the hygroscopic brown sodium salt of a nitrogenous acid which separated on acidification as an amorphous flocculent mass. Cellonic acid nitrate C2,H3,O,,(NO,! was obtained as a colourless powder by the action of alcoholic potassium hydroxide (1'8 equivalents to each nitric acid residue) on collodion wool and its formation from glucosidohexonic acid C,,H,,O, was probably preceded by the removal of 5H,O (3 by auhydridisation and 2 by lactonisation) from 2 rnols.of hexonic acid ; it decomposes a t 163' ; the phenythydraxone C,,H,,01,(N0,)5(C,H5N2H)3 a brown amorphous substance and the p-bromophenythydrcmone C24H,30,3(N0,)5(CGH4Br*N2H)3 a brick-red powder were also prepared. A molecular mixture of glucosidohexono- lactone trinitrite and glucosidodihexonolactone trinitrite was isolated from the alcoholic mother liquors in the form of an orange-yellow crystalline powder.The hydrolysis of cellulose nitrate with ammonium sulphide iu absolute alcohol yielded a voluminous precipitate which after elimina- tion of free sulphur was found to consist of hexonolactone (90%) and hydroxypyruvic acid (10%). The Nitrogen-free Products from the Alkaline Hydrolysis of Cellulose Nitrate. ERNST BERL and ANDOR FODOR (Zeitsch. get?. Schiess. and Sprengstofwesen 1910 5 296-297 313-316. Compare J. SOC. Chern. Ind. 1908 27 534; Abstr. 1908 i 504 505).-A detailed account of experiments on the detection and isolation of the nitrogen-free decomposition products obtained by the alkaline hydrolysis of cellulose nitrate. The relative proportions of the different acids formed were observed to vary according to the concentration of the alkali employed a dilute solution yielding compounds containing 4-5 carbon atoms whilst with concentrated alkali acids with 1-3 carbon atoms predominated.The products detected were hydroxy- pyruvic acid which was probably accompanied in the solution by i t s aldehydo-form CHO*CH(OH)*CO,H and the keto-form CH,(OH)*CO*CO,H with malic trihydroxyglutaric malonic tartronic oxalic glycollic and dihydroxybutyric acids as secondary oxidation products. The p-nitrophenylosaxone CI5Hl2OfiN6 a red crystalline powder m. p. 260° and an osazone m. p. 213-215" were also prepared. F. M. G. M. X-M. G-X- Iso- and Hetero-poly-acids. 111. The Basicity of Some Hetero-poly-acids. ARTHUR ROSENHEIM and JACOB PINSKER (Zeitsch. anorg. Chem. 1911 70 73-85 Compare this vol. i 109 ; ii 116).-The extension of Werner's co-ordination theory t o poly-acids VOL.c. i. ai. 266 ABSTRACTS OF CHEMICAL PAPERS. by Miolati and Pizzighelli (Abstr. 1908 ii 595) facilitates the correct formulation of these acids. Many hetero-poly-acids have 12 acid anhydride molecules associated with the acid containing the central atom. As it is probable that the dimolybdate and ditungstate radicles (Mo 0 )" and (W207)" are often present the formulae of some '' 1imiti;g ' hetero-poly-acids and salts may be written ,a HB[IO,I H7 [Pod H f P O I %LI(MOO~)G] x7[p(M0207),l XJSi(Mo,O7),1 XdI(WO4)J x7[p(w207h1 xdsi( w207),1* Actually molybdo-periodic acid and tungsto-periodic acid are known to be tribasic and the corresponding hetero-silicic acids octobasic but only salts of tribasic 12-molybdo- and 1 2-tungsto-phosphoric acids have hitherto been obtained.It is now found that these and the corresponding hetero-arsenic acid yield heptabasic salts which are proved by conductivity measure- ments to be normal whilst the tribasic salts are acid. The acid H,P04(Mo0,),,,30H,0 is prepared by extracting an acidified solution of its salts with ether. A solution in water is then gradually mixed with a 10% solution of guanidinium carbonate when a deep yellow microcrystalline precipitate is formed but dissolves on further addition of the carbonate to the warm solution. Crystals of the heptabtcsic salt (CH,N8)7H7[P(Mo,07),],SH20 separate on cooling and have a greenish-yellow colour. The tribasic salt is prepared more conveniently by dissolving 12 mols. of molybdenum trioxide in a boiling solution of guanidinium carbonate (12 mols.) adding 1 mol.of phosphoric acid and acidifying strongly with hydrochloric acid. This salt has then the composition (CH5N3)5H7[P(No207)6] 10H2U. The conductivity of the sodium salt (which is more soluble in water) indicates the presence of acid hydrogen whilst the conductivity of tbe heptabasic salt is that of a normal salt. Two tribasic salts of an arsenoinolybdic acid containing 12 mols. of molybdenum trioxide are known but the new heptabasic salt contains only 10 mols. It is prepared similarly to the phosphate and has the composition ( CH,N,),H7[ As(Z02O7)5 ,5H2@ but decomposes when recrpstallised. The conductivity corresponds with its formulation as a normal salt. It has not been found possible to obtain an octobasic molybdo- silicate.and crystallises in deep yellow leaflets. When warmed with guanidinium carbonate silica separates and the filtrate deposits felted needles of guaizidinium molybdate ( CH5N,)2112M030,,,5H20. I The guanidinium salt has the composition (CH5N3),Hs[Si(Mo207)~~~6H~0~ C. H. D. The Compounds of Hydrated Metallic Salts with Hexa- methylenetetramine. (Labile Hydrated Forms Fixed by means of an Organic Base.) 11. GIUSEPYE A BARBIERI and F. CALZOLARI ( A t t i R. Accad. Lincei 1911 [v] 20 i 119-126. Compare this vol. i 184).-Cornpounds of other metallic salts have now been prepared by the method adopted in the case of the halides previously described.ORGANIC CHEMISTRY. i. 267 Magnesium tbiocyanate yields a compound Mg(SCN),,1OH,0,2C,H,,N whilst the thiocyanates of manganese iron cobalt and nickel give compounds of the type M(SCN),,4H20 2C6H,,N4.The magnesium and manganese compounds can be recrystallised from water unchanged but the others lose a molecule of hexamethylenetetramine forming substances of the type M(SCN),,4H,0,C6H12N4 which are isomorphous. The nitrates of magnesium manganese cobalt and nickel form isomorphous compounds of the general formula M”(N0,)2,10H,0,2C6H12N4. The perchlorates of the same metals form compounds of the type M”(ClO,),,8H2O,2C,Hl,N4 which are isomorphous and can be recrystal- lised from water. The compound Mg(SCN),,l OH2O,2C,Hl2N forms thin colourless tablets which show holosymmetry of the trlclinic system [a b c = 0.9342 1 0.9223 ; U = 134O12’ p= 47’4’,.y= 120°56’].The compound Mn(SCN),,4H20,2C,H1,N4 crystallises in colourless tablets which exhibit holosymmetry of the tetragonal system [a c = 1 1.03661. The compound Fe(SCN),,4H20,2C,H,,N crystallises in colourless males w bich on recry stallisation yield the compound in canary-yellow crystals which exhibit holosymmetry of the triclinic system a = 124’57’ p = 29’54‘ y = 121’36’1. The compound Co(SCN),,4H~0,2C,Hl~N4 forms lustrous rose-coloured scales. On recrystalhation i t yields the compound Co(SCN),,4H20,C6HI2N4 in dark red tabular crystals which show holosymmetry of the triclinic system [a b c = 1.4232 1 1.6034 ; a- 128’23‘ p= 31°6’ y - 123’33’1. Ni(SCN),,4H20 2C6H,,N is a green crystalline powder. When recrystallised i t gives the compound Ni(SCN),,4H20,C6H,,N4 in emerald-green tabular crystals which show holosymmetry of the triclinic system and forms mixed crystals with the corresponding cobalt compound in all proportions.The compound Mg(NO,) 10H20,2C,Hl,N forms colourless tabular crystals which exhibit holosymmetry of the rhombic system [a b c = 0.8261 1 :0.4813]. The compound Mn(N03)2,1013[20,2C6H12N4 c r p t a l - lises similarly showing holosymmetry of the trimetric system [a b c = 0.8388 1 :0*4894. The compound Co(N0,),~10H,0,2C,Hl,N crystal- lises in rose-coloured scales and forms solid solutions with the two preceding substances in all preportions. The compound forms emerald-green scales and gives solid solutions in all proportions with the three preceding compounds. The compound Mg(C10,),,8H,0,2C,Hl,N crystallises in small colourless lustrous needles.The compound Mn(C10,),,8H20,2C6Hl,N crystallises similarly. The compound Co( ClO,! 8H20 2C,Hl,N forms rose-coloured needles and yields solid solutions wlth the analogous manganese and magnesium compounds. The compound Ni (CIO,) 8 H,O 2 C6Hi2N4 cr ys tallises in green u eed 1 es. The crystallographic measurements were ejfected by E. Billows. Fe(SCN) 4H@,C6H12N4 [rc b c = 1.4012 1 1.5723 ; The compound i(N03)2,1 0H20,2C6H1,N K. v. s. zc 2i. 268 ABSTRACTS OF CHEMlCAL PAPERS. Hydrated Additive Products of Metallic Dichromates. (Labile Hydrated Forms Fixed by means of an Organic Base.) 111. GIUSEPPE A. BABBIERI and F. LANZONI ( A t t i R. Accad. Lincei 1911 [v] 20 i 161-164. Compare Barbieri and Calzolari this vo!.i 184; also Parravano and Pasta Abstr. 1907 i 961).- Hexamethylenetetramine compounds of magndsium zinc manganese cobalt and nickel diciwomates are readily obtained by acting on a con- centrated solution of the acetates or sulphates of those metals with a concentrated solution of hexameth ylenetetramine in the presence of potassium dichromate. For the most part they crystallise in lustrous scales but may also be obtained in prisms. They are not very stable; even in the dark the base reduces the chromic acid and in bright light the orange-red crystals become green superficially in a few minutes. Analysis shows that all the compounds have the composition MCr,0,,7 H,O,ZC,H,,N where M” represents Mg Zn Mn Co or Ni so t h a t there is complete analogy to the mercuric cyanide compounds of Kriiss and Unger (Abstr.1895 ii 355). R. V. S. Compounds of Salts of [Metals of] the Rare Earths with Hexamethylenetetramine. GIUSEPPE A. BARBIEHI and F. CALZOLARI ( A t t i R. Accad. Lincei 1911 [v] 20 i 164-169).-By the action of very concentrated solutions of hexamethylenetetramine on concentrated aqueous solutions of cerium lanthanum and neodymium chloyides compounds of the type M”’CI 1 4H20 2C6H12N mere obtained whilst t h e nitrates of the same elements yielded substanc2s of the type M”’(N0,),,8H2O 2C,H,,N4. Yttrium and erbium chlorides gave compounds of the form M”’Gl,,l 1H,0,2C,H!,N4 and the nitrates of these metals yielded products of the composltlon M”’(N03) 10H,0,2C6H,,N4. All these compounds are crystalline and are more hydrated t h m the corresponding simple salts of the same metals.The compound NdCl 1 4H20,2C,Bl2N4 forms lilac-coloured silky needles belonging to the triclinic system. The compound Nd( N0,),,8H20 2C,H,,N fprms minute lilac-coloured crystals which show holosymmetry of the monoclinic system [a b c = The compound Er(N0,),,10H20,2C,H,,N4 like the other erbium and yttrium compounds described is more exactly represented by a formula (Er,Y)(N0,),,10H20,2C6H$4 (Er,Y ) having apparent atomic weight 140; it forms pale red crystals which show holosymmetry of the monoclinic system [a b c = 1.1501 1 1.4892 ; p= 57’1. Combination of Amines with Acetylenic Ketones. Preparation of Ethylenic @Substituted Amino-ketones. MILE ANDRE (Conzpt. Tend. 1911 152 525-527) -The neighbour- hood of a CN or C0,R group to a triple linking confers on the compound the property of combining adclitively with primary and Eecondary amines (Xoureu and Lazennec Abstr. 1906 i 956).The carboriyl group is effective in the same manner acetylenic ketones of the type CRiC*COR (Abstr. 1910 i 563) uniting readily with Crystallographic data are given in some cases (by E. Billows). 0.7336 1 0.4329 ; p = 57’29.5’1. R. V. S.ORGANIC CHEMISTRY. i. 269 amines to form amino-ketones of the types R*C(NHR"):CH*COR and ROC( NR'R''):CH*COR respectively. These compounds are hydro- lysed by acids with formation of an amine and a P-diketone. When a primary amine acts on an acetylenic ketone the principal reaction is one involving elimination of water.The mixtures rapidly blacken however and no definite condensation products have been isolated. The following additive compounds have been prepared a-cyclo- Nexylamino-a-phenyl-Aa-penten-y-one C,Hll*NH*CPh:CH*C'OEt m. p. 100". a-cycloHexylnrnino-a-phenyl-Aa-hexen-6-one m. p. 75". Benxyl- aminostyryl pAeny2 ketone CH,Ph*NH*CPh:CH*COPh m. p. looo a-diethy lanaino-a-p~ny I- ha-penten- y-one N E t2* CPh C H COEt. m. p. 45". a-Diethylamino-a-plwayZ-Aa-hexen-8-one m. p. 40". a-Dipopyl- amino-a-phenyl-ha- buten-y- one NPr,a*CPh:CH*COMe m. p. 47'. Diethyk6minostyryl phenyl ketone NEt;CPh:CH*COPh m. p. 63' ; the corresponding pipe~idyl compound has m. p. 8 lo and the methylanilino- compound m. p. 87". w. 0. w. Method of Characterising Certain Ureides [Carbamides].HENRY J. H. FENTON and WILLIAM A. R. WILKS (Proc. Camb. Phil. Xoc. 1911 16 64).-Methylfuril C,,H,O (Trans. 1903 83 187 ; Abstr. 1906 ii 489) is a very delicate reagent for detecting certain carbamides. Minute quantities of the reagent and of the carbamide are mixed on a filter-paper and treated with a drop of fuming hydro- chloric acid ; an intense blue coloration is developed after a few seconds. Positive results are given by substances containing the open-chain *NH-CO*NH (carbamide methylcai bamide benzyl- carbamide semicarbazide oxaluric acid biuret and hydantoic acid) ; cyclic carbarnides such as parabanic acid and hydantoin and also oxamide succinamide s- and as-dimethylcnrbamiila do not respond to the test. The positive result of the test given by allantoin is evidence in (compare NH*f:O CO-NH favour of the Grimaux formula NH,*CO*NH*CH< Biltz? Abstr.1910 i 594). c. 8. The Carbonyl FerFocyanides. Their Extraction Analysis and Applications. EMILE LECOCQ (Bull. Soc. chim. Belg. 1911. 25 72-80).-1n t h e extraction of ferrocyanides from the spent oxide of the gas purifiers the filtrate from the insoluble calcium potassium ferrocyanide formed during the process contains any carbonylferro- cyanide which may have been present in the spent oxide. Together with this carbonylferrocyanide there is also some calcium potassium ferrocyanide calcium sulphate calcium chloride calcium t hiocyanate and potassium chloride. If this solution is concentrated to a gravity of 30" BB. a granular mass separates containing gypsum the double ferrocyanide of calcium and potassium and also calcium potassium carbonylferrocyanide. The latter salt deposits because it is insoluble in the presence of the calcium salts contained in the mother liquor,i.270 ABSTRACTS OF CHEMICAL PAPERS. and it may be dissolved from the the collected precipitate by treatment with warm water. CaKEe( CO)C,N6,5H,0 and forms straw-coloured crystals with a pearly lustre. I n addition to the reactions of this compound described by Muller (Abstr. 1899 ii 616) the reactions with the following salts are described Cuprous zinc mercurous mercuric silver thallium vanadium stannous and platinum salts. The heat of combustion is 622 Gals. per gram-molecule and the heat of formation - 133 Cals. The method of determining the amount of carbonylferrocyanides in the spent oxide is described in detail.The calcium potassium salt is extracted essentially according to the method indicated above the calcium precipitated as carbonate and the resulting solution of the potaspiurn salt titrated with a standard solution of copper sulphate trhe end of the reaction being indicated when the solution no longer gives a violet colour with ferric salts. Generally speaking carbonylferrocyanides are only found in the spent oxide when Laming's mixture has been used in the purifying boxes. I t is present as the violet-coloured ferric salt to the extent of 0*4-1*1%. This violet salt gives printing inks and paints which are very stable towards the action of light. After recrystallisation i t has the formula T. S. P.Organic Amalgams. Substances with Metallic Properties Composed in part of non-metallic Elements. HERBERT N. McCoy and WILLIAM C. MOORE (J. Amerr-. Chem. Xoc. 1911 33 273 -292).-Tetramethylammonium amalgam has been prepared by the electrolysis in the cold of solutions of tetramethylammonium ,chloride in absolute alcohol using a mercury cathode. The amalgam exhibits certain physical properties of the metals to a high degree and has a crystalline structure. It is lighter than mercury but does not expand or become inflated at or below loo as does ammonium amalgam. I n contact with cold air it becomes coated with a white alkaline crust due t o oxidation. It reacts violently with water producing hydrogen colloidal mercury and tetramethylammonium hydroxide ; the phenomena observed during this reaction point t o the existence of more than one active phase in the amalgam.The amalgam acts on aqueous solutions of ammonium sodium potassium and copper salts and alcoholic solutions of copper and zinc salts the alkylammonium group replacing the respective metals. With rubidium and caesium salts the action is more violent than with potassium salts of equivalent concentration but there is replacement even in the case of the cesium salts. The solution tension of the tetramethylammonium radicle is comparable with that of potassium but it is much less than that of rubidium or cesium. The rate of formation of the tetramethylammonium ion from the amalgam in contact with absolute alcohol is about 5% per minute at 09 The E.H.F. of cells made up of the decinormal calomel electrode and the amalgam in contact with O-SN-alcoholic or aqueous solutions of tetramethylammonium chloride was measured at Oo.With alcoholic solutions the values obtained were 2.6 and 2.0 volts whilst withORGANIC CHEMISTRY. i. 271 aqueous solutions the values were 2.4 and 1.7 volts The two values obtained in each case probably correspond with two phase6 present in the amalgam The following salts were studied to see if amalgams could be formed. Methyl- dimethyl- trimethyl- ethyl- tetraethyl- propyl- and butyl- ammonium chlorides ; iodomethyltrimethylammonium iodide ; aniline dimet hylaniline phenylenediamine pyridine hydroxylamine and hydrazine hydrochlorides ; benzenediazonium chloride ; tetraethyl- phosphonium tetramethylstibium and trimethylsulphinium iodides.Of these the monomethyl radicle yields an amalgam and potential measurements show that it is less stable towards alcohol than towards water in which respect it agrees with ammonium amalgam. The dimethylammonium radicle may possibly form an amalgam as indicated by potential measurements and this is also true of the tetraethyl- ammonium radicle but the amalgams are very unstable. Of all the other substances investigated a number gave faint indications of amalgam formation but none gave results as positive as the three substances just mentioned. The authors consider therefore that it is possible to prepare composite metallic substances from non-metallic constituent elements. T. S. P. Coal Tar Pitch. SIMON BERNUS (Bull. sbc. chirn.Belg. 191 1 25 7-40).-A study of coal tar pitch from the point of view of its use in briquetting coal dust. From ordinary crude coal tar a yield of from 60-80% of residual pitch may be obtained depending on the point at which distillation is stopped and the product may be liquid soft or hard according as more or less high boiling coal tar oil is left in it. A large number of high boiling hydrocarbons have been obtained by distilling pitch but i t is very doubtful whether these substances actually occur in it and are not formed by pyrogenetic decomposition. On treatment with carbon diaulphide pitch dissolves to the extent of 80%. The insoluble matter resembles lampblack is devoid of plastic properties and is therefore of no value as an agglomerant. The portion soluble in carbon disulphide forms the plastic matter on which the agglomerating property of pitch depends.By treatment with solvents it can be separated into two fractions. Fraction A consists of zt brown mass of buttery consistence which liquefies at 45-60' forming a black fluid which adheres strongly to any solid substance placed in it. This fraction appears to be largely composed of hydrocarbons. Fraction B forms a solid black shining crystalline powder which melts at ZOO' forming a slightly adherent varnish. It is soluble in carbon disulphide or tetrachloride but its best solvent is the mixture of hydrocarbons forming fraction A . I n briquetting coal dust A probably plays the chief part as an agglomerant whilst B solidifies at a comparatively high temperature and thus assists in the formation of a hard compact briquette.The rest of the paper deals with the theory of briquetting and points out that t h e formation of a good briquette depends primarily on the adjustmeut of temperature and pressure so that each particle ofi. 272 ABSTRACTS OF CHEMICAL PAPERS. coal is completely enveloped in R layer of pitch and the latter evenly distributed to fill all interstices between the particles of coal. I n valuing pitch for briquetting purposes t.he melting point (55-74') and the total quantity of plastic matter (54-73%) are the chief factors to be considered. T. A. H. Sabatier's Reduction and its Reversibility. ALADAR SKITA and H. RITTER (Ber. 191 1,44 668-676).-The reduction of phenols cyclic ketones and alcohols by Sabatier's method is somewhat analagoiis to that of aliphatic compounds (Abstr.1908 i 855). Aromatic and reduced aromatic hydrocarbons are usually formed especially when a rapid current of hydrogen is used. It is shown that benzene cyclohexane and cyclohexene are formed by the reduc- tion of phenol and methylcyclohexane and toluene by the reduction of m-cresol. cycloHexanone yields cyclohexane and phenol but little cyclohexanol ; 1-methylcyclohexan-2-01 yields methylcyclohexane and o-cresol together with unsaturated and aromatic hydrocarbons. 1 -Met hyl-A1-cycZohexen-3-01 gave met hy lcyclohexane and 1 -methyl- cyclohexan-3-one ; isophorone gave a-hydrocarbon C9H15 b. p. 140-1 4 3 O and d-pulegone gave p-cymene and d-Z-menthane. The reduction process consist's of a number of equilibria as represented by the scheme Phenol cyclohexanone = cyclohexanol -+ The aromatic hydrocarbons are formed by a process of dehydrogena- tion and the amount tends to increase with the temperature but it appears impossible t o work under conditions such that this formation is entirely excluded.l-ChZoro-A1-cyclohexsme C,H,Cl obtained by the action of phosphorus pentachloride on an absolute ethereal solution of cyclohexanone has b. p. 54-56O/20 mm. and Di! 1.0385. When reduced with sodium and methyl alcohol it yields cyclohexene. cyclohexene cyclohexane benzene. Dihydroisophorone and phosphorus pentachloride yield 5-chloro- 1 1 3- trimethyZ-A5-cyclohezene CMe2<CH -- --CC1>CH2 b. p. 70-7 1 "/ 21 mm. and this on reduction with sodium and ethyl alcohol gives 1 1 3- trimethyl-A5-cyclohexene (/I-cycZogeraniolene compare Knoevenagel and Fischer Abstr.1897 i 612) which can also be obtained by the reduc- tion of the chloride of isophorone with sodium and alcohol. The chloride obtained from 1-methylcyclohexan-2-01 (Gutt Abstr. 1907 i 509) has b. p. 156-15So and Dt 0.9676 and when reduced with ziuc and an ethereal solution of hydrogen chloride yields the hydrocarbon methylcyclohexane C,H, whereas when reduced with sodium and alcohol the chief product is methylcyclohexene. The chloride obtained from trans-dihydroisophorol and phosphorus pentachloride has b. p. 184'/756 or 76-78'/18 mm. and D: 0.9281 and when reduced with zinc and an ethereal solution of hydrogen chloride yields the hydrocarbon trinzethylcyclohexane C9HI8 b.p. 137-138' and nI7 1.4327. Sabatier's method of reduction is a convenient one for the prepara- tion of saturated cyclic hydrocarbons ; the compounds obtained appear CH,*CHMeORGANIC CHEMISTRY. i. 273 to be identical with the natural naphthenes and so far the conversion of a 6-membered ring into a derivative of a 5-membered ring has not been observed although such a molecular rearrangement occurs during reduction with hydriodic acid (Willstatter and Kametaka Abstr. 1908 i 401). J. J. 5. Compounds of Antimony Trichloride and Antimony Tri- bromide with Benzene. BORIS N. MENSCHUTKIN (Chem. Zentr. 1910 ii 378; from Izvistn of the St. Petersburg Polytechnic 13 263).- Among the numerous systems of inorganic salts (MgBr MgI AlCl AlBr,) with aromatic hydrocarbons studied by the author there was not one in which the formation of a molecular compound between the components could be proved.It mas also found that the numerous alleged molecular compounds of aromatic hydrocarbons with halogen salts of aluminium could not exist within the temperature ranges studied. As similar additive compounds of antimony trichloride and antimony tribromide with aromatic hydrocarbons have been described the author subjected these systems to a thorough thermo- metric study. It was found that these salts form with benzene the additive compounds 2SbCl,,C,H and 2SbBr,,C,H,. The thermometric analysis of these substances was made by the method of AlexBeff and the composition of the isolated additive products determined by measuring the volume of benzene liberated by means of 20% hydro- chloric acid.The author gives the freezing temperatures and eutectic points obtained for the systems he examined. In the case of the system antimony trichloride and benzene the freezing diagram shows two eutectic points at lo SbC1,,13C6H and a t 62" corresponding with SbCl,,O*lSC,H and in between a distectic at 79" the freezing point of the additive compound 28bC13,C,H which crystallises in very hygroscopic rhombic plates. These compounds were erroneously given the formuh 3SbC1,,2C,H6 and 3SbC13,C,H (Smith and Davies Trans. 1882 41 411 ; Rosenhelm and Stellmann Abstr. 1902 ii 68). I n the case of the system antimony tribromide and benzene the freezing diagram shows two eutectic points at 4*5" corresponding with SbBr3,51 .6C,H,! and at 85O corresponding with SbBr,,O.lPC,H ; between the distectic at 92*5O tbe freezing point of the additive compound 2SbBr C,H which crystallises in liquid rhombic forms.N. c. Investigation of Systems of Substituted Benzenes with Antimony Chloride and Antimony Bromide. I. Halogen- substituted Benzene. BORIS N. MENSCHUTKIN (Chem. Zentr. 19 10 ii 379-380; from Izuistcc of the St. Petersburg Polytechnic 13 277. Compare preceding abstract).-In view of the great chemical differ- ences which benzene derivatives exhibit the author has determined the behaviour of these derivatives towards the halogen compounds of antimony ; thus he examined a number of systems of halogen and nitro- derivatives of benzene with antimony trichloride and tribromide and gives particulars of their freezing temperatures and eutectic points.The freezing diagram of the system antimony trichloride and chloro-i. 274 ABSTRACTS OF CHEMICAL PAPERS. benzene consists of three curves which show a eutectic point at - 47" corresponding with SbC1,,44*5C8H,C1 and a transition point at Oo corresponding with SbC1,,2.56C6H,C1. Both components of the system form a n additive compound SbCI,,C6H5CI which crystallises in long needles and decomposes a t 0'. The system antimony trichloride and bromobenzene is similar with a eutectic point at - 3 2 * 5 O corre- sponding with SbC1,,28*4C6H,Br and a transition point at 3' corre- sponding with SbCI3,1*48C6H5Br ; the additive compound crystallises in needles and in the absence of excess of antimony bromide has m.p. 6.5' ; the two additive compounds are isomorphous ; inoculation with SbCI,,C6H5C\ prevents the crystallisation of SbC1,,CGH5Br. The freezing diagram of the system SbCl and iodobenzene is similar on the whole to the previous ones. It is distinguished from them by the fact that the additive product SbCl,,C,H,I only separates exceptionally. Without inoculating with prepared crystals of this additive compound a freezing diagram is obtained consisting of two curves which cut each other in the eutectic point at - 45O corresponding with SbC1,,2*62C6H,I. Inoculation results in a diagram consisting of three curves with a eutectic point at - 34*5O corresponding with SbC1,,8*37C6H,I and a transition point at - 4.2" corresponding with SbCl,,l *5C,H,I.The metastable additive compound SbCl,,C,H,T forms long needles m. p. - 2'. The freezing diagram of the systemiantimony tribromide and chlorobenzene shows two curves which cut a t the eutectic point at - 47' correspond- ing with SbBr3,58C,H,C1 and that of the system tribrotnide and bromobenzene two curves meeting a t the eutectic point at -32O corresponning with Sb~r,,37%C6H5Br. In the case of the system antimony tribromide and iodobenzene the two curves cut at the eutectic point a t - 3 2 O corresponding with SbBr,,10.5C6H51. I n all these systems only antimony trichloride showed a tendency t o the forma- tion of molecular compounds I t s tendency to combine with hnlogen- substituted benzene derivatives decreases regularly with the increase in the atomic weight of the substituting halogen atom Four more systems of disubstituted derivatives of benzene were studied.The freezing diagram of the system antimony trichloride and p-dichloro- benzene consists of two curves which cut at the eutectic point at 39-5' corresponding with SbC1,,2*4C',H4C1,. I n the case of p-dibromo- benzene the eutectic point is at 49*5O corresponding with SbCI,,O*54C,H4Br,. The diagrams for the systems of antimony tribromide and p-dichloro- benzene and p-dibromobenzene each show t w o curves with eutectio points a t 48.5' corresponding with SbBr,,G*8C,H4C1 and at 6 5 O corresponding with SbBr,,0*92CqH4Br,. Disubstituted benzenes do not form molecular compounds with antimony trichloride. SbCl,,C6H,Br N. C. Examination of Systems of Substituted Benzenes with Antimony Trichloride.11. SbCI,,SbBr and Nitrobenzene. BORIS N. MEWSCHUTKIN (Chern. Zentr. 1910 ii 381-382; from Izvista of the St. Petersburg Polytechnic 13 41 1. Compare preceding abstracts).-The freezing diagram of the system antimony trichlorideORGANIC CHEMISTRY. i. 275 and nitrobenzene shows three curves of which the middle one dividing the area of the solid molecular compound SbCl,,C,H,*NO from the liquid does not always appear. This is because the compound has a very small velocity of crystallisation and is only separated from the liquid by strong freezing. Apart from that the diagram has two eutectic points one a t - 16*5" corresponding with SbCl,,3C,H,*N02 the other at - 6.5" corresponding with SbCI,,O SC,H,*NO,. I n between lies a very flat distectic a t - 6" the freezing point of the additive compound SbCl,,C,H,*NO which crystallises in loog needles.The results for the system antimony trichloride and m-dinitrobenzene are analogous; there is a three-branched curve but the middle one corresponding with the compound SbC13,m-C6H4(N02)2 is only realised exceptionally as the compound is metastable. As a rule a diagram is obtained coasisting of only two curves which cut a t the eutectic point at lo corresponding with SbC13,0-66C,~4(N02)2. Tf the fusion is inoculated with prepared crystals a three-division freezing diagram is obtained with a eutectic point at 21" corresponding with S bC1,,0.53C,H4(N0,) and a transition point at 28.5" corresponding with S bC1,,0* 9 4C,H,(N02)2. The additive compound SbC13,C,H,(N02)2 forms rhombic crystals m.p. 28.5". The diagram for the system antimony tribromide and nitrobenzene shows two curves cutting at a eutectic point at - 15" corresponding with SbBr3,2*34C,H,*NO ; that for the system with m-diuitrobenzene has also two curves the eutoctic point being a t 47*5" corresponding with SbBr3,0*84C,H4(N0,),. Of the two halogen com- pounds with antimony only the trichloride shows a tendency to the formation of additive compounds not only with halogen but also with nitro-derivatives of benzene. N. c. The Constitution of Anthranil. GUSTAV HELLER [and in part Ges. Wigs. MatJ'.-phys. HI. 1910 62 46. Compare Abstr. 1908 i 267 ; 1909 i 832)-It is first shown that substances containing the group (I) in many reactions have a tendency to form substances of the type (11).I n this way the formation of anthranil by the reduction of o-nitrobenzaldehyde can be so explained that it is not analogous to the formation of methyl- anthroxan by the reduction of o-nitroacetophenone and affords no argument as to the formula of anthroxan. II\CH< Aithranil and rnethylanthroxan behave diffarently in (I*) nearly all their reactions. With aniline anthranil con- NH- denses to form a substance C20H1503N or C,,,H,,O,N ; this crystallises in needles m. p. about 172". Prom the' solution in concentrated hydrochloric acid there separates a colourless compound which forms needles m. p. above 280O. By boiling the yellow condensation product for a quarter of an hour with acetic anhydride the acetyl compound C,,H,70,N is obtained as needles m.p. 186". A similar condensation product 1s obtained from anthranil with p - and ERICH GRUNTHAL) (Chem. i?%?at?*. 1910 ii 975 ; from Ber. K. Sdchs. ('I.)i. 276 ABSTRACTS OF CHEMICAL PAPERS. o-toluidines; methylanthroxan does not react in a similar way with aniline. There is a slight formation of anthranil on heating anthroxanic acid with water a t about 150'. At the same time there is formed an acid m. p. 247' soluble in sodium hydroxide; this is not identical with the substance m. p. 245' obtained on heating anthranil with water which is insoluble in sodium hydroxide. When anthranil is boiled with water at loo' it remains to a great extent unchanged; at a lower temperature in addition t o the compound m. p. 245' a substance m. p. 285' is formed which is not basic and seems to be a mixture.That the action of anthranil towards 39% hydrochloric acid and sodium nitrite is analogous to that of methylanthroxan (formation of anthroxan dichloride and o-aldehydobenzenediazonium chloride) is probably t o be explained by its tendency under the influence of strong mineral acids t o suffer intermolecular change and react in the anthroxan form ; by the action of concentrated hydrochloric acid a permanent desmotropic form is not produced. Anthroxanaldehyde is readily converted by dilute alkali into isatin; it immediately gives a blue indophenin reaction but is very resistant towards strong sulphuric acid separating to a great extent unchanged when water i s added after the mixture has been kept for several days.N. C. Nitrophenol Salts. ANTONI KORCZYNSKI (Chem. Zenbr. 19 10 ii 384 ; from Kosmos 1910 35 Rccdxisxewski-Festband 461)-In continuation of previous work (Abstr. 1908 i 977 ; 1909 i 148 639) the author notes the analogy between the colour of nitrophenol salts and the tendency of the nitrophenols to form abnormal salts with ammonia namely that nitrophenols which form yellow salts tend to form abnormal ammonium salts. The following ammonium salts of nitrophenols were prepared NO,*C,H,I*OH,NH at the ordinary temperature and N0,*C7H,I*OH,2NH at - 15' from 5-iodo-3-nitro- 2-cresol ; NO,*C,H,Br,-OH,NH,,C,H,N,(?) from 2-4-dibromo-6-nitro- phenol a t - 15' ; NO,-C,H2C1L*OH,2NH from 4-chloro-6-iodo-2- nitrophenol at - 15' ; N0,'C6H,BrI*OH,2NH from 4-bromo-6-iodo- 2-nitrophenol at - 15'. N.c. Action of Aluminium Chloride on Benzene. ANNIE HOMER (Proc. Camb. Phil. Soc. 1911 16 65-66).-Benzene containing 25% of its weight of aluminium chloride is heated at 100' under a reflux condenser for ten to fourteen days. After treatment with water and hydrochloric acid the product yields in addition to the alkyl- benzenes and phenol mentioned by Friedel and Crafts a fraction b. p. below 160'/10 mm. containing phenol and naphthalene. The formation of the latter is explained on the assumption that o-diethyl- benzene is produced and subsequently dehydrogenised by the aluminium chloride. NaphthaIene is not obtained when the experiment is performed in sealed Gubes at 180' for two days. c. s. The Action of Light on the Bromination of Tertiary 0- and p-Butyltoluene and the Chlorination of tes% -Bu tylbenzene and o-Butyltoluene.JR. SALIBILL (Bull. Acad. Sci. CTUCOW 19 10 A 606-608).-A mixture of bromine and p-butyltoluene in molecularORGANIC CHEMISTRY. i. 2'77 proportions was exposed to strong sunlight when combination rapidly took place giving a liquid that boiled at 156-159' under 32 mm. pressure The bromine replaced a hydrogen atom of the side-chain not in the ring. o-Butyltoluene reacted with bromine slowly a t first more rapidly afterwards. The bromine did not enter the methyl group a phenomenon attributed by the author to steric hindrance ; instead it replaced a hydrogen atom of the ring. Chlorine showed a similar behaviour. tert.-Butylbenzene behaved towards bromine and chlorine like o-butyl toluene.E. J. R. Cyclic Acetylenes. Phenylbutinene. EMILE ANDRB (BUZZ. SOC. chim. 1911 [iv] 9 192-195).-The author proposes to generalise Tiffeneau's met,hod for the preparation of aromatic olefinic hydro- carbons (Abstr. 1904 i 872) and t o prepare from the latter the corresponding acetylenes by bromination and decomposition of the bromides by alcoholic potassium hydroxide. The application of this process to allylbenzene leads to the formation of phenylmethylacetylene Ph-CiCMe. Phenylbutylene CH,Ph*CH,*CH:CK prepared by the action of ally1 iodide on magnesium benzyl chloride contrary to Aronheim's statement (this Journ. 1874 6$9) is readily converted by bromination in chloroform and the subsequent acbion of potassium hydroxide in alcohol into phenylbutinene CH,Ph*CH,*CiCH DO 0.9391 b.p. 189-191°/758 mm. which is best purified through the sodium derivative and then forms a colourless highly refractive liquid. T. A. H. A Convenient Method for the Reduction of Alcohols of the Diphenyl- and Triphenyl-methane Series. ALEXEI E. TSCHITSCHIBABIN (Ber. 191 1 44 441-443).-The methods at present available for the reduction of the above-mentioned alcohols often yield poor results. The author finds that the reduction with hydriodic acid in acetic acid solution proceeds very readily and gives almost quantitative yields. The reduction is carried out by dissolving the alcohol in the smallest possible quantity of glacial acetic acid and adding an excess of a saturated solution of hydriodic acid in the same solvent ; the mixture is heated to boiling and the reduction product precipitated by pouring the solution into water containing sodium hydrogen sulphite which removes the iodine formed in the reaction.Ethers and halogen derivatives may be reduced in the same manner. The method has been applied for the preparation of triphenylmethane d iphenylmethane and diphenylacetic acid from triphenylcarbinol diphenylcarbinol and benzilic acid respectively. F. B. Dinaphthylmethanes and Some of their Derivatives. ALEXEI E. TSCHITSCHIBABIN (Ber. 191 1 44 443-450).-The paper deals with the application of the author's method of reduction (preceding abstract) t o the preparation of the three isomeric dinaphthyl- methanes.i. 278 ABSTRACTS OW CHEMICAL PAPERS. aa-Dinaphthylcarbinol prepared by a modification of the method described by Schmidlin and Massini (Abstr.1909 i 561) is readily reduced to aa-dinsphthylmethane m. p. 109" (compare Schmidlin and Huber Abstr. 1910 i 832) ; the latter compound is also produced together with aa-dinaphthyl ketone by distilling aa-dinaphthyl- carbinol under diminished pressure 2CH(C1!H,),*OH = CH,(C,,H7) + CO(C,,H7),. The hydrocarbon is separated from the mixture by taking advantage of i t,s insolubility in concentrated sulphuric acid. aa-Dinaph- thylmethyl bromide is obtained by the action of hydrogen bromide on the carbinol in glacial acetic acid solution (compare Wheeler and Jamieson Abstr. 1902 i 763). The interaction of magnesium a-naphthyl bromide and P-naphth- aldehyde yields ap-dina~hthyZcccl.bino1 which crystallises in soft needles m.p. 108-109" dissolves in sulphuric acid with a blue colour and on reduction yields a@-dinaphthylrnethane crystallising in glistening flat prisms m. p. 96". The carbinol forms with benzene a crystalline compound 2CH(C,,H7),*OH,C,H6 which decomposes at 78" into its constituents. ap-BinaphthyZmethyZ bromide CH(C,,R7)2Br prepared from the carbinol and hydrogen bromide in glacial acetic acid solution crystallises in needles m. p. 123-123.5'. By the interaction of magnesium P-naphthyl bromide and ethyl formate PP-dinaphthylcarbinol is obtained as an oil which crystallises when left over sulphuric acid (compare Schmidlin and Huber loc. cit.) ; on treatment with hydrogen bromide in acetic acid solution i t yields PP-dinaphtAylmethy1 bromide which forms a cryetalline powder m.p. 168-16g3 gives a violet coloration with sulphuric acid and yields PP-dinaphthylmethane when reduced witb hydriodic acid. The PP-dinaphtbylmethane thus obtained has m. p. 93" and is identical with the hydrocarbon prepared by Richter (Abstr. 1881 281) by the reduction of the corresponding ketone. . . - By reducing di-p-naphthaxanthone C,,H6<(>C,,H with hydriodic acid Clam and Ruppel (Abstr. 1890 511) obtained a hydrocarbon to which they assigned the formula of aa-dinaphthyl- methane; Schrnidlin and Huber consider it t o be the up-compound. The hydrocarbon differs however in properties from the three isomeric dinaphthylmethanes described above so that its constitution remains undetermined. F. B. Halogen Derivatives of Triphenylmethane. ALEXEI E.TSCHITSCHIBABIN (Ber. 191 1 44 450-459).-8 further application of the author's method of reduction (preceding abstracts) to the preparation of the halogen derivatives of triphenylmethsne. p-Chlorotripheuylcsrbinol previously obtained by Gomberg and Cone (Abstr. 1906 i 822) crystallises from light petroleum in large cubes m. p. 85". On rediiction it yields p-chlorotriphenylmetham which erystallises in two forms glistening needles m. p. 59*5" and large transparent crystals m. p. 54". The latter form is unstable and is transformed when kept into t'h6 less fusible moditicatioo.0 RG ANIC CHEMISTRY. i. 279 o-ChZorotriphenyZcarbinoZ prepared by the action of magnesium phenyl bromide on methyl o-chlorobenzoate forms a crystalline powder m. p. 91-92' gives an orangeyellow coloration with con- centrated sulphuric acid and yields o-chlorotri~~~enyl~~aetl~yl bromide m.p. 118-12to. The bromide givep on reduction o-chloro- triphenplmethane which crystallises in short prisms m. p. 7 7 O and forms a crystalline compound with benzene ; this decomposes a t 40' into its constituents. p-Bromotriphenplmetl~yl bromide prepared from the coi*r.esponding carbinol (Cone and Long Abstr. 1906 i 424) has m. p. 132-1334' and is readily reduced to p-bromotriphenyZmethane which resembles the p-chloro-compound in being dimorphous. The stable modification obtained by inoculating a solution of p-bromotriphenylmethane in light petroleum with the stable form of the p-chloro-compound crystallises in glistening needles m. p. 82.5'. The second modi- fication has m.p. 6S0 and is more soluble than the stable form. p-Bromotriphenglmethane differs from the or tho- and meta-isomerides in not forming a crystalline compound with benzene. o-Bromodriphenylccrbinol obtained by the interaction of magnesium phenyl bromide and methyl o-bromobenzoate crystallises from hot glacial acetic acid in soft leaflets m. p. 158' and gives an orange- yellow coloration with sulphuric acid. o-Bromotriphenylmethyl bromide forms a coarsely crystalline powder m. p. 120-125' (decomp.) and yields on reduction o-bromotriphenyl- methane ; the latter crystallises i n short glistening prisms m. p . 81' and forms a crystalline compound with benzene m. p. 45' (decomp.). m-Bromotriphenylmethyl bromide obtained by the action of hydro- bromic acid on m-bromotriphenylcarbinol (Cone and Long Zoc.cit.) separates from light petroleum in glistening crystals m. p. 145-146' ; it is deposited from its solutions in glacial acetic acid in the form of white granules m. p. 75O which apparently contain acetic acid. m-Bromotriphenylmsthane prepared from the corresponding bromide bg reduction separates from benzene i n large crystalline granules of the composition Cl9Hl5Rr,C6H6; these have m. p. 55' and on keeping are slowly transformed into a viscid oil; when heated t o 80' the benzene of crystallisation is lost p-bromotriphenylmethane separates as an oil which could not be obtained in a crystalline form. p-Iodotriphenylcarbinol prepared by the interaction of magnesium phenyl bromide and methyl p-iodobenzoate is converted by the action of acetyl chloride into the carbinyl chloride m.p. 123' Gomberg and Cone (Zoc. cit.) give 125'. p-lodotriphenylmeth~n~ crystallises in yellow needles m. p. 8 1 -5O. Tri-p-bromotriphenylmethane prepared by reducing tri-p-brorno- triphenylmethyl ethyl ether has m. p. 115' (compare Fischer and Hess Abstr. 1905 i 205). F. B. a-Methylanthracene. OTTO FISCHER and A. SAPPER (J. pr. Chem. 191 1 [ii] 83 201-208).-uMethylanthracene and its P-isomeride which both crystallise in white leaflets are stated t o have approxi- mately the same m. p. and yield methylanthraquinones also havingi. 280 ABSTRACTS OF CHEMlCAL PAYERS. nearly the same m. p. Since the two hydrocarbons are produced by the distillation of very different natural substances with zinc dust it is desirable t? have a certain method of distinguishing between them.Tbs authors obtain a very poor yield of impure a-methyl- anthracene by Birukoffs method of distilling 4-hydroxy-1 -methyl- anthraquinone with zinc dust the main product being anthracene. a-Methylanthracene is conveniently obtained by distilling 4-chloro-l- methylanthraquinone (Heller and Schulke Abstr. 1908 i 994) with zinc dust at a very low red heat; it has m. p. 85-86' crystallises in long white needles is much more soluble in most solvents than anthracene or @-methylanthracene forms a blue fluorescent solution in alcohol and yields a picrate red needles m. p. 113-115'- a-Methylanthraquinone m. p. 170-171° does not lose its methyl group by distillation with zinc dust and differs from P-methyl- anthraquinone by rapidly reddening on exposure to light.It is oxidised by dilute nitric acid at 160" to mthraquinone-1 -carboxylic acid which develops a rose coloration when heated with soda-lime ; anthraquinone-2-carboxylic acid turns blue under similar conditions. 4-Chloro-1 -methyZunth~acene CJ311Cl m. p. 1 12" obtained by boiling 4-chloro-1 -methylanthraquinone with zinc dust and aqueous ammonia does not lose its halogen by distillation with .zinc dust. 4-Methoxy-l- methylanthraquinone m. p 128" yellow needles obtained from 4-chloro - 1 -methylanthraquinone and methyl-alcoholic potassium hydroxide at 100" under pressure reddens in light and is converted into 4-hydroxy-1 -methylanthraquinone by glacial acetic and concen- 'trated hydrochloric acids at 100' under pressure.c. 5. Aliphatic Nitro-compounds IX. Action of Phenyl- carbimide on Sodium Nitromethane and Nitroethane. WILHELM STEIKKOPF and H. If. DAEGE (Bey. 1911 44 497-502. Compare this vol. i 4).-When sodium nitromethane and phenylcarbimide in benzene solution are set aside for some weeks nitroacetanilide and a little malonanilide are formed (Michael Abstr. 1905 i 195). Reaction is quicker when the components are warmed for an hour on the water- bath ; in both cases a further investigation has proved that s-diphenyl- carbamide and triphenylbiuret are also formed. The last is converted on boiling with potassium hydroxide into diphenylcarbamide and its formation is obviously due to the action of excess of phenylcarbimide on diphenylcarbamide.The constitution of nitroacetanilide was confirmed by its conversion into nitroacetic acid by boiling with strong aqueous potassium hydroxide. Sodium nitroethane and phenylcarbimide only yield traces of the sodium salt of a-nitropropionanilide the main products here being s-diphenylcarbamide and triphenylbiuret. I n other experiments particularly those made with fresh phenylcarbimide triphenyliso- cyanurate C3N,0,Ph3 together with nit1 ogen and some diphenyl- carbamide ere formed. This reaction is in opposition to Michael's theory (Zoc. cit.) that the course of change followed is that in which a maximum of chemical neutrality is attained. E. P. A.ORGANIC CHEMISTRY. i. 281 Action of Nitrous Acid on Dioitrodialkylanilines. PIETER VAN ROMBURGH ( PTOC. K.Akad. Wetensch. Amsterdam 19 1 1 13 820-822).-The substance m. p. 175-176' obtained by Hantzsch by the action of nitric acid D 1.3 on dimethylaoiline and described as 3 4-dinitrodimethylaniline (Abstr. 1910 i 475) is proved to be 2 4- dinitromethylaniline ; its mixture with the true 3 4-dinitrodimethyl- aniline m. p. 176' causes a large depression of the m. p. The production of the dinitromethylaniline is due to the elimination of one methyl group by the nitrous acid formed during the nitration; in fact 2 4-dinitrophenylmethylnitrosoamine is produced when a solution of dimethylaniline in ten volumes of nitric acid D 1.3 is kept overnight. When however carbamide is added to the nitric acid t o decompose the nitrous acid formed the main product of the nitration of dimethyl- aniline is 2 4-dinitrodimethylaniline m.p. 87". By treating a solution of t h i s substance in five times its weight of nitric acid D 1.3 with sodium nitrite 2 4-dinitrophenylmethylnitrosoamine is obtained from which 2 4-dinitromethylaniline is produced by boiling with acetic acid. Precisely similar reactions are exhibited by 2 4-dinitro- diethylaniline and 2 4-dinitrodipropylaniline. The action of nitrous acid on 3 4-dinitrodialkylanilines in dilute sulphuric acid also results in the elimination of one alkyl group and the formation of a nitrosoamine ; thus 3 4-dinitrodiethylaniline yields a pale yellow nitTom-compound m. p. 79-80'. Also the same behaviour is shown by 3 6-dinit4rodiethylaniline which is converted by nitrous acid into a yellow nitroso-compound m.p. 69' from which 3 6-dinitroethylaniline is produced almost instantly by boiling acetic acid. 3 6-Dinitrodimethylaniline behaves in a similar manner. c. s. A New Preparation of Diphenylmethylamine (Benzhydryl- amine). HEINRICH BILTZ and KARL SEYDEL (Bey. 1911 44 41 1-41 3).-Diphenylmethylamine is readily prepared by heating 5 5-diphenylhydantoin (Biltz and Rimpel Abstr. 1908 i 462) at 230-300" with a n excess of potassium hydroxide and a small quantity of water; it has b. p. 303.6' (corr.). The picrate ClSH1607N2 crystallises in deep yellow needles m. p. 205-206' (decomp.). 5 5-Diphenylthiohydantoin when fused with potassium hydroxide a t 300° is quantitatively converted into diphenylmethylamine ; at 260° 5 5-diphenylhydantoin is produced simultaneously.An improved method for the preparation of the last-mentioned compound is described. F. B. Doubly Linked Carbon Atoms and the Carbon-Nitrogen Linking. V. Fission of Quaternary Ammonium Salts by N a s c e n t Hydrogen. VI. Formation of Mixed Tertiary Amines. VII. Relative Mobility of Allyl- Benzyl- and Cinnaniyl- in the Fission of Quaternary Ammonium Salts by Reduction. HERMANN EMDE [with HANS SCHELLBACH in VI and VII] (Arch. Pharm. 1911 249 106-111 111-117 118-122. Compare Abstr. 1909 i 565 705 709).-Phenylbenzyldimethyl- VOL. c. i. Xi. 282 ABSTRACTS OF CHEMlCAL PAPERS. ammonium chloride (aurichloride m. p. 97-98' decomp. ; plutini- chloride m. p. 181' decomp.) reduces normally (Zoc. cit.) with sodium amalgam in water giving dimethylaniline and toluene but when the reduction is eifected in alcohol toluene is in part replaced by benzyl ethyl ether.It is probdble that in presence of alcohol the substituted ammonium chloride breaks up first into dimethylaniline and berizyl chloride and that the latter then reacts with sodium ethoxide. The general method of carrying out the reaction and isolating the products is described. The fission by reduction method may be applied to the preparation of mixed tertiary amines in the following way (compare J h m e r t Abatr. 1909 i 3763. T~ibenzylmethylaPnmo~i~m iodide m. p. 184" gives a cacinii-iodide m. p. 238" and with silver chloride the corresponding chloride m. p. 202"; the platinichloride has m. p. 209" and the aurichloyide m. p. 188' (decomp.). The iodide itself on reduction with sodium amalgam in aqueous alcohol gives benzyl ethyl ether and dibenzylmethylamine (Abstr 1909 i 709); the latter reacts with allyl iodide to form dibelzxylmet~iytallylan~monium iodide m.p. 149') which on reduction gives benxylmet~ylallylninine b. p. 255-256'1760 mm. (platinichloride m. p 1 39"). From this nmine benxylmethyEalZyZp~opylammonium cAlorzde m. p. 279" was prepared and this on reduction furnished rnethylally~ropylamine b. p. 171-172'1765 mm. which gives a platinichloride m. p. 144' (decomp.) and an oily aurichloride. The foregoing work shows that in the fission of a quaternary ammonium compound containing both allyl- and benzyl- the latter is perferably removed from the N-stom and the following results show thqt cinnamyl- like benzyl- is more mobile than allyl- in t h i s connexion (compare von Braun Abstr.1907 i 899; Wedekind and Paschke Abstr. 1910 i 372). Diciianarnyldietl~yluccmmoniuni chloride on reduction with sodium amalgam in water furnishes phenylpropylene and cirranamyldiet~~ylamins b. p. 263-365"/765 mm. Cplatinichloride m. p. 208' decomp.) which combiDes with allyl iodide to give cenna~yldiethylacZZy2am~oni~n~ iodide m. p. 106" (platinichloride 91. p. 157') and this on reduction with sodium amalgam in water yields diethylallylamine (platinichloride m. p. 166" not 128-1 30° as stated by Liebermann and Paal Abstr. 1883 908). T. A. H. Tetracinnamyl- and Tetrabenzyl-ammonium. HERMANN EMDE (Arch. Pharm. 1911,249 93-106. Compare Abstr. 1909 i 708).- It is now well-established that there is a difference in function between the first three and the fifth valencies of a nitrogen atom but i t is not yet certain whether the fourth valency is of the same type as the first three or has some special function - With a view to throwing light on this point the author is investigating the formation and stability of substituted ammonium compounds containing four similar organic radicles.Tetracirinsmylammoniurn salts are now described but tetra- benzylammonium compounds could not be obtained. [With HANS ScHELmAcH.]-Tetracinnamylamrnonium chloride m. p. 19Yo may be obtained by melting together tricinnamylamiue and cinn- amyl chloride and washing the product with ether. A process for itsORGANIC CHEMISTRY. i. 283 isolation from the mixed amines formed by the action of ammonia on cinnamyl chloride is also described.It is almost insoluble in water but readily soluble in acetone or alcohol. It is stable towards alkalis but is decomposed by silver hydroxide suspended in alcohol giving tetracinnamyylammonium hydroxide which crystallises in colourless compact rods sinters a t 146O solidifies again at 165O and re-melts a t 170"; the hydroxide absorbs carbon dioxide from the atmosphere and on heating decomposes a t 150-175°/20-30 mm. yielding a thick yellow distillate b. p. 154O which rapidly resinifies. Cinnarnyltrimethylammoniurn chloride m. p. 156" was obtained crystalline ; it does not give the corresponding hydroxide by the action of silver hydroxide as decomposition ensues with the formation of trimethylamine.by various methods including Brunner's confirmed Marquardt's experlence that this substance cannot he obtained I t s non-formation is probably a special case of '' steric hindrance." Attempts to prepare tetrabenzylammonium chloride T. A. H. Red and White Silver Salts of 2 4 6-Tribrornophenol. HENRY A. TORREY and WILLIAM H. HUNTER (J. Anler. Chenz. Soc. 1911 33 194-205).-1n an earlier paper (Absbr. 1907 i 1030) the authors described red and white isomeric silver salts of 2 4 6-tribromophenol. This observation was confirmed by Hantzsch and Scholtze (Abstr. 1908 i 17) who also described similar derivatives of 2 6-dibromo- pcresol. It has now been fourid that 2 4 6-tribromoresorcinol methyl ether and 3 4 6-tribromoguaiacol also yield red and white silver salts but in these cases the red salts undergo transformation into the white isomerides too rapidly to permit of their isolation. When solid potassium hydroxide is added to a solution of 3 4 6- tribromoguaiacol in dry acetone a yellow potassium derivative is produced which is immediately decolorised on addition of water.On adding a solution of silver nitrate in acetone to the acetone solution of the salt a red precipitate is produced which rapidly turns black. The two silver salts of 2 4 6-tribromophenol do not show any difference in their behaviour towards acids alkali hydroxides alkyl iodides or other reagents. It is considered probable that the change of the red salt into the white modification is due to tautomerism the white salt being the stable form with the ordinary benzenoid formula and the red salt the labile form with the ortho-yuinonoid constitution O:C,H,Br,:BrAg.Hantzsch however has raised objections to the latter formula aud has stated that if silver could behave in this way mercury ought to show even greater tendency to form such compounds and should therefore give coloured salts whereas the mercuric salts of tribromophenol and other phenols obtained by Hantzsch and Auld (Abstr. 1906 i 471) were white. It is pointed out however that mercuric d t s do not resemble silver salts so closely as do mercurous salts and as the result of experiments i t has been found that 2 4 6- tribromophenol and 2 4 6-tribromoresorciuol both yield yellow mercurous salts and tri-iodophenol an orange mercurous salt. Yellow precipitates were also obtained on the addition of uerc~~rous x 2i.284 ABSTRACTS OF CHEMICAL PAPERS. nitrate to alcoholic solutions of tribromoresorcinol methyl ether and tetrabromoguaiacol. 2 4 6-TribromoresorcinoZ dimethyl ether m. p. 68-69' forms a orystalline powder. E. G. Salt Formation by Aminophenols. WILHELM SUIDA (J. pr. Chem. 1911 [ii] 83 233-242).-The problem of t,he formation of salts by amphoteric organic substances has been approached by dissolving equivalent quantities of an aminophenol and of an aromatic amino-acid in just sufficient hot water heating the solution rapidly to boiling filtering cooling and examining the crystals obtained. The unexpected result has been obtained that of the three amino- phenols only the ortho-compound forms salts with anthranilic acid (orange-red prisms decomp.below loo') m-aniinobenzoic acid (stout red prisms decomp. 1 OOO) and p-aminobenzoic acid (brownish-red prisms m. p. 139'). The explanation suggested namely that salts Of the type c6H4<Ni0 o->C(OH)*C6H,*NH .O are formed is supported by the fact that agaii only o-aminophenol forms salts with benzoic acid (yellowish-brown or brownish-red prisms which lose benzoic acid a t loo') phenylacetic acid (colourless leaflets m. p. 130-131') and sulphanilic acid (brownish-red prisms nearly unchanged at 250'). o-AminophenyZ fornaute has m. p. 119-120'; all of these salts can be recrystallised from boiling water ; when animal charcoal is added however the substance separates in two distinctly different crystalline forms.The salts lose weight continuously at 100-105' owing partly to the volatilisation of the salt itself partly to the escape of the more volatile constituent ; oxazoles are not formed. o-Aminophenol does not form additive compounds of the above type with other substances containing a carbonyl group. It condenses under the conditions mentioned with methyl oxlate to form o-arninophenol o-hydroxyphenyl- oxamate CI4Hl4O5N2 and with acetylacetone t o form a substance m. p. 186-187' which is probably OH*C6H,*N:CMe*CH,*COMe. c. s. Phenyl Ether and Some of its Derivatives. ALFRED N. COOK (J. Amer. Chew. Xoc. 1911 33 254-255).-An addendum to tho earlier paper (Abstr. 1910 i 731). Yetrabromo-p-tolyl ether O(C6H,MeBr,) b. p. 310-330°/40 mm. is obtained by the action of bromine in direct sunlight on a warm solution of p-tolyl ether as a light yellow viscous substance which crystallises on cooling.A more highly brominated derivative could not be obtained Dibromo-p-tolyl ether was obtained in small yield by adding bromine gradually to p-tolyl ether heated at 150'. The results of experiments on the action of bromine on o-tolyl ether were not satisfactory but were sufficient to show that the bromine enters the nucleus and not the side-chain. Attempts to Prepare Optically Active Phosphorus Com- pounds. FRITZ EPHRAIM (Ber. 1911,44 631-637. Compare Caven Trans. 1902 8'1 1362; Luff and Kipping ibid. 1909 95 1993 ; Meisenheimer and Lichtenstadt this vol. i 344).-Atterrrpts to resolve E. G .ORGANIC CHEMISTRY. i. 285 compounds of the types NH,*PO(ONa)*OPh and .NH,*PS(ONa)*OPh into optically active components were unsuccessful. A better yield of Stokes' diphenyl aminophosphate (Abstr.1893 i 315) is formed when a n excess of phosphoryl chloride is used. The ester reacts with a hot boiling solution of barium hydroxide (equal weights of ester and crystallised hydroxide in 100 C.C. of water) yielding the barium salt of phenyl aminophosphoric acid [NH,*PO(OPh)*O],Ba,H20 which crystallises in microscopic needles readily soluble in water. The corresponding cinchonine salt NH,*PO(OPh)*OH,C,,H,,ON crystal- lises in minute needles m. p. 194O and then in flat prisms but both fractions had the same value for [.ID namely + 11.5' The chloyide PSCl(OPh) prepared by the addition of sulphur to the chloride of diphenyl phosphite a t 20@-300' crystallises from alcohol in brilliant colourless glistening needles m.p. 68'. It is decomposed when boiled with water and its alcoholic solution reacts with concentrated aqueous ammonium hydroxide yielding the diphenyl aminothiophosphate NH,*PS(OPh) which crystallises in thin rhombic leaflets m. p. 112'. This ester IS hydrolysed by alcoholic sodium hydroxide solution yielding the sodium salt OPh- PS( NH,) ONa 2 H,O which dissolves readily in both alcohol and water; its aqueous solution yields precipitates with silver nitrate lead acetate and copper sulphate. The corresponding cinchonine salt C2,H300,N,SP obtained by the action of .the sulphate of the base on the sodium salt in absolute alcoholic solution forms a syrupy mass and has [a] + 11.06'.J. J. S. p-Aminothiophenol [p-Aminophenyl Mercaptan]. 111. THEODOR ZINCKE and P. ZORG (Ber. 1911,44 614-626. Compare Abstr. 1909 i 789 ; this vol. i 39).-A dye C,,H,,N,S,Cl which crystallises in violet-black lustrous plates and yields deep blue alcoholic solutions is formed by the oxidation of an alcoholic solution of p-methylthiolaniline @-aminophenyl methyl sulphide) with a 1 5 N - aqueous solution of ferric chloride. The free base prepared by the action of dilute ammonia on the hydrochloride forms a heavy brownish- red flocculent mass which readily undergoes decomposition when in solution or when dried. The dye is decomposed when left in contact with dilute hydrochloric acid for some time and yields p-methylthiol- aniline and reacts with a met hyl-alcoholic solution of p-toluidine yielding a compound SMe*C,H4*N:C,H,(NH*C7H7),:N*C7H7 which crystallises from toluene in dark reddish-brown glistening plates m.p. 238'. The Zeuco-compound C,,H,,N,S obtained by reducing the dye with stannous chloride crystallises from dilute alcohol in slender colourless needles resembling asbestos and has m. p. 105'. The hydyochloride crystallises from alcohol in colourless plates and both base and hydrochloride are readily oxidised t o the dye by means of ferric chloride or nitrous acid. The acetyl derivative C,,H,,ON,S crystallises from dilute acetic acid in glistening prisms m. p. 155" and the trimethylammonium iodide C,7H,,N,S,T forms a colourless crystalline powder m. p. 186-190' (decomp.). The leuco-base isi.286 ABSTRACTS OF CHEMICAL PAPERS. regarded as R derivative of p-phenylenediamine and is given the formula NH,*C,H,(SMe)*NH*C,H,*SMe and the corresponding dye the structural formula HCI,NH:C6H3(SMe):N*C6H4*SMe. The para- formula is preferred as the leuco-compound does not give the reactions characteristic of an orthodiamine for example it does not yield an azimino-derivative with nitrous acid but this formula necessitates the assumption of tbe wandering of a *SMe-group during the oxidation of the methylthiolaniline to the dye (compare Bamberger Abstr. 1901 i 140; Zincke 1901 i 330; Kumazai and Wolffenstein 1908 i 159). When oxidised with hydrogen peroxide the acetyl derivative yields the disulphone NHAc*C,H,( SO,Me)*N€€*C,H,*SO,Me which crystallises from nitrobenzene in yellow needles m.p. 273-275' (decomp.). The leuco-compound reacts with Q glacial acetic acid solution of phenanthraquinone yielding 4 2 1 4' C,F14<yh?,t>C N*C,H,( SMe)-NH*C,H,*SMe in the form of a dark carmine-red crystalline powder m. p. 281". I t has feebly basic properties and its salts have an intense deep-blue colour. The leuco-base also reacts with carbon disulphide in the presence of alcohol at loo' yielding a thiocarbamide derivative CS[N H*C,H,(SMe)-NH* C,H;SMe] which crystallises from glacial acetic acid in small colourless needles m. p. 160". The compound obtained by shaking t i e leuco-base with a chloroform solution of o-xylylene bromide for two days crystallises from alcohol in colourless needles m. p. 139". Axoxgphenyl methyl sulphone ON,(C,H,*SO,Me) prepared by oxidising p-methylthiolaniline with hydrogen peroxide crystnllises from glacial acetic acid in yellow prisms m.p. 264'. The dye formed by the oxidation of p-snisidine with ferric chloride has not been obtained in a pure state. p-Aminothiophenol is not readily oxidised and does not yield a dye analogous to that obtained from p-aminopheml (Willstatter and Piccard Abstr. 1909 i 517). It is suggested that the leuco-compound derived from the dye from p-aminophenol is 4-amino-3 4'-dihydroxydiphenylamine. J. J. S. Action of Thionyl Chloride and of Sulphur Dioxide on Magnesium Alkyl Halides. BERNARDO ODDO (Gazzetta 19 1 I 41 i 11-16. Compare Strecker also Grignard and Zorn Abstr. 1910 i 532).-Thionyl chloride reacts with magnesium ethyl iodide forming ethyl sulphide and with magnesium phenyl bromide i t yields pbenyl sulphide in addition t o ,.mall quantities of phenylsulphoxide and diphen yl.Sulphur dioxide and magnesium phenyl bromide react producing phenpl sulphide as well as small quantities of phenylsulphoxide and dipheny 1. R. V. S.ORGANIC CHEMISTRY. i. 287 Sulphur Derivatives of p-Cresol. TIXEODOR ZINCKE and J. KEMPF (Ber. 19 1 I 44 413-424).-€'0tctssium 5-bronzo-p-cresoZ-3- sulphonate HO*C,€I,MeBr*SO,K prepared by the addition of a mixture of bromine and glacial acetic acid to an aqueous solution of potassium p-cresol-3-sulphonate forms lustrous white leaflets ; the methyl ester crystnllises in long prismatic needles m. p. 79-SO"; the ethyl ester in stout prisms m. p. 54-55'. 6- Bromo-p-cresoZ-3-sulphon~Z chEoride OH*C6H,MeBr-S0,C1 obtained by treating the corresponding pot.assium salt with chlorosulphonic acid crystallises in needles m.p. 94-95'. The action of phosphorus pentachloride or phosphoryl chloride on the potassium salt yields besides the sulphonyl chloride an ester having the formula S0,CI *C,H,MeBr 0 POCl and crystallising in colourless prism9 m. p. 147'. The acetyl derivative of 5-bromo-p-cresol-3-sulphonyl chloride forms lustrous apparently monoclinic prisms m. p. S4-S5'. When anhydrous potassium acetate is added to solutions of the sulphonyl chloride in ncrtone or ether a yellow coloration is produced due to the removal of hydrogen chloride and the form a t i on of 5- bromo-a- toluosulphonoquinone (annexed formula). A similar action takes place on the addition of amriionia to an alcoholic solution of the snlphonyl chloride but the snlphonoquinone thus produced unites with the alcohol to form an ester of the sulphonic acid.By evaporating the yellow acetone or ethereal solutions a white crystalline powder consisting of the polymeric form of the sulphonoquinone is obtained; the same substance is also produced by the action of chloro- sulphonic acid on 5-bromo-p-creeol-3-sulphony1 chloride. On reduction with zinc dust and hydrochloric acid in alcoholic solution the sulphonyl chloride yields 5-bromo-p-cresol 3-mevcaptan OH*C,H,MeBr-SH crystallising in long lustrous silky needles m. p. 32-33" ; the diacetyl derivative is a liquid ; the dibenxoyE derivative forms colourless needles m. p.93-94' 5-Bromo-p-c~esol 3-disulphide S,( C6H,MeBr*OH),? prepared by oxidising the mercaptan with ferric chloride crystallises in lustrous pale yzllow needles m. p. 76-77'; the dibenzoyt derivative forms colourless needles m. p. 130-131'. On methylation with methyl iodide and sodium methoxide in methyl- alcoholic solution the mercaptan is converted into 5-bromo-3-methyZ- thiol-p-cresol OH-C H MeBr-SMe which forms a colourless strongly refractive oil b. p. 162-163'/13-14 mm. yields an clcetyl derivative crystallising in colourless needles m. p. 51-52' and when treated with bromine in chloroform solution gives 2 5-dibromo-3-methyZthiol-p- cresol dibrornide HO*C,HMeBr,-SMeBr2. The latter compound crystallises in stout almost black needles and prisms strongly resembling iodine in appearance; it sinters a t loo' and melts at 128-130° with the evolrition of bromine and hydrobromic acid.It loses bromine on exposiire to air and when treated with bromine in chloroform solution yields 2 3 5-tribromocresol. 2 5-Dibromo-3-methyZthioZ-p-cresoZ OH*C6HMeBr2*SMe prepared Me /\ Br I!,) SO 0 ..i. 288 ABSTRACTS OF CHEMICAL PAPERS. from the dibromide by shaking with aqueous sodium hydrogen sulphite or by boiling with glacial acetic mid forms small compact colourless crystals m. p. 53-54'; from hot glacial acetic acid it separates in colourless prisms containing acetic acid; i t unites with bromine to form the original dibromide. On treatment with nitric acid in glacial acetic acid solution it yields 2 5-dibromo-3-nitro-p-cresol.The acetyl derivative of 2 5-dibromo-3-methylthioly-cresol crystal- lises in short colourless prisms m. p. 88-89" 2 5-~ibromo - p - cresol - 3 - methylsuZphoxide OH*C,HMeBr,*SOMe obtained together with the pseudo-bromide described below by shaking an ethereal solution of 2 5-dibromo-3-methylthiol-p-cresol dibromide with water forms small lustrous prisms which sinter a t 185" and melt at 188-190" (decomp.) ; on treatment with saturated aqueous hydrobromic acid it is reconverted into the dibromide. 2 5-Bibromo-p-cresol- 3-methyZsulphone HO*C,HI~eBr;SO,Me pre- pared by oxidking 2 5-dibromo-3-methylthiol-p-cresol with hydrogen peroxide in glacial acetic acid solution crystallises in lustrous needles m. p. 160-161". 2 5-Dibromo-3-methyZt~iol-p-cresoZ +-bromide (annexed formula) is obtained from the above-mentioned dibromide either by shaking with CH,Br water in ethereal solution or by the action of glacial acetic acid and anhydrous potassium acetate ; it crystal- lises in long colourless needles m.p. 130-131' yields lSMe an orange-red additiwe product with bromine and in contact with alkali slowly acquires a greenish colour finally becoming almost black. On treatment with aqueous sodium acetate and ether it is converted into an intensely black quinone probably belonging to the stilbene series. ROBERT BEHREND and WILHELM LUDEWIG [and in part THEODOR KLINCKHARD J (AnnuZen 19 1 1 379 35 1 -362).-4-Hydroxyphenanthrene has been sy nthesieed by a method analogous to that for the synthesis of a 4-naphthol from phenylisocrotonic acid.Full details are given of the best method for preparing P-naphthaldehyde from calcium a-naphthoate and calcium formate the yield being about 65% of the theoretical. /\Br yH BJ F. B. Synthesis of 4-Hydroxyphenanthrene. - CH(CozH)*?Hz obtained by 0 -co P-Nuphthylpuraconic acid C,,H,*CH< heating the aldehyde with anhydrous sodium succinate (1.2 mols.) and freshly distilled acetic anhydride (1.3 mols.) a t 108-114° for six to eight hours after keeping overnight in a closed vessel at the ordinary temperature is extracted with hot carbon disulphide to remove colouring matter dissolved in sodium hydrogen carbonate solution precipitated with hydrochloric acid and crystallised from hot water. It has m. p. 169-170" (decomp.) when the bath is previously heated to 160".When dissolved in the theoretical amount of iV/3- potassium hydroxide solution then well cooled and acidified with the theoretical amount of sulphuric acid and extracted with ether P-naphthylitamalic acid C,,H,*CH(OH)*CH( CO,H)*CH,*CO,H is obtained. It has m. p. 124-125' (decomp.) and is transformed readily jnto the paraconic acid.ORGANIC CHEMISTRY. i. 289 p-Naphthylisocrotonic mid C,0H7*CH:CH*CH2*C0,H is formed together with 4-hydroxyphenanthrene (Pschorr and Jnckel Abstr. 1900 i 488) and naphthylbutyrolactone when the paraconic acid is heated a t 200-275' or when it is distilled slowly. The acid dissolves in dilute sodium carbonate solution crystallises from carbon disulphide in glistening rods or from toluene in glistening plates m. p. 163-164' and when heated for some time at 100' yields 4-hydroxyphenanthrene.P-Na~htrh~Z6utyroZuctone C,oH7*CH<o~~0 2 crystallises from water in small glistening colourless plates m. p. 120-121' after sintering at 115-1 16'. CH *CH J. J. S. Reactions which lead to the Formation of I o d i n e Deriv- atives. G. GI~RARD (Chem. Zentr. 1910 ii 1050; from Bull. Sci. PharmacoZ. 1910 17 381-382).-When a solution of 2 grams of resorcinol and 1 gram of iodine in 10 grams of alcohol and 20 grams of water is mixed with a solution of 2 grams of borax and 1 gram of iodine in 10 grams of alcohol and 20 grams of water a colourless solution is obtained which does not yield a blue coloration with starch paste; on boiling the solution or exposing it to light a n intense red coloration is produced and the mixture gives a reaction with starch paste.When the solution is concentrlted violet hexagonal plates are deposited which are soluble in water alcohol and ether (tri-iodoresorcinol 2). Another colourless solution in which free iodine cannot be detected is obtained by mixing a solution containing resorcinol iodine and sodium benzoate with a solution containing resorcinol iodine and sodium salicylate. If the resorcinol is replaced by tannin brown solutions m e obtained ; these show no reactions for free iodine and when dried a t a temperature of 50° yield brown scales having a sweet and not a n astringent taste. w. P. s. Basic Properties of Oxygen Compounds of the Halogen Acids with Benzene Derivatives Containing Oxygen. 0. MAASS and DOUULAS MCTNTOSH (J.Amer. Chem. SOC. 1911 33 '70-71).- Baeyer and Villiger (Abstr. 1901 i 658) have stated that the substitution of positive groups such as alkyl groups for the hydrogen in water renders the oxygen basic whilst negative groups like phenyl do not have this effect and t h a t such compounds as phenol and benzophenone do not yield salts with acids. It is now shown that this generalisation is not correct since many substances containing the phenyl group dissolve in liquid hydrogen bromide or chloride with formation of compounds. The following compounds have been obtained in the crystalline state resorcinol hydrobromide C6H,(OH),,4HBr m. p. - 71"; benzoic acid hydrobromide C7H,O2,2HBr m. p. - 44' ; benzophenone hydro- bromide COPh,,GHBr m. p. - 42' ; and resorcinol hydrochloride C6H4( OH),,3(or 4)HCl and benzophenone hydrochloride (C H )2C0,7HC1 both with m.p. below -85'k %he benzophenone compounds contain more acid than would unite with the oxygen if it were quadri- or eveni. 290 ABSTRACTS OF CHEMICAL PAPERS. sexa-valent and i t is therefore suggested that they should at present be regarded merely as substances with acid of crystallisation. E. Gc. Derivatives of Butylcyclohexane. GEORUES DARZENS and H. ROST (Compt. rend. 191 1 152 607-609).-p-tert.-Butylphenol is readily hydrogenated by Sabatier and Senderens' method if the nickel is prepared by reduction below 260' ; the yield is practically theoretical if hydrogenation is effected below 160'. tert.-ButyZ- cyclohexan-4-oZ C,,H,,O m. p. 83' b. p. 110-115'/15 mm.has a camphoraceous odour ; on oxidation with chromic acid it yields tert.- butyZcyclohezan-4-one b. p. 106-109°/18 mm. 65-67'/3 mm. ; the ssmicarbazone has m. p. 315-216'. l-Methy2-3-tert.-butyZcyclol~xan-6-one b. p. 118-1 22'/31 mm. has a fruity odour. 5-tert.-ButyZ-m-xyZen-2-02 prepared by sulphonating butylxylene and heating the product with potassium hydroxide has m. p. 75' b. p. 107'/6 mm. On hydrogenation i t yields 1 3-dimethyZ-5-tert.-butyl- cyclohexan-2-ol a viscous liquid b. p. 123-124'/22 mm. 1 3-Dimethyl- 5-tert.-butyZcyclohexu~-2-olne has b. p. 120-121°/21 mm. and like the w. 0. w. foregoing ketone does not form a semicsrbazone. Crystallography of Some Organic Additive Compounds. GIOVANNI BOERIS (Zeitsch. Kwpt. &fin. 1911 49 72-73 ; from Hem. R.Accnd. Sci. 1st. Bologna 1907-2 9OS [vi] 5 303-308).-The additive compound of isoapiole and picryl chloride forms dark garnet-red triclinic crystals [a b c = 05453 1 0.4847 ; C12H1,O,,C,H2Cl(NOz)R a = 86'6' p = 11 1'58' y = 106O57'1. The compound of isoapiole with s-trinitrotoluene C,,~II,O,,C,H,Me(NO,) forms scarlet triclinic crystals [a b c = 0.5495 1 0.490i; a = 87'36' /3 = 112'34' y = 105'1 6'1. This and other examples not quoted confirms the author's view that the groups C1 and Me replace one another isogonically. L. J. S. Oxidation of Tertiary Alcohols of the Tolylallyl Series. 1543-1552).-The author has studied the products of oxidation of some of the alcohols previously described (Abstr. 1909 i 161 ; 1910 i 108) by means of potassium permanganate.p - p - to1 yl pen tane-P&-triol C,H,Me*CMe(OH)*CH,*CH(OH)*C H2*OH needles m. p. 10 1-1 03O and (2) the unstable /3-p-tolyl-/3-methplhydracrylic acid m. p. 103-106' ; on dry distillation this acid yields P-p-tolylpropylene (compare Matschurevitsch Abstr. 1909 i 304). E. GRISHKEWITSCH-TROCHIMOWSKY (J. Ru8s. phys. Chem. &kc. 1 9 10 42 p-To1 y lm e t h ylall y lcarbi no1 yields ( 1 ) p-Tolylethylallylcnrbinol yields (1) y-p-toZyZhexane-y€r-trioZ C,H,Me-CEt(OH)*CH,*CH(OH)*CH2*OH colourless needles m. p. 89-90.5G and (2) P-p-toZyZ-/3-ethylAydracrylic acid C,H,Me*CEt(OH)*CH,*CO,H short prisms and plates m. p.ORGANIC CHEMISTRT i. 291 109-111' decomposing at 125'; the silver and barium salts were prepared On dry distillation the acid yields P-p-tolyl-Aa-butylane C,H,Me*CEt:CH b.p. 206-209'/750 mm. DY5 0.8926 ng'5 1.52735. p-Tolyl propylallylcarbinol gives ( 1) 6-p-toZ?lliLeptane-apG-triol C,H,Me*CPra(Onr)*CH,*CYH(OH) =CH,*OH a very viscous yellow liquid and (2) P-p-tolyl-P-propylhydracrylic acid C,H,Me*CPra(OH)*CH2* C02H thin needles m. p. 99-101' of which the barium and sodium salts were prepared. On dry distillation the acid yields P-p-tolyZ-Aa-am.ylelze CsH4Me*CPra:CH2 as a colourless liquid b. p. 22 1-224'/76O mm. y-Tolylisopropylallylcarbinol yields (1) /3-methyl-y-p-tolyMexane- yet-triol CHMe,=C(C,H,Me)(OH) *CH,-CH(OH)*CH,-OH as a viscous pale yellow liquid and (2) P-p-tolyl-P-isopro~yZhydl.ncrylic m i d C,H,Me=CPrS(Ol~)*CH,*CO,H thin colourless needles m. p. 106-108° ; the potassium sodium and silver salts were prepared On dry distillation the acid gives P-p-tolyZ-y-methyZ-Aa- butylene C,H,Rle*CPr~:CH as a colourless liquid b.p. 210-212' Df 0.8538 n$ 1.52543. T. H. P. Preparation of Secondary Amino-alcohols. LES ETABLISSE- MENTS POULENC FRBRES and ERNEST FOURNEAU (D.R.-P. 228205).-The preparation of numerous secondary amino-alcohols of the general formuh OR*CH,,CH(OH)*CH,*NP,,R (where R is a n aryl or substituted aryl residue; R an hydrogen alkyl aryl or substituted aryl or alkylaryl group; R an alkyl aryl or fiubstituted aryl or alkyl- nryl residue) by the interaction of glycerol ehhers on primary or secondary aliphatic or aromatic amines or on amino-phenols or -naphthol* has previously been described (coinpare Fourneau Ab*tr. 1910 i 246 832). p-TolyZ ylycide ether C,H,Me.OCH,.CH<XHZ a liquid b.p. 165-166'/20 mm. is obtained by heating together p-cresol dichloro- hydrin and sodium hydroxide (2 mols.); t h i s when boiled during several days with dimethylamine (in petroleum solution) yields dirnethylumino- p-toly loxypropanol a colourless oil b. p. 175-176'/10 mm. and strongly alkaline t o litmus; the hydrochloride of the benxoyl derivative has m. p. 156'. The glycide ether prepared from t bymol and epichlorohydrin or dichlorohydrin is stated to have m. p. 61' and b. p. 176°/20 mm. (Abstr. 1910 i 246 gives 88' and 180' respectively). 0 C H,Me*O*CH,*CH(OH).CH,.NiMe Dimethylamino-/3-phenoxy-a-methoxypropunol OMe*C!H;O* CH,*CH( OH)*CH,-NMe crystals m. p. 60-61 is prepared by t h e action of dimethylamine on the corresponding glycide ether (b.p. 166-168'/12 mm.); the rnethiodidrt has m. p. 114". The glycide ether prepared from P-naphthol and dichlorohydrin has b. p. 2 12-2 13'/12 mm. and y-dimethylamino-P-naphthosypropanol b. p. 217'/16 mm. (Zoc. cit. gives 217'/11 mm.). The action of dichlorohydrin on sodium p-nitrophenoxide yields the glycide ether b. p.i. 292 ABSTRACTS OF CHEMICAL PAPERS. 250-255'/15 mm. m. p. 69" accompanied by glycerol di-p-nitrophenyl ether. y-Dimethylamino-a-phenoxypropanol has a fish-like odour and b. p. 162'/11 mm. (Zoc. cit. gives 161'/13 mm.); its ethobromide has m. p. y-Anilinophenoxypropanol yields with gold chloride a violet-red precipitate which rapidly changes to green ; and with potassium mercury iodide an oily green precipitate ; the picrate separates as an oil which after crystalisation from alcohol forms needles m.p. 1 2 1-1 22'. Two New Methods for Synthesising Nitriles. VICTOR GRIGNARD (Compt. rend. 191 1 152 388-390).-Cyanogen chloride preferably prepared by Held's method is dried over calcium chloride and passed into dry ether at 0". An ethereal solution of an organo-magnesium halide is now allowed to flow in drop by drop. After some hours the liquid is treated in the usual way and a good yield (55-80%) of a pure nitrile is thus obtained. The reaction is represented as RMgX + CNCl= MgXCl + R*CN. The other halogen derivative of cyanogen are not suitable for this preparation ; thus with cyanogen iodide the reaction proceeds entirely according to the equation RMgBr + CNI = RI + MgBr.CN.I n the case of cyanogen bromide both reactions occur the latter predominating. Benzonitrile l-naph- thonitrile anisonitrile and phenylpropionitrile have been prepared by this process. The second method consists of substituting cyanogen itself for the halogen derivative. I t has been used to prepare benzonitrile iso- hexonitrile and phenylbutyronitrile but the yield,p are inferior to those obtained with the chloride. If the order of mixing the organo- magnesium compound with the cyanogen or its chloride is reversed 3 5-Dibromoanthranilic Acid. FRITZ ULLMANN and EDUARD KOPETSCHNI (Ber. 191 1 44 425-431).-3 5-Dibromo-2-amino- benzoic acid (Wheeler and Oates Abstr. 1910 i 481) is readily obtained by passing bromine vapour into a dilute solution of anthranilic acid in aqueous hydrochloric acid ; it is converted by bromine water into tribromoaniline and yields diazonium salts which are very stable in aqueous solution.3 5-Dibromophthalic acid prepared from the preceding acid by the Sandmeyer reaction crystallises in colourless needles ; when rapidly heated it melts at 198' and is simultaneously converted into the anhydride m. p. 121.5'. 2 3 5-Tribromobenzoic acid has been obtained in colourless needles m. p. 190' (compare Rosanoff and Prager Abstr. 1909 ii 32) ; the methyl ester crystallises in long silky needles m. p. 7'. When boiled with aqueous potassium carbonate and copper 2 3 5- tribromobenzoic acid is converted into 3 5-dibromosalicylic acid m. p. 228' (Lellmann and Grothmann Abstr. 1885 265 give 223'). The dibromosalicylic acid obtained by Lassar-Cohn and Schultze (Abstr. 1905 i 893) by the action of potassium hypobromite on 1 loo (ZOC.cit. 112"). F. M. G. M. ketones are produced in the usual way. w. 0. w.ORGANIC CHEMISTRY. i. 293 potassium salicylate and considered by them t o be the 5 6-derivative is identical with the above-mentioned 3 5-dibromosalicylic acid. 4 6-Dibromophenylglycine-2-carboxyiic acid is produced in small quantities by the interaction of 2 3 5-tribromobenzoic acid and glycine in the presence of copper. It is best prepared by brominating phenylglycine-o-carboxylic acid in sulphuric acid solution ; i t crystal- lises i n pale yellow microscopic needles m. p. 248' (decornp.) ; the methyl ester has m. p. 88'. When boiled with anhydrous potassium acetate and acetic anhydride 4 6-dihromophenylglycine-2-carboxylic acid yields 5 7 5' 7'-tetra- bromoindigotin (Grandmougin Abstr 19 10 i 259).The interaction of p-toluenesulphonyl chloride and 3 5-dibromo- Br 2-aminobenzoic acid either in aqueous potass- Br/\*C'O*O - ium carbonate or pyridine solution leads to I I ' / \ the formation of dibromoccnthrano$dibromo- \/*N=C\-/ antbanilic acid 0-cmhpdride (annexed formula) NH2 Br which crystallises in citron-yellow needles Br m. p. 342' (corr.) F. B. Action of Nitrous Acid on Methyl Dimethylanthranilate. JOSEF HOUBEN (Ber. 1911 44 547).-1n consequence of a n error in the estimation of the nitrogen the azomethine compound obtained from methyl dimethylanthranilate has been stated t o be a mono- methyl derivative (this vol.i 128). This is incorrect; the percentage of nitrogen found corresponds with the formula of a dimethyl derivative and the condensation follows a normal course. c. s. Turmeric Oil. 111. Synthesis of 7-p-Tolylvaleric Acid. HANS RUPE and A. STEINBACH (Ber. 1911 44 584-588. Compare this vol. i 69).-Since it has been shown that curcumic acid is possibly y-p-tolylvaleric acid the synthesis of this acid has been effected; the product however is not curcumic acid although very similar to it. C,H,Me* CMe C H* CH,* C02H m. p. 86-87' is obtained by adding ethereal magnesium methyl iodide to ethyl P-p-toluoylpropionate in ether (when the order of addition is reversed hardly any reaction occurs) and decomposing the product with water and dilute sulphuric acid a t 0'.When boiled for four hours with 10% sulphuric acid it is converted into y-p-toZ$y-vaZeroZactone C,H,Me-CMe< oL-bo m. p. SS' which is reduced by boiling hydrioclic acid D 1.702 and red phosphorus to y-p-tolylvaleric acid C,H,Me*CHMe*CH,*CH2*C02H m. p. 32' b. p. 173-174'/9 mm. Like curcumic acid (m. p. 33-34' b. p. 168-170°/ 12 mm.) this acid is extremely soluble in the usual solvents; also its calcium salt melts in boiling water. The two acids however liquefy when mixed and yield different p-toluidides that from curcumic acid having m. p. 126-127" whilst the toluidide of the synthetic acid has m. p. 77-79'; also the two acids yield different y-p-27oly E y-nzethy Zisocrotonic acid CH .CH,1. 294 ABSTRACTS OF CHEMICAL PAPERS. products by oxidation.When p-tolylvaleric acid is treated with 4% potassium permanganate and sodium carbonate at Oo the chief product is the lactone mentioned above; a small amount of p-tolylmethyl ketone (identified as t h e semicarbazide) and a substance m. p. 150-15lo(not identical with the acid m. p. 150-151° obtained amongst the products of oxidation of curcumic acid) are also formed. This result is important hilice it proves that curcurnic acid must havea constitution which does not admit of the formation of a lactone when the acid is oxidised. c. s. Condensation of P-Naphthaldehyde with Methylsuccinic Acid. ROBERT BEHREND and THEODOR KLINCKHARD (Annulen 1 9 1 1 3'79 362-376).-According t o Fittig and Liebmanu (Abstr. 1890 775) two structurally isomeric phenyl-a-methylparaconic acids are obtained by the condensation of benzaldehyde with sodium methyl- succinate and acetic anhydride and the two acids yield a-methyl- phenylisocrotonic acid and the isomeric P-methyl derivative when distilled.Keptaldehyde (Fittig and Riechelmann Abstr. 1890 593) and valeraldehyde (Fittig and Feist ibid. 591) each yield two structurally isomeric paraconic acids when condensed with methyl- succinic acid. When P-naphthaldehyde is used it is shown that two isomeric P-naphthylmethylpmaconic acids are formed but these are stereoisomeric as they yield the same naphthyl-P-methylisocrotonic acid when distilled. The constitution of the condensation products follows from the fact that the hydroxymethylphenanthrene obtained by the removid of water from the isocrotonic acid yields on distillation with zinc dust a niethylphenanthrene which is not identical with Pschorr and Quade's 3-methylphenanthrene (Abstr.1906 i 848). The separation of the two naphthylnuethylparaconic acids can be effected by fractional crystallisation from dilute alcohol. The one acid CBH1404,H20 separates from 60% alcohol in transparent mono- clinic crystals and when slowly heated has m. p. 199-200" (decomp.) after sintering at 198-1999'. The anhydrous compound has the same m. p. The stereoisomeride C16H,,04 crystallises from 50% alcohol in nodular masses of minute plat,es or in well developed prisms m. p. 174-175O (decornp.). When distilled slowly under reduced pressure the two acids yield napht?~yl-~-methylisocrotonic acid together with 4-hydroxy-%methylphenanthrene naphthylisobutylene and unaltered acid.The unsaturated acid can be separated from unaltered paraconic acids by extraction with cold citrbon disulphide and crystallisos from the solvent in rectangular plates m. p. 137-138'. 4-Hydroxy-2-n1ethylphenanth~ene C15H120 crystallises from dilute alcohol and its alcoholic solution gives an orange-red coloration with ferric chloride and a lemon-yellow with bleaching powder solution. Its acetyl derivative C17H 402 cryatallises from dilute alcohol in slender needles or glisteniug plates rn. p. 110-5-1 1 1 - 5 O . 2-iVethpl- phenantfwene CI5Hl2 has m. p. 52-53" and when mixed with the isomeric 3-methyl derivative has m. p. 40-42". ~-Na~~~th?/lisoBut~Zene Cl,H7*CH:CMe i d a colourless oil with 1). p. 287-288".J. J. S .ORGANIC CHEMISTRY. i. 295 Chemical Investigation of Resin from the Pine (Picea excelsa). 11. Lzevo-pimaric Acid. JOHN KOHLER (Arkia. Kern. Min. Geol. 1911 4 No. 5 1-29. Compare Abstr. 1906 i 92 100 ; 1907 i ZlS).-Hitherto the only source of pimaric acid has beeh galipot resin; it has now been found to occur universally in pines from Rottanue (Yicecc excelsa) usually accompanied by weaker laevo-rotatory more easily soluble and easily oxidisable acids probably sapinic acids [a]. A very pure specimen was found in the winter-resin from the upper h;ilf of the trunk of one of the pines and after recrystallisation from methyl alcohol it gave [a] = - 280-5° which is a higher rotation than has hitherto been found. Analysis and deter- mination of the molecular weight by titration with alkali confirm the formula C20H8002.It does not possess a definite melting point since at the melting-point temperature it undergoes a partial change into colophonic acids the amount of change depending on the rapidity of heating. LGG b c = 0.80975 1 0.61021. On being heated I-pimaric acid changes into a mixture of an inactive colophonic acid and lievo-ro tatory colophonic acids which are identical with the a-colophonic acids prepared from sapinic acids [?I. The active colophonic acids crystallise in the monocliuic system and are completely isomorphous with each other so that it is not possible with certainty to isolate any given acid by fractional crystallisation. Inactive colophonic acid like I-pimaric acid crystallives in the rhombic system although it is not isomorphous with it [a b c = 0.47698 1 00 .c].Analysis of a colophonic acid with [a]:= - 83*3" and determina- tion of the molecular weight by titration with alkali gave results axreeing with the formula C2,H,o02. The colophonic acids possess th6 general property of forming a gel when their solutions in alcohol and ammonia are diluted with water; in this way they may be distinguished from the naturally occurring resin acids. They are a general transformation product of the action of best on the naturally occurring acids such as I-pimaric acid and the sapinic acids The crystals have tho axial ratio The followins classification isxiven A . Ncctural IZesin Acids.-(1) Acids which do not oxidise in the air and are relatively stable on heating.(2) Acids which readily oxidise in the air and are very sensitive towards heat. Class (1) includes the pimaric acids and class (2) the sapinic acids. On heating both classes change into B. Colophonic Acids.-( 1) a-Colophouic acids lEvorotatory. (2 ) P-Colophonic acids dentrorotatory. Both the a- and P-acids are readily oxidised in the air and on heating change into acids in the Conversion of Stable Stereoisomerides into Labile Modifica - tions by Ultra-violet Light. 11. RICHARD STOERMER [with EGON FiiIDERICI BR:iUTIGAM and w. NECKEL] (Be?.. 1911 44 637-668. Compare Abstr. 1910 i 114).-The stable less fusible forms of the following compounds are tramformed into the labile same group. (3) Inactive coloplionir acids. T. s. P.i. 296 ABSTRACTS OF CHEMICAL PAPERS.more fusible stereoisomerides when their benzene or alcoholic solutions are exposed to the action of the ultra-violet rays from a uviol lamp for several days coumaric acid 75 ; methylcoumaric acid 75 ; ethylcoumaric acid over 90 ; propylcoumaric acid 85 ; .methyl- coumaraxnide 50 ; ethylcoumaramide 100 ; propylcoumaramide 95 ; methyl coumarate -+ coumarin ; acetylcoumaric acid over 90 ; methyl benzoylcoumarate ; methyl a-o-nitro-0'-methoxycinnamate 80 ; a-o-nitro-0'-methoxycoumaric acid 40 ; p-methoxycinnamic acid 25 ; sodium o-chlorocinnamate 10 ; piperonylacrylic acid 17 ; maleic acid ; bromofumaric acid 50 ; o-anisylcinnamic acid 35-40 ; o-snisylcinnamide 70 ; o-anisylcinnam-methylamide 36 and corre- sponding ethylamide 40 ; b-o-anisyl-a-methylcinnsmic acid 5 and the corresponding amide 5; cinnamic -+ isocinnamic acid m.p. 42" 30-40 ; phenyl tolyl ketoxime 40 ; phenyl anisyl ketoxime. I n most cases the reaction is a balanced one and the number given for each compound represents the percentage of the less fusible compound which has been transformed when equilibrium is established. Crotonic acid is not transformed to any appreciable extent. The method is recommended as a suitable one for the preparation of ullo-stereoisomerides in several cases and also for the detection of spatial isomerism between a pair of compounds. I n a few instances the addition of methyl or ethyl alcohol to the unsaturated compound occurs during the exposure to the ultra-violet light but the amounts of such products are usually small.It is suggested that the trans- formation and the percentage amount transformed depends on the energy differences bet ween the stereoisomerides. Sodium f umarate is not transformed although the corresponding acid yields 30% of maleic acid. The following new compounds are described propylcoumuric [a-o-~ro~oxycinnumic] acid OPr *C H,- CH CH*CO,H obtained by hydrolysing the corresponding methyl ester crystallises from dilute alcobol in glistening needles m. p. 104-105" and the stereoisomeric propylcoumarinic [ b-o-propoxycinnamic] acid has m. p. 83-84'. The solubilities of the two acidsin light petroleum a t 18" are 0.106 and 0.301% respectively. Both compounds with sodium amalgam yield b-propoxyphenyZpropionic ucid OPr*C,H,*CH,*CH,*CO,H m. p. 63". b-o-Methoxycinnumamide can be obtained by the action of phos- phorus pentachloride on a dry ethereal solution of b-o-methoxy- cinnamic acid (compare Perkin Trans.1877 31 422) and treating the product with ice-cold ammonium hydroxide solution ; it crystallises from carbon disulphide in needles m. p. 62-5-6335". a-o-Ethoxycinnamamide C,,H,,02N has m. p. 1 61° and the stereo- isomeric b-o-ethoxycinnamanzide m. p. 115-1 16". a-o-Propoxycinnamumide C12H1502N hiw in. p. 145" and p-0- propoxycinnamarnide m. p. 1 04". b-o-Acetoxycinnccmcn~ic cccid OAc*C,H,*CH:CH-C'O,H prepared by the action of acetic anhydride on dry sodium p-coumarate a t O" crystallises from carbon disulphide has m. p. 85" and when boiled with water for some time yields coumarin. b-o-Benxoyloxycinnumic ucid C16H1204 forms compact crystals from carbon disulphide and has m.p. 96-97". Methyl a - o - benxoyloxycinnarnate CI7Hl4O4 obtained by benzoylatingORGANIC CHEMISTRY. i. 297 methyl coumarate crystallises from alcohol in slender needles m. p. 87" and on hydrolysis yields benzoic and coumaric acids. iWt?th$ b-o-benxoyloxycifinamate prepared from the silver salt of the corresponding acid has m. p. 46". Bthyl b-o-methyloxycinnamate obtained from the sodium salt and ethyl sulphate has b. p. 291-292*5" and the isomeric methyl b-o-ethyloxycinnamate b. p 288*5-289*5" ; each ester gives the corresponding acid on hydrolysis and this points t o the conclusion that p-coumaric acid cannot have the dihydroxylic structure C6H,<CH:CH o--Q(oH)2 as the two esters should then be identical.p-Methoxyallocinnccmic acid CloHI0O3 separates from light petroleum in triclinic crystals rn. p. 64-65". Its solubility in benzene at 18" is 34% and in light petroleum 0.28%. It does not show the properties of a crystalline liquid and is readily transformed into t,he less fusible stereoisomeride when its carbon disulphide solution is mixed with a little bromine and exposed to sunlight. The aniline salt C,,H,706N crystallises from benzene in slender needles m. p. 68' ; the amzde prepared by the action of phosphorus pentachloride on the acid in presence of ether and treatment of the product with ammonium hydroxide has m. p. 129"; in the absence of ether the amide of p-methoxycinnamic acid (m. p. 186") is formed. o-Chloroallocinnamic acid C H70,C1 cry stallises from water and has m.p. 127'. o-Chloro- cinnamic acid has m. p. 205" (Gabriel and Herzberg Abstr. 1883 1123 give 200°) and its solubility in benzene is 0.04%. When this acid or its sodium salt is exposed to ultra-violet light it is partly transformed into the aZZo-acid but when glacial acetic acid solutions are used part of the acid combines with a.cetic acid giving a product Cl~Hl104CI m. p. 212-213". The aniZine salt of the allo-acid forms slender needles m. p. 136"; the ccmide C,H,ONCl which crystal- lises from dilute alcohol in blue fluorescent needles has m. p. 112" and the isomeric amide has m. p. 163-1 63.5'. allo-Piperonylacrylic acid CloH$04 crystallises from water and has m. p. 96-97O. Its solubility in benzene a t 18' is 5.9%. Its aniline salt has m.p. S3*5-84' ; the amide C,,H,O,N crystallises from ether i n glistening plates m. p. 131" and the isomeric amide from alcohol in slender needles m. p. 180". The piperidine salt of o-anisylcinnamic acid has m. p. 145" not 54-55" and the silver salts of both isomeric acids are soluble in benzene. o-Anisylcinnamccmide C1,Hl,?,N has m. p. 137" and its solubility in benzene is 0.8% ; the stemotsomeride has m. p. 115-1 16') and its solubility in benzene is 1.7%. o-Anisylcinnccnwmethykamide CI7Hl7O2N has m. p. 121' ; the corresponding ethylamide C1,H,,02N m. p. 101" and the respective stereoisomerides m. p.'s 104-105" and 74-80" o-Anisylcinnambenxylamids has m. p. 144-1 46" ; the amyl- amide m. p. 102-103° and the anilide m. p. 138". The /3-anisyl-a-methylcinnamic acids are most readily prepared from o-methoxybenzophenone and methyl a-hromopropionate ; the condensa- tion product methyl /3-phenyl-/3-anis yl-a-meth y lhydracrylate C,,H,,O Its solubility in benzene a t 18" is 1.83%.VOL. c. i. Yi. 298 ABSTRACTS OF CHEMICAL PAPEKS. crgstallises from alcohol in brilliant rhombic crystals m. p. 82-83' and when treated with dry 'hydrogen chloride in met,hyl-alcoholic solution containing sodium sulphate yields methyl P-anisyl-a-methyl- cinnamate m. p. 60-61° together with the allo-ester. The solubilities of the two acids in benzene are 11.6 and 20*2% and the arrcides C,7H,,0,N of the two acids melt at 137-138" and 115- 118" respectively. The conversion of b-o-ethoxycinnamic acid in carbon disulphide solution by means of iodine (compare Michael and Lamb Abstr.190'7 i 134) depends on the concentration of the iodine solution. It is shown that the methoxy-groups in the methyl ether of o-nitro- salicylic acid and in In,-nitro-o-methoxybenzaldehyde are readily hydro- lysed when boiled with sodium carbonate solution. m-Nitro-o-methoxy- benzoic acid has m. p. 194" (compare-Keller hbstr. 19OS i 2S5). When a solution of mesaconic acid is subjected to the action of ultra-violet light water or methyl alcohol appears t o combine with the acid. J. J. S. Hydroaromatic Compounds. Carboxylic Acid of the "Semi- benzene" Group. KARL AUWERS ( B e r . 1911 44 588-601. Compare Abstr. 1907 i 399 400 4Ol).-It has been shown that the changes CHC12>/=\<0H -+ cHcl,>/=\ = CHR Me \=/ CH,R Me \=/ >-.-+ MeH b H R * C H C l readily occur when R is hydrogen or an alkyl group. The present communication shows that R may also be a carboxyl group. Ethyl 4-hydroxy-l-meth~l-l-dichloro~et~~~Zcyclohe3cccdiene-4-acetate (I) C0,Et*CH2*C(OH)<c-&H>CMe*CHC12 is obtained in an impure state as a viscous yellow oil by heating a benzene solution of 4-ketO- 1-methyl-1-dichloromethylcyclohexadiene with ethyl bromoacetate and zinc and decomposing the product wibh dilute sulphuric acid. The ester cannot be purified owing to its tendency to lose the elements of water but by the careful hydrolysis of its concentrated alcoholic solution by potassium hydroxide a t 0' i t yields the corresponding m i d C,,H,,O,CI m. p. 119" (which cannot be kept long) and the de- hydrated derivative thereof 1 -methyl- 1 -clichZorometh~lcyclo?~exadie4ze- A4-acetic acid (11) C O H * C H C < ~ ~ ~ ~ ~ > C ~ ~ e ~ C H C l ~ m.p. 107-108" the two acids being separated by the greater solubility of the latter in benzene. The ethyl ester of the latter acid can be obtained by treating the preceding ester (I) with 98% formic acid or in a pure state from the silver salt of the acid (11) and ethyl iodide. It has Dy'9 1.2151 n 1.56911 and the presence of three conjugated double linkings is denoted by the exaltations of the specific and mole- cular refractions and the dispersion. By treatment with concentrated sulphuric acid at 0" for eighteen hours tho ester is converted into ethyl 4-aldehydo-2 (or 3)-rnethylphenylcccetute CH~*CGT-I,Ms.CI~,*CO,Et b.p. 160-1 72"/13 mm. which is isolsted as the sernmcnrbaxons C1,HI7O3N3 \=/ CH'CHORGANIC CHEMISTRY. i. 299 m. p 191-192O (compare Abstr. 1907 i 399) ; the semicarbccxone of the free acid has m. p. 234-235”. 1 -Methyl - 1 - dichloromethylcyclohexadiene-A4-acetic acid (11) can also be obtained by the hydrolysis of its ester by 50% alcoholic potass- ium hydroxide in the cold or by treating 4-hydroxy- 1-methyl-1-di- chloromethylcyclohexadiene-4-acetic acid with 98% formic acid ; in the latter method l-methyl-4-/3/3-dichloroethylbenzerie (IV) (Abstr. 1907 i 400) is obtained as a by-product by the elimination of carbon dioxide and simiiltaneous intramolecular change of the ‘ I semibenzene ” acid (11). Ethyl pp-dz‘chloro-a-p-toZyZp~.opionate CGH,Me*C€~(CHC12)*C0,Et b.p. 162-164O/15 mm. 1 . 2 0 1 1 ~ ~ ~ 1.52137 is obbained by heating the ester (I) or in a purer state the ester of 11; its aromatic character is proved by the very small exaltations of its molecular refraction and dispersion. By hydrolysis with alkalis the e-ter yields either a mixture of the acid and P-chloro-a-p-tolylacrylic acid or the latter alone. PP-L)ichZoro-a-p-tolyZpro~ioni~ acid C H,,O,Cl~ m. p. 156O therefore is best obtained by heating tho ‘; semibenzene ” acid (11) on the water-bath; when heated over a naked flame the acid I1 yields a considerable quantity of l-methyl-4-~~-dichloroethylbenzene (IV). @3-Dichloro-a-p-tolylpropionic acid can be titrated with sodium hydroxide but is much more sensitive to the attack of an excess of the alkali than the isomeric acid (TI) ; for whilst the latter can be warmed with 10% sodium hydroxide without decomposition the former is converted into P-chloro-a-p-toZy Zucvylic ucid CHCl C( C,H,Me) *CO,H m.p. 112’. This acid is obtained from each of the preceding com- pounds-most conveniently from the ester (1)-by heating with aqueous or alcoholic alkalis. It forms an ethy2 ester C,,H,,O,Cl b. p. 155--156O/ 15 mm. D:0’9 1.1353 nD 1.53579 which is oxidised in aqueous acetone by potassium permanganate yielding ethyl p-tolylglyoxyiate. Unsuccessful attempts have been made to obtain compounds similar to t h e preceding from 2-keto-1-methyl-1-dichloromethylcyclohexadiene and 2-keto-1 5-dimethyl-1-dichloromethylc~cZohexadiene. c. s. Action of Ethyl Chlorocarbonate on Sodium Derivatives of Ketones Prepared by means of Sodamide ALBIN HALLER and ~ D O U A R D BAUER (Compt. r e r d .191 1 152 551-558).--The sodium derivatives of aliphatic or mixed aromatic-aliphatic ketones of the type R*CO*CHR’R’’ on treatment with ethyl chlorocarbonate in benzene solution form carbonates of the type CRR”:CR*O*CO,Et. Under the same conditions however ketones of the type CPh-CO*CH,R yield compounds having the constitution C02Et*CR :CYh*O*CO,Et. On hydrolysis with alcoholic sodium hydroxide these foi m sodium ethyl carbonate and monoalkyl derivatives of ethyl benzoylacetate ; the latter ale thus obtained in a purer condition than when prepared by direct alkylation of the ester. The sodium derivative of phenyl isopropyl ketone reacts vigorously with ethyl chlorocarbonate giving a 70% yield of a-ethglcarbonato-a- yhenyl-ha-isobutylene CMe2:CPh*O*C0,Et m.p. 41-42’. The con- stitution of thig compound follows from its conversion into sodium ?I 2i. 300 ABSTRACTS OF CHEMICAL PAPERS. ethyl carbonate and phenyl isopropyl ketone when treated with t4he calculated amount of water and sodium ethoxide. It is the enolic form of ethyl benxoyllisobutyrate COPh*CMe,*CO,Et a liquid of b. p. 145-146'/13 mm. also obtained by the action of methyl iodide and sodium ethoxide on Perkin and Colman's ethyl methylbenzoylacetate (Trans. 1886 49 156); the oxinae has m. p. 135-136'. Propiophenone gives rise to a-ethyZcarbonato-a-phenyl-ha-propylene CHMe:CPh*O*CO,Et b. p. 140-145'/11-12 mm. together with ethyl p-ethylcarbonato-a-rnethylcinnamate CO,E t *O* CPh :CMe*CO,Et b.p. 182-185°/11-12 mm. Butyrophenone gives a-ethylcarbonato-a-phenyl-Aa-butylere b. p. 143O/10 mm. and ethyl P-ethylcadomto-a-ethylcinnamate m. p. about 35O b. p. 183-184"/10 mm. Acetophenone in the same way gives diethyl benzoylmalonate together with an oil containing (1) a compound C,,H,,O b. p. 128-129°/11 mm. ; it forms an unstable bromo-derivative m. p. 78'; (2) ethyl P-carbethoxycinnamate. Pentamethylacetone forms y-ethylcarbonato-~88-trimethyl-A~-pentene CMe,:C( O*CO,Et)*CMe b. p. 89-90°/1 3.5 mm. cycZoHexanone yields an oil containing (1) a substance b. p. 108-1 lOo/20 mm. having the composition of ethyl cyclohexanone- carboxylate ; (2) Wallach's dicyclohexanone characterised by the oxime m. p. 155' and the semicavbaxone m.p. 210-212'; (3) ethyl- curbonato-Al-cyclohexene C,H9*O*C0,Et b. p. 108-1 10°/ZO mm. an enolic form of the ester of Gardner Perkin and Watson's cyclohexa- CHEt CPh 0. C0,Et CO,Et*O*CPh:CEt*CO,Et none-2-carboxylic acid (Trans 1910 97 1796). w. 0. w. Phenolphthalein and its Colourless Salts. PHILIP A. KOBER and J. THEODORE MARSHALL ( J . Amer. Chern. Xoc. 1911 33 59-70). -During the course of certain work on tests for blood (Kober Lyle and Marshall Abstr. 1910 ii 910) it was observed that the colour of a standard solution cjf phenolphthalein gradually faded. Although this phenomenon has been observed by others it has not hitherto been fully investigated and the present work was therefore undertaken. The rate of fading has been determined colorimetrically and a curve has been obtained which resembles that of a n irreversible unimolecular reaction.It has been shown by conductivity measurements t h a t the change of colour is due to a chemical reaction in which alkali hydroxide takes part. From a study of concentrations at equilibrium it has been found that the intensity of the colour depends on two factors (1) dissociation or hydrolysis of the coloured dibasic salt and (2) hydration with the formation of a colourless tribasic salt (compare Meyer and Hantzsch Abstr. 1907 i 932). If follows therefore that phenol- phthalein is not an accurate colorimetric standard. The tvipotassium salt CO dK.c~H~>C<22'0K,5H20 K*C H has been isolated ; it forms colourless microscopic plates and is fairly stable ; when however an aqueous solution is boiled or left for a consider-ORGANIC CHEMISTRY.i. 301 able time it develops an intense red colour. The corresponding trisodizcm salt crystallises in cubes. When the tripotassium salt is administered hypodermically to dogs it produces a purgative effect. Phenolphthalein Derivatives and t h e i r Behaviour as Indi- cators. ERWIN RUPP (Arch. Pharm. 1911 249 56-68).-The behaviour of phenolphthalein derivatives containing negative sub- stituents towards ammonia and alkaloids indicates t h a t this is better explained by the chromophore theory of indicators than by the dis- sociation theory. E. G. Tetrabromophenolphthaleim C6Br4<~~>C(C6H4*OH)2 m. p. 280-285’ (decornp.) prepared by heating tetrabromophthalic anhydride with phenol in sulphuric acid crystallises from warm alcohol or acetic acid and gives a violet colour with alkalis which is discharged by acids.When heated with bromine in acetic acid i t gives octccbromophenol- phthalein C6Br4<OO)C(C,II,Br2*OH) which crystallises in colour- less needles and gives a blue colour with alkalis. I’eti.aiodo~~enolphthaZein was not obtained crystalline ; i t gives a violet colmation with alkalis and on heating with bromine in acetic acid gives tetrabromotetruiodophenolphthcclein c61,<zO>c( C6H2Br200H.)2 which crystallises from dilute alcohol and gives a bluish-green coloration with alkalis. These and other halogenated phenolphthaleins as well as nitrophenol- phthalein and dibrornodinitrophenolph thalein were tried as indicators with ammonia and morphine and the results are tabulated in detail in the original. They show that the mere acidification of the phenol- phthalein molecule by the introduction of negative groups does not effect any marked improvement in the values of the phthtleins as indicators for weak bases.The introduction of negative substituents in the phenol nucleus leads to a diffuse gradual colour change whilst their introductiou into the phthalein nucleus gives rise to a rapid colour change with bases. This is best explained on the assumption that the free phenolphthaleins exist in the pseudo-form and their salts in the quinonoid form. The value of any phthalein as an indicator depends on the rapidity with which this change may occur and this is influenced by the position of the substituents.This view is supported by the fact that acylated phenolphthaleins are unsuitdble for use as indicators. T. A. H. A c y lated Salicylosalic ylic [ o-2-Acyloxybenzoyloxybenaoic] Acids. ALFRED EINHORN [witJh GUSTAV HAAS ALEXANDER VON BAGH CARL LADISCH and LEO ROTHLAUF] (Bey. 1911 44 431-439).-In the preparation of o-ethylcarbonatobenzoic acid by the interaction of ethyl chlorocarbonate and salicylic acid in pyridine solution o-%ethyl- carbonatobenzoyloxybenzoic acid is produced simultaneously. The relative proportions of the two acids depend on the time the reactioni. 302 ABSTRACTS OF CHEMICAL PAPERS. is allowed to proceed the last-mentioned acid being produced in larger quantity the longer the reaction mixtare is kept. o-2-Bthylcarbonatobenzoyloxybenxoic acid CO,Et .0 * C ~ ~ 4 * C O * 0 . C ~ 4 * C 0 H crystallises from benzene in small white needles m. p. 119O. It dissolves in strong aqueous ammonia with a yellow colour and at the same time is converted into salicylic acid :ind ~alicylamide. When hydroly~ed with dilute ammonia according to Fischer's method or when heated with aluminium bromide in benzene solution it yields o-sdicyloxybenzoic acid 0~*C,H4~CO*O*C,H4*C0,H (Abstr. 1909 i 803). It has also been obtained (1) by the action of ethyl chloro- carbonate on salicylic acid in benzene solution in the presence of dimethylaniliae (2) by the action of ethyl o-ethylcarbonatobenzoyl- carbonate CO2Et*O*C,H4*CO*O*CO2Et on salicylic acid in dimethyl- aniline or pyridine solution and (3) by the interaction of ethyl chloro- carbonate (9 mol.) and sodium salicylate (I mol.) in acetone solution. When excess of ethyl chlorocarbonate is employed in the latter reaction the main product is o-ethylcarbonatobenzoic acid which forms leafy crystals m.p. 95'; from carbon tetrachloride it separates in pearly leaflets of the composition 2C0,Et*O*CGH,*C0,H,CC14 ; these rapidly lose carbon tetrachloride on being exposed t o the air. C0,Me*O*C,H4*CO*O*C6H,*C0,H prepared by the action of methyl chlorocarbonate on salicylic acid in pyridine solution crystallises in clusters of tapering needles m. p. 112'. OAc*C,H,-CO* O*CGH4*CO2H prepared by the prolonged action of pyridine on ethyl o-acetoxy- benzoylcarbonate crystallises in leaflets m. p 16 1-162' (compare Einhorn and Seuffert this vol.i 53). It has also been obtained (1) by the action of ethyl o-acetoxybenzoylcarbonate on salicylic acid in the presence of dimethylaniline and on sodium salicylate in dilute alcoholic or acetone solution (2) by the interaction of pyridine and o-acetoxybenzoic anhydride and (3) by the action of o-acetsxybenzoic anhydride on Falicylic acid in the presence of pyridine or on sodium salicylate in acetone solution. 0-2-Methylcarbo~~atobenxoylox~benzoic acid 0-2- Acetoxy benxoyloxy benxoic (acet y Zsalicylosalicylic) acid F. B. Ketones Derived from Phenylpropionic Acid. JEAN B. SENDERENS (Compt. rend. 191 1 152 384-386. Compare Abstr. 1909 i 286 627; 1910 i 11 179 318 489; this vol i 134).- When a mixture of phenylpropionic acid (1 mol.) and a n aliphatic acid (3 mols.) are passed over thorium oxide at about 460° the product consists almost exclusively of the mixed aromatic ketone and the symmetrical aliphatic ketone.The following compounds prepared by this method are liquids with an agreeable odour; except in the first case their oximes are oily. a-Phenylbiitsn-y-one h. p. 228-5'/750 mm. (corr.) DS 0.9877 ; the oxime m. p. 80' ; the semicarbasone m. p. 136'. a-Phenylpentan-yone CH,Ph*CH,*COEt b. p. 244'/750 mm. (corr.) Di 0.9793; the semi- cavbaxone m. p. 8 2 O . a-Phenglhexan-y-one C12H160 b. p. 263'/ORGANIC CHEMISTRY. i. 303 760 mm. (corr.) Di 0.971 9. a-PhenyZ-6-methyZpentan-y-orae C,,H,6Q b. p. 256'/760 mm. (corr.) Dj 0.9756; the semicarbaxone m. p. S6O. a-Phen2/Z-r-met?~~Zhexc~n-y-one C13€I180 b. p. 268*5O/760 mm.(uorr.) Dj 0.9619. ae-Diphenylpentan-y-one CIII,Ph*CH,*CO.CH,*CH,Ph produced in small quantity during the preparatiou of the foregoing ketones is best prepared by passing phenylpropionic acid over thorium oxide a t about 440'. It has b. p. 347*5"/760 mm. (corr.) D! 1.0356; the senzicccrbazone has m. p. 105". Attempts to prepare un~%t~ri.tted ketones by the catalytic method have not been successful. Cinnamic acid for example yields meta- styrene as the chief product whilst crotonic acid furnishes only decomposition products. w. 0. w. Desmotropism of Formyldeoxybenzoin. WILBELM WISLI- CENUS and ALEXANDER RUTRING ( A r m a h 191 I 3'79 329-261).-1t is shown that Claisen and 3Teyerowitz's formyldeoxybenzoin (Abstr. 1890 359) exists in two isomeric modifications which are repreaented by the two formulae a = COPh*CPh:CH-OH and P = CHO*CPh:CPh*OH.A 60-70% yield of the formyl derivative can be obtained by the action of deoxybenzoin on a mixture of sodium ethoxide and ethyl formate under specific conditions. The crude produot obtained by the addition of dilute mlphuric acid to the alkaline solution is partly molten a t 75" but resolidifies and then has m. p. 1 1 0 O . a-Eormyldeoxp benzoin (hydroxy methylenedeoxybenzoin) crystallisee from light petroleum (b. p. 100-120') in sulphur-yellow needles or prisms; it is partly molten a t 76-80' but is quickly transformed into the P-isorneride. It has b. p. 183'/14 m a . It can be kept for a few days at the ordinary temperature but is stable a t temperatures above 110'. The a-compound is more saluble than the P-isomeride in most solvents and the solutions have a yellow colour.I n benzene solutions a portion of the P-compound is transformed into the a so that an equilibrium mixture is formed whereas alcohol readily trans- forms the a- into the P-isomeride even when the greater portion of the compound is not dissolved. The a-compound is partly trans- formed into the p- by dissolving in benzene and alcohol and an equilibrium mixture is obtained. P-Formyldeoxybenzoin crystallises from alcohol in colourless micro- scopic plates m. p. 112-1 1 3 O and the fused mass when cooled rapidly yields crystals of the a-isorneride. Both compounds give colorations with ferric chloride ; in the case of the a-compound this is best shown by using benzene solutions of the compound and of ferric chloride. The enol-ketonic structure is ascribed to the a-compound on account of its yellow colour and similarity to benzoin; the aldo-enolic formula is given to the P-isomeride as it gives a coloration with Schiff's reagent (decolorised magenta). Both compounds form salts but it is probable that during salt formation the P-compound undergoes molecular rearrangement and all the salts obtained appear to belong to the a-series although the product obtained by acidifying the solution ofi.304 ABSTRACTS OF CHEMICAL PAPERS. the salts may be the a- or &compound according t o the conditions of the experiment. The p-compound can be transformed into the a- by dissolving in alcohol containing the theoretical amount of sodium ethoxide keeping for twelve hours and then diluting with water and precipitating by adding sulphuric acid (dil.) drop by drop.The copper derivative (C,,H,,02),Cu cry stallises in green plates and has m. p. 220-221'. When a dilute alcoholic solution of the P-compound is kept €or some time a slow change takes place ; at the end of two days the solution no longer yields a copper derivative and gives only a faint coloration with ferric chloride. This is probably due to the formation of a third isomeric form namely a y-form which is regarded as the aldo-keto-compound O:CH*CHPh*COPh. The transformation of the p- into the y-compound takes place more readily in methyl-alcoholic solution The y-compound does not form a copper derivative and does not give colorations with ferric chloride but reacts readily with SchiE's reagent.It has not been found possible to isolate the solid y-compound as on concentrating its solutions it passes over into the Py and possibly a-compounds. The a- and @forms yield identical derivatives although the rates a t which they react are different. Both yield an additive compound with ammonia C,,H1,0N2 in the form of a colourless solid m. p. 161° after sintering at 154'. COPh*CPh:CH*NHPh crystallises from alcohol has m. p. 92-93' does not give a coloration with ferric chloride but forms a yellowish-brown copper derivative (C,,H,,ON),Cu m. p. 2 13-2 14'. Hydrazine hydrate reacts with the a-compound yielding Curtius and Blumer's bispbenylhenzylazimethylene (Abstr. 1895 i 608). When an alcoholic solution of hydrazine hydrate is used the product >N in the form of yellow needles is 3 4-diphenylpyrazoZe1 m.p. 154-155'. m. p. 210-211° is formed when phenylhydrazine is used. 4 5-Di- crystallises in phelnyl-l -p-brornophe fiylpyraxok C,H,Br N< colourless felted needles m. p. 182-183'. Formyldeoxybenzoin reacts with an aqueous alcoholic solution of benzenediazonium chloride and sodium acetate yielding benzil mono- phenylhydrazone and with phenylcarbimide both forms yield the additive compound COPh*CPh:CH*O*CO*NHPh in the form of colourless plates m. p. 129-130'. The benxoyl derivative C22H1603 prepared from either the a- or /I- compound crystallises from benzene in colourless prisms m. p. 105-106° and the p-nitvobenzoyl derivative C,,HI,O,N forms pale yellow needles m.p. 118-1 19'. COPh* CBrPh* CHO crystallises from light petroleum 2nd has m. p. 60-61'. The compound with aniline ?H=== N CHPh-CPh The corresponding 1 4 5-triphenylpyraxo2e C2lH,& CPh YPh N=ZCH ' Bromoformyldeoxybenzoi~ J. J. S.ORGANIC CHEMISTRY. i. 305 Some Derivatives of Hydroxyquinol. GUIDO BAHQELLTNI ( A tti R. Accad. Lirtcei 1911 [v] 20 i 22-26. Compare this vol. i 68). -The present paper deals with 2 4 5-trimethoxypropiophenone (annexed formula) and some of its derivatives. The substance is obtained by the action of MeO/-\CO*CH2Me propionyl chloride on hydroxyquinol trimsthyl ether in carbon disulphide solution in the presence of aluminium chloride. It crystal- lises in small white needles m. p. 106-108’ and is identical with the ketoasarone of Paolini (A bstr.1910 i 394). It gives a yellowish- green coloration with concentrated sulphuric acid no coloration with ferric chloride and with sodium nitroprusside and potassium hydroxide an intense red coloration which quickly becomes pale yellow. The semicai-bazone C,,H,,O,N forms colourless hexagonal crystals m. p. 166-167”. The semicarbazone obtained by the author from a sample of Paolini’s ketoasarone also had this m. p. so that the semicarbazone of m. p. 182-183’ descrihed by the latter may be a stereoisomeride. Trimethoxypropiophenoneoxime C1,Hl70,N forms colourless laminae m. p. 106-108°. I n the preparation of trimethoxypropiophenone a substance is also formed which crystallises in small colourless needles m. p. 110-1 12’ (softening a t 108-log’) and is probably 2 4 5-t~il~~droxypropio- d e n o n e 4 5-dirnsthvZ ether.It dissolves in alkali with production of Me0 \-/ OMe \ yellow coloration,Lnd yields a green coloration with ferric chloride. R. v. s. Relation between Chemical Constitution and Fastness to Light and Other Agencies of Polyhydroxybenzophenone Dyes. EDWIN R. WATSON and JATINDRA M. DUTTA (J. fioc. Chem. Ind. 191 1 30 196-197).-The following values have been obtained for the fastness of polyhydroxy benzophenones and xanthones to light. ( a ) Polyhydroxybenzophenones 2 3 4- trihydroxg - 111 2 3 4 4’- tetrahydroxy -IV-V 2 3 4 3’- tetrahydroxy - 111-IV 2 3 4 2’ - tetrahydroxy - 111 (3 4 3’ 4’ - tetrahydroxy - 111 2 3 4 2’ 4’-pentahydroxy-11 2 3 4 3’ 4’ 5’-hexahydroxy-I-II ; ( b ) Polyhydroxyxanthones 1 2-dihydroxy-11 1 2 7-trihydroxy-11.The roman numerals indicate the fastness of each compoiind as recorded according to the British Associalion Committee’s scale. It is evident that an increase in the number of hydroxyl groups tends to diminish the fastness t o light with the exception of the 2 3 4-tri- hydroxy -com pound. 2 4 3’ 4’-Tetrahydroxybenzophenone is the only dye appreciably faded by alkali and those dyes which do not contain two hydroxyl groups in the ortho-position to one another and adjacent to the carbonyl group are most affected by acids. Most of the dyes are brightened and deepened by treatment with alkali and the xanthones are not so fast to acid or light as the polyhydroxybenzophenones. 1 2 7-Trihydroxyxanthone is formed when the pentahydroxy- benzophenone is heated with water in sealed tubes at 180-220° fori.306 ABSTRACTS OF CHEMICAL PAPERS. two and a-half hours. not molten at 28rio and its alkaline solutions are highly fluorescent. J. J. S. It crystallises from dilute alcohol in needles is Ketems. XVI. Formation and Fission of Four-membered Rings. HERMANN STAUDINGER (Ber. 19 11 44 521-533).-The extreme ease with which the conversion of ethyl ethylketencarboxylate into ethyl 1 3-diethylcyclobutan-2 4-dione-1 3-dicarboxylate and the reverse change occur (hbstr. 1910 i 89) suggests that the two simple molecules may be united in the bimolecular substance by some kind of valency other than that operating between the ring carbon atoms of trne cyclobutaae derivatives.However the decompositions described below show that the facile fission of ethyl diethylcydo- butandionedicarboxylate is different in degree not in kind from the disruption of other cyclobutandiones obtained by the polymerisation of ketens such as dimethylketen and diphenylketen. Attention is called t o the polymerisation of phenylcar bimide nitroso-compounds and other substances also to the additive compounds obtained from ketens and carbonyl compounds or anils whereby p-lactones or p-lactams are produced (Abstr. 1909 i 410; thisvol. i 215). I n all of these cases four-membered heterocyclic substances are obtained which can be converted by comparatively simple weans either into their generators or into a pair of new substances. A general connexion cannot be traced between the stability of the rings and their ease of formation ; thus for example the p-lactams are easily obtained and yet are very stable in comparison with the p-lactones which are produced only with difficulty.[With Sr. BEREZA and MODRZEJEWSKI.]-E~~~~ 1 3-diethylcycZo- butan-2 4-dione-1 3-dicnrboxylate suffers rupture when shakep with water yielding ethyl diethylacetonedicarboxylate and carbon dioxide. The molecule i R also ruptured by the following reagents boiling dilute barium hydroxide produces impure butyrone cold alcoholic potassium hydroxide yields ethylmalonic acid (2 mols.) and alcoholic semicarbazide hydrochloride and potassium acetate cause the formation of dieth yl heptane-6-one- yr€-IricarboxyZateaemicurbaxide CO,Et*CHEt*COCEt( CO,Et)*CO*NH*NH*CO*NHq m.p. 140° which develops a deep violet coloration with ferric chloride. MAYER.1-2 2 4 4-Tet,ramethylcycZobutan-l 3-dione (Abstr. 1906 i 234) undergoes fission aniline a t 200' under pressure producing the anilide of isobutyric acid and water at 260-180' or boiling dilute sodium hydroxide producing iaobutyrone. G o ~ ~ ~ a . 1 - 2 4 4-Tetra~henyZcyclo~~ta~-~ S-dio~ie [With J. [With H. CPh,<CO>CPh co m. p. 244-245O is best obtained by heating diphenylketen-quinoline in benzene at 170° for eighty hours ; amongst other substances two polymerides are formed one m. p. 176' (as yet unexamined) in large amount and the other tetrsphenylcyclo- butandione in poor yield. It is very stable but suffers depolymerisa- tion when strongly heated.It is ruptured by 50% potassium hydroxideORGANIC CHEMISTRY i. 307 and methyl alcohol on the water-bath yielding tetraphenylscstone CO(CHPh,),,. m. p. 135' and a little diphenylacetic acid. The additive compound of diphenylketeri and cyclopentadiene is converted with considerable loss into its generators by distillation a t 160-180"/15 mm. in carbon dioxide. The p-lactam of P-anilino-aa/3-triphenylpropionic acid is very stable and can be distilled without appreciable decomposition. When however it is heated under a reflux condenser in a current of carbon dioxide phenylcarbimide is removed leaving tripheny letbylene in the residue. The p-lactam of p-anilino-aaPP-tetrapheny Ipropionic acid (Zoc. cit.) by slow distillation in carbon dioxide decomposes partly into tetraphenylethylene and phenylcarbimide and partly into its generators diphenylketen and benzophenonennil.The p-lactarn of P-~-dimethylaminoanilino-aapp-tetraphenylpropionic acid (Eoc. cit.) however decomposes a t its m. p. or better still by distillation at 200-250°/15 mm. yielding diphenylketen ; tetraphenylethylene is not formed and p-dimethylaminophenylcarbirnide cannot be detected with certainty. c. s. Ketens. XVII. Phenylketen and Methylketen. HERMANN ethyl ethylketencarboxylate is obtained so easily by heating its polymeride ethyl 1 3-diethylcyclobutnn-2 4-dime- 1 3-dicarboxylate (Abstr. 1910 i S9) attempts have been made to prepare the very unstable phenylketen (Abstr. 1905 i 444) in R similar manner. When an ethereal solution of phenylchloroacetyl chloride (which can be obtained in 66% yield by heating mandelic acid and phosphorus pentachloride [2 mols.] at 120-140' for about four hours whereby the phosphoryl chloride is mainly removed as it is formed) is treated with zinc and kept for two hours after the addition of petroleum the initially formed phenyl keten polymerises completely.In addition to other substances two polymerides are obtained 1 3-diphenylcyclo- STAUDINGER (Ber. 1911 44 533-543).-[With ST. BEREZA.]-sinCe butan-2 4-dione CHPh<GO>CHPh co m. p. 73' and its enolic modification 1 3-diphen yl- Al-cyclobuten- 2 -oE-4-one CHPh<zgz!>CPh. The former does not react with ferric chloride phenylcarbimide or a solution of bromine and yields a cliPemicarbaxone (?) m. p. 220-230' (decomp.).It distils undecomposed a t about 133' in a high vacuum and does not yield phenylketen when more strongly heated. In other respects however it suffers fission like other polymeric ketens (compare preceding abstract) ; thus with sodium hydroxide i t yields dibenzyl ketone and with methyl-alcoholic ammonia diphenylaceto- acetamide. Diphenylcyclobutenolo~~e which is also obtained by treating diphenyl- cyclobutandione with 5% sodium hydroxide separates from n mixture of benzene and ethyl acetate in crystals m. p. 160° containing I mol. of benzene. It develops a deep violet coloration with ferric chloride decolorises a solution of bromine and of potassium permanganste and is rapidly decomposed by warm water or dilute acids ; its solution ini. 308 ABSTRACTS OF CHEMICAL PAPERS.sodium hydroxide however can be boiled for some time without decomposition. [With H. W. KLEVER and J. MA~~~.]-Attempts t o prepare methylketen give results similar to the preceding. A 0*4-0*5% ethereal solution can be obtained in 6-8% yield by treating a-bromo- propionyl bromide in ethereal solution with zinc and removing the methylketen and the solvent by distillation. From this solution by fractional distillation in a high vacuum fairly pure methylketen is obtained as a white crystalline mass in a receiver cooled by liquid air ; at higher temperatures the substance polymerises rapidly yielding a small amount of a volatile substance with an unpleasant oclour (dimethylcyclobutandione ?) together with 1 3-dimethyLA1-cycZo- buten-2-01-4-one (m. p. 140' decomp.when pure). The latter polymeride is obtained better by keeping a dilute ethereal solution of methylketen for two days; it does not yield methylketen when heated gives a deep-reddish violet coloration with alcoholic ferric chloride and dissolves unchanged in warm sodium hydroxide. c. s. Ketene. XVIII. Decomposition of Benzilic Acid. HERMANN STAuDINaER (Ber. 1911 44 543-547).-Nef has shown that the decomposition of benzilic acid by heating yields benzophenone diphenylacetic acid and a red resin and explains the formation of these substances by assuming the initial production of diphenyl- methylene CPh,:. This explanation is incorrect. [With M. R. SCHoLLER.]-when benzilic acid is heated at 155-165'/15 mm. it is partly converted into benzilide; this at a higher temperature decomposes into carbon dioxide and a ketone (unisolated) CPh,(-,>CPh which suffers tha typical fission of cyclobutanones (compare preceding abstracts) yielding diphenylketen and benzophenone together with a red resin. I n the decomposition of benzilic acid by heat therefore the diphenylacetic acid is produced by the interaction of the diphenylketen and the water formed during the decomposition.[With H. G o ~ ~ ~ ~ . ] - B e n z i l i d e is decomposed by water and benzene at 200° yielding diphenylacetic acid benzophenone and other products. Benzilide must be boiled with 50% potassium hydroxide in order to reconvert it into benzilic acid. When benzilide is heated a t 200' for two days with aniline (2 mols.) and benzene it yields benzophenone and the anilide of diphenylacetic acid.When boiled with aniline under a reflux condenser for sixty hours benzilide yields the anilide of anilinodiphenylacetic acid and a substance m. p. about 200'. co *c. s. Isomerism of Naphthaquinone Derivatives. I. OSWALD MILLER (J. Russ. Phys. Chem. Soc. 1910 42 1418-1446).-The author has studied the transformations undergone by amino-a-naphtha- quinoneimide (di-iminonaph thol) and its hydrochloride in aqueous solutions. This base acts as a niixture of isomerides the action of water resulting in the simultaneous formation of 2-amino-a-naphtha- quinone and 4-amino-P-naphth'iquinone in addition to ammonia.ORGANIC CHEMISTRY. i. 309 According to Martius and Griess (Anrzalen 1865 134 377) and Graebe and Ludwig (AnnaZel-L 1870 154 31 Z) amino-a-naphtha- quinoneimide hydrochloride forms anhydrous crystals but the author finds t h a t it crystallises from water or 95% alcohol as the dihydrate; it also forms crystals with &H,O.I n order to effect the separation of the base the action of water on the hydrochloride was carried out in presence of excess of ammonia. The results show that the yield of 2-amino-a-naphthaquinorle (or 4-amino-P-naphthaquinone) increases in arithmetical progression as the concentration of the amino-a-naphthaquinoneimide hydrochloride diminishes (or increases) in geometrical progression. T. H. P. Chrysophanic Acid. OTTO FISCHER FERDINAND FALCO and HANS GROSS ( J . pr. Chem. 191 1 [ii] 83 208-214).-Chrysarobin and the chrysophanic acid dorived from it have frequently been regarded as derivatives of a-methylanthracene.By demethylating chrysarobin by hydriodic acid under pressure and distilling the chrysophanhydranthrone obtained after purification with zinc dust the authors have obtained P-methylanthracene which is identified by its m. p. 203-204* and by its conversion into P-methylanthraquinone and dibromomethylanthrayuinone (Abstr. 1909 i 563). The oxidation of crude chrysophanhydranthrone by acetic and chromic acids on the water-bath yields chry sophanic acid containing as much as 10% of frangula-emodin ; when the chrysophanhydranthrone has been purified however the amount of frangula-emodin in its products of oxidation is only 2-3% (compare Oesterle and Johann Abstr. 1910 i 860). A solution of diacetylchrysophanic acid in acetic acid and acetic anhydride is oxidised by chromic acid to the diacetyl derivative (m.p. 246' [decomp.]) of rhein. It only remains now to discover some means of smoothly eliminating carbon dioxide from rhein (which is most probably 1 :S-dihydroxy- anthraquinone- 3-carboxylic acid) in order to settle definitely the con- stitutions of chrysophanic acid aloe-emodin and barbaloin. Preparation of a Nitrogenous Oxidation Product of Ace- naphthene. KALLE & Co. (D.R.zP. 228698. Compare Abstr. 1903 i BOO).-The oxidation of acenaphthene with potassium dichromate and acetic acid gives an unsatisfactory yield of acenaphthenequinone which is not improved by substituting manganese dioxide and sulphuric acid or nitric acid as the oxidising agent. It is now found that by the action of nitrous acid esters in the presence of condensing agents (such as concentrated mineral acids zinc chloride or sodium ethoxide) on acenaphthene a yellow compound m.p. about 220' and having the composition of acenaphthenequinoneoxime is obtained ; this on hydro- lysis yields acenaphtheneyuinone. C. s. F. 1%. G. M. o-Menthene-5-one. ARTHUR KOTZ and ERWIN ANGER (Ber. 191 1 44 466-467).-8 number of new derivatives of the menthenone ( l-methyl-2-isopropylcyclo-A6-hexene-5-one ; compare Rabe and Rahm Abstr. 1904 i 747 j 1905 i 348; Merling Abstr. 1905 i 349 ;i. 310 ABSTRACTS OF CHEMICAL PAPERS. Wallach 1908 i 813) obtained by Cttllenbach from Hagemann's ester have been prepared. The semicarbaxone occurs in two forms melting at 138' and 152' respectively.The oxime has m. p. 90-9lo and the hydrochloride of this m. p. 135-136'. The corresponding methylisopropylcyclohexanone b. p. 95'125 mm. or 204'/760 mm. furnishes an oxime m. p. 75'' and a benxylidene derivative m. p. 162'. Terpenes and Ethereal Oile. CIII. Studies in the Fenchone Series. OTTO WALLACH (Annalen 191 1 379 182-215).-The hydrocarbon C9HI6 previously described (Abstr. 1909 i 812 ; compare Bouveault and Levsllois ibid. 1910 i 572 627 686 863) is now shown t o be an equlibrium mixture. The proof is based on an examination of the products of oxidation with dilute permanganate at O' and on a n examination of the nitroso-chlorides and their derivatives. When oxidised with 2% permanganate solution at O' using 3 gram- atoms of oxygen for each gram-molecule of hydrocarbon the chief products are unaltered hydrocarbon a small amount of a glycol and a mixture of two ketonic acids.One of the acids yields a semi- carbaxone which crystallises from methyl alcohol in sparingly soluble needles m. p. 173-175' and an oxinze CgH170,N iu the forrri of plates m. p. 118-119'. The acid has m. p. 19' and [a] +0*61' and when oxidised with hy pobromite yields Bouveault and Levnllois' P-isopropylglutaric acid. The ketonic acid is therefore regarded as p-iso- propyl-7-acetylbu tyric acid CH,* CO*CH2*CHPrP*CH;C02H although not identical with the acid described by Crossley (Tram. 1902 81,676)' and the hydrocarbon from which i t is formed as 1-methyl-3-isopropyl- The second ketonic acid yields A5-cyclopentene a semicarbazone which is amorphous and has m.p. 138-140' or 150-152' according t o the method of heating. The corresponding oxime is an oil and the acid itself has b. p. 175-180'/19 mm. and [a]= - 6.18'. On oxidation with hypobromite the ketonic a d yields a dibasic acid which after purification by conversion into its anhydride has m. p. 92-93'; the anhydride drystallises from light petroleum has 1x1. p. 64-66' and [a] + 3.6'. The dibasic acid is regarded as 1-a-isopropylglutaric acid (compare Abstr. 1903 i 568)' although the corresponding anilic acid has a lower m. p. than that previously given. [With FRIEDRICH RITTEB.]-T~~ nitroso-chloride prepared by the action of concentrated hydrochloric acid a t 0' t o - 10' on a mixture of the hydrocarbon C9HI6! glacial acetic acid methyl alcohol and freshly-prepared ethyl nitrite is not homogeneous ; i t consibts of 40% of solid together with oily compounds.The ,solid appears to consist of a mixture of two nitroso-chlorides but it has not been found possible to isolate both of these as one is excessively unstable iu solution. The nitroso-chloride no. p. 115' (compare Abstr. 1909 i SlZ) has [a)? - 272' and yields a nitrolpiperidide m. p. 160-161'. By decomposing the oxime (loc. cit.) with dilute sulpliuric acid and T. A. H. >CMc. $XT,*CH C,H7-CH*CH:,ORGANIC CHEMISTRY. i. 311 distilling in steam a considerable amount of resin is formed and comparatively small amounts of volatile products. These contain in addition to the ketone C,H,,O a saturated nitrogen dei-ivative b. p. 250-252" which yields ft senaicnrba,xone Cl0Hl80N in the form of colourless plates LU.p. 17 1-1 72". The ketone reacm but slowly with a n aqueous semicarbazide solutioti but in methyl-alcoholic solution yields a semicarbaxone C H :N*NH-CO*NH,. ju the form of colourless needles m. p. 210-212'. %he ketone 1 egenemted from this semicarbazone has b. p. 191-192' and an odour of thujone. If the nitroso-chloride is not purified by repeated crystallisation the ketone prepared from it yields a mixture of two semicarbazoues namely the one with m. p. 210-812" and the one with m. p 149-150" (Abstr. 1909 i 813). When reduced with zinc dust and glacial acetic acid the crystalline nitroso-chloride yields a n appreciable amount of a saturated ketone together with a saturated primary arnine and unsaturated ketone.The formation of the saturated ketone is represented by the Following scheme >CCl-?:N*OH -+ >CH *?XH -+ >CH*Y:O. The saturated ketone C,H160 freed from the unsaturated compound by oxidation with 1% cold permanganate solution has b. p. 184O D20 0.887 and ~ 1 1.4402. The ketone is however non-homogeneous as it yields two semicarbazones. The one has m. p. 197-198" and when hydro- lised yields a ketone identical in all respects with dihydropulegenone (dihydrocamphorphorone) (Abstr. 1903 i 568 569). The formation of this ketone leads to the conclusion that the original hydrocarbon contains l-methyl-3-isopropyl-A1-c~cEopentene. CgH,,ON [With LUDWIG oLL)ENBERG.]-'rhe nitvile of fencholic acid CHMe,-FH'CH '>CMe.CN CH,*CH Z L prepared by the action of phosphoric oxide on the amide is a colour- less oil b.p. 217-218" has D19 OaS660 n1,9 1.4433 and a,+6'45' in a 1 dcm. tube. When reduced with sodium and alcohol it yields 1 -r)aet~~yZ-3-isopropylcyclopentylnaethyZomine *CloH,,*NH2 with b. p. 204" D20 0.8500 and n 1-4545. The hydrochlorade has m. p . 172-173" the benzoyl derivative m. p. 81-82' and the plLenyEcarbumide NHPh*CO-NH~C,,Hlg m. p. 104- 105". The base readily absorbs carbon dioxide and combines with fenchylcarbimide yielding the niixed corbarnide CgH,7*NH*CO*NH*C,o'lg m. p. 127-1 28". The amine reacts with nitrous acid yielding a mixture of an alcohol and a hydrocarbon. The alcohol Cl0H,,O is tertiary has b. p. 212-214O DlS 0.903 and ng 1.4603 and is probably either p-menthanol or a mixture of the meta- and para-compounds.The hydrocarbon C1oH1s has b. p. 175-176' D20 0.824 n2,0 1.4571 and aD + 32'13' in a 1-dcm. tube and is somewhat similar to carvomenthene. It is highly probable that by the action of nitrous acid on the base the 5-membered has been transformed into a 6-membered ring (compare Abstr. 1907 i 602). Fenchylamine (1-amino-1 -methyl-3-isopropylc?jclopentane) (Eoc. cit. 812) reacts with nitrous acid yielding the corresponding tertiary alcohol and hydrocarbon. 1 -~UethyZ-3-isopropyZcyclopent~n- 1-02 C9Hl80 has b. p.i. 312 ABSTRACTS OF CHEMICAL PAPERS. 186-1237" m. p. 76" and the corresponding hydrocarbon C9H16 which is probably a mixture of A1- and A5-derivatives has b. p. 142-143'. [With H. wIEN~Aus.]-Diff erent specimens of fenc'nonitrile differ somewhat in properties as they are mostly mixtures.The a-compound forms a crystalline nitrosochloride CloH15N NOCl ; this crystallises from acetone has m. p. 123-124' and is strongly laevorotatory. It reacts with alkalis or organic bases regenerating the nitrile which has DlS 0.749 and [a] + 43'19'. The nitrile prepared from the amide of fencholic acid and also specimens prepared from fenchoneoxime yield dihydroxydihydrofencho- laitrile CN*C,H,,(OH) when oxidised with 1% permanganate at 0'. The hydroxynitrile forms a viscid brown oil b. p. 168-220'/12-14 mm. and crystallises from ethyl acetate in colourless tabular prisms m. p. 86'. The nitrile is readily hydrolysed by sodium hydroxide solution to dihydroxydihydrofencholenic acid CO,H*C H,,(OH) which crystal- lises from ethyl acetate in short slender prisms m.p. 111'. When boiled with dilute sulphuric acid the hydroxynitrile yields a ketonitrile m. p. 62-63' the sernicarbaxone of which has m. p. 204-206'. When further oxidised with permanganate the hydroxynitrile yields a keto- nitrile-carboxylic acid CloHl,O,N the oxime of which has m. p. 260-262' and the semicarbaxone m. p. 190-192'. P-Fencholenic acid when reduced with hydrogen and colloidal palladium yields fencholic acid and is therefore presumably CMe, $!-CH a-Fencholenic acid when reduced in a CH,*CH similar manner yields a product which appears to be identical with Mahla's dihydrofencholenic acid (Abstr. 1902 i 107). The amide has m. p. 133-134'. The amides of U- and P-fencholenic acids are reduced more readily than the acids themselves.Terpenes and Ethereal Oils. CIV. OTTO WALLACH (Annalen 191 1 379 2 15-228).-[With PAUL V~~crr.]-The author confirms Angeli and Rimini's statement (Abstr. 1897 i 88 ; compare Rimini 1900 i 554 ; Tiemann and Mahla ibid. 1897 i 85) that the isomeric nitro-imines C10H1602N2 from fonchoneoxime and camphoroxime yield the same unsaturated ketone 1 -met h y 1-5 -isopropyl-A6-cyc~ohexen- 2 - oneisocamphor when treated with coucentrated sulphuric acid and then poured into water. It is shown that the ketone is not formed by the acid but by the subsequent treatment with water. The compound Cl,Hl,O,N from fenchoneoxime crystallises from dilute methyl alcohol has m. p. 59-60' (Rimini 66-67'; Tiemann and Mahla 58') and [a]= + 25-83'.The ketone although optically active on oxidation yields dl-a-isopropylglutaric acid (compare Angeli and Rimini). The ketone is extremely unstable; it has D2' 0.9260 n$' 1.4758 and b. p. 216'. The b. p. is somewhat lower than that of the isomeride of the para-series namely carvotanacetone 5. p. 228". The b. p. of 1-methyl-3-isopropyl-A6-hexene-5-one namely 244-245' (Knoevenagel Abstr. 1893 i 419) is too high. 1 -Methyl-5-isopropyI-h6-cycZohexene-2-one forms an oily additive compound with hydrogen sulphide and also yields a solid Condensation >CMe*CO,H. J. J. S.ORGANIC CHEMISTRY. i. 313 product with benzaldehyde. When reduced with sodium and moist ether the ketone yields the saturated alcohol 1-methyl-5-isopropylcyclo- hexcme-%ol CHMe2-cH<cH2-CH2 CH2*cHMe>CH*OH and this on oxidation yields l-rnethyl-5-isopropylcyclohexan-2-one CloHl,O b p1 2 11-21 2' D21 0.8885 n 1.4466. The alcohol has b.p. 215-216" D21 0,889 and rzg 1,4563 (compare Spica Abstr. 1902 i 43). [With PRIEURICH HENJES.]-I~ is pointed out that various unsatur- ated nitriles of the camphor series combine readily with nitrosyl chloride. Menthonitrile nitrosochloride CloH,,N,NOC1 crystallises from methyl alcohol and has m. p. 96,-95'; the corresponding nitrol- piperidide C,oH,7N=NO*C,NH,o~ has m. p. 83-85'. The nitroso- chloride when treated with alkalis or reducing agent regenerates the nitrile. Citronellalnitrile nitrosochloride C,,H,,N*NOCl has m. p. 106O ; the nitrolpipesidide m. p. 88-90' ; and the rzitrol-p-toluidide m. p. 107-1 08'.Camphonitrile and pulegenonitrile yield bluish- green oils when treated with nitrosyl chloride The semicurbaxone has m. p. 162-1633. J. J. S. Action of Piperidine on d-Pinene Chloro-oxime. L. V. BUSCHUEFF (J. Russ. Phys. Chem. Xoc. 1910 42 1447-1448).-1n Schimmel's Bericht (Oct. 1910 171) it is stated that the results of the author's investigations on the action of piperidine on d-pinene chloro-oxime (Abstr. 1910 i 122 j confirm thove of Wallach (Abstr. 1888 1098). The author points out however that he obtained nitrosopinene and pinene nitrolpiperidine as the products of this reaction (compare Golubeff Abstr. 1908 i 902) whilst Wallach obtained pinene nitrolpiperidine only. T. H. P. New Constituent of Angelica Root Oil. E. BOCKER and ALFRED HAHN (J. pr. Chem.1911 [ii] 83 243-248).-The least volatile fraction of angelica root oil deposits after long keeping a small amount of a crystalline substance m. p. 84' (compare Ciamician and Silber Abstr. 1896 i 595) which exhibits the properties of an unsaturated y-lactone. It has the formula C,,H,,O is not changed by hot or cold aqueous alkalis or cold alcoholic potassium hydroxide but is hydrolysed by boiling N/2-alcoholic potassium hydroxide (saponification number 238) the product regenerating the lactone by acidification. It forms a dibromide C15H1603Br2 m. p. 143-145' and an additive compoutzd C,,H,70,C1 m. p. lolo with ethereal hydrogen chloride. c. s. Constituents of Essential Oils. Identity of the Alcohol CloHI6O of Gingergrass Oil with Perilla Alcohol. Tricyclene- carboxylic Acid.FRIEDRICH W. SENMLER and B. ZAAR (Ber. 1911 44 460-463).-The supposed dihydrocuminol obtained by Schimmel Ct Co. from gingergrass oil (Abstr. 1905 i 536) and examined by Wahlbaum and Huthig (loc. cit. p. 53) has been re-investigated and proved* to be identical with the alcohol obtained by reducing Perilla- aldehyde (Semmler and Zaar this vol. i 218). The alcohol purified as far as possible from geraniol has the following constants b. p. VOL. C. i. xi. 314 ABSTRACTS OF CHEMICAL PAPERS. 107-110°/12*5 mm. Dzo 0,946 n 1.4968 uD - 7'(100 mm.). The low optical activity is doubtless due to partial racemisation. With phos- phorus pentachloride it gives a chloride C,,H,,Cl b. p. 97-102'/ 14 mm. DZo 09848 n 1.50058 a - 16' (100 mm.) and this on re- duction with sodium in alcohol furnishes limonene identified by means of its tetrabromide. These data and the fact that the alcohol yields Perilla-aldehyde on oxidation prove that it is identical with Perilla alcohol.Comparison of tricyclenecarboxylic acid (Bredt and May Abstr. 1910 i 32) with teresantalic acid proves that the two are not identical (compare Semmler Ather. Ole 1906 ii 90 and Abstr. 1907 i 703 1062). T. A. H. DAVID SPENCE and J. C. GALLETLY (J. Amer. Chem. Soc. 1911 33 190-194).- Although the action of chromyl chloride on terpenes has been extensively studied its action on caoutchouc has not hitherto been investigated. When chromyl chloride is added to a solution of caoutchouc in carbon disulphide the cornpound C,,H,,,2Q;rO,CI rapidly separates as a voluminous dark brown precipitate which is insoluble in organic solvents; on exposure to the air it absorbs moisture and rapidly undergoes decomposition.Tho same product was obtained from several caoutchoucs of different botanical origin. When the compound is treated with water it is immediately decomposed with formation of a dark green solution from which on heating a brown gummy mass separates. By extracting the latter product with ether or chloroform a substance is obtained in an impure state which gives the reactions of an aldehyde and when treated with phenylhydrazine yields a crystalline compound m. p. about 92'. If the solution obtained by the action of water on the chromyl chloride compound is submitted to dialysis an opalescent colloidal solution is produced from which an insoluble substance has been isolated containing definite proportions of chromium and chlorine.The investigation is being continued. E. G. B. V. BYSOFF (J. Rzsss. Phys. Chem. Xoc. 1910 42 1358-1362. Compare Abstr. 1910 i 865).- The author finds that given constant conditions OF vulcanisation the ratio between the proportions of total and free sulphur (extractable by acetone) is approximately constant. In preparations containing small amounts of sulphur this ratio increases as the total proportion diminishes. When caoutchouc is vulcanised with steam under three atmospheres pressure the curve showing the relation of the proportion of free sulphur to the time is asymptotic t o the time axis. Hence in order to compare the proportions of free sulphur in different vulcanised caoutchoucs i t is necessary to vulcanise until the amount of free sulphur becomes practically constant ; under the above conditions this requires two hours.A series of mixtures of caoutchouc and sulphur containing 1.0 1.2 1.4 1.6 1.8 and 2% of sulphur respectively were vulcanised with steam as above. Examination of* the various samples showed that Action of Chromyl chloride on India-rubber. Vulcanisation of Caoutchouc.ORGANIC CHEMISTRP. i. 315 (total sulphur)'l/(free sulphur) =a constant. The value of n was 3.1 and that of the constant 26.692 but these values may vary with the kind of caoutchouc and with the method of vulcanisation. T. H. I?. Bixin. ALFB. HEIDUSCHKA and El. RIFFART (Arch. Pharm. 1911 249 43-48).-The results of an investigation of the action of halogens on bixin are given and the old formula C,,H,,O is adopted for this dye in preference to C,,H,,O suggested recently by van Hasselt (Abstr.1909 i 598). On adding bromine t o bixin dissolved in chloroform a colourless amorphous compound C,8H,,0,Br,o,4HBr m. p. 143' is obtained. This on heating at 100' decomposes yielding a yellow decabrornide which can be crystallised from alcohol but decomposes when heated or when kept (compare van Hasselt Zoc. cit.). The analogous substances C2,H,,O,C1,,,4HCl m. p. 9 lo and C,7H,,0,C1,,,4HCl m. p. 102' the latcer obtained from nwbixin are siw~larly prepared by the action of chlorine and are amorphous. Bixin and norbixin each combine with 11 mols. of hydrogen chloride to form amorphous pale yellow additive products ; the one has m.p. 74') and the other m. p. 108'. T. A. H. The Benzotetronic Acid Group. 11. Ketonic Hydrolysis of Benzotetronic Acid [4-Hydroxycoumarin] and its Homo- logues. RICHARD ANSCHUTZ and MAX EUGEN SCHOLL (AnnaZen 191 1 379 333-350. Compare Abstr. 1909 i 660).-o-Hydroxyaceto- phenone and its three methyl derivatives can be obtained by hydro- lysing benzotetronic acid and its methyl derivatives with potassium hydroxide solution at relatively high temperatures. When the ethyl ether of benzotetronic acid [4-ethoxycoumarin] is hydrolysed the first product is the free acid and finally o-hydroxyacetophenone ; the inter- mediate product o-hydroxybenzoylacetic acid OH* C,H,*CO-CHI,* CO,H cannot be isolated For the preparation of the hydroxyacetophenones it is not necessary to prepare the benzotetronic acids but to start with the condensation products of acetylated salicylic acid chlorides and ethyl sodiomalonate.o-yo c 6 H 4 < ~ ( OH) C* CO,Me* Methyl 4-hgdroxycoumarin- 3-carboxg late prepared from acetylsalicyl chloride and methyl sodiomaloiate crystallises from alcohol in colourless needles m. p. 136' ; when hydrolysed with 33% potassium hydroxide solution at 115' for ten hours it yields potassium benzotetronate but at 180' gives an 80% y9ld of o-hydroxyacetophenone b. p. 96-97"/10 mm. (compare Friedlander and Neudorfer Abstr. 1897 i 124) ; the oxime has m. p. 117q not 112' (Dunstan and Henry Trans. 1899 76 66) and the phenylhydrazone is only sparingly soluble in sodium hydroxide solution.The benzoyl derivative COPh-O*C,H,*COMe crystnllises from alcohol in colourless needles m. p. 88' ; the sernicarbazona OH=C,R,.CMe:N*NH*CO*NH x 2i. 316 ABSTRACTS OF CHEMICAL PAPERS. also crystallises in colourless needles and when heated at 225O is rapidly transformed into o-hydroxyacelophennonectxine N,(:CMe*C,H,*OH) which is also formed when the hydroxyacetophenone is shaken for several days with an aqueous solution of hydrazine sulphate. The azine crystallises from alcohol in glistening pale yellow needles m. p. 197-198'. Acetyl-o-cresotic [2-acetoxy-m-toluic] acid OAc*C6H,Me*C02H [CO,H OAc Me = 3 2 11 crystallises from benzene in colourless needles m. p. 113' and reacts with phosphorus pentachloride in the presence of light petroleum yielding the chloride Oih*C6H,Me*COCI which can be distilled under extremely low pressures.Nethyi 4-ht~dGo~y- 8-methyZcozcrnarin-3-carbo~yEate 0-yo C,H3Me<c(0~) c *CO,Me' crystallises from alcohol in colourless plate; m. p. log' and with aqueous potassium hydroxide solution at 100' yields 4-hydroxy- 8-methylcoumarirt (3-methylbenzotetronic acid) CloH80s which crystal- lises from water in colourless glistening needles m. p. 228' (decomp.). 2 - Hydroxy - 3 - methylacetophenone OH*C,H3Me*COMe has b. p. 106-107°/10~5 mm. ; the phenylhydraxone C,,H,,ON crystallises from alcohol in yellow needles m. D. 123' the semicarbaaone. Cl,Hl,02N3 in colohess needles m. p. 2i8' and ihe axi*lie in slender orange-yellow needles m. p. 237'. c* sH2002N29 Methyl 4-hyd~oxy-7-rnethyEcoumuri~-3-carboxyZa,te C,,H1,02 crystal- lises from alcohol in colourless needles m.p. 208O (decomp.) and on hydrolysis with potassium hydroxide solution at 200' yields 2-hydroxy- 4-methylacetophenone which has b. p. 105-106'/9 mm. (compare Xykman Abstr. 1904 i 664). The phenylhydruxone of the latter crystallises from alcohol in yellow glistening plates m. p. 105'; the semicarbaxone in colourless needles m. p. 214O and the mine in slender yellow needles m. p. 219'. Methyl 4-hydroxy-6-methy?coumarin-3-carboxylate C,,H!,O obtained from acetyl p-cresotyl chloride crystallises from alcohol in soft felted needles m. p. 210' (decomp.) and on hydrolysis yields 2-hydroxy- 5-methylacetophenone (compare Auwers and Muller Abstr. 1909 i 223). The beitxoyl derivative of the latter C16H1403 crystallises from alcohol in stout colourless prisms m.p. 65'. forms small colourless needles m. n. 145' ; the sernicarbaxone The oxirlne OH C,H,Me* CMe:N*OH ClOH&2% in colourless rhombic crystals m. p. 212O and the azine C18H2,,02N2 in orange-yellow needles m. p. 223'. J. J. S. The Grignard Reaction. Syntheses of Fluoran. ENOS FERRARIO [and in part M. NEUMANN] Gaxxetta 1911 41 i 1-11).- By the series of reactions described below the author bas effected the synthesis of fluoran. Another method by which this was attempted yielded only phenolphthalein diphenyl ether.ORGANIC CHEMISTRY. i. 317 Magnesium o-methoxyphenyl iodide (in ethereal solution) reacts with phthalic anhydride (in benzene solution) yielding 2 2'-dinzethoxy- phthalophenone Cg2Hl8O4 which crystallises in colourless needles CI in small cubes m.p. 145-146" and dissolves in concentrated sulphuric acid producing a bluish-violet coloration. On reducing it with zinc and glacial acetic acid 2 2'-dimethoxytriphenylmethcne-2"-carboxylic acid (OMe*C,H,),CH*C,H,*CO,H is obtained ; i t forms colourless needles m. p. 249-250' (on rapid heating; if the m. p. is taken slowly the substance begins to melt at 235" is almost melted a t 240° and completely so a t 245'). The acid forms potassium and sodium salts which crystallise in lamins ; amorphous barium and calcium salts and a silver salt which blackens quickly. The methyl ester has m. p. 149-150'. When the acid is demethylated preferably by heatigg it with hydrochloric acid (D 1.4) for two hours in a sealed tube at 130-140° it yields fluoran.This synthetic fluoran crystallises with two molecules of alcohol part of which it retains for a time even when fused. PhenolpAthaZei!n diphenyl ether is obtained by heating together phthalic anhydride phenyl ether and zinc chloride for six hours a t lSO-190° and also (but not so well) by the action of phthalyl chloride on phenyl ether. It has m. p. 105-106' and dissolves in cencentrated sulphuric acid producing a cherry-red coloration. R. V. S. Thalleioquinine. EZIO COMANDUCCI (Pamphlet 1910 7 pp. Compare Abstr. 1910 i 581).-The author gives a more detailed account of the properties of *his substance and of its behaviour with a number of reagents. It has m. p. 148-149' (corr. sintering at 130'). Analysis gave C 59*00% H 8*47% N 7.53-8.52% C13*88-4.13%.I n alcoholic solution the compound has [a] - 187.5'. The molecular weight determined ebullioscopically in various solvents varies from 300-450. The hydrochloride is an amorphous residue m. p. 120-122' (sintering at looo) and has [a] -255.1". The platinichloride is a greenish-white precipitate which becomes brown at 230' sinters at 240" and melts at 263". The picrate is an amorphous yellowish-green powder m. p. 135' (sintering at 130'). An account IS given of the absorption spectrum of the substance and also of that of quinine. Volatility of Cocaine. 13. C . FULLER (J. Ind. Engin. Chem. 1910 2 426).-Attention is drawn t o the fact that cocaine is appreciably volatile a t temperatures of and exceeding 984 a fact which is of importance in the method usually employed in the assay of coca leaves.Experiments showed that cocaine can be heated at 60° 80° and 90' without loss of weight and the conclusion is drawn t h a t these residues should be dried at a temperature not exceeding 90° or preferably desiccated without heating over sulphuric acid. R. V. S. P. M. G. M. Alkaloids of the Perennial Papaveracem. Papaver orien- tale and P. lateritium. JOHANNES GADAMER (Arch. Phurm. 1911 249 39-42).-With a view to obtaining data bearing on the function and method of formation of alkaloids in plants the avtbori. 318 ABSTKACTS OF CHEMICAL PAPERS. proposes to examine a number of the perennial plants of the Papaveraceax The distribution of protopine will be specially studied. This alkaloid does not occur in P.orientale or P. Zateritiuum. [With WALTER I(LEE.]-~. orientale contains an azkaloid m. p. 204-205' which separates from ether in colourless crystals and since it is soluble in alkali must contain a phenolic hydroxyl group. Y. ZatePvitilum also contains a phenolic base or mixture of bases from which no crystalline substance could be separated. Gorydalis Alkaloids. Corycavidine a New Alkaloid of the Gorycavine Series. JOHANNES GADAMER ( ATCIA. Pharm. 19 1 1 249 30-39).-The mixed amorphous alkaloids of CorydnZis cam tubers prepared as described already (Abstr. 1902 i 306) on conversion into thiocyanates can be separated into two groups one giving crystalline thiocyanates soluble with difficulty in alcohol and the other readily soluble amorphous thiocyanates.From the second group a new alkaloid corycavidine closely related to corycavamine has been isolated and characterised. Corycavidine C2,H2,05N [ u x + 203.1' in chloroform crystallises from hot chloroform with ICHCI on addition of alcohol. When heated it changes at 209O and melts at 212-213'. The change at 209' is into i-corycavidine (m. p. 193-195' after re-crystallisation) and resembles that brought about by heating corycavamine ( Abstr. 1902 i 391). The hydrochloride nitrate and suzphate were prepared ; the two former are crystalline. The aurichloride BHAuCl is a red powder which sinters at 85' and decomposes at 170'. Corycavidine contains two methoxyl groups and a methyl group attached to the N-atom. It appears to be corycavamine in which a dioxyrrtethylene group is replaced by two methoxyl groups and this view finds support in the similarity of the colour reactions of the two alkaloids and their similar behaviour on heating.Corycavidine like corycavamine is unaffected by hot iodine solu- tion. With methyl iodide it gives a methiodide B*CH,I,SH,O m. p. 207-210' (decomp.) which is optically inactive and forms small colourless crystals from alcohol. When boiled with alkali hydroxide the methiodide gives the corresponding methins base m. p. 141 *5-142.5' which forms colourless crystals from ether and with methyl iodide furnishes a methiodide which was not isolated but treated directly with alkali when it decomposed giving trimethylamine and a neutral substance. The lazter polymerised very readily forming a yellow amorphous mass and on oxidation with permangarlate yielded a crystalline acid and a crystalline neutral substance probably a glycol. T.A. H. T. A. H. Constitution of Tropilen. ARTHUR KOTZ and RICHARD ROSEN- BUSCH (Ber. 191 1 44 464-466).-Tropilen C7HlOO the final product of the '' exhaustive methylation " of tropine was supposed by Merling to be tetrahydrobenzaldehyde (Abstr. 1892 i 36S) and by Willstatter (Abstr. 1898 i 540) t o be cycloheptenone QH,-CH,*CH,>C()* CH,*CH=CHORGANIC CHERIISI'RY. i. 319 Willstatter's attempt to confirm this formula by the reduction of tropilen to suberone (Abstr. 1901 i 649) wag unsuccessful. By the use of Paal's reduction method with palladium as catalyst the authors have now effected this reduction and confirmed Willstatter's formula.T. A. H. Preparation of isosparteine. Action of Methyl Iodide on the Base. CHARLES MOUREU and AMAND VALEUR (Compt. rend. 1911 152 386-387).-A 90%. yield of isosparteine can be obtained from a-methylsparteine by heating the dihydrochloride of the latter at 230-230' in a current of hydrogen chloride. When isosparteine is boiled with methyl iodide in methyl-alcoholic solution a mixture of two methiodides is formed ; the a-compound has [.IL - 16*8" and is identical with the methiodide previously described (Abstr. 1908 it 44) whilst the isometic isosparteine a'-methiodide has [aJD - 33.3'. The two substances are separated by taking advantage of the different solubilities of their hydriodides in water. w. 0. w. isosparteine. A Case of Stereoisomerism of Nitrogen CHARLES WOUREU and AMAND VALEUR (Compt.rend. 1911 152 527-529. Compare preceding abstract).-The two isomeric a- and a'-methiodides of isosparteine are now shown to owe their existence to a different spatial arrangement with regard to one nitrogen atom. If they correspond with the fixation of methyl iodide on two different nitrogen atoms the bases arising by decomposition of the correspond- ing methylisosparteinium hydroxides should not be identical. It has been found however that a-methylsparteine is produced when either the a- or a'-hydroxide is heated in a vacuum. I n the latter case a new base methylisosparteine Ci6H2*N is also formed. This has m. p. 2 4 O [a] + 23.6" and may be separated from a-methylsparteine by mixing with methyl iodide in methyl-alcoholic solution when methyl- isosparteine dimethiodide C1,H,8N,,2MeT m.p. 281-282' (decomp.) is formed. A better method which allows of isolating both bases consists in heating with dilute sulphuric acid when a-methylsparteine alone is converted iuto the methosulphate. Methylisosparteine dipicrate has m. p. 203'. The platinicliloride blackens a t 240° and has m. p. 256' (decomp.). w. 0. w. Synthesis of Pyrrole and F u r f u r a n Derivatives from Dichloroethyl Ether Ethyl Acetoacetate and Ammonia. ERICH BENARY (Ber. 1911 44 493-496).-By the interaction of dichloroethyl ether ethyl acetoacetate and aqueous ammonia in the cold a mixture of ethyl 2-methylpyrrole-3-carboxylate and ethyl 2-methylfiirfuran-3-carboxylate is obtained. The mechanism of the reaction is precisely similar to that between chloroacetone ethyl acetoacetate and ammonia studied by IIsntzsch (Abstr.1890 i 11 65) and Feist (Abstr. 1902 i 488). Ethyl 2-methylpyrrole-3-carboxylate crystallises in colourless leaflets m. p. 78-79" and dissolves in concentrated sulphuric acid with a,i. 320 ABS'I'RACTS OF CHEMICAL PAPERS. reddish-violet coloration. It is hydrolysed to the corresponding acid already described by Ciamician (Ber. 1878 14 l056). Ethyl 2-methylfurfuran-3-carboxylate is an oil b. p. 85-87'/20 mm. The corresponding acid forms colourless needles m. p. 101-102° (Plancher and Albini Abstr. 1904 i 334). Synthesis of Pyridine Derivatives from Dichloroethyl Ether and Ethyl-P-aminocrotonate. ERICH BENARY (Ber. 191 1 44 489-493).-By the interaction of ethyl-/3-aminocrotonate and 1 2-dichloroethyl ether ethyl 2 6-dimethyl- 4 - crTLlorometilyldihydro- E.F. A. p yridine-3 5-dicarbox ylate NH<CMe CMe:C(CoZEt)>CH*C~2CI ~ is ob- tained in tiny colourless needles m. p. 133-134'. On oxidation with dilute nitric acid (D 1.1 7) the corresponding ethyl 2 6-dimethyl- 4-chloromethylpy~idine-3 5- dicarboxylate is formed ; i$ is a colourless viscid oil m. p. 197-198'. It was mixed with a small quantity of a chlorine-free substance crystallising in needles m. p. 72-73'. A further by-product of the oxidation is ethyl 3 6-dimethylpyridine- 3 5-dicarboxy late- 4-methylnitro lie acid which crystallises in colourjess Inekdles m. p. 1 10' (decomp.) ; it gives a red coloration with alkali hydroxide only in concentrated solution.When boiled with dilute nitric acid the diethyl ester of 2 6-dimethyl- pyridilne-3 4 5-tricarboxytic acid is formed N'CMe ~ ( C O ~ E t)>C*C*2H ; CMe*C( CO,E t) it crystallises in tiny needles m. p. 181' (decomp.). Ethyl 2 6-dimethyl-4-iodomethylpyridine-3 5-dicarboxylate is ob- tained by the interaction of the corresponding chloro-compound with sodium iodide in acetone solution ; it crystallises in granular crusts m. p. 77-78'. Et?yl 1 2 6-tr~meth~~-4-chlosomethy~d~hydro~yr~d~lne-3 5-dicar60xyl- NMe<CMe:C( CMe:C(Co2Et)>CH*CH,C1 CO,Et) from dichloroethyl ether and ethyl P-methylaminocrotonate crystallises in four-sided platelets m.p. 88-49'. E. F. A. Condensation of Crotonaldehyde with Ammonia and Ethyl Acetoacetate. E. GRISHKEWITSCH-TROCHIMOWSKY (J.Buss. Phys. Chem. Soc. 1910 42 1377-1 380).-Ethyl 2 6-dimethyl-4-aElyldi- prepared by the condensation of crotonaldehyde with gmmonia and ethyl acetoacetste forms colourless crystals m. . p. 144.5-1 45.5'. When oxidised it yields a viscous pale yellow liquid b. p. about 205"/45 mm. and when treated with platinum chloride in concentrated hydrochloric acid solution it gives ethyl 2 6-dinzethyZ-4-alZy~pyr~dine- 3 5-dicarboxylate plathichloride C1,H,10,N,H2PtCl forming orapp needles m. p. 177*5-178".ORGANIC CHEMISTRY. i. 321 When the dihydropyridinedicarboxylic ester is hydrolysed and the salt subsequently subjected to dry distillation with slaked lime i t yields a colourless liquid b. p. 175-178" which is probably 2 4 6 - t r i - methylpyridine ; it forms a platinichloride m.p. about 220' (decomp.) an aurichloride and a mercurichloride compound m. p. 155-155-5'. T. H. P. New Diethyltrimethylenepyrrole Derivatives. MARIO GHIGLIENO (Atti R. Accad. Sci. Toyino 1911 46 87-95).-1n order to test the accuracy of the explanation giveo (Abstr. 1910 i 427) for the existence of two isomeric forms of 3 5-dieyano-4-methyl-4-ethyl- trimethylenedicarbonimide and of similar methylethyl compounds the author has examined various diethyl derivatives homologous with methylethyl derivatives already described (loc. cit. ; Abst,r. 1910 i 505). The results confirm the hypothesis of spatial isomerism since in no case could two isomeric diethvl derivatives be preDared. The mono-amide of 3 5-dic"arbozy-4 4-diet~,yitri;nethyZen~~icarb*~- imide NH<Co.&co"H) Co*c(Co*NH~CEt prepared by the action of dilute sodium hydroxide s&ution on the corresponding 3 5-dicyano- compound has m.p. 247-260O (Maquenne block) and behaves as a dibasic acid owing to the mobility of the iminic hydrogen under the influence of the neighbouring groups ; the second basicity is however weak and in N/lO-solution can only be estimated to the extent of about 50% by means of sodium hydroxide and phenolphthalein. The silver C,,H,,0,N,Ag2,H20 lead copper and barium salts are all sparingly soluble. 4 4-Uieth yl trimeth y Zened icar bonirnide- 3 5-d icarboxy 2 ic acid >CEt CO*F](C02H) obtained by the action of nitrous acid on the preceding compound forms coloiirless needles ( + 14H20) the anhydrous acid having m.p. 188-189° (Maquenne block); it behaves as a dibasic acid although not so sharply as tbe corresponding methylethyl homologue and forms insoluble lead copper silver and mercurous salts. When heated it NH<co~c(co,€€) L I . loses ZCO forming 4 ; 4-diethyltrim~,thylenedicccybonimide NH<Co* Co'FH>CEt2 CII as a yellow semi-fluid mass; this compound gives sparinuly soluble silver C,H,,02NAg lead copper and zinc salts. k. H. P. Constitution of the Pseudo-ammonium Bases. ADOLF KAUFMANN and PAUL STRUBIN (Ber. 1911 44 680-690).-The constitution of the pseudo-ammonium bases has long been a subject of discussion (compare Hantzsch and Kalb Abstr. 1900 i 113). I n particular the first product formed on oxidation of the alkyl- quinolinium bases has been assumed to be a carbinol base (Decker Hantzsch) or on aldehyde bqse with the CH:FH c 6 H 4 < ~ ~ - c ~ 0 0 ~i.322 ABSTRACTS OF CHEMICAL PAPERS. pyridine ring opened NHR*CGH,*CH:CH*CHO (Roser Gadamer Reissert) or the anhydride of the carbinol. (La Coste Hantzsch). It is now sho*m that the carbinol a t first formed slowly undergoes transformation into the isomeric aldehydearnine which is an exceedingly reactive substance. The aldehyde group can be identified by the specific colour reactions with diazobenzenesulphonic acid ; corresponding derivatives are aIso formed with phenyl hydrazine hydrcxylamine and aniline. The aldehydeamine combines with alcohols forriling unstable additive products NHR*C,H,-C!H:CH*CH(OH)*OR from which water is eliminated and the closed-ring alcoholates formed.It forms an additive compound with the carbinol which on the elimination of water is converted into the anhydride dihydro- quinoly lquinolanol Alkali converts the aldehyde into an oxidation product (acid) and a reduction product (alcohol) from which water is eliminated and quinolone and dihydroquinoline are formed. Two molecules of the aldehyde undergo a benzoin condensation forming dyes whkh are probably identical with the cqocyauines. The aldehyde combines further with substances containing a reactionary Gethylene or methyl group. dihydroquinoline derivatives C6H,< Water is eliminated uand are formed from CH:$?H NR=CH*CHXY' the aldol i n termediat e product NHR*C6H,-CH:CH *C H (OH)*CHXY in addition to unsaturated substances NHR*C,Hp*CH:CK*CH:CXY.Both types when oxidised form dyes belonging ta the class of cynnines and apocyanines. Similar transformations to the above have been observed in the isoquinoline and pyridine series. Thus with isoquinoline the pseudo- base is transformed iuto the aldehyde C HO*C,H;CH:CH*NHR which reacts as described above. When condensed with reactive methylene compounds dihydroisoquinolines are formed closely related t o the alkaloids. isoQuinoline and pyridine differ from quinoline in that the aldehydes tend to lose alkylamine and form nitrogen-free alcohols or the isomeric aldehydes. The rnethochloride of the pseudobase from 6 8-dinitroquinoline is obtained by heating with the theoretical quantity of methyl sulphate dissolving t h e fused mass in water and precipitating with sodium chloride ; it forms brownish-yellow crystals m.p. 203' (decomp.). Alkali hydroxides ammonia and sodium carbonate precipitate the pseudo-base dinitromethylpuirzolnol from an aqueous solution of the salt as a light yellow indefinitely crystalline substance; it is obtained from chloroform in yellow plates m. p. 114". When boiled with alcohols the alcoholates separate in well defined crystals ; the rnetl.yZ ether has rn. p. 1 1 0 O ; the light yellow needles of the ethyl ethey sinter a t 124O. The pseudo-base dissolved in the nascent state i wORCtANlC CHEMlS'I'RY. i. 323 benzene or toluene readily separates again in light yellow flakes which sinter at 199O and have the composition C,,H:l,O,N of the anhydride dinitromethylpuinoline oxide ; attempts to recrystallise it from ethyl alcohol result in the formation of the ethyl ether Dinitromethylquinolanol reacts with phenylhydrazine forming a phenylhydraxone crystallising in yellowish-brown needles m.p. 141O. The corresponding anil separates in well formed yellow needles m. p. 186'. The evidence is insufficient t o decide whether the pseudo-base has the carbinol or aldehyde structure. On heating quinoline ethiodide hydroxylamine hydrochloride and potassium hydroxide a compound C,2H260N3 crystallising in short almost colourless needles m. p. 2 14' (decomp.) was obtained which appears to be a condensation product of two quinoline nuclei with one molecule of hydroxylamine. A red dye is also formed. E. F. A.. Preparation of Bromo-fatty Acid Derivatives of Amino- aceto-p-ghenetidines.CHEMISCHE WERKE VORM. DR. HEINRICH BYK (D.R.-P. 228835).-Aminoaceto-p-phenetidine has long been employed in pharmacy and it is now found that its higher acyl derivatives containing bromine and an amino-residue have an enhanced therapeutic value. a- Bromoisovalerylaminometo- p-phenetidine OEt*C6H,*NH*CO*CH,*NH=CO-CHPrpBr slender colourless needles m. p. 155-156' is prepared by slowly treating a cold benzene suspension of aminoaceto-p-phenetidiue with a molecular proportion of a-bromoisovaleryl bromide allowing the mixture to remain during several hours removing the benzene in a vacuum and subsequent crystallisation from alcohol. F. M. G. M. Strongly Coloured holo- and meri-Quinonoid Imonium Salta of Benaidine and their Use for Determining the Active Value of Oxidising Agents.WALTER XADELUNG (Be7*. 19 11 44 636-631).-The author does not agree with Willstatter and Kalb's view (Ber. 1906,39,3476) that meri-quinonoid derivatives are deeply coloured whereas holo-quinonoid compounds are yellow (compare Will- stiitter and Piccard Abstr. 1908 i 475 915; Schlenk and Knorr 1909 i 36 808). When an aqueous solution of benzidine is oxidised with halogens permanganate dichromate or iron cyanate under such eonditions that the solution is kept neutral the product is a crystalline solid with a deep cornflower-blue colour and is very sparingly soluble. This compound probably has a constitution analogous to Schlenk's meri- quinonoid salt of diphenoquinonedi-imine. When further oxidised the compound deepens in colour and gives a deep violet-coloured product which is regarded as the holo-quinonoid compound.When bromine water in presence of potassium bromide is used as oxidising agent and an amount insufficient to completely precipitate the benzidine is used it is found that the amount of bromine required to transform the blue into the violet product is equal to the amount of brominei. 324 ABSTRACTS OF CHEMICAL PAPERS. required to oxidise the benzidine to the blue compound and that the addition of more bromine water leads to the formation of a reddish- brown product which is regarded as the quinonoid dibromoimide. When benzidine solution or thiosulphate solution is added to this the change to the violet and then t o the blue compound can be observed. It is suggested that Willstatter and Piccard’s second chromate is in reality a holo-quinonoid derivative. The salts of the meri- and holo-quinonoid compounds with mineral acids are quite stable at the ordinary temperature but decompose when warmed and cannot be recrystallised.On addition of alkali they yield the yellow readily soluble diphenoquinonedi-imine which is readily decomposed by acids for example hydrochloric yielding benzidine and the quinonoid dichlorobromide. It is shown that when the blue compound formed by the action of a given amount of an oxidising agent of known concentration on benzidine is removed acidified with hydrochloric acid and the dichloro- imine treated with excess of potassium iodide an amount of iodine is liberated which corresponds exactly with the oxidising value of the original volume of oxidising agent employed.The method is recom- mended for the estimation of small amounts of oxidising agents. As the volume of iodine solution to be titrated can be quite small compared with the volume of the original solution it is also recom- mended in cases where the original solution is coloured for example in the case of peroxydases and blood. J. J. S. Colloidal Form of Nastvogel’s Osazone. HENRY J. H. FENTON and WILLIAM A. R. WILKS (Proc. Camb. Phil. Xoc. 1911 16,85-86). -A colloidal solution of Nastvogel’s osazone of glyoxalcarboxylic acid is obtained by boiling phenylhydrazine dihydroxymaleate with water (Trans. 1905 87 808). It is readily coagulated by minute quantities of electrolytes moves to the anode in an electric field is not precipitated by electronegative colloids but yields a dark brown precipitate with colloidal ferric hydroxide; in general it behaves as a negative colloid of the suspensoid class.The most remarkable pro- perty of the colloid is its extreme sensitiveness to hydrogen ions; a solution which is unaffected by several drops of 5N-sodium chloride is coagulated under similar conditions by one drop of N/1 O-hydro- chloric acid the hydrogen ion being about 300 times as effective as the sodium ion. It is suggested that a minute quantity of some basic substance is present in the colloidal solution and that its “protective” influence is removed on neutralisation by the acid c. s. Action of Hydrazine Hydrate on Ortho-diketones. THEODOR CURTIUS and RICHARD KASTNER (J.pr. Chem. 191 1 [ii] 83,215-232). -Curtius and Thun (Abstr. 1891 1355) have shown that hydrazine hvdrate reacts with ortho-diketones such as benzil to form derivatives NH NH’ of the hypothetical hydrazimethylene CH,< I The present work has been undertaken mainly to show that p-tolil bebsves in a similar manner.ORGANIC CHEMISTRY. i. 325 Hydraxi-p-tolif (p-toluoyl-p-tolylhydrazimethylene) $E>c( c6 K,Me) ' CO*C,H Me rn. p. 139-140° is obtained by heating an alcoholic solution of p-tolil with hydrazine hydrate (1 mol.). It yields deoxy-p-toluoin when heated under reduced pressure and in benzene solution is oxidised by yellow mercuric oxide to azo-p-told (p-toluoyl-p-tolylaxomethylene) fl>C(C6H4~e)*~o*~6H4Me N m. p. 84' red crystals which behaves like azobenzil (Curtius and Lang Abstr.1892 451) being converted by bromine in carbon tetrachloride into dibromodeoxy-p-toluoin C,H4Me*CO*CBr2*C,H4Me m. p. 120'. When equal molecular quantities of deoxy-p-toluoin and hydrazine hydrate are heated on the water- bath bis- p - toluoyl- p- to lylnzimethylene [C,H,Me-CH,*C( C,H,Me):],N m. p. 155-156O is produced. Bish y draxi- p - toli 2 (di- p- t oly lbish ydraximeth y lene) ?' H > ~ ( ~ ~ ~ ~ e ) . ~ ( ~ ~ ~ e ) < ~ ~ N H NH m. p. 137' is obtained by heating p-tolil with a little alcohol and an excess of hydrazine hydrate at looo for twenty-four hours ; it yields 4 4'-dimethyltolane when its solution in benzene is treated with yellow mercuric oxide. When a solution of hydrazibenzil in concentrated sulphuric acid is poured into water at O' the products obtained are benzil benzalde- hyde benzaldazine and bisbenzilketazine.The last substance which is also produced by heating hydrazibenzil and benzil together at 200° is identical with Curtius arid Blumer's bisbenzoylphenylazimet hylene obtained from benzoinhydrazine (Abstr. 1895 i 600). Bia-p-tolil- htazine N,[:C(C,H,Me)*CO.C,H~Me] m. p. 24B0 is similarly obtaiued from hy drazi-p-tolil and concentrated sulphuric acid from hydraai-p-tolil and p-tolil at 180° and by heating p-toluoinhgdrazine at 185' for five hours. (A by-product in the last reaction is tetra-p- tolylpyraxine m. p. 287'. The corresponding by-product C,,H,,N obtained by Curtius and Blumer [loc. cit.] by heating benzoinhydrazine is proved to be tetraphenplpyrazine as suggested by Snape and Brooke [Trans. 1897 71 5321.) p-Y'oluoinhydrazine C,H,Me*CH(OH)*C(C,H,Me):N*NH m.p. 147-148' is .obtained together with tetra-p-tolylpyrazine by heating toluoin and hydrazioe hydrate for five hours on the water- bath and keeping the mixture for three weeks before treating it with ether to remove the second product. Bisbenzilketazine is not hydrolysed by boiling alcohol and dilute sulphuric acid or by dilute sulphuric acid at 160' but is decomposed by tbe prolonged action of concentrated sulphuric acid or rapidly by boiling aqueous alcoholic sodium hydroxide yielding hydrttzine and benzil. c. s. Decomposition of Alloxan. Ross AIKEN GORTNER (J. Arner Chem. Soc. 1911 33 86).-Wheeler and Bogert (Abstr. 1910 i 466)i.326 ABSTRACTS OF CHEMICAL PAPERS. have recorded explosions due to the decomposition of alloxan in closed bottles. The author has examined a sample of :illoxan which had been kept for about a year. On the outside of the neck oE the bottle was an incrustation which had evidently been forced out between the stopper and the bottle and consisted chiefly of carbamide oxalic acid and alloxantin. There was considerable pressure in the bottle due to carbon dioxide and some unaltered alloxan still remained. It is obvious therefore that the decomposition of alloxan takes place slowly at the ordinary temperature in accordance with certain well- known reactions. This confirms the explanation offered by Franklin ( J . Amer. Chern. Soc. 1910 32 1362). Constitution of Indirubin. LOUIS C.MAILLARD (Bull. Xoc. chinz. 1911 [iv] 9 202-205. Compare Abstr. 1910 i 138).- Polemical with Wahl and Bagard (this vol. i 164). MAX SCROLTZ (Bey. 1911 44 480-488. Compare Abstr. 1'310 i 634)- 2-Phenyl-1 o-xylylene-6-methylpiperidinium bromide has been shown (Abstr. 1910 i 634) to exist in two inactive stereoisomeric modifica- tions. Similar compounds have been prepared from o-xylylene bromide and coniine conhydrine and a-stilbazoline all of which con- tain a nitrogen atom common to two rings and attached to an asymmetric carbon atom. I n neither case could more than one modification be observed. E. G. T. A. H. Asymmetry of the Quinquevalent System N a b c d. Compounds of the general formula CH,*C H CH2<CH2- CH CH2*CH,>?JBr<CH2*cGH4*cH2 CH,*C,H,*CH >NBKCH,($>C H have been prepared by the combination of 0- rn- and p-xylylene- dipiperidide with 0- ma- and p-xylylene bromide.With the exception of that from p-xylylenedipiperidide and p-xylylene bromide they are all of the type N a2 b c d. The combination of p-xylylene dipiperidide with m-xylylene bromide yields two isomerides one m. p. 215O readily soluble in alcohol the other m. p. 244O which is formed in small proportion only being sparingly soluble. The same two isomerides are formed by the combination of m-xylylene dipiperidide and p-xylylene bromide in which case the amount of the less fusible isomeride is larger although the more fusible form still predominates. The two dibromides also form different derivatives. They are not converted into one another on heating and attempts to resolve them into optically active compounds were unsuccessful.They are prepared by mixing equivalent quantities of the components in chloroform solution ; after twenty-four hours the condensation product has either separated as a colourless mass or it is precipitated by ether. The bromine cannot be estimated by direct titration but good results are obtained by the Carius' method. p-Xyl ylene dipiperidide CGH4( CH2*C,NH,J2 has m. p. 90' (compare Manoukian Abstr. 1901 i 528 who gives €36'). m-Xylylene-p-xylylene-dipiperidinizcrn bi-ornide forms a microcrystalline a-isomeride m. p. 2 15O and a granular crystalline P-isomeride m. p. 244' The a-isomeride forms the following salts platinicldoride m. p.ORGANIC CHEMISTRY.i. 327 234'; aurichloride m. p. 165' decomp. above 200"; picrate m. p. 161-162" decornp. 230'. The salts of the P-isomeride are plativbi- chlo~ide m. p. 248"; auricfiZo?.it?e m. p. 274" (decomp.); picrate darkens at 3 N 0 but is not melted at 300'. 0- X y l y l ene-m -x yl yl ened ipiperid inium brorrzid e d oes not form an isomeride; it is a eandy powder m. p. 170-173" (decomp.) ; the platinichloride has m. p. 220" (decomp.) ; the picrate m. p. 168-170'. o-Xylylene-p-xylylenedipiperidinium browtide has m. p. 165' (decomp.) ; the platinichloride has m. p. 225' (decornp.) ; the picmte m. p. 143-145'. Di-p-xylylenedipipevidinium bromide is not melted at 310" ; the platinichloride decomposes at 234' ; picrate m. p. 241' (decornp.). o-Xylyleneconhydrinium bromide was obtained as a syrup.The platinichloride crystallises in golden-yellow cubes and octahedra m. p. 232" (decornp.). o-Xglylenestilbazoliniurn bromide is also a syrup ; the platinicbloride has m. p. 132'. It was shown previously (Abstr. 1901 483) that 2 6-diphenyl- piperidine exists in two inactive forms. One of these m. p. 71" reacts with ethyl iodide and sodium hydroxide to form 2 6-diphenyl- 1 -ethyZpiperidine which crystallises in long lustrous needles m. p. 83'. It reacts with benzopl iodide one modification only of 2 6-di- phenyl-l- benxyl -I -eth ylpiperidiniurn iodide CR,<:Ef :E;k>N IEt C,H7 1 being obtained; this crystallises in colourless needles m. p. 261'. Accordingly 2 6-diphenylpiperidine m. p. 71° corresponds with the mesotartaric type and cannot be resolved.E. P. A. Syntheses of Derivatives of 1 8-Naphthyridine from a-Aminopyridine. F. CARLO PALAZZO and ASTORRE TAMBURINI ( d t t i R. Accnd. Lincei 1911 [v] 20 i 37-44).-By heating a-aminopyridine with ethyl acetoacetate for an hour and a-half in a sealed tube at 120-1 25" a-acetoacetylaminopyridine C,H,N.NH*CO*CH:CMe*OH is obtained. It crystallises in colourleas needles m. p. 113' (softening towards llOo) is soluble in acids and alkalis gives a green precipitate with ammoniacal copper acetate and an intense reddish-violet coloration with ferric chloride. C,NH,*NH*CO-CH :CPh*OH similarly prepared crystallises in colourless needles m. p. 1 10" (softening at 106') and has properties similar to those of the aceto- acetyl derivative. When heated for twenty t o twenty-five minutes at 100" with concentrated sulphuric acid it condenses to 4-phenyl- 1 8-naphthyrid-2-one (annexed formula) which can be CPh obtained on neutralising the solution and forms colourless silky needles m.p. 150' (previously soften- ing). The substance has only basic properties; it dissolves in acids and is reprecipitated by alkals. N NH It yields a ptutinichloride. It gives no coloration with ferric chloride. Acetoacetylaminopyridine behaves with a- Benxoacetylarninopyridine \/\\cH ( / I \/\/"Oi. 328 ABSTRACTS OF CHEMICAL PAPERY. concentrated sulphuric acid like the benzoyl derivative but for lack of substance the analogous naphthyridine could not be isolated. R. V. S. Quinoline Dyes. I. apoCyanines. ADOLF KAUFMANN and PAUL STR~JBIN and in part A.ANASTACHEWITCH N. POPPER and L. SZNAJDEB\ (Ber. 1911 44 690-701).-By the action of alkali on the quaternary salts of quinoline particularly on warming red to black dyes are formed together with resins in a manner analogous to the well-known cyanines and isocganinea. The name apocyanine is suggested for the new dyes and distinction is made between the red erythroapocyanines and the more yellow xanthoapocyanifies which are formed side by side. They are characterised by the fact that their aqueous solutions are not instantaneously decolorised by mineral acids. When quinoline ethiodide is boiled with potassium hydroxide in methyl alcohol the solution changes from yellow to red then becomes reddish-violet and yellow crystals of the xclnthoapocyanine separate.These are separated by filtration and after a time red needles of coppery lustre of the erythroapocyanine crystallise the proportion of the red dye being considerably greater than that of the yellow dye. Erythroapocyanine C2,H2,N21 decomposes at 21 0-220' ; the nitrate crystallises in dark red prisms m. p. 169-170'. The homologous dillaethyler~throapocyccnine hydriodide forms deep red lustrous needles m. p. 238' (decomp.). The erythroapocyanines are probably the monoacid salts of 2 2-diquinolenyls ; they have weak basic properties. The neutral colourless salts are dissociated on dilution with water and form the coloured basic salts. Oxidising agents destroy the double bond between the two quinoline nuclei which appears to be the carrier of the chromophoric properties with the formation of 2 2-diquinolyl derivatives. Thus the diethy2 picrats of a diquinolyl CS4H2P0J4NS is obtained in slender yellow needles m.p. 1 8 6 O by the action of picric acid on diethyl- 2 2-diquinolenyl hydriodide. At the same t h e a more soluble red substance m. p. 162' is obtained which is converted into the above picrate on oxidation; it possibly represents a neutral picrate of diquinolen. Diethyldiquinolyt chromate forms yellowish-red needles and becomes black a t 190° m. p. 210° (decomp.). 2 2-DipuinoEyl diethiodide prepared by the action of iodine on diethyldiquinolenyl hydriodide crystallises in long citron-yellow needles m. p. 198'. It yields the dipicrate described above. A second iodo-derivative the periodide C22EL22N217 is formed in smaller quantity ; it is a dark brownish-red crystalline powder 113.p. 152O (decomp.). A similar perbromide C Kz2N2IBrG crystallises in lustrous golden- yellow plates m. p. 197-199O. Diethyldiquinolenyl hydriodide was converked into the correspond- ing chloride which is more soluble and oxidised with cold alkaline potassium ferricyanide ; the oxidation product C,2H2,02N2 forms slender colourless needles m. p. 176'. It has faintly basicORGANIC CHEMISTRY. i. 329 properties and forms a pZc&&hEoriJe m. p. 1'36-197' which readily dissociates. The corresponding product from dimethgldiquinolenyl bydrochloride forms yellow rhombic crystals m. p. 243'. The xanthocyocyanines are more sparingly soluble melt above 300° have a yellowish-green fluorescence in solution and are more stable towards mineral acids.They are not oxidised by iodine or potassium ferrocyanide. The orange-yellow dye C22H23N21 from quinoline ethiodide crystallises in long matted needles rn. p. 320' (decornp.) ; the corre- sponding yellow dye from quinoline methiodide crystallises in needles m. p. above 300'. The nitrate separates in orange-yellow needles which are partly decomposed on drying at 120'. The xanthoupo- cyanines have no basic properties ; alkalis precipitate almost colourless bases which rapidly change have no definite melting point and are characterised by the blue fluorescence when dissolved in alcohol or concentrated sulphuric acid. E. F. A. Tri-indylmethane Dyes. A LEXANDER ELLINGER and CLAUDE FLAYAND (ZeitscJh. physiol.CJLem. 1911 71 7-13. Compare Abstr. 1909 i 846).-The dye obtained as sulphate on heating %methyl- indole-3-aldehyde with dilute sulphuric acid whereby formic acid is formed crystallises in long reddish-violet needles which sinter at 175' xn. F. 212' (decornp.). By treatment with ammonia the dye C HP3N3 is obtained as bright yellow narrow plates m. p. 234-237'. ?'he dye is even more readily formed in the cold from 2-methylindole formic acid and 20% sulphuric acid. It is also obtained by the condens;ttiou of methylindolealdehyde and met hylindole in concentrat,ed alcoholic solution with the addition of two drops of concentiated hydrochloric acid. On boiling with water at 230' under pressure i t is hydrolybed t o these two components. The Zeuco-compound C2gH25NA is formed along with the dye by the last-described method; it has a faint rose tint m.p. 319'. E. F. A. Reactions of 1-Chloro-2 6- dinitrobenzene. TTTALTIIER EORSCIIE and D. RANTSCHEFF (Annalen 1911 379 152-182. Compare Abstr. 1909 i 232).-The product described by Jungfleisch (Jdresb. 1868 345) as 1-chloro-2 :g-dinitrobenzene i s shown t o be a mixture of 25% of this compound with 75% of the 2 4-dinitro-compound and this accounts for the statement that the 2 6-compound is transformed into the 2 4- when impregnated with a crystal of the latter. The separation of the two isomeric dinitro-derivatives is accomplished most readily by means of ethyl sodioacetoacetate which reacts with the 2 :4-compound much more readily than with the isomeride. The ethereal solution of t h e chloro-2 6-dinitrobenzene and the ethyl 2 4-dinitrophenylacetoacetate is extracted with .water and then 2% sodium hydroxide solution which removes the ester. 1-Chloro- 2 6-dinitrobenzene C,H,CI(KO,) csystallises from alcohol in slender yellow needles m. p. 52" and when finely divided has an irritating action on the mucous membrane. Its constitution has been proved by VOL. C. i. cc ui. 330 ARSTRACTS OF CHEMICAL PAPERS. conversion into 2 6-dinitrophenol 2 6-dinitrophenetole and 2 6- dinitrosniline. The atom of chlorine is reactive and can be replaced by various types of substituents. 2 6-Dinitrophenyl ether OPh*C,H,( NO,) prepared from sodium phenoxide and 1-chloro-2 6-dinitrobenzene crystallises from alcohol in colourless plates m. p. 99-100'.When reduced with an alcoholic solution of ammonium sulphide the chloro-derivative yields m-nitro- aniline but with stannous chloride solution yields 2-chloro-nz-phenyl- enediamine C6H7N,CI m. p. 85-S6" which forms a dibenzoyl derivative C,,H,,O,N,CI m. p. 196-1 97". 3-Nitro-o-phenylenedzamine N0,*C6H,(NH2) obtained by reducing 2 6-dinitroaniline with an alcoholic solution of ammonium sulphide crystallises from dilute alcohol in dark red needles m. p. 158-159O and in the presence of pyridine yields a benmyl derivative C,,H,,O,N in the form of dark yellow refractive needles m. p. 206'. 4-Nitro-2-methylbenzximinazole N ~ 2 * C H < ~ ~ > C M e is formed when the nitro-o-phenylenedinmine is boiled for several hours with acetic anhydride and crystallises from dilute alcohol in compact yellow needles m.p. 21 7". o-A'itro-1 2 3-benztriazole No,* C6H3<i:>N obtained by dissolving nitro-o-phenylenediamine in hydrochloric acid and treating with sodium nitrite solution crystallises from alcohol i n compact glistening brown needles which decompose at 230'. The o-diamine also condenses with a-diketones ; for example when boiled with an alcoholic solution of benzil for several hours it yields 5-nitro- 2 3-dip~~enyZpuinoxaZine N0,*C6H,<Ni~ph which crystallises from N.CPh a mixture of alcohol and chloroform and hss m. p. 169-170". Its solution in concentrated sulphuric acid has a blood-red colour. 2 6-DinitrocEimethylanilina NRle,*C,H,(NO,) obtained by the action of a 33% aqueous solution of dimethylamine on an alcoholic solution of 2 6-dinitrochlorobenzene crystallises from dilute alcohol in slender orange-yellow needles m. p.7S0 and when reduced with alcoholic ammonium sulphide ields 3-nitro-o-phen1~ZenedimethyZdi- umine N02*C,H,(NH2)(NMe,) as a dark red pasty mass. The corre- sponding benzoyl derivative C16H1509N3 crystallises in yellow needles m. p. 114". Piperidine and chloro-2 6-dinitrobenzene in alcoholic solution yield 1 -di-o-nitrophenylpiperidine ~ ~ ~ s ( N 0 ) * ~ < c H ~ . C H 2 > ~ ~ 2 CH *CH which crystallises in long brittle yellow needles m. p. 10E-107". 2 6-DinitrodiphenyZamine C6H,(N0,)2*N€€Ph is formed when chloro-2 6-dinitrobenzene is boiled for several hours with an alcoholic solution of aniline and sodium acetate and crystallises from alcohol in brilliant orange-red plates m..I>. 107-10s'. An 80% yield of the corresponding 6 - n i t r o - 2 - a m i r ~ o d z ~ n ~ ~ a ~ & i r ~ e C,,H,,O,N is obtained by reducing the dinitro-cornpoitud with ammonium shlphide; i t crystallises from alcohol in black prisms with a green 2ORGANIC CHEMISTRY. i. 331 reflex has m. p. lolo and when finely divided has a dark red colour. With nitrous acid it yields 7-nitro-1-phenyl-1 3 3-benxtriaxole -N C,H,<Nph>N Y i n the form of pale yellow needles m. p. 152-153'. This latter does not yield a nitrocnrbazole when heated (compare Ullmann Abstr. 1904 i 776) but when reduced with stannous chloride and con- centrated hydrochloric acid in the presence of alcohol yields a mixture of 4-chloro-7-amino-1 -phenyZ-1 2 3-benxtriaxole and 7-amino-1-phenyl- 1 3 3-benxtriaxole.The former crystallises from hot alcohol in pale green needles m. p. 211° but the latter could not be obtained in a pure form. 2 6-Diccminodiphen~la~~i~e C,H,( NH,),*NHPb obtained by re- ducing the dinitro-derivative with iron and dilute hydrochloric acid crystallises from a mixture of ether and light petroleum in colourless prisms which turn brown on exposure to the air and have m. p. 17s'. 2 6-Di~itrophenylhydr~~~ne C,H3(N02),*NH*NH2 crystallises from dilute alcohol in red needles m. p. 144-145'; the hydrochloride crystallises from hot water in brilliant red needles and with excess of alkali yields salts of 7-nitrobenztriazole from which the trinzole can be obtained by the action of nitric acid.7-Nitro-l-?~ydroxybenzt4.ioxole NO,*C,H,<-'-N>N crystallises from hot water or dilute alcohol in orange-coloured needles containing 1H20 and decomposingwithviolence at 229'. 2 6-Dinitrophenylhydr- azine condenses with quinones and quinoneoximes in the presence of dilute hydrochloric acid in much the same manner as the isomeric 2 4-dinitro-compound (Abstr. 1908 i 66). 2 6-Dinits.o-4'-h?/drox~~~o~enxe~e C,H,( NO,)*N N C,H,*OH crys- tallises from dilute alcohol in brownish-yellow needles m. p. 172'. p-Benxopwinoneoxire-2 6-&initro~.,1~ei.~yll~?/drazone C,T-13(N0,),.NH*N :C,H,:N*OH forms a brown crystalline powder decomposing a t 230'; i t is readily transformed by dilute sodium hydroxide solut,ion into 4 4'-di(S G- tZinitrobenzeneaxo)-azoxybelaxene ON,[C6H4-N:N*C6H,(N0,),] m.p. 355-256' and is oxidised by a mixture of glacial acetic and nitric acids to 2 6 4'-trinitroaxobenxene C,H,(N0,)2*N2*C,H,*N02 which crystallises in slender reddish-yellow needles m. p. 168'. 4-Nitro-2-phenyl-2 1 3-benxlriaxoZe NO,-C,H,<&>NPh obtained by heating an alcoholic solution of chloro-2 6-dihitrobenzene and phenylhydrazine with sodium acetate crystallises from alcohol in glisten- ing yellow needles m. p. 160'. 2 6-Dinitroplt,enylpyridonium chloride C,H,(NO,),.C,NH,CI crystallises from alcohol in nearly colourless needles rn. p. 201'. A small amount of 2 6 2' 6'-tetranitrodiphen?/~ C1,H8(NO2), is formed when chloro-2 6-dinitrobenzene is heated with nitrobenzene and copper powder (compare Ullmann and Bielecki Abstr.1901 i 586) It crystallises from glacial acetic acid in slender yellow needles m. p. 217-21s'. The chief by-product is 2 6-dinitrodiphenylamine. W H ) N a a 2i. 332 ABSTRACTS OF CHEMICAL PAPERS. I-Chloro-3 6-dinitrobeozene does not react so resdily with ethyl sodioacetoacetste as the 2 4-isomeride and in order t o complete t h e reaction the mixture must be heated for about four days. Ethyl 2 6-dinitrophenylucetoacetute C1,H1207Nz cry stallises from alcohol in compact yellow needles m. p. 90'. I t s 0-benxoyl derivative C1913[loOs~2 also forms yellow crystals m. p. 130-131° and when tlrssolved 111 concentrated sulphuric acid and diluted with water yields 2 6-dinitrobenzyl methyl ketone. The ester does not react with ammonia aniline or phenylhydrazine but when reduced with stannous chloride yields ethyl 4-arnino-2-methyEindole-3-carboxyZute NH,* C6H4<gFEt>CMe.This crystallises from alcohol in colourless plates m. p. 148' which t u r n brown on exposure t o the air. 2 6-Dinitrobenxyl methyl ketone C,H,( NO,),*CH,*COMe crystallises from alcohol in yellow needles m. p. 106-107". It does not react with diazonium salts but forms a phenylhydrunone C15H1404N in the form of orange-red needles in. p. 1 1 2 O which dissolve in alkalis yielding deep blue solutions. When reduced with alcoholic ammonium sulphide the ketone yields -CH 4 -nit ro-1-h ydroxy-3 -methylindole NO,*C,H,<N (OH ,>C Me as orange- \ / red needles m. p. 186-187" which react with sodium methoxide and methyl iodide yielding the methyl ether CloHlo03N2 in the form of greenish-yellow needles m.p. 91-92'. EtIql 2 6-dinitrophen~Znzatonate C,,N,,O,N crystallises from alcohol in compact yellow needles m. p. 54-45' and when hydrolysed with acetic and sulphuric acids yields 2 6-dinitrophenylacetic acid C,~I-I,(NO2),*CH,=CO,H which crystallises from glacial acetic acid in yellow plates m. p. 501-202' (decomp.). has m. p. 57' and reacts with salicylaldehyde and a fern drops of piperidine at 1 50' yielding 2 6-dinitropJ~en?/Zcoumcn.in The methyl ester C,HSO,N,* C6H4<*4lO 9 CH C*C6H,(N0,) as a yellow crystalline powder m. p. 233-234'. 1-Chloro-2 4-dinitrobenzene reacts with an alcoholic solution of potassium xanthate yielding Beilstein and Kurbatoff's 2 4-dinitro- phenyl sulphide (AnnaZen 1879,197 77). The 2 6-isomeride does riot react in a similar manner.2 4-Dinitrophenyl-o-phenylenediun~ine C12H1004N4 obtained by the action of an alcoholic solution of o-phenylenediamine on chloro- 2 4-dinitrobenzene crystallises from alcohol in orange needles m. p. 150-1 5 lo. The hydrochtoride crystallises in brilliant yellow plates and reacts with nitrous acid yielding 1-0 p-cliizit?.o~~l~eizyE-l 2 3-benx- tyiaxote C,K4<~~2H3(N0,)21> which crystallises from glacial acetic acid in broad yellow needles m. p. 186-187' b u t cannot be transformed into a carbazole derivative. ADRIAN0 OSTROGO- v~~:'EI (Atti K. Accud Lincei 1911 Lv] 20 i lSB-lS6).-When a J. J. S. action of Amidines on Cyanoguanidine.ORGANIC CHEMlSTRY. i. 333 mixture of cyanogaanidine and acetamidine hydrochloride is gradually heated to 230' and the temperature maintained at t h a t point for a short time ammonia is evolved and on dissolving the reaction product in dilute hydrochloric acid 4 6-diamino-2-methyl-1 3 5-triazine dihydrochloride (Ostrogovich Chem.Zentr. 1905 ii 1360) is obtained. The yield is 65-70% of the theoretical so t h a t the method is convenient for the preparation of t h i s substance. From benzamidine 4 6-diamino-2-phenyl-1 3 5-triaxine is similarly obtained in about the same yield. It crystallises in small colourless needles m. p. 225O and is identical with the benzoguanamine of Elzanowski (Diss. Freiburg [Switzerlnnd] 189s). It gives a platinichZo&de which crystallises i n pale yellow needles R dic?uonzate which forms orange.red needles and a ?hydrochloride C,H,N5,HCL,H,0 crystnllising in lustrous prismatic needleg. The picl.de U,H9N,,C,€€,0,N3 forms yellow needles m.p. 255-256O. R. V. S. Substituted Rhodanic Acids and their Condensation Pro- ducts with Aldehydes and Ketonic Substances. XI. EGON BUTSCIIER (Moncctsh. 191 1 32 9-19).-Hitherto only the con- densation products of substituted rhodanic acids with aromatic alde- hydes and with furfuraldehyde have been described. The following substances have now been prepared 5- VuZeryli&ene-3-phenyZr?iodanic m. p. 113" yellow needles is acid CHi\le,*CH,* CH:C< obtained by heating 3-phenylrhodanic acid and valeraldehyde for two hours in glacial acetic acid. The following compounds have been prepared i n a similar manner from alloxan and the substituted rhodanic acids ; 5- A lloxan-3-phenyZrhodanic cicid R:C< s-7s COO NPh' s-7s (where R = CO-NPh NH-CO decomp.270-2SOo yellow needles. 5-AlZoxan-3-allyZr~odanic acid R:C<Co,r;.C m. p. 166' (decomp.) yellow leaflets. 5-Alloxnn- 3-naeth~l~hodccnic acid C,H,04N3S2 decomp. 220-325O yellow needles. 5-Alloxan-3-p-tolylrhodanic acid C,4H904N3S2 m. p. 270" (de- camp. ) microscopic yellow needles. 5 5'- Phenanthrenebis- 3-phenyl- dtodanic acid ? '-'>C:C-- C-C<CO,Nph - m. p. 291-202O is obtained from phenanthraquinone and 3-phenylrhodanic acid ( 2 mols.) in hot glacial acetic acid ; a substance C24H1802N2S4 m. p. 216-218" of similar constitution is obtained from 3-ethylrhodanic acid. When 5-p-methoxybenzylidene-3-phenylrhodanic acid is hydrolysed by boiling baryta the expected a-thiol-p-methoxycinnamic acid is obtained i n the form of the corresponding disulplhide [ OBle C,H,* CH C( CO,H)],S m.p. 202-2039 In another experiment in which the hydrolysis was e$ected by alcoholic potassium hydroxide the mercaptan was CO<NH. c o x ) s-cs 3 5 76H4*QP4 s-ys NPh* COi. 334 ABSTRACTS OF CEIEMICAL PAPERS. isolated as its belzzyl derivative OMe*C,H,*CH:C(CO,H).S*C,H? m. p. 131-134". c. s. Intramolecular Changes. MAX BUSCH and OTTO LIMPACH (Bey. 191 1 44 560-583).-0f the two isomeric substances obtained by the interaction of carbonyl chloride and pa-dipbenylthiosemicarbazide (Marckwald and Sedlaczek (Abstr. 1896 i 231) the labile more fusible compound was shown by Busch Reinhardt and Limpach (Abstr.1910 i 142) to be 5-thio-n-1 4-diphenylurazole and the stable isomeride to be 5-thiol-1 4-diphenyls?zdooxydi hydrotriazole. The latter still retains its constitution but the labile compound which is more conveniently obtained by the action of an excess of 20% carbonyl chloride in toluene on a benzene solutionof PG-diphenylthiosemicarbazide at 60-70' (the two isomsrides are separated as described Zoc. cit.) is proved to be 3-phenyl-1 3 4-thiodiazole-5-one-2-ani2 s-yo NPh:C<NPh.NH' by the evidence quoted below. It reacts with phenylhydrazine or primary bases yielding two products ane of which does not contain sulphur. Thus with aniline on the water-bath as-diphenylsemi- carbazide and thiocarbanilide are formed whilst with phenylhydrazine (2 mols.) the labile compound yields a8-diphenylthiosemicarbazide and diphenylcarbazide.This facile fission of the ring suggests that the labile compound cannot be a urazole derivative since true urazoles such as 1-phenylurazole 1 4-diphenylurazole and 1 4-diphenyl- 2-methylurazole are stable to aniline or phenylhydrazine even at 150O. (5-Trio!-1 4-diphenylendooxydihydrotriazole the stable isomeride is not attacked by boiling aniline.) The key to the constitution of the labile compound is obtained by the behaviorir of the substance on methylation. Wben heated with methyl iodide i t yields methyl mercaptan and 1 4-diphenyl-2-methylurazole amongst other products. When kept overnight in contact with an excess of methyl sulphate however it yields two products neither of which contains the group *SMe.The by-product m. p. 77-78' is S-fi *OMe 5-methoxy-3-phenyZ-1 3 4-thiodiaxole-2-ani1 NPh:C<NPh.N 9 has basic properties gives a quantitative yield of methyl iodide by Zeisel's method and is probabIy identical with the methyl compound m. p. 74-5-7755" obtained by Nirdlinger and Acree (Abstr. 1910 i 785). The chief product of the methylation has m. p. 93O is decom- posed profoundly by hydriodic acid and reacts with primary bases even more vigorously than its parent substance. It is decomposed by boil- ing 8% alcoholic potassium hydroxide yielding @-dipheny2-a-methyzthio- semiccwbazids NHMw NPh*CS*NHPh m. p. 138" which is trans- formed a b 160° into the P-isomeride NHPh*NMe*CS*NHPh m. p. 176-17 7" obtained by Marckwald. The formation of PG-diphenyl- a-methylthiosemicarbazide from the methylated product m.p. 92" proves that the latter must be either NPh:C< s - y o or NPh'NMeORGANIC CHEMISTRY. i. 335 The latter constitution does not harmonise with the pronounced basic character OF the substance whilst the former is sup- ported by the formation oE the compound from carbonyl chloride and @-diphen yl- a-m e thy1 thiosemicarbazide in benzene a t 5 0-6 0". The proof that the substance m. p. 9a0 has the former constitution is obtained by carefully heating the compound with alcoholic ammonia or potassium hydroxide; by this means it is converted into an isomeridrz m. p. 165" which has no basic properties and is easily desulphurised by mercuric oxide and benzene at 140-150" yielding 1 4-diphenyl-S- methylurazole.Consequently the isomeride ni. p. 165" has the latter of tbe two constitutions given above the methylated product m. p. 92' has the former constitution and finally therefore the parent substance the labile compound formerly regarded as 1 4-diphenyl-5- thiourazole must be 3-phenyl- 1 3 4-thiodinzolone-2-anil as mentioned above. 1 4-l)iphenyl-2-methylurazole is conveniently obtained by warming 5-thiol-1 4-diphenylendooxydihydrotriazole with an excess of methy 1 sulphate and treating the product still in the presence of methyl sulphate with dilute sodium hydroxide ; by the elimination of methyl mercaptan and the eimultaneous entrance of a methyl group 1 4-di- phenyl-2-methylurazole is formed together with a small quantity of CO--lfPh NPh<C(OMe):N ' m* '* 3-methoxy-1 4-diphenyl-1 2 4-triaxolone 110-111". The latter is stable to alcoholic alkalis whilst 1 4-di- phenyl-2-methylurazole is converted by 10% alcoholic potassium hydroxide into a mixture of approximately equal quantities of US- dipheny l-P- methylsemicar baxide NHPh*CO-N Me* N HPh ni.p. 138" (which like other members of the @series does not possess basic properties) and ~~-d~pheny~-a-meth?/~sem~ccc~bax~de N B Ph*CO*NPh*NHlSfe m. p. 140". The attempt to prepare 5-tbio-1 4-diphenyl-%methyl- urazole from either of these compounds and thiophosphoryl chloride failed altogether wikh the P-compound. PG-Diphenyl-u-methylsemi- carbazide and thiophosphoryl chloride in benzene solution however yield the thiocarbon y l chloride NHP h* COO N Ph- NMe CS C1 which loses hydrogen chloride a t its 111.p. 150° and forms 3-thion- "*TMe m. p. 165 5'. This CO-NPh ' 1 4-cliphenyl-2-methylurazoZe NPh< substance which yields 1 4-diphenyl-2-methylurazole by desulphurisa- tion by mercuric oxide and alcobol is also obtained by the action of alcoholic ammonia on 3-phew?/I-4-methyt-l 3 4-thiodiazoZone-5-anit - 1 p. 102" prepared by the interaction of carbonyl chloride and as-diphenyl-P-methylthiosemicarbazide in the same manner as 3-phenylthiodiazolone-5-anil from carbonyl chloride and PGdiphenylthiosemicarbazide. The preceding facts leave no doubt as to the course of the reaction between carbonyl chloride and Pa-dialkylthiosemicarbazides. Thei. 336 ABSTEtACTY OF CHEMICAL PAPERS. labile compound first formed is a thiodiazoloneanil which is easily converted (by fusion or in alcoholic solution) into the stable thiolendooxydihydrotriazole (annexed RhT-- N I I formula) the thiourazole Rr*NH>CO being an SH 6 <Nli> U intermediate twoduct. Bv desulthurisation the -0- SC -NR L .I L thiclendooxydihydrotriazole regenerates the urazole ring >co.RY*NH UC*NR >C*OH or RT -N OC*NR The authors deny that the interconversion of the salts of 5-thiol- 1 4-diphenylurnzole (endooxy-5-thiol-1 4-diphenyldihydrotriazole) and 5-thion-1 4-dipben~lurnzole (3-phenyl-1 3 4-thiodiztzolone-5-anil) is a reversible process a s stated by Nirdlinger and Acree (Zoc. c i t . ) ; they shorn that the change only proceeds i n the direction thiodiazolone -+ thioltriazole and in aqueous solution is completed in twelve hours a t 100' and in thirty-six hours at 80'.c. s. Derivatives of Hydrazodicarbonamide and of Urazole. GUIDO PELLIZZARI (Gazzetta 1911 41 i. 30-38. Compare Abstr. 1907 i 874).-[ With L. Acc~~~.]-E'rom aminophenylcarbamide and potassium cjaoste in aqueous solution in the presence of acetic acid phenpZhydruxodica~bonamide N H,*CO*NPh*NH*CO*NH is obtained as a colourless crystalline precipitate m. p. 281' (decomp,). When heated a t its melting point the compound yields phenylurazole. The preparation of phon?lll~ydraxo-P-thiodicarbonanzide NH,*CO*NPh*N H*CS*NH is effected by mixing in alcoholic solution aminophenylcarbamide hydrochloric acid and ammonium thiocyanate. The precipitate of ammonium chloride is filtered off and the liquid is boiled for three hours The precipitate so obtained forms after recrystallisahion colourless crystals m.p. 235' (decomp.). [With A . L ~ ~ T ~ - ~ ~ ~ ~ ~ . ] - l > / l e n y ~ h y d r a x o - a - t ~ ~ ~ o d i c ~ ~ b o n NII,*CS*NPh*NH*CO.NH is prepared from aminophenylthiocarbamide and potassium cyanate in the presence of hydrochloric acid and forms lustrous crystals m. p. 213' (decomp.). A sample when heated began to evolve ammonia at 190° and the evolution increased at 2103 at which t,emperature the substance was maintained for half an hour. From the product NH-FO~ was CS-NH' obtained on cooling l-pJ~enyl-5~thiouruzoZe NPh< isolated. I t forms very small yellowish-white crystals m.p. 227-230". Attempts to obtain the substance fram cirbamide and aminophenyl- t hiocarbnmide yielded only resinous pro lucts.When aminophenylthiocarbamide is boiled in alcoholic solution for several hours i t is transformed into phenylsemithiocarbazide. The change can be explained on the lines of the well-known transformations of carbamide and thiocarbsmide on heating. The preparation of a salt of aminophenylgusnidine is more easilyORGANIC CHEMISTRY. I. 337 effected by the interaction of cyanamide and phenylhydrazine hydro- bromide than by the method formerly given (Abstr. 1897 i 47) because the hydrobromides of the two products can be separated by crystallisa- tion. Phenylaminoguanidine hydrohomide is recrystallised from water containing hydrobromic acid and forms slightly coloured small needles m. p. 2 10'.Aminophenylguanidine hydrobromide crystal- lises in hexagonal tablets m. p. 219O and is more soluble in water than its isomeride but less soluble in aIcohol. From amiaophenylguanidine hydrobromide and potassium cyanate or thiocyanate no product could be prepared and even with cyanamide the introduction of a second guanidine group could not be effected When aminophenylguanidine by drobromide and carbamide are heated together at 200' for half a n hour however 5-imino-l-pl~enylurazoZe It forms long lustrous needles m. p. 372-273O (decomp.) and is soluble in ammonia. From this solution it is precipitated by acetic acid but it is soluble in dilute hydro- chloric acid. From the mother liquors from i t s preparation a substance m. p. towards 235-240" was also isolated.NH- f is obtained. NPh <C(:NH)*NH' R. V. S. Condensations of Hydrazoic Acid with Cyanoformic Ester and with Cyanogen Bromide. 111. E. OLIVERI-MANDALA (Gaxzetta 1911 41 i 59-63. Compare Abstr. 1910 i 593).- Ethyl cyanoformate and a concentrated ethereal solution of hydrazoic acid when heated together under pressure for several days a t 50" yield in slhall quantity ethyl tetrazolecarboxylate CN,H*CO,E t which crystallises in small needles m. p. 85-86O (previously soften- ing). When i t is warmed with alcoholic potassium hydroxide a substance is deposited probably the potassium salt which on addition of acid forms tetrazole. Cyanogen bromide and hydrazoic acid under similar conditions yield bromotetrazole CN,HBr also in small amount. The substance after previously softening has m.p. 147-14S0 (decomp.). It has a strongly acid reaction and does not lose bromine when treated with acids or with dilute alkalis. I n the air and especially in sunlight it The substance has an acid reaction. becomes yellow. R. v. s. Some Derivatives of Alloxan. GUIDO PELLIZZARI and C. CANTONI (Gazzetta 1911 41 i 21-29. Compare Abstr. 1887 1100; 1889 5 19).-Alloxanphenylhydrszone can be obtained directly from alloxan by the use of phenylhjdrazine hydrogen sulphite. The preparation is effected by saturating with sulphur dioxide an aqueous solution of alloxan in which phenylhydrazine is suspended. Hydrazine hydrogen sulphite under similar conditions yields in the cold alloxan bisulphite which forms colourlcss crystals. When it is boiled with water a reddish-yellow substance is formed which is also obtained in addition t o alloxantin when alloxan reacts with hydrazine hydrate at the ordinary temperature.The slight solubility of the substance its acid cliaracter and the fact that it does not reacti. 338 ABSTRACTS OF CHEMICAL PAPERS. with benzaldehyde accord with tho formula (I) but the analytical figures agree with formula (IT) which is therefore preferred by the authors. Efforts have also been made to obtain substances of aldehydic nature by the action of alkalis or acids on phenylmethylpyrazolonealloxnn in a manner similar to that which has been described in the case of other alloxan derivatives (compare Bohringer and Sohne D.R.-P. 108026 [lSSS] 112174 [1899]). I n no case was an aldehydejproduced and the formation of carbon monoxide or formic acid (which would accompany it) was not observed.When phenylmethylpyrazolone- alloxan is boiled with hydrochloric acid (D 1.12 diluted with an equal volume of water) phenylmethylpyrazolonemalonylcarbamide (A bstr. 1889 517) is first formed. This decomposes when the ebullition is continued and a hydyochloride is obtained of which the free buse has m. p. 175-1 80" ; phenylhydrazine oxalate and pbenylmethylpyrazolono are also produced. Action of Cyanogen Halides on Phenylhydraxine. 111. Gum0 PELLIZZARI (Gcbazetta 191 1 41 i 54-59. Compare Abstr. 1892 1323 ; 1907 i 873).-Another sobstance can be isolated from the mother liquors of the products of the reaction between phenyl- bydrazine and cyanogen bromide in aqueous solution. It forms trans- parent crystals of a reddish tinge which contain alcohol of crystal- lkation and have m.p. 180". The compound is identical with that described in the first paper resulting from the polymerisation of Pqanophenylhydrazide but since it is stable towards alkali and acid it bas not the constitution there assigned to it but is the correspond- ing cyclic compound diphenykcminoguanaxole R. V. S. NPh--lfH NH:C<N(NH€'h)* C :NH* The hydrochloride and picrate have the properties formerly described. a-Cyanophenylhydrazide reacts with oyanogen bromide in alcoholic solution at the ordinary temperature in the course of several days forming tricyanophen ylhydrazide to which the constitution CN*NPh*N(CN) is provisionally given. It is a crystalline substance having a red or yellow tinge and does not melt a t 300".The molecular weight in phenolic solution is normal. Peculiar Reactions of the Diazo-compound of p-Amino- benzeneazosalicylic Acid. CARL BULOW [with KARL HAAS] (Ber. 191 1 44,601-614).-Previously the author has observed that diazo- salts of certaiu substances containing the p-aminobenzeneazo-group yield intensely blue solutions by treatment with sufficient sodium carbonate or acetate. The source of this blue coloration has now been investigated in the case of the diazo-compound of p-aminobenzene- azoealicylic acid. R. V. S.ORGANIC CHEMISTRY. i. 339 p - Ace t y lccnzino be )meuecczoscc lic9 Zic cc cicl N H Ac*C,H,* N,*C,H,(OH) CO,H yellowish-brown prisms m. p. 235" obtained by coupling diazotised acetyl-p-phenylenediamine and salicylic acid i n a solution containing sodium carbonate and hydroxide and acidifying the product is hydrolysed best by concentrated sulphuric acid on the water-bath ; the solution yields after dilution with water a sulphate (Cl?HII0,N,),,II,SO,! from which sodium carbonate produces a sodium salt which is decornpoaed by acetic acid yielding p-amino- benxaneaxosalicylic acid a dirty greyish-green powder decomp.2 3 3 O . The aminoazo-compound is dissolved i n dilute potassium hydroxide treated with hydrochloric acid and finally with sodium nitrite a t 20-25' whereby the chloride of the diazotised p-aminobenzene- azosalicylic acid is obtained in small brick-red needles. By stirring a suspension of the chloride in cold water for four hours a black anhydq-ide exploding a t 132" is obtained to which the constitution N*C,H,(OH)*CO When the diazo-chloride is added to an excess of aqueous sodium carbonate (not hydrogen carbonate acetate or hydroxide) at Oo an intense blue solution is obtained the colour of which persists for more than two hours and then becomes brown. By passing carbon dioxide into the blue solutiort the colour changes to yellow; both solutions couple with 22-salt.When the diazo-chloride is dissolved in dilute sodium hydroxide at 0' a blue solution is not obtained but by passing in carbon dioxide the solution becomes blue and finally yellow. These colour changes are explainod by ascribing tho blue coloration to t h e formation of the normal diazotate and the yellow t o the hydroxy-compound in sodium hydroxide the normal diazotate adds on NaOH to form which is converted by carbon dioxide successively into the blue and the yellow compounde.8*C6H4*N:N.? is ascribed. ONa*N:N*C,H,*N:N*C,H,(OH)*CO,Na OH-N N*C,H,*N :N*C,H,( OH)* C0,Na ; ONa*N(OH)-NNa*C,H,*N N* C6H3( ONa) - CO,Na Ethyl acetoacetate-axoben~e:elze-p-azoscclicycZic acid C02Et*CHAc*N2*C,H4* N2* C,H,(OH) CO,H m. p. 236" (decomp.) yellowish-brown needles obtained by condensing the diazo-chloride of p-aminoben zeneazosalicylic acid with ethyl aceto- acetate in dilute alcohol in the presence of sodium acetate has beon converted into the following substances. With 60% hydrazinc hydrate in glacis1 acetic acid it yields 5-iL~droxy-3-melhylp~raxole-4- azobenxene-4'-p-azosnlic1ylic acid l$==CbTe N H - C (OH) >CON C,H,*N2 C,H3( OH) C02H m.p. above 300". . With phenylhydrnzine in hot glacial acetic acid it yields 5 - h y d ~ o x p l -;nlwwJ - 3 - methylpyraxole - 4 - axobenzene-4'-p-nxo- salicylic acid C23H,S0,N m. p. 2'72-273" (decomp.). With 2 :Cdinitro- phen y lhydrazin e 1 t y 1 elds a dinitrophen ylh ydraxone C,,H,,O,N m. p. 258-253' (decornp.) which is converted by hot acetic anhydridei. 340 ABSTRACTS OF CHEMICAL PAPERS. into Ei-hydro~y- 1 - o p-dindrophen yl- 3-wzethylpymxole-4-nxobenzene-4'-p- azosalicylic acid C,,H,,O,N,~ m. p. 202-203'. With hydroxyl- amine in diluted acetic acid it yields 5-hydroxy-3-meth?~lisooxaxole-4- axobenxene-4'-p-azoscc~~cylic acid xu. p. 243-2 44'. By prolonged boiling with semicarbazido in diluted acetic acid it yields 5-hydroxy-1- carbam~do-3-methyl~~~ir.axole-4-axobe~z,yene-4'-p-~~~~al~~~~~~ acid m..p. above 280". '1SHl 5'5"7 The colour reactions of these substances with various reagents are described. c. 8. Some Derivatives of p-Aminobenzhydrol. HENRY ,4. TORREV and C. W. PORTER (J. Amsr. Chena. Xoc. 1911,33,56-59).-'l'he work described in this paper was carried out a? part of an extensive in- vestigation of the derivatives of p-aminobenzophenone. BenzJ~ydroZ-4-azo-/3-napl~tl~oZ OH* CHPh*C,H,* N,* ClOH6* 0 H m. p. 169.5' is a bright red dye which is precipitated when a solution of P-naphthol in sodium hydroxide is added to the diazotisation product of p-aminobenzhydrol. The comp07~nd C,H~*CU.C,H,.N,.C!,H~*OH m. p. 185-186.5' obtained in a similar manner from p-aminobenzo- phenone is a dye of a much lighter red colour and forms feathery crystals.Benzl,ydroZ-4-ccxodimethyZaniZine OH c1 H Ph C6H4*N C,H,*NMe m. p. 145O is a dye which forms red lustrous flakes ; its acetyl and beneoyl derivatives were prepared. SalzcyZidene-p-aminobenxhydl.ol OH* CU[Ph* C,H,*N CH*C,€€,*O 13 m. p. 76-79' obtained by heating a solution of p-aminobenzhydrol and salicylaldehyde in alcohol forms yellow crystals. S'cdicyZidem-p- ccminobenxophenone C,H5- CO-C,H4*N C H C,H,*OII is a yellow crystalline solid which is insoluble in solution of sodium hydroxide. P-Naphtholaldehyde condenses with p-aminobenzhydrol to form the compound OH*CHPh*C,H4*N:CH-C,,H,*OH m. p. 167*5" which is obtained in yellow crystals. C,H,* CO*C,H,*N:CH~C1,H,~OH rn. p. 152" obtained from p-aminobenzophenone also forms yellow crystals. E.G. The corresponding compound The Stability towards Light of Methylated Hydroxyazo- dyes. S o m e Derivatives of 1-Methoxynaphthalene. N. N. VOROSCIICOFF (J. Russ. Pl2ys. CIiem. Soc. 1910 42 145S-1465).- The introduction of an alkyl group into the hydroxy-group of a hydroxyazo-dye might be expected to result in an increase of the stability towards light since the hydroxy-group is the most highly reactive of the molecule ar;d since replacement of its hydrogen by a metal is in general accompanied by increase of this stability. Examination of the rnethoxy-derivatives corresponding with a number of hydroxyazonaphthalenesulphonic acids prepared by Colombano's method (Abstr. 1907 i 1091) shows however that the stability of these colouring matters towards light is not increased by the replacement of the hydroxy- by methoxy-groups.Reduction of 2-sulphonaphthalene-4-azoanisole by means of zinc and acetic acid yields p-anisidine which was identified through its acetylORG hNlC CHEMISTRY. i. 341 derivative. In a similar manner colouring matters containing the 1-methoxpnaphthalene group may be converted into 4-ucetylamino- l-~,rs~hoxyizapithu~ene OMe*C,,H,*NHAc which forms colourless prisms m. p. lSO-lS1° and may also be prepared by reducing 4-nitro-1-methoxynaphthalene and subsequently xcetylating. Sodium l-methoxyna~hthalene-4-sulp~or~a~e OMe*C,,H;SO,Na pre- pared by treating a-naphthol-4-sulphonic acid with methyl sulphate and sodium hydroxide forms shining plates containing 3H,O and tho corresponding barium salt forms nacreous crystals.4-Nit~*o-l-metrl~oxynctphtAaZene OMe*C,,H,*NO obtained by adding a mixture of sodium I-methoxynaphthalene-4-sulphonate and sodium hydrogen carbonate to a solution of carbamide in nitric acid forms yellow needles m. p. 81'. T. H. P. Azo-derivatives of 3-Phenylisooxazolone. ANDR~ MEYER (Cow@. rend. 1911 152 610-612. Compare Abstr. 1910 i 593). -The following derivatives of Claisen's 4-benzeneazo-3-phenyliso- oxazolono ( Abstr. 189 1 465) mere prepared by dissolving phenyliso- oxazolone in aqueous alkali and sodium acetate and adding the calculated amount of a diazonium salt. The required compound was obtained in theoretical yield by precipitation with acetic acid. All the substances described melt with decomposition.4-m-Nitrobenxeiaeaxo-3-phelz?/Eisooxazoloi~e C15H1004N4 bright yellow needlm m. p. 200-201" ; the p-iiityo-compound crystallises in orange needles m p. 224-225'. 4-o-ToZuenenzo-3-phenylisooxazoZone C ,H,,0,N3 orange needles m. p. 151-152'; the p-toluene derivative has m. p. 1'77-178'. The m- nit?-o-p-toluene compound has m. p. 205-206° ; the o-nityo-p-toluene compound forms deep orange needles m. p. 31 3-214". 4-m-Xgleneazo- 3-pheit~lisooxcczolone C,,H .500N3 orange needles m. p. 187'. 4-$1- Czlmeneaxo-3-pT~enylisoox;cLxolone bright red needles m. p. 215-216O. 4-a-Naph~l~aleneazo-3-phenylisooxn~oZone C,,Hl,02N slender brown needles m. p. 172-173" ; the /?-derivative forms deep yellow needles m. p. 3 02 - 2 03". bright yellow needles m. p.about 245'; the m-carboxy-acid has m. p. about 260° and the p-curboxyl acid m. p. about 290O. Phenyldinaethyl- pyrazolone~~xophennylisooxu~olone C2,.HISO3N5 ruby-red needles m. p. 19 6-1 9 7". ~~pheny~b~scceob~sp?~eny~isooxazo~o?ae C3,H2,,04N6 is a brick- 4-o-Carboxybenzeneu~o-3-pl~en ybsooxazolone C16H1104N3 red powder m. p. above 300". w. 0. w. The Refractive Indices of Certain Proteins. 111. Serum Globulin. IV. Casein in Alcohol-Water Mixtures. T. BRAILSFORU ROBERTSON (J. Biol. Chern. 1910 8 441-448 507-511. Compare Abstr. 1910 i 526,793) -The value of a for serum globulin under different conditions varies from 0.00229 to 0.00119 and for casein from 0.00157 to 0.00125. W. D. H. Hydrolysis of the Protein of Linseed. F. W. FORENAN (J. Agric. Science 1911 3 358-383 ; P ~ o c .Cmd. Phil. Soc. 1911 16 S7-SS).-The protein OF linseed meal extracted with 0.2% potassiumi. 342 ABSTRACTS OF CHEMICAL PAPERS. hydroxide contains 17.45% nitrogen. When hydrolysed with hydro- chloric acid (D 1.16) the following substances were obtained alanine 1-03 ; valine 12.71 ; leucirie and isoleucine 3.97 ; proline 2.55 ; phonylalanine 4-14 ; aspartic acid 1.65 ; glutamic acid 11.58 ; tyrosine 0-65 ; arginine 6.06 ; histidine 1.66 ; lysine 1.19 ; and ammonia 1.94%. Small amounts of glycine serine and tryptophan were also found. The most striking result is the high amount of valine ; the highest percentage hitherto obtained by the hydrolysis of proteins seems to be only 2%. N. H. J. $1. Thymic Acid. HERMANN STEUDEL and P. BRIGL (Zeitsch.physiol. Chem. 1910 70 398-403).-Sy the action of dilute nitric acid in the cold on thymus-nucleic acid the alloxuric bases are eliminated and a compound C,,H,,O,,N,P remains for which the name thymic acid is suggested. This contains all the phosphoric acid of nucleic acid in an organic complex is dextrorotatory and forms a barium salt. It does not reduce Fehling’s solution after purification. When hydrolysed it yields thymin and uracil in the proportions required by the formula given. E. F. A. The Action of Dilute Acids and Salt Solutions on Gelatin. HENRY R. PROCTER (Koll. Chem. Beihefte 1911 2 243-284).-The action of solutions on the connective tissue is complicated by their capillary absorption between the fibres of collagen of which it mainly consists.To avoid this difficulty the author has studied the action of solutions or thin sheets of gelatin which is a chemically closely related substance. I n opposition to the view that gelatin jelly has ordinarily the microscopic cellular structure attributed to it by Butschli and van Bemmelen normal jelly is considered t o be a net- work of protein molecules in which the absorbed liquid is dissolved and subjected to its molecular attractions and internal pressure. The swelling of gelatin is thus an osmotic phenomenon which however is influenced not only by the presence of altered products formed by hydrolysis but also by the solid elasticity dependent on its volume at the moment of solidification. Gelatin jelly is insoluble in alcohol and semipermeable to it and its dehydration is due to the exterual osmotic pressure of the alcohol.If however alcohol is incorporated with gelatin solution before ‘‘ setting,” it forms a mixture which although apparently homogeneous must really be an emulsion of diluted alcohol. Such a jelly smells in water more than a purely aqueous one since the alcohol globules become diluted in equilibrium with the jelly. Such jellies mould probably show microscopic cellular structure. dwelling with acids is a more complex phenomenon and apparently involves chemical combination as well as osmotic action. Gelatin which absorbs only seven or eight times its weight of pure water may absorb over fifty times its weight of 0-005N-hydrochloric acid solution but it contracts again when the acid solution is concen- trated absorbing only twenty times its weight of 0-2N-acid.I n more concentrated sdiitions the jelly dissolves.ORGANIC CHEMISTRY. i. 343 The amount of acid in the jelly increases with that in the outer solution and is always in excess of that corresponding with the solution absorbed. Since only a portion of the absorbed acid can be estimated by titration with methyl-orange as indicator it is evident that part of the acid is in some way combined. -4ssuming that the concentration of the free acid in the absorbed solution is the same as that in the outer solution and deducting this from the total acid in the jelly it is found that the acid “fixed” by 1 gram of dry gelatin increases rapidly up to a concentration of about 0.005N-acid and afterwards remains nearly constant. This constant value corresponds with about 0.78 mg.mol. of acid per gram of gelatin. I n hydrochloric acid solutions of greater concentration than O*OOSX the swelling is repressed by increasing the concentration of the chloriue ion. By addition of sodium chloride this repression can be carried almost to dehydration although neutral gelatin is swollen by salt solutions. The total acid in the contracted jelly is diminished by that expelled but the (‘ fixed I’ acid is increased and sodium chloride is expelled from the solution absorbed. The effect is evidently due to osmotic forces although since both hydrogen and sodium chlorides and their ions diffuse freely through gelatin the condition of equilibrium would appear to resemble that which is set up in the distribution of a substance between immiscible solvents. It is assumed that the amphoteric gelatin forms a hydrolysable chloride in equilibrium with the acid having a much greater affinity for water than for neutral gelatin. If x is the molar concentration of the external acid p the number of millimols. in the jelly per gram of gelatin and k the hydrolytic constant then p = x/z + k is the proportion of urihydrolysed salt. Taking /3 as 1-28 and k as 0,005 a curve representing the values of fixed acid is obtained which corresponds closely with the experimental curve when the swelling is repressed by large quantities of sodium chloride although it is higher than the experimental curve in the absence of salt. The assumption t h a t the free acid in the absorbed solution is of the same concentration as %he outer solution is however not strictly permissible for the chlorine ion concentration in the ionised gelatin chloride must be equal to that of the outer solution and since the gelatin ion cannot diffuse this equality can only result from the expulsion of water and acid. The experimental curve of swelling can be represented by the expression 7.8 Jlx/x+ k and the curve of total acid absorbed by (7*8xg/x + k) + 0.8 or by the adsorption formula 7 =- 8 7 ~ O . ~ ~ . If the hydrolytic constant k be taken as 0.005 the ionisation constant of neutral gelatin is of the order of 1 x Similar considerations to the above are applicable to the equilibrium between gelatin and solutions of weak acids and their salts data for which are also recorded in the paper. H. M. D. Trypain and Pancreas Nucleo-protein. LEONOR IcHAEim and HEINRICH DAVIDSOHN (Biochepi. Xeitsch. 19 1 1 30 48 1-504) .- The isoelectric point of trypsin was determined by two methods namely by dissolving the trypsin in solutions with different hydrogen ion concentrations and determining the range of concentration ini. 341 ABSTRACTS OF CHEMICAL PAPERS. which it is neither distinctly anodic or cathodic when in an electric field (method of electrocataphoresis) and by determining the hydrogen ion concentration in which aggregation most readily takes place. 111 the former experiment a silver anode in concentrated sodium chloride and as cathode copper wire and a moderately concentrated cupric chloride solution mere employed. By the first of the ahove-mentioned methods the isoelectric point was found to be about H = 1.35 x lo-* and by the second 2-6 x 10-4. This is almost the same as the isoelectric point found for Hammaraten's a-nucleo-protein and differs considerably from that of the P-nucleo-protein (H = 1.2 x and of the protein which can be obtained from this (H=1*7 x Furthermore no organ other than the pancreas yields a substance oC the same isoelectric point. If trypsin be aggregated from its solution under the optimal conditions a strong trypsin preparation is obtained as the greater part of the enzyme is carried down in the precipitate which does not give the normal protein reactions. From the results the authors conclude that there is probably an intimate chemical relationship between trypsin and a-nucleo-protein. S. B. S. Optically Active Compounds of Phosphorus. JAKOB MEISEN- HEIMER and LEO LICHTENSTADT (Be?-. 1911 44 356-359. Compare Abstr. 1909 i 30).-It has been shown previously that the bases obtained from d- and Lhydroxyphenylmethylethylammoniurn chlorides OH.NMeEtPhC1 by the action of barium hydroxide are optically active but i t was left uncertain whether they had the formula 0:NNeEtPh or NMeEtPh(OK),. The conclusion is now arrived at that the crystalline solid is an amine oxide but that j9 aqueous solution the dihydroxy-form is present. A cyclic amine oxide kairoline oxide has been observed to behave similarly and the same process has been investigated with phosphine oxides. Pheizylmethylethylphosphine oxide O:PMeEtPh prepared by the addition of methyl iodide to ethyldiphenylphoephine and subsequent boiling with water is a colourless hygroscopic substance crystallising in needles m. p. about 50' b. p. above 360' without decomposition. With d-bromocamphorsulphonic acid a well crystallised salt is formed having m. p. 94-95' and [a] + 6'7.4' which values did not change on fractional crystallisation. The value for the rotation indicates the presence of an optically-active phosphorus ion. d-~~et~yZet~?/Zp/LenyZphosp?~~ne oxide is obtained by the action of ammonia on the salt in benzene solution in crystalline needles [.ID + 23.1' in water and 33.8' in benzene. Accordingly the free phosphine oxide is optically active and the satisfaction of the five valencies of phosphorus with only four different radicles is sufEcient to give asymmetric compounds. E. F. A.

ISSN:0368-1769    

DOI:10.1039/CA9110000249

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 270 ABSTRACTS OF CHEMICAL PAPERS. Inorganic C h emist ry. Dehydration of Salts. P. E. LECOQ DE BOISBAUDRAN (Compt. rend. 1911 152 356-358).-The author takes exception to a statement of Rosenstiahl to the effect that no salts lose only lH,O except those which contain only 1 mol. Earlier observations are cited (Compt. Tend. 1867 64 1249; 65 111 ; Ann. Chim. Phys. 1869 [iv] 18). w. 0. w. Polymerised Water and Water of Crystallisation. AUGUSTE ROSENSTIEHL (Compt. rend 19 11 152,598-601).-The observations of Lecoq de Boisbaudran (preceding abstract) are not incompatible with the author’s conclusions since the latter refer to the elimination or fixation of several molecules of water whereas the experiments of the former observer showed the influence of isomorphism on the addition or removal of one molecule only.A statistical study of one hundred and seventy-nine salts containing wateiof crystallisation appears to show that the water may be present as H,O or as the groups (H,O) and (H,O) or else as a mixture of tbe two latter. Thus salts containing 4 7 and 10 molecules behave on partial dehydration as if the water was combined as 1 +3 1 + 6 and 1 + 9 molecules respectively. The complex (H20) is the one of mostINORGANIC CHEMISTRY. ii. 271 frequent occurrence. On dehydrating salts such groups may be split off without themselves undergoing disruption. w. 0. w. Determination of the Ratio between Chlorine and Bromine and Sodium. JACOB S. GOLDBAUM (J. Amer. Chern. Xoc. 1911 33 35-50).-This investigation was undertaken primarily as a test of the applicability of electrolytic methods t o work demanding extreme accuracy rather than with the object of revising the atomic weights of chlorine and bromine.Experiments were carried out in which aqueous solutions of sodium chloride and sodium bromide respectively mere electrolysed with a rotating silver-plated platinum gauze anode and a mercury cathode. The halogen combines with the silver and the increase in the weight of the anode thus represents the amount of halogen in the salt corrections being made by means of the nephelometer for tho quantity of silver halide dissolved in the liquid in the inner cup. A tull description is given of the mode of preparing the anode and the methods of purifying the materials and conducting the experiments. The average of the results of a preliminary series of eight experi- ments with sodium chloride gave the atomic weight of chlorine 35.456 +_ 0,0037 (Na= 23*00) whilst that of n final series of eleven experiments gave the value 35,462 f 0.0005 or a value f o r the atomic weight of sodium 22.997 rfI 0*0003 (C1= 35.458).The average of the results of eight experiments with sodium bromide gave t h e atomic weight of bromine 79.927 f 0.0014 (Na= 23*00) or of sodium 23.998 f 0.0003 (Br = 70.920). E. G. Solubility of Oxygen in Sea-Water. GEORGE C. WIIIPPLE and MELVILLE C. WHIPPLE (J. Amer. Chern. Xoc. 1911 33 362-365). -The authors were engaged in determining the solubility of dissolved oxygen in sea-water of known chlorine content a t teniperatures of Oo lo" 20° and 30' when FOX'S paper on the same subject was published (Abstr.1910 ii 29). As far as they had gone tbeir results are in agreement with those of Fox. For convenience of reference they have re-c~alculated Fox's results in terms of the solubility of oxygen in parts per million of sea-water exposed to an atmosphere containing 20.9% of oxygen. T. M. P. The Nature of the Uppermost Layers of the Atmosphere. ALFRED WEGENER (Physikal. Zeitsch. 1911 12 170-178).-A theoretical paper in which various geophysical phenomma attributed to the influence of the earth's atmosphere are examined and from which conclusions are drawn relative to the constitution of the gaseous envelope. According to these there is a comparatively sudden change in the character of the envelope at a height of about 70 kilometres and a further similar change at about 300 kilometres.The chief constituent of the outermost layer is a gas lighter than hydrogen to which the name geocoi*oniurn is given. The spectrum of this gas is supposed to be responsible for the polar light line at 557 pp. By making certain assumptions the percentages of nitrogen oxygen argon helium hydrogen and geocoronium at diff erenii heights are 19-2ii. 272 ABSTRACTS OF UHEMIOAL PAPERS. calculated. atmosphere in the intermediate layer between 70 and 200 kilometres. These show that hydrogen is the chief constituent of the H. 1\11. D. A Simple Hydrogen Sulphide Generator. J. T. D. Hrms (-1. Amev. Chew. Soc. 191 1 33 384-385).-'J!he apparatus consists essentially of a cylindrical vessel containing the ferrous sulphide the bottom of which ends in a goose-neck tahe.The top of the vessel is fitted with a tap-funnel for containing the acid and a tube with :I stopcock for the delivery of the hydrogen sulphide. The goose-neck tube is of such dimensions that a sufficient head of pressure is maintained for the delivery of the gas for ordinary purposes. The apparatus possesses the advantages that if the acid is added drop by drop and not in large excess i t will be practically exhausted before i t passes out through the goose-neck and when the stopcock is closed the pressure of the hydrogen sulphide generated automatically expels the waste acid. T. S. P. Chemistry of the Lead Chamber Process. FRITZ RASCHIG (J. Soc. Chern. Imd. 1911 30 166-172. Compare Abstr. 1905 ii 700).-R rBsum6 of our present knowledge of the chemistry of the lead chamber process for the manufacture of sulphuric acid.Some of the conclusions drawn are (1) Nitrosulphonic acid (uitrosyi sulpliate) cannot be an intermediate product in the chamber process as i t is completely destroyed by sulphuric acid concentrations such as those present in the chamber and Glover tower. (2) Nitrosisulphonic acid H,NSO,. is probably the true intermediate product ; this is formed k)y the reaction of sulphur dioxide with nitrous acid 2HN0 + SOz = H,NSO + NO and decomposes into sulphuric acid and nitric oxide. The relations between nitrosisulphonic acid nitrilosulphouic acid hydroxylamino-mono- and -di-sulphouic acids nitrososulphonic acid and their oxidation products are discussed.The conclusion is drawn t h a t a purple or blue colour is due to the preseqce of a quadrivalent nitrogen atom and hence the nitrosisulphonic acid should contain quadrivalent nitrogen. As this acid appears to be foriried by tbe oxidation of hydroxylaminosulphonic acid and on f iirther oxidation yields iiitrosiilphonic acid the formula O:X(OH)*SO,H is suggested. The reaction between nitrous acid and sulphur dioxide leads to the formation of nitro~osulphonic acid O:N*SO,H and this with a f l i t thcr qiirtntity of nitrous acid yields nitric oxide and nitrosisulphotiic a o d which dissociates into nitric oxide and sulphuric acid. The purple acid sometimes formed in the Gay-Lussac tower is regarded a s nitrosisalphonic acid and as it continually undergoes deconi- position yielding nitric oxide its formation produces appreciable loss of nitre.This loss can be avoided by allowing the nitric acit3 which is usually supplied t o the Glover tower t o trickle down the G~Y-LLISSRC tower when it oxidises the nitrosi-acid to ui trobulphoijic acid and loss of nitric oxide is avoided. The nitrous oxide which is met with in the exit gases from the leuden chaubers (Inglis J. SOC. Ciiem. I~rzcl. 1904,25 149) is probably due to the reaction of the nitroscsulphoriic acid with water instead ofINORGANIC CIiEMISTRY. ii. 273 with nitrous acid. The formation of this oxide is got over by blowing dllute sulphuric acid instead of Wiitf!r into tho leaden chambers. Hydrosylamine and ammonia may aho be formed i n the Ciiauiber atid these with nitrous acid would yield nitrous oxide and nitrogeii. When excess of nitrous acid is absent ammouin can be detected 111 the chamber acid.J. J. S. Theory of the Lead Chamber Process. 0. WENTZKI (Zeiisch. angew. Chern. 1911 24 392-4011. Compare itid 1910 23 1707 ; Lunge and Berl Ahtr. 1906 ii 438 ; Manchot Abstr. 1910 ii 1055).-Mainly a reply to l-:aschig and Berl (ibid. 1910 23 2241 ; compare also preceding abst rac t). Raschig’s blue nitrosisulphonic acid is regarded ae O< I and is termed nitrosglous s ? A . $ ~ L ? ” L c acid The objection is raised t h a t Raschig’s acid should be IL feeble acid whereas i t is cnpnble of displacing sul phuric acid from copper sulphate. Itaschig considers t h a t nascent hydrogen combines with t h e nitro- sulplionic to form nitrosisulphonic acid whereas no hydrogen is formed by the action of mercury on sulphuric acid ; the reduction consists in the retnovltl of oliygeri from the nitro-scid arid the characteristic deep hlue copper salt is ~epresented as CuO,N,S (compare Manchot this vol.ii 107). The aiithor agrees with Raschig and Berl that sulphurous acid does uot reduce the blue copper compound. The view that nihrosisulphonic acid is a n irnportan t intermediate product in the leaden chamber process is not accepted. The formation of this compound under the conditions prevailing in the chambers is considered impossible and nitrogen peroxide is consiclared to be the most probable catni y s t . Sulphuric acid of 50” B contains its oxides of nitrogen in the form of free oxides (N,?,) and only with stronger acid for example 53-60” I; is nitrosulphonic acid (hitrosylsulphuric acid) formed and it is only nitro-acids of the higher concentrations which give a blue colour with sirlphuroue acid.With more concentrated acids for example 88% the nitrosulphonic acid does not appear to be reduced by sulphur dioxide. N*O*SO ti N*O*SO F-l ’ ‘l’he existence of nitrososulphonic acid is questioned. Hydroxynitrosylsulphuric Acid. EVERARDO SCANDOLA (Chem. Zentr. 19 10 ii 543. Repriut from Bol. SOC. srmi!.-chirurg. Pavia 1910 1 1 pp:).-The acid OH*NO*SO,H tei Died hydroxynitrosylsulphuric acid described by Lunge Frerny Raschig and others as nitrosylsulphuric acid [nitrosisulphonic acid] is also obtained by the careful decomposition of sulphuric acid solutions of alkyl nitrates or nitrites best when concentrated sulphuric acitl is rriixecl with a fern drops of nitric acid and some drops of the alcohol and then added to a cold Concentrated solution of copper sulphate the mixture being heated.Methyl ethyl propyl imbuty).l and isoamyl alcohols give positive reactions ; octyl alcohol gives an uncertain reaction but at a higher temperature a blue coloration is formed whilst cetyl alcohol does not react. isoYropy1 and 8ec.-butyl alcohols both give the reaction but inenthyl alcohol forms a resin. lert.-Rutyl imd tert -amyl alcohols react easily at the J. J. S.ii. 274 ABSTRACTS OF CHEMICAL PAPERS. ordinary temperature without the formation of blue compounds which seem t o appear on heating the alcohols with amyl alcohol at 140 - 1 5 0 O .Glycerol mannitol erythritol and many carbohydrates give the reaction; ally1 alcohol form3 only a brown resin. Lactic malic and tartaric acids react easily citric acid with difficulty whilst benzyl and cinnamyl alcohols become resinous. Nitro-ethane and -butane give a positive nitromethane a negative result ; in the same way n trobenzene nitrotoluene and trinitrophenol do not react The ethers behave like the alcohols; of the aldehydes ouly form- aldehyde gives the reaction ; others become resinous without turning blue. Chloral neither gets resinous nor gives the reaction ; acetone immediately gives a brown resin; tho results were negative in the case of benzddehyde and salicylnldehyde also with formic acetic oxalic benzoic and cinnamic acids but positive with the esters of the acids.Carbamide arid uric acid give no reaction ; phenol gives a reddish-brown to a bluish-green coloration which is a different from the lustrous colour of copper hydroxpnitrosylsulphonate. Anisic acid gives the reaction. The mechanism of the formation of nitrosisulphonic acid by the decom- position of alkylnitrates and nitrites can be explained by a reaction between the ester arid the acid which leads t o the formation of alkyl sulphuric acids which form addition or condensation products of nitric acid with the sulphonic acid N. C. The Action of Sulphur Dioxide on Ammonia. FRITZ KPIIRAIM and HENRYK PIOTROWSKI (Ber. 19 I I 44 379-386. Cornpare Divers and Ogawa Trans. 1901 79 1102).-Depending on the conditions of experiment three different compounds are formed by the interaction of sulphur dioxide and ammonia.With excess of sulphur dioxide amidosulphinic acid NH,*SO,H is always formed but with excess of ammonia either whito ammonium amido- sulphite NH,*SO;NH is obtained or a red compound (Abstr. 1000 ii 271) of tlie same percentage composition as the amidosulphite bnt with double the molecular weight 280,,4NH,. This red corn- pound is tricammoniurn irrLidodis261~~~i?Late NH,*N:(S0,*NH4) ; i t must contain four nitrogen atoms since one quarter of the nitrogen is differently linked from the other three quarters. This is shown by the preparation of a silver salt AgN:(SO,!g) which is also red in colour such coloured salts being often obtained when metals are directly combined with nitrogen.The above explanation of the reactions between ammonia and sulphur dioxide has been arrived at chiefly from a study of I,he reactions between thionyl chloride and ammonia. When thionyl chloride is added drop by drop t o liquid aiumouia the liqaid assumes t h e Eame intense red colour as that possessed by the product formed from sulphur dioxide and excess of ammonia On evaporation a cinnabar-red residue is left contaminated with ammonium chloride and other products. On digestion with absolute alcohol at - 5" a deep red solution is obtained which on evapwation in a vacuum gives a residue consisting of amorphous red flakes easily soluble i n water and mixed with a small quantity of stable golden-yellow crystals (not enough to analyse completely) which are only slightly soluble in water.ThsINORGANIC CHEMISTRY. ii. 275 red flakes consist of the above - mentioned triammonium imidosul- phinate (no analyses are given) which gradually decomposes with loss of colour. The freshly prepared aqueous solution when added to amrnoniacal silver nitrate gives a purple-red precipitate of the silver salt AgN:(SO,Ag) which mas analyced. The snnie silver salt can be obtained from the red product from the interaction of sulphur dioxide and ammonia. The reactions taking place are 2SOC1 + 7NH = 4NH,Cl+ HN:(SO*NH,),. This diamide is readily hydrolysed by water,.giv.ing NH(S0,aNH4) from which the silver salt is obtained by precipitation. The solution of the diamide in liquid ammonia is red probably con- taining t h e compound NH4N :(SO*NH,) ; although not stated in the text there is presumably enough water in the liquid ammonia to convert this amide into the above-mentioned triammocium imidosul- phinate on evaporation.In the preparation of imidodisulphinic acid by Divers and Ogawa (Zoc. cit.) a by-productl was obtained having the composition N,H,,O,,S,. Its formula and properties are readily explained by the constitution SO,H*[NH*SO],*NH*SO,H (compare Abstr. 1909 ii 994). An investigation of the precipitate obtained by the interaction of silver nitrate and amidoeulphinic acid led to no satisfactory results. T. S. P. It is not very stable gradually lo.;ing nitrogen. Action of Sulphur and of Compounds Containing Sulphur on Hydrazine. FRITZ EPHRATM and HENRYK PIOTROWSKI (Be?.. 191 I 44 386-394).-When sulphur dioxide is slowly passed into a cooled solution of hydrazine in absolute alcohol a white crystalline precipitate of the ftydrazine salt of hydraxinecliszlzpfiinic acid is pro- duced namely N?H,(SO,*N,H,),.It sinters at 50° and then gives a cloudy liquid which at 70-80' decomposes with evolution of gas. The aqueous solution is weakly acid smelling slightly of sulphur dioxide and gives precipitates with solutions of barium calcium lead and silver salts sulphur dioxide being evolved at the same time. The - N*SO barium salt has the composition Ba< I >Ba the hydrogens of N*SO L the hydrazine residue being replaced by metal as well as those in the sulphinic radicle. The salt gradually decomposes with loss of nitrogen. The silver salt could not be obtained pure.Sulphur readily dissolves both in hydrazine and hydrazine hydrate giving a dark brown solution which on pouring into water deposits sulphur. A t the ordinary temperature anhydrous hydrazine dissolves about 60% of its weight of sulphur. After a short time a reaction occurs according to the equation NzH4 + 25 = N + 2H,S nitrogen being evolved and a n unstable hydrazine hydrosulphide remaining in solution. This equation was supported by quantitative measurements Hydrogen sulphide readily dissolves in hydrazine hydrate but no solid is obtained. With anhydrous hydrazine however a crystalline compound is obtained in the form of long needles. More hydrogen sulphide is absorbed that corresponds with the formula ZN2H,,H2S but not enough for the formula N,H,,H,S.It is probable t h a t theii. 270 ABSTRACTS OF CHEMICAL PAPERS. latter compound is formed and by surrounding part of the hydrazine prevents further absorption of hydrogen sulphide. The compound readily loses hydrogen sulphide on exposure to the atmosphere becom- ing liquid because of the liberation of hydrazine. Its vapour tension was determined approximately and found to be 760 mm. a t about 35". Sulphur trioxide is immediately reduced by hydrazine under all conditions sulphur sesquioxide S,O being formed. The behaviour of hydrazine towards thionyl chloride depends oh the concentration of its solution. With a concentrated solution of hydrazine sulphur is produced which then reacts with the excess of hydrazine in the way mentioned above. I n dilute solution an hydrazide of sulphurous acid is probably formed but so far the authors have not been able to isolate it.T. S. P. Nitrosulphamide and Sulphohydrazide. FRITZ EPHRAIM and EDUARD LASOCKI (Ber. 1911 44 395-403).-Sulphamide (Abstr. 1'310 ii 19s) readily dissolves in cold concentrated nitric acid (D = 1-48) without being decomposed or nitrated. Nitratioh takes place immediately however if concentrated sulphuric acid is added to the solution the nitro-compound thus formed precipitating in the solid form. It is necessary to avoid any rise in temperature during the reaction and to work with small quantities only since the nitro- sulphamide formed very readily decomposes with explosive violence when present in large quantity. When dry it is much more stable than when moist.As so prepared it is fairly pure and i t may be further purified from ether. When heated carefully it decomposes quietly a t 95-96' but ordinarily it decomposes with a slight puff but without detonation white vapours being evolved. The composition corresponds with the formula NH,*SO,*NH*NO and this formula is further confirmed by analysis of the silver salt NHAg*SO,-NAg*NO which is obtained as a flocculent white precipitate when silver nitrate is added to the aqueous solution of the nitrosulpharnide and then ammonia until the precipitate no longer increases in volurne. Hydrogen is evolved when zinc dust is added to the aqueous solution of nitrosulphamide the zinc salt being formed. If the solution is then acidified with sulphuric acid complete reduction to hydrazine- sulphonamide NH,*SO,*NH*NH occurs.The reaction does not stop at this point but proceeds further with the formation of amino- sulphonic acid and hydrccxinesulphonic acid or their zinc salts. The zinc salt of the latter is much more soluble in alcohol than that of the formor compound but the quantity of substance obtained was too small to admit of complete separation and identification. I f the nitric acid solution of sulphamide is well cooled there is at times n deposition of a white substance on the addition of the first few drops of sulphuric acid. I n contradistinction to nitrosulphamide this substance is deliquescent and cannot be dried by spreading on a porous plate. It is probably a salt of sulphaniicle and nitric acid. Attempts to nitrate amidosulphonic acid NHS*SO,€€ were un- successful owing to its insolubility in both nitric and sulphuric acids.The methyl ester NH,*SO,-OMe was obtained from the silver salt and methyl iodide in the form of microscopic rhombohedra which sinter a tINORGANIC CHEMISTRY. ii. 277 170' and have m. p. about 198' (decornp.). The ester cannot be nitrated but by treatment with liquid ammonia sulphamide can be obtained from it. Sulphuryl chloride reacts with hyclrazinecarboxylic acid or prefer- ably with hydrazine hydrazinecarboxylate (Abstr. 1905 i as) accord- ing t o the equation swlphohydraxide SO,(NH-NH,) being formed. The hy drazine hy drazinecarboxylate is suspended in light petroleum or carbon tetrachloride and the sulphuryl chloride gradually added the mass obtained being well kneaded in order for the reaction t o become complete.It was not found possible t o obtain the pure sulpho- hydrazide owing t o the difficulty of separation from the accompany- ing hydrazine hydrochloride but the hydrazine salt was obtained from the reaction product as follows The reaction product was dissolved in water and the solution digested at 50' with freshly precbitated and washed lead hydroxide for several hours. The suspension of lead hydroxide is alkaline enough t o prevent the decom- position of the sulphohydrazide which is very sensitive towards acids. On evaporating the filtrate in a vacuum a n uncrystallisable syrup was obtained which proved to be the above-mentioned hydrazine salt analysis giving the required ratio of 8.1 for the nitrogen and sulphur. The compound is stable in neutral or alkaline solution but readily decomposes in the presence of acids.It gives no precipitate with the salts of the heavy metals except mercury. When the solution is evaporated with lead nitrate (8 mol.) a syrupy residue is left from which hgdrazine nitrate may be crystallised out by in- oculation leaving an oil corresponding with the formula of lead hydrazine sulphohydrazide Pb[ N(NH2).80;N( N,H,) *N 1i2l2. A crys- talline benzoyl derivative sodium dibenzoylsulphohydrazide SO,(NNa*NHBz) mas obtained by the action of benzoyl chloride on the alkaline solution of hydrazine sulphohydrazide. Sulphammonium and its Relation to Nitrogen Sulphide. OTTO XUFF and LEOPOLD HECHT (Zeitsch. anorg. Chem. 1911 70 49-69.Compare Ruff and Geisel Abstr. 1905 ii 699).-l'he freezingpoint curve of solutions of sulphur in liquid ammonia has been determined. The curve falls from the freezing point of ammonia - 77*34O to a eutectic point at - 79.7" and 16.3% 9 ; i t then rises to a maximum at - 78.3' and 24% S corresponding with the compound S(NH3)6 and falls to -84.6" at the composition correeponding with S(NH3)? the existence of this compound being iudicated by the solubility curve. Both compounds are associated a t least to double molecules in solution. Moissan's sulphammonium S(NH3) is not present in such solutions. An examination of t h e absorption of light of six different wave- lengths by solutions of hydrogen sulphide and nitrogen sulphide in liquid ammonia shows that several compounds must exist.The results are complicated and it is not yet possible t o fix the formulae SO,Cl + 2NH,*NH*C0,H,lSu',H = SO,(N H*NH,) + 2N2rH4,HC1 + 2C02 SO,"(N,*,)*NH,I T. 5. P.ii. 278 ABSTRACTS OF CHEMICAL PAPERS of these compounds. Only dilute solutions can be used on account of their high absorbing power. The apparatus used for their preparation and examination is described. C. H. D. The Preparation of Pure Hyposulphites and the System Hyposulpbite-Water. KARL JELLINEK (Zeitsch anorg. Chem 191 1 70 93-134).-The preparation and analysis of hyposulphites must be conducted in absence of air. Purified carbon dioxide or nitrogen is used with water previously distilled in a stream of nitrogen. An apparatus in which the analytical operations are conducted is described in detail.The titration is carried out by adding an excess of ammoniacal copper sulphate and titrating back with a standard solution of sodium hyposulphite using indigotin a s an indicator. The presence of sulphites is without influence. Sulphates are estimated by precipitation after boiling with hydrochloric acid and removing separated sulphur and thiosulphates by oxidation with iodine when sul phites and hyposulphites are converted into sulphates and thio- sulphate into tetrathionate. The latter is estimated by reduction with aluminium and hydrochloric acid followed by addition of iodine and titration with thiosulphate Na2S406 + 6A1+ 20HCl= 2NaCI + 3Al,C1 + 6H,O + 4H,S ; 4H,S + S I = 8HI + 4s. Sulphites may be estimated by difference after oxidising the whole of the sulphur by means of ammoniacal hydrogen peroxide and precipitating as barium sulphate or directly.For this purpose the solution is oxidised with a n excess of ammoniacal copper solution the cuprous salt re-converted into cupric salt by exposure to air and then treated with mercuric chloride and hydrochloric acid when thiosulphates are decomposed according to the equation Na,S,O + HgCl + H,O = Na,S04 + HgS + 2HC1 mhilbt sulphur dioxide is evolved from the sulphite arid is absorbed in bulbs containing iodine and estimated in the usual manner. Sodium hyposulphite is purified by saiting out with sodium chloride the quantity added being such t h a t precipitation is instantaneous. The salt Na,S20,,4H20 is unstable and must be dehydrated.The best results are obtained by adding solid salt to a concentrated solution of the commercial hyposulphite filtering by means of a vacuum filter and pressing the residue until as much mother liquor as possible is removed. It is then several times stirred with saturated salt solution and filtered finally leaving a paste of the hydrate. This is stirred and the temperature is gradually raised. Dehydration takes place a t 60'. If the mass is too dry partial decomposition takes place After filtering rapidly the crystals are washed successively with hot 50% alcohol and hot and cold absolute alcohol. Dehydration by means of alcohol is not successful. The anhydrous salt dried at 60' in a vacuum remains stable for months. Freezing-point determinations with the purified salt show t h a t the eutectic point of its aqueous solutions lies a t - 4.58" and 19.0 grarus Nn2S,04 per 100 grams water (1.93 molecular % Na2S204). The freezing-point measurements confirm the formula Na2S204.The hydrated salt is best prepared by cooliog the concentrated solution and then forms glassy prisms up to 1.5 cm. in length. TheINORGANIC CHEMISTRY. ii. 279 solubility curve has been determined up to and slightly beyond the transition point anhydrous salt hydrate which lies a t 52' and 2.8 molecular % Na2S,0,. C. H. n. New Anhydrous Selenites. R. L. ESPIL (Compt. rend. 1911 152 378-380).-Anhydrous selenites can be prepared in the amorphous state by passing the vapour of selenium oxide over a heated metallic oxide or by heating the oxides together in a sealed tube.By using excess of selenium oxide in the latter method crystalline selenites are obtained. Copper selenite CuSe03 forms green rods. The nickel salt is yellow and the cobalt salt crystallises in long violet prisms. Ceric selenite is an insoluble yellow powder. The seleiiites of praeeodymium lanthanum and samarium are colourless whilst the neodymium silt is rose-coloured ; t h e solubility of theie substances in aqueous solenious acid furnishes a method for sepsr~ting the metals from cerium and thorium. Thorium oxide is uijchanged by boiling with seleniolis acid whilst cerium oxide under these conditions readily forms tho selenite. A s the latter is easily decomposed by heat this rewtion I I I ; L ~ be used to estimate the two metals in mixtures of their oxides.The Action of Metallic Sodium on Hydrazine Hydrate. NVERARDO SCANDOLA (Citern.. Zmtr. 1910 ii 544 ; Reprint from Boll. Soc. naed.-chiruyg. Pavia 1910 8 pp.).-By the action of sodium on hydrazine hydrate Lobry de Rruyn (12ec. t r a v . chim. 1896 15 174) obtairied n crystalline substance to which he as4gned the formula N213,*ONa ammonia and hydrogen being evolved. Under somewhat different conditions hydrazine hydrate was added drop by drop to fine granulated sodium suspended in ether the mixture t)eirig heated for some time on a water-bath in a reflux apparatus. In t h i s way a white substance was obtained which exploded by simply drying it in air but on leaving it longer in contact with the ether it lost this property. It decomposes at 58" and burns on platinum foil with a slight explosion.Tine polution reduces ammonincal silver nitrate and Fehling's solution. The gases which are given off in the reaction are ammonia and hydrogen. The dry white compound which has been suspended longer in ether liquefies and shows no action with amrnoniacal silver uitrate. Contrary to the view of 1,obr-y de Bruyn the w. 0. w. 1 - substance is regarded as having the formula rH>NNa or NH >NH; in accordance with its cyclic nature i t easily decomposes. Na "a N. C. Two New Methods for the Preparation of Hydrogen Borides. JOSEF HOFFMANN (Citern. Zeit. 1911 35 265).-When ordinmy commercial iron boride i d dissolved in dilute sulphuric acid a gas is evolved consisting of a mixture of boron hydride and hydrogen. An undissolved residue remains which contains Folid hydrogen borides; on heating a mixture of hydrogen and boron Iiydride i8 ,evolved.ii.280 ABSTRACTS OF CHEMICAL PAPERS. Similar results are obtained with manganese boride. Borides prepared by Goldsclimidt’s riiethod always coutain some solid hydrogen boride. T. S. P. Chlorobromides and Chloroiodides of Silicon. ADOLPHE BESSON and L. FOURNIER (compt. relid. 1911 152 603-605. Com- pare this vol. ii 38).-Silicon chlorobromides can be obtained by the action of hydrogen and bromine on silicon tetrachloride under the influence of the silent electric discharge. The comporinds SiCI Br3 SiCl,Br SiC1,Br can readily be isolated by fractionating t h e product,. The dibromitie is the chief constituent of the mixture aird when this is submitted in tho p1ebence of hydrogen to the further.action of the discharge i t undergoes decomposition in. accordance with the equation 2SiCI2Br2 = SiCI,Br + SiCIBr3. If a mixture of the three chloro- bromides is treated in the bame way derivatives of the type Si,X appear to be formed but their separation has not been satisfactorily accomplished. Chloroiodides are formed under the same conditions as ohloro- bromides. w. 0. w. The Ratio of Argon to Nitrogen in Gases from Springs. B. WALTER (Pliysiica(. Zeitsch. 191 1 12 178-179).-The data obtained by Moureu and by Riqnard in tho analysis of the gases collected from twenty-eight spring waters show that whereas tho helium conteut varies between very wide limits the proportion of argon varies to only a ,.mall extent.By taking the ratio of argon to nitrogen it is foubd that this vaties from 0,009 to 0.0183. Ti10 approximate constancy of the ratio iridicntee that the argon prrseut i u the spring waters has beeu derived from the atmosphere. On the other hand the enormous variations in the helium content show that it is mainly derived from radio-active constituents of the p;rr.tic-iilar geological formations. H. M. 1). Lithiumimide. Oryo RUFF and HANS Gomum (Ber I91 1 44 502-506).-Dafert and Miklauz (this vol. ii 38) have obtained a substance which they designate as trilithium aiiirno~ti~~m Li,N H,. Its properties and appearance however are in accordance with its being a mixture or it may be a solid solution of 1 mol. lithiumari,ide and 2 mads. lithium hydride. It is formed from lithium nitride by the s,ddition of hydrogen (Zoc.cit.) and according to the prepent authors the reactions which take place are as follows Lithiuniirmide $nd hydride are first formed according to the eqrratiou Li,N + SH,= I,iNH,+ZLiH. The resulting mixture of ami& and ttydricle at 340-480° gives lithiumimide and ammonia from the declmposit ion of the amide and the ammonia immediately combines wilh the hydridtA forming iniide and hydrogen so that the total reaction is given by the equation BLiNH + 4LiH = 2Li,NI-I + ZLiH + 2H,. This explanation is supported by the fact t h a t lithiumamide does decompose into the h i d e and ammonia at 240-450° and that at a slightly higher tempeia- ture lithium hydride reacts with ammonia with the formation of lithiumamide.INORUANIC CHEMISTRY.ii. 281 Lithiumumide LiN H was prepared by the interactipn of lithium and liquid ammonia in a sealed tube a t the ordinary temperature for two weeks. It forms white shining crystals consisting of regular hexahedra mixed with octahedra and tetrakishexabedra. I n sealed tubes it has m. p. 373-375" and may be sublimed under pressure OF ammonia D175 1.178. Lithiumimide Li,NH was obtained by heating the amide in a d v e r dish a t 360" until most of the ammonia had been expslled rind finally a t 450". It forms a white partly 'sintered mass which does not melt at9 60O0 but nssiimes a yellow coloiir becoming white again on cooling. A t higher temperature3 i t decomposes giving the blue lithium ammonia compoiind and a white powder probably lithium nitride.It has D19 1.303. T. S. P. Alloys of Silver and Cadmium. G. J. PETRENKO and A. S. FEDOROFF (Zeitsch. amrg. Chem. 191 1 70 157-169).-1n the preparation of alloys of silver and cadmium bilveris lost by volatiIisa- tion ns well as cadmium so that i t is necessary to analyse each alloy. The freezing-point curve shows that six types of crystals are formed a p. y 6. c and 7 all of which are solid solutions the principal gap being from 7 to 19% Ag. At 200° the a and y crystals react to form the compound AgCcl on cooling. The existence of the compounds AgCd and AgCcl is probable whilst the y-crystals appear to contain a compound Ag,Cd,. Another compound Ag,Cd is possible. There is 110 eutectic point the freezing point of cadmium being raised by silver.The diagram obt tinod differs From that of Bruni and Queiacigh (Abstr. 1910 ii 953) in the interval from 19 to 100% Ag these arithors having observed an unbroken series of solid solutions thronghout Ghis range. Ternary System Silver-Tin-Lead. NICOLA PARRAVANO ( A tti R. A ccad. Lincei 19 1 I [v] 20 i 170- 1 T2).-1n the present paper the author reproduces and discusses the diagram obtained by the thermal aud microgrnphic study of the above ternary system which belongs to the sclme type as the system copper-antimony-bismuth previously investigated (Parravano and Viviadi Abstr. 1910 ii 1068). C. I€. D. R. V. S. Constitution of Photo-halides. A. P. H. TRIVELLI (Chem. TPeek- blud 19 11 8 101-115. Compare Reinders this vol. ii 39).-The author criticises the theory that the photo-halides are absorption compounds of colloidal silver and normal halides.He conciders that they are sub-halides. Decomposition of Silver N i t r i t e by Heat. MARCEL OSWALD (Compt. rend. 1911 152 381-384).-Divers (Trans. 1871 9 85) and Shimidzu (Trans. 1885 47 630) have shown that the decom- position of silver nitrite by heat proceeds in accordance with the equation AgNO = Ag + NO this action being accompanied by another Ag + N,O = AgNO + NO. It IS now shown that a second aubsidiaryrettction occurs represented as AgNO + NO = AgNO + NO. A. J. W. w. 0. w.ii. 282 ABSTRACTS OF CHEMICAL PAPERS. Normal Barium Orthothioarsenate Ba3As,0,,6H,O. EMANUEL GLATZEL (Zritsch. aclzory. Chem. 191 I 70 86-93).-Bnrium orthothio- arbenate Ba,As2U8 was obtained by Berzelius by a dry procers and in a hydrated form by Nilson from barium hydrogen sulphide and arsenic pentahulphide being regarded by the latter author as a double arsenat e-arseni I e.Arsenic pentasulphide prepared by the action of a rapid stream of hydrogen sulphide in excess on a solution of arsenic acid and hydro chloric acid (McCay Abstr. 1902 ii 135) reacts with a freshly prepared solntion of barium hydrogen sulphide according to the equation 3Ba(Stl)2 + As,O = Ba3As208 + 3H,S. After evaporation transparent pale yellow needles of Itit3As,O8,6H.,O separate sometimes 5-10 mm. in length. I t is partly docowposed by water and is darkened by heating burning in air. C. H. D. Action of Potassium Hydrogen Carbonate on Magnesium Chloride and on Soluble Magnesium Salts in General.NANTY (Compt. rend. 1911 152 605-607. Compare this vol. ii 103).-0n mixing aqueous solutions of potassium hydrogen carbonate and magnesium chloride a t the ordinary temperature a precipitate is formed consisting of the double salt MgC03,KHC03,4H,0 or of MgCOs,3H,0 o r of a mixture of the two. The composition of the precipitate depends solely on t h e concentration of the original salt$. The limits for the formation of each substance have been experimentally determined and the results are shown graphically by Gibb’s method for ternary mixtures. w. 0. w. Z i n c Peroxide. P. KAZANECKY (J. Russ. Phys. Chem. Xoc 1910 42 1452-1458).-The action of 30% hydrogen peroxidc solution on potassium sodium or ammoniuru zincoxide results in the formation OE a white microcryEtalline precipitate which is found to consist of a zinc peroxide Zn0,,H20 containing an admixture of zinc carbonate the presence of the latter being due to t h e strong alkalinity of the solution in which the reaction takes place. -When the peroxide is heated explosive evolution of oxygen and water occurs at 1784 When treated with dilute sulphutic acid it yields hydrogen peroxide whilst with concentrated hydrochloric acid chlorine is evolved.The peroxide must indeed be regarded as consisting of three molecules of ZnO one of which is the dioxide corresponding with a n acid anhydride the other two representing true zinc peroxide z~<?,~z~:o:o,~II~o. 0 The three molecules form a salt-like compound. Those zinc peroxides which have been described previously by various authors consist either oE mixtures of zinc peroxide and oxide or of cotupounds of the two oxides.T. H. P. Nature of the Peroxides of Zinc. ORESTE CARRASCO (Gaxxetta 1911 41 i 16-20. Compare Abstr. 1909 ii 808 and de Forcrand Abstr. 1902 ii 606).-Pure zinc oxide react8 with an ethereal solution of hydrogen peroxide yielding under all conditions (providedINORGANIC CHEMISTRY. ii. 283 that sufficient hydrogen peroxide is present) the same com- pound which after drying at 60-7O0 always has the composition Zn40,,2H2O. The substance is stable a t 7O-SO0 and is not further oxidised even by 50% ethereal solutions of hydrogen peroxide. It is unaffected by cold water but when heated with water at loo' i t loses oxygen and the compound Zo,O,,HpO is formed which is stable even under those conditions.The two peroxides are reddish- yellow powders which explode at 212-216' although the first- mentioned compound shows signs of decomposition a t about 150'. It follows that these two substances are true compounds of which higher hydrates were obtained by de Forcrand. They are hydrated peroxides not additive compounds of condensed hydrates of zinc oxide with hydrogen peroxide because they contain less water molecules than active oxygen atoms. I n structure they differ from the peroxides of other metals and are to be considered as perxincic acids of the follow- ing probable constitutions HO*Zn*O*O*Zn*O*O*Zn*O*O*Zn*O H and HO*Zn*a*O*Zn*O*O*Zn*OH. R. V. S. The Influence of Lime on the Sulphur Content of Roasted Blendes.EUGBNB PROST (Bull. SOC. cluth. BeZg. 1911 25 lO3-115),-1t is generally admitted that the lime contained in zinc blende is converted into sulphate during the roasting but some metallurgists have maintained that during the operation the sulphate thus formed is deccmposed for the most part and that the sulphate existing in the roasted blende is present as zinc sulphate. The latter view is contrary to what would be expected from a knowledge of the behaviour of the sulphates of calcium and zinc a t different tem- peratures but it is impossible to disprove it by analysis of the roasted ore since on extraction with water any zinc sulphate which may be present would react with the lime forming calcium sulphate. The author has therefore carried out a series of experiments with a pure Trahsvaal blende containing only 0.74% of lime.Two experiments were generally carried out side by side the one corisisting of roasting the pure ore the other of roasting the ore mixed with a certain proportion of pure lime or of lime mixed with known quantities of silica lead oxide or iron oxide. From the analyses of the resulting products conclusions could be drawn as to the amount of calcium sulphate present. I n the first set of experiments the roasting was done in a muffle at a temperature of 1025-1050° that is 100-250' higher than the temperature in a zinc furnace. The results show that at least 71-85% of the lime is present as sulphate. Similar results were obtained in a second series of experiments in which the mixtures were heated in a Delplace zinc furnace.Attempts to find a method for analysing a mixture of lime and zinc sulphate were unsuccessful. T. S. P. Zinc Chromates. MAY GR~GER (Zeitsch. anorg. Chern. 1911 70 135-144).-By shaking zinc oxide with chromic acid solution in different quantities for several days in R thermostat filtering through asbestos at constant temperature and estimating the zinc andii. 284 ABSTRACTS OF CHEMICAL PAPERS. chromium in the filtrate and in the precipitate the nature of the phases in equilibrium may be determined. Chromic acid is estimated iodometrically and zinc by weighing the ignited residue consistiug of Crz03 and ZnO. Mixtures rich in chromic acid lose a portion of this by volatiiisation and it is therefore necessary to add a weighed quantity of zinc oxide before ignition.Whilst the composition of the solution varies continuously that of the solid phase shows discontinuities the following five salts being assumed to be present 4Zn0,Cr03,3 H,O ; 3Zn0,Cr0,,2H20 ; 4Zn0,2Cr03,3H,0 ; 3Zn0,2Cr0,,Hz0 ; Zn0,Cr0,,H20. All of these are crystalline except the fourth. The solutions contain zinc dichromate together with some zinc monochromate. The monochromate ZnO,CrO,,H,O does not lose its water a t 125O. It has not been found possible to convert it into the anhydrous insoluble salt (Schulze Abstr. 1896 ii; 24 ; Briggs Abstr. 1908 ii 113). C. H. D. Double Salts of Lead Fluoride and the Other Halides of the Same Metal. CARLO SANDONNINI ( A t t i R. Accad. Lincei 1911 [v] 20 i 172-176).-The present paper deals with the thermal study of the system PbC1,-PbF,.The melting points of the four lead halides employed in the work were determined from their cooling ciirves with the aid of a platinum platinum-rhodium thermoelement and were found t o be lead fluoride 824'; lead chloride 495' ; lead bromide 366" ; lead iodide 400". This last value differs from those of previous investi- gators. The thermal diagram of the system PbC1,-PbF exhibits the following facts. From the m. p. of the pure chloride the curve descends to an eutectic point at 454O the concentration being about 10 mol. % of fluoride. It then rises to a maximum at 601" which corresponds to 50 mol. % of fluoride and it afterwards descends again t o another eutectic point at 554' (composition 75 mol. % of fluoride). When the concentration of fluoride is further raised the curve rises slowly to 570' (composition 80 mol.%),where an evident pause occurs. Finally the curve ascends rapidly to the m. p. of pure fluoride. The existence of a compound PbC1,,PbF2 melting without decomposition is thus established whilst the pause at 570' shows the existence of a compound PbC1,,4PbF2 which decomposes on fusion. R. V. 53. Oxidation of Lead Oxide in Presence of Light and Air. GEORG KASSNER (Arch. Pharrn. 1911 249 22-30).-1n a previous paper (Abstr. 1904 ii 124) the author stated that dry lead monoxide underwent oxidation on exposure t o light and dry air. On repeating this experiment with well dried lead monoxide sealed in n glass tube with air kept dry by means of phosphoric oxide no oxidation of the lead monoxide took place even after seven years' exposure to sunlight.The oxidation previously noted must therefore have been occasioned by the presence of a trace of moisture which probably facilitated indirect autoxidation. It is suggested that in presence of a trace of moisture lead hydroxide is formed which under the influence of light undergoes dissociation whereon a molecule ofINORGANIC CHEMISTRY. ii. 285 oxygen is taken up by the liberated lead atom or the water which is formed thus giving rise directly or indirectly to lead dioxide. T. A. H. Reactions of Mercurous Chloride. WALTER HERZ (ZeitscA. anorg. Chem. 1911 70 170-172. Compare Abstr. 1910 ii 945).- The reaction Hg2Cl + 2KOH2-Hg2O + H,O + 2KC1 has been studied. A constant is found for the ratio k = [KOH]j[KCl] and also for the constant k = [ Na2C031/[NaC1]2 for t h e reaction Hg,CI + Na,C03 = Hg,CO + 2NaCI.The Hydrazinatss of Some Metallic Salts. 11. HARTWIG FRANZEN and HUBERT L. LUCKING (Zeitsch. anorg. Chem. 19 11 70 145-156. Compare Franzen and Rlayer Abstr. 1909 ii 40).-The hydrazinate of mercuric nitrate (Hofmann and Marburg Abstr. 1899 i 486) is exceptional in being formed in acid solution whilst most hydrszinatcs are decomposed by very dilute acid. It may be assumed that a double salt Hg(NO,)?,N,H,NO is first formed which then undergoes hydrolysis the insoluble hydrazinate being precipitated CobaZt iodide dihydrazine COT,( N2F4)2 from cobalt iodide and hydrazine iodide or hydrate forms a pink sparingly soluble powder; the nichZ compound NiT2(N2H,) is yellow.The following hydrazine compounds of cyanides have been obtained cadmium Cd (CN),( N2H4) ; zinc Zn( CN),( N,H,),; silver AgCN,N,H ; copper Cu( CN)2,N2H ; mercury Hg(CN),,N,H ; nickel Cobalt cyanide forms a complex compound (N,H,),Co(CN),. hpdrazinates but double salts CoBr,(N,H,,HBr),,4H20 ; NiBr,(N,H,,HBr) 4H,O ; NiCI,(N,H,,HCl),,H,O. C. H. D. Fractionation of the Yttrium Earths by means of the Succinates. RAYMOND C. BENNER (J. Amer. Chem. Xoc. 1911 33 50-56).-1t has been stated by Lenher (Abstr. 1908 ii 385) that a separation of the earths of the yttrium group obtained from samarskite cau be effected by fractionally precipitating a solution of the nitrates with sodium succinate. The method has now been applied to yttrium earths extracted from several minerals of widely different character.The results show that a satisfactory separation can be obtained provided that the concentration of the earths does not exceed 2-3% by adding sodium succinate solution drop by drop t o a nearly neutral boiling solution of the nitrate$. Yttrium succinate Y t2( C4~H,0,),,2~H,0 is a white crystalline salt which is slightly hygroscopic and is soluble in boiling water t o the The Atomic Weight of Neodymium. I. Analysis of Neodymium Chloride. GREGORY P. BAXTER and HAROLD CANNING CHAPIN (Zeitsch. an0s.g. CILem. 191 1 70 1-33 ; J Amer. Chem. Xoc. 191 1 33 1-28).-A quantity of 3.5 kilograms of neodymium C. H. D. Similar compounds have now been prepared. Ni( CN)p (N2H4)3* The chlorides and bromides of cobalt and nickel do not yield CoCI,( N2H Hal) 2H,O ; extent of 0.1435 gram per litre.E. G; VOL. C. ii. 20ii. 286 ABGTRACTS OF CHEMICAL PAPERS ammonium nitrate was fractionally crystallised from dilute nitric acid samarium being removed in the more soluble fractions and praseo- dymium in the less soluble. The atomic weights of the last fractions were determined by titrating the oxnlates with permanganate. Samarium was easily eliminated praseodymium only with great difficulty Crystallisation from concentrated nit! ic acid removed all impurities except traces of praseodymium after a long series of fractionations. The absorption spectra of the purest fractions of neodymium were examined and tabulated. I n order to determine the atomic weight the neodymium was precipitated as oxalate ignited to oxide and dissolved in hydrochloric acid.The chloride was then crystallised three times and precipitated by hydrogen chloride a t Oo dried in a vacuum and finally heated in hydrogen chloride just below its melting point. It was then converted into silver chloride by means of silver nitrate prepared from pure silver. A small correction was made for the trace of moisture retained by the neodymium chloride. The result obtained is Nd 144.27 for Ag 107.88. Neodymium chloride has DY 4.134. Holmium. OTTO HOLMBERG (Arkiv. Kern. Min. Geol. 1911 4 No. 2 1-$).-Twenty-nine kilos. of finely powdered auxenite were decomposed in small portions at a time with hot concentrated sulphuric acid the excess of acid being finally expelled. After cooling the resulting mass was powdered and gradually added to cold water whereby the ytterbium earths oxides of cerium iron uranium and some of the acid oxides were dissolved.The solution was completely precipitated with ammonia the washed precipitate dissolved in concentrated nitric acid and the solution heated to boiling ; the filtrate from the precipitate so formed was precipitated with oxalic acid and the oxalate collected and ignited. The resulting oxide amounted to 5.5 kilos. and contained the holmium piesent in the original euxenite. The oxide was transformed into oxalate and separated into two fractions by repeated treatment with a hot saturated solution of ammonium oxalate the oxalstes of scandium thorium and of the ytterbium earths with the highest atomic weights being much more soluble than the oxalates of yttrium terbium etc.The lesser soluble oxalates gave 4773 grams of oxides and were treated for holmium as follows The oxides were converted into the m-nitrobeazenesulphonates (compare Abstr. 1907 ii 90) and sub- mitted to a long series of fractional crystallisations. The five least soluble fractions consisted of a mixture of yttrium erbium holmium dysprosium terbium gadolinium europium and samarium ; they were converted into the nitrates and fractionally crystallised in the presence of bismuth nitrate (Bodman and Urbain's method) whereby gadolinium is eliminated. The fourteen chief fractions consisted chiefly of holmium dysprosium terbium and yttrium but europium samarium and erbium were also present. The holmium in these fractions was further Concentrated by the ammonium oxalate method ; the nitrate solution of the three most soluble fractions ( = 14.2 grams) showed a strong holmium spectrum but also tl weak erbium and C.H. D.INORGANIC CHEMISTRY. ii. 287 dysprosium spectrum. The oxide was yellow in colour showing the presence of terbium and the atomic weight ( = 144) indicated a considerable content of yttrium. It was converted into the nitrate and again submitted to a long series of fractionations (160) and the fractions richest in holmium submitted to spectral examination ; they were found to be practicallyifree from erbium but contained a trace of terbium a small quantity of dysprosium and some yttrium (about 19%) the atomic-weight determination giving the value 150.Further experiments are being made to separate the yttrium depending on the great difference in basicity between this element and holmium. Two partial precipitations with aniline raised the atomic weight from 150 to 156. T. S. P The Ovifak Iron a Natural Carbon Steel. CARL BENEDICKS (Metallurgis 191 1 8 65-68).-The mass of iron weighing twenty- five tons from Ovifak in Greenland was regarded by Nordenskiold as a meteorite but has been considered by others to be derived from basalt by reduction. A micrographic examination has now been performed in order to decide its character. The iron is principally composed of pearlite and free cementite thus resembling a high-carbon steel. Analysis shows 1.64% of carbon. The fine grain of the pearlite shows that the iron must have cooled rapidly from 700'.Thus the slowly cooled meteoric irons even when containing much carbon do not exhibit pearlite the carbide having completely segregated. Portions of the iron contain oxide arranged in a lamellar form alternating with cementite. The name '' oxide-pearlite " is proposed for this structure. Its arrangement in dendritic forms indicates a primary crystallisation of a constituent containing both oxide and carbide which would only be possible under pressure. Iron sulphide (troilite) is present in the usual segregated masses. C. H. D. A Revision of the Atomic Weight of Iron 111. GREaoRY P. BAXTER THORBERGUR THOBVALDSON aild VICTOR COBB (J. Amer. Chern. Xoc. 1911 33 319-337).-The change in the atomic weight of silver from 107.93 to 107.88 having destroyed the agreement between the atomic weights of iron determined by the reduction of ferric oxide (Abstr.1900 ii 407) and analysis of ferrous bromide (Abstr. 1904 ii 177) respectively it has been found necessary to redetermine the atomic weight of the latter metal. The various reagents used such as :silver hydrobromic acid nitric acid etc. were purified according t o methods previously described. Three different samples of pure iron were prepared. Sample A was obtained by dissolving a pure ribbon iron in redistilled nitric acid and recrystallising the ferric nitrate three times. The nitrate was dried and partly decomposed by heating in a platinum dish and the resulting mixture of oxide and bssie nitrate reduced to metal by means of ammonia. Sample B was prepared from another pure iron by con- version into the nitrate recrystallising five times converting into the oxide and reducing the oxide with hydrogen. Sample C WAS obtained by dissolving iron in hydrochloric acid and precipitating the insoluble 20-2ii.288 ABSTRACTS OF CHEMICAL PAPERS. sulphides with hydrogen sulphide. The filtrate was oxidisecl with nitric acid and the irou precipitated as hydroxide several times in order t o remove nickel and cobalt experiments having shown that this method is satisfactory when only traces of these latter metals are present. The ferric hydroxide was dissolved in sulphuric acid and the forric sulphate reduced electrolytically to ferrous sulphate using a platinum dish as the cathode. Iron was then deposited electrically from the ferrous sulphate so obtained using an ammonium oxalate electrolyte thus removing aluminium chromium alkali metals and silica.This iron was then treated as described for sample B. Ferrous bromide was made by dissolving the iron in freshly distilled hydrobromic acid in a quartz dish. ‘The solution so obtained was evaporated to crystallisation either in a large desiccator filled with hydrogen or in tho air any ferric bromide thus formed being removed by the subsequent treatment. The ferrous bromide was recrystallised several times. The anhydrous salt mas prepared by fusion in a cuirent of nitrogen and hydrogen bromide gases and the bromine in a weighed quantity of the bromide precipitated as silver bromide according to the method used in similar determinations of atomic weight.Before the precipitation was carried out however 99% of the ferrous salt was oxiclised to the ferric condition by means of potassium dichromate and sulphuric acid in order t o prevent the action of the ferrous salt on the silver nitrate. The precipitated silver bromide was collected and dried a t 170° allowance being made for any remaining in solution by measurements with the nephelometer. As a result of twenty-one determinations the value obtained for the A Revision of the Atomic Weight of Iron. TV. The Atomic Weight of Meteoric Iron. GREGORY P. BAXTER and THORBERGUR THORVALDSON (J. Amer. Chem. Xoc. 191 1 33 337-340). -In order to ascertain if there is any difference between terrestrial and meteoric iron the atomic weight of iron contained in a meteorite from Cumpas Sonora Mexico has been determined.Some of the meteorite was dissolved in hydrochloric acid and any precipitate formed by passing hydrogen sulphide into the acid solution and into the solution after neutralisation with ammonia collected. The filtrate was made alkaline with ammonia and saturated with hydrogen sulphide until there was no further precipitate formed. The coilected sulphides were treated with 4%1 hydrochloric acid to dissolve the iron leaving the greater part of the cobalt and nickel sulphides undissolved. This process was repeated and then the ferrous chloride solution was oxidited with nitric acid and the iron precipitated with ammonium hydroxide i n order to remove the nickel and cobalt. The precipitate was again dissolved in nitric acid and the iron reprecipitated this process being repeated nine times before all the niJckel and cobalt was removed.The resulting ferric hydroxide was then dissolved in sul-phuric acid and ferrous bromide prepared as described in the previous abstract. Atomic-weight determinations with the ferrous bromide thus obtained gave the values 55.537 aiid 55.835 respectively as the means atomic weight of iron is 55.838 (Ag = 107.880). T. s. P.INORGANIC CHEMISTRY. ii. 289 in two series of experiments. I n taking these means the results where 98% only of the ferrous salt was oxidised with dicbromate before addition of silver nitrate have been neglected since they give slightly lower values,. probably because of the action of the unoxidised ferrouj salt on the silver precipitate. There thus seems to be no evidence of dissimilarity between this specimen of meteoric iron and the ordinary metal.T. s. P. Formation of Graphite in Iron Alloys. I<. A . JERIOWN (Zeitsch. EZektrochem. 191 1 17 93-98).-A discussion o€ Goerons’ view that graphite is alwaoys produced by the decomposition of cementite. The literature of the subject is reviewed and the hypo- thesis found to be in accordance with existing experimental evidenco. T. E. The Formation of Iron Disulphide in Solutions and Some Reactions of Thionates. WALTER FELD (Zeitsch. anyew. Cl~srn. 191 1 24 290-294).-The formation of iron disulphide from ferrous thiosulphate and hydrogen sulphide had been observed in 1900 by Carpenter and Linder the reaction being then assumed to be complete.I n cold solutions however the reaction may be arrested a t an earlier stage. Ferrous thiosulphate free from sodium salts is prepared by passing hydrogen sulphide into a cold solution of ferrous sulphate and sodium thiosulphate. The precipitate of ferrous sulphide and sulphur is collected washed with cold boiled water suspended in water and added slowly t o water through which sulphur dioxide diluted with hydrogen is passed the mixture of gases being made more dilute as the operation proceeds. The reactions occurring are (1) 2FeS + 3S0 = 2 FeS,O + S ; (2) FeS + 3s0 = FeS,96 ; (3) FeS + 330 = FeY,O + S. A further quantity of the sulphide IS then added to remove excess of sulphur dioxide the polythionates being raduced a t the same time (4) FeS,O + FeS = 2FeS,O + S ; ( 5 ) FeS,O + FeS = 2 FeS2.03.I n order t o analyse such a solution ammonium chloride is added and the solution is. titrated first with AT/lO-iodine and then with N/lO-sodium hydroxide using methyl-orange as indicator. The quantity of alkali required gives the free sulphur dioxide and one-half of this figure subtracted from the quantity of iodine gives the quantity of thiosulphate. Yolythionates may be estimated as follows. The solution is added to a n excess of cold saturated mercuric chloride solution. Polythionates set free twice as much acid as thiosulphates Na,S,O + ZHgCl + H,O = Na,SO + Hg2Cl + 2HC1+ S ; Na,S,O + 2HgC1 + 2 K,O = Na,SO + Hg,Cl + H,SO + 2HC1+ S ; After heating a n excess of ammonium chloride is added and t h e solution is titrated with sodium hydroxide.The difference between the result obtained and that found by the iodine titration gives the polyt hionates. Polythionate if present may be removed by hydrogen sulphide and after removing sulphur by filtration a solution of ferrous thio- sulphate is obtained. ID the preparation of this salt from bariu.m Nfi,S,06 + 2HgC1 + 2H,O = Na,SO + Hg,CI + H,SO + 2HCl+ 2s.ii. 290 ABSTRACTS OF CHEMICAL PAPERS. thiosulphate and ferrous sulphate tetrathionate is always obtained as an impurity owing to the presence of ferric sulphate. The Ferronitrosulphides and Their Relation t o the Nitro- prussides. 111. J. 0. ROSENBERG (Arkiv. Kern. Min. Geol. 1911 4 No. 3 1-’76).-The author brings forward various objections t o the constitutional formula proposed by Bellucci and Cesaris (Abstr.1908 ii 593) and others for the ferronitrosulphides or Roussin’s salts. I n a former communication (Arkiv. Kern. Min. Geol. 2 No. l) the preparation of a dark brown insoluble compound of iron sulphur and nitric oxide which is considered to be the parent substance of Roussin’s salts has been described. To this compound has been given the name fel.ronitrososu~p~~~d~. Further investigation has shown that this substance is best prepared by the addition at - 2’ of an N/lO-solution of sodium trisulphide to a 2/5N-solution of ferrous chloride saturated with nitric oxide ; sodium disulphide and sodium sulphide do not give such good results as the trisulphide. Ferronitrososulphide can only be preserved under water ; even in the moist condition i t decomposes on exposure to the air.Under the action of a N/25-solution of potassium sulphide the black Roussin’s salt is formed; the red salt is formed primarily and this is then con- verted into the black salt by the excess of ferronitrososulphide. With N-potassium sulphide the red salt is formed and is stable in the presence of excess of the alkali sulphide. Ferronitrososulphide is also decomposed by a hot normal solution of potassium hydroxide the red Roussin salt being formed together with ferric hydroxide potassium thiosulphate and evolution of nitrogen. This is a new method for the preparation of the red salt. The transformation of the black Roussin’s salt into the red salt under the influence of alkali hydroxide and the reverse transformation under the influence of carbon dioxide dilute acids or ferrous chloride were studied but the results were not such as to lead to a definite rational formula for these compounds.A redetermination of the water of crystallisation of the red potassium salt gave 4H20 agreeing with the formula Fe2(NO),S,K,,4H,0. Further experiments showed that when ferronitrososulphide is acted on by a solution of sodium sulphide in such a way that the time of reaction is reduced to a minimum a solution of the red Roussin’s salt is obtained sulphur being left behind. By evaporation in a vacuum the pure red salt was obtained as crystals. Analysis of the ferronitrososulphide was attended with great difficulties and the results depended largely on the method of preparation ; they point to the formula Fe(NO),S or Fe(NO),S,.From the above results it is concluded that the following reactions take place in the formation of Roussin‘s salts (1) FeCI + 2NO = c1 C1>Fe<No. NO (2) ON oN>Fe<g + Na,S = 2NaClf gg>Fe<i>S (ferronitroso- U. H. D. Further fresh observations are recorded. sulphide).INORGANIC CHEMISTEtY. ii 291 (3) The formation of the’red salt from the ferronitrososulphide (ON),Fe*SNa (ON),Fe-SNa I + 5s. 2E:>Fe<s>S S + Na,S = (Red RhGssin’s salt.) (4) Change from the red salt into the black salt 2Fe(NO),S,+ Fe2(N0),S2Xa + H20 = Fe4(N0)+3,Na + NaNO + H,S + 4 5 ; the (Black salt. I SNa ’black salt having the annexed constitu- tion. The relation of these compounds with the nitroprussides is reserved for a future N 0- be* NO Fe*S*ke*S*Fe(No) 60 communication.T. S. P. Complex Molybdates of the Rare Earths. GIUSEPPE A. BARBIERI (Atti B. Accad. Lincei 1911 [v] 20 i 18-21. Compare Abstr 1908 ii 595).-The ammonium ceromolybdate formerly described is not monoclinic but triclinic [a b c = 0.3523 1 0,3409 ; a = 102’22’ /3 = 54’30’ y = 103’4’1. The ammonium lanthnnomolyb- date also mentioned (Zoc. cit.) forms crystals which show holosym- metry of the triclinic system [a b c = 0.3502 1 0.3416 ; a = 102’29’ p = 54O18‘ y = 1 03’10’1. The two compounds readily form mixed crystals. !Che following salts were prepared in the same way as the foregoing and belong to the same class of symmetry Ammonium neodymomolybdate ( NH,),NdMo702 1 2H20 ; triclinic Ammonium praseodymomolybdate ( NH4)3PrMo7024 1 2H,O forms a [CC h c = 0.3492 1 0.3385 ; a= 102’15’ p= 54’8’ y = 103’29’].microcrystalline powder ; triclinic [a b c = 0,3514 1 0.3461 ; a = 102’1 l’ fl= 54’15’ y = 103O44’30’’]. Ammonium sccnmromolybdate The crystallographic measurements are by E. Billows. ( NH,),S~MO~O?~ 12H,O ; triclinic [Q b c = 0.361 1 1 0.3330 ; a = 54’45’ = 54’45 y = 102”36’30’’]. R. V. S. Vanadium Chlorides. OTTO RUFF and HERBERT LICKFETT (Bev. I91 1 44 506-521).-0f the various vanadium chlorides the easiest to prepare is the vanadyl trichloride VOCI,. I n addition to the various methods which have hitherto been used for its preparation the authors give the following three methods (1) Chlorine is passed over vanndiurn pentoxide heated to a dull red heat ; oxygen is evolved and the yield of vanadyl trichloride which is thus obtained pure is quantitative.(2) A mixture of vanadium pentoxide and sulphur is chlorinated at the ordinary temperature ; the reaction takes place vigorously with marked development of heat. (3) Vanadium tri- chloride when hetted in a current of oxygen is converted quantitatively into the vanadyl trichloride. Vanadium tetrachloride VCl is readily obtained by the action of chlorine on finely-powdered vanadium carbide. The reaction com- mences at the ordinary temperature. It is best prepared however by heating vanadium trichloride in a stream of chlorine.ii. 292 ABSTRACTS OF CHEMICAL PAPERS. Vanadium trichloride VCl is most easily obtained from vanadyl trichloride or vanadium tetrachloride or from a mixture of both by heating with sulphur under reflux and then distilling off tho excess of sulphur from the trichloride in a stream of nitrogen.This method is quicker and better than those hitherto used. On heating vanadium trichloride in a current of nitrogen to a dark red heat it is decomposed into vanadium tetrachloride which distils off and into vanadium dichloride which remains behind. The quantity of vanadium tetrachloride which is formed according to the equation 2VC1 = VCI + VCl is determined for each temperature by the partial pressure of the chlorine since together with the above reaction a second occurs namely 2VC1 = 2VC1 + Cl,. For the first reaction the relation (VC1,)/(VC1,)2 = k holds since the vapour pressure of the VCl in the presence of the solid is constant ; for the second reaction the relation (VCI,)2(C12)/(VC1,)2 = k holds. Both these equilibria exist at the same time and by multiplication we have (Cl,)/(VCl,) = k,k that is the quantity of vanadium tetra- chloride formed by heating the trichloride is determined by the partial pressure of the chlorine over the trichloride. It is con- sequently an easy matter to transform vanadium trichloride completely into the tetrachloride by heating in a current of chlorine which is free from oxygen. Similar phenomena are observed when vanadium trichloride is heated at a dull red heat in a current of carbon dioxide instead of nitrogen. Green vanadium dichloride VCl is formed according to the equation 2VC1 If the heating is carried out at a bright red heat the carbon dioxide is reduced by the vanadium dichloride with the result that vanadyl chloride VOCI and carbon monoxide are formed as shown by the equation 3VC1 + 2C0 = 2VOCl+ VC1 + 2CU. On still stronger heating the reaction goes further according to the equation 4VC1 + 3C0 = V,O + ZVCI + 3C0 and pure vanadium sesquioxide is left behind. Thus it is quite umecessary to reduce vanadium trichloride in a current of hydrogen in order to obtain the dichloride. VCI + VC1,. Full descriptions of the various processes are given. Vanadium tetrachloride has b. p. 153*7'/768 mm. Vanadium dichloride is stable in the air at first but gradually deliquesces to a brown solutiou water and oxygen being absorbed. This is in contradistinction to the statements of Roscoe. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9110005270

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 292 ABSTRACTS OF CHEMICAL PAPERS. Minera logical C h emi s try. Gases Enclosed in Tektites. RICHARD BECK (Jahrb. Min. 191 1 i Ref. 39 ; from Xonatsber. Deutsch. geol. Ges. 1910 No. 3 240-245). -Billitmite from Dendang Billiton wben heated in a vacuum at 900' yields per kilo. of material NH,Cl 5 mg. ; (Na,K)CI 60 mg. ;MINERALOGICAL CHEMISTRY. ii. 293 CO 98.0 C.C. ; CO 100.4 C.C. ; H 14.2 C.C. ; SO 0.4 C.C. ; N trace ; H,S 0 not present. Moldavite from Moldauthein Bohemia gave from 20 grams CO 0.6 C.C. ; CO 2.2 C.C. ; N + H 0.7 C.C. A com- parison of tektites with obsidian shows that the former are characterised by the presence of much carbon dioxide and carbon monoxide and by the absence of free chlorine and hydrochloric acid. L. J. 8. WALDEMAR T. SCHALLER (J. Amer.Chem. Soc. 1911 33 162-166).-Bnalyses have been nirrde of one grey and two yellow amorphous bismuth ochres from the mines a t Pala San Diego Co. One of the yellow specimeus consisted of a mixture of bismuth vanadate BiVO and hydroxide Bi(OH) (anal. I) whilst the composition of the other agreed with that of pucherite BiVO (anal. 11). There does not appear to be any previous record either of the occurrence of pucherite in bhe United States or of the existence of this mineral in an amorphous form. The grey sample consisted mainly of bismuth hydroxide Bi(OH) (anal. 111). The author has shown previously (Abstr. 1910 i i 220) that the crystalline form of the bismite of the Goldfield district of Nevada differs from that of artificial crystals of bismuth trioxide.The additional evidence now obtained tends to confirm tohe view that natural bismite is a bismuth hydroxide and not the t rioxide. Bismuth Ochres from San Diego Go. California. Gangue - Sol. in Insol. H,O at H,O at H,O Bi,O,. V,O,. HNO,. in HNO,. 107". 240". ignition. Total. I. 64-43 12-11 2-27 17'63 0.32 0'24 3.43 100-43 11. 66'14 25.80 - 7.37 0-21 0.32 0'84 100.68 111. 64.9 0-8 9.5 13.5 0'4 0.3 1 1 4 100.8 E. G. Mixed Crystals of Sodium Chloride and Silver Chloride (Huantajayite). W. BOTTA (Centr. Min. 1911 138-139).-By adding sodium chloride to fused silver chloride there is obtained on cooling a brittle crystalline mass which under the microscope appears to be homogeneous. Those crystals containing but little silver chloride (as in the natural humtajayite 3-11% AgC1) dissolve in water leaving a curdy residue.The solidification points of mixtures in various proportions vary continuously from that of pure-silver chloride (460') to that of pure sodium chloride (792O) proving that the two salts form an unbroken series of mixed salts. Iron-salts in the Potash-salt Deposits. HENDRIK E. BOEKE (Jalhrb. Mim. 191 1 i 48-76).-.The iron compounds found in the Prussian potash-salt deposits include rinneite ferric chloride haematite magnetite iron-pyrites and iron-boracite. Ferrous chloride may also be present in carnallite to a small extent in isomorphous mixture with the magnesium chloride. The red colour of some specimens of carnallite is due to the presence of enclosed haematite. The crystallisation of mixed solutions of ferrous chloride and magnesium chloride of ferrous chloride and potassium chloride and (of all three chlorides together was studied and the equilibrium L.J. S.ii. 294 ABSTRACTS OF CHENLCAL PAPERS. diagrams deduced. The tetrahydrate of ferrous chloride (FeC1,,4H20) in contact with the saturated solution passes into the dihydrate at 72.6'; but in a saturated solution of ferrous magnesium chloride the dihydrate forms at the lower temperature of 4302~. A new crystallised (triclinic) double salt FeC12,MgCl,,8H,0 separates at 22.89 The double salt FeCl,,KCl,2H20 separates at 38.3' whilst below this temperature potassium chloride and FeC1,,4H20 are deposited separately from the mixed solution. The observation of Schabus (1850) of the salt FeC1,,2KC11,2H20 is not confirmed.L. J. S. Origin of DoIomite. GOTTLOB LINCE (Jahrb. A h . 1911 i Ref. 18-20 ; from Zeitsch. Deutsch. geoZ. Ges. 1909 61 230-241).- A review is given of the occurrence and paragenesis of dolomite- rocks and of previous results in the artificial production of dolomite. A solution of magnesium chloride (1 mol. = 2.4 grams) and magnesium sulphate (1 mol. in 50 C.C. of water) when mixed with a solution of ammonium sesquicarbonate (1 8 mols. in 150 C.C. of water) remains clear ; but on the qddition of a solution of calcium chloride (1 mol. in 100 C.C. of water) and shaking a thick gelatinous precipitate appears. On warming the solution this precipitate appears more quickly and becomes crystalline. This material consists of minute spherules with practically the composition of dolomite ; it is however optically positive and only feebly birefringent D 2-6-2-7 and is slowly but completely soluble in cold dilute acetic acid.This is regarded as a mixed salt of calcium and magnesium carbonates. When it is heated with the solution in a sealed tube for several hours at 40-50° t h e crystalline precipitate changes in character ; the spherules being then optically negative with strong birefringence D>2*72 almost insoluble in acetic acid and containing MgCO 44.8 CaCO 49.5%. From more dilute solutions rhombohedra with all the characters of dolomite were obtained. The composition of the precipitate varies with the amounts of calcium and other salts (ammonium carbonate or sodium chloride) in the solution. The conditions of equilibrium are discussed and it i H held that dolomite is formed as a result of the chemical equilibrium between the solution and the precipitated material.Mineralogy of the Mine of Calabona (Alghero). AURELIO SEBRA (Atti R. Accad. Lincei 1911 [v] 20 i 129-132).-The minerals found in this locality include smithsonite pyrolusite calcite quartz pyrites chalcedony jasper igneous stone and clay. The smithsonite is usually white but some specimens are yellow or green the latter colour being due to copper. Analysis of the whito variety gave ZnO. CaO. COP. Total. 63-13 2'22 34.65 100*00 so that the mineral contains an unusual quantity of calcium carbonate in isomorphous mixture. L. J. S. The pyrolusite gave on analysis YnO. FeO. 0 (by diff.). H,O. Total. 73'20 6'38 19'19 2-23 100*00 R.V. S.MINERALOGlICAL CHEMISTRY. ii. 295 Red Glauberite and Polyhalite from Varanghille near Nancy. V. D~RRFELD (Mitt. geol. Landesanstalt Elsms- Lothringcn 191 1 7 345-348).-Nodules of brick-red glaubsrite and polyhalite have long been known from the beds of rock-salt a t Vic in Lorraine and a t Varanghille near Nancy but they have frequently been mistaken the one for the other. The glauberite is of a darker brick- red colour with a bright greasy lustre; it forms an aggregate of irregularly intergrown crystals with a distinct cleavage parallel to the basal plane. The polyhalite is paler in colour and dull; it forms compact masses without any distinct cleavage. Both minerals enclose iron hydroxide (which remains as flakes when the material is dissolved in water) and small quartz crystals; and the polyhalite encloses abundant lamellze and specks of anhydrite.Analyses of material from Varang6ville gave I. for the polyhalite agreeing with the formula K,S04,&IgS0,,2CaS04,2~H20 (the slight excess of water over 2H20 as in the usual formula being due to the hygroscopic nature oE the powder and to the fact that the material analysed was not quite fresh) ; and 11. for the glauberite agreeing with the usual formula Ns2S04,CaS0 CaO. RlgO. K,O. Na,O. SO,. C1. Fe20,. SiO,. H20. Total. I. 18.33 6'48 14-76 0.72 52-25 0-15 0-13 0'18 7-31 100'31 11. 20.13 0.43 1'63 20.49 57.50 0.11 0'46 0.22 - 100-97 L. J. S. Comparison of Anhydride Celestine Barytes and Anglesite in Respect to the Change of their Geometrical and Optical Characters with Temperature.R. KOLB (Zcitsch. Rryst. &fin. 191 1 49 14-61).-Numerous observations were made of the inter- facial angles refractive indices and optic axial angles at various temperatures ranging from - 60" to + 570". The appreciable although relatively slight variations are plotted on curves. For example for barg tes Prism angle c 6 b c ('111) (iio). a. 8. Y. At - 60"" 0'8161 1 1.3121 73O26.2' 1'6369 1.6383 1.6496 At +570"+ 0.8124 1 1'3047 78'11' 1.6252 1.6283 1'6345 * - 53" to - 50" for a p y ; t + 550' for /3. L. J. S. Two Uranifarous Columbo-titanates from Madagascar. ALFRED LACROIX (Bull. Soc. fray. Min. 1910 33 321-323).-The two minerals euxenite and blomstrnndite (of G. Lindstrom 1874 ; not the blomstrandine of 'CV. C. Bragger 1906) were found in decom- posed pegmatite at Ambolotara near Betafo.The euxenite as masses without form or rarely as indistinct crystals with a greasy lustre and a brownish-black colour. It weathers to an earthy-yellow sub- stance on the exterior. Thin slices are translucent and the mineral is optically isotropic. D 4.862. The composition (anal. I. by Pisani) is very near to that of the euxenite from Arendal in Norway. Loss on Cb,O,. TiO,. Tho,. UO,. Y,O,. Ce,O,. A1,0,. FeO. CaO.ignition. Total. 1. 33'70 19.10 1-54 16'40 18-38 2-44 1'30 1-10 2'27 4-00 100'23ii. 296 ABSTRACTS OF CHEMICAL PAPERS. The blomstrandite is represented by a single massive specimen with a greasy lustre and greenish-brown colour; D 4.07-4.17. The mineral is attacked by hydrochloric acid.Cb,O,. TiO,. SnO,. Thol. U,O,. A1,0,. Fe,O,. Ce,O,Y,O,. MgO. CaO. H,O. Total. 34'80 18'30 0.30 1.30 26-60 2-10 2.87 0'60 0'90 0-40 3-45 7-60 99-22 Anal. 11. by Pisani. L. J. S. Radioactive Minerals from Madagascar. ALFRED LACROIX (Compt. rend. 1911 152 559-564. Compare Abstr. 1908 ii 705 ; 1909 ii 58 813 ; 1910 ii 46 307; and preceding abstract).-A description of hatchettolite blomstrandite euxenite and fergusonite has already been given. Microlite occurs i n small crystals associated with triphnne and rhodizite. Samarskite from Antanamataza black t o yellomish-brown (analpis by Pisani) Cb20,. Ta,O,. TiO,. Tho,. UO,. (Y. Er),O,. (Ce La Di),O,. A1,0,. 43'60 11.15 1'42 1-05 8'70 9-50 4'05 0-80 FeO. CaO. H,O. Total. D. 5.40 2'43 11-14 99.24 4'20 Autunite apparently of recent secondary origin is met with in pegmatites.It is suggehted that this has been formed by the action of phosphoric acid from organic sources on soluble calcium and uranium salts. w. 0. w. Molengraaffite a New Mineral in Lujaurite from the Transvaal. H. A. BROUWER (Centr. Min. 191 1 129-132).-This mineral occurs together with microcline nepheline zgirite pseudo- morphs of catapleiite after an eucolite mineral etc as a constituent of lujaurite (a rock of the nepheline-syenite group) in the Pilandsherg north of Rustenburg in the Transvaal. It forms small yellowish- brown prisms with perfect cleavage parallel t o the orthopinacoid and resembles astrophyllito in appearance. The refraction and bi- refringence are high (u = 1.735 y = 1 *770). The optical characters and the lamellar twinning on the orthopinacoid point to the monoclinic system.SiO,. TiO,. A1,O3. Fe,O,. FeO. MnO. CaO. MgO. Na,O. K20. H,O. Total. 28-90 27-70 3.75 0'95 2.07 2'72 19.00 2-38 10.30 0.60 1-00 99-37 This is compared with analyses of netrophyllite yttrotitanite eucolite-titanite and wohlerite from which it differs especially in the high percentage of sodium. The mineral fuses easily to a brown enamel and is decomposed by hydrochloric acid. Titanite results by its alteration. L. J. S. Analysis by F. Pisani gave The Pegmatite of Ytterby Sweden. IVAR NORDENSKJOLD (Jahrb. Min. 1911 i Ref. 33-35 ; from Bull. Geol. Inst. Univ. Upsals 1910 9 183-227).-8 general account is given of the history of tho minerals including the several rare-earth minerals and the felspar quarries of this well-known locality.The following analyses are given of felspars I and 11 of potash-felspar corresponding with t h e formula Or,( Ab An) and III-X of plagioclase these being mostly oligoclase with the formula Ab,.,An to Ab,.,Anl. Of the potash-felspars,MINERALOGICAL CHEMISTRY. ii. 297 microcline predominates but orthoclase also occurs. found rarely as crystals The oligoclase is Loss on SiO,. A1,03. Fe,O,. CaO. bfg0. K,O. Na,O. ignition. Total." I. 64.32 19'41 0.14 - 0.35 12.90 2.10 0.57 99-79 II. 64'40 19.30 0.30 0.40 - 12'56 2.68 - 99-64 111. 61'55 23.80 - 3 18 0.80 0.38 9-67 - 99.38 IV. 64.23 23.57 - 2.51 - 0.81 8.47 - 99 09 V. 63.19 23.52 - 4'81 - - 9.01 - 100.53 VI. 62.81 23-21 0.10 3-81 0.18 0.58 8 18 0 81 99.68 VII.63.66 23.45 - 3.53 0.05 1.59 7.91 - 100.19 VIII. 64.81 22'99 - 3-15 - 0.82 8'89 - 100'66 IX. 63.38 22.98 - 3-63 - 0.55 9-10 0.37 100.00 X. 63.00 23.00 0.30 2-60 0.03 0'38 10'84 - 100-13 The micas present in the pegmatite include biotite and muscovite the former being frequently altered to chlorite. Analysis XI is of the fresh biotite and XI1 of altered biotite Totsi* (less 0 SiO2. Al2Oy. Fez03. FeO. CaO. MgO. KzO. Na@. HzO. Moisture. F. Y,Op (Ch,Ta)205. for F). XI. 32.23 15.97 7.57 26.06 0.23 2.75 '7.93 1'91 2'bO 0'31 - - - 100.18 XII. 'LiYii8 1.5'48 14% 19.39 3'43 6'38 0.57 1-69 7-51 - 0.14 1-54 1.36 100 09 Several of these totals are incorrect. * L. J. S. The Scapolite Group. ALFRED KINMELBAUER (Jcchrb. .Vim 191 1 i Ref. 22-23; from Xitxunysber. dkad.Wiss. Wen 1910 119 (I) 65 pp).-The chemical and physical characters were determined in detail for the following members of the scnpo:ite group. Within the errors of observation due to imperfections in 1 he material the results indicate that these minerals form an isomoiphous series of mixed crystals of which the end-membeis are meionite (Me) ............ and marialite (Ma). ........... 2CaA1,Si2O + Ca,Al,Si,O 2NsAlSi,C)8 + NriA1Si3C10,. I. Sc4ipolite from Malsja Sweden. 11. Scapolite from Arendal Norway. ILI. Scapolite from Gouverneur New Yor k. IV. Meionite from Vesuviue. V. Scapolite from Grasse Lake New York. TI. Scapolite from Bolton Massachusetts. VII. Scapolite from Gulsjo Sweden VIII. Couzeranite from AriBge. IX. Marislite from Pianurn near Naples. SiO,.A1,03. Fe,O,.CaO.MgO.Na,O.K,O. C1. SO,. CO,. H,O. I. 52.48 25-56 0.39 12.44 - 6-52 0.79 0 70 0.58 0.14 0.61 I1 52.57 24'24 0.26 11'57 - 7-19 0'42 1.63 0.90 0'39 0'69 III. 52-65 25.32 0.11 11.30 0.23 6.64 1.58 2-14 0'14 - 0.42 I v . 41-42 - - - - - - - - - - V. 47.30 25.99 0'32 17'34 0.15 - - - - - - VI. 47.09 25-39 0.10 16.62 0.20 - - - - - - VLI. 51-09 23-86 0.16 12.40 0.02 - - - - - - VIII. 56.67 19'47 0.20 7.08 0.23 - - - - - - IX. 59'29 22-66 - 2.74 - - - - - - - Total. Sp.gr. 100*21 2.675 99.86 2.676 100'53 2.660 - 2.713 - 2 736 - 2.668 - 2-625 - - - - As determined from the plotted curves the sp. gr. oE pure meionite A selection of the should be 2.815 and of pure marinlite 2.560. physica 1 constants of the materials analysed is :i I 298 ABSTRACTS OF CBIEMICAL PAPgRS.Ma%. n:c. W E W - - E . Ti." Tp* (yellow). (yellow). IV. 4 1:0'4394 1'58526 1.55436 0'03090 1138" 1178" V. 31 1:0'4407 1-58284 1.55120 0'03164 1125 1198 11. 54 1 :0'4410 1.56645 1.54642 0'02003 1150 1238 IX. 85 1 :0*4460 1-54630 1.53949 0.00681 1088 1233 * TI temperature at which edges are rounded; T temperature a t which the material is completely fused. Numerous other values are given for the refractive indices and the theoretical values for the pure end-members of the series are calculated. Determinations of the composition of the silicic acid by Tschermak's method gave metasilicic acid (H12Si6018) for the Vesuvian meionite and for the others mixtures in various proportions of H,,%,O and HlOSi9Oz3. L. J. S. Mesolite from Palagonia Sicily.G. PONTE (Zeitsch. Kryst. Min. 1911 49 111 ; from Atti Accud. Gioenia Sci. Nat. Cutania 1908 [v] 1 No. XV).-White radially fibrous masses from cavities in a palagonite tuff gave on analysis the following results agreeing with the formula ??a,CaA16Si,030,6H20 + H20 SiO,. A1,0,. CnO. Na,O. K,O. H,O. Total. Sp. gr. 46'61 26-36 4'82 11.28 0'24 10.87 100*18 2.188 Over sulphuric acid there is a loss of 2.89% of water and with increasing temperature a gradual loss amounting to 7.49% at 360'. L. J. 5. Chemistry of Cancrinite. STANISLAUS J. THUGUTT (Jcchrb. Min. 19 11 i 25-47).-Previous analyses of cancrinite show appreciable variations amongst themselves ; for example A1,0 SiO ranges from 1 2 to 1 2.5. The best analyses give Al,O Na,O= 1 1. Analysis of rose-red cancrinite from Brevig Norway being a portion of the same material as that analysed by Lemberg in 1887 gave the results under I.This material is quite fresh and pure; the small amount of ferric oxide represents hzematite to which the red colour of the mineral is due and the small insoluble residue is ggirite. The percentage of water shown in the analysis is that given by the coarse powder; the finely-powdered mineral gave 6.80% water (compare Thugutt Abstr. 1909 ii 1027). From this analysis the formula is deduced as H18C%Na24A122si24G60119 = - 8NazAl2Si3O1,,3Na2A1,O4,5CaCO,,Na2CO3 9H20 SiO,. AI,O,. Fe,O,. CaO. K,O. Na,O. COY H,O. Insol. Total Sp. gr. I. 35.58 28.24 0'12 6'91 0'16 18'46 6.35 4-36 0.16 100.34 2'46 11. 37'92 26-74 0'23 2.98 0.29 20.06 5.40 5.10 1'61 100.33 2.44 111.34.92 24-58 0.17 1.77 0'26 19-70 4-38 7-96 6'22 100'36 2-43 Yellow cancrinite from Brevig gave anal. IT. ; this material is however impure containing haematite agirite and 13.07% of a decomposition product (natrolite). Four other analyses are given of fractionations obtained in heavy liquids from this material the lightest portion containing 44.26% natrolite wikh a little hydrargillite.MINERALOGICAL CHEMISTRY. ii. 299 The cause of the yellow colour of the mineral is discussed; it is attiibuted to t h e presence of mosandrite (two of the analyses show the presence of small amounts of cerium earths). Colourless transparent crystals of oaucrinite from Sarna Sweden gave anal. 111. ; this material is however impure and not fresh containing Regirite and 28.72% of secondary natrolite.Cancrinite when moistened with a 0.1% cobalt solution and strongly ignited gives an intense blue coloration thus differing from nephelite sodalite natrolite etc. and from diaspore and hydrargillite which give the blue colour a t a much lower temperature. Although can- crinite is analogous in constitution to nephelite and sodalite and has been derived from these yet it differs from them in its mode of alteration it passes through a soda-cancrinite to an end-product consisting mainly of natrolite. L. J. S. Aluminium Silicate Minerals in Soils. RUDOLF VAN DER LEEDEN (Centr. Mim. 1911 139-145).-A discussion of the opposed views as to whether the alkalis and alkaline earths present in soils in combina- tion with aluminium silicate exist as zeolites or as “adsorption compounds.” L.J. S. Relations of Some Aluminous Silicate Weathering Products. RUDOLF VAN DER LEEDEN (Centr. Min. 1911 173-179. Compare preceding abstract).-Experiments were made on the decomposition of silicates by pure water. Stilbite from Iceland (anal. I.) vras Gnely powdered and one gram shaken for ninety-six hours with 100 C.C. of distilled water. The filtrate was turbid and on keeping deposited a slight sediment ; the clear liquid contained SiO 3.6 A1,0 4.0 CaO 5-0 mg. Loss on SiO,. A1-0,. Fe,O,. CaO. MgO. CuO. Alkalis. ignition. Total. I. 54-55 17‘81 0’24 8.71 1-10 - 1-57 16.03 100-01 11. 21-37 32’89 0.81 1-91 0.91 0.69 1-77. 39.67 100’02 When allophane from Vise Belgium (anal. II.) was treated in the same way there passed into solution SiO 2-4 AI,? 2.8 CaO 1.5 mg.These results can be more directly compared by dividing the weights obtained by the percentages of each constituent in the mineral (for example for SiO 2-6/54*55 = 0.04’7). Stilbite. Allophane. SiO ..................... 0 ‘047 0 -1 A1,0 .................. 0 ‘23 0-085 CaO ..................... 0-6 0.8 These factors would be unity if the material were completely soluble whilst if it were partly soluble without decomposition they would be equal for each constituent. They therefore give a measure of the solubility of each oxide and further indicate that there has been a decomposition of the mineral in each case. Analogous results were obtained when dilute acetic acid was used instead of water. L. J. S.ii. 300 ABSTRACTS OF CHEMICAL PAPERS.[Titaniferous Melanite from Assynt Sutherlandshire.] ALEXANDER GEMMELL (Trans. Edinburgh. Geol. Xoc. 191 0 9 41 7-41 9).-Several analyses are given of borolsnite and related rocks from the neighbourhood of Loch Borolan. A garnet D 3.663 isolated from ledmorite-pegmatite (a cosrse-grained melanite-augite- syenite) from Bad na h'achlaise gave the following results agreeing with the garnet formula 3(Ca,Fe,Mg)0,(Fe,A1,Ti),0,,3(Si,Ti)02. H,O H,O SiOP TiO,. A1,03. Fe,O,. FeO. CaO. MgO. K,O. (110"). (+llO"). Total. 33.51 6'74 S.20 17-90 2.70 28-86 1.80 0'46 0 09 0.54 100.81 As described by 8. J. SHAND (tom. cit. p. 389)' this melanite is dark brown with a rhombic-dodecahedra1 form L. J. 5. Constitution of Ilvaite. ENNIC) BASCHIERI (Zeitsch.Kryst. Min. 1911 49 112; from Proc. verb. Soc. Toscnna Sci. Nut. 1908 17 3 1 -34).-Employing Tschermak's method for the isolation of the silicic acid tbe author concludes t h a t ilvaite is a diorthosilicate whilst according to Himmelbauer it is a basic metasilicate. This discrepancy is t o be ascribed t o the imperfection of the method Analysis of ilvaite from Elba used in the experiments gave SiO,. A120,. Fe20,. FeO. CaO. H,O. Total. 28.87 0.85 19'79 34.49 13.58 1-91 99'49 L. J. S. A New Thermal Water. Prototype of a Modern Physico- chemical Study of a Mineral Water. Methods for the Estimation of Small Quantities of Lithium Manganese Antimony Bromine Fluorine Rare Gases etc. ARMAND GAUTIER and CHARLES MOUREU (Compt. rend. 1911,152,546-551).- A n examination stated to be more complete than any previously carried out has been undertaken in connexion with a new spring at Nancy yielding 1870 litres per minute.The degree of ionisation of the dissolved salts as determined from the conductivity was about 90%. The radium emaration expressed in mg.-minutes per 10 litres was 0.46 for the evolved gas and 0.088 for the water. Radium was determined after removal of emanation and corresponded with 1.2 x 10-11 grams of radium bromide per litre. The following analytical results are in parts per 100,000 K 1.712 Na 37.888 Li 0.048 NH 0.054 Mg 1.560 Ca 9.114 A1 0-017 F e 0.300 Mn 0*0008 Sb and Sn traces. C1 57.838 Br 1*152,10*0004 F 0.114 SO 11 448 S 0.080 BO trace SiO 2.026 CO 9.272 HASO 0.00028 NO 0.036 PO and NO nil. Total 134.05; residue dried at 180° 134.95. Oxygen consumed 0.105. Dissolved gases argon (with traces of krypton and xenon) 15 C.C. ; helium (with traces of neon) 19 C.C. The gas evolved at the spring contained CO 1.75 N 95.36 A 1-29 He 1.60%. For lithium 30 litres of water were concentrated and the sulphates precipitated by lead acetate and barium chloride. Calcium barium magnesium and ammonium were removed and the dry residue taken up three times with con- centrated hydrochloric acid which extracts lithium chloride with small The following analytical methods are new.PHYSIOLOQICAL CHEMISTRY. ii. 301 ttillounts of the othor alkali chlorides. After evaporation to dryness the lithium was removed by extraction with a mixture of absolute amyl alcohol and ether. The metal was finally precipitated as phosphate. Bromine was estimated by distillation with chromic and sulphui ic acid into potassium iodide solution and titration of the liberated iodine. E’luorine was determined after removal of silica calcium and magnesium by precipitation in alcoholic solution as barium fluoride followed by conversion into the sulphate. Antimony mas detected by conversion into the bromide and extraction with carbon disulphide. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110005292

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

PHYSIOLOQICAL CHEMISTRY. ii. 301 Physiological Chemigltr y. The Influence of Compressed Air on Blood-formation ADELE BORNSTEIN (P’Eiger’s Archiv 19 1 1,138 609-6 16).-Prolonged exposure of dogs and monkeys to compressed air (two atmospheres) produces a hydrEemic condition with a diminution per C.C. of corpuscles and hsmoglobin. W. D. H. Physiology of Blood-sugar. E. FRANK (Zeifach. pAysioZ. CJLenE. 19 11 70 29 1-299).-1n confirmation of Baudouin’s statement it is shown that the dextrose in the blood increases when large doses of dextrose (100-200 grams) are given by the mouth an hour or two previously ; the urine is usually free from sugar or only traces are present. Alimentary hyperglyczmia and glyrosuria are probably due to insufficiency of liver action. There may however be certain slighter cases of a diabetic nature in which although the blood is rich in sugar it may not pass into the urine owing to funotional disturbance of the kidneys.W. D. H. The Distribution of Reducing Substances in Human Blood. H. LYTTKENS and J. SANDGREK (Bzochem. Zeigsch. 1911 31 153-158. Compare Abstr. 1910 ii 785).-The sugar was estimated in corpuscles and serum both before and after fermentation with yeast by means of Bang’s method. The difference was taken to indicate the amount of dextrose. It was found that human blood-corpuscles contain practically no dextrose the whole amount in the blood being in the serum. The normal sugar content of urine is not much less than that of blood. The normal dextrose content of rabbit’s blood is much higher than that of human blood.The amount of dextrose in rabbit’s blood- corpuscIes is also extremely small. The authors explain the diff crences between their results and thoso obtained by other investightors (Michuelis Rona etc.). $3. B. 8. VOL. C. ii. 21ii. 302 ABSTRACTS OF CHEMICAL PAPERS. The Dipeptide-Splitting Action of Blood-plasma and Pathological Fluids. I. WALKER HALL and G. Sco1-T WILLIAMSON (J. Pat?&. Bact. 191 1 15 351-352).-Specirnens of blood-plasma and aerum pleuritic and other dropsical effusions but not cerebro-spinal fluid split up glycyl-tryptophan. The substance responsible for this action is precipitated with the globulin fraction and obeys the lams of ferment-action but its properties do not agree with those of erepsin or trypsin. W. D.H. Ester and Fat Hydrolysis in Blood and Serum. PETER RONA and LEONOR MICHAELIS (BiocAsm. Zeitsch. 191 I 31 345-354).-The hydrolysis of monobutyrin in aqueous solution can be measured by determining the changes in the surface-tension by Traube’s drop method from a capillary tube the number of drops falling in a given time from a given apparatus diminishing as hydrolysis proceeds. By this means the action of serum and blood from various sources ou monobutyrin was determined. The sera of guinea-pigs and rabbits exert a strong action whereas tbose of ox pig and sheep exert a weak action. I n general the sera act more weakly than the whole blood. S. B. S. The Behaviour of Calcium in the Serum and the Calcium Content of the Blood-corpuscles. PETER RONA and D. TAKAHASHI (Biochem.Zeitsch. 191 1 31 336).-By means of the compensation dialysis method i t was found that 25-35% of the calcium in serum is not diffusible. The calcium content of blood-corpuscles was also estimated by means of separate estimations in the whole blood and the serum and the determination of the amount of corpuscles by the haematocrite method. By this means it was found that the corpuscles contain calcium (0.0025- 0.0035%). The results confirm those of Hamburger obtained by physiological methods as to the calcium content of the corpuscles. S. B. S. Blood-sugar. IX. The Permeability of Blood- corpuscles to Dextrose. PETER RONA and A. DOBLIN (Biochem. Zeitsch. 191 1 31 215-220).-Sugar was estimated in the whole blood and in the serum and the percentage of corpuscles determined by the hzematocrite method.In this way the percentage of sugar in the blood-corpuscles could be determined both in the untreated blood and in the blood after addition of sugar. The sugar mas estimated polarimetrically after separation of protein by dialysed iron hydroxide. The results lead the authors to the conclusion that the red blood-corpuscles are permeable t o sugar. S. B. S. The Amount of Oxyproteic Acids in Serous Fluids and in the Blood in Normal and Pathological Gases. WIKCENTY CZERNECKI (Bull. Acad. Sci. C?*acow 1910 A 399-413).-The method employed was to separate the proteins by heating the liquid after acidifying by acetic acid acidify the concentrated filtrate with sulphuric acid precipitate the sulphates of the alkali metals by alcohol and to precipitate the phosphates urates etc.by barium hydroxide. ThePHYSIOLOCIICAL CHEMISTRY. ii. 303 filtrate was then evaporated to dryness and then extracted with alcohol-ether and finally alcohol. The nitrogen in the residue which contained the oxyproteic acids was estimated. The following estimations were also made the total nitrogen the total extractive nitrogen (that is the total nitrogen after separation of proteins) the nitrogen in the copper acetate precipitate obtained from the protein- f r t e liquid and the specific gravity. The author tabulates the results obtained which are chiefly of clinical interest from serous fluids and bloods from a large numger of normal and pathological cases. s. B. s. The Influence of Ether Narcosis on Body Temperature and Carbohydrate Metabolism. KARL GRUBE (PfEiiger’s Archiv 191 1 138 601-608).-ILn confirmation of Selig’s statement it was found that ether narcosis is followed by temporary glycosuria often accompanied by albuminuria in dogs.There is also a fall of body temperature but if this is avoided by artificial warming the effects ou the urine do not occur. Nitrogenous Metabolism of the Coyote (Canis Latrans). ANDREW HUNTER and MAURICE H. GIVENS (J. Biol. Chewz. 1910 8 449-464).-The coyote employed whether in equilibrium or fasting did not show so far as nitrogen metabolism is concerned any essential difference from a dog under similar conditions. The principal numerical details given relate to urea ammonia creatinine CI eatine (exogenous in origin) allantoin and purines.Urocanic acid was not found in the urine. The Effect of Chloroform on the Intermediate Protein Metabolism of the Dog. DOROTEY E. LINDSAY (Bia-Chem. J. 191 1 5 407-426).-1n chloroform anaesthesia the excretion of totai nitrogen is distinctly increased ; the urea nitrogen falls ; the ammonia nitrogen the allantoin nitrogen and the amiuo-acid nitrogen rise ; the creatinine nitrogen is unaffected but creatine usually appears in the urine two or three days after the inhalation. W. D. €1. W. D. H. W. D. H. Nuclein Metabolism in the Dog. PHCEBUS A. LEVENE and FLORENTIN MEDIGRECEANU (Amer. J. Physiol. 191 1 2’7 438-44’7).- If allantoin is given 31% is excreted unchanged and the rest oxidised to urea; when sodium urate is given 60% is excreted in the urine 15% as allantoin 2% as sodium urate and the rest as urea; when hypoxanthine is given 56% is excreted oE which SO% is in the form of allantoin 2% as uric acid and the remainder as urea.When inosin is given 40% is excreted as allantoin 4% as uric acid 2% as purine 4% as undetermined nitrogen and the rest as urea. Feeding on hypo- xanthine and inosin is often followed by prolonged disturbances of nitrogenous equilibrium -Hhich can be avoided by giving sodium carbonate a t the same time. When nucleic acid is given 50% appears in the urine of which 85% is in the form of allantoin and the rest urea. After feeding on thymus 17% of the nitrogen is excreted RS allantoin 5%as uric acid and the rest as urea. There was no increase of amino-acids in the urine in any experiment.The highest allantoin 21-2ii. 304 ABSTRACTS OF CHEMICAL PAPER% output follows feeding on nucleic acid and hypoxanthine. The first step in the disintegration of nucleic acid in the body is probably the liberation of purines and not of inosin. W. D. H. Phosphorus Metabolism. J. P. GREQERSEN (Zsitrrcil. physiol. Cham 191 1 71 49-99).-0n nitrogenous diet which contain8 phosphorus in an inorganic form only the organism remains in phosphorus equilibrium or may put on ph )sphorus. Organic phosphorus compounds can therefore be built up in the body from phosphates. On a nitrogen-free diet the loss of phosphorus is not affected if phosphates are given. On a nitrogenous diet free from phosphorus but capable of maiutaiuing nitrogenous equilibrium the excretion of phosphorus falls marikedly.On a phosphorus-fi ee nitro- genous diet containing calcium and magnesium salts the utine con- tains a minimal amount of phosphorus but more leaves the body by the faeces. If calcium and magnesium salts are absent from the food the urine usually contains more phosphorus thsn the fzces. The experiments were made on rats. W. D. H. The Utilisation of Yeast in the Human Body. WILHELM VOLTZ and AUBUST~BAUDREXEL (Biochem. Zeitsch. 191 1,31,355-357). -In continuation of a former investigation (this vol. ii 216) the food-value of constituents of yeast othor than protein were determined. The amounts resorbed in the organism were found as follows organic substances 90% ; proteio 86% ; fat 70% ; fibre 40% ; nitrogen-free Fasting Studies. I. Nitrogen Partition and Physiological Resistance as Influeilced by Repeated Fasting. PAUL E.HOWE and PHILIP B. HAWK (J. Artier. Chem. Xoc. 191 1 33 215-253).-An account in full detail of the eflfect on a dog of two sacces-ive fasts a reliminary account of which has already appeared (corn pare A. bstr. f910 ii 728). E. G. Further Remarks on the Relationship between the Magni- tude of Oxidation and Cytolysis of Sea-urchin's Eggs. JACQUES LOEB and HARDOI~PH WASTENEYS (Biochem. Zeitsch. 19 1 1 31 168-169).-A reply to some recent criticisms of 0. Warburg (Abstr. 1910 ii 628 ; this vol. ii 60). extractives 100%. s. B. s. S . B. S. Increase of Protein during the Fattening of Full-grown Animals. THEODOR PFEIFFER and K. FRISKE ( Lnndw. Versuchs-Xtnt. 1911 74 409-455).-l>uring the fattening of full-grown sheep the animal puts on nitrogen in the form of flesh The worse the condition of the animal beforehand the more marked is the putting on of flesh and this occurs even although the diet is poor in protein especially if given for long periods.W. D. H. Tho Behaviour of Fats of Animal Organs in Antiseptic Preservation. NAGIAMICHI SH~RATA (Niochem. Zeitsch. 191 1 31 321-335).-The Kamagama-&to method of examination wasPHYSIOLOGICAL CHEMLSTRY. ii. 305 employed. Concordant results were almobt always obtai~iecl in the case of the fatty acids soluble in light petroleum but in the cholesterol estimations the results were not always so satisfactory. After prolonged preservation (up to forty-seven days) even a t si~rnmer temperature no changes could be detected in higher fatty acids and as a rule also in cholesterol. There is therefore no evidence of new fat formation during autolysis and the results negative the suggestion that fat is formed from protein during fatty degeneration. The fact that there is an increase of stainable fat can he explained by assuming that during the changes fat is set free from certain very ARTHIJR LAPWORTH (J.Path. Bact. 191 I 15 854-26 l).-Windaus’ digitonin method for estimat- ing cholesterol and its esters was found to be accurate. Extraction of the organs by methods which involve desiccation with plaster of Paris or anhydrous sodium sulphate does not lead to erroneous results. Free cholesterol and esters were found in kidneys ttdrsnals a dermoid cyst and brain.The proportion of free to combined cholesterol varies considerably with age in the same organ ; more than 99% in the braiu is free. complex combinations. s. 13. s. Cholesterol in Animal Tissues. W. D. H. The Fate of Cholesterol in the Animal Organism. J. BROWINSHI (Chem. Zentr. 1910 ii 1072; from Kosmos 1910 35 Badziszewski Festband 56 7-56 1). -The substance extracted from the faeces of dogs kept on a flesh diet is shown to be cholesterol on account of the chemical and optical properties and the olementary analyhes both of the substance itself and of certain of its derivatives. Cholesterol is not therefore reduced to coprosterol in the intestine of the dog (compare Kusumoto Abstr. 1909 ii 79). CHRISTOPH ULRICH (Arch. Pham. 19’1 1 249 6S-92).- The author has determined the ‘‘ edible matter,” moisture fat ash pure ash (free from sodium chloride) phosphoric a d “ total nitrogen,” protein and ‘‘ nitrogen-free extract ” for twency-five species of fish figures being given in most cases for fresh preserved and cooked specimens of each species.The results are tabulated in detail in the original. The fish are classified into ‘‘ fat,” containing 24.03% or more fat and (‘ lean,” containing below 7.03% fat both figures being calculated on the dry matter of the fresh fish. I n general the ‘‘ edible matter ” shows great variation and over the whole series now examined ranges for fresh specimens from 54.1 to 76.5% the former being yielded by herrings and the latter by haddock. Frying or baking as opposed to boiling generally increases the yield of “ edible matter.” Boiling usually reduces the amount of water fat and nitrogenous substance in the edible matter.Frying and baking increase the amount of fat in “ lean ” fish due to absorption of added fat but reduce the amount in “ fat ” fisb. The various methods of preservation such as ‘‘ salting,” “ pickling,” and “ smoking,” generally reduce all the constituents but especially the nitrogenous matter. W. J. Y. Fish. T. A. H.ii. 306 ABSTRACTS OF CHEMICAL PAPERS. R e a c t i o n s in Gelatinous Media. RAPHAEL E. LIESIWANU (Zeitsch. anal. Chenz. 191 l,5O782-87).-The phenomena which result from the formation of precipitation membraiies and dead space by diffusion in gelatinous media are shown to be of importance in connexion with chemico-physiological changes and with certain opera- tions involved in histological preparation work (compare Abstr.191 0 ii 936 1052). H. 31. D. The Effect of Ions Transported by ’the C u r r e n t on the Primary Affinity f o r Colours and the Conductivity of Polarised Nerves. Influence of the C a t i o n s Ca Na R on the Anodic Region. ALFRED SCHWARTZ (PfEiiger’s Archiu 191 1 138 487-524). -A contribution t o olectro-physiology ; the effect of the various constituents of Ringer’s solution is studied. W. D. H. Changes in the Excitability of bhe Vegetative Nervous System by Removal of Calcium. RICHARD CHIARK and ALFRED FR~HLICH (Arch. exp. Path. Phurm. 191 1 64 214-227).-Poisoning with hydrochloric acid oxalic acid and sodium oxalate increases the excitability of the nerve-endings of the vegetative (that is sympathetic and autonomic) iiervous system towards adrenaline and pilocarpine.Adrenaline mydriasis can be produced in cats after chronic poisoning with arsenic mercuric chloride and sodium chlorate. The increase of excitability is attributed to precipitation of calcium or washiog ollt of the calcium from the tissues. W. D. B. The Influence of Phloridzin on Glycogen Formation in the Liver. BERNHARD SCHONDOKFF aud FRITZ SUCKROW (PJiiger’s Archiv 191 1 138 538-546).-This investigation was undertaken on account of the differences i n the views held on the relative importaiice of the liver and the kidney in phloridzin diabetes. Phloridz n was found to have no effect a t all on glycogen formation in the liver. W. D. H. The Origin of Glycogen from Formaldehyde.BERNHARD SCHONDORFF and FRIEDRICH GREBE ( PJEiiyds Archiv 191 1 138 525-537).-Grube (Abstr. 1908 ii 307 ; 1909 ii 3‘28) stated t h a t the liver of the tortoise is able t o form glycogen from a dilute solution of formaldehyde perfused through it. A repetition of these experi- ments failed to confirm them. The usual result is that t h e perfused lobe is usually poorer i n glycogen than the control lobe. W. H. D. Cysteine in Animal Organs. VINCENZ ARNOLD (Zeitsch. physiol. Chem. 19 11 70 314-325).-After precipitation of extracts of liver hpleen and thymus with ammonium or sodium sulphate the filtrate gives an intense purple with sodium nitroprusside and ammouia. This is attributed to cysteine and the substance in the organ extract agrees in all its reactions with those of cysteine prepared from cystine.Cysteine is regarded as an important primary conetitnent of animal cells. W. D. H.PHYSIOLOGICAL CHEMISTRY. ii. 307 Study of Autolysis by Physico-chemical Methods. REHARD CHIARI (J. Biol. Chem. 1911 9 61-63).-Polemical and explana- t o r y a reply to Benson and Wells (Abstr. 1910 ii 975). The author dealt with alterations in the state of the cells ; Benson and Wells with direct effects on enzymes. The author’s results agree with those of Claypon and Schryver in the existence of a latent period of five or six hours in the commencement of autolysis of the liver after death. W. D. H. Cutaneous Pigmentation in Normal and Pathological Conditions. WILLIAM DYSON (J. Path. Bact. 191 1 15 29S-322).- Melanotic pigment is a product of the nucleus of the epidermal cells ; melanin is regarded as the protein portion aftar separation from complex lipoids i n the nucleus.It is disposed of by thelymph stream. An increase of pigment can occur as a result of over-activity of the epidermis provoked by light heat etc. or of deficient drainage by the lymphatics. W. D. H. The Chemical and Biological Differentiation of the Three Proteins of Cow’s and Human Milk. 3. BAUER and ST. ENam (Biochem. Zeitsch. 191 1 31 46-64).-The caseinogen was separated cbemicslly partly by thawing after loag freezing and the remainder by acetic acid ; the globulin was separated from the caseinogen-free filtrate by magnesium (full saturation) or ammonium sulphate (half saturation); from the filtrate of the latter the albumin was precipi- tated by lactic acid. The biological differentiation was carried out by quantitative me.xsurements of the antigen-complement binding capacity when anti-sera for the various proteins were used as the source of complement the haemolytic action being employed as the test.A biological diff ercntintion of caseinogen albumin and globulin could be detected. The globulin is more nearly allied t o caseinogen than albumin. The colostrum proteins are similar to those of milk The globulin and albumin from milk serum and colostrum appear t o be identical. The proteins of human milk are similar to those of cow’s milk. s. B. s. The Response of the Colostral Milk of Cows to the Schardinger Reaction. RICHARD REINHARDT and ERNST SEIBOLD (Biochern.Zeitsch. 19 1 I 31 294-320).-The Schardinger reaction (decoloration of methylene blue-formaldehyde mixture) was investigated with the employment of Schern’s thermodiascope. The reaction varies under different conditions and with different fractions of a single milking. The results obtained by the authors are chiefly of veterinary interest. S. B. S. The Cutaneous Elimination of Nitrogen Sulphur and Phos- phorus. ALONZO E.TAYLOR (J. Bid. Chem. 1911,9,21-24).-Two men did daily uniform work wore clothes of the same weight aud did not suffer from obvious perspiration ; their bodies and underclothing were daily washed with alcohol and 0.5% solution of sodium carbonate. The washings were collected concentrated and analysed. The averageii. 308 ABSTRACTS OF CHEMICAL PAPERS.elimination in the two individuals was in case A (average of twenty- eight days) sulphur 0.028 phosphorus 0.003 and nitrogen 0.1 90 gram per diem. In case B (average forty-five days) the respective figures were 0.015 0.002 and 0.160. The figures are too low as the hair was omitted to be washed. W. D. H. Analyses of the Urine of the Fox Dog and Coyote. PHILTP B. HAWK (J. Biol. Chsm. 1910. 8 465-1178).-The three animals named were placed on uniform diets and estimations of total nitrogen ammonia creatine and creatinine made in their urine The figures obtained are given in full and slight differences are noted. Urocanic acid was not sought for. W. D. H. The Presence of Allantoin in Certain Foods. H. ACKBOYD (Bio.-Chem. J . 191 1 5 400-406).-The whole quantity of allantoin excreted by man on a milk and vegetable diet may be derived directly from the food.Milk white bread French beans and green peas all contain small quantities of allantoin but none could be isolated from eggs bananas or rhubarb. W. D. H. Tbe Oxyproteic Acids and their Part in Animal Metabolism. STANISLAUS BONDZYNSKI (Chem. Zentr. 1910 ii 1069,from liosmos 1911 35 Radzigzewski Pestband 680-694).-A general account of the work of the author and his pupils on the derivatives of oxyprottlic acids in the urine and other fluids of the body. Four of these compounds have been isolated from buman urine autoxyproteic acid (C 43.21%; H 4.91% ; N 24.40% ; S 0.61% ; 0 26.33%) ; oxyproteic acid (C 39.62 ; H 5.64; N 18.08 ; d 1.12 ; 0 35.54%); aZZo-oxyproteic acid (C 41-33 H 5.70 ; N 13 55 ; S 2.19 ; 0 37.23%; and urochrome (C 43.09 ; H 5.14 ; N 11-15; S 6 09 ; 0 35*53%) the two last of which are probably direct oxidation products of protein.From the barium contents of their salts (‘24.6-37% Ba) the molecules must contain a large number of tarboxyl groups and these compounds cannot therefore be classed as polypeptides as was done by Abderhalden. prochrome forms the chief pigment of the urine and the daily egcretion of this substance in normal human urine is 0*54-0.69 gram which may rise t o 1.19 gram under pathological conditions. Prom 1*5-6*8% of the total nitrogen and about 98% of the sulphur of normal urine are derived from these acids. u r i n e also contains other organic acids which may be extracted with sther and of these the daily excretion i s equivalent to about 11 grams of Rodium.Oxyproteic acids also occur in human blood-serum in sufficient quantity t o account for 25*9-40% of the total nitrogen. Under certain pathological conditions as much ab 81 7% of the oxyproteic acids present in serum consists of urochroms. The author draws the conclusion that most of the nitrogen of blood- serum is present in the form of oxyproteic acids and other organic acids and not as urea. These acids must play a part in the neutralisa- tion of the bases of the body and in the reaction of its tissues. W. J Y.PHYSIOLOcfICAL CHEMISTRY. ii. 309 Estimation of Urobilin in the Excreta and its Value as a Measure of Hamoglobin Metabolism. G. C. E. SIMPSON (Bio.- Chem.J. 1911 5 378-389).-Mout of the urobilin formed is sxcrsted usually with the fsces. In constipation t'he urobilin of the urine ribes. The total output of urobilin represents the total breakdown of hsrno- globin; that in the urine indicates the absorption capacity of the intestinal wall. The liver can deal with a very large amount of hmnoglobin before unaltered hamoglobin overflows into the urine. W. D. H. Urarosein Pigments of t h e Urine. VINCENZ ARNOLD (Zeitsch. yhysiol. Chem. 191 1 71 1-6).-The uroroseiu group contains three members a- or normal urorosein p-nrorosein and nephrorosein. The colour and spectroscopic appearances and the changes these undergo when exposed in amylic alcohol solution t o sunlight are described. They are absent from normal urine but are found in various patho- logical cases nephrorosein in convalescence from ecnrlet fever in chronic tuberculosis etc. Accepting the view of Salkowski and Herter that urorosein has a chromogen which is P-indoleacetic acid a product of intestinal putrefaction the view is advanced that the occurrence of the pigments is related t o intestinal conditions and is principally seen when there is constipation or when proteins are not readily abeorhed as on a milk diet.W. D. H. Origin of Immune Substance. J. P. MCGOWAN (J. Path. Ract. 191 1 15 262-281).-After spleen thyroid kidney tho lencocyte and lymphatic organs are excludediby extirpation and otherwise the injection of ox corpuscles into the rabbit still produces the production of the immune substance on the third day.As the game result follows feeding on ox-blood the conclusion is drawn that the production of such substances is an exaggeration of a normal process which deals with food protein; and the liver situated as it is on the direct path of foreign material entering the circulation is regarded as the possible seat of the formation of anti-substances. 1%'. D. H. The Limit of Glycuronic Acid Combination in Rabbits Immunised Against Enzymes. Juno HAMALAINEN and LENNART SJ~STROM (Skand. Arch. Physiol. 1910 24 113-126).-In rabbits immunieed against emulsin and then fed on borneol and its com- pounds the amount of borneol excreted in the urine in combination with glycuronic mid is increased and may be doubled. The effect is more marked with I- than with d-borneol. A similar effect is noted if thymol is given instead of borneol and this is regarded as evidence that thymolglycuronic acid has a P-glucoside structure.The N a t u r e of Turbid Swelling. [Parenchymatous Albuminous or Granular Degeneration.] MARTIN H. FISEIER (Zeitsch. Chem. Ind. Kolloide 191 1 8 159-1 67).-Experiments have been made to determine the nature of the tiirbid swelling exhibited by the cells of the liver kidney etc. under certain pnthologicbal ponditions W. D. H.ii. 310 ABSTRACTS OF CHEMICAL PAPERS. When pieces of fresh liver or kidney are placed in distilled water the organs develop a grey colour and exhibit the phenomenon of turbid swelling. I n dilute (0.005X) solutions of acids (lactic formic acetic tartaric hydrochloric sulphuric or nitric) the swelling takes place much more quickly.The addition of salts to the acid solutions sometimes increases the rapidity of the change in other cases i t causes a diminution. In the absence of acids the specific effects of the various salts are exhibited in the same manner. I n alkaliue solutions the turbid swelling is not observed. The turbid swelling is supposed to be connected with the production of acid in the affected cell^ and this increases the affinity of the colloids for water. The development of the turbidity resembles closely the precipitation of casein in its general characters. The swelling and the turbidity are therefore both primarily due t 9 the formation of acids in the cells. This results in an increased absorption of water whereby swelling is caused and also in the precipitation of proteins within the cells.Experirriental observations are cited in support of t h i s view. Chemical Changes in the Liver in Certain Pathological Processes. B. J. SLOWTZOFF and L. W. SOBOLEFF (Biochem. Zeitsch. 191 1 31 234-242).-Concurrently with pathological-morphological changes in the liver the chemical changes were investigated in certain cases of disease (syphilis cirrhosis etc.). Preliminary investigations showed that the amount of blood still contained in the washed-out liver made but little difference in the results. I n cases of cirrhosis due to congestion it was found that side by side with degeneration as studied histologically there is an increase in the water-content and the quantity of fat becomes sub-normal. The liver becomes richer in extractives and poorer in nucleins and peroxydases.I n syphilis the composition of the liver remains normal but there is a marked decrease in ferment-content. s. B. s. H. M. D. The Peptide-splitting Ferments of Gastric Contents in Cancer. I. WALKER HALL and G. SCOTT WILLTAUSON (J. Path. Bact. 1911 15 352-353).-The gastric contents in cases of cancer decom- pose glycyltryptophan. This confirms a statement previously made by Neubauer and Eiseher (Arch. klin. Med. 97 Hefte 5-6) ; certain . . precautions however are necessary in carrying out the test. W. D. H. Creatine and Creatinine Excration in Diabetes Mellitus. M. Ross TAYLOR (Bio-Chem. J. 1911 5 362-377).-Creatine is constantly present in diabetic urine even if the diet is free from creatine. This is regarded as due to increased endogenous protein katabolism.Total creatinine excretion is not increased in diabetes even on a diet rich in meat; but the amount even on a creatine- creatinine-free diet varies to a certain extent with the intake of nitrogen. W. I>. H. The Theories of Experimental Diabetea. E. FRANK and S. ISAAC (Arch. exp. Pccth. Yliarm. 191 1 64 293-328).-A discussionPHYSfOLOGICAL CHEMISTRY. ii. 311 of the causes of diabetes when experimentally produced by adrenaline by extirpation of the pancreas and by phloridzin ; the importance of the liver functions in producing the cotdition is insisted on. The internal secretion of the pancreas is believed to act as an amboceptor to enable the liver to fix glycogen ; pancreatic diabetes is therefore due to interference with glycogen fixation whereas phloridzin diabetes is a condition in which the kidneys themselves participate and is due to interference with dextrose fixation.W. D. H. Studies on Glycosuria. EDWARD S. EDIE BENJAMIN MOORE and HERBERT E. ROAF (Bio-Clkem. J. 1911 5 325-361).-A general consideration of the varied caiises of glycosuria. Some experimental facts on the production of this condition by inhalation of carbon dioxide and by anaesthetics are given. I n one dog deprived of its pancreas a combination of extracts of pancreas duodenum and liver caused n temporary disappearance of the sugar from t h e urine; but Inter in the same dog and in other dogs the administration of the extracts produced no effect whatever. W. D. H. Does DextrJse Arise from the Digestion of Cellulose? GRAHAM LUSK (Amer.J. Physiol. 191 1 27 467-468).-From experiments on phloridzinised dogs this question is answered in the negrt tive. W. D. H. So-called Oxaluria. S. SERKOWSKI and MOZDZENSKI (Zeitsch. pkysiol. Chevn,. 19 11 70 264-278).-Tbe examination of a large number of urines is given in detail and the possible meanings of excretion of oxalates discussed but no general conclusions are drawn. The most important point however appears to be that increase in acid phosphates favours the precipitation of oxalates and therefore the occurrence of such a precipitate does not necessarily mean an increase of oxalate excretion. W. D. H. Lzevulosuria. OSCAR ADLER (PJiiyer's A rcl'iv 19 1 1 139 93-130).-A historical review of laevulosuria is given together with an account of the methods of deteoting laevulose and separating i t from dextrose in the urine.Alimentary laevulosuria is fairly readily produced but in diabetes the condition is a rare one. I n 1490 cases of diabetes it occurred in 0.13%. Some clinical details of a few cases are given ; in a few cases there is evidence of heredity. Laevulose is not found in acidosis. W. D. H. The Clinical Importance of E. Goldschmiedt's Glycuronic Acid Reaction in Infants' Urine. ERNST MAYERHOFER (Zeitsch. physiol. Cham. 1911 70 391-397. Compare Abstr. 1910 ii 555 759).-'l'he importance of this reaction in the urine of suckling children is that it is an indication of intestinal putrefaction; urines often give i t which do not give the indican reaction.Employment of Chromium Salts for Combating Plague. PAUL KOENIG (Shem. Zeit. 191 1,% 205-206).-The process consists W. D. H.ii. 312 ABSTRACTS OF CHEMICAL PAPERS. in applying 5-10% solution of sodium dichrornate to bodies of animals excrementitious matters and places infected with plague. Other dichromates and chromates may be employed but are less convenient and permanganates are loss eff ectivo. The results of numerous experiments with plants showed that chromates act with extraordinary power and rapidity as poison8 on protoplasm. N. H. J. M. The Action of Lecithin from Different Sources in the Wassermann Reaction. CARL H. RROWINB J. CHUICKSHANK and W. GILMOUR (J. Patlr. Buct. 1911 15 361-362).-The general reaiilt obtained shows that the amount of comploment absorbed in the presence of syphilitic serum is greatest with heart lecithin and least with brain and egg-yolk lecithin.Such biological differences confirm observations as t o differences in the chemical constitution of phosphatides from various sources. It has not been yeti determined which of them is of chief importance in bringing about the syphilis reaction. W. D. H. The Influence of Adrenaline on Muscular Activity. Mme. WANDA RADWA&SKA (Bull. Acad. Sci. Cracow 1'310 B 8 728-736).- From experiments on frogs the following conclusions are drawn injection of adrenaline into the Rubstance of voluntary muscles increases their contractile force and relieves fatigue ; the total amount of work done is diminished by removal of the snprarenal capsules but can be raised to t h e normal by treating such frogs with adrenaline.Normal frogs and frogs without suprarenals but treated daily with adrenaline posjess in their nerves a higher excitability (ten-fold) than those without suprarenals simply. W. D. 11. The Effect of Oxygen and the Salts of the Blood on the Action of Adrenaline. ERICH YIEGEL (P'iige#s Archiv 191 1 138 617-637).-1n previous researches it has been stated that the activity of adrenaline is destroyed by oxidation. It was however found that the power adrenaline possesses of dilating the frog's pupil was not affected by oxidieing agents. I n the presence of blood-serum this is also true Distilled water after some hours dilates the piipil ; physiological salt solution usually contracts tho pupil but does uot affect tho subsequent action of adrenaline. The chlorides of calcium and potassium in the concentrations in which they occur in serum hnve no effect either on the pupil or on the action of adrenaline. A mixture of the three salts in the proportion in which they occur in serum has the same effect as physiological sodium chloride solution.W. D. H. Influence of Urethane in the Production of Glycosuria in Rabbits after the Intravenous Injection of Adrenaline. FRANK P. UNDERHILL ( J . Bz'ol. Cham. 191 1 9 13-18).-The subcutaneous administration of adrenaline in the dilution 1 1000 produces glycosuriit in rabbits more readily than the same amount introduced intravenouslyP€€YSIOLOGTCAL CHEMISTRY. ii. 313 in greater dilution. If the dilution is 1 500,000 or 1 125,000 no glycosuria ensues unless the animal is under urethane narcosis.W. D. H. The Relation between Chemical Constitution and Physia- logical Action ; Subatances with Unstable Carbon-Nitrogen Linking. HERMANN EMDE (Cherra. Zentr. 1910 ii 1477; from E’estschrzjl Deut. Apoth. Vw. 1910 85-105).-A number of instances are discussed in which unsaturated compounds are more poisonoue than the corresponding saturated compounds with a view t o deter- mining whether the double linking in those compounds which owe their toxcity to its presence causes at the ~ a m e time a marked instability in the molecular linking. A number of experiments mere carried out on quaternary ammonium cornpounds containing a double linking t o ascertain the effect of the position of this double bond on the stability of the carbon-nitrogen linking and the ease with which cleavage took place a t this point under the action of nascent hydrogen was taken as the measure of the stability of this linking. It was found that this carbon-nitrogen linking is unstable in those substances containing an aliphatic double bond in the ap-position (C:C*N) but not in the &-position (C:C*C*N) whilst the opposite held in the case of n double bond in the benzene ring.The presence of a benzene radicle in the molecule however modities this rule in those substances containing a double bond in the open-chain since cinnamyltrimethyl- ammonium chloride shows little stability although the double bond is i n the &-position. When compounds containing more than one cinnamyl or benzyl group in the molecule are acted on by sodium amalgam only one of these groups is split off as phenylpropylene or toluene and the others remain attached to the nitrogen in the tertiary amine.If both cinn- amyl and benzyl groups are present only the cinnamyl group is split off. Similar experiments have been carried out by Runne with compounds obtained from benzylamine by substitution in the side- chain. The quaternary ammonium compounds corresponding with aminophenylpropanol and with aminophenylbutanol are acted on by sodium amalgam according to the equations NMe,Cl*CHPh*CHMe-OH + H = CH,Ph*C€TMe*OH + NMe + HC1. NMe,Cl*CHPh*CH2*CHMe*OH + H = CH,Ph*CH,*C€IMe*OH + NMe + HCl. The carbon-nitrogen linking i n pheuylethyltrimethylammonium chloride is reudered unstable by the double bond in the benzene ring in the y8-position (C:C*C-C*N) since this cornpound is decomposed by sodium amalgam and t o this instability is attributed in part the physiologicd action of derivatives of phenylethylamine such as p-hydroxyphenyl- ethylamine hordenine adrenaline ephedrine and +-ephedrine.From the observation of Runne and of Schmidt and Butnming that the hydrochlorides of the amino-alcohol NHl\le*CHPh*CHbIe*OH and of ephedrine are converted by heating into methylnmine hydrochloride together with benzyl methyl ketone aiid phenyl ethyl ketone the conclusion is drawn that ephedrine and $-ephedrine are &methyl- amino-a-phenylpropanol NHMe*CHMe*CHPh*OH.ii. 314 ABSTRACTS OF CHEMICAL PAPERS. Phen?/leth?/Ztrimethylc~mmonium chloride CH,Ph*CH,*NMe,CI WM o-Nitrostyrene was reduced at 0' prepared in the following manner.with zinc dust and acetic acid to the phenylacetaZdeT~ydeoxime CH,Ph*CH:NOH m. p. 105'. and this further reduced by sodium amalgam tophenylethyl- ctmine CH,Ph*CH,*NH,. The aurichloride forms yellow needles melting a t 98-1 OOO and the platinichloride orange scales decomposing at 216-248'. This was then converted into phonylethyltrirnethyl- ammonium iodide colourless plates and needles m p. 230.5' and then to the chloride by means of silver chloride. The aurichloride forms yellow plates and needles melting at 156O and the platinichlwide orange-red needles. Sodium amalgan decomposes it into trimethyl- amine and a non-nitrogenous substance probably ethyl benzene.W. J. Y. Physiological Action of Some Sodium Camphenephos- phinates. JOEN A. GARDNER and W. LEWE SYMES (Bio-Chem. J. 191 1 5 390-399).-Sodium a- and /3-camphenephosphinates differ but little in their physiological effects; both are far less active than sodium pyrophosphate but more so than the orthophosphate. The effects are chiefly on the cerebral nervous systems and their cornparatjive inertness is due to rapid excretion. ALFRED CHISTONI (Chem. Zerntr. 1910 ii 989 from Arch. Farmacol. sperim. 1910 9 416-429).-Experiments carried out in vitro on this compoiind O( CH,*CO*O*C,H,*CO,H) show that it is converted into its con- stituents to some extent in distilled water at 20° completely and rapidly in weak alkaline aolution in weak acid solution after one and a-half hours at ZOO or forty minutes at 39O and in the gastric juice from dogs after twenty-five minutes at 39O.The maximum doso which may be given to animals without causing vomiting is 0.20 gram per kilo. ; the minimum lethal dose is 0-55 gram per kilo. for dogs and 1.80 gram per kilo. for rabbits. The salicylic acid appears always in the urine and not in the fseces of the animals and the normal reaction of the urine is not altered by it. Diglycollic acid O(CH,*CO,H) is less poisonous than the abovo compound W. J. Y. The Behaviour of p-Hydroxyphenylaminoacetic Acid in the Animal Body. KONRAD FROMHERZ (Zeitsch. physiol. Chem 191 1 '70 351-359).-Schotten first showed t h a t pheoylaminoacetic acid was in part excreted as mandelic acid. It was found in the present research that the hydroxy-acid is reduced in vitro t o p-hydroxyphenylglyoxylic acid and p-hydroxymandelic acid ; the latter is racemic and so differs from that found in the urine of cases of atrophy of the liver by Schultzen and Ries.If p-hydroxyphenyl- glyoxylic acid is given to animals there is no p-hydroxymnndelic acid in their urine. Further on feeding with p-hydroxyphenylaminoacetic acid the corresponding ketonic acid is formed of which the laevorotat- ing constituent is largely excreted unchanged but there is no reduction to p-hydroxymandelic acid. W. D. H. Pharmacology of Diglycolloealicylic Acid. W. D. H.PHYSIOLOGICAL CHEMISTRY. ii. 315 The Effects of Certain Animal Extracts on the Blood- Vessels. J. A. CAMPBELL (Quart. J. exp. Physiol 1911 4 1-18).- Experiments with suprarenal and pituitary extracts were made in the vessels of the limbs lung heart kidney spleen portal vein carotid artery superior vena cava and superior mesenteric artery. Suprarenal extract causes marked constriction in all cases except on the vessels of heart and lungs.I n the heart it has usually no effect but sometimes slight constriction is seen ; slight constriction in the lung vessels is rather more frequent than in the heart vessels. The pituitary extract contains at least two substances one causing contraction and the other relaxation; each produces its characteristic effect on all the arteries except the renal where contraction is hardly ever obtained the r e d t being nearly always relaxation. The Laboratory Air and its Deleterious Constituents.Chem. 19 11 50 1-1 l).-The present article relates to hydrogen sulphide. The authors examined fifty samples of air from laboratories the volume of hydrogen sulphide varying from 0.00015 to 0.2 volume per 1000. In no case did any of the workers complain of unpleasant The Disordered Metabolism in Phosphorus Poisoning. E. FRANK and S. ISAAC (Arch. exp. Path. Phurm. 1911 64 274-292). -In the early stages of phosphorus poisoning the liver cells are stimulated so that their glycogen disappears and sugar passes into the circulation ; i n later stages the liver loses its power to store glycogen and its assimilating functions are destroyed. Chemical Changes in the Liver after Phosphorus Poisoning. B. J. SLOWTZOFF (Bzochent. Zeitsch. 191 1 31 22’7-233).-After acute phosphorus poisoning the weight of the liver decreases.The quaritity of fat thereby increases whereas that of the protein decreases. This is due chiefly t o the breakdown of the phosphorus-free protein con- stituents. Of the nucleoproteins the water-soluble undergoes the greatest amount of decomposition. The liver after phosphorus W. D. H. JOSEF HABERMANN WILHELM KULKA and E. HOMMA ( ~ e i l s c h . anal. eymptoms. L. DE K. W. D. H. poisoning contains less peroxidme and protease but more &nylnse. s. B. s. The Removal of the Poisonous Properties of Strychnine and Cocaine by Peripheral Nerves. TOYOTANE WADA (If2iiger’s Archiu 191 1 139 141-163).-An emulsion of strychuine or cocaine with the sciatic nerves from several kinds of animals was filtered after three hours and injected into frogs.The toxic charncters of the alkaloids were found t o be removed. Previous heating of the nerves a t 100” does not affect the result. Blood and striped muscle do not produce the effect. I n the central nervous system the white matter is more effective than the grey in this connexion. W. D. H. Persistence of Strychnine in a Corpse. MARSHALL P. CRAM and PHILIP W. MESERVE (J. Biol. Chem 1910 8 495-496).-Strychnine was still found in a corpse which had been buried twelve monthsi. 316 ARSTRACTS OF CHEMICAL PAPERS. previously in R damp grave. The spinal cord was the only organ where’ it was discoverable as this was better protect.ed than the other organs from the action of the water iu the grave which was acid from the embalming fluid which had been used.W. D. H. Veronal. A. GR~BEB (BiocAem. Zcitach. 191 1 31 1-31).- Veronal is far more toxic than has hitherto been supposed being 3-4 times more toxic for cats and rabbits and 2-24 more toxic for dogs. It has a marked action on the abdominal vessels which caused a periodic rise and fall in the blood-pressure. It is therefore contraindicated in cases where there is au injury in the functions of the vessel8 (116 in typhus abdominalis etc.). I n treatment of cases of poisoning the abdominal vessels should be compressed and the patient kept warm The Action of Cobra Poison. IVAR BANG and EirNsT OVERTON (Riochem. Zeitsch. 1911 31 243-293. Compare Abstr. 1910 ii 229).-With tadpoles in cobra poison solution ( 1 in 1,000,000) the whole nervous system is completely paralysed within twehty- four hours If the strength of the solution does not exceed 1 in 400,000 or 1 in 500,000 the circulation remains even after several days intact and the animals recover although very slowly if transferred back again to pure water.If the concentrations exceed this amount the toxic effects are no longer reversible and the skin epithelium ig gradually a t tacked. After several immersions and recoveries the animals are still paralysed by the s.rme concentration as ivvcts active a t the first immersion. The poison penetrates about as quickly as chloral hydrate but somewhat more slowly than most narcotics. Calcium salts depress the toxicity and in solutions OF 4% calcium chloride (solutions above this concentration are themselves deleterious to tadpoles) about one hundred times more poison is necessary to produce the ef€ect which can be produced in the absence of the salt.Solutions of calcium hydroxide are still more efficient in this respect than are those of the chloride. Magnesium and sodium salts have a similar action but it is very much weaker than that produced by the calcium salts. Antivenin in the solution also diminishes the toxic effects. The so-called neurotoxin which is apparently identical with haemolysin is absorbed by blood-corpuscles much more rapidly from isotoiiic sugar solutions than from isotonic salt solutions. The corpuscles charged with neurotoxin can give it up again t o solutions which are weaker in the poison. Neurotoxin is also taken up by lecithin cholesterol and olive oil. The process is reversible. The toxicity of bee-poison to tadpoles is also diminished by the presence of calcium chloride although not to the same extent as is cobra and given oxygen iuhalations. s. 16. P. poison. 8. B. s. Crotalotoxin from the Venom of the North American Clapper Snake (Crotalus adamanteus). EDWIN S. FAUST (Arch. ezp. Path. Pharm. 191 1 64 244-273).-Crotalotoxin was prepared from the dried venom by Schmiedeberg’s ‘‘ copper alkali ” method and is the substance t o which is due the effect on the central nervouesystem especially on the respiratory centre. It is free from nitrogen and has the formda C,,H,,O,I or C,7H,,0,0,;lH,0. Ophiotoxin from the cobra has the formula C17H2sOlo. These two substances have much the same action but the local action of the crotalotoxin is more manifest. Given by the mouth i t is practically harmless. It has no effect on blood-coaguln- tion ; it is a neurotoxin a cytotoxin a cytolysin a haemorrhagin and a haemolysin. Crotalotoxin ophiotoxin and bufotalin (from the toad C,rH,tO,o) are all in the same pharmacological group and are regarded as derivatives of cholesterol. It is a member of the sapotoxin group. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9110005301

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

Chemistry of Vegetable Physiology and Agriculture. Formation of d-Gluconic Acid by Baoterium Savastanoi CARL L. ALSBERG (J. Biol. Chem. 1911 9 1-7).-The olive tubercle organism above named when grown aerobically in certain sugars forms acid. I n the case of dextrose the acid formed is d-gluconic acid. The amount of material metabolised is large when compared with that in germinating seeds or man. This bacterium converts daily an amount of energy equal to 448 calories per kilo. of organisms. The correspondirtg figure in man is 35. Antigen Formation in Protein-free Uulture Media. f. Tuberculin. ERNST LOWENSTEIN and EHNST P. PICK (Biochem. Zeitsch. 19 11 31 142-158).--The medium employed for the tubercle bacillus contained i n 1 litre of water 6 grams of asparagine 6 grams of ammonium lactate 3 grams of neutral sodium phosphate 6 grams of sodium chloride and 40 grams of glycerol.The tuberculin was obtained after several months’ culture. The active product pras a heat-stable dialysable uncoagulable substance yielding no biuret reaction but capable of precipitation by tannic acid potassio- mercuric iodide and mercuric sulphate. It is destroyed by pepsin in acid solution and trgpsin in alkaline solution but not by either acid or alkali in the concentrations employed in these experiments. Its possible polypeptide character is suggested. S B. S. Methods of Detecting Indole in Bacteria Cultures. Formation of Indole by Typhacea. K. TELLE and E. HUBER (Celt&. Bctkt. Pay. 1911 i 58 70-79).-Indole can be detected in dilutions of 1 200,000 by means of the Salkowuki-Kitauato test and in dilutions of 1 2,000,000 and 1 5,000,000 by Ehrlich’s reaction and by Crossonini’d modification respectively (Arch.IJyg. 1910 72 161). In both cases the results are better in distilled water and in peptone water than in broth. Salts especially nitrites in the Ehrlich test interfere with the reaction. The red coloration frequently observed when nitrites and aulphuric acid are added to cultures hardly ever occurs with Ehrlich’rJ test in absence of indole. W D. H. VOL. c. ii. 21ii. 318 ABSTRACTS OF CHEMICAL PAPERS. The sensitiveness of the nitrosoindole reaction is increased by extracting the red colouriag matter with amyl alcohol or ethyl acetate ; with Ehrlich's reagent chloroform may be employed. In cultures of Typhus Paratyphus Bacillus Suipestifer and in Gattner cultures the production of indole could not be detected either directly or by distillation even after prolonged growth in cultures containing 5-10% of peptone.N. H. J. M. Two New Isomerides of Thymol. C. GUILLAUMIN (Chern. Zentr. 1910 ii 1049 ; from Bull. Sci. PhawnacoZ. 1910 1'7 373-380).-The two new isomerides of thymol (Abstr. 11310 i 375) are rather less poisonous than naturally-occurring thymol. Bacillus typhosus is killed with the same quantity of p - or m-thymol whilst the o-thgmol is only half as active. Naturally-occurring thymol is also superior to the others as a n anthelmintic. W. J. Y. Action of Bacillus lactis aerogenes on Dextrose and Mannitol. 11. Investigation of the py-Butanediol and the Acetylmethylcarbinol Formed ; Effect of Free Oxygen on their P r o d u c t i o n ; Action of B.lactis aerogenes on Fructose. GEORGE S. WALPOLE (Proc. Boy. SOC. 2911 B 83 272-286).-The crude glycol produced by the action of B. lactis aerogenes on dextrose contains two optically inactive py-butanediols which yield diphenyl- urethanes melting respectively at 199.5' and 157'. The former greatly predominates (over 90%). Small quantities of the phenyl- urethanes of other unknown glycols were obtained. Acetylmethylcarbinol is formed from py-butanediol by B. lactis uerogenes in presence of oxygen and the yield from dextrose is increased by oxygen. Lzevulose is decomposed in similar manner. N. H. J. M. The Fermentation of Citric Acid in Milk. ALFRED We BOSWORTH and M.J. PRUCHA (J. Biol. Chem. 1911 8 479-482).- During the souring of milk the citric acid contained in it is changed into acetic acid and carbon dioxide. Of the common dairy bacteria tested the one only one found to have the power to decompose citric acid was Bacillus lactis aerogenes two molecules of acetic acid originating from every one of citric acid. I n the process of cheese-making the citric acid of milk is entirely fermented before the curd is pressed. W. D. H. Decomposition of Different Sugars by Bacteria. JOH. MENDEL (Cents-. Bakt. Par. 1911 ii 29 290-330).-The optimum concentration of sugars for fermentation varies from 6 to lo% accord- ing t o the bacteria employed. Decomposition will however continue with much greater concentrations and only ceases with 30-50%.Dextrose is attacked by all bacteria in concentrations up to 25-30%. Ma; tose is attacked by Bacillus Zactis ccerogenes in solutions contain- ing 50%. Lactose is readily altacked except by B. vulgccre. The amount and composition of the acids produced depend on the bacteria on the kind of sugar employed and on the concentration.VEGETABLE PHYsIoLoay AND AGRICULTURE. ii. 319 The total acid is generally high with B. coli B. Fitxianus and B. lccctb aerogenes. The relations of volatile to non-volatile acids do not show any regularity except in the case of lactose which with all the bacteria employed yielded greater proportions of volatile acids with increased concentration. Bacteria such ns R. cloaccce and B. lactis aerogenes which ferment vigorously oxidiae the cleavage products more completely with production of gas than other microbes under similar conditions.The relation of carbon dioxide to hydrogen varies with different bacteria different sugars and different concentrations. Methane was never produced. Indole is produced in 2% peptone solutions containing 5% of sodium chloride more frequently in presence of maltose than with other sugars. The production of indole does not seem to be influenced by acidity (compare Smith J. exper. Bed. 2). Fat-splitting by Bacteria. N. L. S~HNCEN (Proc. Akucl. Fetensch. Amsterdam 19 11 19 667-680).-Numerous bacteria exist which sepal ate fats anaerobically oxidise them aerobically and dinitrify nitrates and nitrites when present all these processes being due to the secretion of lipase by microbes.Several fat-splitting organisms produce two lipases a-lipase which acts both in acid and in alkaline solutions and P-lipase which is forme’d in acid media but only becomes active after neutralisation. The bacteria thrive well when supplied with fat as exclusive forni of carbon and ammonium chloride as source of oitrogen. The injurious effect of fat-splitting organisms on the quality of dairy products is chiefly due in addition t o their lipolytic properties to the production of bitter and odoriferous substauces from proteins and casein N. H. J. M. N. H. J. M. The Bulgarian Ferment. JEAN EFFRONT (Conzpt. rend. 191 I 152 463-465. Compare this vol. ii 6 I).-The discrepancies between the author’s earlier results and those of Bertrand (this vol.ii 140) as to the action of the Bulgarian ferment on milk are explained by the fact that the ferments employed by the two observers were not identical tbis having been established by an examination of Bertrand’s ferment by the author. The difference in the action of the two ferments is due however to differences in their mode of cultivation rather than to any specific difference in the bacteria themselves. The commercial Bulgarian ferment employed thern- peutically contains bacteria characterised by an intense proteolytic activity. The total acidity produced in milk by Bortrand’s preparation is high and the volatile acidity low whilst the converse tends t o be the case with the therapeutic products. The results confirm the author’s view that the clinical effects following the sour milk treabt ment depend not on the production of lactic acid but on the proteolytic The Temperature Optimum of Physiological Processes.Miss J. VAN AMSTEL and G. VAN ITERBON jun. ( P ~ o c . K. Akad. Weetertsch. Amslerdarn 191 1 598-607).-From the investigation of activit’y of the enzymzs administered. w. 0. w. 22-2ii. 320 ABSTRACTS OF CHEMICAL PAPERS. the action of yeast the conclusion of Rutgers is confirmed that the theory of Duclaux-Blackman will not explain the occurrence of an optimum temperature. W. D. H. S u g a r - f r e e Yeast Fermentation I. CARL NEUBERG arid ARNOLD HILDESHE~MER (Biochem. Zeitsch. 191 1 31 170-176).-1t was found that by the action of hydrogen peroxide and iron salts on acetone in addition to methylglyoxal (pyruvaldehyde) a Don-volatile substance fermentable by yeast was formed.It is suggested that this is possibly either the corresponding alcohol or acid formed from the aldehyde by Ctznnizaro's reaction. Experiments indicate that the salts of pyruvic acid can on treatment with yeast undergo fermentation with evolution of carbon dioxide. S. B. 8. Chemical Composition and Formation of Enzymes. 111. HANS EULEIi and SIXTEN KULLBERG (Zeitsch. physiol. Chem. 1911 71 14-30. Compare Abstr. 1910 i 345 796).-A. Infuence of Phos- phates on the Invertase and Zymase System of the Li oing Yeast-cell.-Yeast was treated during several hours on the one hand with water and on the other with dilute solutions (less than 1%) of pure or neutral- ised monosodium or monopotassium phosphate. It was then quickly dried in a vacuum and the amount of invertase determined. The phosphate treatment was without effect ; trebtrnent with stronger solutions (1 0%) of phosphate weakened the invertase.Similar experiments made on the fermentative power of yeast using pure monophosphate showed that the treatment diminished the activity of the dried yeast but increased that of the fresh yeast. Treatment with neutralised phosphate was favourable to the activity of both yeast preparations. B. Dynccrnics of Enzyme Reactions of Yeast-cells.-The invertase of living yeast-cells within the limits of experimental error shows tho characteristics of a unimolecular change. The relation between the inversion constants at 20Oand 30' is 2.04. Chloroform has no influence in retarding the invertase which is considered to be independent of the protoplasm. The inversion and fermentation constants of a number of samples of yeast are compared.For any one yeast with the same sugar ,concontration the ratio appears t o be constant but varies with the nature of the yeast. Top yeast appears t o contain a very small proportion of invertase. The inversion of sucrose takes place inside the cells and the invertase does not pass out into the aqueous solution. Dried yeast preparations only give qualitative and not quantitative information as t o the enzyme content of the living cell. E. P. A. Soil-bacteriological Investigations. B. HEIN ZE (Chem. Zentr. 1910 ii 404; from Landw. Jahrb. 39 h'rg.-Gccnd III 314-343).-The number of organisms in the soil is increased by repeated mechanical operations and by addition of str.tw sugar starch and organic nitrogen but not to any extent by sodium nitrate or ammonium sulphate. FalIom is favourable to peztin cellrilose and humus ferments to the organisms which produce ammonia and nitrates and to Azotobacter.VEGETABLE PHYSIOLOGY AND AGRICULTURE.ii. 321 Fixation of nitrogen by Azotobacter and other organisms requires arr abundance of organic matter and a neutral or slightly alkaliue reaction. The power of fixing nitrogen when diminished or lost can be restoied by suitable cultivation Humus and phosphoric acid are very favourable to Azotobacter. N. H. J. M. The Bactericidal Action of the Emanation from Radium. HANS JANSEN [with PRYTZ] (Chenz. Zentr. 1910 ii 1076-1077 ; from ovs.K. Danske Vidensk. Selskccbs. J’orh. 1910 295-331).-Surface cultures of Bcccilluspodiyiosus were exposed to air charged with different quantities of radium emanation. The air was charged by circulating it over radium bromide in a closed apparatus by means of a Prytz pump the circulation being continued until the desired concentration of emanation was obtained which was determined by Sieveking’s method and was expressed in Mache units. The cultures were contained in glass vessels connected with the apparatus. It was shown that the bactericidal action was not great 345 to 400 units per C.C. of air being necessary to kill the cultures. The action also required time; thus 1150 units per C.C. had only a slight action in one hour and 766 units per C.C.required forty-eight hours t o render the cultures sterile. Air containing less than 127.5 units per C.C. had no noticeable action. W. J. Y. The Fatdestroying Action of Moulds and the Behaviour of the Fat of Organs in Putrefaction. KOHSHI OHTA (Biochem. Zeitsch. 1911 31 177-194).-The Kamagawa-Suto method of fat and cholesterol estimation vas employed. The investigations with pure cultures on air-dried beef confirm the observation of Rumagawa that a loss of fat takes place. Five different kinds of moulds were investigated the actions OF which differed quantitatively from one another. Actinomucor repens has the strongest action destroying 60% of liver fat within six weeks. Penicillium glaucunz under the same conditions destroys only 6-8%. The attempts to cultivate Actinomucm on simple fat media did not succeed.The author shows that sources of error may take place in fat estimations during hydrolysis owing to the fact that the moulds are not destroyed by alkali and enclose certain quantities of fat. They must therefore be specially extracted. During ordinary putrefaction certain coloured substances in addition to the fat pass into the light petroleum extract and increase of this extract gives no evidence as to the formation of new fat during putrefaction. S. B. S. Production of Lactic Acid by Moulds. K. SAITO (Gentr. Bcckt. Par. 191 I ii 29 289-290).-Cultivations of Rhizopus chinensis in Koji worts beer worts and in a mineral nutritive solution with peptone and dextrose produced Z-lactic acid when kept for a week at 35’. Previous experiments with cultures of Rhizopus in mineral solu- tions containing sugar and ammonium nitrate (ibid.1904 13 154) failed to show production of alcohol. Recent results however obtained with Linduer’s method showed that Rhizopus fermentsii. 322 ABSTRACTS OF CHEMICAL PAPERS. dextrose laevulose maltose galactose melibiose and dextrin but not sucrose lactose inulin and raanose. N. H. J. M. The Action of Strontium Salts on AlgB. OSCAR LOEW (Flora 1911 102 96-1 12).-Since algae will live for some time in solutions of strontium salts i t may be supposed that strontium does not displace any of the essential metallic elements calcium magnesium etc from their position in the protoplasm complex. Such injurious effect as is produced is mainly on the chlorophyll bodies which lose their power of making starch and their normal green colour and finally die.Calcium chloride has no such action even in 1% solution. Needle-shaped crystals appear in the cells of Spirogyra growing in solutions of strontium chloride but not of calcium chloride ; they are probably an organic salt and their presence shows that something is being precipitated which normally remains in solution or is oxidised. The author considers that the nuclei and the chloroplasts of the higher alga are calcium compounds of nucleo-proteins because any thing that precipitates calcium. e g. potassium oxalate or sodium fllrorido has a strongly toxic effect. Hence calcium chloride is inert towards the chloroplasts while strontium chloride is not. On the other hand the lower algae do not require calcium and therefore are not affected by potassium oxalate or to any great extent by sodium fluoride neither are magnesium salts toxic E.J. R. Influence of Acidity on Germination. Mlle. G. PJXOMSY (Compt. soend. 1911 152,450-452).-The author does not agree with t h e usual view that the presence of acids ia unfavourable to germina- tion. Experinients carried out with citric tartaric malic oxalic and acetic acids show that these acids have a distinctly beneficial action on germinating grains the respiratory quotient beiug raised and the rate of growth accelerated. The optimum concentration of citric acid in the case of tomato seeds was 0.3%) a solution of this strength raising the respiratory quotient from 0.72 to 1.08. Tho effects observed however do not appear to be general; thus R'icinus seeds were unaffected by organic acids.The respiratory quotient of seeds is not affected by mineral acids. w. 0. w. Protein Formation in Ripening Seeds. 11. ERNST SCHULZE (Zeitsch. physiol. Chem. 1911 71 31-48. Compare Abstr. 1910 ii 644)-Unripe fruit of the vetch (Vic'ia satioa) were gathered late in August divided into bulls and unripe seeds and these analysed heparately. Tbe hulls contained very much more asparagine than the unripe seeds but less arginine although the difference in thia respect was not so great as with peas and with Phaseol~ vulgaris owing probably to the Yicia seeds being nearly ripe. Asparagine in quantities varying from 1 to 2% of the dried plant was found i n young plants harvested during May and June of TJicicc sativa Tv-folezcm prntense and Medicago satiucc.The two former &o contained guanosine whilst leucine mas obtained from t h e Vicin and perhaps also from the Medicago. The amount of asparagine in youngVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 323 leguminous plants increases when they are stored for a few days in the dark. A detailed investigation has shown t h a t young leguminous plants only contain mere traces of arginine ; in peas a little was obtained from the roots but none from the above-ground portions. It is considered that the influx of arginine to the seeds must a t the best be very small and that therefore arginine is formed in the seeds. In the ripening seed as in young leaves asparagine is used for the synthesis of protein and in general the synthesis of protein takes the same course in both parts of the plant.A comparison of the non-protein nitrogen compounds in the unripe seeds and in the rest of the plants shows that tryptophan is rapidly used by the seeds glutamine only slowly. Further investigation in this direction is expected to indicate more completely those of the non-protein nitrogenous constituents which pass into the seed and are used for protein synthesis. E. F. A. The Respiration Enzymes of Plants. \V. ZALESKI (Biochern. Zsitsch. 1911 31 195-214).-The author has investigated the effect of extrdction with various solvents on the respiration enzymes in different plants. Extraction with ethyl alcohol generally diminishes the respiratory process as compared with similar treatment with acetone and ettier.Methyl alcohol as in the case of ymsts destroys the respiratory processes entirely. The nature of the substances exerting influence on these processes is still unknown. When the process has been partly destroyed by extraction with alcohol i t can be restored by the addition of dibasic phosphates. Methyl alcohol on the other hand appears either to destroy the ferments entirely or to remove the co-fermen ts. S. B. S. The Physiological R61e of Calcium Salts. OSCAR LOEW (Miinch. med. Woch. 1910 No. 49).-A summary of the author’s work on this subject intended for pharmacologists. E. J. R. Production of Amino-acids in Plants and the Action of Formaldehyde on Potassium Cyanide. HARTWIG FRANZ EN (Chew,. Zentr. 1911 i 983-985 ; from Sitxungsber.HeideZ6erger Akad. Wiss. 1910) -It is suggested that amino-acids are produced from form- aldehyde the first assimilation product of carbon dioxide and hydrogen cyanide the first assimilation product of nitrates. Treub assumes that nitrates are first converted into hydrogen cyanide and that this unites with formaldehydes and ammonia forming amino-nitriles which are then hydrolysed to amino-acids. This hypothesis is extended and a number of examples are given showing how the production of v a r i o s amino-acids can be explained. Glycine for instance would be formed by the union of formaldehyde with hydrogen cyanide the subsequent addition of ammonia with elimina- tion of water followed by the hydrolysis of the nitrile. Alauine could be produced in a similar manner from acetaldehyde formed by the plant from malic acid ; phenylalanine from phenylacetaldehyde or from cinnamic acid with addition of ammonia,ii. 324 ABSTRACTS OF CHEMICAL PAPERS.Aspartic acid is produced by the condensation of the nitrile of glycollic acid (2 mols.) to malic acid nitrile which with ammonia yields aspartic acid nitrile. It is suggested that polypeptides may be formed by the interaction of acid amides and a-hydroxynitriles. N. H. J M. Aotive Albumen and Tannin in Plant Cells. OSCAR LOEW and THOMAS BOKORNY (Flora 191 1 102 113-1 18).-Polemical against C. van Wisselingh and against Czapek E. J. R. Excretion of Mineral and Organic Substances by Roots and Stomata. PIERRE MAZS (Compt. rend. 1911 152 452-456). -The results of experiments on maize are quoted,from which it is seen that the composition of the plant ash is altered from time to time by excretion of organic and inorganic salts through the roots and stomata.Dextrose and malic acid have been shown to pass out from the roots. w. 0. w. Soluble Carbohydrates in Asparagus Roots. FRED W. MORSE (J. Amer. Chern. Xoc. 1911 33 211-215).-The work described in this paper is part of an investigation of the composition of the asparagus plant with special reference to its manurial requirements. Analyses were made of roots collected in November of the second year after setting and dried at 50'. The average composition of the dry material of sixteen roots was as follows proteins (N x 6-25) 11.03% ; fat 1.00% ; fibre 15.39% ; nitrogen-free extract 66.34% ; ash 6.24%.The roots contained little or no reducing sugars but the total sugars amounted to 41.43% (calculated as invert-sugar) the pentosans to 8.78% and galactans to 1.04%. The chief carbohydrate present was not sucrose but on hydrolysis yielded dextrose and laevulose in proportions varying with different root extracts. Thew results agree with those of Wichers and Tollens (Abstr. 1910 ii 885 t386) but the latter authors found that solutions of the sugar- like carbohydrate reduced Fehling's solution before hydrolysis. This difference is probably due to the fact that Wichers and Tollens examined roots collected in April and July instead of November. Tanret (Abstr. 1909 i 634) isolated two distinct carbohydrates from asparagus roots but the author has not had an opportunity of confirming these observations.E. G. Basic Constituents of Helianthus annuus. E. BUSCHMANN (Arch. Pharm. 19 11 249 1-6).-Sunflower florets which are largely employed as a domestic remedy in Russia are shown to contain betaine and choline. A concentrated alcoholic extract of the Borets was dissolved as far as possible in water the bases precipitated with bismuth-potassium iodide solution and recovered from the precipitate by decomposing this with white lead and extracting with water. On adding dilute hydrochloric acid and concentrating betaine hydrochloride crystallised out. TheVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 325 mixture of betaine and choline hydrochlorides remaining in the mother liquors was separated into its constituents by precipitation with mercuric chloride the mercuri-chloride of choline being insoluble in water.T. A. H. Chemical Examination of the Root of Lasiosiphon Meissnerianus. HAROLD ROGERSON (Arne?.. J. Pharm. 191 1 83 49-56).-It is shown that the acrid properties of this root are due to the presence of a n amorphous resin. That portion of an alcoholic extract of the root which was soluble in water contained tannin and a reducing sugar which furnished d-phenyl- glucoeazone. The portion insoluble in water consisted of a dark brown resin which when inhaled was irritating t o the nostrils. and when applied t o the tongue produced a burning sensation. On extraction with light petroleum it yielded some dark green resin which on hydrolysis with alcoliolic potassium hydroxide gave (1) a mixture of palmitic and oleic acids with a small amouut of a third acid more unsaturated than oleic acid and (2) a phytosteyol C,7H,,0,H,0 'm.p. 132-133' [aID - 30*6O crystallibing from a mixture of ethyl acetate and alcohol in flat needles and yielding an acetyl derivative m. p. 110". On Eusion with melted potassium hydroxide the resin gave a mixture of volatile fatty acids composed chiefly of formic and butyric acids. A small amount of a substance giving a green coloration with ferric chloride was also obtained. No evidence of the presence of an alkaloid or glucoside in the root was obtained. T. A. H. The Composition of Malt-embryos. KIYOEISA YOSHIMURA (Biochem. Zeitsch. 191 1 31 221-226).-Hietidine choline and betaine were isolated but not arginine vernine or asparagine.The division of the nitrogen between protein ammonia and non- protein nitrogen was also determined. The ordinary methods of isolation which are described in detail were employed. Sucrose was not present but maltose and dextrose were. The conclusions as to the sugars were drawn by the application of Jolles' method of determining the changes in polarisation due to treatment with sodium hydroxide s. B. s. The Tannin Substances of the Roots in the Genus Vitis in Relation to the Disease Caused by Phylloxera. L. PETRI (Atti R. Accad. Liizcei 1911 [v] 20 i 57-65).-The loots of many kinds of vine contain a substance which gives a blue coloration with ferric chloride. The sap shows with varying intensity the characteristic tannin reactions and the substances responsible for them can be extracted with alcohol at 70-80'.The quantity of t h e tannin substances present appears to bear some relation to the susceptibility of the species t o Phylloxera the amount being greatest where t h e susceptibility is least. R. V. S. Analysis of Zygadenus intermedius. I. FRED. W. HEYL and L. CHARLES RAIFORD (J. Amer. Chem. Soc. 1911 33 206-211).-Anii. 326 ABSTRACTS OF CHEMICAL PAPERS. account is given of a preliminary investigation of Zygadenus inter- snedius a plant which sometimes causes the poisoning of sheep and cattle. Estimations have been made of the pentosans fibre proteins and ash in the leaf flower bulb and root and the results are recorded Starch was present in the bulb to the extent of 23 53% but was absent f[om other parts of the plant.Examination of alcoholic extracts showed that the leaf bulb and root contained resin sucrose reducing sugars and dextrin which were estimated in each case An alkaloid was found in all parts of the plant the leaves containing about 0.3-0*5% and the bulbs 0.24-0*39%. KARL FEIST (Arch. Pharrra. 191 1 249 7-9).-Gaw evolred during tho roasting of clay ironstone near Giessen contained about 0.3% of sulphur dioxide and caused damage to pine woods in the neighbourhood. Comparison of the ash from ( a ) pine needles from healthy trees and ( b ) pine needles from trees injured by the furnace gases showed that the latter was greater in amount contained more sulphates and was less alkaline than the former in spite of the fact that the s3ils in which the two trees were growing contained about the same quantities of sulphates.Invastiga- tions by Fricke and other$ have shown on the contrary that plants damaged by furnace gases do not accumulate sulphates in the leaves but as a rule these investigations have been made on plants the leaves of which have a shorter life-period than pine leaves. Comparative Toxicity of Essential Oils Towards Higher Vegetation. HENRI COUPIN (Compt. rend. 1911 152 529-531).- Fifty-one essential oils have been examined as to their effect on plants when these are exposed for several days to the action of the vapours. Three were without toxic effect the others were detrimental in different degrees and iu some cases (aniseed aud neroli oil) brought Lead Arsenate in Viticulture and the Consumption of Fresh and Dried Grapes.L. MOEEAU and E. VINET (Ann. Chim. anal. 19 11 18 94-96).-When vines are sprayed before flowering only a minute quantity of poison can be detected on the grapes even at a period long anterior t o picking and at picking time none could be detected. On the other hand when the spraying took place after flowering there waq a little arsenate found on the grapes and in these circumstances danger might arise to the consumer. Transformation of Proteins into Fats during the Ripening of Cheese. MAXIMtLIAN NIERENSTEIN (proc. Roy. soc. 19 1 1 B 83 301-304).-01d Cheddar cheese was found t o contain free choles- terol cadaverine putrescine and aminovaleric acid the amounts of these substances being sufficient t o account for the increased weight of the ether extract frequently observed.The assumption that fat is produced from proteins during ripening does not seem to be justified. E. G. Injury to Pines by Furnace Gases. T. A. H. about death of the plants. w. 0. w. E. J. R. N. H. J. M. Biological Investigation of Honey. EDMOND MOREAU ( A nm. TcdsiJ 1921 4 65-66).-The author has detected the presence of catalase amylase and invertin in honey but anaeroxydasesVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 327 and aeroxydaees could not be discovered. The volume of oxygen liberated from hydrogen peroxide by the cstalase present in various samples of Freoch honey (5 grams) varied 4 to 6 C.C. mhon the honey contained much protein and from 0.3 to 0.7 C.C. in the cme of samples containing but a small amount of protein.The samples showing the higher catalsse content 8130 contained the greater quantities of EDMUND C. SROREV and ELBERT C. LATHKOP (J. Arne?.. Chem. SOC. 1911 33 'i5-'78).- Robertson Irvine and Dobson (hbstr. 1907 i 894) found that two specimens of humic acid obtained from peat when treated by Zeisel's method yielded results showing the presence of 1.71 and 2.47% of methoxyl whilst an artificial specimen prepared from sucrose gave 6.47%. Methoxyl estimations have been made with the te7 soils which were used for the pentosan estimations (this vol. ii 146). Two of these soils did not contain any methoxyl; five of them gave results showing a ratio of methoxyl carbon to total carbon varying from 0.051 to 0.087 ; and the remaining three gave ratios 0.517 0.717 and 1.500.These results show that the quantity of methoxyl in a soil does not bear any relation to the total organic matter present. The origin of the methoxyl group in the soil is discussed and it is pointed out that the most important source is the lignocellulose of vegetable tissues. E G . OSWALD SCIIREINER and EDMUND C. SHOREY (J. Biol. C'hem. 1911 9 9-11).-In previous work the authors have described a cholesterol in soils in the free condition. It was named agrostrrol and differs from any cholesterol previously described in its melting point. I n plants cholesterols are usually combined as esters. The most common of thete phytosterol was identified in soils in the present research. It is in combination probably as an unchanged plant residue.Function of Manganese in Manuring. LUIGT BERNARDINI (Chem. Zentr. 1910 ii 406 ; from Stax. sper. agrar. itul. 1910 43 2 17-340).-The chief effect of mangnriese is the production of soluble calcium aud magnesium compounds from in~oluble forms so that manganese manure may be consldered as an indirect calcium- magnesium manure. Diesolved Matter Contained in Rain- Water Collected a t Lincoln New Zealand. GEORGE GRAY (Cmterbwy Ayric. CoZZ. Nag. 1910,24; Reprint 12 pp.).-Analrses of monthly samples of rain-water from July 1907 to June 1909. The average yearly amounts were as follows amylase. w. P. s. Methoxyl in Soil Organic Matter. Cbolesterols in Soils Phytosterol. W. D. H. N. H. J. M. N. per million N. per acre (lb.) % of Total N. Rainfall <-*- c-~~-. ,-'- inches. as as as as as as 1907-8 ... 21.48 0.170 0.238 0'795 0.766 1'561 50.9 49'1 ammonia. nitrates. ammonia. nitrates. Tot 11. ammonia. nit1 ates. 1908-9 ... 32.11 0'094 0.117 0'686 0*85$ 1'537 44'6 55.4ii. 328 ABSTRACTS OF CEEMICAL PAPERS. Fer million Per acre (lb.) dissolved sulphuric dissolved sulphuric A L / \ r - \ solids. chlorine. anhydride. solids. chlorine. anhydride. 1907-8. .. .. . 24.7 6'1 3 -28 120.18 29.75 15'79 1908-9.. . .. . 22.6 5.5 2.86 164-34 40.02 20.78 A n analysis of the dissolved solids in a sample representing the year 1908-9 gave the following results volatile solids 2.37 ; K20 0.77; Na,O 8*14 ; CaO 1.35 ; MgO 0.63; SiO 1.60 ; SO 2-86 ; C1 5-53 and CO 1.74 per million of rain. Compared with the earlier analyses made in 1884-8 (Proc. Austrcd. ASSOC. 1388 1 138) the results show a slight increase in the amount of ammonia and an increase in sulphates due to the increase in population and manufactories. The chlorine is a good deal lower than in the earlier period owing to diminished winds. A sample of rain (three days) from Campbell Island contained total solids 172.5 ; N as ammonia 0.084 ; N as nitrates 0.084 ; and C1 77.5 per million. Sea-water collected off the New Zealand coast was found to contain 0.025 and 0.090 per million of nitrogen as ammonia and as nitrates respectively. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9110005317

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 328 ABSTRACTS OF CEEMICAL PAPERS. A n aly tic a1 Chemistry . Air-Trap for Burettes Reagent Reservoirs etc. HEINRICH GC~CKEL (Chem. Zeit. 191 1 35 279).-A small absorption apparatus for attaching to the tops of burettes etc. is described. It consists of two glass bulbs connected at their tops by means of a glass tube. This tube extends into both bulbs and reaches nearly to the bottom of each. A side-tube a t the top of one bulb enables the apparatug to be attached t o the top of a burette or a reservoir whilst a tube on the other serves as the inlet for the air. The bulbs are about one-tbird filled with a liquid such as sulphuric acid alkaline pyrogallol bolution etc. so that moisture oxygen or other gas may be absorbed from the air before the latter enters the burette or reagent reseri-oir.The passage of the air causes the liquid to flow backwards and forwards trom one bulb to the other as the air enters or is expelled froui the burette etc. the current of air at the same time bubbling through hhe liquid. w. P. s. Capillary Analysis. ISIDOR ‘FRAUBE (Bey. 191 1 44 556-360). -The capillarity constant a physical property of liquids which is very easily measured by the author’s dropping method has been neglected almost entirely for analytical purposes. The alithor indicates how the property may be utilised for the detection of very minute traces of colloid poisons (anions cations alkaloids acids) in colloidal media and for the examination of milk. c. s.ANALYTICAL CHEMISTRY. ii. 329 A Modifled Drying Tube. W. H. MCINTIRE (J.Amer. Chew. Soc. 1911 33 450-451).-1n order to add to the rigidity of the ordinary U-tube a strut of glass with practically the same coeflicient of expansion connects the upper ends of the limbs. Sealed to the middle of the strut is a perpendicular glass rod with a loop at the upper end 8‘) that the tube may be suspended for weighing thus obviating the use of platinum or copper wire. T. S. P. The Scientific Foundations of the Systematic Separation of Combuetible Gases. GEORUES DE VOLDERE (Zeitsch. anal. Chem. 1‘31 1 50 137-l53).-‘l1he author discusses the principles of quanti- tative gas analysis in reference to gaseous mixtures containing hydrogen oxygen nitrogen carbon monoxide carbon dioxide and hydrocarbons ,of the series C,H + 2 C,H, C,H - 2 C,H - 4 and CnH2n-6.The relationship between the usual gasometric method and the theoretical scheme is indicated. H. M. D. Estimation of Bromine in Presence of Chlorides and Iodides. PAUL CLAUSMANN (Bull. Xoc. chim. 1911 [iv] 9 188-192).-The process described is a modification of that used by DQchan (Trans. 1886 49 682) and in a modified form by Carnot (Trait6 d’anal. min. Tome 2 p. 366) and consists in heating the material usually the residue of a mineral water with a solution of chromic acid in dilute sulphuric acid in a flask having a long neck drawn out into a sealed capillary. When the reaction is complete the flnsk is cooled attached to a condenser the capillary broken the bromine formed distilled into a slightly acid solution of potassium iodide and the liberated iodine titrated with N/lOO-sodium thio- sulphate.If very little bromine is present the iodine set free is estimated colorirnetrically by extraction with carbon disulphide and comparison with solutions of iodine of known strength i n the same solvent. If both iodides and bromides are present in the residue a preliminary estimation of the iodine should be made by means of nitrous sulphuric acid and carbon disulphide. Traces of bromine in such residues may be detected by Baubjgny’s fluorescein test (Abstr. 1897 ii 385). The water of the Lanternier spring Nancy contains 0.01 152 gram bromine (= 0.01713 KBr) and 0.000004 gram iodine per litre. The “ alum ” spring at Aix-les-Bains Savoy contains 0.000168 gram bromine and 0.000032 gram iodine per litre and the “sulphur” spring 0.000288 gram bromine and 0.000042 gram iodine per litre as determined by this method.T. A. H. Estimation of Bromine Fluorine Lithium and Antimony in ARMAND GAUTIER and CHARLES MOUREU (Compt. Min0r&l waters. rend. 1911 162 546-551).-See this vol. ii 300. Estimation of Dissolved Oxygen. LUDWIG W. WINKLER (Zeitsch. anyew. Chem. 19 11 24 34 1-343).-The method proposed depends on the formation of a brownish-yellow coloration when water containing dissolved oxygen is treated with ammonia and a chloro-ii. 330 ABSTRACTS OF CHEMICAL PAPERS. derivative of quinol which is sold as photographic developer under the name of “adurol.” The water to be examined is filled into a flask 0.5 C.C. of an ammoniacal ammonium bromide solution are added (this solution is prepared by dissolving 50 grams of ammonium bromide in 10% ammonia so that the wholo has a volume of 100 c.c.) and then a small quantity of the reagent.After completely filling the flask with the water the contents are mixed and the coloration compared with that given by water completely saturated with oxygen. The ammonium bromide is added for the purpose of preventing the precipitation of calcium carbonate and magnesium hydroxide. I n the case of waters containing but little dissolved oxygen sodium chloride solutions of various concentrations may be used as comparison liquids. Under 760 mm. pressure 1 litre of saturated sodium chloride solution at 20’ contains 1.07 C.C. of dissolved oxygen after it has been thoroughly aerated ; a t the same pressure arid temperature 1 litre of 3N-sodium chloride solution contains 2.25 C.C.of oxygen and 1 litre Estimation of Total Sulphur in Urine. STANLEY R. BENEDICT (J. Biol. Chem. 1910 8 499-502).-The author defends his method against the criticisms of Denis (this vol. ii 66). W. D. H. R RICHTER (Pharm. Zeit. 1911 56 148-149).-Total sulphur dioxide.-Fiftyc.~. of the sample are delivered from a pipette into a flask containing 25 C.C. of N-potassium hydroxide; the end of the pipette should dip into the liquid. After gently shaking a few times the solution after an interval of fifteen minutea is mixed with 10 C.C. oE dilute sulphuric acid (1 3) and then titrated with A:/50-iodine with starch as indicator. Tree sulpl~ur dioxide.-Fifty C.C. of the sample are delirered from a pipette into a flask filled with carbon dioxide 5 C.C.of dilute sulphuric acid are added and the solution is titrated with iodine. The organically-combined sulphur dioxide is found by difference. New Method for Estimating Sulphuric Acid and Sulphates. VICTOR AUGER and M. GABILLON (Compt. rend. 191 1 152 441-443). -The method which consists in reducing the sulphate by means of hydrogen iodide and titrating t h e hydrogen sulphide formed with standard iodine solution is said to be accurate to the extent of 1 in 300. It is not applicable to the estimation of barium sulphate. The sulphate is heated a t 80-110’ for twenty to twenty-five minutes with potassium iodide and a mixture of phosphorous phos- phoric and pyrophosphoric acids in a long necked flask having a side-tube. The gases liberated are carried away in a current of dry carbon dioxide the iodine vapour removed by passing through a tube containing calcium iodide arid the hydrogen iodide absorbed by a solution of the gas containing phosphorous acid.The hydt ogen sulphide is absorbed in zinc acetate solution and titrated in the usual way It is important to avoid the presence of metaphosphoric acid (which causes too vigorous reduction) and of moisture in the reduction flask. w. 0. w. of N/l-sodium chloride 4.39 C.C. of oxygen w. P. s. Estimation of Sulphur Dioxide in White Winee. L. DE K.ANALYTICAL CHEMISTRY. ii 331 Volumetric Estimation of Sulphuric Acid or Sukphates. FEHNAND REPITON (Non. Sci. 1910 [iv] 24 382-384).-Briefly the process is as follows the solution is acidified with hydrochloric acid heated to boiling and mixed with a known volume of N/4-barium chloride.The liquid is transferred to a 150 C.C. measuring flask and after adding ammonia in excess a volume of N/4-patassium dichromate equal to that of the barium chloride wed is added. It is recommended to add to the ammonia a little calcium chloride to decompose any carbonate present. When cold the solution is diluted t o the mark and 50 C.C. of the clear filtrate are taken for the purpose of estimating the excess of chromic acid present. The solution is mixed with an excess of hydrochloric acid and 0.1 gram of mercuric chloride dissolved in water is added. After introducing a few lumps of marble to create an atmosphere of carbon dioxide N/4-stannous chloride recently titrated with Nl/4-potassium dichromate is added until a slight turbidity of mercurous chloride is formed.The difference between the two chromate titrations represents the sulphuric anhydride. Qualitative Analysis of Complex M i x t u r e s of Salts. B. R~OREAU (Bull. Sci. Pharmcccol. 1910 17 ; Reprint 6 pp.).-A number of tests and processes are given for detecting the prebence of two or more substances in mixtures of the same when the substances interact with one another or yield similar reactions. The following substances are dealt with an outline of the tests recornuieucled being given'in parentheses Sulphate in the presence of sulphide (boil with hydrochlot ic acid to :expel hydrogen sulphide and test for sulphate in residual solution) ; sulphate and sulphite (liberation of sulphur dioxide) ; sulphite and thiosulphate (precipitation of sulphur from the thiosulphate by acids ; sulphites yield a red coloration when treated successively with sodium nitroprusside zinc sulphate and potassium ferrocyanide) ; nitrate sulphite and siilphide (nitrate detected by formation of ammonium picrate) ; phosphate and arsenate (molybdic acid does not yield a precipitate with arsenates in the cold); chloride bromide or iodide and sulphide (precipitate sulphide with a zinc salt) ; nitrate and chlorate (the nitrate yields ammonia wheu treated with zinc and [Analysis of Hyposulphites.] KAIEL JELLINEK (Zeitsch.anorg. Chem. 1911 73 93-134).-See this vol. ii 278. Estimation of Ammonia in Urine. OTTO POLIN (J. Biol. Chenz. 1910 8 497-498).-The use of sodium carbonate is still main- tained t o be better in most cases in spite of Steel's criticisms (this vol.ii SS) for even if a sediment of magnesium-ammonium phosphate is present in certain twines t h a t deposit can be dissolved by acid and kept in solution by potassium oxalate. The Phenolsulphonic Acid Method for the Estimation of N i t r a t e s i n Water. 111. and IV. The Chief S o u r c e s of Error in the Method. Ebm M. CHAYOT D. S. PRATT and H. W. REDFIELD (J. Arner. Chem. Soc. 1911 33 366-381 381-384. Compare Abstr. 19 10 ii 545).-111. Phenolsulphonic acid reagents A new process for this is described. 1,. DE K. sodium hydroxide) etc. w. P. s. W. D. H.ii. 332 ABSTRACTS OF CHEMICAL PAPERS. containing monosulphonic acids are subject to change with age and yield results which are greatly affected by temperature concentration variations in the character of the alkali used and in time of contact between the reagent and the water residue etc.They cannot be satisfactorily employed with permanent standards. I n order that accurate results may be obtained chlorides carbonates and organic matter must be removed before applying the test. Chlorides are best eliminated with silver sulphate and organic matter by the use of “ aluminium cream.” Nitrites present in small amount do not aopreciably affect the final results but when present in large amount they must be destroyed or corrected for. Waters containing much magnesium or iron compounds yield residues the particles of which are penetrated only with great difficulty by the sulphonic acid reagent.IV. The phenolsulphonic reagent which must contain no mono- sulphonic acid (compare preceding section) is best prepared as follows 25 grams of pure phenol are dissolved in 150 C.C. of concen- trated sulphuric acid 75 C.C. of fuming sulphuric acid containing 13% SO are added and the mixture heated for two hours at looo. The results are not always trustworthy with this reagent when the water contains over 50 parts par million of nitrogen as nitrates whilst serious discrepancies arise should the nitrate content be over SO parts per million. I n determining the nitrates in water chlorides and organic matter must first be removed as mentioned in the preceding section. If the nitrites present are in excess of one part per million of nitrogen they must first be destroyed by heating the sample with a few drops of hydrogen peroxide. The phenolsulphonic reagent prepared as above may be used as a permanent standard. A series of standards prepared from tripotsssium nitrophenoldisulphonate (Abstr.1910 ii 545) are also recommended. This latter compound is best prepared by adding finely powdered potassium nitrate in very small portions at a time to the cold disulphonic acid reagent prepared as above The resulting sollition is diluted dry barium carbonate added until a deep yellow colour is obtained the precipitate collected and well washed with boiling water. The barium in the filtrate and washings is precipitated with potassium carbonate and the required potassium salt obtained in the usual manner.The standards are not prepared by direct weighing but by comparison with a known weight of potassium nitrate treated with the sulphonic acid reagent in the usual manner. All attempts to sulphonate 0-nitrophenol with fuming sulphuric acid Estimation of Inorganic and Organic Phosphorus in Meats. HARRY S. GRINDLEY and E. L. Ross (J. Biol. Chern. 1910 8 483-493).-The neutral ammonium molybdate method as modified by Emmett and Grindley the magnesia mixture method of Forbes and his colleagues and the barium chloride method of Siegfried and Singewald give practically the same results for inorganic phosphorus at 100’ resulted in violent explosions. T. s. P.AXALYTICAL CHEMISTRY ii. 333 i n cold aqueous extracts of beef. The coagulation of the protein i n such extracts does not change organic into inorganic phosphorus t o any appreciable extent.W. D. H. Estimation of Phosphoric Acid by Neumann’s Method. J. M. KRASSER (Zeitsch. Nahr. Genussm. 19 11 21 198-200).-The author finds that this method (precipitation of the phosphoric acid with molybdic acid boiling the washed precipitate of ammonium phosphomolybdate with a known quantity of N/2-sodium hydroxide solution and titration of the excess of the latter the loss of alkalinity due to the removal of the ammonia being a measure of the phosphoric Partial Analysis of Natural Phosphates as a Guide to Their Conversion into Superphosphates. P. HARDY and JOS. VANDORMAEL (Bull. SOC. chim. Belg. 1911 25 43-57).-In convert- ing natural phosphates into superphosphates sulphuric acid is used up not only in converting tricalcium phosphate into calcium hydrogen phosphate but also in decomposing the subsidiary constituents such as iron phosphate aluminium silicate c,tlcium fluoride and calciuin and magnesium catbonates.Complete analyses are given of three natural phosphates. From comparison of these results with (1) results of analyses of superphosphates made from the phosphates (2) factory data regarding the manufacture of these superphosphates and (3) calculated quantities of sulphuric acid necessary for the con- version of all the ingredients known to be present in the crude phosphates used it is shown t h a t all the data necessary for determin- ing the quantity of sulphuric acid needed to effect the conversion of :I given sample of natural phospliates can be obtained with sufficient accuracy by determining the total lime phosphoric acid sulphuric acid alumina and ferric oxide.Estimation of Potassium as Potassium Platinichloride. HEINRICH FBESENIUS and PAUL H. M. P. BRINTON (Zeitsch. anal. Chem. 1911 50 21-35). Experiments with pure potassium chloride and mixtures of i t with sodium chloride calcium chloride magnesium chloride and barium chloride; also on the use of alcohol of different strength when separating potassium and sodium chlorides by the platinum chloride process. Small proportions of calcium magnesium or barium chlorides do not interfere but when present in excess it is advisable t o remove these before the treatment with platinum chloride. Alcohol oE 80 vol. % is recommended for removing the excess of platinum chloride and the double sodium compound.The weighed potassium platinichloride if at all lumpy should be redissolved in boiling water and evaporated in the platinum dish on a not quite boiling water-bath and then again dried at 130’ for at Volumetric Estimation of Potassium by the Cobaltinitrite Method. OLIVER M. SHEDD (J. Ind and Engin. Chenb. 1910 2 379). -A detailed account of numerous experiments bfised on the work of acid) yields trustworthy results. w. P. s. T. A. H. least two hours. L. DE K. VOL. C. ii. 23ii. 334 ABgTRACTS OF CHEMlCAL PAPERS!. Drushel (Abstr. 1908 ii 66 735) on the estimation of potassium (especially in soils) by the cobaltinitrite method ; the following procedure was found to give the most uniform results; The solution containing the potassium salt (after the preliminary work to bring i t to this stage is completed) is evaporated down to a volume of about 5 c.c.slightly acidified with acetic acid and 15 C.C. of fresh nitrite reagent added. The larger amount of nitrite reagent facilitates filtration and ensures an excess of reagent after evaporation; the salution is then evaporated on the water-bdth until the contents became a thick syrup but long heating must be avoided ; the remainder of the anakysis is carried out as previously described. F. DI. 0. M. Estimation of Lithium. ERNST MURMANN (Zeitsch. anal. Chenc. 1911 50 171-174).-Lithium chloride may be extracted from its mixtures with alkali chlorides by means of pyridine. The solution is evaporated and the residual mass converted into lithium sulphate and weighed as such.It is as well to dissolve the undissolved chlorides in water t o evaporate to dryness and to once more extract with pyridine which is then added to the main solution although i t is almost superfluous to do so. The old phosphate process for the estimation of lithium gives very untrustworthy results and should not be employed. L. DE K. Colour Reactions of Caloite and Aragonite STANISLAUS J . THUGUTT (Cheni. Zentr. 1910 ii 1084; from Kosmos 1910 35 RadziszewBki Festband 506-612).-The sensitive reaction proposed by Meigen for the identification of aragonite is not suitable for use in the case of dark-coloured specimens of the mineral. For such specimens Congo-red or an alkaline solution of alizarin may be employed ; with these reagents aragonite is coloured pink whilst calcite remains uncoloured.Silver chromate is a still better reagent as under definite conditions as to temperature and concentration it colours aragonite a deep red whilst calcite remains unaffected. The coarsely-powdered mineral should be treated with N/ 1 0-silver nitrate solution for one second then washed and moistened for a moment with 20% potassium dichromate solution. Aragonite is 1800 times more sensitive towards silver chromate than is calcite. w. P. s. Separation and Estimation of Barium in the Presence of Calcium and Magnesium by the Action of Acetyl Chloride in Acetone on the Mixed Chlorides. FRANK A. GOOCH and C . N. BOYNTON (Amer. J Xci. 1911 [iv] 31 212-220).-The method depends on the precipitation of hydrated barium chloride from its aqueous solution by means of a mixture consisting of four parts of acetone and one part of acetyl chloride; calcium and magnesium chlorides if present are not precipitated by this reagent. A con- centrated solution of the mixed chlorides is placed in a beaker which is immersed in a water-bath at a temperature of 1 5 O and about 30 C.C.of the reagent are added a t the rate of 2 drops a second; thisAhJALYTlCAL CHEMISTRY. ii. 335 Pate ihhay be increased to about 5 drops a second when most OF the barium chloride has been precipitated. The precipitate is 1 hen collected on an asbestos filter washed with acetone dried at 1 3 5 O or ignited at a dull-red heat and weighed as anhydrous barium chloride. The quantity of reagent mentioned is sufficient for the precipitation of 0.1 gram of barium chloride in the presence of 0.5 gram of calcium and magnesium chlorides; the salts should be dissolved in the smallest possible volume of water.The method cannot be recommended for the beparation of barium from strontium. w. P. s. The Electrolytic Estimation of Zinc in Ores. GEO. KEMNERER (J. I n d . Bngin. Chem. 1910 2 375).-The account of an investigation undertaken to ascertain whether the zinc content of an ore can be rapidly and accurately determined electrolytically previous workers having stated that too high results are usually obtained; the conclusions drawn are that if the electrolyte contains 20-25 grams of sodium hydroxide and a current of ND, = 3.1 A is employed that rapid and accurate determinations can be carried out.The electrolytic cell consisted of a cylindrical nickel gauze cathode which fitted loosely into a 150 C.C. Jena beaker and a revolving propdsr-shaped anode. The cathode surface was about 160 sq. cm. whilst the anode was rotated about 600 times per minute Weighed pieces of zinc were dissolved in nitric acid 2 C.C. of sulphuric acid added and the solution evaporated until dense fumes of sulphur trioxide were evolved; after cooling it was transferred to the beaker diluted to 100 c.c. solid sodium (or potassium) hydroxide added and the hot solution rapidly electrolysed. When deposition was complete the cathode was removed without opening the switch plunged into a large beaker of water dried with absolute alcohol and ether which had been distilled over sodium heated a t 70-looo cooled and weighed atonce.The application of this method t o a carbonate ore which mas previously treated by the modified Waring method (compare Low’s “Technical Methods of Ore Analysis”) is also described in the original. I?. M. G. &I. Estimation of Copper in Pyrites. I. MAJEWSKI (Chem. Zentr. 1910 ii 1092 ; from liosmos 1910 35 IZadzisxewvlci irestband 697-601).-The author prefers to fuse the pyrites with six times its weight of potassium yersulphate instead of the treatment with bydrochloric and nitric acids recommended by Fresenius in order to obtain the copper in solution. w. P. s. Volumetric Estimation of Free Acid and Basic Alumina in Aluminium Salts. THOHAS J. I. CI~AIU (J. SOC. CAem.Ind. 1911 30 184-185).-To estimate the free sulphuric acid an excess of normal potassium fluoride is added to the solution of the aluminium sulphate ; this yields potassium sulphate and insoluble potassium aluminium fluoride (AlF,,SKF) ; as both the.-e salts are neutral the free sulphuric acid can be titrated by means of standard alkali using phenolphthalein as indicator The potassium fluoride solntion is 23-2ii 336 ABSTRACTS OF CHEMICAL PAPERS. prepared by dissolving the pure salt in distilled water bringing to U 1.45 and neutralising if necessary with potassium hydroxide or sulphuric (hydrofiaoric) acid until about 1 C.C. i n 10 C.C. of distilled water shows a faint pink colour with phenolphthalein. lnsoluble matter is removed the clear solution diluted until it has I) 1.35 (0.5 gram of potassium fluoride per c.c.) and preserved in a glass b d t l e internally coated with wax.I n the actual estimation a solution containing about 1-3 grams of alumina per 200 C.C. is used; 20 C.C. of the clear solution are added gradually and with constant stirring to 10 C.C. of the potassium fluoride solution previously diluted with 50 to 60 C.C. of distilled water and 0.5 C.C. of 0.2% phenolphthalein solution. Standard alkali is then added until a faint but permanent pink colour is obtained. If the original sulphate is basic that is contains the salt Al,O(SO,) a deep red colour is developed on the addition of the fluoride and phenolphthalein. A rough titration ig then made by adding standard acid until the colour is destroyed.To another portion of the clear basic solution an excess of standard sulphuric acid is added heat is applied to enswe combination between the basic salt and acid and the excess of acid left is titrated as in the case of a specimen containing free acid. If sodium salts are present i t is advisable to add 20 to 30 C.C. of a neutral saturated solution of potassium sulphate to the solution of the aluminium salt before i t is mixed with the potassium fluoride. By this means the formation of insoluble basic double fluorides is avoided. If ammonia is present i t must be removed by heating with a known excess of standard alkali and it is essential t h a t in every case insoluble matter should be removed before adding the potassium fluoride. Free acid cdn be estimated in the case of iron and zinc salts by a similar method but a larger excess of potassium fluoride is necessary.J. J. S. Application of ‘‘ Cupferron ” in Quantitative Analysis. REMIGIUS FRESENIUS (Zeitsclh. a n d Chent. 191 1 50 35-43).-A series of experiments to try the accuracy of Baudisch’s “ cupferron ” process (Abstr. 1910 ii 76). The results show that the method is trustworthy for the estimation of ferric iron in the presence of aluminium chromium nickel cobalt zinc alkali earths and also manganese ( ferromanganese ores of manganese). Copper is pre- cipitated with the iron but may be removed from the precipitate by treatment with ammonia. I n the estimation of copper the “cupferron” process gives good results in the absence of lead and bismuth. L. DE K. Efficiency of Borax Bead Tests for Nickel and Cobalt.LOUIS J. CURTMAN and P. ROTHRERG (J. Amel.. Chem. Xoc. 1911 33 188-189).-Experirnents have been made to ascertain the extent to which nickel and cobalt can be detected in presence of each other by means of borax bead tests. It has been found that a blue bead jndi-ANALYTICAL CHEMISTRY ii. 337 cating the presence of cobalt is obtained up to a point at which the ratio Ni Co is 30 1. If the proportion of nickel is still further increased beads of an uncertain brownish colour are produced until the ratio Ni Co= 50 1 when a decidedly brown bead is formed demonstrating the presence of nickel. It follows therefore t h a t borax beads can only serve as confirmatory tests and are not trustworthy unless the results are positive.E. G. An Organic Reagent for Chromium. PAUL KOENIG (Chem. Zed. 19 11 35 277-278).-Ari aqueous solution of sodium 1 S-dihydroxy- naphthalene-3:6-disulphonnte is a very sensitive reagent for chromium ; i t yields a red or violet coloration with chromic acid chromates or dichromates the reaction being obtained with as small a quantity as 0.0008 mg. of chromium. The reaction also allows chromium to t x detected in the presence of iron as solutious of iron salts yield a green coloration which is destroyed immediately by the addition of phosphoric acid whilst the violet coloration due t o chromium is iiot affected. The test may be rendered quantitative by comparing Ihe coloration obtained with. that produced by a known quantity of chromium and is particularly useful for detecting the presence of small quantities of chromium in the ashes of plants.w. P. 8 Volumetric Estimation of Molybdenum. EDMUND I(NEcHvr and F. W. ATACK (Analpst 1911 36 98-100).-The apparatus consists of an eight-ounce conical fl<tsk carrying a trebly perforated riibber cork. Ous perforation is fitted with a Buusen valve not closed as customary with it solid glass bead but fitted*at the top with a glass tube into which fits a small india-rubber stopper. Through this passes a platinium wire to which is attached a rod of pure zinc. Another hole carries a tube connected with an apparatus for generating csrbon dioxide and the third one carries the adapter for the burette. The molybdenum solution ( = about 0.05 gram of the metal) is placed i u the flask and after adding a few pieces of granulated zinc (tho zinc rod being lifted out of the solution) t h e strenrn of carbon dioxide is kept up until the zinc has completely dissolved.The rod is then lowered for a short time to ensure complete reduction and then removed and washed with recently boiled water introduced down the valve from a wash-bottle. The warm solution is then titrated with a 4% standardised solution of methylene-blue (Knecht J. SOC. Dyers 1905 21 9) until t.he characteristic blue shade is obtained. Thepresence of iron does not interfere with the process but titanium tungsten chromium and vanadium should be absont. L. DE R. Determination of Minerals by Colour Reactions. PAUL GAUBERT (Bull. SOC. fi'anp Mirc. 1910 33 324-326).-L. Ltivy (Abstr.1887,304 305) employed the colour reactions given by certain organic substances (morphine codeine a- and &naphthol resorcinol phenol etc.) dissolved in strong ~ulphuric acid for the detection of titanic columbic tsntalic stannic molybdic vanadic antimonic arsenic acids etc. When this method has been applied to minerals it has been usual first t o decompose the miueral. This is howPTer,ii. 338 ABSTRACTS OF CHEMICAL PAPERS. unnecessary; the finely powdered mineral need only be treated for some hours with the acid solution in a match-glass or test-tube. I n certain cases the addition of a suitable nmonnt of water accelerates the production of the colour. In addition to the organic substances indicated by Lhy pnpaverine may also be used. This gives with sulphuric acid a red tint which turns to blue with vanadic tungstic chromic and titanic acids and to brown with stsnnic acid This rtff ords a ready means of distinguishing between cassiterite rutile and zircon ; and by the rapidity of the coloration between wulfenite (very quickly) and vnnadinite and crocoite (slowly).The titanium minerals rutile brookite anatase ilmenite sphene and keil haui te give a crimson colour with morphine and they can be distinguished the one from the other by the velocity of the reaction L. J. S. Detection and Estimation of Small Quantities of Antimony PHILIP SCHIDROWITZ and kIAROLD A . GOLINBROUGH (Analyst 19 1 1 36 101-103).-A colorimetric method in tended for fractions of a milligram of antimony in a volume of 10 C.C. After adding 0.5 C.C.of hydrochloric acid and 0.1 C.C. of a 10% solution of gum acacia so as to ensure a colloidal sulphide hydrogen sulphide is passed and the coloration compared with a standard solution in a colorimeter as usual. I n some cases a provisional separation of the antimony by Reinsch's test is unavoidable. The copper with the deposit is heated at 70' for a few minutes with 5 C.C. of 5% potassium hydroxide 10 C.C. of water and anexcess of permanganate. The solution is poured off boiled filtered and any permanganate still present destroyed by boiling with 1 C.C. of solution of tartaric acid. The colourless soIution is then suitably diluted and an aliquot part made up to 10 c.c. when it is tested as directed. The results are decidedly too low but admissible in the circumstances.L. 1)E K. Estimation of Gold and Silver in Rich Copper Ores. JULIUS LOEVY (Chew&. Zeit. 191 1 35 278).-It is recommended that ores containing large quantities of copper be mixed with sand in such quantity that the quantity of copper is reduced to 6%; the mixture is then Fiisect in a crucible in the ordinary way. The resulting button of lead may be cupeiled directly in order to obtain the gold and silver present. w. P. s. Separation of Platinum and Tin. LOTHAR WOHLER and A. SPENGEL (Zeitsch. and. Chem. 191 1 50 165-171).-The authors arrive a t the following conclusions The Separation of platinum and tin cannot be effected by means of reducing agents ; from alloys the tin cannot be properly extracted with acids and the sulphides cannot be separated by means of strong hydrochloric acid or sodium hydroxide.The separation may be carried out by volatilising the tin sulphide in a current of hydrogen sulphide or in a current of bromine but this is a tcilious process. Hydrolytic decomposition by means of sulphuric acid requires heating at 150-200° in a sealed tube. The best and safest plan is to heat the solution of the mixed chloridesA NA LYTICATJ CHEMISTRY. ii. 339 with dilute sulphuric acid which precipitates the tin oxide Without removing the deposit the platinum is then recovered electrolytically using a current of at first 1.1 lator 1.5-1.7 volt ; ND, = 0.2 ampere temperature 5 0-60”. L. DE K. The Action of Potassium Permanganate on Organic Com- pounds. JOSEPH HICTPEI~ (Bull. Acacl. Sci Cracow 1910 A 601 -605)-The author finds that under certain definite conditions n large number of organic compounds can be oxidised completely by potascium psrmanganate which can therefore be used for their estimation. I n general all cornpounds soluble in water alkalis or phosphoric acid and containing *OH groups can be oxidised such as polyhydric alcohols sugars phenols and hydroxy acids.The solution of the substance is heated on the water-bath for one and a-half hours with itT/5-potassiurn perm tnganate solution containing 20 grams of crystdlised phosphoric acid per litre. The excess of permanganate is then determined. On the other hand compounds containing the radicle CH3*C-/ are \ not fully oxidised neither are those containing CH especialiy if it is near to a CO,H group.The author has worked out a schematic representation for the analysis of known organic substances. Incidentally he points out that solutions of potassium permanganate containing phosphoric acid undergo practically no change on keeping. E. J. R. Estimation of Quinol. JOHANNES PINNOW (Zeitsch. anal. Chem. I 9 1 I 50 154-164).-Quinol may be completely extracted from its aqueous solutions by extraction with ether in a Partheil apparatus. ‘The ether is then evaporated and the residue dried in a water-oven 1to constant weight. Quinol may also be estimated by boiling for six minutes with Pehling’s solution ; the precipitate is ignited and then convei ted into ,metallic copper by heating in a current of hydrogen. As however 4he reduction depends on the concentration of the solution reference should be had to tables.Potassium quinolsulphonate also similarly Ireduces the Fehling’s solution ; 1 mol. of quinol = about 6 atoms of copper. Although Fehling’s solution is not reduced by sulphites these strongly affect the reducing power of quinol which may be increased one and a-quarter or even one and a-half times. A. GOLDSOBEL and E. SONNEN- BERU (Chern. Zerttr. 1910 ii 1095; from Kosmos 1910 35 Radxisxewski Festband 571-584).-The authors have investigated this test and recommend the following method of applying i t Twenty C.C. of the solution under examination and 20 C.C. of the same solution diluted with 10 parts of water are treated in separate flasks with 2 C.C. OF Nylander’s reagent (basic bismuth salt with 12.5% of sodium hydroxide) ; the mixtures are boiled €or ten minutes under a reflux apparatus. While the mixtures are still hot the precipitates L.DE K. Nylander’s Test for Dextrose. . _ii. 340 ABSTHACTS OF CEEMICAL PAPERS. are collected on filters washed thoroughly with water and examined for any traces of blackening this coloration being obtained when dextrose is present. The control experiment with the diluted solution is necessary,for the reason that the reaction does not take place if the solution contains more than 5% of the sugar. w. P. s. Estimation of Reducing Sugars. STANLEY R. BENEDICT (J. Biol. Chern. 1911 9 57-59).-1n place of Pehling’s solution the following mixture is recommended as i t is more sensitive and keeps well indefinitely copper sulphate 18 sodium carbonate 200 sodium citrate 200 and potassium thiocyanate 125 grams 5% potassium ferrocyanide solution 5 c.c.and water up to a litre. The copper sulphate is the only constituent which needs careful weighing. Twenty-five C.C. of the mixture are reduced by 0.05 gram of dextrose and by 0.053 of laevulose. The ferrocyanide prevents precipitation of the cuprous oxide and the end-point is the disappearance of the blue colour. W. D. H. [A Simple Method for the Estimation of Sugar in Blood.] E. FRANK (Zeitsch. physiol. Chem. 19 11 70 408. Compare Michaelis and Rona this vol. ii 73 ; Aloeckel and Frank Abstr. 1910 ii 116). -A question of priority in relation to the methods of removing protein from blood. It is admitted that Michaelis and Rona were first. W. D. H. Estimation of Amylaceous Substances in Dresaed Pro- visions.P. CARLES (Ann. Chim. anal. 1911 16 89-90).-Food chemists are often called on to ascertain whether starch has been fraudulently added t o dressed provisions such as pat& galantjnes etc. and the general method of procedure is t o convert the starch into sugar. The author has examined the fresh and genuine livers of various animals and finds t b a t all of them contain reducible sub- stances which must be allowed for in the estimation. The quantities found were equivalent to the following percentage amounts of starch duck 1.39 goose 1.93 bullock 2.23 pig 2.77 calf S.01. E. J. R. Some New Tests. FRED KLEIN (J. Ind. Engin. Chem. 1910 2 389).-The following distinctive reactions are described (1) To distingujsh between anhydrous and glacial acetic acid the former yields a red precipitate of amorphous selenium when boiled with a crystal of selenious acid (or preferably sodium selenite) whilst with glacial acetic acid the solution remains clear.(2) To differentiate between methyl and ethyl alcohols if dilute the alcohol must be concentrated by distillation; a small quantity is then treated with a few drops of selenic acid (H,SeO,) and a trace of silver halide (preferably bromide) when ethyl alcohol yields a colour- less amorphous precipitate soluble on the addition of water whilst a solution of methyl alcohol (common wood spirit) remains clear or in exceptional circumstances a crystalline precipitate is deposited. This test can also be employed for esters. (3) To distinguish between the alkaloids the extracted alkaloid isANALYTICAL CHEMISTRY.ii. 341 (a) dissolved in sulphuric acid (94-95%) and (6) a trace of sodium selenite (Na,SeO,) then added the solution warmed and the following colour reactions are observed. Digitaline ( a ) slight coloration ( b ) brown. Aconitine ( a ) slight coloration ( b ) brown. Atropine (a) slight coloration ( b ) brown. Brucine ( a ) rose-pink ( b ) brown. Morphine and cocaine (a) green in cold ( b ) black precipitate. Codeine (a) light brown ( b ) black precipitate. Caffeine and sparteine (a) no coloration ( b ) no coloration. Veratrine ( a ) cherry-red ( 6 ) purple. Quinine (a) slight coloration on heating ( b ) purple. Cantharidine ( a ) no coloration ( b ) with addition of alcohol a slight purple coloration in the cold which darkens on heating.(4) To detect small quantities of petroleum in turpentine when the official test has proved unsatisfactory a copper sulpbate solution (5- 10%) is treated with about half its volume of petroleum and a crystal of potassium iodide added to the clear solution; this dissolves with a purple coloration and after shaking slowly turns a yellowish-brown ; in the case of turpentine the mixture with copper sulphate is not clear; potassium iodide gives a purple-red colour which with pure turpentine turns green after shaking. The presence of “ rosin ” can be detected by its odour and the brown coloiation of the solution. (5) A test for nitric acid the acid must have a minimum concen- tration of 40% and if more dilute should be evaporated to dryness in the form of a salt; the reagent employed conbists of a truce of powdered tellurium in fuming sulphuric acid (2-3 c.c.) which forms an eosin-coloured solution and is then treated with 95% sulphuric acid (1-2 c.c.).Two equal portions of this solution are heated until decolorised to one is added the nitrate to the other a drop or more of the reagent both tubes are slightly warmed and the one containing the nitrate treated with a further quantity of the reagent when immediate decolorieation occurs whereas the other one remains an eosin-red colour. This method is stated to be applicable to the quantitative estimation of nitric acid. Strychnine ( a ) slight coloration (b) brown. F. M. G. M. Estimation of Tartaric Acid. ARNOLD HECZKO (Zeitsch.anal. Chern. 191 1 50 12-2O).-A criticism of the Goldenberg method for the analysis of crude tartars etc. (ibid. 1907 4’7 57). This process although technically accurate suffers frotn three defects (1) The end- point in the titration must be ascertained by means of an external indicator (litmus paper). (2) The solubility of potassium hydrogen tartrate is sensibly affected by the temperature and presence of other salts. (3) Calcium tartrate is not always entirely decomposed by boiling with potassium carbonate. In the author’s opinion the direct standardisation of the volumetric alkali with 1 gram of pure potassium hydrogen tartrate cannot be recommended. 1.5 Gram of the acid tartrate should be submitted in every respect to the same process as the actual sample using in fact the same amount of potaesium carbonate acetic acid and alcohol as directed by Goldenberg.The source of error (2) will thus be eliminated. L. DE K.Ji. 342 ABSTRACTS OF CHEMICAL PAPERS. Erstimation of Total Tartaric Acid [in Crude Materials]. ARNOLD HECZKO (Zeitsch. anal. Chem. 1911 50 73-811).-From 3 to 6 grams of the snrripla (according to grade) are treated with 20 C.C. of 2T-sulphuric acid and tho whole is then boiled for two minutes. When cold the mass is transferred to a 200 C.C. flask and ,diluted with 93-94% alcohol up to the mark. One hundred C.C. of lthe filtrate are then treated in a 300 C.C. Erlenmeyer flask with 3 C.C. (of glacial acetic acid and 10 drops of a cold saturated solution of !potassium chloride. Sixteen C.C.of a solution of 20 grams of potassium acetate in 100 C.C. of alcohol are then added drop by drop fiorn a %nrette with constant stirring. After half an hour the liquid is poured off from the precipitate which is then washed twice by decan- tation with 40 C.C. of 97% alcohol and finally on the Gooch filter \with another 80 c.c of alcohol. After removing the adhering alcohol by suction at the pump the tpotnssium hydrogen tartrate is dissolved in 200 C.C. of boiling water and at once titrated with N/S-potassium hydroxide using litmus paper as external indicator. The volumetric alkali is checked by operating on 1.5 gram of pure potassium hydrogen tartrate in the way described but using only half the quantities of the various reagents. Lo DE K. Assay of Vintage Marcs for Tartaric Acid.Separate Estimation of Potassium Hydrogen Tartrate and Calciuni Tartrate. P. CARLES (Bull. 80c. chim. 1911 [iv] 9 199-202; Bull. Assoc. chirn. Sum. Dist. 1911 28 561-564).-The process consists in extracting the marc (residues from the wine-presses) first with water containing sodium carbonate to remove potassium hydrogen tartrate (solution A ) and then with dilute hydrochloric acid t o remove the tartaric acid present as calcium tartrate (solution B). Both solutions are concentrated and the tartaric acid they contain separately precipitated dried and weighed as calcium tartrate. Full details of the method of carrying out the estimation are given in the original. T. A. H. R a p i d Estimation of the Volatile Acidity of Wines and Fermented Beverages.PXILIPPE MALVEZIN (Bull. Aseoc. china Sucr. Dist. 1911 28 560-561).-The method depends on the solubility of the volatile acids in ether. Ten C.C. of the mine or other liquid are shaken with 10 C.C. of ether and after separation has taken place 5 C.C. of the ethereal solution are pipetted into a flask con- taining 5 C.C. of neutral alcohol. The contents of the flask are then titrated with N/lO-sodium hydroxide solution using phenolphthalein as the indicator. The acidity is calculated from t h e formula w. P. s. ( 2 i - 0.2) x 25 x 1.63 6 Estimation of the Acidity of Fats and Oils Especially Lubricating Oils. HEINRICH LOEBELL (Chem. Zeit. 19 1 1 36 276-277).-Results of experiments carried out by the author show that a mixture of alcohol and ether is an unsuitable solvent t o employ for dissolving a f a t or oil previous t o the titration of itaANALYTICAL CHEMISTRY.ii. 343 acidity; when phenolphthalein is used as the indicator the end-poinh of the titration is not distinct and the results obtained are always too high. Still less satisfactory results are obtained if alkali-blue is employed as the indicator. The employment of a mixture of alcohol and benzene however allows concordant and trustworthy figures to be obtained. Aqueous N/lO-barium hydroxide may be used for titrating the acidity of oils when the latter have been dissolved i n a mixture of alcohol and benzene. w. P. s. Estimation of Lecithin in Oil. WILHELM FRESENIUS and LEO GRUNHUT (Zeitsch. anal. Chem. 1911 50 90-!06).-The method is based on the estimation of the phosphoric acid yielded by oxidation of lecithin; the phosphoric acid is weighed as yellow phospho- molybdate precipitate.Fifty grams OE the oily liquid are introduced into a 200 C.C. cylinder divided to 1 c.c. and 100 C.C. of absolute alcohol are added. After shaking gently for twenty minutes the layers are allowed t o separate and the volumes of the lower oily layer and the upper alcoholic layer (ol and al) are read off. Of the latter 75 C.C. (2)) are taken for the first phosphoric estimation (p1l3 and the pipette being rinsed with absolute alcohol the original volume is restored by adding alcohol up to the mark. The mixture is again shaken and allowed t o settle when the volumes (02 and az) are read off nod 75 C.C. of the alcoholic layer are taken for tho second phosphoric acid estimation ( p z ) .The calculatiop is effected by means of the following formula cL:= P 1-JL-- 2a 0 +PIP2(01"2 - o,a,)* +lor - P202) Tbe alcoholic solution is evaporated to dryness and the residue fused with a mixture of sodium carbonate (3 parts) and sodium nitrate (1 part). The mass is then dissolved in the smclllest possible quantity of hot water cooled neutralised with nitric acid made up t o 50 c.c. and then 2-5 C.C. of nitric acid (D 1.4) arid 75 C.C. of Jorgensen's molybdate solution added. L. DE K. The Occurrence and Quantitative EEltimation of Trimethyl- a m i n e in Human Urine. TOSAKU KINOSHITA (Zentr. Physiol. 24 No. 1'7. Reprint 4 pp.).-The ammonia etc. was distilled off from urine under diminished pressure in the presence of magnesium oxide and collected in hydrochloric acid.The acid solrition was then evaporated to dryness and the mehhyl groups in the residue thus obtained determined by the Herzig-Meyer process. As the result extremely small traces of trimethylamine could be detected in human urine and these the author suggests are possibly due to decomposition of other products. s. B. s. Estimation of Eexaruethylenetetramine (Urotropine) in Urine. FRITZ SCHROTER (Arch. exp. Path. Pharm. 1911 64 161-166).-The urine is ncidifietl with acetic acid and a saturated solution of mercuric chloride added Tbe precipitate so obtained after washil-rg is transferred to a flask containing a concentrated solution of sodium chloride aqd heqted QIL the watepbath. Aftgr cooling thieii.344 ABSTRACTS OF CHEMICAL PAPERS. is filtered and the mercury precipitated from the filtrate by potassium hydroxide and filtered off. The nitrogen is then estimated by Kjeldahl’s method and from this the urotropine present is calculated.- W. D. H. Estimation of Urea. ALONZO E. TAYLOR (J. Biol. Chem. 1911 9 25-28).-Benedict’s method is preferred to Folin’s because it is easier ; “there is no use in calculating results to the third place of decimals when the interpretation cannot go beyond the first place.” W. D. H. Analysis of Coca Leavee. E. BIERLING K. PAPE and A. VIEHOVER ( A ~ c h . Pharm. 1910 248 303-336).-The authors have investigated upwards of twenty methods which have been proposed for t h e analysis of coca leaves and find that the methods described by Keller Panchaud de Jong Fromme and the Swiss Pharmacopoeia are the simplest but have the drawback that the filtration of the ethereal extract of the leaves causes some of the solvent to evaporate and consequently the percentage of alkaloid found is too high. These methods are similar in principle the alkaloid being liberated from the leaves by means of ammonia and extracted with ether ; the ethereal solution is then extracted with hydrochloric acid the alkaloids are again liberated by means of ammonia and separated with ether.Cucaine cinnamylcocaine benzoyl-I)-tropine and isoatropylcocaine are estimated together but not hygrine or benzoylecgonine ; the latter is insoluble in ether whilst the former although slightly soluble is removed when the residue of alkaloids is warmed.For pharma- ceutical purposes a modification of de Jong’s process (Abstr. 1909 ii 276) is recommended. The authors consider that the broad-leaved Bolivian and Peruvian coca leaves should be made official as these leaves are free or practically free from cinnamylcocaine benzoyl- $ tropine and isoatropylcocaine and the cocaine is accompanied by only hygrine and benzoylocgonine. w. P. s. Sources of Error in the Folin Method of Estimating Creatinine. ALONZO E. TAYLOR (J. Bid. Chem. 191 1 0 19-20).- The personal equation and the absence of a standard light are sources of error in this colorimetric method. The influence of the urinary pigment and the presence of bile are very disturbing factors. W. D. H. Estimation of Nicotine in Concent rated Tobacco Juice.RICHARD KISSLING (Chem. Zeit. 1911 35 98).-A reply to Schioder (this vol. ii 163). The author who is now engaged on a colorimetric process thinks that by his method a complete separation of nicotine from ammonia and allied bases is guaranteed. L. DE K Estimation of Nicotine in Concentrated Tobacco Juice. H. ULEX (Chem. Zeit. 1911,35 I2l).-Ten grams of the sample are diluted with 1-3 C.C. of water and then mixed with a sufficiency of a mixture of 1 part OF soda-lime and 5 parts of gypsum. The mwsANALYTICAL CHEMISTRY. ii. 345 obtained is powdered sifted and placed for an hour in a desiccator over sulphuric acid to get rid of ammonia fumes The nicotine is now isolated by distillation. For this purpose the powder is placed in a flask containing 14 litres of boiling water and an extra 3 or 4 grams OF alkali are added also 4 grams of paraffin to prevent frothing.After collecting 1 litre of distillate another litre of water is introduced into the distilling flask and a second litre of distillate is collected. The nicotine is finally titrated with iV/2-hydrochloric acid ; 1 C.C. = 0.081 gram of the alkaloid. L. DE K. Estimation of Nicotine in Concentrated Tobacco Juice. JULIUS TGTH (Chem. Zeit. 1911 35 146).-A reply to his critics (this vo!. ii 163; preceding abstracts). The author upholds the techuical accuracy of his process. L. DE I(. Estimation of Nicotine in Concentrated Tobacco Juices. RICHARD KISSLING (Chem. Zeit. 191 1 35 200. Compare preceding abstracts).-The author points out that the high results obtained by Ulex’s method for the estimation of nicotine in tobacco juices is probably due to the liberation of large quantities of ammonia by the action of the soda-lime on the nitrogenous substances present.The method also possesses certain other defects. w. P. s. Estimation of Nicotine in Tobacco Extracts. J. LEISTER (Chem. Zeit. 1911 35 239-240).-A4 reply to Schroder (this vol. ii 163). The author states that the method proposed by Ulex (preceding abstracts) gives trustworthy and concordant results if care is taken to thoroughly powder the soda-lime mixture so as to facilitate the evaporation of any ammonia present. L. DE K. Estimation of Morphine in Opium and in Opium Preparations. L ~ O N DEBOURDEAUX (Chem. Zentr. 1910 ii 1097 ; from Bull. Xci. Pharmacol. 1910 17 382-385).-It is pointed out that about 10% of the morphine contained in opium is insoluble in water and alcohol and is only obtained in solution by the addition of calcium hydroxide.I n the analysis of preparations containing opium these should always be treated with calcium hydroxide before the morphine is extracted. w. P. s. Glucoside Reactions Convallamarin and Convallarin. C. REICHARD (Pharm. 2entr.-h. 191 1 52 183-188).-The author describes the reactions of convallamarin and convallarin two glucosides occurring in the roots and leaves of ConvalZaria rnajulis; the former is soluble in water and in alcohol and it is similar to digitalin in its physiological action whilst the latter is insoluble in water and acts solely as a purgative. When treated with nitric acid convallamarin yields a colourless solution which changes in a few hours to yellow whilst convallarin gives a yellow solution which gradually becomes red.If the nitric acid solutions are evaporated and the residues treated with a drop of ammonia convallamarin yields a yellow coloration changing in tt few hours to dark green and con-ii. 346 ABSTRACTS OF CHEMICAL PAPERS. vallarin gives a pure white precipitate. The most characteristic reaction of the two glucosides is that obtained with sodium iodate. Convallarin when treated with equal quantities of sodium iodate and water gives a white residue on drying the mixture whilst convallamarin yields ti moist amorphous mass which is coloured bright yellow on the addition of hydrochloric acid ; this acid does not change the colour of the convallarin-sodium iodate residue.Stannous chloride gives a yellow coloration with convallamarin after several hours’ contact and a red coloration with convallarin. Reaction8 with many other reagents are also described. IV. P. s. Estimation of Glyoyrrhiein and Sugars in Liquorice Root and Extract. ELLA ERIKSSON (AT&. Pharm 1911 249 144-160). -A process is described for the estimation of dextrose sucrose and glycyrrhizin in liquorice root and extract and the i*esults of the application of this process to various commercial samples of these products are tabulated (compare Hafner Abstr. 1900 ii 318 775 ; Zetzsche Pharnz. Centr.-A. 1901 277 ; Tschirch and Cederberg Abstr. 1907 i 545; Tschirch and Gauchmann ibid. 1908 i 898; 1909 i 328; ii 8 5 ; Parry C h n .and Drug. 1910 Jan.). Parry’s process gives results in good agreemelit with those obtained by the method now described. Ten grams of the powdered root or extract are extracted in the cold with slightly alkaline water and the solution made up to 200 C.C. if necessary. Of this 40 C.C. are taken and 40 C.C. of alcohol added and the mixture filtered quickly. To the filtrate 30 C.C. of Fehling’s solution prepared by Allihn’s method are added ; the mixture is set aside for thirteen to fourteen hours and the precipitated cuprous oxide collected in an Allihn tube washed reduced (or oxidised) and weighed and the amount of dextrose calculated from the result. The filtrate is poured into 30 C.C. of boiling Fehling’s solution the mixture boiled during three minutes diluted with half its volume of water and the cuprous oxide formed collected treated as before and weighed and the amount of sucrose calculated from the result.I n the filtrate glycyr- rhizin may be estimated directly by long boiling with Fehling’s solution or it may be precipitated with dilute sulphuric acid re- dissolved in alkali Fehling’s solution added and the mixture boiled1 during fifteen hours. I n either case the amount of glycyrrhizin may be calculated from the weight of cuprous oxide produced with the. knowledge that a reduation corresponding with 960 parts of dextrose is equivalent to 896 parts of glycyrrhizin. I n the roots examined the dextrose varied from nil to 3.8% sucrose from 2.4 to 6*5% glycyrrhizin from 6.49 t o 8.15%. I n the extracts- the corresponding raages were 2.7 to 7-S% 4.5 to 13*6% 9.8 t o 23-9% It is probable that dextrose does not occur in the fresh root hut is produced by fermentation during drying.In preparing the extract a considerable loss of glycyrchizin appears often to occtur. T. A. H. Estimation of Indigotin in the Presence of Starah. WILLIAM’ TIIONSON (J. ~ O C . Uyers 1911 27 49-51).-Synthetic indigo is oometirnes adulterated by the addition of btmrab arid the pr’esaeuce of4ANALYTICAL CHEMISTRY. ii. 347 this substance interferes with the estimation of the indigotin in such samples. The author has employed several different methods for ehtimating indigotin in mixtuies coutaining known quantities of synthotic indigo and starch and finds that Rawson’s permauganate process (with salt precipitation of the sodium indigotindisulphonate) yields low results the loss increasing with the quantity of etarch present j after the samples had been treated with 4% hydrochloric acid 111 order to invert tho etarch and the resulting sugar witshed away K~WSOLI’S process yielded better results Bloxam’s tetrasulphonate .process gave more uniform results ; synthetic indigo however showed only 82% of indigotin by this process. w. P. 8. Identiflcation and Estimation of Proteins in Honey. EDNOND MOREAU (Ann. Palsif 1911,4 36-41).-The proteins of honey which are coagulable by heat may be separated into two substances albumin and globulin by treatment with magnesium sulphate. A 20% solution of the honey is neutralised and the solution is saturated with magnesium sulphate; after the lapse of twenty-four hours the precipitated globulin is separated by filtration washed with a saturated solution of magnesium sulphate and then heated to a temperature of 100”.The globulin is thus coagulated and may be washed with water and weighed. The filtrate from the globulin is now acidified with acetic acid and boiled when the albumin is precipitated. The filtrate from the albumin gives a precipitate with potassium mercuric iodide in the presence of acetic acid denoting that honey contains proteosea or peptones or both. Albumoses may be detected by means of a reagent (Esbach’s) consisting of an aqueous solution of picric and citric acids whilst the biuret reaction when applied to a solution of honey from which albumoses have been precipitated with ammonium sulphste will show the presence of peptones.I n 10 samples oE honey examined the author found from 0.394 to 1.50% of total proteins 0.09 to 0.40% of albumin and 0.09 to 0.92% of globulin. I n certain samples the albumin was present in greater quantity than the globulin whilst in others the contrary was found to be the case. w. I?. s. An Improved Form of Heller’s Test for the Detection 0% Albumin Especially in Urine. FRANZ MICEIEL (CI~en2. Zeit. 19 1 1 35 183).-I.n carrying out this test in the usual way care has to be taken that the concentrated nitric acid and the solution to be tested do not mix as otherwise the nitric acid tends to dissolve the albumin and a turbid zone between the liquids is riot obtained. Tho author in order to prevent the liability of mixing saturates the nitric acid with ammonium nitrate.I n testing urine for the presence of albumin 2 C.C. of the reagent are placed in a test-tube and 1 C.C. of the urine is introduced by means of a pipette; if albumin is present a turbid zone appears at the junction of the two liquids and if the test-tube be shaken gently the whole of the urine layer becomes turbid. This is not the case if ordinary concentrated nitric acid is used as the turbidity dissolves at once. ’uv. P s.ii. 348 ABSTRACTS OF CEEMICAL PAPERS. Assay of [Commercial] Gelatin. JULIUS HEROLD jun. (Chem. Zeit. 191 1,35,93-94).-A 20% jelly is prepared and after congealirig for half an hour a t 19’ its melting point is ascertained. Simultaneously a 207L jelly is prepared from a mixture of equal parts of pure gelatin and glutose (prepared by heating.gelatin with ammonia in a sealed tube at looo) and its melting point is taken or a 10% jelly OF pure gelatin may be used. From the difference in the melting point (a) the proportion of glutin may be deduced from the formula a/Z*2 = x/82 ; x = % of glutin. A special form of apparatus for determining the melting points is described. By melting point is understood the temperature a t which a column of the jelly no longer adheres to a glass vessel which consequently commences to sink. L. DE K. Benzidine as a Reagent for the Recognition of Blood Stains. TORQUATO GIGLI (Boll. chirn. furm. 19 10 49 955-956).- The stained fabric or an aqueous extract of it is treated with 2 to 4 drops of a solution of 5 grams of pure benzidine in 10 C.C. of glacial acetic acid and 1 or 2 drops of hydrogen peroxide (3%) are added. The presence of blood is indicated by the immediate appearance of a blue coloration. The sensibility of the reaction carried out in this way is very great much more in fact than was supposed by Adler who first suggested the test. I n the absence of blood a blue coloration may appear but only after a time. The author considers that tho reaction does not suffice t o affirm the presence of blood with finality but the absence of the coloration does prove that blood is absent from a suspected stain. R. V. S. Characteristic Reactions of Toad Poison. GIOVANNI BUFALINI (Chem. Zentr. 1910 ii 1670-1671 ; from Arch. I-iu~mucol. sperim. 1910 9 559-568).-An aqueous solution of toad poison (secretion of skin glands) yields a red coloration when submitted to Ehrlich’s diazo- reaction ; this red colour is insoluble in ether and is similar to that given by cholesterol. The addition of mineral acids changes the coloration to yellowish-red or gellow. The coloration is not produced when the pokon has been treated previously with hydrogen peroxide. p-Aminoacetophonone gives a violet coloration which changes to orange-red on the addition of ammonia ; in hydrochloric acid solution p-dimethylaminobenzaldehyde yields a blue coloration which is insoluble in ether chloroform benzene carbon disulphide light petroleum etc.; this reaction does not take place in acetic acid solution and only feebly in alcoholic solution. When the poison is treated with sulphuric acid an emerald-green coloration is produced which is destroyed by the addition of oxidising or reducing substances. Michler’s ketone does not give a coloration (compare Abstr. 1910 ii 1096). w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9110005328

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

i. 345 Organic Chemistry. py-Dimethylhexane. LATHAM CLARKE (J. Arne?.. Chem. Soc. 191 1 33 520-531).-1n continuation of the work on the octanes (Abstr. 1907 i 169; 1908 i 493 593; 1909 i 125 350) fly-di- methylhexane has been synthesised by the two following methods (1) Ethyl dimethylacetoacetate on hydrolysis yields dimethylacetone (P-methyl-y-butanone) which on treatment with magnesium propyl bromide gives by-dimethyl-y-hexanol. This compound is converted into y-iodo-py-dimethylhexane by the action of iodine in presence of amorphous phosphorus and on reducing this substance with zinc and hydrochloric acid py-dirnethylhexane is produced. (2) Ethyl methylpropylacetoacetate on hydrolysis yields y-methyl-P-hexanone which on treatment with magnesium methyl iodide is converted into &dimethyl-p-hexanol.From the latter compound P-iodo-Py-dime thyl- hexane is prepared which on reduction gives By-dimethylhexane. Py-Dimeth yl- y-hexanol CHMe CMe( OH) CH,* CH,Me b. p. 158-158*2°/758 mm. has a eucalyptus-like odour. ,8y-DimethyZ- hexane CHMe,*CHMe*CH,*CH,Me b. p. 11 3.8-1 14O/758 mm. is a colourless mobile liquid which has a rather strong odour Dii 0.7246 and nz 1,4075. Py-Dimethyl- P-hexanol OH*CMe,*CHMe*CH,*CH,Me b. p. 150-151"/756 mm. is a colourless liquid with an odour recalling that of musty apples. The physical constants of eight octanes are compared and it is shown that these compounds fall into three classes according to the number of methyl groups they contain n-octane containing two the methylheptanes three and the dimethylhexangs four methyl groups.The volatility increases with the number of methyl groups present. The position of the methyl group in the methylheptanes makes only a slight difference in the boiling point but the density increases as the methyl group is moved successively from the P- to the y- or 8-position. Pyrogenic Decomposition of s-Tetrachloroethane and Trichloroethylene. 0. NICODEHUS (J. pr. Chem. 191 1 [ii] 83 312-322).-The liquid under examination is heated nearly to the boiling point in a flask through which a current of purified carbon dioxide is drawn ; the gas and vapour pass into a quartz combustion tube packed with pumice and heated electrically by about six metres of nickel wire (1 mm. thick resistance 2.2 ohms) wound round the tube and insulated by asbestos cord loss of heat being diminished by wrapping the tube and wire in layers of asbestos paper.The current is supplied at 72 volts; the temperature desired is attained after one and a-half to two hours and is determined by a platinum-iridium thermocouple. The quartz tube is connected with a series of condens- ing vessels consisting of a large Woulf's bottle two washing-bottles y-Methyl-P-hexanone has b. p. 136-137'/760 mm. E. G. VOL. C. i. b bi. 346 ABSTRACTS OF CHEMICAL PAPERS. containing ether (in ice) two containing water and the gasometer. The gas and vapour pass through the tube at such a rate that the deposition of carbon in the tube is as small as possible and the vapour streaming into the Woulf's bottle has a light brown colour. The products obtained by the decomposition of s-tetrachloroethane a t 700' under these conditions cannot be separated satisfactorily by fractional distillation ; consequently the author collects fractions a t every loo and treats each with bromine in sunlight whereby the saturated chlorinated components are unattacked whilst the unsaturated constituents are converted into chlorobromo-derivatives of high boiling point the separation of which is readily effected by fractional distilla- tion.I n this way the author has obtained s-dichloroethylene 1-50/,; chloroform 5-8% ; carbon tetrachloride 5 4 3 % ; trichloroethylene 50-60% ; tetrachloroethylene 5-1 0% ; pentachloroethane 1-3% ; and hexachloroethane 1-3% the percentages being calculated on the amount of crude decomposition products ; the remainder consists of carbon and hexachlorobenzene.Under conditions similar to the preceding trichloroethylene decom- poses violently and yields dichloromethane (a trace) ; dichloroethylene 6-10% ; chloroform 5-10% ; tetrachloroethylene 5-10% ; carbon tetrachloride 5-10% ; aPPP-tetrachloroethane 3-5% ; pentachloro- efham 3 4 % ; and hexachloroethane (a trace). When the decom- position is performed slowly a large quantity of carbon and hexachlorobeneene is produced ; by rapid distillation free chlorine is formed together with dichloroacetylene (?) which partly polymerises and partly explodes in the delivery tube. The fraction b. p. 180-230' contains about 15% of aaayss-hexachloro-A~-~~tylene CCI,*CH:CCl*CHCl (?) b. p. 210-212' (decornp.) or 98-99'/17 mm.Dit 1.6610 the con- stitution of which is deduced from the facts that quinoline diminates hydrogen chloride (1 mol.) yielding a substance C,HCl b. p. 227-230° or 130°/S0 mrn. sodium ethoxide produces an ether C3HC1,(OEt) b. p. 240-245O/120 mm. and reduction by zinc and acetic acid gives products from which ally1 chloride and trichloro- propylene have beeu isolated. The fraction b. p. 240-300° contains pentachlorobenzene m. p. 85-86O (identified by conversion into penta- chloronitrobenzene by nitration) and 2 3 4-trichlorobenxylidene chloride C,H,CI,*CHCl m. p. 83-84' b. p. 275-280' which is converted by hpdrochloric acid into the trichlorobenzaldehyde m. p. 919 The fraction b. p. 300-340° representing 20-25% of the crude products of decomposition consists almost entirely of hexa- chlorobenzene but also contains about 0*3-0.5% of 2 3 5 6-tetra- ~loro~nxotrichloride C,HCl,*CCI m.p. 101-102° b. p. 320-330' which is not attacked by chlorine bromine or potassium perman- ganate but is oxidised by chromic acid t o chloranil and is converted by alcoholic potassium hydroxide into the ester C,HCl,*C(OEt) b. p. 240-245O/120 mm. c. s. Tribromotert.-butyl Alcohol C,H70Br,. THOMAS B. ALDI~ICH (J. Amer. C?tmz. SOC. 191 1 33,386-3S8).-WillgeXodt (Abstr. 1882 493) has described the preparation of ch1orotert.-butyl alcoholORGANIC CHEMISTRY. i. 347 (chloretone) by the action of alkali hydroxide on a mixture of chloroform and acetone. An account is now given of the corre- sponding tribromo-derivative (brometone) the pharmacological action of which has been studied by Houghton and Aldrich (Abstr.1903 ii 315). Tribromotert.-butyl alcohol CBr,*CMe,*OH m. p. 167-176' forms white crystals has a camphor-like taste and odour is slowly volatile in the air and can be distilled with steam. This compound like the trichloro-derivative contains varying amounts of water which are present in the form of a solid solution (compare Cameron and Holly Abstr. 1899 i 323). Attempts have been made to convert tribromo- tert.- butyl alcohol into a-hydroxyisobutyric acid which was obtained by Willgerodt (Zoc. cit.) from the trichloro-derivative but although an organic acid was produced the quantity was too small for it to be identified. E. G. Method for Preparing Certain True Acetylenic Alcohols. ROBEBT LESPIEAU (Compt.rend. 1911 152 879-881).-The next higher homologue of butinene-y-ol has been prepared by the method previously described which appears to be of general application (Abstr. 1910 i 149). AU-Pentinene-y-oZ OH*CHEt*C!iCH b. p. 125'/761 rum. has D15 0.8926 n 1.434'7. It forms a crystalline precipitate with aqueous silver nitrate soluble in excess having the composition C5H70Ag AgNO,. The precipitate formed with cuproqs chloride is soluble in ammonia ; on treatment with iodine it yields aap-t&iodo-A~-penten-y-oZ OH*CHEt*CI:C12 m. p. 142-144'. P-Bromo-Aa-penten-y-o~~ OH*CHEt*CBr:CH has b. p. 165-166'/?55 mm. D15'5 1,351 n 1.482 ; the phenylurethane has m. p. 42-44O. Rcetylenic alcohols can also be obtained although not in good yield by the action of acraldehyde on zinc alkyl derivatives or organo- magnesium halides. ap-Dibromopentan-y-01 heated with sodium ethoxide gave the oxide CH*CH2Br b.p. 165-166'/768 mm. D'5'5 1.4096 n 1.4725. w. 0. w. O<bHEt Quantitative Dehydration of Pure Pinacone. MAURICE UELACRE (Bull. Xoc. chim. 1911 [iv] 0 240-247).-Couturier has pointed out that quantitative yields of pinacolin should be obtained by the dehydration of pinacone (Abstr. 1893 i 344) and this conclusion has been confirmed by Richard and Langlais (Abstr. 1910 i 455). f n the present paper details are given of the yields obtained by the use of sulphuric and oxalic acids as dehydrating agents and it is shown that high yielde are obtainable when pure pinacone is employed and if this condition is fulfilled Friedel's process gives results as good as thoae obtained by methods suggested more reamtl y.T. A. H. b b 2i. 348 ABSTRACTS OF CHEMICAL PAPERS. Pyrogenic Decomposition of Metallic Xenthates. ALEXANDRE H~BERT (Compt. rend. 1911 152 869-871. Compare Fleicher and Hank6 Abstr. 1878 29)-A tabular statement shows *the relative proportions of the principal products obtained by decom- posing a t 350' the xanthates of potassium barium iron cobalt nickel zinc copper lead mercury silver and tin. The gases liberated consist of hydrogen sulphide and carbon dioxide with small quantities of combustible gases containing carbon monoxide. The liquid products as a rule contain carbon disulphide carbon oxysulphide ethyl alcohol ethyl hydrogen sulphide and ethyl sulphide and disulphide. I n the case of the nickel and silver salts however the liquid is composed almost entirely of ethyl xanthate and the dry distillation of the nickel salt is recoinmended as a useful method for preparing this substance.w. 0. w. Catalytic Scission of Esters by Certain Metallic Oxides. PAUL SABATIER and ALPHONSE MAILHE (Compt. rend. 1911 152 669-673. Compare Senderens Abstr. 1908 i 494 495; 1909 i 127 286 ; Colson Abstr. 1909 i 302).-If the catalyst is heated above 330' during the esterification of acids by the method previously described (this vol. i 258) the yield of ester is diminished; a t 400° the principal reactions are those involving decomposition of the acid and alcohol. When the vapour of an ester is passed over the catalyst decom- position may occur in several ways.I n each case it is supposed that an unstable salt and alkyloxide are first formed and that the course of the subsequent reactions depends on the relative stability of these substances. They are produced in accordance with the equation 2M.O + 2R*C02*C,,H2,+ = (R*CO,),M + (CaH2,+10)2M. (1) If the salts are equally unstable a ketone and ethylenic hydrocarbon (2 vols.) with carbon dioxide (1 vol.) and water are formed for example when ethyl acetate is passed over alumina. (2) When the alkyl oxide is more stable the water formed in (1) reacts with it giving an alcohol Thus ethyl propyl and isobutyl acetates propyl propionate and ethyl hexoate in presence of thorium oxide yield a ketone and alcohol with approximately equal volumes of hydrocarbon and carbon dioxide. A t high temperatures however the alcohol undergoes dehydrogenation.(3) When the converse holds as for example when titanium oxide is the catalyst the salt (R*CO,),M is decomposed by water yielding the acid. (4) If the ester is a benzoate or toluate or if boric anhydride is used as catalyst exclusive forma- tion of acid and unsaturated hydrocarbon occurs. Thus ethyl valerate is decomposed by boric anhydride at 400' into ethylene and valeric acid. w. 0. w. Density of Soap Solutions. E. C. V. CORNISH (Zeitsch. physikaZ. Chenz. 1911 '76 210-211).-The measurements were made by the pyknometer method at 90'. Some of the results are as follows Sodium palmitate N/1 DT = 0.9625 N/2 0.9658 N/10 0.9654 A'/lOO 0.9655 ; sodium stearate N/2 0.9599 N/10 0,9629 N/100 0.9639.DY for water is 0.9653. G. S,ORGANIC CHEMISTRY. 1. 349 Constitution of Soap Solutions Solutions of ‘( Sodium Palmitates.” JAMES W. MCBAIN and MILLICENT TAYLOR (Zeitsch. ph!p/sikal. Chem. 1911 76 179-209. Compare Abstr. 1910 ii 177). -The high electrical conductivity of aqueous solutions of sodium palmitate at 90” (Eoc. cit.) shows t h a t the normal soaps are not simple colloids. The nature of the dissolved electrolyte is not conclusively established ; i t is certain that free sodium hydroxide is present and presumably normal sodium palmitate is present in ordinary solution and acid sodium palmitate mainly in the colloidal form As the conductivity does not alter with time there is a completely reversible equilibrium between electrolyte hydrosol and coagulum.The mole- cular conductivity-dilution curve of sodium palmitate is unlike any previously observed in aqueous solution inasmuch as i t shows R pro- nounced maximum in half-normal and a distinct minimum between N/5- and N/lO-solution The conductivity of solutions containing sodium hydroxide and sodium palmitate i n varying proportions has also been investigated; the results show that even in normal solution sodium palmitate is considerably hydrolysed. The solubility of palmitic acid and of acid sodium palmitate in water has been investigated. If it is assumed that the palmitic acid is dissociated to the extent of 50% in aqueous solution the concentm- tion of the undissociated acid and also of the ions is about 0.6 x mol. per litre a t 90’. The conductivity of a saturated solution of acid sodium palmitate is due mainly t o ionised normal and acid palmitate and to a much smaller extent to the presence of sodium hydroxide.The precipitate obtained by ‘( salting out ” sodium palmitate with sodium hydroxide consists mainly of sodium acid palmitate with proportions of the normal palmitate depending upon the conditions of precipitation The boiling point and vapour-pressure methods are inapplicable t o the investigat-ion of soap solution owing to the great difficulty of removing adsorbed air. G. S. Direct Synthesis of the Glycerides. G. GIANOLI ( A t t i Iz. Accad. Lincei 1911 [v] 20 i 348).-The author points out that the method described by Bellucci and Manzetti in a recent paper under this title (this vol. i 259) is not new for it was introduced by him on the large scale i n 1891 and was referred to in a recent publication (Gianoli Atti VI.Congr. chirn. appZ. 1907 3 51). R. V. S. Mode of Formation of Ethyl Chloroethoxyacetate. Use of this Ester in the Synthesis of a-Alkyloxy-acids. EDMOND E. BLBISE and L. PICARD (Compt. rend. 1911 152 960-962).-Tn a n attempt to prepare diethoxyacetyl chloride by the action of thionyl chloride on diethoxyacetic acid a liquid was obtained giving on fractionation an anhydride of glyoxylic acid with the chloride OEt*SOCI and a liquid b. p. 79-Slo/l0 mm. The latter has the composition of the expected chloride but proved to be ethyl chloroethoxyacetccte OEt*CHCI*CO,-Et. This yields a-alkyloxy-esters on treatment with zinc alkyl halides ; thus zinc propyl iodide furnishes ethyl a-ethoxyvalerate.i. 350 ABSTRACTS OF CHEMICAL PAPERS.Ethyl chloroethoxyacetate is not formed in the chlorination of ethoxyacetic acid but may be prepared by the action of thionjl chloride on the alcoholate of ethyl glyoxylate. The production of the ester from diethoxyacetic acid is probably preceded by the formation of the chloride which then undergoes transformation involving inter- change of the chlorine atom with an ethoxy-group. w. 0. w Keto-enolic Tautomerism. KURT H. MEYER (Annulern 1911 380 2 12-242).-I. The Quantitative Estimation of Keto-e~olic Tautome.rides.-It is shown by experiments with compounds which exist in both the ketonic and enolic forms that the unsaturated hydroxylic compound reacts instantaneously with an alcoholic solution of bromine and that the amount of bromine used up corresponds with the formation of a dibromide.The ketonic forms on the other hand are coloured by the-first drop of bromine solution and the colour disappears gradually";' The compounds experimented with were the two forms of dibenzoylacetylmethane mesityl-oxide-oxalic ester and diacetylsuccinic ester and the pairs of compounds anthranol and anthrone anthraquinol and hydroxyanthrone. When other solvents are used for example benzene or chloroform the difference betmeen the ketonic and enolic forms is not so marked (compare also Lapworth Trans. 1904 85 30). The reaction between the enol and bromine undoubtedly consists in the formation of a dibromide (compare Lippmann Zeitsch. C'hem. 1869 5 29) although such products cannot be isolated as hydrogen bromide is immediately liberated and a bromo-ketone is formed.The amount of the enolic compound in a mixture of the tautomeric forms can also be determined by the aid of bromine. A simple method consists in titrating the alcoholic solution with an alcoholic solution of bromine of known concentration until the colour of the bromine remains permanent. The method has the disadvantage that alcoholic solutions of bromine rapidly deteriorate. A more general method consists in titrating with an alcoholic solution of bromine of unkDown concentra- tion and then determining the amount of bromo-ketone formed. This is accomplished by adding potassium iodide solution and warming gently when iodine is liberated owing to the reduction of the bromo-ketone to ketone.The iodine liberated is titrated by means of standard thio- sulphate without the aid of starch. The reaction probably consists in the addition of hydrogen iodide to the carbonyl group and the replacement of bromine by iodine and ultimately in the elimination of iodine from the di-iodo-compound O:&CBr< -+ OH*bI*CI< -+ OH*b:C< + I,. When a N/50-solution of either the enolic or ketonic form of dibenzoylacetylmethane in alcohol is kept for twelve hours an equili- brium mixture containing 75% of the anolic compound is obtained. I n the case of the enolic form of methyl mesityl-oxide-oxalate CMe,:CH*CO*CH:C( OH)*CO,Me rather more than one molecule is used up before the red colour of the bromine persists for a momentORGANIC CHEMISTRY.i. 351 or two. This is probably due to the addition of bromine to the second ethylene linking Benzoylacetone reacts with a carbon disulphide solution of bromine,. yielding a hydrobromide of the ketone which gives up hydrogen bromide on exposure to the air. 11. Tawtomerism of Ethyl Acetoacetate.-Titrations of freshly- prepared solutions of ethyl acetoacetate indicate the presence of 7.71% of the enolic form. Similar results are obtained for the following solvents when the solutions are titrated immediatelyafter they are prepared methyl ethyl propyl and amyl alcohols and chloroform at - IS0 provided the titration is made in the presence of an excess of alcohol. These results indicate that the liquid ester contains 7.71% of enol and 92.29% of ketone (compare Hantzsch Abstr.1910 i 811 ; Briihl 1905 i 407). Different results are obtained when the solutions are kept for some time. The. following numbers indicate the percentage of enol present after forty-eight hours a t 18' Water U*4 glacial acetic acid 5-74 methyl alcohol 6.87 acetone 7.3 chloroform 8.2 nitrobenzene 10.1 ethyl alcohol 12 ethyl acetate 12.9 benzene 16.2 ether 27.1 carbon disulphide 32.4 and hexane 46.4. I n all cases an appreciable excess of ethyl alcohol was added before the titration with the bromine solution. I n solution a rise of temperature favours the formation of the ketonic form for example boiling methyl and ethyl alcoholic solutions contain respectively 4-74 and 7.5% of enol. Heating the liquid ester to 80° for an hour scarcely affects the equilibriixrn but the freshly distilled ester contains 20-25% of enol.When an alkaline solution of ethyl acetoacetate is acidified an oil is precipitated which gradually dissolves. The oil is the enolic form which is then transformed into the keto-form (99-6%) and these phenomena are in harmony with Dirnroth's conclusion (this vol. ii 31) that the relative proportions of the two components in a given solution when equilibrium is reached depend on the relative solubilities of the components. The enol on the other hand is readily soluble in hexane or light petroleum and is removed when the liquid ester is shaken three times with twice its volume of well-cooled hexane; the residual oil after freeing from hexane contains only 1.5% of the enol.The solubility of the keto-form in water at 0' is 11*6O/ and in 2% sodium chloride solution 10.9%. The solubility of the enol in 2% sodium chloride solution is 0.5%. The value for the van 't Hoff-Dimroth constant G is thus 0.09. The velocity of transformation has been calculated by means of the equations k + k = l / ( t - tl)log 8 - xI/s - x2 and kl/k2 = C,!C,. Where k is the velocity constant of ketonisation Ic that of enolisation s the value of cc when equilibrium is attained and C and C the concen- trations of the two forms in the equilibrium mixture For liquid ester which has been freshly distilled the value for k1 is 0*00055 and k 0*000046 at 15". I n aqueous solution the values are k = 2.4 and Ic = 0.010 a t Oo. The velocity of enolisation can also be determined by the rate of addition of bromine to the ketone since this includes the enolisation of the ketone and the instantaneous addition of broniine to the enol (compare Lapworth Zoc.cit.).i. 352 ABSTRACTS OF CHEMICAL PAPERS. I n 99.8% ethyl alcohol k = 0.077 and k = 0.0105 at 0' ; in hexane k = 0.0041 and 4 = 0,0035 at Oo. Acids have a catalytic action ; thus in aqueous O*lN-hydrochloric acid at O" k = 0.018 ; in non-ionising solvents the catalytic effect is much more marked. For example when the ester is shaken for a few seconds with hexane containing a little hydrogen bromide 45-46% of enol is found. It is suggested that the action of the acid is due to its addition and subsequent removal O:C*QH -+ OH*CBr-F]H -+ OH*C:$!. The frequency of the molecular change has been calculated by Dimxoth's method and the conclusion is drawn that the ultraviolet absorption bands characteristic of the ester cannot be due to the oscillations between the keto- and enolic forms (compare Baly and Desch Trans.1905 87 768 ; Hantzsch Abstr. 1910 i 811). Experiments have been made with the following tautomeric substances the numbers indicating the % of enol present in the liquid a t the ordinary temperature Methyl acetoacetate 4.1 methyl methylacetoacetate 3.16 ethyl bromoacetoacetate 4.0 methyl benzoylacetate 16.3 ethyl benzoylacetate 31.9 ethyl acetone- dicarboxylate 16.8 acetylacetone 80.4 benzoylacetone (solid) 99 dibenzoylmethane (solid) 102. Some Reactions of Calcium Oxalate. WILLIAM OECHSNER DE CONINCK and A. RAYNAUD (Bull.Xoc. chim. 1911 [iv] 9 301-306).-Calcium oxalate CaC,O,,H,O undergoes the following reactions On gentle warming chlorine reacts quantitatively giving caleium chloride and carbon dioxide. Bromine and iodine react similarly. On warming with concentrated hydrochloric acid it dissolves completely a small quantity of carbon dioxide being evolved only on boiling. With dry hydrogen chloride at a red heat carbon monoxide and dioxide are evolved. Hydrobromic acid and hydrogen bromide react similarly to the chlorine compounds. Concentrated nitric acid reacts according to the equation CaC,O + 3NH0 = Ca(NO,) + NO + H,O + 2C0,. Concentrated sulphuric acid gives the ordinary reaction with oxalates. Calcium oxalate loses its water of crystallisation only at tem- peratures above looo; towarde a red heat carbon dioxide commences to be evolved carbon being liberated at the same time.At a bright red heat carbon monoxide is evolved the evolution of gas taking place suddenly. Sodium and potassium oxalates behave similarly towards heat. The action of a red heat on mixtures of calcium oxalate with various oxides has been studied With silica carbon dioxide only is evolved and calcium silicate formed either SiO,,CaO or 3Si02,2Ca0 or a mixture of both according to the proportions taken. Boron trioxide gives carbon dioxide and a calcium borate of indefinite composition. Titanium dioxide gives carbon dioxide and a residue of indefinite com- position. Uranium trioxide hydrate UO,,H,O gives calcium carbonate carbon dioxide and uranium dioxide; the green oxide of uranium U,O acts similarly.With stannic oxide a mixture of carbon monoxide I 1 I 1 I I J. J. S.ORGANIC CHEMISTRY. i. 353 and dioxide is evolved leaving a residue of calcium stannate and calcium oxide. Ferricoxide as also black oxide of iron Fe304 gives calcium carbonate ferrous oxide and carbon dioxide. With lead dioxide carbon dioxide is evolved a mixture of calcium oxide red lead and litharge remaining. Red lead reacts similarly the lead compound remaining being litharge. Manganese dioxide gives carbon dioxide calcium oxide and the oxide Mn,04. Antimonious oxide is reduced to antimony carbon dioxide being evolved and calcium oxide formed. Bismuth oxide is similarly reduced to the oxide BiO. Careful heating of a mixture of calcium oxalate and barium peroxide gives a residue of calcium oxide barium oxide and barium carbonate carbon dioxide being evolved.T. S. P. Yttrium Potassium Oxalate. L. A. PRATT and CHARLES JAMES (J. Amer. Chew. Soc. 1911 33 488-492).-Cleve and HGglund (this Journ. 1873 136) described two yttrium potassium oxalates A study has been made of the solubility of yttrium oxalate in potassium oxalate solutions at 25" and the accompanying solid phases have been examined. Varying quantities of potassium and yttrium oxalates were shaken with 75 C.C. of water until equilibrium was established. The results of the experiments are tabulated and plotted as curves. It has been found that the only yttrium potassium oxalate formed at 25" is the salt Y,(C,04),,4K,C20,11 2H20. This compound can exist in contact with an aqueous solution of potassium oxalate containing more than 27.5 grams of the oxalate per litre.Condensations in the Mesoxalic Ester Series. RICHARD 8. CURTISS and EARLE K. STRACHAM (J. Amer. Chem. Xoc. 1911 33 396-400).-In an earlier paper (Curtiss and Spencer Abstr. 19U9 i 763) an account has been given of the preparation and reactions of methyl oxomalonate. A study has now been made of the corresponding ethyl ester. Ethyl oxomalonate CO(CO,Et) b. p. 117'/31 mm. obtained by distilling ethyl dihydroxymalonate with phosphoric oxide is a green oil which has DZ 1-119 and. when cooled with a mixture of solid carbon dioxide and ether crystallises in aggregates of radiating colourless plates m. p. below - 30'. When the ester is treated with hydrogen chloride at - 60" to - 70° it is converted into a white crys- talline mass which melts between - 29" and - 10" with evolution of hydrogen chloride and consists of a mixture of additive compounds containing HCI 2HC1 and 3HCL respectively.Hydrogen bromide unites with the ester in a similar manner. Methyl oxomalonate combines with only 1 mol. of a halogen hydride (Curtiss and Spencer loc. cit.). When ethyl oxomalonate is treated with urethane ethyl ca.r*bethoxy- aminotartronate OEt*CO*NH*C(C02Et)2-OH m. p. 32-33O is pro- duced which forms colourless crystals and yields a disodium salt probably of the enolic form. If this ester is left in contact with phosphoric oxide for t wenty-four hours a colourless crystalline com- pound m. p. 1 2 1 . 5 O is formed which is being investigated.y,( C204)3,4K2C,O4,12H2O and Y,(C,0*),,K?c20*,H~0. E. G.i. 354 ABSTRACTS OF CHEMICAL PAPERS. Carbamide reacts with ethyl oxomalonate with production of a crystalline substance m. p. 132-133' which appears to consist of ethyl carbamidotartronate NH,*CO*NH*C(CO,Et),.OH together with about 5% of carbamide. E. G. The Solution Densities of Dextrom Lzevulose and Maltose. ARTHUR R. LTNU LEWIS EYNON and JOSEPH H. LANE ('7th Intern. Congr. Appl. Chem. London 1909 Sect. I. 137-138).-The specific gravities of solutions of dextrose lmulose and maltose are tabulated for concentrations from 1 to 24% specially purified sugars having been used for the determinations. C. H. D. Digestive Ferments for Hexotrioses and for Stachyose. HENRI BIERRY (Compt.rend. 1911 152 904-906. Compare this vol. i 263)-Although the enzymes of the digestive system of vertebrates are without action on trioses these sugars are hydrolysed with facility by ferments present in the gastro-intestinal juice of molluscs and crustaceans. The juice from Helix and Astacus hydrolyses raffinose gentianose rhamninose and the tetrose stachyose. w. 0. w. isoRhodeose. EMIL VOTO~EK (Ber. 19 1 I 44 8 19-824. Com- pare Abstr. 1910 i 223 274).-isoRhodeose from purgic acid has the annexed constitutional formula and is the optical antipode of Pischer's OH isorhamnose. On oxidation with I l l nitric acid the same trihydroxy- CH,*CH(OH)*C-C-C*CHO xyloglutaric acid is formed as is bH GH obtained from isorhamnose. Crys- talline isorhodeose has [.ID + 31.5' (isorhamnose having [.ID - 30O); it does not form insoluble hydrazones.isoRhodeosephenylosazone has in. p. 186-1 87" ; 0.2 gram dissolved in 10 C.C. of a mixture of pyridine and alcohol in a 100 mm. tube has a - 2.9' ; under similar conditions the phenylosazone of rhamnose (identical with that of isorhamnose) has a - 3.5'. isoRhodeose-p-bromo- phenylosazone has m. p. 221.5-222'. Further proof of the constitution is afforded by the oxidation of isorhodeose to isorhodeonic acid conversion of this into alntirhamnonic acid by means of pyridine reduction t o ccntirhamnose addition of hydrogen cyanide forming antirhamnohexonic acid and oxidation of this to mucic acid. The intermediate products were not isolated but muck acid was identified. E. F. A. Photochemical Synthesis of Carbohydrates. I.Sorboae. GIUSEPPE INGHILLERI (Zeitsch. physiol. Chew. 191 1 71 105-109)- Tubes containing 40% formaldehyde and crystallised oxalic acid were exposed to sunlight for fourteen months. The product contained a carbo- hydrate which separated in regular orthorhombic crystals m. p. 9S0 and formed a phenylosazone crystallising in dark yellow stellate crystals m. p. 164O. The phenylrnethylosazone was dark yellow. The carbohydrate was optically inactive ; it is assumed t o be sorbose. E. F. A.ORGANIC CHEMISTRY. i. 355 Stereochemical Configuration of the Sugars Fucose and Rhodeose. C. 8. HUDSON (J. Amer. Chem. Soc. 1911,33 405-410). -The constitution and configuration of fucose and rhodeose have been established by Mayer and Tollens (Abstr.1907 i 588) and Votohk (Abstr. 1906 i 378 483; 1910 i 223). I n an earlier paper (Abstr. 1910 i 220) the author has pointed out a relation between the constitution and optical rotatory power of the sugar lactones and has shown that it can be applied to the determination of the constitution of the sugars. By means of this relation it is now shown that since rhodeonic and rhodeohexonic lactones are strongly l~vorotatory (Krauz Abst,r. 19 10 i 224) rhodeose and fucose must have the configurations which have already been assigned to them. Colorimetric Method of' Determining the Molecular Size of Polysaccharides. LEONHARD WACRER (Zeitsch. physiol. Chem. 191 1 '71 143-152. Compare Abstr. 1908 i 135; 1909 i 633).-The intensity of the colour given by carbohydrates with p-phenylhydrazine- sulphonic acid in presence of sodium hydroxide when that of dextrose is 100 varies after inversion from 107.1 in the case of a carbohydrate with three hexoses to 110.9 in that of a polysaccharide with one hundred hexoses.The mean value is 109 and this divided by the colour intensity shown by the polysaccharide before inversion by acid gives the number of hexoses in the molecule. Lavulose and carbohydrates yielding hvulose on hydrolysis give a somewhat deeper coloration. The influence of acids and alkali on the intensity of the colour for the various sugars is shown to be negligible. The method shows erythro- and acro-dextrin to contain four hexoses ; E. G. starch seven hexoses a i d glycogen eight or nine hexoses. E. F. A. Cellulose. Hydrocellulose.H. JENTGEN (Zeitsch. angew. Chem. 1911 24 585-586).-A reply to Schwalbe (this vol. i 115). T. S. P. Mercerisation of Cellulose. OSWALD MILLER (Ber. 191 1 44 728-731).-Mainly a reply to the criticisms of Cross (this vol. i 114) of previous work of the author (this vol. i 17). The fact that mercerised cellulose when kept over fused calcium chloride at 23-25' loses its water at a gradually diminishing rate supports the view that mercerised cellulose is not a hydrate but contains adsorbed water. F. B. Nitrous Estem of Cellulose. M. MARQUEYROL and D. ELORENTIN (Bull. Xoc. chim. 1911 [iv] 0 306-309).-The experimental evidence given by Nicolardot and Chertier (Abstr. 1910 i 818) in support of the existence of nitrous esters of cellulose is not satis- factory for several reasons (a) It is improbable that nitrous esters could be formed in a nitric acid medium.(b) It is well known that nitrated celluloses with a low nitrogen content are insoluble in the usual solvents for guncotton namely ethyl acetate acetone etc. (c) Various investigators have shown that the nitric esters of cellulosei. 356 ABSTRACTS OF CHEMICAL PAPERS. when saponified with aqueous or alcoholic alkali give rise to consider- able quantities of nitrite since reduction accompanies the saponifi- cation. It is furthermore shown that if cellulose is nitrated by the prolonged action of nitric acid (DF=ccr,. 1.5) to which excess of carbamide has been added to destroy all the nitrous acid present or formed during the reaction products are obtained which cannot be nitrous esters but which nevertheless possess the properties ascribed to these compounds by Nicolardot and Chertier.Action of Ultra-violet Radiations on Starch. L. MASSOL (Compt. rend. 191 1 152 902-904).-Soluble starch becomes hydro- lysed when its aqueous solution is exposed to the light from a quartz- mercury lamp. Changes in the rotatory power of the solution show that the transformation is probably into dextrins and maltose although the amount of sugar isolated was insufficient for identification. The hydrolysis is not due to the small amount of hydrogen peroxide Catalytic Transformation of Starch Paste. AUGUSTE FERNBACR and JULES WOLFF (7th. Irztern. Congr. AppL Chem. 1909 Sect. VI B 124-128).-When to 50 C.C. of 5% starch-paste a few drops of hydro- gen peroxide (corresponding with 5 mg.of oxygen) and of a ammonia solution (corresponding with 4 mg. of ammonia) are added the paste rapidly becomes liquid and in about fifteen minutes has a viscosity comparable to that of water. Other alkalis act similarly; there appears to be an optimum quantity of these and if excess is added the liquefaction is retarded. There is partial neutralisation of the alkali during the change corresponding with 1.6 mg. of ammonia per gram of starch. A similar liquefying effect is exercised by hydrogen peroxide and certain salts (Wolff Abstr. 1908 i 137). The optimum reaction in presence of fixed quantities of hydrogen peroxide and ferrous sulphate takes place when sodium hydroxide is added until the mixture is very faintly alkaline to methyl-orange.The slightest excess of acid very materially retards the liquefaction. Lactic and succinic acids in equivalent proportions are only one-third as harmful as succinic acid. Ferric sulphate has only one-half to one-third the activity of ferrous sulphate. Copper sulphate is about twice as active as ferrous sulphate and its effect is less susceptible to the presence of acids sodium hydroxide having no influence. Manganese sulphate is very slightly active. Mono- and di-sodium phosphate retard the change particularly the latter. The minimum quantity of hydxogen peroxide in time brings about liquefaction provided the reaction remains neutral or feebly alkaline but this is probably due to the influence of impurities in the starch. When a large proportion of hydrogen peroxide is used at 70-75" the starch after two hours no longer gives an iodine coloration the liquid has a marked reducing power and is acid. The reducing substance is insoluble in alcohol and is precipitated from a concentrated solution by copper sulphate.E. F. A. T. S. P. formed under the action of the rays. w. 0. w.ORGANIC CHEMISTRY. i. 357 Characteristic Properties of Amylose and Amylopectin. Mme. Z. GATIN-GRUZEWSKA (Compt. rend. 191 1 152 785-788. Compare Abstr. 1908 i 320 ; Maquenne &id.).-The envelope of a potato-starch graih consists of amylopectin associated with inorganic substances. Neither crude nor pure amylopectin shows the phenomenon of ageing or spontaneous precipitation from solution on cooling (Maquenne and ROUX’S retrogradation). On the other hand amylose has this property the precipitation being more complete the purer the substance.When starch paste is cooled the hydrosol granules of amylose are precipitated and carry with them the gel of amylopectin in which they are suspended. w. 0. w. Oxidation of Humic Acid. A. G. DOJARENKO (7th Intern. Congr. AppZ. Chem. 1909 Sect. VIT. ll-l8).-When humic acid is oxidised with 30% hydrogen peroxide a part of the nitrogen is detached in the forms of ammonia and soluble amides and amino-acids. The amide- and amino-acid nitrogen pass into the oxidised form of humus compounds perhaps apocrenic acid whilst the rest of the nitrogen of humic acid the “humin nitrogen,” serves as source of ammonia and simple amides. The properties of humic acid as regards the production of assimilable nitrogen when oxidised can be ascertained from the amounts of the different forms of nitrogen especially the amount of ‘‘ humin nitrogen.” The solution of humic acid in alkalis results in the production of apocrenates and crenates and also in the breaking off of nitrogen in the form of ammonia and other simple compounds.The former are derived from amide- and amino-acid nitrogen whilst the ‘‘ humin nitrogen ” yields the less complex nitrogen compounds. N. H. J. M. Preparation of Ethyl Oxalhydrazinate. ROBERT STOLL~ (Ber. 19 11 44 776-777).-EthyZ oxalhydraxinate CO,Et*CO*NH*NH is formed by the action of hydrazine hydrate on an alcoholic solution of ethyl oxalate at - 10’ t o - 15’ and is most readily isolated as its bemxyl- idene derivative CO,Et*CO-NH*N:CHPh which crystallises from alcohol in colourless refractive needles m.p. 133’. The oxalate CO,Et~CO~NH*NH,,H,C,O crystallises from hot alcohol and reduces hot Fehling’s solution. J. J. S. Sodium Derivatives of Bromo-amides and their Role in Hofmann’s Reaction. CHARLES MAUGUIN (Ann. Chim. Phys. 19 11 [viii] 22 297-369. Compare Abstr. 1909 i 892).-A further study of these compounds the preparation of which has already been described. Owing to their explosive character the preparation is not free from danger. When bromoacetamide is prepared by Hofmann’s method the product consists of a mixture of the anhydrous compound (slender needles m. p. 106’) with a monohydrate. The latter separates from warm solutions in orthorhombic hemimorphic crystals (compare Franqois Abstr.1909 i 13 140). Brornoisobutyrarnide prepared bgi. 358 ABSTRACTS OF CHEMICAL PAPERS. adding bromine (2 mols.) and potassium hydroxide (1 mol.) to the amid8 (2 mols.) in chloroform at -15' forms monoclinic needles m. p. 92O. The sodium derivatives of bromoamides react with urethanes in benzene solution giving substituted allophanates of the type NHR* CO * N H*CO,R' termed by the author ureocarbonic esters (compare Diels and Jacoby Abstr. 1908 i 613). Thus urethane and sodium bromoacetamide form ethyl nzethylcarbamidecarboxylote NHMe*CO*NH*CO,Et needles m. p. 134'; this compound was also obtained by the action of ethyl chlorocarbonate on methylcarbamide. The metl~yl ester crystallises in lamells m. p. 163" ; the p ~ o p y l ester has m.p. 130'. Sodium bromo- propionamide gives methpl ethylcarbami~ecarboxyla~~ NHEt*CO*NH*CO,Me needles subliming at 40-50° m. p. 95'; the ethyl ester has m. p. 72' (Jacoby Thesis 1907 gives 64-65'); the propyl ester has m. p. 81' ; the isobutyl ester lamellze m. p. 87' ; the isoarnyl ester needles m. p. 67-68'. Methyl isopropylc~rbamidecarbox~lat~ forms monoclinic prisms m. p. 70"; the ethyl ester m. p. 40'. Amides react with their sodium bromo-derivatives forming ureides of the type NHR-CO*NH*COR ; thus acetamide yields acetylmethyl- carbamide. Butyramide furnishes a mixture of acetylmethylcarbamide butyrylpropylcarbamide and acetyl'opylcarbamide NHPra*CO*NHAc micaceous lamellze m. p. 115'. When oxamethane is warmed with an aqueous solution of potassium bromoacetamide there is formed urethane ethyl allophanate and the potctssium salt of a new uzeide C0,Et*NH*CO*NH*CO*C02K crystal- lising in slender needles.The copper and silver salts are sparingly soluble ; on treating the latter with ethyl iodide the ester C02Et *NH*CO*NH-CO*CO,Et was obtained. This substance occurs in brilliant needles m. p. 146O; its constitution was established by a study of its behaviour towards water alcohol and ammonia as well as by the action of these sub- stances on the potassium salt. The latter is decomposed by water giving potassium oxalate and ethyl allophanate. Ethyl malonate and sodium bromoacetamide react to form acetyl- methylcarbamide and ethyl ethylenetetracarboxylate. The paper contains crystallographic details illustrated by diagrams of most of the substances mentioned. w.0. w. The Catalytic Action of Potassium Carbonate on the Absorption of Nitrogen by Calcium Carbide. GINO POLLACCI (7th Intern. Congr. AppZ. Chem. 1909 Sect. 11,278-282).-1t is kuown that the absorption of nitrogen by calcium carbide is accelerated by calcium fluoride (Foerster and Jacoby Abstr. 1907 i 397) and by various chlorides (Bredig Fraenkel and Wilke ibid. 396 903). It is now found that potassium carbonate has an accelerating action lower- ing the temperature at which absorption takes place the best result being obtained when 4% of potassium carbonate is added. There is no advantage in raising the pressure of the nitrogen above one atmosphere. C. H. D.ORGANIC CHEMISTRY. i. 359 Action of Nitrous Acid on Aminoguanidine and on Semi- carbazide.Difference between the Tetraaen C,H,ON and Azoimides in their Behaviour Towards Hydriodic Acld. KARL A. HOFMANN HEINRICH HOCK and HEINRICH KIRMREUTHER (Anncclen 1911 380 131-147).-The compound obtained by the action of sodium nitrite on a solution of aminoguanidine dinitrate and termed aminoguanidine diazohydroxide (Abstr. 19 10 i 232) or guanyldiazo- guanyltetrazen (ibid.,446) is formed in larger quantity when an excess of sodium nitrite is used. The compound cannot contain the hydrate of an azoimide NH F.N3 H,O as carbarnideimideazoimide NH,-C( :NH)*N and carbamic acid azoimide NH,*CO*N are readily decomposed by acids alkalis and silver salts yielding hydrazoic acid. Hydriodic acid reacts with hydrazoic acid and azoimides yielding nitrogen amine and free iodine N,:NK.+ 2HI = N + NH,R + I but with the derivative from aminoguanidine the acid merely forms the pale yellow iodide or with a mixture of hydrochloric and hydriodic acids the chloroperiodide ( C,HloN7),C113. The compound is thus a base and yields salts by the introduction of acid in place of water. It is regarded as a P-nitrosohydrazine derivative with the formula NH,*C(NH)*NH.NH*N:N*C(:NH)*NH-NH*NO and in the formation of salts water is eliminated and a terminal diazo-group is formed. The nitroso-compound (tetrazen) is extremely stable and is not attacked by sodium acetate solution nitrous acid sodium hydrogen sulphite ammonium hydrogen sulphide hydroxylamine hydrazine sulphate phenglhydrazine hydrogen peroxide formaldehyde acetone benz- aldehyde aniline pyridino or acetic anhydride. When reduced with stannous chloride and hydrochloric acid it yields tetrazylhydrazine which is isolated as its benzylidene derivative (Thiele Abstr.1893 i 441). The sulphate (C2H7Nlo),S04 crystallises in long colourless prisms and is hydrolysed by water ; the acid sulphate yields fhe double sulphate C2H~Nlo-S0,H,Ag,S04 in the form of glistening doubly refractive needles. The double salt C,H70N,,AglAgN0,,3H,0 crystallises in pale yellow glistening needles and when boiled with dilute hydrochloric acid evolves nitrogen (3 atoms). With ammonia the silver salt yields silver cyanamide and the silver derivative of tetrazyl- azoimide. The iodide C2H7N101 forms pale yellow flat needles only slightly pleochroic and is extremely explosive.The periodide C2H7NI0T5 forms glistening greenish-black rhombohedra1 crystals and the chloroiodide (C,H7Nl,),C11 forms pointed prisms strongly pleochroic from pale yellow to deep black and also doubly refractive. Semicarbazide hydrochloride and sodium nitrite yield the azoimide of carbamic acid which is decomposed by copper acetate solution yielding hydrazoic acid in the form of the double salt N~*CU*C~H,O~. This forms long dark green needles and when kept under water yields copper hydrazoate. Semicarbazide hydrochloride and sodium nitrite in the presence of sodium acetate yield hydrazoic acid hydrazodicarbonamide (Thiele Abstr. 1892 1298) as represented by the equation NH,*CO*NH*NH + NO*OH + NH,*NH*CO*NH = N€€,*CO*NH*NH*CO*NH + N,H + 2H20,i.360 ABSTRACTS OF CHEMICAL PAPERS. The formation of guanylnitrosoguanyltetrazen from arninoguanidine dinitrste and sodium nitrite probably proceeds in a similar manner. J J. S . Reaction of Iodoacetonitrile with Silver Nitrate. S. K. Lor and SALOMON F. ACREE (Amer. Chem. J. 1911,45 224-230).-It has been stated by Acree and Shadinger (Abstr. 1908 ii 163) that in the reactions between urazoles and alkyl halides i t is probable that in some cases; the anion first unites with the alkyl halide t o form an unstable complex anion which then decomposes thus (1) CH,I + Ag' + NO' (2) CH,I + AgNO,(orAg' + NO',)= CH,I,AgNO -+ CH,*NO + AgI. It was shown that in certain urazole reactions not more than traces of the complex salt could be present. I n order to obtain evidence as to the existence of appreciable quantities of such a salt in solution a study has been made of the double compound AgNO,,CH,I*CN obtained by Scholl and Stsinkopf (Abstr.1907 i 116) by the action of silver nitrate on iodoscetonitrile. Assuming that the complex salt is not more highly ionised than silver nitrate and that the complex ion NO',-ICH,*CN must migrate more slowly than the NO' ion it follows that if the complex salt is actually formed and decomposes slowly enough to be studied the conductivity of a standard solution of silver nitrate should be reduced on the introduction of acetonitrile to a degree depending on the amount of complex salt formed. Measurements have therefore been made of the conductivity of aqueous mixtures of silver nitrate and iodoacetonitrile in comparison with solutions of silver nitrate of the same concentration. The con- ductivities have also been determined of solutions in methyl alcohol ethyl alcohol and acetone.The results show that the double compound AgNO,,CH,I*CN does not exist to any appreciable extent in such mixtures and its rapid precipitation from solutions of its components must therefore be due to its small solubility and not to its appreciable concentration at any moment. Direct Preparation of Metallic and Organic Sulphonates from Crude Sulphonation Products. ALPHONSE SEYEWETZ and L. POIZAT (Bull. Soc. china. 1911 [iv] 9 247-253).-An extension of Gattermann's method (Abstr. 1891 1226) for the preparation of sulphonates without the intervention of the barium salt.The precipitation of sodium salts of sulphonic acids when sodium chloride is added to crude sulphonation products is due to the slight solubility of these salts in the excess of sulphuric acid present. This property is shown by all salts of sodium which are decomposed by sulphuric acid and by similar salts of the alkali and other metals and also of certain organic bases and a large number of metallic benzene- sulphonates have been prepared by this method and are described in this paper. HydroxglamiGe benxenesulphonate colourless leaflets and p-amino- phemyl bemzenesulphonate colourless needles or leaflets were also obtained in like manner. The corresponding scclts of phenylhydraxine m. p. 176q and of carbamids m. p. 162-163* were obtained by CH,I,NO' + Ago-+ CH,*NO + Ag' + I'.E. G.ORGANIC CHEMISTRY. i. 361 adding the respective bases suspended in water to the crude sulphona- tion product ; both are crystalline. These four salts are best purified by crystallisation first from water and then from alcohol T. A. H. Conversion of Benxenesulphondibromoamide into Dibromo- benzenesulphonamide by means of Concentrated Sulphuric Acid. JOSEPH H. KASTLE (Amer. Chem. J. 1911 45 219-223).-It has been shown by Benedikt (Abstr. 1879 717) that when tribromo- phenol bromide is treated with concentrated sulphuric acid it is con- verted into tetrabromophenol. Since benzenesulphondibromoamide shows many analogies to tri- bromophenol bromide it was considered of interest to ascertain whether it is similarly transformed by sulphuric acid.It has been found that a reaction occurs instantly a t the ordinary temperature with liberation of traces of bromine and formation of a dibromo- benzenesulphonamide m. p. 194" which is probably the p-dibromo- compound. A small quantity of another substance m. p. 135-140° is simultaneously produced which contains 36% of bromine but has not yet been identified. E. G. Triphenylmethyl. XX. MOSES GOBIBERG and DONALD. VAN SLYKE (J. Amer. Chem. Xoc. 1911 33 531-549).-1n earlier papers (Gomberg Abstr. 1907 i 504 ; 1909 i 144) it has been stated that triphenylmethane compounds exist in both benzenoid and quinonQid forms. The present work was undertaken with the object of ascertain- ing whether ortho-quinonoid nuclei occur in the products of tautomerisa- tion or whether only para-quinonoid rings are formed.If the former is the case the halogen atom should be just as reactive in the ortho- position as it has been found to be in the para-position in the tautomerised products whilst if the o-halogen is inert it may be concluded that ortho-quinonoid modifications are not produced. o-Chlorotr@henyZcarbinoZ C,H4C1*CPh,*OH m. p. 95O obtained by the action of ethyl o-chlorobenzoate on magnesium phenyl bromide forms white crystals ; the chloride has m. p. 136O and the ethyZ ether m. p. 77". o-ChZorotriphenylmethyZaniZine C,H,C1*CPh2*NHPh has m. p. 1 2 1 O . o-Chlorotetraphenylethane C6H,C1*CPh2*CH,Ph prepared by Gomberg and Cone's method (Abstr. 1906 i 414) has m. p. 165.5O. o-Bpomotriphenylcarbinot C,H,Br*CPh,*OH m. p. 104O obtained by the action of ethyl o-bromobenzoate on magnesium phenyl bromide forms white crystals ; the chloride was also prepared. The ethyl ether has m.p. 69-70'. o-Bromotriphen?llmet~~yzaniZ~ne C,H,Br*CPh,*NHPh has m. p. 126O and o-bromotetraphenylethane C!,H,Br*CPh,'CH,Ph m. p. 153'. Di-p-chloro-o-bromotriphemyZcarbino2 C,H,Br*C(C6H,C1),*OH m. p. 1079 obtained by bhe action of magnesium p-chlorophenyl iodide on ethyl o-bromobenzoate forms white crystals ; the crllZoride has m. p. 165" and the ethyl ether m. p. 107". Di-p-~hZo.ro-o-bromotr~p~~nyl- meth&niZine C,H,Br*C(C,H,Cl),.NHPh has m. p. 2 1 2 O and di- VOL. C. i. c oi. 362 ABSTRACTS OF CHEMICAL PAPERS. p-cldoro-o-byornotets.aphelz~Zethane C,II,Br*C(C,H,CI),*C)H',Ph m. p. 162'. Di-p-cl~loro-p-bromotriphen ylcarbinol C,H,Br * C( C,H ,Cl),*OH ha8 m.p. 106'; the chloride has already been described (Abstr. 1907 i 506) ; the ethyl ether has m. p. 188'. Di-p-chloyo-p-bromotriphnyl- rnethyZa&%e C,H,Br*C(C6H,C1),*NHPh has m. p. 182". The action of molecular silver on the halogen-substituted triphenyl- methyl chlorides has been studied with the following results (compare Gomberg and Cone Abstr. 1906 i 824). Not a trace of the halogen in the ortho-position was removed in any case and there is therefore no indication of the formation of an o-quinonoid nucleus. The total amounts of halogen in the para-position removed in relation to the number of p-halogen atoms present are in accord with Gomberg and Cone's results. Bromine in the para-position is more reactive towards molecular silver than is chlorine.The colorations produced by the action of molecular silver on the o-halogen derivatives are deeper and more brilliant than those produced with the corresponding para- derivatives. Experiments have been made t o ascertain the action of silver sulphate on ortho- and para-halogen derivatives of triphenylmethyl chloride and Gomberg's conclusion (Abstr. 1907 i 505) that the coloured triphenylmethyl sulphates have a quinonoid structure is con- firmed One para-halogen atom and one only becomes unstable and can be readily removed by further action of the silver. The ortho- halogen atoms are not affected. When one or two nuclei contain bromine and the other nucleus or nuclei chlorine all in the para- position the transformation of the sulphate into the quinonoid form in methyl sulphate solution takes place almost entirely in the brominated nuclei.The para-halogen atoms in the acid sulphates unlike those in the normal sulphates cannot be removed by the action of silver sulphate owing t o the sulphuric acid in the acid sulphates being directly combined with the para-halogen of the quinonoid nucleus. When o-bromo- and di-p-chloro-o-bromo-triphenylmethyl chlorides are treated with sulphur dioxide and silver chloride in sealed tubes no silver bromide is produced in either case. There was not any evidence of the formation of o-quinonoid nuclei in any of the experiments with the o-bromo-derivatives and the conclusion is therefore drawn that only p-quinonoid rings are formed. E. G. Decacyclene and its Alleged Property of Dissolving Graphite.MAURICE PADOA (Atti R. Accad. Lincei 1911 [v] 20 i 345-347).-The yield of decacyclene by the mebhod of Dziewonski (Abstr. 1903 i 431) is poor. If however the sulphur and acenaphthene are heated together in a sealed tube for two hours a t ZOOo the high pressure then reduced and the heating resumed for an hour a t 250° a yield of 12 grams of decacyclene is obtained for every 100 grams of acenaphthene. From an observation of the cooling curve the m. p. was found to be 389.5O.ORGANIC CHEMISTRY. i. 363 When in repetition of Ostromisslensky's experiment; ( Abstr. 1907 ii 864) the hydrocarbon was heated a t 500' for an hour with various samples of graphite decomposition occurred. If a lower temperature was employed (430°) the cooling curve was that of the pure substance and the graphite was recovered unchanged.R. V. S. Colorations Produced by the Interaction of Aromatic Amino- and Nitro-compounds. JOHANN WALTER (Zeit. .@'arb,- In&. 191 1 Reprint).-A description is given of the colorations produced when commercial dimethylaniline is treated with picric acid styphnic acid nitronaphthalene nitrobenzene m-dinitrobenzene o- and p-ni trotoluenes and dinitro-a-naphthol. Nitronaphthalene is coloured reddish-orange by dimethylaniline (or better by dimethyl- or diethyl- p-toluidine) the solution being yellow or orange-yellow ; the reaction possibly could be used to detect the addition of nitronaphthalene to oils. The colorations produced by the following aromatic bases on filter- paper soaked in a solution of trinitrotoluene in toluene and dried are described dimethylaniline aniline o-toluidine p-toluidine ethyl- aniline benzyle t hy laniline dimot hyl-a-nap ht h y lamine diet hy laniline amylaniline dimethyl-p-toluidine diethyl-p-toluidine dimethyl-o- toluidine nitrosodimethylaniline diphenylamine quinoline tetra- methyldiaminodiphenylmethane tetramethyldiaminobenzophenone di- aminotriphenylmethane tetramethyldiaminotriphenylmethane hexa- methyltriaminotriphenylmethane a-naphthylamine P-naphthylamine anthranilic acid p:aminobenzoic acid dimethyl-p-aminobenzoic acid and its amide anilide and ethyl ester o-tolylglycine ethyl phenyl- glycine phenylaminoacetonitrile diethyl-maminophenol m-amino- phenol indigotin and tetramethyl-m-phenylenediamine.The prepared filter-paper did not give colorations with acridine indolecarboxylic acid phthalimide benzamide acetamide acetanilide carbamide and bisphenylmethylpyrazolone. Many of the preceding substances are only the commercial prepara- tions; consequently too much reliance must not be placed on the colorations. By a systematic study and comparison of the colorations produced by pure materials the author thinks it should be possible to ascertain the presence of definite groups their position and method of union in substances of unknown or doubtful constitution. One or two interesting suggestions are made in the paper. The use of ether in the extraction of large volumes of dilute aqueous solutions of certain substances (dimethylaniline is the instance quoted) may be avoided by shaking the solution with trinitrotoluene filtering and decomposing the precipitate with dilute acid whereby the substance is isolated (after basification i f necessary).Dimethylaniline or dimethyl- or diethyl-p-toluidine probably could be used to detect trinitrotoluene in explosives. When a solution of dimethylaniline in benzene is distilled on the water-batb the presence of dimethylaniline in the distillate can be shown by the yellow coloration produced by trinitrotoluene. This proves that the solvent recovered by the distillation of a solution c r 2i. 364 ABSTRACTS OF CHEMICAL PAPERS. in a solvent of low b. p. is not pure as is frequently assumed to be the case. The naphthionic acid used in the preparation of dyes must be of good quality and free from a-naphthylamine in particular; the presence of the latter can be detected by the brownish-red coloration produced by trinitrotoluene paper.c. s. Quantitative Investigations on the Nitration of Aniline. ARNOLD F. HOLLEMAN J. C. HARTOGS and T. VAN DER LINDEN (Bey. 191 1 44 704-728).-The authors have investigated the composition of the products obtained when aniline and its acyl derivatives are nitrated under various conditions. By nitrating aniline a t -20' in sulphuric acid solution m- and p-nitroanilines are produced in approximately equal quantities ; the amount of the ortho-compound varies from 1.-2%. When the nitration is effected by adding aniline nitrate to sulphuric acid the amount of m-nitroaniline diminishes whilst that of the ortho- and para-isomerides increases.Formanilide when nitrated with pure nitric acid yields 2 4-dinitro- formanilide; with SO% nitric acid the product consists of 0- and p-nitroformanilides the latter being present in the greater proportion ; on nitration a t - 20' with the calculated amount of nitric acid in sulphuric acid solution the product consists almost exclusively of the para-isomeride. Similar results were obtained in the nitration of acetanilide and of benzanilide. The product obtained by nitrating acetanilide with acetyl nitrate at - 25' consists of 7607% of ortho- 4.1% of meta- and 20.2% of para- nitroacetanilide ; the relative proportions are very similar when the nitration is carried out in carbon tetrachloride solution. Since the concentration of the nitric acid employed has a consider- able influence on the relative proportions of the isomerides the effect of partly or wholly replacing the water by acetic acid was studied.I n the case of acetanilide partial replacement of the water by acetic acid causes an increase in the amount of the para- and a diminution in that of the ortho-isomeride. By nitrating acetanilide with pure nitric acid containing 20% of glacial acetic acid the product consists entirely of 2 4-dinitroacetanilide. By the removal of water from aniline nitrate by means of acetic anhydride a t O" o-nitroaniline is formed to the extent of S2.1% meta- 2*9% and para 15%. The product obtained by the interaction of 74% sulphuric acid and phenylnitroamine at - 20' consists almost exclusively of o-aitroaniline.From these results the authors draw the conclusion that by the direct nitration of aniline and its derivatives the product consists mainly of the para-compound together with small quantities of the ortho-compound. This is however modified by two causes (1) the formation of aniline sulphate and the introduction of acyl groups in the amino-group both of which lead to tho formation of the meta-substituted product ; (2) the intermediate formation of phenyl- nitroarnine which gives rise to o-nitroaniline.ORGANIC CHEMISTRY. i. 365 For the determination of the relative amounts of the three nitroanilines in a mixture thermal methods of analysis were employed. The freezing-point curves of binary mixtures of the three nitro- anilines together with certain portions of the eutectic lines leading from the three binary eutectics to the ternary eutectic point were first determined.The composition of a mixture of the nitroanilines mas then deduced from these portions of the ternary diagram by determining the first and second freezing-points of the mixture. Since the freezing point of any one of the nitroanilinea is depressed to the same extent by the addition of equal quantities of either of the other two isomerides the composition of a ternary mixture may be determined by adding a sufficient quantity of one of the nitro- milines to the mixture so t h a t this isomeride crystallises out a t the initial freezing point. From the position of this point on the binary freezing-point curves the relative amount in the original mixture of that isomeride which crystallises out may be calculated. An apparatus for the determination of freezing points is described.It closely resembles Thiele's melting-point apparatus but the open tube of the latter is inserted in one of the side limbs which is widened and contains a test-tube in which is placed the mixture t h e freezing point of which is to be determined. F. B. Unsymmetrical Aromatic Derivatives of Oxamide. 11. HERMANN SUTDA jun (Monatsh. 191 1 32 197-223).-1n continutt- tion of the former investigation (Abstr. 1910 i 665) unsymmetrical oxanilides have been prepared containing the -CO,H -NH -OH and -N:NPh groups. Also a phenyl-a-naphthyloxamide has been obtained containing a nitro-group in each nucleus. An oxanilide monosulphonate could not be obtained from ethyl oxanilate and aminobenzenesulphonate.I n all cases the yields were very unsatis- factory. In some cases the desired reactions become subordinated to other reactions for example in the interaction of ethyl oxanilate with p-pbenylenediamine or with m-aminophenol. The material so far obtained is insufficient to determine the influence of the substituentq on the course of fission with alcoholic potassium hydroxide. Oxarzilicle-o-carboxylic acid NHPh*C,O,*NH*C,~,*COzH,HzO is obtained by heating ethyl oxanilate and anthranilic acid for three hours at 140-150'; it forms colourless shining needles m. p. 226-2247' ; the water of crystallisation is lost a t 105 -1 10'. With dichromate and sulphuric acid it gives a blood-red colour (Tafel's reaction). and loses ammonia a few degrees below 226-2247'.The potussium salt C,,Hl,0,N,K,4H,0 forms rhombic needles [b c = 1 0.34'71. The silver calcium barzum and copper salts were also prepared. Under the action of alcoholic potassium hydroxide the acid decomposes into aniline and kynuric acid (oxalylanthrauilic acid). p-.PhenyZczo-oxanilide NHPh*C,0,*NH*C6H,*N:NPh results from the interaction of ethyl oxanilate and p-aminoazobenzene at 130-150" and repeated extraction of the cold fusion with benzene. It forms ochre-yellow crystals m. p. 256-257' and gives a dark carmine The ammonium salt is an acid salt C,,H1,0,N,~c1!,,H11'4N,0NH,,i. 366 ABSTRACTS OF CHEMICAL PAPERS. colour with Tafel's reaction. Alcoholic potassium hydroxide decomposes it into p-aminoazobenzene and oxanilic acid.p-Amino-oxanilide NHPh* C,O,*N H*C,H,*NH could not be pre- pared by the reduction of either p-nitro-oxanilide or p-phenylazo- oxanilide. It is obtained by the condensation of ethyl oxanilate and pphenylenediamine a t 150-155" in an atmosphere of carbon dioxide. If the condensation is carried out in the air a deep blue mass is obtained. The amino-oxanilide is obtained from t h i s as colourless prisms and plates m. p. 215O by extraction with alcohol ; it gives a dull carmine-red colour with a brownish tinge with Tafel's reaction The h,ydvochZoride C,,H,,O,N,,HCI and the sulphute (Cl,Hl,02N3),,H,S0 ara prepared by adding the respective acids to the hot alcoholic solu- tion of the base. Alcoholic potassium hydroxide decomposes the oxanilide into aniline p-phenylenediamine oxanilic acid and p-amino-oxanilic acid.The residue insoluble in alcohol is also practically insoluble in all organic solvents but soluble in hot concentrated sulphuric acid It could not be identified. Ey the nitration of phenyl-a-naphthyloxamide (loc. cit.) with concentrated nitric acid (D = 1 -4) a mixture of p-nitrophenyl-4-nitro- a-naphthyloxamide NO2*C,H,*NH*C,O2*NH*C1,H,*NO and o-nitro- phenyl-4 -nitro-a-naphth yloxamzde is obtained. The former com- pound is the chief product of reaction and can be separated from the latter by recrystallisation from glacial acetic acid; it forms slender yellow needles which sinter at 230' (decomp.) ; it does not give Tafel's reaction. The latter compound gives a dark brownish- red colour with Tafel's reaction. Fission with alcoholic potassium hydroxide gives the p- and o-nitroanilines respectively and 4-nitro- 1-naphthylnmine; the acids formed at the same time could not be separated and identified.Ethyl oxanilate and m-aminophenol interact readily a t 150-1 60°. The main product of the reaction is extracted with alcohol and gives pale rose-coloured monoclinic tablets m. p. 246-247". Analysis points t o the formula 4C,,H,,0,N2-H,0 that is an anhydride compound formed from three molecules of m-hydroxyanilide and one molecule of oxanilide. This formula is confirmed by the preparation of a triacetyl derivative C,,H,,O,,N m. p. 176 -17S0 although the ebullioscopic determination of the molecular weight in glacial acetic acid points t o the simple formula C,,H,,O,N,.With alcoholic potassium hydroxide aniline nz-aminophenol and oxalic acid me formed. On shaking with dilute aqueous sodium hydroxide m-hydroxyoxanilide NHPh*C,O,*NH*C,H,* OH is continually extracted and this compound is also obtained from the alcoholic mother liquors of the above-mentioned anhydride compound. If forms peach-red coloured leaflets m. p. 246O and is decomposed by alcoholic potassium hydroxide into oxanilic acid m-hydroxyoxanilic acid aniline and m-aminophenol. T. S. P. Keto-ester Additive Products with Arylamines and Alcohols. RICHARD S. CURTISS HARRY S. HILL and R. H. LEWIS (J. Amer. Chem. Xoc. 1911 33 400-405).-Curtiss wd SpencerORGARIC CHEMISTRY. i. 367 (Abstr. 1909 i 763) have given an account of a study of the action of alcohols and amines on methyl oxomalonate. The investigation bas now been extended t o ethyl oxomalonate.When ethyl oxomalonate is treated with arylamines additive compounds of the type W*NH*C(CO,Et),*OH are first produced which are capable of undergoing further reaction with formation of com- pounds of the type (NHR),C(CO,Et),. I n the case of aniline evidence was obtained of the formation of the compound NHPh*C(CO,Et),*OH but this substance could not be isolated as it immediately reacts with another molecule of aniline with production of ethyl dianilinomalonate (Curtiss Abstr. 1897 i 556). 0- and p-Toluidine react with ethyl oxomalonate to form ethyl o-toluiclinotartronate C,H,Me*NH*C( CO,Et),*OH m. p. 92O and ethyl p-toluidinotartronate m. p. 96O which crystallise in radiating needles ; the acetyl derivative of the latter compound has m.p. 150'. m-Tolui- dine also reacts with ethyl oxomalonate but the product was not obtained in a pure condition. When a solution of ethyl p-toluidino- tartronate in dry ether is treated with phosphoric oxide a thick green oil is produced the properties of which resemble those of methyl phcnyliminomalonate (Curtiss and Spencer Zoc. c i t . ) ; whm left in the air it absorbs moisture and is reconverted into ethyl y-toluidino- tartronate. Phosphorus trichloride also reacts with ethyl p-toluidino- tartronate with production of ethyl p-tolyliminomalonate C6H,Me*N C( CO,Et) which is decomposed by potassium carbonate into p-toluidine and ethyl mesoxalate. Benzylamine reacts with ethyl oxomalonate but the product could not be isolated in a pure state.When ethyl oxomalonate (1 mol.) is treated at - 13" with methyl ethyl or benzyl alcohol (1 mol.) a colourless syrup is obtained in each case which dissociates into the original constituents on heating and cannot be crystallised or distilled. These compounds are doubtless ethers of ethyl dihydroxymalonate OH*C( CO,Et),*OR corresponding with the product obtained by Curtiss and Spencer (Zoc. cit.) by the action of ethyl alcohol on methyl oxomalonate. E. Gt. Isomerism and Polymorphism. EINAR BIILMANN (Bey. 19 11 44 827-837).-The classification of isomerism by Kruyt (Abstr. 1910 ii 285) into three classes for example phase isomerism com- ponent isomerism and dynamic isomerism. IS criticised as quite unnecessary dynamic isomerism being regarded as only a special case of phase isomerism.Two substances of the same molecular composi- tion are either identically constructed (polymorphic) or of different structure (isomeric). Isomerisation denoting the conversion of a substance A into another B of the same composition is either spontaneous and complete or when a mixture of A and B is formed whichever was originally taken it is reciprocal. Homochromoisomerism (Hantzsch Abstr. 19 20 i 474) in which the isomerides differ in rn. p. and solubility but are identical chemically and optically is considered to be completely explained by the ordinaryi. 368 ABSTRACTS OF CHEMICAL PAPERS. conceptions of polymorphism. The case of picrylphenylmethylamine studied by Hantzsch (Zoc. cit.) which exists in two modifications m.p. 108-110' and m. p. 128-129' respectively has been further investigated. The amine m. p. 128O crystsllised from benzene yields the amine m. p. 108' but contrary to Hantzsch the reverse change could not be effected. The two amines are converted into one another by fusion and innocu- lation. The amine rn. p. 108" when heated a t looo or at a tem- perature above 108* is converted into the amine m. p. 128O. The reverse change takes place when the amine m. p. 128' is heated for a short time above this temperature and quickly cooled Chlorination of a-Naphthol. ARNOLD REISSERT (Bey. 1911 44 865-869).-4-Chloro-a-naphthol which cannot be obtained by the direct chlorination of a-naphthol is readily produced by treating a methyl-alcoholic solution of 1-hydroxy-2-naphthoic acid with chlorine (1 mol.) a t 30-40' and heating the resulting 4-chloro-1-hydroxy-2- naphthoic acid m. p.234O with aniline and naphthalene at 170-180° whereby carbon dioxide is eliminated. 4-Chloro-1 -hydroxy-2-naphthoic acid reacts with boiling aqueous sodium nitrite to form a compound C,,H,O,NCI,C,,~~O,Cl of chloro- hydroxynaphthoic acid and 4-chloro-~-naphthaquinoneox~1ne. 4-t%ZOYo- C 0-Q:NOH P-r)2ap~t~quinoneoxime C,H,< m. p. 157' pale yellow CCKCH needles is obtained by treating an alcoholic svliition of 4-chloro-1- naphthol at 0' with concentrated hydrochloric acid and sodium nitrite ; it is purified by means of its sparingly soluble red sodium salt. E. F. A. c s. 4-Nitroresorcinol. HUGO KAUFFMANN and W. RUGEL (Ber.191 1 44 753-756).-The nitro-derivatives of dihydric phenols are most readily prepared by nitrating their monobenzoates. Resorcinol monobenzoate yields two isomeric nitro-derivatives but both yield 4-nitroresorcinol (Weselsky and Benedikt Abstr. 1881 727) on hydrolysis. Resorcilzol monobenzoate crystallises from benzene and has m. p. 133O; it is best nitrated by dissolving in ten times its weight of glacial acetic acid cooling to 20-22' adding nitric acid (D 1.2) and allowing the temperature to rise to 36-38' and then diluting with its own volume of water. It is essential to work under specific con- ditions as otherwise resinous masses or the original compound are obtained. The 1 3 4-derivative is sparingly soluble in chloroform and crystallises from 50% alcohol in colourless needles m.p. 189'; it dissolves in dilute sodium carbonate yielding a yellow solution ; the isomeric 1 3 6-de~ivatiue is readily soluble in chloroform crystallises from glacial acetic acid in yellow needles m. p. 124' and with sodium carbonate yields a sparingly soluble orange-coloured sodium derivative. 4-Nitroresorcinol has m. p. 122' (not 115O) and its dimethyl ether m. p. 75". New Series of Aromatic Sulphur Compounds. THEODOR ZINCKE (Ber. 191 1 44 769-'771).-Compounds of the type J. J. S.ORGANIC CHEMISTRY. i. 369 C,H,*SCl can be obtained by the action of chlorine on the benzyl ethers of aromatic mercaptans. The reaction is entirely different from that between the corresponding methyl ethers and chlorine (Abstr. 1909 i 644; 1910 i 314; this vol.i 40). The same type of com- pound is also formed by the action of chlorine on the mercaptans or their disulphides. 4 4'-DichlorothioZdi~henyl SC1-C6H,*C6H4*SC1 crystallises from carbon tetrachloride in yellow prisms m. p. 1 1 5 O and decomposes a t 140'. 4 6-DichZoro-l 3-dichZorothioZbenxene C,H,Cl,(SC1)2 obtained by the action of chlorine on a chloroform solution of 1 3-dithiol- benzene crystallises from hexane in yellow needles m. p. 103'. o-Nitrochlorothiolbenzene N02*C,H,*SCl prepared by the action of chlorine on o-0'-dinitrodiphenyl disulphide suspended in carbon tetra- chloride crystallises in long yellow needles m. p. 75'. The chlorine derivatives are transformed into disulphides when boiled with alcohol or treated with aqueous alkali solutions.They also react with acetone the chlorine of the *SC1 group being replaced by *CH,'CO*CH,. The corresponding bromine derivatives are not so easy to prepare and the compound described by Otto (AnnaZen 1868 145 329) as C,H,*SBr is shown to be the disulphide (C6H,Br),S2. Action of Ethyl Alcohol on Toluene-p-diazonium Hydro- chloride and of Sulphuric Acid on p-Tolyl Ethyl Ether. PERCIVAL RIJDOLPH ROBERTS and GELLERT ALLEMAN (J. Amer. Chem. Soc. 191 1,33,391-396).-1n an earlier paper (Alleman Abstr. 1904 i 202) it was shown that p-tolyl methyl ether can be readily obtained by the action of methyl alcohol on p-toluenediazonium sulphate and that when treated with sulphui-ic acid it is converted into p-methoxy- toluene-m-sulphonic acid. Attempts to prepare p-tolyl ethyl ether in a similar manner did not yield good results but a method is now described by which it can be obtained in a yield of 35% of the theoretical.The diazonium compound is prepared from p-toluidine hydrochloride instead of the sulphate as the former is more soluble in ethyl alcohol. The ethyl ether is thus obtained as an oil b. p. 187-191" [n] 1.51069 which is identical with the compound described by Engelhardt and Latschinow (Zeitsch. Chem. 1869 619). p-Tolyl ethyl ether reacts with concentrated sulphuric acid at the ordinary temperature with formation of p-ethoxy-m-toZuenesuZphonic acid OEt*C,H,Me*SO,H m. p. 92-92*5' which forms colourless transparent crystals ; its barium potassium sodium calcium zinc nickel copper and lead salts are described. J.J. S. E. G. Hexahydrohippuric Acid. MARCEL GODCHOT (BUZZ. SOC. chim. 191 1 [iv] 9 26 1-864).-The preparation of hexahydrohippuric acid and of-a number of its derivatives is described. cycZoHexanecarboxy1 chloride b. p. 1 79-180°/760 or 100°/40 mm. (compare Meyer and Scharvin Abstr. 1897 i 612) reacts with glycine to form hexahydrohippuric acid C6H11*CO*NH*CH2*C0,H m. p. 152O which crystallises in colourless needles is sparingly soluble in water alcohol or ether but much more so on warming reddens litmus,i. 370 ABSTRACTS OF CHEMICAL PAPERS and gives a characteristic copper salt. The methyl ester .m. p 100-lolo and the ethyl ester m. p. 75-76' both crystallise in needles. The amide m. p. 195-196" obtained from the ethyl ester by the action of ammonia solution separates from warm water in small crystals.On distillation at atmospheric pressure with zinc chloride the acid furnishes c?jcZohexanecarboxylonitrile b. p. 184-ld5c/760 mm. (compare Dernranoff Abstr. 1964 i 410). T. A. H. Ethyl Polycinnamate. CARL LIEBERMANN and MILAN ZSUFFA (Ber. 191 1,44 841-849).-1n connexion with attempts to accelerate the rate of spontaneous polymerisation of the esters of cinnamic acid the authors have prepared methyl isoamyl benzyl allyl and octyl cinnamates. The last is obtained by boiling equal molecular quan- tities of cinnamyl chloride and octnn-/3-ol in three times the weight of benzene to which pyridine (1.5 mol.) is added and has b. p. 240°/60 mm. However only the ethyl and the isoamyl esters polymerise to an extent suitable for practical purposes.After many trials the following process is adopted by which polymerised ethyl cinnamate is obtained in com- paratively large quantities. Ethyl cinnamate about 100-200 grams is distilled under ordinary pressure and the distillate is inoculated with the polymeride and heated for some days at 80-85". The liquid becomes gelatinous and contains about 6% of the isomeride ; the latter is precipitated by ether and removed whilst the unchanged ester after being recovered is redistilled and again treated as above. I n this way about 20% of the ethyl cinnamate can be converted into its poly meride. The esters of polycinnamic acid are white infusible friable substances which are almost insoluble in all solvents and are odourless even after very long keeping.When heated ethyl poly- cinnamate at first blackens but as depolymerisation occurs the dis- tillation proceeds smoothly and almost the whole of the polymeride is obtained as ethyl cinnamate. Ethyl polycinnamate resists hydrolysis even by prolonged boiling with concentrated aqueous or alcoholic potassium hydroxide acetic and 50% sulphuric acids or p-toluidine. The hydrolysis can be effected although not completely by the following two methods. The polymeride is covered with a little acetic anhydride and heated for ten to twelve hours at 160° with hydriodic acid D 1.96 whereby ethyl iodide is produced; the product is washed with very dilute sulphurous acid and with very dilute alkali is dissolved in boiling water and the polycinnamic acid is precipitated in gelatinous flocks by hydrochloric acid.I n the second method the ethyl polycinnamate is intimately mixed with aluminium chloride and antimony chloride and is heated for some hours on the water-bath and finally at 130-140° for two to three hours; the product is digested with 25% hydro- chloric acid washed with 35% tartaric acid and with water and is finally dissolved in hot alkali and precipitated as above. Polycinnarnic acid (a) m. p. above 260° is stable to alkaline potassium permanganate. Its analysis points to the composition C,7H,,0 that is 3 mols. of cinnamic acid minus 1 mol. of water whilstORQANIC CHEMISTRY. i. 371 titration with N/lO-sodium hydroxide and phenolphthalein shows that it is dibasic. The authors make the following deductions from the preceding results.Ethyl polycinnamate which is undoubtedly a true polymeride of ethyl cinnamatc probably has the constitution QH(CO,Et)*CHPh*yH*CO,Et CHPh-CHPh-CH*CO,Et' The polycinnamic acid (1) obtained by its hydrolysis would then be Since however an acid of this con- yH(CO,H)*CHPh*QH*CO CHPh-CHP h-CH CO stitution would be either mono- or tri-basic and moreover since in the ester the carbethoxg-group between the two CHPh groups very probably is unattacked during hydrolysis polycinnamic acid (3) might have the constitution does not agree quite as well as the former with the analytical results but has the advantage of representing polycinnamic acid ( P ) $0. ~H(C02Et)~CHPh.7H*C0 a formula which CHPh-CHPh-CH*CO>o' as the anhydride of a dibasic acid. c. s. The Utilieation of Carbalkyloxy-derivatives for the Estima- tion of Hydroxyl Groups.K. C. R. DANIEL end MAXIMILIAN NIERENSTEKN (Ber. 1911 44 '701-704).-The method of estimation consists in hydrolysing the carbalkyloxy-derivative by heating it with 50% pyridine at 11 5-1 20° and weighing the carbon dioxide evolved thta gas being freed from pyridine vapour by passing through a tube containing a mixture of oxalic acid and calcium chloride. A sketch of the apparatus employed is given. The following new compounds prepared according to Fischer's method are described m-Ethylcarbonnatobenxoic acid CO Et*O* C,H,*C!O,H crystallises in needle? m. p. 98'. p-Nilrophenyl ethyl carbonate CO,Et*O*C,H,*NO forms needles m. p. 67-68'. 4-~thylcarbonato-m-nitrobenxoic acid,CO,E t*O*C,H,(NO,) CO,H crys- tallises in pale yellow cubes m.p. 176-177O. F. B. Carbamides Derived from a-Amino-p-hydroxyphenylacetic Acid and its Methyl Ether. JULES ALOY and CHARLES RABAUT (Bull. Xoc. chim. 1911 [iv] 9 253-255. Compare Abstr. 1910 i 558).-Phenylcarbamide and carbamide derivatives of these two acids have been prepared similar to those obtained by Hugounenq and Morel from tyrosine and leucine (Abstr. 1906 i 85). The sodium salt of a-amino-p-hydroxyphenylacetic acid reacts with phenylcarbimide to form diphenylcarbamide and a mixed carbctmide NHPh*CO-NH-CH(CO,H)-C,H,*OH m. p. 193' which is sparingly soluble in water readily so in alcohol and insoluble in ether or chloro- form. a-Amino-p-methoxyphenylacetic acid gives a similar derivative m. p. 198' (tpprox.).When the sodium salts of the two amino-acids are treated with earbonyl chloride they give rise t o the corresponding symmetrical derivatives of carbamide CO[ NH*CH( CO,H)*C,H,*OH],i. 372 ABSTRACTS OF CHEMICAL PAPERS. and CO[NH=CH(C02H)*C,H4*OMe]2 respectively. Both are amor- phous pale yellow powders; the second has m. p. 150' (decomp.). T. A. H. Preparation of 3 5-Di-iodotyrosine from Iodoproteins. 11. The Obtaining of the Same from Iodoglidin. ADOLF OSWALD (Zeitsch. physiol. Chem. 1911 71 200-203. Compare this vol. i 203).-It has been shown previously that 3 5-di-iodotyrosine is obtained from the commercial iodised protein called iodo-albacid. The same product is also obtained from iodo-glidin an iodised protein containing 9.2% of iodine in organic combination prepared from wheat.W. D. H. Reduction of the Anhydroxime of o-Benzoylbenzoic Acid. ROBERT EVSTAFIEFF ROSE (J. Amer. Chem. Soc 1911 33,388-391)- The oxime of o-benzoylbenzoic acid like those of other compounds con- taining a carboxyl group in the ortho-position to the carbonyl group cannot exist in the free state but when liberated from its alkali CPh :N salts is instantly converted into the anhydride C,H,<CO-b (Thorp Abstr. 1893 i 446 589). When reduced with zinc dust and glacial acetic acid it yields a stable crystalline lactam C,H4<CO->NH m. p. 218-220' which furnishes an acetyl deriv- ative m. p. 153-155'. If the lactam is heated with concentrated sulphuric acid for four hours a t 160-170" a sulphonic acid is produced which yields a bavium salt ( C,,H,,O4NS),Ba,2H,O. On distilling the lactam with zinc dust a strongly fluorescent oily product was obtained which contained carbazole ; the fluorescent substance was not present in sufficient quantity to enable it to be identified.E. G. This anhydro-compound has m. p. 161-163'. CHPh Benzoylphenylacetamide. TREAT B. JOHNSON and LEWIS H. CEERNOFF (J. Amer. Chem. A'oc. 1911 33 517-520).-Sy t,he action of benzoyl chloride on phenyl-phenylethenylamidine Wheeler Johnson and McFarland (Abstr. 1903 i 859) obtained benzoylphenylacotamide m. p. 129-1 30'. Benzoylphenylacetamide mas previously described by Colby and Dodge (Abstr. 1891 409) who obtained it by heating benzonitrile with phenylacetic acid or phenylacetonitrile with benzoic acid and found its m. p. to be 171".On repeating Colby and Dodge's experiments it has been found that the product obtained is not benzoylphenylacetamide but a mixture of dibenzamide and diphenyl- diace t amide. Benzoylphenylacetamide m. p. 129-130' can be prepared in nearly theoretical yield by the action of benzoylcarbimide on phenylacetic acid at the ordinary temperature and the product thus obtained is identical with that described by Wheeler Johnson and McFarland When benzoylthiocarbimide is heated with phenylacetic acid at (Zoc. cit.). 104-1 1 0' diphenyldiscetamide is produced.ORGANIC CHEMISTRY. i. 373 Benzoylcarbimide reacts readily with P-phenylpropionic acid with formation of P-phenylpropionylbenzarnide m. p. 104-106° (Colby and Dodge Zoc. cit.). E. G. Fulgides. HANS STOBBE (Annalm 1911 380 1-129.Compare Abstr. 1904 i 588 589 672 673; 1905 i 857; 1906 i 22 91 92 101 183 278,4219 361 960; 1908 ii 339).-I. Relation between Colour and Constitution of 3ulgides.-The absorption spectra of chloroform solutions of the following compounds have been determined using a Nernst lamp placed 30 cm. from a 10 mm. layer of a 1/32N-solution and giving an exposure of three minutes a-phenyl- u p - t 01 y 1- a-cum yl- a-o-nitrophen yl- a-m-nit rophen yl- a-o-anisy 1- a-anisyl- a-veratryl- and a-piperonyl- 66- dimethyl - fulgide ; a-phenyl- a86-triphenylfulgide ; as-diphenyl- as-dipheny1-6-methyl- aa-diphenyl- 66-dimethyl- a-anisyl$-phenyl- a-piperonyl-6-phenyl- ai?-dicumyl- as-dianisyl- as-diveratryl- as-dipiperonyl- and a66-triphenyl-fulgide ; a-p-tolyl- a-cumyl- a-p-chlorophenyl- a-o-nitrophenyl- a-nz-nitrophenyl- a-p-nitrophenyl- a-o-anisyl- a-anisyl- a-veratryl- and a-piperonyl- 66-diphenylfulgide ; aa66-tetraphenylfulgide.Photographs of the absorption spectra and the value of the absorption limit in the violet end of the spectrum are given. The absorption depends on three factors (a) the unsaturated (quinonoid) structure of the fulgide ring ; (6) the number of aryl groups present and ( c ) the nature and position of the auxochromes present in the aryl groups. An increase in the number of aryl groups increases the absorption in the violet end; the presence of alkyl nitro- and methoxy-groups also tends to increase the absorption more especially when they are in the para-position. When present in the meta-position the effect is only slight By suitably varying b and c it is possible to obtain fulgides with any desired nuance.The colour tone can also be altered by the introduction of a large number of olefine linkings in the fulgide molecule ; for example by introducing styryl in place of phenyl groups. Thus a-phenyl-66-di- methylfulgide is sulphur - yellow whereas the corresponding a-styryl cornpound is golden-yellow ; tho as-diphenyl compound is lemon-yellow and the a-atyryl-6-phenyl derivative orange; the a%-triphenyl compound orange-red and the a-styryl-66-diphenylfulgide ruby-red (compare also Fittig and Batt Abstr. 1904 i 744). Naphthylfulgides have deeper colours than the corresponding phenyl derivatives and similarly the a-diphenylenefulgides have deeper colours than the corresponding a-diphenyl compounds.11. I7termoelwornic PlLenomena (compare Stobbe and Vigier Abstr. 1904 i 672 ; Hantzsch 1906 i 353 ; Senier and Shepheard Trans. 1909 95 1943)-The colours of the various fulgides have been examined at the ordinary temperature at -SOo to - lSOo and at higher temperatures namely 70' to 1 4 0 O . A rise of temperature produces a change in colour indicated by the order greenish-yellow yellow orange brown red purple violet blue and a fall in tempera- ture a change in the opposite direction. For any given compound each temperature has a corresponding colour tone and the colour of the compound always returns to tho tone corresponding with thei. 374 ABSTRACTS OF CHEMICAL PAPERS. temperature a t which it is kept. The changes which the pale yellow monoarylfulgides undergo are not so marked as those characteristic of the deeper coloured polyaryl ccmpounds that is the latter compounds are more sensitive t o thermochromic influences. The solid fulgides are also phototropic (Abstr.1908 ii 339) and the deepening in colour produced by exposure to light can be removed by a slight increase in temperature and by a further rise of temperature a second deepening of the colour is produced. The conclusion is drawn that all compounds which are both phototropic and thermochromic undergo two distinct reversible changes which are characterised by colour alterations. 111. Monoarylfulgenic Acids and their FuZgides.-By the condensation of an aromatic aldehyde with ethyl tetraconate in the presence of sodium ethoxide a single fulgenic acid is usually obtained.Cuminaldehyde however yields two stereoisomeric a-cumyl-66- dimethylfulgenic acids (Abstr. 1906 i 22) together with an isomeric lactonic acid and p-chlorobenzaldehyde yields mainly a lactonic acid. All the monoarylfulgenic acids are oxidised by permanganate to oxalic acid acetone and the aldehyde from which they mere synthesised. Acetpl chloride transforms the acids into their yellow anhydrides each acid yielding as a rule a corresponding f ulgide. The two stereoisomeric cuminyldimethylf ulgenic acids yield stereoisomeric fulgides ; the allo- fulgide has a somewhat broader absorption band (A= 412pp) than t h s isomeride (A = 407pp). a.Pheny1-68-dimethylfulgenic acid yields two stereoisomeric fulgides the one colourless and the other yellow ; both have the same m.p. and the same chemical properties but the colours of their solutions are different. [With ALFRED LENZNER]. -a- Veratvyl- 66-dimeth yvulgenic mid CMe, C( C0,H) C( C0,H) CH-C,H,( OMe) crystallises from water in nodular masses m. p. 194.5" (decomp.) after sintering a t a lower temperature ; the corresponding fulgide C,,H,,O crystallises from light Fetroleum in yellow prisms resembling sodium picrate and has m. p. 127.5". a-Piperonyl-88-dirnethylji.dgeBic acid C 1110, C( C0,H) *C( C0,H) CH*C,H, 0, CH separates as colourless crystals from ethyl acetate and has m. p. 203-204'; when reduced with sodium amalgam in alkaline solution it yields a-piperonyl-P- meth yl-AP-pentene- y6-dicc6rboxylic acid CH,O, C,H,*CH,* CH(CO,H)*C( C0,H) :CMe which crystallises from 10% acetic acid and has m.p. 135" (decomp.). a-Pzperonyt-66-dimet~y?~~lgide C15H1,05 forms yellow crystals m. p. 145-146'. A by-product formed in the preparation of the fulgenic acid crystallises from chloroform in yellow needles m. p. 191' and is proba blg dimethylenedioxystilbene C,H,(C,H,:O,:CH,) ; it yields a dibvomide m. p. 173". [With EMIL WAHL.]-T~~ lactonic acid obtained by condensing p-chlorobenzaldehyde with ethyl tetraconate and sodium ethoxide in the presence of anhydrous ether is either y-p-chlorop?~enyl-a-isopropylene- paraconic acid CGH,C1*CH<CH(co,CU?>C:CMe O- or a - p - chloro- benzylidene- y y -dimethylparaconic m i d C,H,C~*CH C < ~ ~ ( ~ O ~ ' ~ > C M ~ .ORGANIC CHEMISTRY.i. 375 It crystallises from ether has m. p. 220° and when warmed with acetyl chloride the greater portion is recovered unaltered but a small amount of a-p-chlorophenyl-88-dimethylfulgide is obtained as pale yellow crystals m. p. 1 3 3 O and X = 415pp. IT. The Stereoisomeric Ethyl Phenylmethylitaconates and their CO~OUT Reactions (compare Abatr. 1904 i 503).-The cis-acid with concen- trated sulphuric acid yields a yellow methylindoneacetic acid the solution of which in sulphuric acid has a deep violet coloration. The normal and acid esters of the cis-acid give the same coloration. The trans-acid and its esters on the other hand dissolve in concentrated sulphuric acid yielding yellow solutions and this difference in coloration affords a basis for determining whether in such compounds the phenyl and carboxyl groups are in the cis- or trans-positions with respect to one another.[With FERDINAND GADEMANN.]-E~~~~ phen y lme t h ylisoi ttrconate (Abstr. 1899 i 902) is best prepared from the silver salt of the ethyl hydrogen ester and has b. p. 305-307°. [With ROBERT Ros~.]-Ethyl phenylmethylitmonate C16H2004 when prepared by the hydrogen chloride or sulphuric acid catalytic method contains a certain amount of anhydride; it is hest prepared from the silver salt and is a pale yellow oil b. p. 314-316’. The corre- sponding methyl ester C14H,,04 has b. p. 183*5-183°/20 mm. v. The Stereoisomeric Yl~enyltrimethylfulgen~c Acids and their E”ec1gides. -[With FERDINAND G~~~~ANN.]-a-Phenyl-a88-trimethy1- fulgenic acid exists in two stereoisomeric modifications - and allo c6H~>C:C<~~~H):CYe’2.The fulgenic acid alone is CH obtained by t h i condensation of acetone with ethyl phenylmethyliso- itaconate whereas a mixture of the two stereoisomeric fulgenic acids and phenylmethylitaconic acid is obtained when acetone is condensed with ethyl phenglmethylitaconate and sodium ethoxide. Acetophenone and ethyl dimethylitaconate condense in the presence of sodium ethoxide yielding a mixture of the two fulgenic acids. a-Phenyl-a8s-tiimethylfulgenic acid crystallises from water in small colourless needles m. p. 221-223O (decomp.) and gives an intense violet ,coloration with sulphuric acid. With acetyl chloride it yields a-p~enyl-as8-trimethylf~lgade C,,H,,O which forms colourless crystals with a yellowish-green reflex and has m. p.112-113°. a-Phenyl- a8Strimethylallofulgenic acid is identical with the compound described by Stobbe and Rose (Abstr. 1905 i 857) as 6-phenyl-aa8-trimethyl- fulgenic acid and has m. p. 2OS-21O0 (decomp.). Details for its preparation are given. The corresponding aldofulgide is identical with the compound described as 8-phenyl-aa8-trimethylfulgide. It forms lemon-yellow needles m..p. 132-133’ and is the stable form as it can be obtained from its stereoisomeride (1) by exposing a chloro- form solution containing a little iodine to sunlight ; (2) by prolonged boiling of its xylene solution; (3) by heating with naphthalene for twelve hours at 190’. An N/32-chloroform solution of the ccllofulgide has a rather broader absorption baud (A = 405pp) than a similar solu-i. 376 ABSTRACTS OF CHEMICAL PAPERS.tion of its isomeride (A= 402pp). As in the case of many other pairs of stereoisomeric fulgides the more stable and less fusible compound is the more deeply coloured. VI. Diarylated Fulgenic Acids and their Fu1gides.-Good yields of as-diarylated fulgenic acids can be obtained by condensing the ester of a y-arylated itaconic acid with an aromatic aldehyde in the presence of an alcoholic solution of sodium ethoxide or of the solid ethoxide and anhydrous ether. Hydroxy-acids of the type R-CH( OH)*CH( CO,H)*C( CO,H):CHR' are sometimes formed. Although the fulgenic acid can exist theoretic- ally in three (R=R') or four stereoisomeric forms the acids obtained are usually homogeneous. The same acids can also be synthesised by condensing ethyl succinate with an excess of an aromatic aldehyde in the presence of sodium ethoxide (compare Abstr.1906 i 102). This method is less expensive but is complicated by the formation of various by-products for example y-arylsted paraconic and itaconic acids lactonic acids isomeric with the fulgenic acids and aromatic monobaeic acids and alcohols formed by the action of the alkali on the aldehyde. The various aldehydes react differently with ethyl succinate. Benzaldehyde p-isopropylbenzaldehyde anisaldehyde and piperon- aldehyde give 40% yields of the corresponding diarylated f ulgenic acids. Low temperatures ( - 10' to - 17') favour the formation of these acids whereas higher temperatures tend to form resins or substituted itaconic acids.Veratraldehyde gives but a poor yield of diveratryl- fulgenic acid and nitrobenzaldehydes yield resins. Practically all the acids can be reduced to the corresponding diarylated butanedicarboxylic acids which yield colourless anhydrides. The lactonic acids formed during the condensation of aromatic aldehydes with itaconic esters can be transformed into the isomeric fulgenic acids by boiling with sodium ethoxide solution and it is probable that in all cases lactonic acids are intermediate products in the formation of fulminic acids. [With ROBERT Ros~.]-Ethyl hydrogen a6-dipheny1-6-methylfcclgenate C,,H,,O prepared by allowing a solution of benzaldehyde y-phenyl- y-methylitaconic ester and sodium ethoxide in ethyl alcohol to remain for four hours at the ordinary temperature forms colourless rhombic crystals m.p. 172-173". The corresponding acid crystallises from 50% acetic acid in colourless prisms m. p. 222-214' (decomp.) after softening a t 180° and appears to be a mixture of the acid with a monohydrate. a6-DipheizyZ-s-methy~~~g~de C,,H,,O crystallises from ether in glistening lemon-yellow hexagonal prisms m. p. 148". [With GEORG POSNJAK.] - au-Diphenyl-66-dimethylfulgenic acid (Abstr. 1905 i 857) can also be prepared by condensing acetone with diphenylitaconic ester and sodium ethoxide and its solution in concen- trated sulphuric acid has a deep green colour similar to that of diphenylitaconic acid in sulphuric acid and in both cases an indone derivative is formed. [With KARL KAUTZSCH and TH. BADENHAUSEN.]-~-PJL~~/L~fulgenic acid CH,0,:C,H,*CH:C(C02H)*C(C0,H):CHPh is obtained mixed with the corresponding hydroxy-acid by condensing piperon- aldehyde and phenylitaconic ester.The mixture forms pale yellow nodular masses from ether m. p. 203-206" (decomp.) and the corre-ORG ANlC CHEMISTRY. i. 377 sponding f d y i d e CI9Hl2O5 crystallises from a mixture of ether and chloroform in pale orange-coloured prisms m. p. 169-170°. VTI. as-Dicumylfulgenic Acids Cunaylitaconic Acid ccnd Cuntyl- paraconic Acid.--[ With RICHARD HBRTEL.].-A mixture of the four acids is obtained by condensing cuminaldehyde with ethyl succinate in the presence of pure sodium ethoxide and anhydrous ether. The yellow as-dicumylfulgenic acid C6H4P1 +CH:C( C0,H) 4 C!CO2H):CH*C6H4Pr p separates from light petroleum in sulphur-yellow crystals or from chloroform in whitish-grey crystals containing chloroform of crystalli- sation.The corresponding fulgide C,,H,,O separates from light petroleum in orange-red triangular plates or long needles m. p. 112-1 13'. The colourless a6-dzcumylisofulgenic ncid is found as its methyl hydrogen salt in the light petroleum mother liquors of the yellow acid. I t crystal- lises from chloroform with solvent of crystallisation and has m. p. 325' (decomp.). The corresponding fulgide is not YO readily prepared as the iaomeride and crystallises in lemon-yellow plates or needles m. p. 112-113'. Both the fulgenic acids on reduction with sodium amalgam in the presence of carbon dioxide yield a ~ - d ~ c ~ m y ~ b u t a n e - ~ y dicarboxylic acid C6H,Pr~*CH,-CH(C02H)-CH(C02H)*CH2*C6H4Pr~ which crystallises from benzene and has m.p. 220'. The colourless ieo-acid is not so readily oxidised by permanganate as the yellow acid and both fulaides react with bromine,- yielding amorphous-products. It has m. p. 220' (decomp.). oil which solidifies after several months crystallises from water or chloroform and has m. p. 158'. Cumylituconic acid C6H4Pra* CH C( CO,H)*CH,*CO,H crystallises from a mixture of ether and light petroleum has rn. p. ZOO' and gives a bluish-green coloration with concentrated sulphuric acid. The anhydride C,,H,,O crystallises from light petroleum in colourless glistening prisms m. p. 138O. Both paraconic and itaconic acids yield cumylisoparuconic acid when boiled with 50% sulphuric acid.This acid crystallises from water in colourless needles m. p. 131" and when moistened with concentrated sulphuric acid gives no coloration for the first moment but gradually develops a yellow colour. VIII. as-Diwnisylfulgenic Acid and an IsonzGric Lactonic Acid.- [With ERICH B~N~nY.]-a8-Dianisy?fulgenic acid OMe*C,H,*CH C( CO,H)*C(CO,H):CH C,H,*OMe and the isomeric lactonic acid a-anisylidene-y-p-methoxyphenylparaconic m i d OMe*CGH,*CH<O CH(Co2H)>G:CH~C6~4.0Me GO are obtained by the condensation of anisaldehyde with ethyl succinate in the presence of sodium ethoxide and can be separated by means of benzene in which the fulgenic acid is insoluble. This acid crystallises from glacial acetic acid or alcohol in lemon-yellow prisms m. p. 242-243' (decomp,) after softening at 220'.crystallises from carbon disulphide in chrome-yellow needles m. p The corresponding fulgide C,OH,,O VOL. c. i. d d378 ABSTRACTS OF CHEMICAL PAPERS. 170-1 71O. The lactonic acid crystallises from benzene is colourless and has m. p. 108-109". It is transformed into the fulgenic acid when boiled for twelve hours with potassium ethoxide solution. IX. a Zi-Diveratr ylfulganic Acid .-I Wi th KARL LEU NEE .J - as-Divera- trylfulgenic acid and y-veratrylitaconic acid are formed by the condensa- tion of veratraldehyde with ethyl succinate and the yield of the former is greater when an excess of aldehyde is used but as much resin is also formed under these conditions the purification of the acids is rendered more tedious. A modification of Tiemann's method (this Journ.1876 i 76) for the preparation of veratraldehyde from vanillin is described. Diveratrylfulyenic acid C H,(ORle),*CH C( CO H) *C( C0,H) CH*C,H,(OMe) is insoluble in chloroform crystallises from dilute alcohol and has m. p. 220" (decomp.). The fulgide C,,H',,07 crystallises from benzene in brilliant red monoclinic plates or large double pyramids m. p. 172-1 73". C6H3( OMe),-CH:C(CO,H) *CH,*CO,H crystallises from water or chloroform in slender colourless needles m. p. 1 7 5 O and yields an insoluble barium salt. The anhydride Cl3HI2O5 crystallises from benzene in orange-red needles containing benzene or in crusts of yellow prisms free from benzene. The hydro- carbon is removed at SO" and then both forms melt at 167'. X. a8-Piperony?fulgenic Acid and an Isomeric Lactonic Acid.-[With WALTER VIEWEG RICHARD ECKERT and GUSTAV REDDELIEN.]-T~~ lactonic acid a-pipes.onylidene-y-methylenedioxyphenylp~~aconic acid CH,O, C6H,*CH<gH ( Co2ti>C:CH C,H,:O,CH is the chief pro- duct formed when ethyl succinate and piperonaldehyde are left in contact with dry ether and sodium ethoxide for a short time at low temperatures.The product formed is the sodium salt of the corresponding hydroxy-acid but when acidified this yields the colour- less lactonic acid which crystallises from acetic acid and has m. p. 182". The acid is not affected by acetyl chloride but with acetic anhydride yields a compound C2,B,,Og with m. p. 265'. a8-Dipiper- onylfulgenic acid CH2:0, C,H,*CH C( C0,H) *C( C0,H) CH*C6HB O,:CH is formed when the reaction mixture is kept for eight days at low temperatures or when the lactonic acid is boiled for twelve hours with potassium ethoxide solution.It crystallises from glacial acetic acid in yellow prisms containing 2 molecules of acetic acid which it loses a t the ordinary temperature The acid has then an orange-yeliow colour and m. p. 210' (decomp.). The potassium salt C,,H,,O,K crystal- lises from SO% ethyl alcohol in yellow needles ; the ethyl ester C,,H,,08 in greenish-yellow felted needles m. p. 133" and the fulgide C,oH1207 separates from chloroform in orange-coloured crystals m. p. 210". When reduced with sodium amalgam in the presence of carbon dioxide the f ulgenic acid yields colourless a8-dipiperonyZbutccne- /3y-dicclrboxyZic acid CH,:0,:C6H,*CH,* CH( CC),H)* CH( CO,H)*CH,-C6H3:O2 CH m.p. 228' (dscomp.) after turning yellow a t 210' and softening at 2 2 0 O . With concentrated sulphuric acid it yields a pale red and y- Yerutry Zitaconic acid,ORGANIC CHEMISTRY. 1. 379 ultimately a purple-red coloration. A comparison is made between the colours of various acids containing phenyl and piperony 1 groups. XI. Two Stereoisomeric a-Piperonyl-6-phenyl-6-methylficlgenic Acids. -[With FERDINAND GADEMANN and ROBERT ROSE.]-Piperonaldehyde condenses with the ester of phenplmethylisoitaconic acid in the presence of dry ether and sodium ethoxide a t low temperatures yielding as the only product a-p~perony1-6-phenyl-6-met~ylSzclgenic acid C6H5>(3:C/c02H Co2H\C C<C6H3:02:CH7- which crystallises from CH3- H glacial acetic acid or water has m. p.196-198" (decornp.) and give' a malachite-green coloration with concentrated sulphuric acid. The corresponding fulgide C H1405 crys tallisea from glacial acetic acid in greenish-yellow needles m. p. 159-161". The ester of phenylmethyl- itaconic acid does not condense with piperonaldehyde so readily as its isomeride arid yields a-piperon yZ-6-~~l,enyl-6-),oet~~yZa~l~fu Zgervic acid CH 3>>c:c /GO - 2 H C0,H,C:C<~~H3:0,:CH ' which crystallises from C,H bO%-acetic acid in colourless plates m. p. 201-202" (decomp.). Its solution in concentrated sulphuric acid has a reddish-yellow colour. The corresponding fulgide C,,H,,O crystallises from glacial acetic acid in pale orange-coloured needles m. p. 201-802". In the preparation of the a h a c i d it is advisable to isolate the barium salt and to extract this with alcohol before decomposing with hydro- chloric acid as small amounts of impurity interfere with the crystallisation of the acid.ALFRED LENZNER.] -The a- and P-naphthyl methyl ketones condense with ethyl succinate in the presence of dry ether and sodium ethoxide a t low temperatures yielding the acid esters of y-(u- or P-)naphthyl-y- rnethylitaconic acid C1,H7*CMe C(C0,Et) *CH,* C0,H. 1 he a-naphtb yl compound crystallises from carbon disulphide in colourless prisms m. p. 132O and the corresponding dibasic m i d has m. p. 168" (decomp.). The /?-naphthyl derivative crystallises from a mixture of benzene and light petroleum and has m. p. 103-104°; the correspocding dibasic acid has m.p. 265" (decomp.) and the diethyl ester C,H,,O has b. p. 280-282Oj64 mm. This ethyl ester condenses with piperon- aldehyde a t low temperatures in the presence of dry ether and sodium ethoxide yielding the crude fulgenic acid which on treatment with acetyl chloride yields a-pip~ronyl-6-2-nap~tT~~Z-s-methy?fulgide in the form of a dark orange-coloured powder. XIII. I'riarykated Eulgenic Acids and Their Pulgides. Dyeing Experiments (compare Abstr. 1904 i 672; 1906 i 91).-Good yields (80%) of triarylated fulgenic acids can be obtained by condensing aromatic aldehydes with ethyl diphenylitaconate in the presence of sodium ethoxide. The acids isolated are homogeneous and do not consist of mixtures of stereoisomerides. The acids aro yellow or orange-coloured and the corresponding salts and esters are colourless or only slightly coloured.The corresponding f ulgides arc readily prepared and are coloured red ; they show pleochroism and are XII. a - Pipsronyl- 6 - naphthyl- 6-rnethyZjidyide. - [With C,*Hl,O d d 2i. 380 ABSTRACTS OF CHEMICAL PAPERS. strongly phototropic. The product obtained by the condensation of ethyl phenylitaconate and benzophenone is a lactonic acid and is only slowly transformed into the triphenylfulgenic qcid when boiled with sodium ethnxide solution. The di- tri- and tetra-arylated fulgides in the form of extremely fine suspensions in water are capable of dyeing wool and in this respect resemble the dyes described by Vignon (Abstr. 1910 ii 272 [With ERICII B~~~~~.]-a66-Triphenylf ulgide yields a dibromide C,,H1~O,Br which separates from carbon disulphide in yellow plates containing solvent of crystallisation ; i t loses the solvent on exposure to the air turns a paler colour and then has m.p. 129' (decornp.). [With CURT K o ~ ~ ~ ~ ~ ~ . ] - ~ ~ - D i p h e n ~ ~ - a - p - c h l o r o ~ h e n y l f u l y c acid C6H,C1 C H C( CO,H)*C( CO,H) CPh crystallises from 60% acetic acid in pale yellow needles m. p. 242' (decomp.). The sodium salt crystallises in colourless plates containing alcohol the barium salt is insoluble and the fulgide C,,H1,O,C1 crystallises in orange-red triclinic prisms m. p. 1914 and is strongly pleochroic. [With GUSTAV REDDELIEN.]-T~B methyl ester of 86-diphenyl-a- o-methoxyphenylf ulgenic acid separates from methyl alcohol in colourless crystals m.p. 137'. [With CURT KOHLMANN and GUSTAV REDDELIEN.]-66-Di~~l~elLyZ- a-veratrylfulgenic acid C26H2206 crystallises from 60% acetic acid has a very pale yellow colour arid melts at 154' (decomp.). The sodium salt is sparingly soluble in water and crystallises from 80% alcohol ; the dimethyl ester has m. p. 112' and the fulgide C,,H,,O forms monoclinic plates m. p. 164.5'. [With CURT KOHLMANN THEODOR BADENHAUSEN and HAHALU I(ALNINu.]-66-Di~henyl-a-piperonylfulgenic acid C,,H,,O6 crystallises from chloroform or benzene in pale yellow needles m. p. 221' (decomp.) and the fulgide C,,H,,O forms red monoclinic pleochroic crystals m. p. 20 1'. 66-DiphenyZ-a-1PiperoizyE6utane-Fy-dicarbox ylic acid CH,O,:C,H,*CH,*CH(CO,H) - CH(C0,H) CHPh crystallises from light petroleum in well-developed prisms m.p. 182' (decomp.). The alnhydride forms colourless flat needles m. p. 170-172'. XIV. Styrylfulgenic Acids a g b d Rulgides.-[With ERICH BENARY and SIEGFRIED SEYDEL.]-T~~ styrylfulgenic acids aro best prepared by the condensation of cinnamaldehyde with esters of substituted itaconic acids and can be isolated in the anhydrous form or as com- pounds containing 1H,O which is readily removed on gently heating. CHPh:CH*CH:C( CO,H)*C(CO,H) :CYh has m. p. 212-214' (decornp.). It absorbs water readily yielding the acid C,,H,,O m. p. 200° after sintering at 150-160' when rapidly heated. 66 -Biphenyl - a -stgrylfulgide C2AH1803 crystallises in ruby-r ed needles m. p. 186-189' and yields a dibromide m. p. 167-168' (decornp.).8-Phenyl-a-styryvulgide C2,HI4O3 separates from benzene in orange- coloured crystals rn. p. 126" and a-styryZ-66-dimethy?fuficlgide Cl6Hl4.O3. forms large golden-yellow crystals m. p. 203'. The corresponding 273). 66-Diphenyl-a-styrylfulgenic acid,ORGANIC CHEMISTRY. i. 381 fulgenic acid exists in two forms melting respectively a t 170-173 and 223'. XV. Diphenylenefulgenic Acids the Isome& Lactonic Acids anc Diphenylenefulgides. - [With THEODOR BADENIIAUSEN RUDOLI HENNICKE and EMIL WAHL.]-T~~ diphenylenefulgenic acids art formed by the condensation of fluorenone with esters of substitutec itnconic acids but the conditions vary in the different condensations. a-PAenyl-6-diphen?lZen~~ulgenic acid is orange-coloured has m. p 206-20S0 (decornp.) and yields a fulgide CZ4Hl4O3 which crystalliser from light petroleiim in dark red needles m.p. 182-183". y-Phenyl a-jluoreny Zpcwaconic acid C,,K, C <CH(CozII) c o- '>CHPh crystallises in yellowish-green cubes m. p. 193". aa-Diphenyl-6-dipheny ZenQfuZgenic acid cry stallises from ben Zen e ha m. p. 201" and yields a fulgicle C,oH,sO with m. p. 269'. 6-DiphenyZene-aa-climethy~ulgenic C G C Z ~ C20H,604 crystallises f ron diliite acetone in yellow plates m. p. 308'. The f d g i d e C20H140.1 crystallises from ethyl acetate in orange-coloured needles m. p. 1 80' and when reduced yields a dihydrofulgide C,oH1603 in the form o colourless rods m. p. 218'. Complete Synthesis of Ethylapocarnphoric Acid. GUSTAT KOMPPA and 0. ROUTALA (Ber. 1911 44 858-863).-If Blanc an( 't'horpe's contention that the metbylntion product of methyl diketo npocamphorate is an 0-methyl derivative is correct (Trans.1910 9'7 836) i t is immaterial what alkyl group is introduced because bein attached to oxygen it will be eliminated by hydriodic acid. It wil he seen therefore thzt the following synthesis of ethylapocamphorit ncid in the course of which the ethyl group withstands the a t t a d of hydriodic acid renders Blanc and Thorpe's position still les! tenable. A methyl-alcoholic solution of methyl diketocqoramphorste i! treated with cold methyl-alcoholic sodium methoxide ; ethyl iodidt is then added and the mixture is boiled for twenty hours. Tht resulting ethyl and diethyl derivatives are separated by sodiurr carbonate the former after being liberated from the alkaline solutior by dilute hydrochloric acid being freed from unchanged methy diketoupocamphorate by means of ethereal copper acetate in whicl the copper derivative of methyl diketoapocamphorate is insoluble Methyl dikstoethylapocampho~ate 69-70*5' obtained in this way forms brilliant rhombohedra anc develops a reddish-brown coloration with aqueous alcoholic ferric chloride.Its solution in sodium hydrogen carbonate and a littlt sodium carbonate is reduced by 2.5% sodium amalgam in ar atmosphere of carbon dioxide yielding ultimately an amorphour glassy mass of di?bydToxyethylapocamphoric acid which withoui further examination is heated on the water-bath for thirty hours witk J. J. S. vO-CH( C0,Me) CO* CEt (C0,Me) >CMe rn. p hydriodic acid D 1-7 and red phosphorus whereby ethyldehydroapo camphoric acid I C(Co2H)>CMe m.p. 190-1 9 lo is obtained CHz= CH,*CEt(CO,H)i. 382 ABSTRACTS OF CHEMICAL PAPERS. By heating this acid with hydrogen bromide in glacial acetic acid for twelve hours a t 125O and reducing the product with zinc dust and glacial acetic acid the two stereoisomeric forms of ethylapocamphoric acid are obtained. These are separated by treating them with acetyl chloride dissolving the product in ether and shaking the ethereal solution with aqueous sodium carbonate. trans-Eth?lZapoctcmhoric acid obtained from the sodium carbonate solution is an oil. The ethereal solution contains the anhydride m. p. 93O (cow.) of cis-ethylapo- caniphoric acid; the cis-acid itself CH2-cH(Co2H)>CMe I has m.p. 183.5-184'. CH,*C Et(C0,H) Methyl 4-keto-5-ethoxy-3-ethyZdehydroapocarnpT~orate >CMe v(OEt):C(CO,Me) CO-CEt(CO,Me) the diethyl derivative obtained in the ethylation of methyl diketo- ccpocamphorate has b. p. 166-167'/9 mm. D$E 1.1270 and n:.' 1.48990 and does not give a coloration with ferric chloride. c. s. Tannins. IV. Galloyl-ellagic Acid. MAX NIEREKSTEIN (Ber. 19 11 44 837-840).-TetragalZoyZ-elZugic acid Yo* ~,H[O*CO* C,H,( OH),],* (? O-C,H[O*CO*C,H,(OH),l,.CO' prepared by the interaction of ellagic acid in sodium hydroxide solution with tricarbomethoxygalloyl chloride crystallises in small yellow noedles m. p. 297-300'. It gives a bluish-green coloration with ferric chloride ; on acetylation an amorphous powder is obtained. It is absorbed quantitatively by hide powder and casein and pre- cipitated by gelatin Partial hydrolysis could not be effected.E. F A. N-Alkylated Aldoximes. JOHANNES SCHEIBER (Ber. 19 11 44 761-769. Compare Mills and Bain Trans. 1910 98 1866).-All attempts to prepare N-a1 kylrtted aldoximes in optically active modifica- tions have proved unsuccessful (compare Kipping and SaluTay Trans. 1904 85 438). [With H. FLEISCBMANN.]-T~~ N-6enxyZ derivative of opianic acid aldoxime C02H*C,H,(OMe)2*CH< I obtained by condensing opianic acid with P-benzylhydroxylamine crystallises from alcohol in colourless prisms m. p. 153'. The cinchonine salt C,,H,,0,N,,3H20 crystallises from water in long brilliant transparent needles m. p. 97O ; the anhydrous compound has m. p. 115-1 17O and rapidly absorbs moisture on exposure t o the air.The salt has [a] + 78-15' in alcoholic solution and on treatment with ammonium hydroxide solution yields an inactive ammonium salt. [With K. KLOPPE.]-~~ has not been found possible to obtain isomeric alkylated oximes by condensing P-benzyl- or P-phenyl-hydroxyl- amine with an optically active aldehyde for example helicin. N-Benzyl- helicinaldozime C,H,,0,*O*C,H,*CH<~'C7H7,H,0 crystallises in N*C,H 0ORGANIC CHEMISTRY. i 383 small felted needles m. p. 165O and has -56.82' in alcoholic solution. The corresponding phsnyl derivative C19H2107N H20 forms small colourless needles m. p. 180° and has [a] - 59.27' ; it rapidly absorbs water yielding a trihydrate m. p. 125'. When hydrolysed by emulsin the phenyl derivative yields inactive N-phenylsalicyl- aldoxime (Plancher and Piccinini Abstr.1905 i 705). N- Phenyltetru- acetylhelicinaldoxime C,H,O(OAC),*O*C,H~*CH<~~~,H~O obtained by condensing tetra-acetylhelicin with P-phenylhydroxylamine and also by the action of P-acetobromoglucose on the sodium derivative of phenylsalicylaldoxime separates from benzene in colourless crystals with m. p. 166" and [a]; - 29.68'. J. J. S . Hydroaromatic Compounds. Chloro-derivatives of Hydro- aromatic Ketones and Sernibenzenes. KARL AUWERS (Ber. 191 1 44 788-809. Compare Abstr. 1907 i 399-403).-Doubly unsaturated ketones of the type of l-methyl-l-dichloromethylcyclo- hexndien-4-one form additive compounds with $wo or four atoms of chlorine and these compounds react with alkalis losing hydrogen chloride and yielding chloro-derivatives of the original ketones.From these chlorinated ketones for example O C < ~ ~ i ~ ~ > C M e * C H C l tertiary alcohols can be syathesised by means of magnesium alkyl iodides and from the alcohols alkylidenechlorocyclhexadienes (semi- benzenes) are obtained by the action of anhydrous formic acid. When heated the alkylidene derivatives readily undergo molecular rearrange- ment and by the wandering of the *CHC12 group yield benzene derivatives of the type 3~chloro-4-~~-dichloroe~hyltoluene. The position of the ring chlorine atom has been proved by the elimination of hydrogen chloride from this compound and the oxidation of the resulting styrene derivative to 2-chloro-p-toluic acid. 5 6-Dicldoro-l- rnethyZ-l-dichlo~*omethyl-A2-cyclohexen-4-one obtained by the action of dry chlorine gas or of a carbon tetrachloride solution on the corresponding hexadiene forms glistening regular crystals m.p. 118-l~Oo (decomp.). It is volatile with steam and decomposes when kept for some time 5 -Chloro- 1 -me thy Z- 1 -dichZoromethyl-A25-cyclohexad~en- &one C,H70CI 3 crystallises from dilute methyl alcohol in small needles m. p. 67" b. p. 1 8 9 . 5 4 90°/22 mm. and yields a semicadazone C,Hl,ON,Cl in the form of compact colourless needles m. p. 181-182" which are hydrolysed by 30% sulphuric acid. 3 -ChZoro - 4 - hydroxy-1 4-dirnethyl-l- dichloromethyl- A2:'-cyclohexa- cliene CKCI,>CGH'<OH Me Me crystallises from light petroleum in colour- less needles m. p. 104" and when shaken for ten minutes with eight to ten times its weight of concentrated formic acid yields 3-chlo~o-1- methyl- 1 -dicliZorometliyl-4-nzethyle~e-~z~~-cyclohexccdiene C,H,CI ; this is transformed at 85' into 5-chloro- l-methyl-4-~P-dichZoroethylbenxsne,i.384 ABSTRACTS OF CHEMICAL PAPERS. C,H,CI which is acolourless oil b. p. 147*8-148°60/19 mm.,DiO 1.2873 la' 1.54528 n 1.55012 rtg 1.56130 !any 1.57143. exists in two stereoisomeric modifications. The trans-compound is formed when the ketone is treated with a carbon tetrachloride solution of chlorine (3 mols.) in the presence of a little iron powder ; it separ- ates from light petroleum in regular crystals m. p. 135-1 36O (decomp.) and is more stablo than the dichloride. The cis-compound is formed when carbon disulphide is used as 8 solvent and the solution exposed to light.It crystallises in brilliant cubes has m. p. 176" (decomp.) and is not SO soluble as the isomeride. 3 5 - Dichloro-1-methyl -:I - dichloromethyl -Az '- cyclohexatliene-4-one C,H,OCl obtained by warming gently either the cis- or tvans-corn- pound with alcoholic potassium hydroxide or with an acetic acid solution of potassium acetate crystallises from light petroleum in colourless flat needles m. p. 97" and does not yield a semicarbazone. When reduced with zinc dust and acetic acid i t yields o-dichloro-p- cresol (Claus and Riemann Abstr. 1883 11 11). 3 5-DichEoro-4- hydroxy-1 4-dimethyl- 1 -dich lorowzethyZ-A2 5-cycloT~exadiene C,H,,OCl exists in two stereoisomeric forms The one crystallises from light petroleum in short glistening brittle needles m.p. 104' or with &.C,H in glistening needles m. p. 97-98' the other crystalhes from light petroleum and has m. p. 60-70'. 3 5-DichZoro-l-rnethyl-1- ~icT~loromet?~~Z-4-methylene- A2 5-cycloThexccdie?ae C,H,C I obtained by heating the hydroxy-compound with formic acid has D:"' 1 *4084 na 1.57462 n 1.58005 and n p 1.59387 at 16.7'. 3 5-Dich Zoro-4-PP-dici2loroeth yltoluene C,H,CI ,Me*CH CHCI is a colourlessoil b. p. 158.6-159*5°/15 mm. and has D:91a3976 n 1.56306 n 1.56754 228 1.57991 and nny 1.59033 a t 19'. Ice-cold concentrated sulphuric acid transforms the alcohol (m. p. 104') in to 3 5-dic?tloro-2 4-dirnetl~ylbenxylidene chloride C,HCI,Me,*CHC12 which crystallises from light petroleum in glistening needles m.p. 44-45O. The corresponding aldehyde C,HCI,Me;CHO crystallises in long opaque needles m. p. 108-112" and yields a sernicarbazone ClpH110N,C13 m. p. 231-232'. 3 5-Dichloro-2 4-dimethyEbenxoic aczd C,HCI2Me2*CO2H crystallises in colourless glistening plates m. p. 19l0 and its methyl ester in slender needles m. p. 49". 1 3-Dimethyl-1 -dichloromethyl-A2:5-cycZohexadiene-4-one yields a dichloride only namely 5 6-dichloro-1 3-dimethyl-1-dichloromethyl- A2-cyclol~exen-4-one CO<CHCl~~HC1>CMe*CHCI C M e Z C H which crystallises from hot alcohol in small colourless needles m. p. 100'. 5-Chloro- 1 3-dimethpl-1 -dichloromethyl-A2~:5-cyclohexad~ene-4-one cQH,oc13 crys- tallises from dilute alcohol in nacrBous plates m. p. 56" and reacts with magnesium methyl iodide yielding 5-chloro-4-hyd~oxy-l 3 4- tr~~nethy~-~-d~chZorometlzyZ-A2~5-cyclohexad~ene Cl,H130Ci3 which crys- tallises from light petroleum in needles m.p. 80'. When shaken with formic acid for half an hour the alcohol yields 6-chloro-1 :3- 2 3 5 6-~etrccchlo~~o-l-methyZ-l -dichZoromethylcyclohexan-4-one CSH80CI 6,ORGANIC CHEMISTRY. i. 385 d~lmetiLyZ-l-dichloromethyl-4-met~ylene-A2' '-cyclohxadiene CloH~lCl 3 as a pale yellow oil Di7'3 1.2693 n 1*56255 wPD 1.56812 and np 1.58230 at 17.3". B-C?bloro- 1 3-dimethyl- 4-PP-dicldoroethyE benzene C,H2C1Me2*CH,*CHCl is a yellow oil b. p. 155'/17 mm. DtG" 1.2622 n 1.54788 nD 1*55878 ng 1.56427 and n 1-57091 a t 16.1° and reacts with alcoholic potassium hydroxide yielding 6-W-dichloro-2 4-dirrzethylstyrene C,H,Me2Cl*CH:CHCl which crystallises from methyl alcohol in slender needles m.p. 38-38.5'. When oxidised it yields an aldehyde and from the aldoxime by the (elimination of water 6-cldoro-2 4-dimethyl- benaonitrile C H NCI is obtained. This forms brittle glistening needles m. p. 5i0 and is identical with the nitrile obtained from 6-chloro-2 4-dimethylztniline. The corresponding amide has m. p. 167". J . J s. Catalytic Hydrogenation of aycZoPentanone. MARCEL GODCHOT and FELIX TABOURY (Compt. rend. 191 1 152 S81-S83).-On hydro- genating cyclopentanone in presence of reduced nickel a t 125O water is formed with cyclopentane cyclopentanol (50%) and a ketone (40%) having an odour of menthol. The latter is probably a-cyclopentyl- cyclopentanone C1,H,,O arising by hydrogenation of an intermediate unsaturated ketone.It has m. p. -13'. b. p. 115-117"/12 mm. D1 0.9801 ; the oxime has m. p. 76" ; the semicarbaxone m. p. 210'. w. 0. w. Action of Light on Cinnamylideneacetophenone. HANS STOBBE and CONRAD RUCKER (Ber. 1911 44 869-S72. Compare Stobbe and Wilson Trans. 1910,9'7',1722).-When a saturated solution of cinnamylideneacetophenoae in benzene or chloroform is exposed to sunlight a white precipitate consisting of a bimolecular ketone and a resin is obtained after two to three days; the same result is obtained by using a quartz mercury lamp the precipitate in this case contain- ing a larger proportion of the resin. The precipitate is recrystallised from a mixture of alcohol a& chloroform and is then repeatedly extracted with acetone whereby the pure ketone (C17H140)2 m..p. 192" is obtained. By distillation in a vacuum or by heating its solution in phenetole or phenylcarbimide at 140-1 BOO the bimolecular ketone is depolymerised and yields not the original ketone but an isomeric isocimamyZideneacetophenone Cl7H,,O? m. p. 235". The question whether the three ketones are interconvertible has not yet been satisfactorily answered. Chloroform solutions of the zsoketone and of the bimolecular ketone are more or less resinified by exposure to sunlight. When however a saturated solution of cinnamylideneacetophenone in chloroform is exposed to sunlight for about a month and the precipitate is removed the mother liquor after exposure to diffuse daylight for a year and a-half contains the yellow ~8ocinnamy~idelneacetophenone together with the bimolecular ketone. c.s.i. 386 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Alkylanthraquinones from Alkylbenzoyl ahlorides and Aluminium Chloride. I. CHR. SEER (Momotsh. 191 1 32 143-166).-When m-toluoyl chloride and aluminium chloride are heated at 130' for two hours and finally a t 130-140O for sixteen hours the product is a mixture of probably three dimethyl- anthraqiiinoneq the least soluble of which m. p. 235-236' is obtained in 19% y3ld by crystallisation from acetic acid and from nitrobenzene. This compound which is identical with the substance obtained by Lavaux by the interaction of rnethylene chloride toluene and aluminium chloride is also produced in the following manner m-l'oluoyl chloride and m-xylene in carbon disulphide yield with aluminium chloride m-tolyl m-4-xylyl ketone C,H,Me*CO*C,H,Me b.p. 315-320 which is converted after being boiled for five days into 2 6-dimethylanthracene m. p. 243O; the latter is oxidised by chromic and acetic acids to the dimethylanthraquinone m. p. 235-236'. A consideration of the anthor's and of Lavaux's methods of preparing the substance leads by the process of exclusion to the conclusion that the compound must be 2 6-dimethylanthra- quinone ; Dewar and Jones' supposed 2 6-dimethylanthraquinone (Trans. 1904 85 212) is probably the 2 7-isomeride. By nitration with concentrated snlphuric acid and potassium nitrate 2 6-dimethylanthraquinone yields (1) 1 5-dinitro-2 6-dimethyl- afithraquinone colourless needles which is converted into the diumino- compound m.p. 255-356O dark red needles by reduction with alkaline sodium hydrosulphide. 1 ; 5-Di-iodo-2 6-dimethylanthru- quinone obtained in the usual way forms orange-yellow needles m. p. 273O. Anthraquiaone-2 6-dicarboxylic acid conveniently obtained by boiling 2 6-dimethylnnthraquinone with chromic and glacial acetic acids for sixty hours forms a chloride C,,H,O,CI m. p. 197-198' from which the amide C1,H,,O,N m. p. above 370° is produced by alcoholic ammonia and 2 6 - ds-a-naphtho ylanthraquinone C36H2004 m. p. 183-185O by naphthalene and aluminium chloride in nitro- benzene at 75-80° after twenty hours. c. s. Phenanthrene Series. XXX. Preparation of 4-Hydroxy- from 4-Nitro-phenanthraquinone. J ULTUS SCHMIDT and OTTO SCHAIRER (Bey. 19 11 44 740-745).-4-Hydroxyphenanthraquinooe has been prepared from the corresponding nitro-compound (Schmidt and Austin Abstr.1904 i 69) by reduction with tin and hydro- chloric acid diazotising and warming with water. 4-ATitrophenanthraquinonedioxime C,,H,O,N separates from alcohol in pale yellowish-green crystals m. p. 210" (decomp.). 4-Arninophsnanthraquinone NH2*C,H3<C@->C0 is a black powder C,H* with a red lustre has no definite m. p and irrTtates the nasal mucous membrane. The hydrochloride of 4-aminophenanthrtcquinol obtained by the reduction of the nitroquinone crystallises in colourless plates and turns brown during the process of drying. The most C,,H,20,N c1,ORGANIC CHEMISTRY. i. 387 characteristic derivative of the aminoquinone is the 4-arninophnanthm- NH,*Y,H3*$XN C,H;C:N pike nu xine >C,H the hydrochloride of which separates from water as a pile ireyish-green crystalline powder m.p. 274-2'75' (decomp.). The base forms an olive-green crystalline powder m. p. 190° (not sharp). The acetyl derivative C16H1,,04 separates from alcohol in pale brown nodular masses m. p. 188-189O. 4-Hydroxyphenanthraquinone- semicarbuzone C1,H,,0,N3. forms brownish-red crystals m. p. 258' (decomp.) and 4-?&ydrox:yphennnthruphenuzine C,,H,,ON dark red microscopic crystals m. p. 333' (decomp.). CARL LIEBERMANN and MILAN ZSUFFA (Bey. 1911 44 852-4358. Compare this vol. i 202). -The following compounds shorn that an extensive parallelism exists between aceanthrenequinone and acenaohtheneqoinone.Aceanthrene- 4-Hydrox~phenunt?maquinone forms a red powder m. p. 285'. J. J. S. Derivatives of Aceanthrenequinone. quinone which is pukfied best by men& of hydrogen sulphite is oxidised by chromic CH CH 'CF' <6->CFH3 Or 'GH4< I >7BH3 I I 7- co -CCI CCI,-bO its-compound with sodium acid to anthraquinone- 1 - carboxylic acid m. p. 293-294' (corr.). By dis- tillation with zinc dust it yields impure aceanthrene m. p. 115-140°. By treatrn en t with phosphory 1 chloride and phosphorus pentachloride it yields dichloroaceanth&enone (annexed formula) yellow needles m. p. 182-184'. Acecmt hren - 2 -ind o le-indigot in ' ' [ rndoxylacennthlre.none] co c"->c C i 4 H s < & ~ ~ ~ 6 49 m. p 266" brown needles,%obtained by heating aceanthrenequinone and indoxyl in glacial acetic acid containing a little hydrochloric acid gives a brown coloration with concentrated sul phuric acid which changes to grey and then t o blue.66 Aceanthren-2-thionaphthen-in- c-c*s prepared in a similar manner from hydroxg thionaphthen (compare Friedlander and Bezdzik Abstr. 1908 i 673). Azonium bases are readily obtained by the interaction of ace- anthrenequinone and semidine bases. Thus the quinone and 5-ethoxy- 2-aminodiphenylamine hydrochloride in boiling glacial acetic acid "yield ty the addition of a little lydrochloric acid ethogpheylace- anthraphenazoniwm chloride C,,H,<&N >C,H,*OEt a dark green metallic mass ; the corresponding nitmte forms reddish-brown needles. Ethox~phenylacenaphthuphenuzoniuin chloride C,,H,<~~~hC1>C,H3-OEt prepared in a similar manner from acenaphthenequinone for the purpose of comparison forms brownish-yellow needles and dyes wool co co->c 13[ digotin " [Ox~t~ionaphthenyEnceanth~enone] C,,H,< I - I 6 4 is CNPhC1i.388 ABSTRACTS OL' CHEMICAL PAPERS. yellow; the preceding anthracene derivative dyes wool a dirty ponceau-red. vPh*oH m. p. 160-163" pale CPh*OH' DiphenyTaceanthrene y Zyco! C,,H,< yellow needles obtained from aceanthrenequinone and magnesium phenyl bromide is converted by concentrated hydrochloric and glacial acetic acids into dipiLenny7acea.lzthl.enolze C',,H,< I m. p. 215-217° yellow needles (compare Beschke arid Kitnj Abstr. 1909 i 917). nipl~enyZ-4-carboz?lZic acid CO,H~C,H,~C,H m. p. 224" obtained by heating diphenyl oxalyl chloride and aluminium chloride in carbon disulphide is best purified by means of its sparingly soluble sodium salt,.Retenecnrboqlic m i d C1,H,7*C0,H prepared and purified in a similar manner has m. p. 121-123O. Xanthone yields a dicarbos3Zic ncid Cl,H,0(C02H)2 m. p. above 265O under similar conditions. co CPh c. 8. Oxidation of Camphene. GUSTAV KOMPPA (Bey. 191 1 44 863-865).-When preparing rqvocamphoric acid by the oxidation 6f camphene by nitric acid the author has always obtained an acid which does not yield an anhydride by treatment with acetyl chloride and which he has always regarded f t ~ ! trccizs-c~z~oc,zmphoric acid. By further examination however the acid which has the composition Cl,,H1403 and m. p. 233*5-234*5" and forms a phenylhydrazone m.p. 146" proves t o be ketopinic acid. This discovery is of interest became now all of the compounds- campheneglgcol hydroxycamphenylanic acid tricyclenic ncid hydroxy- qocamphanecarboxylic acid ketopinic acid carboxyapocamphoric acid- which represent the successive steps in the oxidation of camphene to apocamphoric acid have with the exception of hydrouyupocamphan- carboxylic acid been isolated from the products of oxidation of camphene. c. s. Components of Essential Oils. 6 6 False Camphor W o o d Oil " (faux camphrier). Natural Occurrence of Myrtenal and d-Perilla Aldehyde. FRIEDRICH W. SEMMLER and B. ZAAR (Ber. 1911 44 815-819).-False camphor wood oil in addition to d-limonene and cineol consists mainly of an aldehyde CIoHl40 b. p. 99-104"/9 mm. Dls 0.965 nD 1.50803 [.ID] + 135*6" which 1s the optical isomeride of Z-perilla aldehyde.I n addition the oil contains R dicgclic aldehyde C,,H,,O identical with the synthetical myrtenal (Semmler and Bartelt Abstr. 1907 i 429). This is the first occurrence of myrtenal in an essential oil. Myrterial and perilla aldehyde are related in the same manner as pirieue and limonene and the occurrence of both in t h e same oil is remarkable. E. F. A. Oil of Thea Sasanqua. H. KIMURA (Ber. Deut. Phama. Ges. 1911 21 209-212).-The young leaves of the Japanese Fhea &sanqua are steeped in water for twentg-four hours and then distilledORGANIC CHEMISTRY;. i. 389 with steam. The oil the yield of which varies from 0*4-1-0%,according t o the period elapsing between the gathering of the leaves and their treatment (no oil is obtained after three months' keeping) is optically inactive has a sweet pleasant odour and Dzl 1.061. It contajns about 97% of eugenol a very small amount of an aldehydic or ketonic substance and an ester.By hydrolysis with 2% alcoholic potassium hydroxide the ester yields a n alcohol with the odour of geraniol and a malodorous acid ; these aro being further examined. c. s. Hydrogenation of Turpentine Oil. GUSTAVE V a v o ~ (JaZd. SOC. chim. 191 1 [iv] 9 256-261. Compare Darmois Abstr. 1908 ii 747 ; 1910 i 52).-The hydrogenation of French Germail and American turpentine oils has been studied and it is shown t h a t (1) these all consist of CL- and /3-pinenes; (2) the two pinenes yid(1 t h e same hydro- carbon on reduction ; (3) sophistication of turpentine oil may be detected by ( a ) fractionation and (b) reduction and examination of the resulting products.One hundred and thirty-six grams of the fraction of turpentine oil boiling at 155-165" on reduction with platinum-black in presence of hydrogen absorbs 1 gram-mol. of hydrogen giving a Iqld~ocarbon Cl0Hl8 b. p. 166" m. p. -SO" DE 0.861 and [u] +23.8" to -23,s" for X = 578 depending on the source of the oil used. The relationship between the rotations of fractions of the same turpentine oil and those of the same fractions after reduction indicates that the tliree oils examined consist essentially of u-pinene and P-pinene. The latter has b. p. 164" m. p. - 50" uJ = 39*6O and on reduction gives a hydrocarbon having aJ = - 40.6". a-Piiione on reduction gives a hydrocarbon having aJ = + 41".French German and American turpentine oils contain respecti,vely 6 3 23 and 72% of a-pinene consisting of the two optically inverse forms in varying proportions. A pure turpentine oil should consist of a t least SO% boiling below 164" and t h a t portion boiling from 155-158" on hydrogenation by platinum-black should give a hydrocarbon boiling constantly a t 166". The platinum-black may be used several times without losing its activity if it is washed with ether after each operation and heated for a few minutes a t 200". 1'. A. H. Caoutchouc Nitrosites and their Application in Analysis. PAUL ALEXANDER (Zeitsch. aclzgew. Chem. 191 1 24 680-687. Com- pare Abstr. 1907 i 433).-This paper is devoted mainly to a criticism of a communication on this subject by Gottlob (Abstr.1908 i 95). The author brings forward fresh evidence in support of his contention that a nitrosite having the comDosition ClOH,507N,Y cannot be obtained directly from caoutchouc as stated by Gottlob (Zoc. cit.) and Harries (Compare Abstr. 1905 i 233). The- nitrosite formed directly from the interaction of nitrous fumes and caoutchouc approximates t o the formula C,H,,O,N but is not to be regarded as a simple substance. The production of carbon dioxide during the reaction has been verified and it has been demonstrated also that thei. 390 ABSTRACTS OF CHEMICAL PAPERS. same gas is liberated when the crude nitrosite is heated at 40-80°; in fact it has been possible to absorb about 87% of the one molecular proportion of carbon dioxide evolved from one molecular proportion of caoutchouc. I n conclusion the author states that this reaction may be employed for the analysis of crude caoutchoucs and in many cases also for the estimation of caoutchouc in vulcanised rubber products.W. H. G. Gold Vulcanisation. B. V. BYSOFF (Zeitsch. Chem. Ind. Kolloide 1911 8 209. Compare Abstr. 1910 i 865; this vol. i 314).- Comparative measurements have been made of the amount of sulphur which is fixed when dry caoutchouc is vulcanised by means of dry and moist benzene solutions of sulphur chloride. In two pairs of experiments with benzene solutions containing 0-5 and 1.0 gram of sulphur chloride per 100 c.c. i t mas found that the amount of fixed sulphur in the vulcanisation with the moist solution was only 76 ( 7 7 ) % of that fixed when the dry solution was emplojed. With undried caoutchouc and a dry benzene solution a similar reduction of the amount of fixed sulphur mas observed.H. M. D. Behaviour of Colloidal Metals (Platinum Gold Silver and Palladium) Prepared by Bredig’s Method on Solutions of Guaiaconic Acid. GEORGE A. BUCKMASTER (7th Intern. Cong~. Appl. Chern. Sect. IV A 2 29).-Guaiaconic acid in oxygen-free alcohol is oxidised to guaiacum-blue by colloidal metals prepared by Bredig’s method for the particles of metal contain occluded or adsorbed oxygen. A given weight of any of these colloidal fnetals oxidises a definite amount of guaiaconic acid. The metallic sol is then inactive but may be reactivated by air or oxygen.Gold sol when first prepared is active for a few hours but rapidly loses the propert,y which is preserved for weeks and months by the sols of platinum palladium and silver. The occluded oxygen of platinum sols can be driven out by boiling or by the passage of pure hydrogen or carbon dioxide and the inactive sols obtained can be reactivated by oxygen. The oxidation of guaiaconic acid is therefore due not to the colloidal metal as such but to the occluded oxygen. The action of platinum- black on guaiaconic acid is similarly due to occluded oxygen. R. V. S. The Pseudo-Peroxgdase Reaction between Hmmoglobin its Derivatives and Guaiaconic Acid (Guaiacum Reaction for Blood Pigment). GEORGE A. BUCKMASTER (7th Intern. Congr. AppE. Chem. Sect. IV A 2 30).-The oxidation of guaiaconic acid aloin or leucomalachite-green in the presence of traces of hydrogen peroxide is effected by minute amounts of haemoglobin or any of its derivatives which contain iron. Pure haematoporphyrin or haematoidin (that is iron-free derivatives) are incapable of causing the oxidation of these substances.Blood solutions which have been heated in a sealed tube at 200’ for three hours still give the reaction. The reaction is therefore not due to a peroxydase but is connected with the presence of the iron contained in the haemoglobin. R. V. S.ORGANIC CHEMlSTRE. i. 391 The Sugar in Sophorin. HENRI TER MEULEN (Gederzlcboek aange- boden aan J. M. van Benmeltm 1910,~:411-P15).-A sugar has been isolated from sophorin a glucoside present in the flower-buds of the Chinese yellow currant (Sophora japonica) and proved to be identical with rhamninose although i t was not obtained pure.Sophorin mas treated with rhamninase solution for a day a t GOo the mixture filtered and after concentration at reduced pressure the filtrate boiled with alcohol to destroy the enzyme. Fractional precipitation with ether yielded a light yellow syrup. With the polarimeter a rotation of - 3 O 2 9 ' was observed the theoretical value for the same quantity of rhamninose being 3'36'. Sophorin is probably iden tical with rutin. A. J. W. Balanophorin. I. M. SIMON (Monatsh. 1911 32 89-104).- Brief references are given t o previous investigations of balanophorin the waxy substance obtained from the Bulcmophorae. It is extracted by ether from the dried Javanese tubers and puri6ed by successive treatment with alcohol and acetone.The purified substance C12H200(?) is ti white amorphous powder bas m. p. 56-57' and is not decomposed by aqueous or alcoholic alkalis even a t 140'. By distillation under 19 mm. or by fusion with potassium hydroxide a t 150-210° it yields palmitic acid aud obher products as yet unexamined. c. s. Dye in the Root of Azafran. CARL LIEBERMANN (Bey. 1911 44 850-851).-The root of a plant obtained from Paraguay and belonging t o the family of the Scrophulariaceae is used under the name azafran or azafranillo t o colour fats. It contains about 1% of a dye called azufrin which is easily extracted by boiling benzene. From the solution the dye is obtained in orange-red crusts which form microscopic needles m.p. 2 14' after recrystallisation. It doea not contain nitrogen or methoxy- or ethoxy-groups but the presence of one hydroxyl group is shown by Zerewitinoff's method. It dyes wool yellow and forms yellow t o orange lakes with Scheurer's mordante but not with the usual mordants ; wool extracts the whole of the dye from a hyposulphite vat. The dye gives a fine blue solution in concentrated sulphuric acid which becomes violet by the addition of alcohol. The examination of the dye is being continued. c. 5. Chlorophyll. XIII. Decomposition and Formation of Chlorophyll. RICHARD WILLSTATTER and ARTHUR STOLL (Annaden 1911 380 148-154)-In continuation of the previous work (this vol. i 141) it is shown that chlorophyllase has synthesising properties and can build up chlorophyll from phytol and chloro- ph yllide. The method consists in hydrolysing chlorophyll f o r example by digesting the meal from leaves of Gallopsis with moist ether for several days then adding phytol and in the course of several days one- third to three-fourths of the original chlorophyll is regenerated.This confirms the view that the enzyme plays a n important functioni. 392 ABSTRACTS OF CHEMICAL PAPERS. in the formation OF chlorophyll in plant tissues. The chlorophyll obtained yields the same phytochlorin-e and phytorhodin-g as are obtained from natural chlorophyll. It is also shown that chlorsphyllase can esterify chlorophyllide in the presence of ethyl alcohol yielding ethyl chlorophyllide. J. J. S. Chlorophyll. XIV. Comparative E x p e r i m e n t s with Chloro- phyll from Different Plants.111. RICHARD WILLSTATTER and MAX ISLER (Anncclen 191 1 380 154-1 76. Compare Willstatter Hocheder and Hug Abstr. 1910 ii 150 ; WillstStter and Oppe this VOJ. i 140).-The solution of the question as to the identity of the chlorophyll obtained from different plants has been attempted by an examination of the phytochlorins and phytorhodins obtained by their decomposition. Previous experiments have indicated that in the great majority of cases the products obtained from dried leaves are phyto- chlorin-e and phytorhodin-g although several exceptions had been met with. It is shown in the present communication that these exceptions are due not to differences in the natural phytochromin but to the methods of treatment of the material producing alterations in the chlorophyll.All these exceptions disappear when the dried material is extracted the chlorophyll solution immediately treated with acid and the resulting phzeophytin hydrolysed in the cold with alkali. Under these conditions the dried leaves of all varieties of plants yield only phytochlorin-e and phytorhodin-g. If the filtered chlorophyll extract is kept the phytochromin under- goes change especially in the case of the extractjrom stinging nettles and the final products of decomposition are phytochlorin;f which is solublo in 11% hydrochloric acid and a phytorhodin with feebler basic properties than phy torhodin-g. OF extreme importance is the sensitiveness of phytorhodin towards alkali the longer the product is left in contact with warm alkali the smaller is the yield of phytorhodin.If however this source of error is avoided the relative molecular proportions of phytorhodin to phytochlorin are approximately 1 2.5. Experiments have beeu made with fresh vegetable tissues as well as with dried and the investigation is complicated by the fact that during the processes of dividing and extracting large quantities of the material fermentative changes of a complex nature can take place. For example in the case of grass phytochlorin-f is obtained whereas dry grass gives the normal product phytochlorin-e. The best method of treating the fresh tissue is the addition of aqueous methyl alcohol by means of which the division and extraction of the material is greatly facilitated.Under these conditions provided the extraction is made immediately after the addition of the alcohol the phsophytin obtained yields in all cases the normal products of decomposition namely phytochlorin-e and phytorhodin-g and in practically the same proportion as obtained from dry leaves. The question as to whether the pbytochlorin and phytorhodin are derived from the same molecule of chlorophyll and phaeophytin is discussed and the conclusion is drawn that in all probability they are derived from different molecules so that chlorophyll consists of two components one of which gives rise t o phytochlorin and the other toORGANIC CHEMISTRY. i. 393 phytorhodin (compare Tsvett Abstr. 1907 i 787). The amounts of phytochlorin-e and phytorhodin-g obtained from tt given quantity of phaeophytin by tbe action of alcoholic potassium hydroxide were estimated colorimetrically by comparison with known quantities of the pure substances.The fresh material examined included leaves of the following Hyloconiurn Aspidium Equisetum Pinzlcl Salix Urtica Platanus Rubus BUXUS Aesculus Petroselinum Heracleum Galeop& Solanurn and Sarnbucus. J. J. S. Chlorophyll. XV. Isolation of Chlorophyll. RICHAND WILL- STATTER and ERNST HUG (Annalen 19 11,380,177-2 1 I ).-The object of the investigation has been the isolation of pure chlorophyll. It occurs in plant tissues mixed with yellow pigments for example carotin and xantbophyll and with fats waxes and salts of aliphatic acids. Many of tbese distribute themselves between solvents in much the same manner as chlorophyll itself and their removal is tedious.The presence of these impurities always reduces t h e magnesium contents of the colouring matter and is indicated by the presence of calcium compounds in the ash derived from the specimen. The chlorophyll was always extracted from dried leaves and esti- mated colorimetrically by Willstatter Hocbeder and Hug’s met hod (Abstr. 1910 ii 151) by comparison with ethylchlorophyllide solutions of known concentration. The expression degree of purity is used to express the percentage of chlorophyll in 100 grams of dried extract when heated for a half to three-quarters of an hour under reduced pressure. Although the amount of chlorophyll extracted is greater the longer the extraction is carried out it is inadvisable to prolong the period of extraction as the chlorophyll can undergo alteration during this time (compare Willstiitter and Oppe this vol.i 141 and Willstatter and Isler preceding abstract). To obtain unaltered chlorophyll i t is essential that the extraction should be rapid although the amount extracted is not so large. The method used is a modification of that of Willstatter and Stoll ( t h i s vol. i 142) and consists in spreading tlhe dried meal on the thimble before the addition of the solvent. With a charge of 2 kilos. the extraction requires two to three hours and the volume of solvent is about 1.5 litres per kilo. of meal. Using ethyl alcohol the degree of purity of the extract is about 14-16 as the chlorophyll contains about six times its own weight of impurities.Before treatment with alcohol i t is an advantage to subject the meal to a preliminary extraction with benzene (3 litres) and then light petroleum (1.5 litres per kilo.). The light petroleum is essential in order to remove the benzene and it is not necessary to dry the meal after extraction with the different solvents. This preliminary extrac- tion increases appreciably the degree of purity of the subsequent crude solution in light petroleum. To obtain such a solution the alcoholic extract is shaken with two- thirds its volume of light petroleum and one-third its volume of water. Fractional extraction offers no advantages and the degree of purity of VOL. c. i. e ei 394 APBSTRACZS OF CHEMICAL PAPERS. the solution is usually 33-40 provided the preliminary extraction with benzene and light petroleum is carried out.By twice washing the light petroleum solution with aqueous methyl alcohol (90%) it is possible to increase the degree of purity to 50-60. It is essential that the alcohol should not be too concentrated as considerable amounts of chlorophyll are then removed. The degree of purity can be increased to 70 by extracting the washed light petroleum solution twice with 95% methyl alcohol saturated with light petroleum (b. p. 30-5O') when about half the chlorophyll is dissolved by the alcohol. The alcoholic solution is finally shaken with light petroleum and to obtain the chlorophyll from this final light petroleum solution (purity 70) it is washed with water until free from methyl alcohol when the pigment is precipitated in a very fine state of division which cannot be filtered.The addition of large amounts of anhydrous sodium sulphate or of smaller amounts and a little calcium carbonate renders the precipitation complete and also deposits the precipitate in such a form that it can be filtered with ease. To purify the chloro- phyll it is dissolved in 96% alcohol precipitated with dilute sodium chloride solution and finally dissolved in ether and precipitated with light petroleum. The yield is 0.75 to 1 gram from 2 kilos. of stinging nettle meal containing 14-16 grams of chlorophyll. A pure specimen should possess the following characteristics 1. The ash must correspond with the theoretical and consist of 2. The phytol content must be 33% and the phytol must be free 3.During the hydrolysis with alkalis the temporary formation 4. By the decomposition of the phzophytin the normal products 5. The specimen must contain no yellow pigments. 6. The spectrum must correspond with that of the chlorophyll in the leaf extract. The pure compound is a bluish-black glistening powder with a metallic lustre and when finely divided gives a greenish- or bluish-black powder. It appears crystalline under the microscope and has no definite m. p.; for example different specimens melt at 93-96' or 103-106° when heated in ordinary m.-p. tubes. Its ethereal solution has a brilliant greenish-blue colour and is strongly fluorescent. It is practically insoluble in cold light petroleum but dissolves readily on the addition of a few drops of methyl or ethyl alcohol.It is also soluble in benzene and pyridine and its alcoholic solution gives Kraus's reaction. The pigment has neither acid nor basic properties but is readily decomposed by both acids arid alkalis. Analyses agree with the formula C55H7,0,N,Mg. Its absorption spectrum is analogous to that of ethyl chlorophyllide and it undergoes alcoholysis or hydrolysis in the presence of chlorophyllase (compare this vol. i 141). The chlorophyll thus obtained is a mixture of two components (compare Willstatter and Isler preceding abstract) which have been isolated and will be described later. pure magnesium oxide. from solid impurities. of the brown coloration must be given. phytochlorin-e and phytorhodin-g must be formed. J. J. S.ORGANIC CHEMISTRY. i.395 The Existence of Two Chlorophyllans. &I. TSVETT (Biocl~ena. Zeitsch. 1911 31 505-506).-The author maintains as a result of his adsorption-spectroscopic analytical researches that two chloro- phyllans exist as also two chlorophyllins. A N e w Vegetable Colouring M a t t e r Thujorhodin. M. TSVETT (Compt. rend. 191 1 152 788-789).-The leaves of Thujcb orientalis as well as of other Conifers (Cryptomerict japonica Juniperus uirgimiuca Tccxus baccata etc.) after grinding with sand and calcium carbonate yield a new colouring matter on extraction with carbon disulphide or light; petroleum. This substance for which the name tlmjorhodin is proposed gives the lipochrome blue coloration with concentrated sulphuric acid. The solution in carbon disulphide is red and shows four absorption bands h 570-560 530-515 470-475 ['I 4551 450-440.The alcoholic solution is rose-coloured and shows less distinct bands whilst three bands are visible in the light w. 0. w. LBON GRIMBERT (Compt. rend. 1911 152 727-728).-The fresh urine is extracted with chloroform. After filtering the chloroform through cotton wool an alcoholic solution of zinc acetate is added until the turbidity first formed disappears ; the appearance of a green fluorescence indicates the presence of free urobilin. I n this case the chloroform is shaken with a few C.C. of aqueous sodium phosphate neutral to phenolphthalein. This removes only the chromogen of urobilin (Saillet's urobilinogen). The chloroform layer now gives the fluorescence only after treatment with a trace of iodine or other oxidising agent.The chromogen cannot be extracted by chloroform from solutions which are alkaline KARL FRIES and WILHELM VOGT (Ber. 19 11 44 756-761).-The products described by Krafft and Lyons (Abstr. 1896 i 297) as thianthren dioxide and thianthrenmonosulphone are shown to be isomeric disulphoxides. Both are readily reduced to thianthren by hydrogen bromide at the ordinary temperature or by warming with zinc dust and acetic acid whereas sulphones are not attacked by hydrobromic acid. The com- pounds possess basic properties and are not oxidised by nitric acid whereas thianthrenmonosulphone is not basic and is readily oxidised to a trioxide. isoThianthren disulphoxide crystallises readily from benzene in slender needles and from water or glacial acetic acid in prisms m.p. 249O. It dissolves in concentrated nitric or hydrochloric acid yielding colourless solutions and is transformed into the isomeric disulphoxide when heated for some time at 250' or more readily at 280'. The same transformation occurs when the iso-compound is dissolved in concentrated sulphuric acid kept for two days and then poured into water. Thianthren disulphoxide is most easily prepared by the action of chlorine on a benzene solution of thianthren and has m. p. 284' (KraEt and Lyons 278-279O). It is less soluble than the iso-corn- pound in glacial acetic acid and in hydrochloric or nitric acids. Its S. B. S. petroleum solution which is yellow. Separation of Urobilin from its Chromogen. to phenolphthalein. w. 0. w. Isomeric Disulphoxides from Thianthren. VOL.c. i f fi. 396 ABSTRACTS OF CHEMICAL PAPERS. solution in concentrated sulphuric acid has a reddish-violet colour and when this solution is kept for two days and then diluted with water a mixture of the kwo isomeric disulphoxides is obtained. J. J. S. Quinine and Euquinine. A. ASTRUC and L. COURTIN (J. YItarm. Chim. 1911 [vii] 3 292-294. Compare Astruc Bull. Xoc. chim. 1907 [iv] 1 192).-The authors briefly recapitulate the points of similarity and difference between quinine aud euquinine ; the most important difference is the fact that euquinine behaves as a mono- acidic base. The formation of euquinine by the attack of ethyl chloroformate on the hydroxyl group in the quinine molecule leads to a constitution containing the group (I).This constitution is not in harmony with the stability of euquinine or with its monobasic nature. The authors suggest that a constitution containing the group (11) is in better agreement with the facts. c. s. Ephedrine and $-Ephedrine. PAUL RABE (Bey. 1911 44 824-827).-Ephedrine and +-ephedrine are optically isomeric P-methylamino-a-phenylpropane-a-ols of the formula OH*CHPh*CHMe*NHMe. The ammonium base of ephedrine decomposes into water methyl- amine and a-phenylpropylene @-oxide b. p. 204O [.] + 65.84'. This oxide when heated with aqueous methylamine in sealed tubes on the water-bath forms the hydrochloride C,,H ON,HCl which melts partly at 148-149O the rest a t 165O and has b]bg +24*2O. It is a mixture of methylated up-hydramines. E. F. A. New Leucomaine.J. UBEDA Y CORREAL (7th Intern. Congr. AppZ. Chern. Sect. IV A 2 112-113).-0n treating 29 kilograms of fresh beef with water containing hydrochloric acid a solution is obtained from which by evaporation to dryness extraction with alcohol p ~ e - cipitation with mercuric chloride and subsequent decomposition with hydrogen sulphide a substance can be prepared which yields a platini- chloride crystallising in red acicular prisms (angles 48'49' and 13 1'1 6' respectively) and containing 47.22-47*31% of platinum. When the platinichloride is decomposed with hydrogen sulphide a solution is obtained which reacts with gold chloride picric acid potassium and cadmium iodides and other reagents. The hydrochloride forms colourless crystals (angle8 31'33' and 148'87' respectively).R. V. S. Luciferesceine the Fluorescent Material Present in Certain Luminous Insects. P. ALEX. MCDERMOTT (J. Amer. Chem. Soc. 191 1 33 410-416).-Coblentz (Phpikal. Zeitsch. 1909 10 955) hasORGANIC CHEMISTRY. i. 397 discovered that the firefly (Photinus pyraZis) contains a substance which gives solutions with a bright blue fluorescence. More recently he has found that Pilot inus co~*ruscus and Photut-is pennsylvanica also contain this substance. The author has detected i t in Yhotinus pyrulis 2'. corruscus and also in P. scintillans but has been unable to confirm its presence in Photuris pennsylvmica. It is particularly abundant in a sticky fluid which the insects emit when irritated. This substance luciferesceine can be obtained in an impure condition from an alcoholic extract of the insects or in a purer form by dissolving in alcohol the sticky liquid on the walls of the vessels in which the insects have been con- fined.The alcoholic solution thus obtained is clear colourless has a bright blue fluorescence and on evaporation yields a pale yellow amorphous residue of luciferesceine. The compound gives a red color- ation with concentrated sulphuric acid and a dense cream-coloured precipitate with potassium ferrocyanide. I n general its reactions indicate that it is probably of an alkaloidal nature. It. seems likely that luciferesceine is contained in a deEensive secretion of the insect but that its fluorescence does not bear any relation to the vital processes or to the defensive function. E. G. Preparation of $-Morphine by Mineral Catalysis.GEORGEEI DENIGES (Bull. Xoc. chim. 1911 [iv] 9 264-266).-Ten C.C. of a 4% solution of copper sulphate just decolorised with potassium cyanide is poured into a solution containing 5 grams of morphine hydrochloride and 20 C.C. of hydrogen peroxide (10 to 12 vols.) in 200 C.C. of water. After a few minutes oxygen is evolved and a precipitate of $-morphine which soon becomes crystalline is formed. The alkaloid may be purified by dissolving i t in ammonia solution (22' B) decolorising with animal charcoal and finally evaporating to a small bulk. The yield is from 20 to 25% of the theoretical. T. A. H. Guaninepentoside from Molasses Residues. KARL ANDRL~K (7th Intern. Congr. Appl. Chem. 1909 Sect. V. 331-33'7).-Molasses residues when boiled with copper sulphate and sodium hydroxide yield about 0.04% of guanine pentoside C,H80,,C5H,N50,2H20 which crystallises in slender colourless sparingly soluble needles.When boiled with dilute mineral acids it is hydrolysed to a pentose [a] - 16.7O (41.9%) and guanine (40%) and the pentoside becomes brown at 234-241° m. p. (decomp.) above 300'; in dilute sulphuric acid it has [a] - 13-95' E. F. A. Nitropyrrole. ANGELO ANGELI and LUIUI ALESSANDRI ( A t t i R. Accad. Lincei 1911 [v] 20 i 311-314).-Pyrrole can be nitrated by the method previously suggested (ibid. 1902 11 ii 16) using ethyl nitrate in the presence of sodium ethoxide or metallic sodium and if the isolation of the sodium compound of nitropyrrole is avoided (for it was found to be spontaneously inflammable Zoc.cit.) nitropyrrole can be prepared. Pyrrole diluted with ether is treated with sodium wire (1 mol.) and ethyl nitrate (1 mol.) ; the reaction is commenced by f f 2i. 398 ABSTRACTS OF CHEMICAL PAPERS. slightly warming and after some days at the ordinary temperature (protected from moisture and carbon dioxide) the sodium will have disappeared. Ice is then added and from the mixture of nitrite and sodium salt obtained the former is removed by taking advantage of the insolubility of the silver salt of nitropyrrole. The sodium salt is then again obtained and from it by the action of carbon dioxide free ndtropywole is prepared. It forms pale yellow glistening scales or prisms or rhombohedra m. p. 63.5'. Of the two possible constitutions that of 3-nitropvrrole is considered the more probable.Nitro-2 4-di%ethylpyrroZe of the probable fo;mula >NH Q(N0,):UMe CMe==CH is prepared similarly but more easily because the slighter solubility of its sodium compound renders purification by means of the silver compound unnecessary. It crystallises in prisms m. p. 11 1'. Both these nitro-compounds are unaffected by permanganate in alcoholic solution. R. V. S. Action of Cyanacetic Ester on 0- and p-Hydroxybenzalde- hydes in the Presence of Ammonia. MARIO SCLAVI (Atti Iz. Accad. Xci. Torino 1911 46 181-194).-By the interaction of p-hydroxybenzaldehyde (1 mol.) with cyanoacetic ester (2 mols.) and ammonia (3 mols.) at the ordinary temperature the author has obtained the ammonium salt of p-hydroxybenzaldicyanoglutaconimide [ 2 6-diketo-3 5-dicyano-4-p-hydroxyphenyltetrahydropyridine] HO* CP4*CQCH( C(CN)-Co>N*NH4,2H,0 CN) .GO and as secondary products the two corresponding (saturated and unsaturated) amides.From salicylaldehyde o-hydroxybenzylidene- dicyanodiacetic ester was chiefly formed along with an ammonium salt which could not be identified. The ammonium salt of 2 6-diketo-3 5-dicyano-4-p-hydroxgphenyl- tetrahydropyridine is a white substance which does not melt below 300° and does not lose ammonia even a t looo. By double decom- position in aqueous solution a number of crystalline salts were prepared from it including those of iron (ferric and ferrous) copper and potassium. The last is sparingly soluble in the cold solutions containing only one part in three thousand of potassium chloride being precipitated after some hours.forms long colourless crystals. cry stallises similarly. The szlwer salt C,,HOO,N,Ag,H,O forms yellowish-white crystals which change in the light. 2 6-Dihto- 3 5 - c l i c y a n o - 4 - p - h y d r o x ~ p ~ ~ e n y l t e t r a h y d ~ C13H703N3 obtained from the barium or silver salt forms lustrous white crystals. a - Cyano- p-hydroxyphernylacrylamide OH*C,H,*CH:C( CN) CO*NH forms bright yellow crystals m. p. 265' (with evolution of ammonia). a-Cyano-P-p-hydq*oxypT.en ylpropionamide OH*C,H4*CH2* CH( CN)*CO*NH forms Io~ig colourless crystals m. p. 1563. The magnesium salt (C13H603N3)2M& 6H209 The barium salt (C,,H,O,N,),Ba?6H,O R. V. 8.ORGANIC CHEMISTRY. i. 399 Rupture of the Pyridine Ring WILHELM KONIG and R.BAYER (J. pr. Chem. 1911 [ii] 83 325-32S).-In this preliminary note the authors mention a number of substances inorganic and organic the additive compounds of which with pyridine are decomposed by primary or secondary amines preferably aniline or 2-methyldihydro- indole yielding by rupture of the pyridine ring the so-called "pyridine dyes " (compare Reitzenstein and Breuning this vol. i 225). c. s. The New Series of Leuco-bases and Colouring Matters from Diphenylethylene. PAUL LEMOULT (Compt. rend 19 11 152 962-964. Compare Abstr. 1909 i 836 ; Busignies Abstr. 1909 i 736).-Wahl and Meyer (Abstr. 1910 i 134) having called in question the author's view that the presence of hydrogen attached to the ethylenic carbon atom in alkyl derivatives of di-p-amino- diphenylethylene is essential for the production of blue dyes from these leuco-bases a further series of the compounds has been examined.Michler's ketone was treated with a magnesium alkyl iodide using the methyl ethyl n-propyl isopropyl n-butyl n-sec.-butyl isoarnyl and cyclohexyl compounds. Two series of derivatives were khus obtained compounds of the type CHR C(C,H,*NMe,) giving intense green or blue colorations with nitrous acid and compounds of the type CRR':C( C,H,*NMe,) which gave extremely pale colorations when oxidised in this way. Corresponding colours were obtained on satinette mordanted with tannin. n- PvopyEidenetetramethyldiaminodiplumy Zmethane CHEt:C(C6H4=NMe2)2 has m. p. 47.5'; the isopropy2idene compound m. p. 89' ; the corre- sponding n-butyEidene compound m.p. 60 -5" ; the n-sec.-butyzidene Tautomerism of Amidines. RUDOLF PUMMERER (Ber. 191 1 44 810. Compare this vol. i 231)-0. Eischer (Abstr. 1907 i 353) has already shown that Meldola's amidines derived from naphthalene (Trans. 1903 83 1185) are not tautomerides. 3. J. S. Compounds of Antipyrine with the Chlorides of Tin. CHARLES ASTRE and J. TIDAL (Bull. Soc. chim. 1911 [iv] 9 309-313. Compare Abstr. 1900 i 362-411).-When a solution of 10 grams of stannous chloride in 100 C.C. of concentrated hydrochloric acid diluted with its own volume of water is added drop by drop to a solution of 10 grams of antipyrine in 100 C.C. of the same acid a white precipitate is obtained having the composition 4C,,H,,ON,,SnCl 4HC1. This precipitate is not formed at loo" but on cooling the solution the compound separates in large tabular clinorhombic crystals which can also be obtained by immersing strips of tin in a hydrochloric acid solution of antipyrine.The crystals become pasty at SOo but the melting point is not definite. The change from stannous to stannic chloride in the presence of antipyrine is not an isolated fact since ferrous chloride is similarly oxidised to ferric chloride. derivative CMeEt:C(C6H,*NMe,) m. p. 79". w. 0. w.i. 400 ARSTRACTS OF CHEMICAL PAPERS. When the stannous chloride is replaced by stannic chloride micro- scopic white clinorhombic crystals are obtained having the compo- sition 3C11H,,0N2,SnCl 3HC1 which also possess no definite melting point. They can be distinguished from the former compound by the fact that their solution in hydrochloric acid does not give precipitates with solutions of mercuric chloride and potassium ferricyanide.With the former compound the precipitates are white and green in colour respectively. T. S. P. Action of ydrazine Hydrate on Ethyl Chloroacetate. THEODOR CURTIUS and LUDWIG HUSSONG (J. pr. Chem. 1911 [ii] 83 249-278).-The anthors mention the complex reactions by which hydrazino-fatty acids have been prepared and also refer to the unsuccessful attempts of Schofer (Diss. Kiel 1892) and of Foersterling (Abstr. 1895 i 3 4) to obtain hydrazinoacetic acid by the action of hydrazine hydrate and phthalylhydrazide respectively on ethyl chloro- acetate. They find at the addition of ethyl chloroacetate to hydr- azine hydrate results in theiformation chiefly of hydrazinoacethydrazide whilst by reversing the order of the addition hydrazinodiacethydrazide is the main product ; in both cases however about 50% of the ester is reduced to ethyl acetate an equivalent amount of nitrogen being evolved. For example ethyl chloroacetate is added slowly to hydrazine hydrate below '70" (the nitrogen evolved is collected and measured) and the product is diluted with water and shaken for a long time with successive small quantities of benzaldehyde.The resulting benzyli- dene compounds (except that which is obviously pure benzaldazine) are treated successively with 95% alcohol light petroleum and The residue obtained by evaporating the cH2*Nig$gph last solution is purified by alcohol whereby tribenxyl- This substance like tribenzylidenehydrazinodiacethydrazide (see below) dissolves in concentrated hydrochloric acid at 60" but is not reprecipi- tated by dilution; by treating the diluted solution with sodium acetate di6enxylidenehydraxinoacet~~yd~c~xide CHPh :N*NH*CH2*CO*NB*N:C1HPh m.p. 161O (decomp.) is obtained. By prolonged boiling with hydro- chloric acid tribenzylidenehydrazinoacethydrazide is decomposed completely into its constituents. Conversely when hydrazine hydrate (3 mols.) is added to ethyl chloroacetate and the product diluted with water and shaken repeatedly with benzaldehyde the characteristic benzylidene compound obtained is tribernxylidenehydruxinodiacethydrazide CHPh:N*N( CII;CO*NH*N:CHPh) m. p. 219O (decomp.) in 15-20% yield.The substance ditjsolves i n concentrated hydrochloric acid at 35-40' and is recovered for the most part by diluting the solution with water; by keeping the undiluted solution at the ordinary temperature in contact with benzene I~ydraxinodiacethydraxide hydrochloride NH2*N(CH,*CO*NH*NH,),,3HC1,H,0 benzene. I N CHPh idenehy~~axinoatcet~yd~ax~~e (annexed for mula) m. p 176" (decomp.) is obtained in dhite needles.ORGANIC CHEMISTRY. i. 401 separates in yellowish-white crystals which darken at 150° and become greyish-black at 180° without melting. By shaking a slightly acidified aqueous solution of the hydrochloride with benzaldehyde hydrated tribenzylidenehydrazinodiacethydrazide C25H,,0,N,,H,0 is obtained as a white powder which sinters at 92' partly melts at about 120° and is fused completely at 190'; by treatment with absolute alcohol the hydrated compound is converted into the anhydrous form mentioned above.I n a similar manner hydrazino- diacethydrazide hydrochloride can be converted into hydrated tvi-m- nitrobenz?llideneT~~d~~~~inodiacetJ~ydraxidd C,,H,,O,N,,H,O m. p. 222-223O (decump.) and tri - m - chlorobenzyZidel.lehydrazinodiacet- hydrazide C,,H2,0,N,CI,,H,0 which sinters at looo and melts between 110-180'; neither of these two compounds loses H20 by boiling with alcohol or by prolonged heating at 60-70'. Hydrazinodiacetic acid NH,*N(CH2*C0,H) m. p. 166-1 67' (decornp.) is obtained by keeping trihenzylidenehydrazinodiacet- hydrazide in contact with concentrated hydrochloric acid and benzene for fifteen to twenty hours separating the benzene layer and distilling the acid solution with steam for twenty to twenty-five minutes.The acid is more conveniently obtained by adding hydrazine hydrate (about 5 mols.) to an alcoholic solution of chloroacetic acid whereby nitrogen is not evolved and a syrup is obtained which is diluted with water and shaken with benzxldehyde ; the hydrazinodiacetic acid which does not react with benzaldehyde is thus obtained mixed with benzaldazine and the two substances are easily separated by dissolving the latter in hot alcohol. From its method of formation hydrazinodiacetic acid might have the symmetrical constitution CO,H *CH -NH*NH*CH *CO,H but this is rejected because although the acid itself does not react with benzaldehyde its hydrazide does yielding the tribenzylidene- hydrazinodiacethydrazide described above Moreover the ease with which hydrazinodiacetic acid reduces ammonincal silver solutions in the cold Fehling's solution at the ordinary temperature and mercuric oxide and potassium permanganate by warming indicates the presence of the group NH,-N rather than *NH*NH*.Ammonia not hydrasine is obtained when hydrazinodiacetic acid is heated with concentrated hydrochloric or sulphuric acid ; the other product of hydrolysis could not be isolated. By the action of hydrazine hydrate on ethyl bromoacetate ethyl iodoacetate ethyl di-iodoacetate chloroacetamide or di-iodoacetamide (all of which are prepared from ethyl diazoacetate) nitrogen is evolved and the whole of the halogen is obtained in an ionic condition. a.s. Action of Hydrazine Hydrate on E thy1 Bromosuccinate. THEODOR CURTIUS and HEINRICH GOCKEL (J. pr. Chem. 1911 [ii] 83 279-3 11. Compare preceding abstract).-When hydrazine hydrate (4-5 mols.) is added to ethyl bromosuccinate and the mixture is heated for eight and a-half hours the product is not a derivative of hydrazinosuccinic acid but a mixture of 5-pyrazolone-3-carboxylo- hydrazide and its hydrazine salt ; the same sybstgncg is obtained morei. 402 ABSTRACTS OF CHEMICAL PAPERS. conveniently by von Rothenburg's method (Abstr. 1895 i 302). The substance which contains 2H20 and has m. p. 253-254" not 2.38-239" forms a yellow dihydrochloride C,H,02N4,2HC1 which easily changes to a white hydrochloride C4H602N,,HCl and a hydrazine salt C4H,02N,,N2H4 m.p. 199-200" (decomp.). When heated with concentrated hydrochloric acid it yields 5-pyrazolone-3-carboxylic acid which is converted by alcoholic hydrogen chloride into its ethyl ester and by nitrous acid into 4-oximino-5-pyrazolone-3-carboxylic acid; these compounds have been described by von Kothenburg (Zoc. cit.) and Ruhemann (Trans. 1896 69 1395). 5-Pyrazolone-3-carboxylohydrazide reacts with benzaldehyde in very dilute hydrochloric acid t o form the benxylidene derivative CllHlo02N4 m. p. 252-253" (decomp.) with ethyl acetoacetate to form the substance ~~~~>C*CO*NH*N:CMe*CH2*C02Et m. p. 182" (decomp.) and with alcoholic benzoyl chloride (14 mols.) in alkaline solution to form 4-benxoyZ-5-~yraxolone-3-carboxylobe~~xo~l~~dra~ide T C H - N > ~ - ~ ~ * ~ ~ - ~ ~ ~ z 0-CHBz m.p. 2 I 4O (d eco m p. ) and 5pyrazolone- 3 -carboxylobenzo y Ihydraxide YH--N >C*C'Q*NH*NHBz C O*CH m. p. 269' (decomp.) the fo;mer being insoluble the latter soluble in sodium hydroxide. ob- COO 7 NO H N=C*CO*N,' 4-0ximino-5-pyrcczoZone-3-carboxyZoaxoimide NH< tained by the action of sodium nitrite (24 mols.) on 5-pyrazolone-3~carb- oxylohydrnzide in dilute hydrochloric acid cooled by a freezing mixture explodes at 100-105°. I t s yellow ethereal solution reacts with ammonia. forming a flesh-coloured ammonium salt of 4-oximino-5-pyrazolone- 3-carboxy lamide 4 darkening a t 220-290° an H<CO*f :NO N H N= C*CO *NH alkaline solution of which by a.cidifica%ion yields 4-oximino-5py?~c6xol- olze-3-carboxylamide a greenish-yellow powder darkening a t 240'.The ethereal solution of the azoimide reacts with aniline t o form a m. p. 211-216O CO*$!:ISOH N=C C 0- N HP h' mixture of the anilide NI3< (decomp.) and its aniZine salt CloH80,N4,PhNH (which exists i n two forms yellow m. p. 161-164" and red rn. p. 158-162") and with p-toluidine yielding the p-toluidide CllHlOO3N4 m. p. 232-223' (decomp.) and its p-toluidine salt. CO *?:NOH N H < ~ = ~ * ~ ~ * ~ ~ M m. p. 218" (decomp.) is obtained by boiling the pure dry' azoimide with an excess of methyl alcohol and separates from methyl alcohol in small red needles containing SMeOH. The 'corresponding ethyl ester prepared in a similar manner has m. p. 174" (decomp.) andalso separates from methyl alcohol in red needles containing fMeOH.The methyl ester is decomposed by boiling 20% hydrochloric acid Methyl 4-oxhino-5 -pyraxolone-3-cai.bamate,ORGANIC CHEMISTRY. i. 403 yielding carbon dioxide hydrogen cyanide hydrazine hydroxylamine ammonia oxalic acid and a yellow substance C,H,O,N which darkens on heating but does not melt below 300° dissolves easily in sodium hydroxide or carbonate develops a dark red coloration with ferric chloride and does not react with benzaldehyde or phenyl- hydrazine ; possibly it is bis-4-oximi~o-5-~yrcaxolidone c. s. YH. NH--NH NH- i 0 c ( N 0 H)>c:c<C(N OH) c 0 Decomposition of Uric Acid by Organic Alkaline Solvents. HANNAH STEVENS and CLARENCE B. MAY (J. Amer. Chern. SOC. 1911 33 434-447).-It is well known that uric acid is decomposed by solutions of alkali hydroxides and carbonates.Experiments have now been made to ascertain the behaviour of uric acid in solutions of certain organic bases namely piperazine urotropine and lycetol (piperazine tartrate). The action of piperazine is of special interest since this substance is used medicinally as a uric acid solvent. Uric acid dissolves readily in piperazine at the ordinary tempera- ture but only slightly in urotropine lycetol or ammonium hydroxide. Piperazine ammonium sulphide and ammonium hydroxide effect the decomposition of uric acid in the absence of neutral salts but the decomposition by piperazine takes place more slowly in presence of ammonium sulphate disodium hydrogen phosphate or sodium chloride. Urotropine exerts but little action on uric acid. When uric acid is boiled with ammonium sulphide solution it is decomposed to almost the same extent as it is by sodium sulphide solution but thiouranil does not seem to be produced.Quadriurates. OTTO ROSENHEIM (Zeitsch. physiol. Chem. 191 1 71 272).-The conclusion arrived at by Kohler (this vol. i 243) that quadriurates are mixtures of biurates and uric acid was reached experimentally by the author in conjunction with Tunnicliffe some years ago (Lancet June 16th 1900). E. G. W. D. H. Recovery of Adenine. GEORGE DE F. BARNETT and WALTER JONES (J. Biol. Chem. 1911 9 93-96).-To free adenine from hypoxanthine the base must be converted into the picrate which as such is useless and can be changed into a non-toxic salt only by the use of an excessive amount of ether. When however the picrate is dissolved in ammonia and the solution treated with ammoniacal silver nitrate the adenine is precipitated quantitatively whilst more than 90% of the picric acid remains dissolved.This forms the basis of a method of recovering adenine and of dealing with filtrates from adenine picrate which contain other purine bases as well as picric acid. W. D. H. Conversion of Arylamineazoisooxazolonee into Azopyrazo- lones. CARL BULOW and ARNULF HECKINU (Bey. 1911 44 467-480).-A third method of preparing pyrazolone dyes is based on the observation of Enorr and Reuter (Abstr. 1594 i 372) that by the action of phenylhydrazine on the phenylhydrazone af ketomethyl-i. 404 ABSTRACTS OF CHEMICAL PAPERS. isooxazolone in acetic acid solution tbe phenylhydrazine of ketophenyl- methylpyrazolone is obtained.This method is now extended to a number of substituted isooxazoles (Bulow and Hecking this vol. i 244) both hydrazine phenylhydrazine and dinitrophenylhydrazine being used. The conversion depends on the strength of the base used and is a function of the solubility of tjhe reaction product. The azopyrazolones possess all the tinctorial properties of the true o-hydroxyazo-dyes in particular the fastness to alkali. Their properties also depend on the nature of the arylarnine azo-residue. and on the group &ached t o the nitrogen of the heterocyclic ring ’ C(0H):FN:NR R”<N==CMe * When IR is a purely aromatic radicle and R is hydrogen the acidity of the compound increases and it dissolves easily in a very small quantity of piperidine.It is not precipitated from the solution by the continued addition of water ; the yellow colour is not altered by the addition of alkali hydroxide. The dissolved salt is decomposed however by carbon dioxide. When R is a purely aromatic radicle the compound also readily dissolves in piperidine but the salt is hydrolysed on the addition of a certain quantity of water. The very finely-divided precipitate dis- solves again in alkali hydroxide. The solutions of the monoazopyrazolone dyes in concentrated sulphuric acid are yellow so long as only benzene residues are present Derivatives of a-naphthylamine are deep bluish-red or reddish-violet ; those of P-naphthylamine are brownish-red. 4-Benzeneazo-5-hydroxy-3-methylpyrazole prepared from the corre- sponding isooxazole and hydrazine hydrate forms reddish-yellow platelets m.p. 199’. 4-p-Nitrobenxeneaxo-5-hydroxy-3-meth ylpyraxote crystallises in slender yellow needles m. p. 264-265’. It behaves towards potassium hydroxide as a very weak dibasic acid ; in dilute alkali it dissolves with a brown colour; in 50%alkali this changes to bluish-red and after a time reddish-violet needles separate ; on dilution the bluish-red solution becomes brown again. Carbon dioxide precipitates the unaltered azo-dye. Many of the other azopyrazoles described behave similarly. 4-p-Nitrobenxemaxo-5-hydroxy-l-phenyZ-3-meth ylpyraxo 2% f orms red needles m. p. 198’ ; tho phenolic potassium salt crystallises in slender matted brown needles. 4-op-Dinitrobenxeneaxo-5-hydroxy - 3 - methy2pyrwoZe crystallises in yellowish-red flat needles m.p. 277-278’. The di(?)pota8~ium salt separates in brownish-blue flakes. 4-op-Dinitrobenneneaxo- 5 - hydroxy - 1 -phenyZ - 3 - methylpyraxole is ob- tained in violet-red needles m. p. above 300’. 4-Benxeneazo-5-hydroxy-l-op-dinitrophenyZ- 3 - rnethyZpyrc6xole crystal- lises in short thick dirty violet needles m. p. 216-217’. 4-o-Folueneaxo-5-hydroxy-3-methytpyrclxoZe separates in rhombic aggre- gates of tiny reddish-yellow plates m. p. 221-2234 The isomeric 4-p ToZuslneaxo-~-hydroxy-3-met~yZpyrazo~~ is obtained in smaller yield ; it crystallises in lustrous orange needles m. p. 195-196O. The twoORGANIC CHEMISTRY. i. 405 isomerides show similar shades in the same solvent the para-derivative being more soluble.in yellowish-red needles m.. p. 181-182O. The same compound is obtained by the combination of l-phenyl-3-methyl-5-pyrrtzolone with the diazo-compound of o-toluidine (D.R.-P. 153861). The isomeric 4-p- t olueneazo-5-hydrox y- 1 -phenyl-3-me t h ylpyrazole separates in red needles m. p. 137' (compare LFpworth Trans. 1903 83 1124). 4-m-XyZeneaxo-5-hydroxy-4-methyZpyraxoZe forms very slender matted silky glistening orange needles m. p. 190-1 91'. 4-m- X y Zeneazo-5-hydroxy- 1 -plienyl- 3-meth ylp yraxo Ze is obtained in aggregates of lustrous yellowish-red rhombic plates or slender orange needles m. p. 167'. 4-a-Naphthaleneaxo-5 -iiydroxy-3-methyZp~raxoZe separates in orange-red plates m. p. 247'. The corresponding 4-a-naphthaleneaxo-5-hydroxy- 1 -phenyl-3-methyZpyraxoZe crystallises in lustrous yellowish-red needles m.p. 202-203'. 4-P-Naphthaleneazo-5-hydroxy-3-methylpyraxoZe is a bright red crystal- line powder m. p. 238-239'. 4-~-NaphthaZeneaz0-5-hydroxy-l -phenyZ- 3-meth.ylpyraxoZe forms short needles m. p. 186-1 87'. The yellow solution in piperidine becomes milky when considerably diluted 4-~-Carbo~ybenxeneaxo-5-hydrox:y-3-meti~yZpyraxoZone prepared by boiling. hydrazine hydrate with the oxime of ethyl o-carboxybenzeneazo- acetoacetate forms microscopic aggregates of brownish-yellow plates m. p. 280'. 4-o-Carbox~~benxeneaxo-5-hydrozy-l-~l~en~L3-methylpyrazole crystal- lises in very beautiful orange-red stunted needles with a blue surface reflex ni. p. 269-270O. 4 - Nitro - o - ccwboxybenxeneaxo - 5 - hydroxy- 1 -pi~enyl-3-met~yZpyraxoZe separates in reddish-violet needles with a lustrous blue reflex m.p. 286O. 4-0- ToZueneaxo-5 -hydroxy - 1 -@en yl-3-meth yZpipccxo Ze crystallises E. F. A. The Heat Coagulation of Proteins. I. Is the Hydrogen Ion Concentration Altered on Coagulation? SOREN P. L. S~RENSEN and E. JURGENSEN (Riochem. Zeitsch. 1911 31 397-442). -The authors in an extensive series of experiments with different acids have determined the optimal conditions of coagulation generally by estimating the amount of nitrogen in the uncoagulated portion of the solution. I n these experiments they have also made numerous measurements of the hydrogen ion concentration in the mixtures both before and after coagulation by means of concentration cells. The optimal concentration for coagulation is about pH = 4.6 but varies slightly with the concentration of the protein (blood-serum or egg-white) and is somewhat lower than the isoelectric point pH = 5.52 as determined by Michaelis and Rona.After coagulation the hydrogen ion concentration becomes smaller and this the authors ascribe to the separation of the protein from solution the protein itself having acidic functions to which the hydrogen ion concentration of the solution are due. This explains the slight variability in the hydrogen ion concenbration which affords the optimal conditions of coagulation i n proteins of varying strengths of solution. (It is higher fori. 406 ABSTRACTS OF CHEMICAL PAPERS. stronger than weaker solutions.) No carbon dioxide is evolved during coagulation.Certain peculiarities in the case of egg-white solutions were observed. The maximal separation under optimal conditions of the coagulum is in this case only reached after several hours after which owing to the action of the liquid some of the coagulum passes again into solution. S. B. S. The Fixing of Acids by Egg-albumin and Viscosity. WILHELM E. RINUER (Gedenkboek aangeboden aan J. M. van Bemmelen 1910 243-260).-The nature of acid protein solutions has been inves- tigated by measurements of the E.M.K of hydrogen concentration cells of electrical conductivity and of viscosity. Solutions contain- ing egg-albumin and variable amounts of hydrochloric acid or podium hydroxide and in addition solutions of egg-albumin serum-albumin and serum-globulin with varying amounts of acetic acid were ex- amined in detail.The results of these measurements indicate that considerable amounts of acid and alkali ara fixed by the proteins and the process is considered to be in the nature of chemical combination rather than adsorption H. M. D. Electrochemistry of Proteins. IV. Dissociation in Solu- tions of the Globulinates of the Alkaline Earths. T. BRAILS- FORD ROBERTSON (J. Phy8icaZ Chem. 1911 15 166-177. Compare Abstr. 1910 ii 679 939; Hardy Abstr. 1906 i l2l).-The conductivity at 30' of solutions of potassium calcium barium and strontium hydroxides neutralised to phenolphthalein with globulin show that the salts obey Ostwald's dilution law The same con- clusion may be drawn for sodium globulinate at 18' from Hardy's measurements.As in the case of the caseinogenates the value of p(vl + v2) is about twice as great for the alkalis as the alkaline earths where q,v2 are the ionic mobilities and p the number of equivalents of salt formed from one equivalent of alkali. It is assumed that p equals 2 for the alkali salts so that (vl + v2) is about the same (26 x cm. per sec.) for all the globulinatee a result in accord with Hardy's measurements of the velocity of the globulin ion. At neutrality to phenolphthalein the globulinates dissociate into two protein ions each possessed of twice as many valencies as there are molecules of base bound up in one molecule of globulinate. The simplest formula of potassium globulinate KX" + X(OH),," does not explain the fact that the alkali globulinates take tip a second equivalent of globulin becoming neutral to litmus.These are repre- sented KHX"" + X(OH),"" ,so that the salt neutral to phenol- phthalein is K,X"" + X(OH)n"" and the corresponding alkaline earth salt which is saturated with globulin although neutral to phenolphthalein only is represented Ca,(X),* * * ' + X,(OH),,"". On this assumption the ions are quadrivalent and the dissociation constants for the globulinates are I( 0.01470 ; Ca 0*00360; Ba 0.00493 ; Sr 0.0021 1. R. J. C.ORGANIC CHEMISTRY. i. 407 Histidine in Pig’s Thyreoglobulin. FRED C. KOCH (J. Biol. Chem. 191 1 9,121-122).-NUrnberg failed to obtain enough histidine from thpreoglobulin (from ox-thyroids) to definitely establish its presence. I n the present research sufficient was obtained for the purpose.The material was prepared from pig’s thyroids. W. D. H. Swelling of Casein Under the Influence of Sodium Chloride and Lactic Acid. W. VAN DAM (Gedenkboek aa9zgeboden aan J. M . van Bemmelen 1910 102-107. Compare this vol. i 91)-The structure of cheese is sometimes dough-like and sometimes granular and the author has endeavoured to trace the cause of this difference by determining the amount of casein dissolved by solutions containing 5% 3% and 1% of sodium chloride and various amounts of lactic acid. Curves showing the relation between the dissolved casein and the concentration of the hydrogen ions are given. Electrochemistry of Proteins. V. The Electrochemical Equivalent of Caseinogen and its Relation to the Combining and Molecular Weights of Caseinogen. T.BRAILSFORD ROBERT- SON (J. Physical Chem. 1911 15 178-196. Compare preceding page).-Electrolysis of potassium caseinogenate with a current of 0.001 ampere liberates gas at both electrodes and on the anode a firm white spongy precipitate is deposited the cellular texture of which is apparently due to gaseous oxygen. The deposit consists of normal caseinogen containing less than 0.2% of ash. The amount OF caseinogen removed from the solution was determined by the refractometer and a correction was applied to the experimental data to compensate for loss of caseinogen from the anode by dissolu- tion in the electrolyte the amount of this correction depending on the alkalinity of the solution and the duration of electrolysis. The electrochemical equivalent of caseinogen in solutions containing 50 x lob5 to 100 x 10-5 equivalents of potassium hydroxide per gram is 0.0242 +_ 0.0019 gram-of caseinogen per coulomb as a mean of fourteen determinations.This must be the equivalent of caseinogen at its minimum since whatever the proportion of potassium hydroxide to caseinogen in the electrolyte no caseinogen will be deposited until the potassium hydroxide in the anode film is saturated. The equivalent of caseinogen is therefore 2336 + 183 at saturation. Since 1 gram of caseinogen saturates 11.4 x 10-5 equivalents of potassium hydroxide the molecular weight of caseinogen is (8772) and the basicity (8772) 4 (2336 f 183) that is 4 or some multiple of 4. The formula of potassium caseinogenate i n solutions neutral to phenolphthalein was deduced from cryoscopic determinations to be K2X**m* +X(OH),”” molecular weight 2200 admixed with a small proportion of (KHX),’..’ + X2(OH)2n)”’ molecular weight 4400 the latter being the main constituent in solutions neutral to litmus. At A.J. W. saturation ihe formula is KH,X4”” + X4(OH)4d’” molecular weight 8800. The conductivity of calcium hydroxide solution in presence ofi. 408 ABSTRACTS OF CIIEiMICAL PAPERS. caseinogen indicates that the alkalis and alkaline earths dissolve caseinogen in equivalent proportions. The author discusses the formula and dissociation of the alkaline-earth caseinogenates in view of the difference between caseinogen and globulin in this repect. The percentage of glutamic acid in coseinogen indicates a minimum molecular weight of 1336 (4008/3) whereas the tyrosine indicates 4022.The sulphur arid phosphorus also indicate a minimum molecular weight of about 4000. R. J. C. Inosic Acid. IV. PHCEUUS A. LEVENE and WALTER A. JACOBS (Bey. 1911 44 746-753. Compare Abstr. 1908 i 931 ; 1909 i 164 540).-The phosphoric acid residue in d-ribosephosphoric acid is attached to the &carbon atom of the ribose molecule since on oxida- tion with nitric acid (D = 1.2) at 40" and subsequent rapid evaporation and treatment with calcium hydroxide calcium phospho-ribonate and calcium phosphate are obtained. The calcium salt is identical with that obtained from the oxidation product of d-ribosephosphoric acid. By the hydrolysis of phospho-d-ribonic acid a t 130° in neutral solution (ammonium acetate) d-ribonic acid is obtained which is identical with the acid formed when d-ribose is oxidised with bromine water.Details for the preparation of d-ribosephosphoric acid are given. J. J. S. Inosic Acid. WALTER A. JACOBS and PHCEBUS A LEVENE (Yroc. Amer. SOC. Biol. Chern. 1910 xxv ; J. Bid. Chern. Q).-Inosic acid is hypoxanthine phosphoriboside. The phosphoric acid group is bound to the o-carbon atom of the ribose. W. D. H. Oxyprotosulphonic Acid. JOZEF BUBACZEWSKI and L. KRAUZE (Zeitsch. physiol. Chem. 191 1,71 153-156).-The oxyprotosulphonic acids (compare Maly Abstr. 1885 824) of egg-albumin serum- albumin and casein are differentiated on treatment with boiling glacial acetic acid into acid compounds (a) insoluble in acetic acid termed a-oxyprotosulphonic acid and ( b ) soluble in acetic acid but precipitated by ether or by water termed P-oxyprotosulphonic acid.On cooling the acetic acid solution an acid substance separates in the case of egg- and serum-albumin which has not been further investi- gated. The relation of carbon to nitrogen in both a- and P-oxyproto- sulphonic acids indicates that the protein molecule has not been hydrolysed in their formation. Some Physico-chemical Properties of Lecithin Emulsions and of Lecithin-Protein Mixtures. HANS HANDOVSKY and RICHARD WAGNER (Biochem. Zeitsch. 19 11 31 32-45).-Lecithin emulsions show an increased viscosity as compared with water which is diminished on the addition of electrolytes. The lecithin precipitation by hydrochloric acid can be inhibited by salts in concentrations in which they themselves do not precipitate it.Indifferent narcotics have no effect on the viscosity Globulin can be Precipitated by lecithins from sera which are poor in electrolytes (that is have just sufficient salts to hold the globulin in solution). The precipitation is E. F. A.ORGANIC CHEMISTRY. i. 409 inhihited by neutral salts. Neither precipitation nor viscosity phenomena give any indication of a colloid complex between lecithin and neutral serum albumin when lecithin is added in the form of an emulsion. S. B. S. The Valency of Iron in Blood Pigment. WILLIAM KUSTE~ (Zeitsch. physiol. Chem. 191 1,71 100-104).-Polemical. Reasons are given why the author disagrees with Manchot’s conclusion that the iron of hzmoglobin cannot be in ferrous but must be in ferric corn bination.W. D. H. The Theory of Enzyme Action. OSCAR LOEW (Biochem. Zeitsch. 1911 31 159-167).-The author claims that his views on enzyme action have been misrepresented in recent text-books on enzymes i n that it has been stated that the labile enzymatic substances decompose explosively. He distinguishes between two kinds of sub- stances with chemical lability the “potentially-labile,” which on small stimulus decompose explosively and the kinetically-labile,’’ where the energy is exerted in a continuously active form. The differences are illustrated by various examples. S. B. S. Reversibility of Enzyme Action. ADOLF WELTER (Zeitsch. anyew. Chern. 1911 24 385-387).-A brief resume is given of the more important cases in which the reversibility of enzyme action has been demonstrated (compare Croft Hill Trans.1898 73 634 ; Proc. 1901 17 184; Kastle and Loevenhart Abstr. i1901 i 178 ; Visser ibid. 1905 ii 577; Hanriot ibid. 1901 ii 175 ; Pottevin ibid. 1.903 ii 494). Details are given for the production of fatty acids on the large scale by the hydrolysis of natural fats by means of the lipatic enzyme present in seeds. Experiments are also described which prove that in the absence of large quantities of water these enzymes are capable of synthesising appreciable amounts of esters from glycerol and the acids derived from certain natural fats. J. J. 8. Composition of Invertaae. ALBERT P. MATHEWS and T. H. GLENN (J. BioE. Chem. 1911 9 29-56).-As ordinarily prepared invertase is probably a combination of a protein and a mannosan.All attempts to free the protein from the gum and retain enzymic activity were failures. Acid alcohol destroys the activity. The parallelism between activity and nitrogen content is believed t o indicate that the active substance is a protein. W. D. H. Temperature-coefficient of the Decomposition of In- vertase HANS EULER and SIXTEN KULLBERCI (Zeilsch. physiol. Chern. 1911 71 134-142. Compare Euler and Ugglas Abstr. 1910 i 345 796).-The influence of heating for half an hour at various temperatures on invertase prepared by autolysis has been determined. Half of the invertase is destroyed under these conditions at 63Of 0.2”. In an extract of dried yeast the presence of proteins and carbo- hydrates has no influence on the heat stability of invertase.Lactose has no protective influence ; phosphate has also no influence. Therei. 410 ABSTRACTS OF CHEMICAL PAPERS. is no difference in the heat stability of invertase from top and bottom fermentation yeasts contrary to statements on this point in the text- books of Effront and Oppenheimer. E. F. A. Nucleases. PHCEBUS A. LEVENE and FLORENTIN MEDIGRECEANU (J. Biol. Chem. 1911 0 65-83).-Plasma of heart muscle liver kidney and intestinal mucosa hydrolyse inosin giving rise to the free base and d-ribose ; plasma of pancreas and blood serum have no effect. Inosic acid is hydrolysed into phosphoric acid d-ribose and hypo- xanthine by the same materials. The same plasmata hydrolyse guanylic acid with the addition of that of the pancreas. (one experi- ment) ; the tendency to gelatinise causes difficulties in the investiga- tion of guanylic acid.Cytidin is regarded as a complex of pentose and cytosine althoagh not in glycosidic linking ; no cleavage occurred with any plasma. The cleavage of yeast nucleic acid by the plasmata into phosphoric acid purine bases d-ribose cytidin and uridin was incomplete. No definite regularity in the velocity of the reactions was noticed W. D. H. Nucleases. WALTER JONES (J. Bid. Chem. 1911 9 129-138). -A nuclease is generally understood to be an enzyme which liberates purine bases from nucleic acid in a form in which they are directly precipitable by the reagents usually employed for that purpose. The definition is however unsatisfactory. There is further no assurance that the enzyme of one gland can decompose the nucleic acid of another organ.The nucleic acids are constituted on one type; according to Levene and Jacobs a phosphoric acid group is linked to a nitrogenous ring by d-ribose. This ‘‘ nucleotide ” structure is common to all nucleic acids but differences occur in the nitrogenous rings and in re-duplication of molecules ; it would therefore be surprising to find one enzyme which can decompose them all. The present investigation deals with guanylic acid a mononucleotide that is a nucleic acid which yields only one purine base guanine. Extract of ox-spleen readily effects its decomposition giving rise to xanthine and uric acid by oxidation of the guanine. Pig’s pancreas cannot do this although it is rich in nuclease. W. D. H.The Physiological Agents Concerned in Nuclein Fermenta- tion with Special Reference to Four Independent De- amidases. WALTER JONES (J. .Bid. Chem. 1911 0 169-lSO).- Although pig’s pancreas will not liberate the purine base from guanylic acid i t nevertheless liberates phosphoric acid and thus con- verts guanylic acid into guanosine. Extracts of pig’s spleen and liver Lave the same action and also liberate phosphoric acid from thymus-nucleic acid. The nucleosides (such as guanosine) which remain are compounds of d-ribose and the purine base; the amino- nucleosides guanosine and adenosine can further be converted into xanthosine and inosine (or hypoxanthosine) the corresponding hydroxy- compounds as Levene and Jacobs showed. Such deamidations are quite analogous to those which occur when guanine and adenine are converted into xanthine and hypoxanthine respectively. Nevertheless,ORGANIC CHEMlSTRY.i. 411 the deamidation is accomplished by different enzymes ; thus guanase and guanosine-deamidase are separate enzymes ; one is present for instance in pig’s liver and the other is not. Similarly adenosine- deamidase and adenase are not identical enzymes. W. D. H. Pancreatic Lipase. ANT. HAMSIK (Zeitsch. physiol. Chem. 191 1 71 238-251).-Previous authors have noticed that filtration of a glycerol extract of pancreas removes its lipoclastic action. I n the present research it is shown that clear glycerol extracts can be prepared from the dried pancreas of the pig and that these retain their fat-splitting properties after filtration through a Chamberland filter.Pancreatic lipase is reversible in its action and synthesises fat from palmitic and stearic acids and glycerol. Neutra,l salts inhibit both fat-splitting and fat-synthesis but soaps act favourably on both. W. D. H. Significance of Colloidal Manganese Oxide Solutions in Biochemical Oxidations. BOUWE SJOI~LEMA (Gedenkboek aangeboden aan J. M. van Bernmelen 1910 399-406. Compare Abstr. 1909 ii 484 and Marck Diss. Heidelberg 1907).-By agitating samples of quinol solution tvith Marck’s manganese solution some in presence of peroxydase from horse-radish (Cochlearia nrmoraciu) and some without it the author found that the oxidation of the quinol and its trans- formation into quinhydrone by the manganese peroxide is facilitated by the presence of the peroxydase.I n the oxidation of quinol a mix- ture of colloidal manganese peroxide and a peroxydase behaves like the system peroxydase + oxygenase so that the manganese plays the part of oxygenase. A. J. W. Relation of Hzemoglobin Derivatives and Peroxydases to Inorganic Catalysts. W. MADELUNG (Zeitsch. physiol. Chem. 191 1 ’71 204-237).-1t is probable that the mechanism of the action of oxydases peroxydases and catalases rests on a n inorganic basis. Such ferment action is t o be expected in all cases where compounds are present which are able t o exist in several stages of oxidation which are capable of forming unstable molecular compounds with molecules of oxygen or hydrogen peroxide and in which the higher oxides can be converted into the lower and vice versa. It is shown in the case of the blood-colouring matter that complex iron compounds fulfil these conditions and it is probable that the greater part if not all such ferments owe their activity to complex iron compounds. When neutral aqueous solutions of benzidine are oxidised in presence of traces of a neutral mineral salt benzidine-blue is precipitated in the form of microscopic matted needles. On separating the dye and adding hydrochloric acid to it brown flakes of the dichloroimide are formed which dissolve in potassium iodide liberating iodine. The free iodine is titrated with thiosulphate and a convenient measure of the oxidising activity is obtained. The benzidine is used in 0.04% solution containing 1% of sodium chloride a considerable excess being employed. With blood the amount of oxidising action is proportional to the amount taken Small quantities of mineral acids prevent thei. 412 ABSTRACTS OF CHEMICAL PAPERS. formation of the blue but the amount formed is doubled on the addition of sodium acetate to the acid or on saturating the neutral solution with carbon dioxide. The optimum amount of sodium chloride necessary for precipitation of the blue is about 1%. The activity of blood is roughly proportional to the haemoglobin present. E. F. A. New Method for the Preparation of a Gatalase from Blood and its Properties. JULES WOLFF and ELOI DE ST~CKLIN (Compt. rend. 1911 152 729-'731).-The following process gives a catalase free from hamoglobin and oxyhaemoglobin free from catalase. Unlike Senter's method (Abstr. 1903 ii 661) it does not diminish the activity of the enzyme. The corpuscles of defibrinated blood are washed with physiological salt solution and removed by centrifugation. The paste of corpuscles is made up to the original volume of blood with distilled water laked with ether and the liquid decanted and filtered. The filtrate is kept for twenty hours at - loo after the addition of one- fifth its volume of alcohol. Oxyhsemoglobin crystallises out and a furtber crop separates on addition of more alcohol. The liquid is now covered with a layer of toluene 0.5 cm. deep which after some days precipitates proteins with the last traces of oxyhaemoglobin. The clear yellow filtrate contains a stable and very active catalase. It has been shown that pure oxyhaemoglobin is decomposed by hydrogen peroxide whereas this is without action on the crude product. I n the latter cape the catalase present exerts a protective influence on the oxy haemoglobin by facilitating the corn bination of oxyhaemoglobin with molecular oxygen. w. 0. w. The Reduction Fermenta. I. The Schardinger Enzyme (Perhydridase). ALEXIS EACH (Riochem. Zeitsch. 19 1 1 31 443-449).-The enzyme acts in the system ferment-methylene blue-aldehyde-water. According to the author's theory scission of water by the oxidisable substance (aldehyde) takes place under the influence of the catalyst which forms with the hydrogen of the water a strongly reducing substance He draws attention to the analogy of the reducing enzymes (for which he suggests the name reducase instead of the etymologically incorrect reductase) with the oxydases and peroxydases. The Schardinger enzyme (that is the enzyme acting in the methylene blue-aldehyde system) can be prepared from calf's liver by extracting the organ with 1% sodium hydrogen carbonate solution and neutralising the extract with acetic acid. From this extract the enzyme can be precipitated by alcohol and from the precipitate it can be re-extracted in purer form by 4% sodium hydrogen carbonate which extract acts readily after neu tralisation with acetic acid. S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9110000345

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 349 General and Physical Chemistry. Refraction and Dispersion of Light in Certain Gases GEORG GRUSCHKE (Ann. Physik 191 1 [iv]. 34 801-S16).-The refractive indices of carbon monoxide and dioxide have been determined for six different wave-lengthe between the limits X = 6678 and X = 4471. Observations were also made on carbon suboxide C,O but this gas was admixed with a large proportion of carbon dioxide. H. M. D. Dispersion and Absorption of Chromium and Manganese in the Visible and Ultra-violet Spectrum. VS~VOLOU FR~EDERICKSZ (Ann. Physik 1911 [iv] 34 780-796).-1n con- tinuation of an investigation of the optical constants of the metals the author has determined the refractive and absorption indices of chromium and manganese by Voigt’s method. Curves are drawu which show the variation of the optical constants with the wave-length of the incident light.H. M. D. Dispersion in Vapours of the Alkali Metals. PENRY V. REVAN (Proc. Roy. Soc. 1911 85 A 58-76. Compare Abstr. 1910 ii 9 14).-Disporsion measurements have been made with sodium and rubidium vapours and the dispersion curves have been drawn for several absorption lines. If attention be confined to the effects of dispersion near any single pair of lines the constant of the dispersion formula appropriate to this line increases with the temperature of the vapour used. -4 relation cannot be found between the constants of different metals as there is no evidence as to what temperatures should be chosen as corresponding temperatures. C. H. D. The Glow Discharge and the Emission of the Alkali- Metal Vapours.GEORG GEHLHOFF (Ber. Deut. physikcd. Ges. 1 9 1 1 13 183-192. Compare Gehlhoff arid Rottgardt hbstr. 1910 ii 679).-Observations have been made relating to the nature of the glow discharge and of the emission spectra exhibited by tubes containing caesium vapour admixed with helium. The helium lines disappear from the spectrum of the positive glow at very small pressures of the cesium vapour. On the other hand these lines are still evident in the spectrum of the negative glow when the pressure of the cEsium vapoiir has attained relatively high values. Experiments at different temperatures in which the partial pressure of the helium are kept constant have shown that the czsium lines of the principal and sub-series are exhibited by the positive glow. The negative glow spectrum shows the sub-series lines and the lines of the spark spectrum brightly and the principal series lines feebly.When a spark gdp is introduced into the circuit the principal and sub-series lines disappear from the spectrum of the positive glow. These and other observations support the author’s view that the VOL. C. ii. 24ii. 350 ABSTHACTS OF CHEMICAL PAPERS. principal series lines are excited by slowly moving the sub-series lines by more rapidly moving electrons and the lines of the spark spectrum by electrons of still greater velocity. H. M. D. The Absorption Spectra of L i t h i u m and C a s i u m . PENRY V. BEVAN (Proc. Bog. Soc. 1911 85 A 54-58. Compare Abstr. 1910 ii 370).-The absorption spectrum of lithium vapour has been examined at a red heat in a steel tube.The lines of the principal series are tabulated and there is in addition a fluted region between X 4500 and X 5500 corresponding fairly closely in position with the sodium fluted region. The wave-lengths of the lines are in good agreement with the values calculated by Hicks’ formula (Phil. Trans. 1910 210 58). Some cmium lines have also been re-determined the vapour being obtained by the action of sodium and potassium on caesium chloride so that the absorption is somewhat masked. The differences from the values calculated from Hicks’ formula all have the same sign. C. H. D. The Effect of Pressure on Arc Spectra. 111. Silver X 4000 to X 4600. TiT. GEOFFREY DUFFIELD (Phil. Truns. 1911 A 211 33-73).-Photographs of the arc spectra of silver and gold have been taken in air a t pressures varying from 1 to 200 atmospheres. For silver data are recorded for the region X = 4000 to A= 4600 and in the case of gold from X = 3550 to X = 5100.The observations indi- cate that with increase of pressure the lines broaden and are dis- placed towards the red end of the spectrum. At higher pressures the line spectrum disappears and is replaced by a banded spectrum which then passes into a continuous spectrum. Details are recorded which show the broadening displacement and reversal effects and the rela- tive intensities of the line and banded spectra a t different pressures. I n the case of gold none of the lines were found to undergo reversal. I n the experiments with the arc spectrum of gold it has been found that the electrodes undergo a physical change which causes the melting point to rise. This may be due to a direct influence of pressure on the metal or to the passage of the arc current through the electrodes or it may be an annealing effect. IV.Gold. H. M. D. An Extremely Long- W a v e d Radiation of Mercury Vapour. HEINRICH RUBENS and 0. YON BAEYER (Sitxungsbei.. K. Akad. Wiss. Berlin 1911 339-345).-It has been found that a mercury arc lamp emits a small proportion of very long-waved rays the mean length of which is about 3QOp (0.3 mm.). These can be isolated by making use of the arrangement of quartz lenses which has been described in a previous paper. To obtain the rays in appreciable quantity the energy consumption in the arc should be fairly high and the authors employed a current of 4 amperes a t 100 volts the length of the arc being 8 cm.The long-waved radiation consists of two parts that of greater mean wave-length being due to the mercury arc the portion of shorter wave-length t o the heated quartz walls. The former can be separated by allowing the rays to pass through a 2 mm. plate of fused quartz or better through a disk of black cardboard.GENERAL AND PHYSICAL CHEMISTRY. ii. 351 The absorption of the filtered and unfiltered rays as well as the long-waved rays emitted by a Welsbach burner has been measured for a large number of different substances. The isolation of these long-waved mercury rays corresponds with an extension of the previously known ultra-red spectrum by one and a- half octaves.H. M. D. The Long-waved Portion of the Spark and Arc Spectra of Copper. MATTHIAS ARETZ(Z&CJL. wiss. Photocltem. 191 1,9,256-259). -Measurements have been made of the wave-lengths and intensities of the lines in the spark spectrum of copper between X=470 and A = 578 ,up and in the arc spectrum between X 500 and X 700 ,up. The photographic records show seventy-one lines which have not been indicated by previous observers. In passing from the arc to the spark spectrum the maximum of the curve showing the distribution of the spectral energy is shifted towards the region of smaller wave-lengths. Both spectra exhibit a consider- able number of blurred and ill-defined lines. There is a marked difference in the structure of two spectra. H. M. D. The Ultra-violet Absorption Spectrum of Aqueous Solutions of Neodymium Chloride.GREGORY P. BAXTER and TRUMAN S. WOODWARD (J. Amer. Chem. Soc. 1911 33 270-272).-The ultra- violet absorption bands furnished by an aqueous solution of neodymium chloride have been examined. The neodymium chloride was a highly- purified sample the only impurity being a trace of the corresponding praseodymium salt. The wave-lengths of the middle of the various bands are recorded and the data compared with those of previous observers. H. M. D. Ultra-violet and Ultra-red Phosphorescence W. E. PAULI (Ann Phpsik 1911 [iv] 34,739-779. Compare Abstr. 1909 ii 777). -The phosphorescent bands emitted by calcium strontium barium and zinc sulphides when admixed with small quantities of various metallic ‘‘ impurities ” have been examined.The methods of prepara- tion of the phosphors which have been found to give the best phosphorescent effects are described in detail. In many cases the temperature and time of heating are of great imp&tance. Strontium phosphors give in general the best results when heated for consider- able periods at a very high temperature. On the other hand barium phosphors become less active if subjected to high temperatures in the course of preparation. When the phosphorescent alkaline earth sulphides are excited by meant? of Rontgen or cathode rays the same bands are exhibited as when excited by sparks between zinc electrodes. In some cases the excitation by means of cathode rays is accompanied by a special momentary phosphorescence effect which extends a long way into the ultra-violet region.A calcium silver potassium phosphor has been found which emits only ultra-violet light the phosphorescent band having a maximum 24-2ii. 352 ABSTRACTS OF CHEMICAL PAPERS at about 350 pp. On the other hand a calcium nickel phosphor containing small quantities of calcium fluoride and potassium fluoride has been prepared which emits ultra-red rays the band having a maximum a t about 790 pp. The influence of temperature between -1SOO and 300° has been examined and the experimental data are discussed from the point of view of the theory put forward by Lenard. H. M. D. Piezo-optical Behaviour of Ammonium Chloride. ST. KREUTZ (Bull. Acad. Xoc. Cracow 191 1 118-123).-The author has investi- gated the changes in the optical properties of crystals of ammonium chloride which are brought about by the application of presslire at right angles to the different faces.These show that arnuouium chloride behaves similarly to fluor-spar but t h a t ammonium sodium and potassium chlorides belong t o three of the four possible different types. From a comparison of the effects produced by pressure on the one hand and by the inclusion of foreign subhtances on the other the conclusion is drawn that the double refraction effects which are observed when small quantities of foreign substances are present in cubic crystals are due t o stresses set up by disturbance of the crystalline structure. H. 1%. D. Natural and Magnetic Rotatory Polarisa tion. EUG~NE DARMOIS (AWL China. Phys.1911 [viii] 22 247-281 495-589. Compare Abstr. 19OS ii 747 ; 1910 i 52 ; i 39S).-The object of the investigation was to ascertain whether Wiedemann’s law (Ann. Phys. Chem. 1851 82 215) is of general application. The law states that the natural rotatory dispersion for an optically active substance is proportional to its magnetic rotatory dispersion but according to the present author the fact that this is approximately true for quartz as Wiedemann found is merely fortuitous other su bstarices examined showing marked departures from the law. The experiments were carried out on a- and P-pioene pinene hydrochloride and hydro- bromide camphene limonene d- and I-camphor borneol and iso- borneol none of wbich were found to obey the law. All the compounds showed considerable absorption in the ul tra-violet and i n the case of P-pinene and camphor abnormal natural dispersion whilst the magnetii dispersion remained normal; in this region of the spectrum also Wiedemann’s lam appears to have no significance whatever The purity of the substances under observation was established by taking advantage of the principle that for a mixtura of two optical antipodes the rotation is different from that of either constituent whilst the dispersion remains the same.The application of this to the case of turpentine oils has already been described in part. The French German and American oils each contain only two hydro- carbons @-pinene identical with Wallach’s nopinene and an a-pinene having a different rotatory power in each oil. d-a-Pinene was obtained by the fractionation of Aleppo oil (Vdzes Abatr.1909 i 818) ; it has [a]L5 +48*4O P 5 0.8625 nz 1.468. Pure P-pinene prepared byGENERAT AND PHYSICAL CHEMISTRY. ii. 353 repeated fractionation of the French oil has b. p. 164O [a] -22*l0 D15 0.875 n 1.478. Application of the method to synthetic borneol (from pinene hydro- bromide) shows that the low rotatory power is due to admixture with I-isoborneol. w. 0. w. Differentiation by Chemical Development of Latent Images Obtained by means of Silver Chloride and Bromide Emulsions. AUGUSTE LUMIII~RE Lours LUMI~RE and ALPHONSE SEYEWETZ (Conzpt. rend. 191 1 152 766-768. Compare Abstr. 1910 ii 916).-A solution containing 1% of sodium quinone- suIphonate and 5% of anhydrous sodium sulphite has the property of rapidly developing the latent image in silver bromide emulsions but is without action on the silver chloride images.This differential action does not occur unless the sulphite is present. Solutions oE pyrogallol quinol or catechol Containing sodium sulphite or sodium hydrogen sulphite act somewhat in the same way but the difference in their reducing power towards the two halides is less distinct. w. 0. w. Condensation Nuclei Produced by the Action of Light on Iodine Vapour. GWILYM OWEN and HAROLD PEALINU (Phil. Mug. 191 1 [vi] 21 465-479).-It has been shown previously (Abstr. 1907 ii ,843; 1908 ii 565) that the gas obtained by the volatilisa- tion of solid carbon dioxide contains large numbersof nuclei which act as centres for the condensation of super-saturated water vapour.Similar experiments with camphor naphthalene benzoic acid and iodine show that such nuclei are not formed in the case of these substances. If however moist air (or oxygen) containing iodine vapour is acted on by light condensation nuclei are produced in large numbers. These nuclei are very unstable and disappear in a few seconds in the dark. The nuclei are not electrically charged and are not produced when the expansion apparatus contains hydrogen carbon dioxide or coal gas in place of air (or oxygen). Further they are not formed if the water in the apparatus is replaced by ethyl alcohol. Experiments in which the moist mixture of air and iodine vapour was illuminated for different short intervals of time indicate that the nuclei increase in size under the influence of the light and attain a maximum size in less than one second.With different sources of light (arc lamp fish-tail burner Nernst light screened by red glass and diffused daylight) the same results were obtained. After the iodine has been allowed to remain in the apparatus for some days the production of nuclei no longer takes place ; the pheno- menon is again observed however if the glass walls of the apparatus are washed with water. If air containing iodine vapour is introduced into the expansion apparatus through a plug of glass wool the number of nuclei produced is much greater than when iodine is in direct contact with the cloud- chamber. This action becomes less marked as the amount of air- iodine vapour mixture thus introduced increases.These observa- tions indicate that the surface of the glass modifies the process ot'ii. 354 ABSTRACTS OF CHEMICAL PAPERS. formation of the condensation nuclei but a satisfactory explanation has not yet been obtained. H. M. D. Measurement of the R a n g e of t h e a-Particles of Uranium by the Scintillation Method. A. FOCH (Le Radium 1911 8 101-104).-A spherical glass flask of 97 mm. diameter was covered internally with a thin layer of uranium acetate by evaporating in it an ethereal solution of the salt. At the centre a screen of zinc sulphide was placed which was viewed by a lens outside the flask and the pressure of the air was varied. From the curve connecting the number of scintillations observed per minute and the pressure of air it was deduced that the range of the a-particles of uranium is 2.68 cm.of air at 760 mm. pressure. The curve was not a linear function of pressure but showed a t the middle of the range a sharp change of direction as if the radiation consisted of two groups of a-particles the second group having less than half the range given. Photographs taken by inclining a photographic plate backing a zinc sulphide screen to a surface of uranium oxide’ also show a decided variation of density a t about half the range of the a-particles. F. s. The Ionisation of Different Gases by the a-Particles from Polonium and the Relative Amounts of Energy Required to Produce an Ion. T. SMITH TAYLOR (Phil. Mag. 1911 [vi] 21 571-579; Amer. J. Sci. 1911 [iv] 31 249-256).-The Bragg ionisation curves for the a-rays of polonium have been taken in various gasei and compared with the formula given by Geiger I= C/(Y - x ) ~ ’ ~ where x is the distance of the source of rays T a constant represent- ing the average range of thea-rays and c a constant.On the assump- tion that the ionisation produced at any point is proportional to the consumption of kinetic energy of the a-particle c depends on the relative energy ’required t o produce an ion in the different gases. The theoretical and experimental curves are in good agreement. The relative energy required to produce a n ion varies from 1.01 for hydrogen to 0.73 for carbon disulphide (air = 1.00) the heavier and more complex gases and vapours being more readily ionised than the lighter ones. The assumption that the ionisation produced by a n a-particle is proportional to the energy consumed is fully confirmed.F. S. The Radiations of the Alkali Metals. J ~ L E HENRIOT (Compt. rend. 1911 152 851-853).-To test the view that czsium may be emitting P-radiations of too low velocity to ionise gases the charge transported by the salts of potassium rubidium and casium in a vacuum was investigated. For rubidium and potassium salts the existence of a negative current in a vacuum due to the expulsion of P-radiations was readily established the current being for rubidium about five times as great as for potassium. But with czesium salts no certain current could be observed. This phenomenon is to be dis- tinguished from the photo-electric effects observed with the alkali metals themselves even in the dark (J.J. Thomson). Some experimentsGENERAL AND PHYSICAL CHEMISTRY. ii. 355 on this effect showed that the current became the more and more feeble as greater precautions are taken and is not then within the range of detection by the electrometer. The only way to follow it beyond this range is by an electroscope biit this involves some illumination of the leaf during readings. The experiments support the views of Dunoyer that the effects are to be ascribed to disturbing influences. F. S. Secondary 7-Rays Produced by /&Rays. J. A. GRAY (Proc. Roy. SOC. 1911 A 85 131-139).-Previous attempts to detect the generation ol y-rays at the point of impact of the ,&rays on metals using the rays of radium have been unsuccessful but with the P-rays of radium-E a clear effect of this kind has been put into evidence the y-radiation normally accompanying the p-radiation of radium-23 being very feeble.The radium-E preparation consisted of lead sulphate which had been separated from an old radium solution to which lead had been added in order to remove the radium-D. It was free from radium. The @-rays were arranged to fall on a radiator so arranged that any y-rays generated in the radiator would affect a y-ray electroscope. A clear effect due to the radiator was observed which could be prevented by cutting off the P-rays by a few sheets of paper. The production of y-rays increased with the atomic weight of the radiator from graphite to lead and was roughly proportional to it. I n other experiments the P-rays were deflected by a magnet on to the radiator and the production of both incident and emergent y-rays from the radiator subjected to P-rays mas observed.In the experi- ments with a layer of active material between 0.3 and 0.4 mm. thick consisting chiefly of lead sulphate the secondary y-rays were equal to about one-fourth of the y-rays from the active material itself. Absorption measurement showed a much higher absorption of the secondary y-rays in materials of high atomic weight than in those of low atomic weight the new radiation resembling X-rays in this respect. The y-radiation of radium-23 may be entirely of secondary origin. F. S. J. H. CLO (Le Badiunz 1911 8 108-112).-An iron vessel heated by an electric current and containing air or hydrogen the pressure of which was measured and used to determine the temperature was subjected to the y-rays of radium.The ionisation was measured by an electro- meter by the constant deflection method. The ionisation was found to be independent of the temperature within 0.2% up to 600° in air and up to 430' in hydrogen. A variation in the mean kinetic energy of the molecule from 1 to 2 does not affect the stability of the atom sufficiently to alter its ionisation by one-tenth per cent. The Charges on Ions in Gases and Some Effects that Influence the Motion of Negative Ions. JOHN S TOWNSEND (Proc. Roy. Xoc. 1911 A 85 25-29).-The principle of the experi- ments was t o allow a stream of ions produced by secondary Rontgen rays in gaaes to pass through a circular aperture in a thin plate. Effect of Temperature on the Ionisation of a Gas.F. 6.5. 356 ABSTRACTS OF CHEMICAL PAPERS. After traversing an electric field of known strength for a certain distance the ions are received (1) on a flat disk the size of the aperture and (2) on a flat ring surrounding the disk the ratio of the quantities of ions in (1) and (2) being found. If the ions follow the ordinary lams of diffusion this ratio depends only on the product of the number of ions ( N ) the charge on the ion (e) and the electric force ( X ) and is independent of the pressure of the gas. Investigations with hydrogen oxygen and carbon dioxide confirmed the results formerly obtained with air. The value of the product Ne for negative ions under a variety of circumstances is always the same as in electro- lysis of liquids namely 1.22 x lolo.This is also true for the positive ions when the secondary X-rays originate a t a bright metallic surface but high values are obtained when the surface is coated with vaselin showing that some of the ions produced by the more penetrating rays carry double charges. I n perfectly dry gases a t low pressure the ratio before referred to is no longer independent of pressure but the determinations of Ne may be made with higher pressures and low electric force. The negative ions assume the corpuscular state in dry gases at low pressure. The mass of the ion can be calculated from its diffusion coefficient. I n ordinary circumstances the mass of the negative ion in air is eleven times the mass of the molecule of carbon dioxide. When X is 0.9 volt per cm.and the pressure is 10 mm. the mass of the negative ion in perfectly dried air is only one forty-third of the mass of the molecule of carbon dioxide. F. S. The Mobility of Ions Produced in Air by Sulphate of Quinine in Process of Hydration. MAURICE DE BROGLIE and L. BRIZARD (Compt. send. 1911 152 855-856).-Owing to the rapid recombination of the ions produced by quinine sulphate in pro- cess of hydration the ions are localised in a very thin layer a t the surface of the salt. On applying an electric field the ions of the corresponding sign are readily extracted but L current of air is then not able to carry them away. The separation has been effected by placing the active salt a t the surface of the small central electrode of a very large cylindrical condenser where the electric field is intense and extracts the ions from the layer in which they are produced. At the sides of the condenser the field is feeble and a transverse current of air partly removes the ions.Concordant results with many specimens of quinine sulphate have shown that the mean velocity for the two ions is 1 cm. per second in a field of 1 volt per cm. F. S Mobility of the Positive Ions Produced in the Oxidation of Copper. ADOLFO CAMPETTI (Atti 12. Accad. Sci. Z’ovino 1911 46 242-254).-The mobility of the positive ions produced during the oxidation of copper in dry air at 500° is found to be about 0.0016 cm. per second and this indicates that they are large ions comparable with those produced in the slow oxidation of phosphorus.It is thus established that ions of considerable mass may be produced and continue to exist even at comparatively high temperatures. R. V. S.GENERAL AND PHYSICAL CHEMISTRY ii. 357 Chemical Actions and Ionisation by Splashing. L ~ O N BLOCH (Ann. Chim. Phys. 1911 [viii] 22 370-417 441-495. Compare Abstr. 1903 ii 206 ; 1904 ii 117; 1905 ii 72; 1908 ii 1032; 1909 ii 395 781; 1910 ii 32 381 480; this vol. ii 176).-A r6sumb of work previously published with further experimental details and diagrams of the apparatus employed. The phosphorescence of DelBpine’s sulphur compounds (Abstr. 19 10 i 295 545) is due to oxidation unaccompanied by ionisation. Homogeneous Rontgen Radiation from Vapours. J. CROSBY CHAPMAN (Phil. Mag. 1911 [vi] 21 446-454).-The value of Alp the absorption coefficient divided by the density in aluminium of the homogeneous secondary X-radiation from bromine has been determined €or vapour oE ethyl bromide solid sodium bromide and bromine hydrate and found to be 16.3 independent of the nature of the compound.The radiation is absorbed exponentially and the value lies on the smooth curve connecting atomic weights with the values of Alp. The same experiments with vapour of ethyl iodide and solid iodine gave the value 2.3 for Alp. The amount of secondary radiation from ethyl bromide when hydrogen and carbon dioxide respectively were used to convey the vapour was nearly the same. This disproves the theory that the secondary X-radiations result from the bombardment of the atoms by ejected corpusc!es ; for carbon dioxide would absorb the corpuscles far more than hydrogen so that in the latter gas more secondary X-radiation should be generated.Cathode Luminescence in Minerals. ALFREDO POCHINETTO (Nuovo Cim. 1911 [vi] i 21-64. Compare Abstr. 1910 ii 89).- The behaviour of artificial minerals under the cathode rays is very closely analogous to that of the natural minerals ; the differences are not greater than those observed between natural minerals from different sources. The most notable difference observed is that only the synthetic specimens of sapphire show dichroism. W ell-crystallised specimens of calcite from diff ererit sources give the same cathode luminescence with the same characteristics whilst aragonite gives a different luminescence. The luminescence of calcite has been ascribed to the presence of traces of manganese and the question is discussed why aragonite which also contains manganese gives a different result.It has been stated by previous observers that the nature of the spectrum of the cathode luminescence is independent of the velocity of the exciting rays but this is not generally true. It applies t o natural and synthetic willemite but not to spodumene or distene. Twin crystals show in general a luminescence much less polarised than do simple crystals of the same substance. The phenomena of dichroism in cathode luminescence are due to the diff erent degree of polarisation of the radiations constituting the spectrum of the light emitted and are undoubtedly due to the presence of impurities in the minerals. The phenomena of double luminescence previously met with only in diopside have now been observed under suitable conditions in spodumene kunzite and distene. w.0. w. F. S.ii. 358 ABSTRACTS OF CEEMICAL PAPERS. The duration of the residual luminescence is the smaller the shorter the excitation and in general the extinction of the luminous vibrations is most rapid for radiations corresponding with short waves. G. S. The Heat Generated by Radioactive Substances. WILLIAM DUANE (Amer. J. Xci. 1911 31 257-268. Compare Abstr. 1909 ii 534 637; 1910 ii 816)-This paper consists for the most part of a connected account of researches already published but contains details of the present method of employing the differential vapour calorimeter designed by the author. The radioactive substance is placed inside of a tube half of which is iron and the other half nickel the surfaces between the metals being parallel to the axis of the tube.A current is passed through t h i s tube to cool the junction and compensate for the heat developed by the radioactive substance inside the tube so that the calorimeter is used as a null instrument and effects varying from 0.001 to 2 gram-calories per hour can be measured without any alteration of the arrangement. The heat generated by a polonium preparation mas found to decrease with time at a rate nearly the same as its known rate of change and was equal to n quantity of radium producing the same ionisation as the polonium. F. S. The Heat Liberated During the Absorption of Electrons by Different Metals. OWEN W.RICHARDSON and H. L. COOKE (Phil. Mag. 191 1 [vi] 21 404-410).-The conclusion before arrived at for platinum that when slow moving electrons are received by the metal part of the heat developed was independent of the kinetic energy of the electrons has been confirmed by experiments with gold nickel copper. silver palladium aluminium phcsphor- bronze and iron. This heat which is considered to be the thermal equivalent of the difference of potential energy of the electrons inside and outside the metal corresponds with from 4.5 to 7.5 volts. Four of the mean values found agree with a mean value 7.11 volts and the other five with a mean value 5.35 the value being influenced by the nature and state of the therrnionic emitter rather than by the nature of the receiving metal.The gas pressure exerts no influence provided it is low. The thermionic emission from an osmium filament becomes unstable at a certain temperature. Two ranges of stability in which the normal laws are followed exist the one a t low and the other at high temperature. F. S. Phenomena which Accompany the Transport of the Active Deposit. 33 M. WELLISCH (Ber. Deut. physikal. Ges. 1911 23 159-171).-An attempt is made to explain the results of different observers who have investigated the behaviour of the particles of the active deposits of radium and thorium in an electrical field and in different gaseous media. It is assumed that atomic residues are uncharged except when associated with a gaseous ion. During the period of this association the atomic residues will move under the influence of an electric field and the fact that the active depositGENERAL AND PHYSJCAL CHEMISTRY.ii. 359 collects almost entirely on the cathode indicates that t h e atomic residues have a very great affinity for a positive charge. In its motion through the electric field a particular ion will be successively associated with different atomic residues but under given conditions its nssociatim period will be represented by a definite fraction of i t s total period OF existence. This theory accords with the fact t h a t the variation of the quantity of the active deposit which collects on the cathode with the strength of the electric field is very closely similar t o the variation of the current with the field strength. An explanation of the observations of Rutherford and others relative t o the dependence of the quantity of the active deposit collected a t the cathode on the pressure of the surrounding gasaous medium is also afforded in terms of the author's theory.H. M. D. Separation of Ionium and Actinium from Certain Residues and on the Production of Helium by Ioniuni. BERTRAM R. BOLTWOOD (Proc. ZZoy. Soc.. 1911 A 85 77-51 ; Le Radium 1911,8 104-106).-A description is given of the technical treatment of certain " actinium residues " derived from the radiferous residues of Jonchimsthal pitchblende. The soliition in hydrochloric acid after treatment with hydrogen sulphide WAS precipitated with ammonia. The hydroxides obtained were dissolved and precipitated with oxalic acid in neutral solution.The precipitate after ignition and solution in hydrochloric acid was precipitated with hydrogen peroxide. The product weighed 160 grams the initial weight of material being 21.2 kilos. It contained 20% of the total initial activity and consisted of rare earths and calcium. The thorium contained i n it separated by the iisual processes weighed as oxide 1.5 grams. It contained the ionium and had a n activity 3000 times t h a t of uranium oxide From a measurement of the iiumber of a-particles emitted per second the amount of ionium was deduced t o be t h a t i n equilibrium with 5.3 mg. of radium. Very little actinium was separated with the hydrogen peroxide precipitate. Some was found i n the mot,her liquor from t h e first ammonia precipitation.The ammonium salts were separated by crystallisation and boiling with hydrochloric and nitric acids. From the resulting solution ammonia precipitated about 10 grams of material containing an amount of actinium estimated to be in equilibrium with 30 rug. of radium. I t s activity increased rapidly for four months when i t was 20,000 times t h a t of uranium oxide and actinium emanation was freely generated. The thorium oxide preparation containing ionium sealed u p for 125 days i n a Jena glass tube generated 0.031 cu. mm. of helium. The theoretical amount calculated from the rate of emission of a-particles is 0.0595 and the difference may be due t o the retention of the helium by the solid even after ignition in a J e n a glass tube. F. 5. Present-day Problems Concerning Radium.WLADIMIR I. VEnNADsKY (Bull. Acad. Sci. St. Pbtersbourg 19 11 61-72).-1n thisii. 360 ARSTRACTS OF CHEMICAL PAPERS. lecture the author traces the discovery of the radioactive elements and the formulation of the theory of radioactivity and discusses the relation of radiation to the energetic theory of matter. T. H. P. The Radium Content of Some Uranium Earths. WrLHELM MARCKWALD and ALEXANDER S. RUSSELL (Bey. 1911 44 771-755). -The method of estimating the radium was to dissolve the minerals in concentrated sulphuric acid with addition of a crystal of potassium nitrate as oxidising agent if necessary t o liberate the emanation which was measured ; barium sulphate and radium sulphate being easily soluble in sulphuric acid the emanation is completely expelled.The ratio of radium to uranium taken for Joachimsthal pitchblende as 100 was 98.1 for thorianite (Java) and 101.5 for African pitchblende the difference being within the experimental error. For autunites (Autun France and Guarda Portugal) the ratio varied from 20.7 to €8.0. I n lieu of the view advanced by Soddy that these minerals are of very recent formation an alternative explanation is favoured. The mineral being of loose formation as compared with the dense oxides of uranium the helium may escape and the lead and radium may be removed by the action of percolating water. Ionium was separated from the minerals by addition of cerium and precipitation with hydro- fluoric acid and estimated by means of its a-radiation. For pitch- blendes the ratio between ionium and radium was constant but for autunites it was less and varied from 76 to 93% of the former ratio.This is in favour of the percolation hypothesis as if the minerals were of recent formation they should be nearly free from ionium. For two specimens of carnotite the ionium ratio was 92 and 72% of that in pitchblende. For rutherfordin (U03,C0,) the alteration product of African pitchblende the radium ratio was 85% of the equilibrium ratio for the surface layers the full amount being present in the interior of the crystal. F. S. The Radioactivity of the Thermal Waters of the Yellowstone National Park. RICHARD B. MOORE and HERMAN SCHLUNDT (7th Intern. Congr. AppE. Chern. 1909 Sect. X. 189-190).-The activity of the thermal waters of Yellowstone Park is of the same order as that of European springs and shows considerable variations. The radio- activity is almost entirely due to dissolved gases.Most of the waters examined contain only radium emanation but sixteen out of eighty-two sources yield also thorium emanation. The deposits of travertine at Mammoth Hot Springs contain about 8 x 10-12 gram of radium per gram or two and a-half times that of the rock from which they are derived and five times that of the general igneous rock of the Park. Less uranium is contained in these deposits than the radium content requires. C. H. D. The Radioactivity "of the Spring Sediments of Teplitz- Schonauer. JOHANN ST~RBA (Jnhrb. Radioaktiv. Elektronik. 19 11 8 23-34).-The sediments of the various thermal springs of Teplitz- Schcinauer and the sediments from the drinking-water reservoirs are all radioactive in the inverse proportion t o the activity of the watersGENERAL AND PHYSICAL CHEMISTRY.ii. 361 themselves. From the nature of the emanation the activity is due to radium in some cases thorium or radiothorium in others and in some cases to a mixture of both. A chemical examination revealed the presence of the same elements but uranium could not be detected. F. S. Conduction of Electricity in Saturated Alkali M e t a l Vapour. CHRISTIAN FUCHTBAUER (Physikal. Zeitach. 191 1 12 225-228. Compare Abstr. 1909 ii 537).-By means of an improved form of apparatus the author has investigated the electric con- ductivity of saturated czsium vapour a t temperatures between 155' and 205' in presence of helium.This gas was introduced with the object of increasing the resistance friction of the ions. For the above v;iriations of temperature the condcctivity iricreases about fifteen times. For small potential differences the current which passes through the vapour is approximately that required by Ohm's law but for greater potentials the current increases much more rapidly than the applied voltage. The conduction exhibits a pronounced uni- polarity which is reversed when t he applied potentia1 difference exceeds a certain value. I n explanation of the observations i t is supposed that the ions are produced in the neighbourhood of the electrodes. Whether in addition the mass of the vapour is ionised to a small extent has not yet been determined. H. M.D. Electrical and Mechanical Properties of Alloys of the Noble Metals. 11. WLLHELM GEIBEL (Xeitsch. anorg. Chem. 19 11 70 240-254. Cornpare this vol. ii lo).-The alloys of palladium and silver behave as a continuous series of solid solutions with a minimum conductivity and therruo-electric power and a maximum tensile strength at 40 atomic % of silver. The temperature-coeflicient of the conductivity of this alloy is exceedingly low. Alloys of platinum with palladium behave similarly but the thermo-electric power is throughout positive against palladium and with the exception of those containing more than 90 atomic % Pd also against platinum. The alloys of platinum and iridium have only been investigated up to 35 atomic % Ir alloys richer in iridium being too brittle to be drawn into wire. The form of the curves obtained indicates that the alloys consist of solid solutions.The thermo-electric power which is positive against platinum reaches a constant maximum value a t 20 atomic % Ir. Annealing these alloys increases the strength of the alloys richer in iridium a temperature of 750" giving the maximum elfect whilst at higher temperatures the strength diminishes. The ductility is increased by annealing. Alloys of platinum and gold can only be satisfactorily drawn into wire when the platinum does not exceed 20%. Solid solutions are present. The thermo-electric power is negative towards platinum and becomes greater on repeated heating a constant value not beiog attained even after heating for two hours a t 900°. Platinum-silver alloys can only be drawn into wire when the proportion of platinum is low.The strength increases with theii. 362 ABSTRACTS OF CHEMICAL PAPERS. temperature of annealing up to 400° and then rapidly falls. The thermo-electric power varies with repeated heating but the differences are smaller than in platinum-gold alloys. C. H. D. Conductivity and Dissociation of Sodium Hyposulphite and Hyposulphurous Acid in Comparison with Analogous Sulphur-Oxygen Compounds. Dissociation of Ternary Electro- lytes. KARL JBLLINEK (Zeituch. phqsikccl. C'hem. 19 11,76 257-354). -The electrical conductivity of aqueous soi utions of sodium hypo- sulphite Na2S204 was measured a t Oo lS0 and 2 5 O and the results compared with those for other oxygen-sulphur salts. All these salts dissociate in stages.A full accour)t of the present knowledge of the dissociation of ternary electrolytes is given and on this basis the degree of dissociation of the sodium salts of the acids in question in the two stages is calculated. The mobility of the SiO," ion is 63 at 25'. ' The conductivity curve of the very unstable hyposulphuroua acid was obtained by adding to a solution of sodium hyposulphite an equivalent of hydrochloric acid and subtracting from the observed conductivity that due to the sodium chloride. The constant kl for first stage of the dissociatiou is at least '0.45 at 2 5 O (the same as t h a t for sulphuric acid) ; k the constant for the second stage of the disso- ciation is 0.0035 a t the same temperature. These results are compared with those for the other sulphur oxyacids and in this connexion some fresh measurements and calculations have been made.The value of k for sulphurous acid is about 0.017 and k is 0.000005. The value of k for thiosulphuric acid is 0.0104. The mobility of the HSO,' ion is 58 at 2 5 O as determined from conductivity measurements with solutions of sodium hydrogen sulphite. G. S. Dissociation of Electrolytes in Non-aqueous Solvents as Determined by the Conductivity and Boiling-point Methods. HENRY R. KREIDER and HARRY C. JONES (Amer. Chem. J. 1911 45 282-324).-A brief review is given of the investigations of Jones and his co-workers on conductivity and viscosity in mixed solvents (Abstr. 1903 ii 55 634; 1905 ii 8 73; 1906 ii 66 737 827; 1907 ii 438; 1908 ii 259 260; 1909 ii 539 717 957).The conductivity a t 0" and 25" of potassium iodide ammonium bromide potassium thiocjanate lithium nitrate sodium iodide copper chloride calcium nitrate and cobalt chloride has been determined in 'methyl and ethyl alcohols at very high dilutions and also in mixtures of these alcohols with water. I n many cases the values of pa were found which generally occurred a t concentrations between Y= 3200 and Y=51,200. A constant ratio was found between the values of pK for lithium nitrate sodium iodide and ammonium bromide in methyl and ethyl alcohols and the corresponding value for cobalt chloride was calculated. The results show that there is one constant for binary electrolytes and another for ternary electrolytes and that there is probably a definite relation between these two constants.Minima were found in most of the curves for mixed solvents. The dissociatiou values obtained by the conductivity method areGEKERAL AND PHYSICAL CHEMISTRY. ii. 363 higher than those obtained by the b.-p. method in both methyl and ethyl alcohols. This may be due to polymerisation of the non- dissociated molecules in the solvent. The results obtained by the b.-p. method would thus be too low since this method takea both the molecules and ions into account whilst the conductivity method deals with the ions only. The Photo-electric Effects of Colloidal Alkali Metals. ROBERT POIIL and P. PRINGSHEIM (Ber. Deut. physikal. Ges. 191 1 13 219-223. Compare Elster and Geitel Abstr. 1910 ii 379 1031).- The relatively high photo-electric sensitiveness of the alkali metals in the colloidal condition is probably not due entirely to increased absorption of light but is influenced by the relationship between the penetrating power of the electrons which are set free and the form of the boundary surface of the metal.If the diameter of a colloidal metal particle is less than the range of the electrons the whole of these will escape from the surface. I n the case of larger particles a certain proportion of the electrons will however be unable to reach the exterior. Observations of the photo-electric effect on potassium and sodium in the ordinary and colloidal conditions have been made which show that the colloidal metals are relatively much more photosensitive for long- waved rays. The photo-electric currents obtained for the exciting rays X=254 and 546 gave a mean ratio of 27 and 1.9 for ordinary and colloidal potassium respectively and a mean ratio of 173 and 18.5 for ordinary and colloidal sodium.The Law of Babo and the Electron Theory of Metallic Mixed Crystals AUGUST L. BERNOULLI (Ber. Deut. physikal. Ges. 1911 13 213-218).-1t is shown that Schenck’s formula (compare Abstr. 1910 ii 1030) for the thermo-electric difference of potential between a metal and a solid solution containing a second metal can be obtained quite readily by application of the equation connecting the relative lowering of the vapour pressure with the molar ratio of solute and solvent if i t is assumed that the same relationship holds between the pressure of the electrons in the pure metal and its solid solutions.H. M. D. Measurements of the [Electric] Charge on Fog Particles. KARL PRZIBRAM (Physikal. Zeitsch. 191 1 12 260-261)-The relatively large number of fog particles which according to previous measurements (ibid. 62) appear to carry electric charges which differ ,from unity or from multiples of the unit charge has been found to be largely due to the form of the apparatus used in the investigation. With an improved form of condensor new determinations have been made of the charges carried by particles of phosphorus and sulphur. The calculated mean charges corrected by Cunningham’s method are respectively 6.25 and 6-23 x 10-10. Rapid Measurement of the Concentration of the Hydrogen Ions in Liquids. WILHELM E. RINGER (Chem. IYeekbZad 1911 8 293-295.Compare Hasselbalch this vol. ii 182).-By experiplental E. G. H. M. 1). H. M. D.ii. 364 ABSTRACTS OF CHEMICAL PAPERS. determination of the concentration of the hydrogen ions in a slightly acid solution of sodium chloride phosphoric acid and sodium hydroxide the author finds that Hasselbalch’s rapid method yields satisfactory results. A. J. W. Employment of an Electrode of the Third Type to Measure the Potential of the Thallium Ion. JAMES F. SPENCER (Zeitsch. physikal Chem. 1911 76 360-366).-Luther (compare Abstr. 1899 ii 5 ) has described so-called electrodes of the third type by means of which the concentration of ions of metals which decompose water can be measured. The author has made use of such an electrode to measure the concentration of thallium ions. I n this case it consists of mercury in contact with a solution of a thallium salt saturated with mercurous and thallium iodides.It is shown that the equation applic- able to all electrodes of the third kind is of the form BT nP E = BP - - log& + i) where E is the observed E.M.P. E.P. the hypothetical potential for N/I-thallium ion c . the ion concentration of the solution t o be measured i the concentration of the commoii ion formed by the depolariser and the other symbols have the usual significance. Measurements were made with solutions of thallium nitrate carbonate chloride and sulphate. As a mean of the four series which are in good agreement the valuesec = + 0.5355 or eh = + 0.2585are obtained for the hypothetical N/1-thallium ion solution.The Potential of the Chlorine Electrode. GILBERT N. LEWIS and FBANK F. RUPERT (J. Amer. Chem. Xoc. 191 1 33 299-307)- Measurements have been made of the potential of the chlorine electrode at pressures ranging from 0.2 to 0.003 atmosphere air being used as the inert diluting gas. A t these low pressures the complications which result from hydrolysis of chlorine in the aqueous solution are eliminated. By arranging the chlorine electrode in series with a calomel electrode in which the potassium chloride solution was replaced by a solution of hydrochloric acid errors resulting from changes in the potential difference at the liquid surfaceswere eliminated and it was found that accurately reproducible values could be obtained. The separate values of the potential for chlorine a t atmospheric pressure calculated from the observations at the different partial pressures agree very well with one another the average deviation from the mean being less than 0.0002 volt.The E.M.F. for chlorine a t atmospheric pressure in contact with a solution containing chlorine$ ions in normal concentration when placed in series with the normal calomel electrode is - 1.0795 volts which differs appreciably from the values given by previous observers. 11. PRANZ HALLA (Zeitsch. Elektrochem. 1911 17 179-182. Compare Abstr. 1908 ii 755).-The E.M.F.’s of the galvanic elements Ag 1 AgBr or AgI (saturated solution) PbBr or PbI (saturated solution) I Pb are measured at different temperatures. Four elements of each kind were examined; the agreement between them was G .S. H. M. D. Thermodynamic Calculation of Electromotive Forces.GENERAL AND PHYSICAL CHEMISTRY. ii. 365 exceedingly close in the case of the bromides but with the iodides differences of 7 or 8 millivolts were observed and the results are regarded as uncertain. The bromide element gave 0.3708 volt at Oo 0 3611 volt at 12O 0.3566 volt at 19O 0.3521 volt at 27" 0.3410 volt at 45" 0.3362 volt a t 53" 0.3320 volt a t 5 9 O and 0,3237 volt at 7 1 O . The heat of the reaction calculated from the individual measurements lies between 12,519 and 12,583 cals. whilst Thomsen found 12,275 cals. The iodide element was measured at seven temperatures; its R.M.F. decreases from 0.2338 volt at - 71" to 0.1965 volt a t + 62". The calculation by Nernst's theorem cannot be carried out until the specific heats of the salts have been determined at different temperatures.T. E. The Influence of Electrolytes on the Maximum Voltage of Electrolytic Valve Action. G~~NTHER SCHULZE (Ann. Physik 191 1 [iv] 34 657-710. Compare Abstr. 1909 ii 371).-Measurements of the potential of electrolytic valve action show that with a constant current the potential line curves exhibit pronounced breaks. The first break in the curve corresponds with the commencement of spark discharge and from this point onwards the potential rises less rapidly than during the preceding interval The second break corresponds with a new type of spark discharge and when this sets in the potential attains a maximum value. The influence of a large number of different electrolytes on the valve potential has been investigated in the case of tantalum.From these experiments it is found that the maximum voltage is dependent on the concentration of the free anions Complex anions containing a metal atom exhibit a characteristic maximum potential which is determined by the nature of the metallic constituent. I n general the maximum potential for such anions is much smaller than for the non- metallic anions. When the maximum valve potentials for such metallic anions are compared the metals can be arranged in a series the first member being palladium with a very small (20 volts) and the last member aluminium with a very large valve potential (660 volts). For non- metallic anions the maximum valve potentials vary from 440 to 500 volt s.The valve action is independent of the cations in the solutions but the metals which lower the valve potential as components of anions are also effective when present as components of undissociated molecules. Experiments were also made with anodes of aluminium antimony and bismuth. These show a true valve effect when they are not dis- solved by the electrolytic solution and the maximum potentials are very nearly the same as in the case of tantalum. I n dilute sulphuric acid aluminium exhibits an apparent valve potential of 20 volts but in fuming sulphuric acid the real valve effect is observed and the maximum potential amounts to 425 volts. H. M. D. Electrolytic Potential of Hyposulphi te Reactions. KARL JELLINEK (Xeitsclt. Elektrochem. 19 1 1 17 157-176).-'1'he E'.M.E'.'s VOL.C. ii. 25ii. 366 ABSTRACTS OF CHEMICAL PAPERS. of combinations of a hycliBogeti electrode and a platinised platinum electrode immersed in well s tirred solutions containing sodium hyposulphite sulphite and hydrogen sulphite are first measured. The B.M.Ii.’s are hardly affected by polarisation and are quite reproducible. The concentrations of the ions in the solutions are calculated by means of the author’s measurements of the con- ductivity (this vol. ii 362) and it is shown that the E.M.B’.’s measured (after correction for the small potential differences between the solutions in the cell) are well represented by the equa- tion r = - 0.245 + 0*02910g[S20,”][S0,“J2/[HSO~]~ a t 20° for the 0.1 N-hydrogen electrode. This indicates that the electromotive reaction is S204” + 2S0,” + 2H20 + 3 .F‘z 4HS0,’. I n order to calculate the potential of the reaction Q2()4/’ + 2H20 + 2P= 2H’ + 21’1SO,’ the dissociation constant of the reaction HSO,’ Z H’ + SO,” is reqaired. The author’s determinations (Zoc.cit.) gave approximately introducing this into the above equation after recalculating i t for the N-hydrogen electrode gives T = - 0.009 - O~02910g[S20,”]/[H’]‘[ HSO,’]’ at 20”. From t’his i t is calculated that a solution containing hyposulphite and hydrogen sulphite ions in normal concentration should be in equilibrium with gaseous hydrogen at two atmospheres pressure and therefore that the reducing power of such a solution is very nearly the same as that of gaseous hydrogen. The E.M.P. of the combination measured above increases by 2.27 millivolts per degree rise of temperature. From these data the heat of the reaction is readily calculated ; i t is S,O,” + 2540,’’ + 2H20 + 2H’ = H + 4HS0,’ - 13920 cals.Subtracting the known value HdO,’= H* + SO,” - 700 cals. gives S20L’ + 2H20 = H + 2HS0,’ - 15,300 citls. The heat of formation of hyposulphurous acid is also calculated with the help of Thornsen’s data 2s + 3 0 + H,O = €I,S,04 + 105,000 cals. Consideration of the free ener,py of the reaction between hyposulphites and water leads to the conclusion that they become much less stable as the temperature rises a rise of 10’ increasing the equilibrium pressure of hydrogen two and a-half times. I n alkaline solutions of hyposulphite and sulphite a fairly definite potential is established at a platinum electrode but the author could not discover the nature of the remtion on which it depends.I n solutioris of hyposulphite and thiosulphate or of thiosulphate and sulphite no definite potential could be observed. The potentials measured were unaffected by the concentration of the thiosulphate. Ii= [H*][SO~’J/[HSO~] = 5 x 10-6 ; T. E. Transference E x p e r i m e n t s with Mixtures of Potassium Chloride and Sulphate in Aqueous Solution. GEORGE M. J. MACKAY (J. Amer. Chem. Xoc. 1911 33 30S-319).-1t has been shown by different observers that in a solution containing two salts with a common ion each salt has a degree of ionisation equal t o that which it has when present alone in a solution in which its ions have a concentration equivalent t o that of the common ion in the mixed solution.To test this empirical principle the author has madeGENERAL AND PHYSICAL CHEMISTRY. ii. 367 transference measurements with solutions containing potassium chloride and sulphate using the apparatus described by Washburn (Abstr. 1908 ii 805). From these measurements the conductances of the ions in the mixture can be separately determined. I n a solution containing chloride and sulphate in O.2009N-concen- tration the quantity of chlorine transferred per farad was found to be 0*289+_0*001. On the assumption that the transference number of the chlorine in the potassium chloride in this mixture is the same as in dilute potassium chloride solutions t h e proportion of the current carried by its ions is found to be 0.573 and that carried by the ions of potassium sulphste 0.427.When these values are multiplied by the conductivity of the mixture the partial conductivities of the component electrolytes are obtained. The partial conductivity of the potassium chloride obtained in this way is 2.0% larger and that of the potassium sulphate 5.2% smaller than the corresponding values which are calculated on the basis of the above empirical rule. H. 35. D. Magneton in Solid Paramagnetic Substances. PIERRE WEISS (Compt. rend. 1911 152 688-691. Compare thievol. ii 91 183).- 'l'he value 1122.7 has been Calculated for the aliquot part (gram- magneton) common to the absolute molecubr saturations of four rare earths employing Urbain's determinations of their coefficients of magnetisation.Results differing very slightly from these mere also obtained from the results of Xlle. Feytis for salts of iron manganese and chromium (following abstract). Curie's results for metallic iron are explained by supposing that the molecule of p-iron contains three atoms rigidly united whilst y-iron has two and %iron is monatomic. This being the case y-iron contains 19.95 magnetons PI- and &-iron 12-08 and 10.04 Inaguetons per atom respectively ; allowing for experimental errors these may be taken as whole numbers. Europium gave abnorrnal results the atom appearing to contain 18.398 magne- tons ; this becomes 13.02 however if i t is assumed that two atoms are rigidly united. w. 0. w. Magnetism of Some Complex Salts. Mlle. E. FEYTIS (Compt. rend. 191 1 152 705-71 l).-The magnetic susceptibilities of thirty metallic salts mostly complex cobaltammines have been determined by means of the Curie balance.The solid substances were employed to avoid the uncertain influence of solvents. No sharp distinction was found to exist between the coefficients for simple and complex salts. Pascal (Abstr. 1'308 ii 756 ; 1.909 ii 487) has shown that in solutions a parallelism exists betweon the variations of the coe6cient of magnetisation with constitution and the variations in chemical properties. The same holds good i n the case of the solid substances. W. 0. W. The experimental results are shown in tabular form. Magne to-chemical Researches on the Atomic Structure of the Halogens. PAUL PASCAL (Compt. rend. 1911 152 862-865. Compare Abstr.1909 ii 487 788 859; 1910 ii 100 179).- Measurements have been made of the magnetic susceptibilities of thirty compounds containing more than one halogen atom united to 25-2ii. 368 ABSTRACTS OF CHEMICAL PAPERS. the same atom OF carbon or of boron silicon phosphorus antimony or tin. The diamagnetic deticits for the whole molecule vary from 29 x for tetrachloroethylene t o 615.5 x 10-7 in the case of anti- mony pentachloride. The specific susceptibilities contain an aliquot part equal to 0.2468 x 10-7 and this is common to the three halogens; it is explained on the assumption that the halogen atom contains smaller elements having a definite relationship to the subsidiary valencies ; mutual saturation of these between neighbouring atoms in the same molecule leads t o a fall in diamagnetism by a constant fraction.w. 0. w. Calculation of Temperatures Especially Below the Boiling Point of the Helium. R. KAMERLINGH ONNES (Geclenkboek accnge- boden aan J. iM. vcm Bemmelen 1910 441-446).-The author has evaporated helium at ft pressure of 0.15-0.25 mm. as compared with 3.2 mm. in 1909 and has calculated by the aid of the vapour-tension formula of van der Waals that the temperature attained is below 1*S0 and is probably 1.S0 absolute Relations between Critical Temperat ure Boiling Point and Expansion Coefficient of Phosphorus Pentachloride. EDMUNU B. R. PRIDEAUX (Trans. Paraday Soc. 1911 6 155-159).-The thermal expansion of phosphorus pentachloride in sealed glass tubes (Trans. 1907 91 1715) is expressed by the formula Vt= V&[l + 0*00107(t - 160)j.The critical temperature found both with rising and with falling temperature is 373'. The ratio of the boiling point to the critical temperature is 0.67 showing that the dissociation does not cause any abnormality in this respect. The product of the co- eficient of expansion and the critical temperature of phosphorus pentachloride is 0.46 that of nitrogen peroxide being 0.458 and the mean value for undissociated substances being 0.494 (Walden Abstr. 1909 ii. 122). The product is also calculated for a number of A. J. W. associated liquids and*is found to be high in many cases. C. H. D. The Molecular Heat Conduction of Gases and the Accommodation Coefficient. MARTIN KNUDSEN (Ann. Physik 1911 [iv] 34 593-656).-The fact that the thermal conductivity of gases at low pressures is appreciably smaller than that which is antici- pated by the kinetic theory has led the author to enquire into the cause of the discrepancy.The experiments made with this object show that the thermal conductivity of a gas is largely dependent on the degree of roughness of the surfaces of the hot and cold plates kletween which the gas is confined. This is supposed to be a conse- quence of the mode of partition of energy between the gas molecules and the surfaces on which they impinge and in taking account of this effect the author introduces the conception of 'I accommodation co- efficient." It is shown that the observations can be satisfactorily explained in terms of this modified kinetic theory. H. M. D. Specific Heat at Low Temperatures.111. WALTREK NERNST (Sitazcngsber. K. Akud. Wiss. Berlin 191 1 306-315).-Using theGENERAL AND PHYSICAL CHEMISTRY. ii. 369 method previously described (Abstr. 1910 ii 263) the author has determined the specific heats of lead silver zinc copper aluminium iodine potassium chloride and mercurous chloride between the absolute temperatmes 23’ and 100”. The curves showing the relation between atomic heat and tem- perature are all similar in character and between the atomic heats 2 and 5.6 their course is in agreement with Einstein’s formula for the atomic heat (Ann. Physik 1907 [iv] 22 184). A t very low tempera- tures the curves fall more slowly than according to Einstein’s formula tending to become tangential to the temperature axis ; this supports the author’s heat-theorem whereby at T= 0 Eirn.dU/dl’= 0. The curve for potassium chloride is similar t o those of the elements whereas that of mercurous chloride is dissimilar.This agrees with the fact t h a t the characteristic frequencies of potassium and chlorine according to Lindemann’s formula (Physikal. Zeitsch. 1910 11 609) arc approximately the same whereas those of mercury and chlorine are quite different. Since potassium chloride and also the diamond behave similarly to the metals doubt is thrown on the electronic theory of electrical resistance. It is found empirically that there is a parallelism between tho temperature-coefficient of the electrical resistance of a metal and the atomic heat and theoretical considerations show that Plnnck’s radia- tion formula may be adapted for calculation of the variation of the electrical resistance with temperature.For example the electrical resistance of lead between the temperatures 1 4 ~ 3 9 ~ and 273*0g3 abs. is given by the expression (0*1626/e38/T - 1) + 0.0007. In this formula the value of the constant in the exponential term is independent of the purity of the metal when only traces of impurity are present whilst the value of the additive constant increases with the amount of impurity. From further considerations i t is shown how the electrical resist- ance of any one sample of metal at different temperatures may be calculated from the results obtained for another sample of the metal a result which is very important in the measurement of low temperatures.T. S. P. Specific Heats at Low Temperatures. IV. F. A. LINDEMANN (Sitxungsber. K. Akad. Wiss. Berlin 1 9 1 1 3 16-32 l).-Assuming that relatively few free electrons exist in a metal and further that the sphere of action of the atomic nuclei with which the free electrons collide increases with the amplitude of the heat vibrations a formula is deduced for the relation between the electrical resistance of a metal and the temperature. where R is the resistance p a universal constant = 4.86 x characteristic frequency of the atoms and A and B are constants. This formula has the form €2 = A2/(&*- 1) + 2AB/ J J ~ ~ v ’ T - 1 + B2 Y the It Heats of Fusion of Substances Melting Near the Atmospheric Temperature WLADIMIR F. LUGININ and GEORGES DUPONT (BUZZ. $oc. chirn 1911 [iv] 9 219-224).-The heats of gives good results for silver and lead.T. s. P.ii. 370 ABSTRACTS OF CHEMICAL PAPERS. fusion of a number of substances have been determined with a view tlo (a) verifying van’t Hoff’s law as expressed in the form P=O 021‘2/k where F is the heat of fusion and k the cryoscopic constant and ( b ) determine or verify the values of k for these substances. The experimental conditions for the determination of P and the errors incidental to these are discussed and the apparatus and method wed are described in detail. The substances used were acetic acid (F= 43.102 calc. 43*1) acetophenone (P= 33.12 calc. 30*3) p-bromo- toluene ( F - 21.33 calc. 21.9) anethole (F= 25.S0 calc. 27*3) veratrole (P= 27.75 calc. 27.3) phenylhydrazine ( F = 36.31 \ paracetaldehyde (E= 25-02) sulphuric acid monohydrate (3” 38.97 calc.33). These results indicate that the law can be verified for relatively mobile liquids but for viscous liquids the agreement between ‘‘ found ” and calculated ” values of P is less satisfactory due to the fact that the experimental value of k for such substances is generally too high. Paracetaldehyde appears to be a promising solvent for cryoscopic determinations. T. A. H. Cryoscopic Anomalies of Elements of the Fourth Periodic Group. PIETRO FALCIOLA (7th Intern. Congr. Appl. Chern. 1909 Sect. X. 159-1 61).-Cryoscopic measurements with titanium tetrabromide dissolved in stannic bromide in a Beckmann apparatus for excluding the entrance of moisture shorn that the freezing point of the solvent is raised.Zirconium tetrabromide is very sparingly soluble in stannic bromide but a slight elevation of freezing point is observed. C. H. D. Monovariant Systems Admitting of a GaseouR Phase. GEORGES URBAIN and C. SCAL (Compt. rend. 1911 152 769-772).- A mathematical demonstration of the fact t h a t in such systems three determinations are sufficient to enable the vapour pressure to be calculated for any temperature whatever. w. 0. w. Vapour Pressures in Binary Systems with Partial Mis- cibility of the Liquids. PHILIYP KOIINSTAMM and J. TIMMERMANS (Proc. R. Akad. Wetensch. Amsterdam 1911 13 865-880 957).- Certain deductions from van der Waals’ theory in reference to the form of the pressure temperature and pressure concentration curves for binary systems containing two liquid phases have been investigated in the case of the following pairs of substances phenol and water cyclohexane and aniline hexane and nitrobenzene hexane and aniline isopentane and nitrobenzene.Contrary to van der Waals’ supposition it is found that the vapour pressure curve for the co-existing liquid phases does not touch the plait-point line in the critical end-point and this result is shown to be theoretically justified. I n opposition to the view that the partial pressures of the components are proportional to the liquid concentra- tions it is found that mixtures of normal substances sometimes give rise to pressure concentration curves with points of inflexion as required by van der Waal’s theory. H.M. D.GEXEKAL AND PHYSlCdL CHEMISTRY.ii. 371 Causes Producing at Constant Temperature Variation in FELIX XICHAUD (Contpt. Tend. the Vapour Pressure of a Liquid. 191 1 152 549-85 1).-A theoretical discussion of the subject. w. 0. w. Heat Content of the Various Forms of Sulphur. GILBERT p\T. LEWIS and MERLE RANDALL (J. Amer. Che?n. sbc. 1911 33 476-488).-This investigation was undertaken in order to obtain the data required for cxlculating the free energy of sulphur. Wigand (Abstr. 1908 ii 677) has calculated the heat associated with the change from SX to Sp but it is shown that this calculation must be erroneous. The total heat change has been determined between rhombic sulphur a t 23' and liquid sulphur (in a state of equilibrium) a t loo' 140" 184O and 390° and the results have enabled the following data to be calculated which are expressed in small calories per gram of sulphur.The heat of fusion at 100" to form liquid sulphur in a state of equilibrium is 14.9 from the rhombic and 11.5 from the monoclinic form. The heat of fusion to form pure liquid SX is 14.5 from rhombic sulphur and 11.1 from the monoclinic form The heat of transformation in the liquid state from SX to Sp is about 13. The specific heat of pure liquid SX is about 0.21 + 0.00016t. A diagram is given showing the approximate values of the specific heat of liquid sulphur in a state of equilibrium from 100' to 450'. E. G . The Heat of Mixture of Substances and the Relative Distribution of the Molecules in the Mixture. RICHARD D. KLEEMAN (Phil. Mag. 1911 [vi] 21 535-553).-From the law of attraction between molecules which has been obtained in a previous paper (Abstr.1910 ii 493) the author deduces formuls for the heat changes which occur on admixture of two or more substances. The formule for special cases such as the formation of a saturated solution of a salt in a liquid and of one liquid in another are discussed. The calculated heats of solution of ammonia hydrogen fluoride bromide and iodide in water are in rough agreement with the experi- mental values but there is a much greater divergence in the case of chlorine hydrogen chloride and carbon dioxide. It is supposed that this is due to the formation of hydrates or dissimilarity in the positions occupied by solute and solvent molecules. Influence of Catalysts in Determinations of Vapour Deniity.ANDM~ KLTNG (Compt. rend. 191 1 152 702-704 ; Bull. SOC. chim. 1911 [iv] 9 276-281. Compare Abstr. 1904 i 545).-The method previously described for differentiating Ijetween primary secondary and tertiary alcohols by determining their vapour densities is only trustworthy when the V. Meyer tube contains 0.4-0.5 gram of washed and calcined sand. The asbestos pad usually placed at the bottom of such tubes is less satisfactory. The method depends for its success on the decomposition of a secondary or tertiary alcohol giving a low result for the vapour density and i t has been found that such H. M. D.ii. 372 ABSTRACTS OF CHEMICAL PAPERS. decomposition does not occur as a rule unless a catalyst such as sand is present. Determinations of the vapour density of a substance such as iso- propyl alcohol at the temperature of boiling naphthalene furnish a method for comparing quantitatively the catalytic activity of metallic oxides since they measure the extent to which decomposition has been effected.The following coefficients obtained in this way represent the ratio of the theoretical density to the actual value Tho 2.3 ZnO 2.0 Al,O 1.9 Fe,O 1.3 SnO 1.2 TiO 1-03. w. 0. w. The Nature of Adhesiveness. MAURICE HANRIOT (Compt rend. 1911 152 704-706. Compare this vol. ii 118 208 258).-The property of adhesiveness to which attention has been drawn previously in connexion with brown gold is only exhibited when this is brought into contact with the yellow variety at the temperature a t which the former is metastable The contraction that occurs when brown gold is heated may be the result of adhesion between contiguous particles.w. 0. w. The Weight of a Falling Drop and the Laws of Tate. 111. An Apparatus for Rapid and Accurate Determination of the Weight of a Falling Drop of Liquid. J. LIVINGSTON R. MORGAN (J. Amer. Chem. Soc. 1911 33 349-362. Compare Abstr. 1908 ii 356 668).-A detailed description is given of an apparatus for measuring accurately the relative surface tensions of liquids by means of the weights of drops of the various liquids formed a t straight-edged tips under such conditions that the speed of formation of the newly- formed drop is very small. For this purpose the apparatus per- mits of perfect control of the speed at which the drops are formed and any loss of liquid by evaporation from either the hanging drop or from drops which have already fallen is eliminated.The apparatus permits of measurements being made up to within a few degrees of the boiling point of the liquid and it ensures constancy of temperature during the drop formation. The apparatus can be readily cleaned without disturbing the setting. For a description of the mechanical details the original must be consulted. AUGUSTE ROSENSTIEHL (Bull. Xoc. chin&. 1911 [iv] 9 224-231).-The argument begun in the previous paeer (this vol. ii 99) is continued and extended to a number of apparently anomalous cases of the application of dyes to fibres and i t is concluded that cohesion plays the principal part in dyeing. Even when the coloured layer is formed by combination between dye and fibre cohesion ensures the adherence of this coloured layer to the bulk of the fibre.H. M. D. R61e of Affinity in Dyeing. T. A. H. Viecosity and Fluidity of Matter in the Three States of Aggregation and the Molecular Weight of Solids. EUGENE C. BINGHAN (Ame~. Chem. J. 191 1 45 264-281).-8 theoretical paper on the viscosity of gases liquids and solids. It is pointed out that inGENERAL AND PHYSICAL CHEMISTRY. ii. 373 gases the viscosity depends primarily on the momentum of the molecules whereas in liquids it is mainly dependent on the volume of the molecules. With regard to solids the amount of damping of the vibration of a wire is usually regarded as a measure of the viscosity but it is now shown to be rather a measure of the fluidity The author has shown (Abstr.1909 ii 382) that the molecular weights of liquids can be determined by means of their viscosities and it is now considered probable that the molecular weights of solids could also be determined by viscosity measurements. REGINALD 0. HERZOG (Zeitsch. Chem. Ind. Kolloide 1911 8 210-21 l).-In reference to Einstein's deduction that the difference between the viscosity of a colloidal suspension and t h a t of the dispersive medium is determined by the relative volume occupied by the suspended phase the author points out that the frequently observed diminution in the viscosity of a colloidal solution may in some cases bs due to the liberation of the dispersive medium in the ageing of the suspeuded particles. Experiments with an arsenious sulphide sol w e recorded in which the time of flow through a viscometer tube diminished from 43'9" to 41'29" after twenty-five days A t the same time the density fell from 1.0069 to 1.0011.H. M. D. Influence of the Acidity of Aqueous Solutions on the Surface Tension of the System Water and Oil. WILLEM REINDERS (Gedenkboek aangehoden aan J. M. van Bemmelen 1910 333-341. Compare Ringer Abstr. 1909 ii 660 and Meyeringb this vol. ii 78).-An investigation of the surface tension of mixtures of various oils with dilute aqueous solutions of primary secondary and tertiary sodium phosphates. KARL DRUCKER and R. KASSEL (Zeitsch. physikal. Chem. 19 11 '76 367-384).-The variation of viscosity with composition has been measured for the following eleven binary mixtures tetrachlorethane-acetophenone tetrnchlorethane- nitrobenzene bromoform-nitrobenzene i-arnyl alcohol with nitro- benzene formamide diethylaniline and paracetddehyde respectively acetic anhydride with paracetaldehyde and with acetic acid and sulphuric acid with acetic acid and with methyl sulphate a t a relatively low temperature (0-15") and a relatively high temperature (7 6-80°).In most cases the results do not correspond with the mixture rule. The authors agree with Bingham (Abstr. 1909 ii 382) that the results are best represented in terms of fluidity rather than of viscosity and curves are given in which fluidity + is plotted against composition expressed as the fraction by weight a of one of the components in the mixture. It is assumed that miscibility is chemical combination and t h a t linear curves are obtained only when complete reciprocal substitution of complexes or components takes place whilst deviations from a straight line are due to incomplete substitution.On this basis the formula +=+1a++2(1-cb) where and +2 represent the respective fluidities of the pure compounds is derived and is shown to represent the experimental results at least as well as any formula E. G. The Viscosity of Colloidal Solutions. A . J. W. Fluidity of Binary Mixtures.ii. 374 ABSTRACTS OF CHEMICAL PAPERS. so far proposed. The deviations from this formula are ascribed to chemical influences. These considerations cannot be expected to represent entirely satisfactorily the behaviour of a liquid in motion as opposed to a liquid at rest and in this connexion i t is suggested that there must be a relationship between fluidity and compressibility.WOLFGANG OSTWALD (Gedenkboek aangeboden uan-J. 1Tf. van L’emnaelen 1910 267-274).- By addition of a colloid to a solution of an electrolyte the electric conductivity of the solution is diminished if adsorption of the electro- lyte takes place. From Dumanski’s data (Zeitsch. Chem. I n d . Rolloide 1906 1 281) for solutions of ammonium chloride to which a constant quantity of colloidal ferric hydroxide was added the author shows that the dependence of the quantity of adsorbed electrolyte on the concentra- tion of the solution can be expressed satisfactorily by means of an exponential equation. The formula no longer holds good when the concentration of the electrolyte is such as to cause coagulation of the sol. This bebaviour is in agreement with Freundlich’s theory of the coagulating effect of electrolytes ; according l o this the coagula- tion is intimately connected with the adsorption of electrolytes by the colloidal substance.H. 3%. D. The Adsorption of Methylene-blue and Cry stal-ponceau by Carbon in its Dependence on the Temperature. LOUIS PELET- JOLIVET and HANS SIEGRIST (Gedenkboek aangeboden aan J. M . van Bern,naeZe?z 19 10 158 - 16 2).- Measuremen ts of the adsorption of methylene-blue and crystal-ponceau from aqueous solutions by animal charcoal have been made a t temperatures of 15O 50° and 70’. I n both cases the coefficients /? and rn of the exponential formula x/a=p.cTn increase as the temperature rises.The sign of the temperature- coefficient of the adsorption is therefore the same for both the basic and acid colouring matters. HERBERT FREUNDLICH and M. MASIUS (Gedenkboek aangeboden aan J. M. van Bsmmelen 1910 88-101).-The phenomena accompanyiug the simul- taneous adsorption of two substances from aqueoiih solution by animal charcoal have been examined. Solutions of oxalic and succinic acids and of oxalic and benzoic acids were chiefly invest,igated. Both substances are adsorbed from the mixed solutions to a smaller extent than from the corresponding solutions of the single substances. The mutual influence is such that the diminution in the adsorption of a given substance in presence OF a second substance increases with the extent to which the latter is adsorbed.If the adsorption of one of the two substances is not altered to any large extent the adsorption of this takes place in accordance with the exponential formula. For the three acids in pure aqueous solution the constants a and l/n in the formnl:L x/m=acl’n were found t o be respectively oxalic acid u = 5.403 l/n = 0.4501 ; succinic acid a = 4.426 l / n = 0.274 ; benzoic acid a = 12.23 l / n = 0,2848. G. 8. The Adsorption of Electrolytes by Sols. H. M. D. Adsorption in a Solution of Several Substances. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 375 Dissociation of Hydrated Salts. LUIGI KOLLA (Atti R. Accud. Lincei 1911 [v] 20 112-119).-1t is known that below a certain temperature the dissociation pressure of magnesium qulphate heyta- hydrate is less and above this temperature greater than that of ferrous sulphate heptahydrate. The author finds that the equilibrium temperature determined directly by the tensimeter is 44*01" as com- pared with the value 45.70° calculated by a thermodynamical method fully described in the paper.The dissociation tension of the mixed salts DlgS04,sFeSOQ,7( 1 + x)H,O has been measured at the equilibrium temperature for different values of x; the results will be communicated in a later paper. G. S. Relation of Osmotic Preasure to Temperature. 11. The Manometers. HARMON N. MORSE WILLIAM W. HOLLAND and J. L. CARPENTER (Amer. Chem. J. 1911 45 237-263).-1n the previous paper on this subject (this vol. ii 191) the method of manufacturing the osmotic cells was described. A detailed descriptiou is now given of the construction and calibration of the manometer and the method of obtaining and applying the correction for meniscus (compare Morse and Lovelace Abstr.1908 ii 1020). The instrument is not yet entirely satisfactory in certain respects but improvements have been devised and will be carried out in future work. E. G. Rate of Diffusion and Relative Size of Dissolved Moleculee. THE SVEDBERG and ANDREA ANDREEN-SVEDBERG (Zeitsch. physikal. Chem. 191 1 76 145-155).-According to the Sutherland-Einstein formula connecting the rate OF diffusion with the size of the diffusing particles the rate of diffusion is under comparable conditions inversely proportional to the diameter of the molecules. This consequence of the theory has been tested by comparing the relative rates of diffusion of organic substances of similar type in methyl alcohol as solvent the relative sizes of the molecules being deduced approximately on the basis of their structural formulz.In this way benzene naphthalene dipheny 1 and triphenylmethane and also pyridine and quinoline mere compared and the results were in qualitative agreement with the theory. The values found for the diffusion coefficients at 14-15" are as follows benzene 1.85 naphthalene 1-38 diphenyl 1.34 triphenylmethane 0.75 pyridine 1.37 quinoline 1 ~13. G. S. The Dialytic Capacity of t h e Colouring Matters. WILHELM BILTZ and F. PFENNING (Gedenkboek aangeboden uccn J. M. van Bemmelen 1910 108-120).-Dialysis experiments have been made with a largo number of colouring matters in order to ascertain the factors on which the dialytic capacity depends.From the measurements which were made with a collodion membrane the conclusion is drawn that the dialysing power of a colouring matter is dependent on the number of atoms in the molecule. If this is less than forty-five dialysis takes place quickly but the rate diminishes as the number of atoms increases beyond this number. Between fifty-five and seventy the dialytic capacity is very small and substances containing more than seventy atoms in theii. 3'76 ABSTRACTS OF CHEMICAL PAPERS. molecule do not dialyse at all. This relationship is however influenced to some extent by the composition and constitution of the substance. I n particular it is found that the presence of sulphonic groups increases the dialytic capacity to a marked extent.For example the colouring matters of the malachite-green series which contain two or three sulphonic groups dialyse quite readily although the number of atoms in the molecule is greater than seventy. On the other hand it appears that substances having the '' alizarin constitution " dinlyse less readily than would be expected from the number of atoms in the molecule. H. M. D. The Amorphous and Crystalline States. CORNELIO DOELTER (Gedenkboek nangeboden aan J. Af. m n Bemmelen 1910 232-239. Compare Abstr. 1910 ii 696 834).-The author considers that many freshly precipitated substances must be regarded as amorphous although many of these undergo transformation into crystalline forms under suitable conditions.In this connexion the author has examined tho gel forms of silicic acid and sodium chloride precipitated zinc sulphide and silver obtained by vaporisation in an electric arc. After prolonged agitation the zinc sulphide was found to have become distinctly crystalline but no change was evident i n the silicic acid or sodium chloride. These gels and the vaporised silver are therefore considered to be amorphous. E. M..D. Abnormal Dependence of the Velocity of Crystallisation on the Temperature. GUSTAV TAMMANN (Gedenkboek aangeboden aan J. M. wan BernmeEen 1910 29?-302).-1t has been found previously that for substances which crystallise quickly the velocity of crystallisx- tion attains a maximum value at 20-30° below the melting point and then remains constant until the supercooling amounts to about 70".Further experiments have shown that this behaviour is not quite general. I n the case of dinitrophenol acetanilide antipyrine and erythritol the velocity of crystallisation increases with the super- cooling in this region whereas it decreases in the case of m-chloro- nitrobenzene m-bromonitrobenzene benzophenone and sodium thio- sulphate pentahydrnte. This abnormal behaviour is attributed to differences in the molecular complexity of the liquid and solid substances. If the liquid is to some extent associated this association will increase as the temperature is lowered and if the reconversion of the polymerised molecules is comparatively slow the molecular condition of the liquid a t the crystallisation surface will vary with the extent of the super- cooling.According to this observations of the dependence of the velocity of crystallisation on the degree of supercooling may in certain cases be utilised as a means of determining whether the liquid consists of simple or polymerised molecules. If the equilibrium between the two kinds of molecules is established with great rapidity the method cannot afford information relative to the molecuIar condition for the velocity of crystallisation in this case will be independent of the temperature H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 377 The Degree of Dispersity and its Influence on the Chemical Composition and the Firmness of the Combination of Water of Hydration. P. P. YON WEIMARN (G'edenkboek aungeboden uun J. M. vun BemmeZen 19 10.50-54).-The cry stallisation process is analysed and it is shown that the increase in the water content of crystalline hydrates which is observed when the degree of disperaity of the precipi- tated substance increases is consistent with the author's view that these so-called amorphous precipitates are crystalline. On account of the action of special forces at the surface of a crystal the surface layer approximates in a way to the molecular condition which is character- istic of highly compressed liquids. This layer is moreover of different composition from the crystalline nucleus and on this account increased dispersity of the crystals is accompanied by increased hydration. The water contained in gelatinous precipitates which owes its origin to the excessive development of the surface layers is only very loosely com- bined as has been shown by the experiments of van Bemmelen and this observation is consistent with the author's views of the origin of this water of hydration. H.M. D. Certain Arbitrary Distinctions which are made in Theoretical Chemistry. GIOVANHI MALFITANO (Gedenkboek aangeboclen aan J. M . van BeinmeZen 1910 368-37Y).-The author maintains that the grounds on which a distinction is drawn between chemical compounds and solutions are more or less arbitrary. It is also claimed that the grounds for differentiating between adsorption and chemical combina- tion are insufficient. H. M. D. The Electrolytic Dissociation Theory. NIELS BJEHRUM (7th Intern. Congr. AppZ. Chem. 1909 Sect. X. 58-60).-1t is suggested that when the colour of a solution changes with dilution the cause is combination of the ions.The decrease in molecular conductivity with increasing concentration is due to retardation of the movement of the ions. The anomalies of strong electrolytes are attributed to electrolytic friction. C. H. D. Chemistry of Colloids. EDUABD JORUIS (Gedenkboek aangeboden uan J. M. van Benmelen 1910,214-225).-1n support of the author's view that the hydrosol and hydrogel forms of various substances are characterised by the presence of more or less definite quantities of electrolytes experiments are described in which the conditiocs necessary for the production of the hydrosols of ferric and aluminium hydroxides and of silicic acid from the precipitated substances have been determined.H. M. D. Colloids and Permanent Chemical Modifications. PIERRE DUHEM (Gedenkboek aangeboden aan J. M. van Bernrnelen 1910,l-6).- A comparison is made between the changes in the properties of colloidal substances which accompany the absorption or emission of water-vapour and changes which have been found to occur in amorphous carbon when its tendency to undergo oxidation is measured at succesaiveii. 378 ABSTRACTS OF CHEMICAL PAPERS. time intervals between which the carbon is subjected to a slow variation of temperature. In the aiithor’s opinion tho introduction of terms which take account of the action of capillary forces into the thermodynamical equations which express the conditions of equilibrium i n hetero- geneous systems cannot give a satisfactory account of the behavioiir of colloidal substances (solutions).H. M. D. Electrolytic Colloids. WILLIAM B. HARDY (Gedenkboek aangeboden aan J. M. van Bemmelen 1910 180-193).-Colloidal solutions may be considered as special cases of molecular solution in which there is a wide departure from thermodynamic reversibility in consequence of the operation of a large internal frictional coiistraint which owes i t s origin to the limited mobility of one of the constituents. Electro- lytic colloids are those in which the relatively immobile constituent of the colloidal solution is a n ion. Such colloids will exhibit electrolytic phenomena at internal surfaces. These electrolytic phenomena are considered from the point of view of Nernst’s solution tension theory and the cbservations of Burton relative t o the charges of colloidal metals produced by cathodic disintegration.Whereas according to Nernst’s theory these colloidal particles should be negatively clfarged i t has been found that the non-noble metals are positively and the noble metals negatively charged. This can be explained by assuming that the non-noble metals react with water t o form a film of hydroxide which ioaises hydroxyl ions passing into the water and leaving the metal positively charged. The noble metals on the other hand form hydrides which ionise and the particles are left negatively charged. This is supported by the fact that the noble metals do not yield colloidal solutions in methyl or ethyl alcohol whereas the non-noble metals behave a s in water. I n ethyl malonate on the other hand the behaviour of the two groups is exactly reversed. This view is developed in detail and applied to other qiihstances which give rise to colloidal solutions.€I M. D. Simultaneous Coagulation of Two Colloids. F. W. Tn BACKX (Zeitsch. Chern. Ind. Kolloide 19 11 8 198-201).-The coagulation of solutions containing gelatin and gum arabic on the addition of acids leads t o the separation of both colloids. Experiments showing the influence of different amounts of hydrochloric sulphuric acetic and citric acids of the relative proportions of the colloids 2nd of the absolute concentration are described. The phenomena observed on addition of salts are very similar. H M. D. Some Reactions in Gels. BMTL HATSCHEK (J. Soc. Chem. Ind. 1911 30 256-258).-The formation of a number of insoluble precipitates from solutions containing gelatin has been studied stratified layers being ohtnined.The micro-crystslline precipitates composing these layers have been photo:raphed. Spherulitic forms are obtained in most cases lead salts giving large spherulites,GENERAL AND PHYSICAL CHEMISTRY. ii. 379 cspeciall y from agar solu t,ions. Barium silicofluoride y ieldh remark- ably perfect and transparent although smaller spherulites. The oniy compound which mas not found to assume this form is lead ferrocy:mide which forms long crystallites terminating in rhombohedra. C. H. D. The Theory of Swelling. KARL SPIRO (Gedenkboek aangeboden cmn J. M. wan Bemmelen 1910 261-2GG).-Experiments are described which indicate that the swelling or contraction of plates of solidified gelatin or agar jelly is to some extent determined by forces acting at the surface of the jelly which tend to contract it.Eoth the swelling and contraction which occur when the jelly is immersed in certain solutions are dependent on the original gelatin or agar content of the solidified jelly. Isosmotic solutioris of sodium and cdcium chlorides are found to give rise to swelling or contraction effects of different magnitudes. The importance of the phenomena in connexion with changes in plant and animal cells is referred to. H. M. D. ‘‘ Pyrosols.” Colloidal Phenomena in Molten Solids. RICHARD LORENZ (Gedenkboek accngeboden acin J. ill. van Bemmelen 1910 395-398).-The coloured turbid liquids which are obtained when metals aie heated in contact with their fused salts are supposed to represent colloidal solutions of the metal and for these the name “ pyrosol ” is suggested.H. M. I). Separation on the Appearance of a Solid Phase. ANDREAS SMITS (G‘edenkboek armgebodennm~ J . A?. van Bemmelen 19 10 434-440). -A theoretical paper on the equilibrium with solid phases. A. J. W. Heterogeneous Equilibrium in Dissociating Conipounds. 111. 9. E. U. SCHEFFER (Zeitsch. yhysikal. Chem. 1911 ’76 161-173). -The three-phase equilibrium in the system NH,-H,S has been redetermined by a more accurate method ; the results correspond very closely with those previously obtained (Abstr. 1910 ii 278). On the basis of these results the properties OF the system a t relatively low temperatures (about 30’) are more accurately stated. The work of Briner (compare hbstr.1909 ii 124) is adversely criticised in some respects. G. S. Equilibria in the System Sulphuric Acid Ammonia and Water at 30’. G. (7. A. VAN DORP (Chem. JVeekblad 1911 8 269-273).-An application of’ Schrcinemaliers’s graphic method with special reference to the possibility of the formation of primary ammonium sulphate in the manufacture of ammonium sulphate. A. J. W. Equilibrium between Sodium Carbonate Sodium Hydrogen Carbonate a n d Water. 11. HEEBERT N. McCoy and CHARLES D. TEST (J. Amer. Chem. Xoc. 1911 33 473-476).-In an earlierii 380 ABSTRACTS OF CEEMICAL PAPERS. paper (McCoy Abstr. 1903 ii 413) an account was given of a study of the equilibrium between sodium carbonates carbon dioxide and water in solutions of N/10- to AT-concentration. The work has now been extended to solutions in equilibrium with solid phases at 25O.Sodium hydrogen carbonate (40 grams) and water (about 200 c.c.) were rotated in a thermostat until equilibrium was reached. About 15 grams of sodium carbonate decahydrate were then added to the mixture of saturated solution and sodium hydrogen carbonate and the mixture was again rotated until a new state of equilibrium was attained. The results obtained by continuing this method are plotted a$ a curve in which the ordinates represent the number of grams of sodium per C.C. of solution and the abscisss the percent- ages of total sodium in the solution in the form of sodium hydrogen carbonate. A t the point at which 1209% of the sodinm is in solution as sodium hydrogen carbonate and 87.1% as aodium carbonate a new solid phase Na2C0,,N;zHC03,2H20 appears in the form of long needles.Between this point and that a t which 5.92% of the sodiumis present as sodium hydrogen carbonate only this one solid phase exists but at the latter point another solid phase Na2C0,,10H,0 appears. E. G. Equilibrium between Alkali-Earth Carbonates Carbon Dioxide and Water. HERBERT N. McCoy and HERBERT J. SMITH (J. Amer. Chem. Xoc. 19 11 33 468-473).-This investigation was undertaken in view of the fact that previous workers had not used modern methods and had not made measurements a t higher pressures than 6 atmospheres. Experiments have now been made with calcium carbonate with pressures of carbon dioxide between 0.06 and 25 atmospheres.It has been found that the maximum solubility of the calcium salt is 0.485 normal molecular and corresponds with a pressure of about 15 atmospheres. The solubility of calcium hydrogen carbonate is thus equal to 4.2 grams per litre at 25'. The mean value of the equilibrium constant k at pressures less than 15 atmospheres was 0.0234. I n the case of strontium carbonate experiments have been made at pressures between 0.05 and 1.1 atmospheres. The eyuilibriuiu constant k = 1.29 x Sr x CO = 1.567 x 10-9. Experiments have also been made with barium carbonate at pressures between 0.2 and 30 atmospheres. A maximum solubility 0.028 is reached a t a carbon dioxide pressure of about 22 atmospheres. The solubility of barium hydrogen carbonate is 7.3 grams per litre a t 26".The equilibrium constant k = 2.24 x 10-2 and the solubility product Ba x CO = 8.1 x The solubility product Cu x CO = 9.3 x 10-9. and the solubility product E. G. The Ternary System Potassium Sulphat.8 Copper Sulphate and Water below 509. P. A. MEEHBURQ (Gedenkboek ccanyeboden acln J. M. van Bemmelen 1910 356-360. Compare Trevor Abstr. 1891 973).-A criticism of Trevor's work on solutions ofGENERAL AND PHYSICAL CHEIPZISTRY. ii. 381 potassium sulphate and copper sulphate. The author employs Schreinemakers's graphic method and disputes Trevor's statement that his solid phases were pure salts and not mixtures. Equilibria in the System Water-Ammonium Chloride-Lead Chloride. J. N. BR~NSTED (7th Intwn. Congr. AppZ. Chern. 1909 Sect.X. 110-1 1 l).-The solubility of lead chloride insolutionsof ammonium chloride has been examined at 2 2 O . The solubility curves of lead chloride and of the double salt 2PbCI,,NH4C:1 intersect at a oon- centration of O*52N-ammonium chloride a t which point both solid salts are in equilibrium with the solution. Equilibria in the System Sodium Chloride Sodium Sulphate Cupric Chloride Cupric Sulphate and Water at 25". FRANS A. H. SCHREINEMAKERS and (Miss) W. C. DE BAAT (Gedenkboek aangeboclen uan J. M. van Bemrnelen 19 10 36 1-367). -An applica- tion of Schreinemakers's graphic method. At 25' the solid phases of the quaternary system are NaCl,Na,SO ; Na,SO,,lOH,O ; CuS0,,5H20 ; Na,Cu(S0,),,2H20 and CuC1,,2H20. Nature of Disperse Systems. P P. VON WEIMARN (Zeitsch. physikal.Chem. 191 1 76 212-230).-A theoretical paper. I n the systems liquid-solid and liquid-liquid there are three types of disperse systems the first being characterised by the gradual diminution and the second by the progressive increase in the degree of dispersion of the disperse phase. The third type occurs near the Doint of transition of the one-phase to a two-phase system; for example in disperse systems near the critical point. The different types are discussed in detail. G. S. The Composition of Eutectic Mixtures. CECIL H. DESCEE (Trans. Paraday Xoc. 191 I 6 160-166).-The methods of predicting the position of the eutectic point in binary systems are discussed and the rules proposed by Flawitzky (Abstr. 1906 ii 152) and GorboE (Abstr. 1910 ii 111) are tested by application to a large number of binary mixtures being found to have only a limited validity.A. J. W. C. H. D. A. J. W. C. H. D. Temperature-coefflcient of Chemical Reaction Velocities. V. Reaction Path and Nascent State. The Upper Limit of Chemical Reaction-Velocity and t h e Temperatures at which it is Reached. MAX TRAUTZ (Zeitsch. yhysikaZ. Chem. 1911 '76 129-144).-A further theoretical discussion of the temperature- coefficient of chemical reaction velocities on the lines of the author's recent communications (compare Abstr. 1910 ii 24 114 1051). The formula already referred to leads to the conception of an upper limit for the speed of reactions and the temperatures at which they are attained. From the available thermal data and making use of Nernst's theorem it is calculated that the temperature of maximum velocity for the thermal decomposition of nitric oxide is 5468Oabs.and the time taken for the decomposition of 99.9% of the gas is 0.66 second when the initial pressure is one atmosphere. On the same lines the rate of combination of nitric oxide and oxygen has been calculated VOL C. ii. 26ii. 382 ABSTRACTS OF CHEMICAL PAPERS‘ at a readily attainable temperature. This reaction i d now being investigated by Bodenstein and it will be possible to test the formula when the experimental data are available. The Hypohalogenous Acids and the Hypohalogenites. 111. Influence of Electrolytes on the Velocity of the Hypoiodite Reaction. ANTON SKRABAL (Monatsh. 1911 32 167-184).-1n continuation of the author’s investigations on the kinetics of the decomposition of hypoiodites (Abstr.1907 ii 448) the influence ofi electrolytes on the velocity of reaction has been studied. Electrolytes- accelerate the reaction but their influence is much less than in t h e analogous hypobromite reaction (Abstr. 1909 ii 224). The acceleration is not a simple function of the electrolyte concentration [El but a complex function of [El [OH’] and [I’]. With large concentrations of iodide ions and small concentrations of hydroxide ions the course of the reaction is best represented by the equation - d[lOH]/dt = R[IOH]2[I’]/[OH’] whereas with small con- centrations of iodide ions and large concentrations of hydroxide ions the equation which best represents the reaction is - d[IOH]/dt = K‘[IOH]2f[I’] + e[E])/fOH’] ; e is only approximately constant its value being of the order 0.01.The second equation best represents the course of reaction under the most varying conditions G. S. The temperature quotient (for 10’) of the reaction is 2.1. If the concentrations are expressed in gram-formula-weights per litre the time in minutes and the temperature in absolute degrees the velocity of the formation of iodate according to the equation 310H + 30H’ = 21’ + 10,’ + 3H,O at temperatures in the neighbour- hood of room temperature is expressed by the equation -d[IOH]/dt = 2.2 x x 10°’03222T([I’] + 0.01[E])[IOH]2/[OH’]. By means of this equation the velocity of formation of iodate from alkali hydroxide and iodine or from alkali hydroxide iodine and potassium iodide solutions can be accurately calculated for all attain- able concentrations.T. S. P. The Hypohalogenous Acids and the Hypohalogenites. IV. The Influence of Electrolytes on the Velocity of the Hypobromite Reaction. ANTON SKRABAL (Xonatsh. 191 I 32 185-196).-The equation previously put forward (hbstr. 1909 ii 224) to represent the velocity of formation of bromate from hypo- bromite namely - d[BrOH]/dt = K’[)3rOH]3([Br’] + e[E]>/[OH’] has been further tested. The value of e is found to be 0.5 but it can be taken as constant only as a first approximation since its value depends on the conditions of experiment. When the ratio [OH’] [Br‘] is very great e becomes greater than 1. The temperature quotient of the hypobromite reaction is 1.7. If the concentrations are expressed in gram-formula-weights per litre the time in minutes and the temperatures in absolute degrees the velocity of the formation of bromate according to the equation 3BrOH + 30H‘ = 2Br’ + BrO,’ + 3H20 a t temperatures in the neighbour- hood of room temperature is expressed by the equation - d[HOBr]/dt = 2-7 x 10-11 x 100’02350T([Br’] + 0*5[E])[HOBr]2/[0H‘]. Owing to the inconstancy and high numerical value of e this equation is not valid forGENERAL AND PHYSICAL CHEMISTRY.ii. 383 so large a range of concentrations as the corresponding equation for the hypoiodite reaction. A t 25') and in solutions free from electrolytes the hypoiodite reaction proceeds 440,000 times as fast as the hypobrornite reaction ; this ratio is somewhat smaller in the presence of electrolytes.The calculated ratios and those experimentally determined are in good agreement with each other. Rate of Reaction between Potassium Dichromate and Iodide in the Presence of Hydrochloric Acid and of Catalysts. GIUSEPPE KERNOT and F. PIETRAFESA (Rend. Accad. Xci. Pis. Mat. Napoli 1911 [iiiA] 16 275-287).-The rate of reaction between potassium dichromate potassium iodide and hydrochloric acid is pro- portional to the concentration of each of the reacting substances. under corresponding conditions the speed of the reaction is more influenced by the iodide than by the dichromate and most of all by the acid. The authors find by the method of Noyes that the reaction is of the fifth order. Colloidal platinum accelerates the reaction proportionally to its concentration but the effect falls off as the reaction proceeds.Ferrous sulphate also accelerates the reaction to an extent proportional to its concentration. The effect of a mixture of colloidal platinum and ferrous sulphate is rather greater than the sum of the separate effects. G. S. The Rate of Dissolution of Metallic Copper in Aqueous Ammonia. EUCHI YAMASAKI (7th Intern. Congr. Appl. Chem. 1909 Sect. X. 172-178).-1n the preparation of Schweizer's reagent by the action of ammonia on copper in presence of air the velocity increases regularly from a certain initial value to a maximum and then decreases. The measurements are made in a thermostat at 24*8' the partial pressures of ammonia and oxygen being kept constant. The copper plates used which are rotated in the solution are weighed at intervals.The initial velocity of dissolution is independent of the concentration of the ammonia. The velocity increases proportionally to the concentration of copper already in solution and the maximum velocity is reached at a concentration of copper which is smaller the smaller the concentration of ammonia. The total concentration of copper dissolved in time t may be calculated from the equation Zn(c + k,/k) = kt/A + Znk,/k; k is found to be 4.48 x lo+ and k 2.24 x The accelerating action of copper may be explained by the reactions CU(NH~)~'' + Cu + yNH = ~CU(NH,)'(,+~,,~ and The first reaction proceeds slowly whilst the second is very rapid. The acceleration is thus proportional to the concentration of the complex Cu(NH?),".When pure oxygen is used instead of air the initial velocity is considerably increased whilbt the acceleration is not affected the actual values found being k 12.86 x 10-8 and k 2.126 x which is approximately in accordance with the changed partial pressure of the oxygen. The addition of sodium hydroxide diminishes the velocity. Rise of temperature accelerates it btlt k and k are only increased by 15% by a rise of 10". T. S. P. 2Cu(NH,)',zty,/ + (X - y)NH + 0 + H,O = 2Cu(NH,)," + ZHO'. U. H D. 26-2ii. 384 ABSTRACTS OF CHEMlCAL PAPERS. Action of Brozlline on Formic Acid. ALFRED F. JOSEPH (Zeitsch. physikcd. Chern. 191 1 76 156-160. Compare Bognar Abstr. 1910 ii 282).-The rate of reaction between bromine and formic acid is retarded by mineral acids as well as by chlorides and bromides but is accelerated by sodium sulphate The effect of the same substances on the vapour pressure of dissolved bromine and on its solubility is parallel to that on the rate of reaction.G. S Catalysis. J ACOB BOESEKEN (Gedenkboek aangeboden acm J. M. van Bernmelen 1910 386-391).-l'he author discusses the formation of by-products in catalytic actions and the relation between the amount of the catalyst employed and the velocity of the reaction induced. A. J-. W. Speciflo Stereochemical Behaviour of Catalysts. LEOPOLD ROSENTHALER (Zeitsch. physikal. Chem. 191 1 76 255. Compare Abstr. 1910 ii 840 ; Fajans ibid. 599).-Polemical. G. 8. Modifloation of the Mechanism of Flame by Convergent Combustion. JEAN MEUNIER (Compt. rend. 191 1 152 706-708.Compare Abstr. 1910 ii 407).-A description illustrated by a diagram of a burner suitable for observing the flame of convergent combustion. An Auer burner from which the cylinder has been removed carries a central metallic stem supported by the wire gauze. The lower third of this is surrounded by a conical spiral of platinum wire terminating in a narrower platinum cone. The burner is lighted to heat the platinum and the gas momentarily cut off by compressing the tube. On allowing gas to pass again the platinum becomes incandescent and on applying a light to the upper part of the central stem a flame of air burning in coal gas appears at the point. I t is protected from draughts by an inverted lamp cylinder held in a wire support. w. 0. w. A Sublimation Apparatus.R. WRIGHT (Chem. News 1911 103 13S).-Tbe apparatus consists of a narrow bell-jar fitted with a cork through which passes the delivery tube of a small glass retort the tube being cut off fairly short. The substance t o be sublimed is placed in the retort which is then connected with the bell-jar and the whole inverted over a watch glass or small porcelain dish resting on a few thicknesses of moist filter-paper laid on a tile. On gently heating the retort bulb the substance sublimes into the dish. Slow beating is necessary otherwise the substance may be deposited on the sides of the jar. By placing the jar on a ground glass plate and connecting with a pump by means of an extra tube through the cork sublimations may be carried out in a vacuum. T. S. P. A Simple Constant-Temperature Bath for Uee at Tempera- tures both Above and Below that of the Room.J. LIVINGSTON R. MORGAN (J. Anzer. Chews. Soc. 1911 33 344-349).-By meansGENERAL AND PHYSICAL CHEMISTRY. ii. 385 of the movement of mercury in the regulator which is immersed in the bath an electrical circuit is completed. This contains a small relay which is so arranged that the house circuit can be either made or broken in a large telegraph sounder. This is so placed as to act on a rod which by means of a suspended weight presses tightly on a piece of rubber tubing through which hot or cold water can be automatically delivered to the thermostat. It is said that any tem- perature between 0.lo and 90' can be maintained with an accuracy of a few hundredths of a degree. Crucible Furnace. NORMAN ROBERTS and F. ALEX MCDERMOTT (J. Amer. Chem. Soc. 1911,33 507-510).-A small crucible furnace is described which is heated by gas the flame entering at the bottom. It consists of an outer container and an inner lining both made of sheet- iron the intermediate space being filled with a non-conducting refractory powder such as light magnesia kaolin or sifted ashes. The inner lining is more durable if made of clay or graphite but these materials are less satisfactory than sheet-iron since the latter can be more easily replaced is free from risk of breakage and is more quickly heated than a more massive lining. The crucibte is supported either by a pipe-clay triangle the wire exposed a t the bends being coated with asbestos or by a riag of graphite clay or iron. The lid consists of a circular disk of sheet-iron with a hole in the middle or may be made of asbestos board or clay. Such a furnace with both iron and graphite linings has been found capable of melting copper brass and even cast-iron. The furnace is superior to those with solid walls of clay or some similar substance since it is lighter less expensive better insulated can be more rapidly heated and can be more easily and cheaply repaired. H. M. D. The insulating layer can be made of any desired thickness. E. G. Pulsating Ultraflltration. HEINRICH BECHHOLD (Gedenkhoek aangeboden ann J. M. van Bemmelen l910,430-433).-1n reference to the possible influence of the pulsations of the blood pressure on the velocity of blood secretion processes the author has compared the rates of filtration through a collodion membrane under continuous pressure and under conditions in which the pressure was periodically removed and allowed to act for thirty seconds. The results indicate that filtration takes place more quickly under the influence of the pulsating pressure. H. M. D. A. BOLLAND (Chem. Zeit. 1911,35 373).-To an ordinary spherical-shaped separating f uonel is added an extra tubulure in the upper quadrant of the sphere. Through this tubulure paps two tubes fitted with stopcocks and so arranged that the .upper layer in the funnel can be removed without first running out the lower layer. Time and trouble are thus saved when a liquid has t o be repeatedly extracted with a lighter solvent. Lecture Experiment on the Extinction of Burning Light Petroleum etc. P. KATHGEN (Chem. Zeit. 1911,35 308).-A wide- A New Separating Funnel. T. S. P.ii. 386 ABSTRACTS OF CHEMICAL PAPERS necked bottle contains sodium carbonate solution to which liquorice extract has been added. A tube with a thin bnlb containing hydro- chloric acid passes through the cork. On breaking the bulb by pushing down the tube foam escapes from a delivery tube and is directed on to the burning light petroleum. C. H. D.

ISSN:0368-1769    

DOI:10.1039/CA9110005349

出版商:RSC    

年代:1911

数据来源: RSC